LI NI U

Nn kinh t nc ta ang trn i mi v pht trin, nhu cu thuc nhum v cht mu hu c dng nhum v in hoa hng dt k c cc mt hng him nh la t tm, len v cc mt hng t nhiu loi s si tng hp tng ln nhanh chng. Thuc nhum v cht mu cn c s dng nhiu trong cc ngnh m trc y cha c nhu cu cao nh: pha ch sn, mu, nhum, nha ho hc v cao su, nhum giy, in vn ho phm v bao b, nhum da thuc v lng th; chng cng c dng nhum chiu ci, my tre, nhum thc phm, dc phm v m phm v.v. Thuc nhum v cht mu ang c s dng to dng p cho cc mt hng tiu dng, phc v cho mt thi trang rt a dng ca hng may mc v trang tr mu sc trong nhiu lnh vc ca cuc sng. Song nc ta cha ch to c thuc nhum, dng nh ton b thuc nhum dng cho cc lnh vc k trn u phi nhp khu. Mt s vin v trng i hc ang nghin cu ch to nhng vn cn giai on th nghim. Thuc nhum v cht mu li l loi vt t kh t, vic nm vng tnh nng ca mi chng loi, la chn cho ng mt hng ch to hay s dng bo m t cht lng v hiu qu mu sc cao nht m li tit kim nht l vic lm khng d dng. Bin son cun sch ny chng ti c nh p ng phn no nhng kin thc c bn nht cho s ng bn c v l thuyt mu sc, v nguyn tc tng hp thuc nhum; v tn gi, cu to ho hc, tnh cht v phm vi s dng ca cc lp thuc nhum k thut; v cc phng php kim tra, nh gi v phn tch thuc nhum. Chng I v chng III do PGS, TS Cao Hu Trng bin son, Chng II v IV do PGS, TS Hong Th Lnh bin son. Phn b sung do PGS, TS Hong Th Lnh bin son. Ni dung trnh by trong tp sch khng nhng l nhng kin thc v hiu bit chung c la chn trong cc ti liu m cn l nhng kinh nghim chuyn mn tch ly c sau nhiu nm cng tc, ging dy. Chng ti hy vng cun sch ny s l ti liu tham kho b ch cho nhiu cn b khoa hc, k s, cn b k thut ang dnh thi gian cho vic nghin cu ch to v s dng thuc nhum; n cng gip cc nh doanh nghip, cc cn b lm cng tc giao dch xut nhp khu. c bit cun sch ny cn gip ch cho nhiu sinh vin, hc sinh cc trng i hc, cao ng v trung hc chuyn nghip ang theo hc cc ngnh ho, cng nh nhiu bn c ang quan tm v vn ny. Mc d chng ti ht sc c gng, song cun sch khng trnh khi cn c nhng thiu st. Chng ti rt mong nhn c kin ph bnh gp ca cc bn ng nghip v bn c gn xa cc tc gi c dp rt kinh nghim v b khuyt. Chng ti rt hn hnh c trao i trc tip hoc bng th t vi bn c theo a ch: B mn Vt liu v Cng ngh Ho dt, Khoa Cng ngh Dt - May v Thi trang, Trng i hc Bch khoa H Ni hoc Nh xut bn Khoa hc v K thut, 70 Trn Hng o, H Ni. Chng ti xin by t lng cm n chn thnh n Nh xut bn Khoa hc v K thut v ch Kim Anh ht sc gip chng ti xut bn cun sch ny. Cc tc gi 3

M U
1. S LC V THUC NHUM Trong cuc sng mun mu ca con ngi thuc nhum c s dng rt a dng trong nhiu lnh vc v nhiu ngnh kinh t khc nhau. Trong k thut v trong sinh hot chng ta thng gp cc thut ng nh: thuc nhum, pigment, bt mu v.v. chng u l cc hp cht c mu nhng bn cht, cu to, tnh cht v phm vi s dng th khc nhau, cn phn bit cho ng. Thuc nhum l tn ch chung nhng hp cht hu c c mu (gc thin nhin v tng hp) rt a dng v mu sc v chng loi, chng c kh nng nhum mu, ngha l bt mu hay gn mu trc tip cho cc vt liu khc. Ty theo cu to, tnh cht v phm vi s dng ca chng m ngi ta chia thuc nhum thnh cc nhm, h, loi, lp khc nhau. Pigment l tn ch mt s thuc nhum hu c khng ho tan trong nc v mt s hp cht v c c mu nh cc oxit v mui kim loi. c im chung ca pigment l khng ho tan trong nc, khng c i lc vi cc vt liu khc, n c dng nhum mu cho cc vt liu khc bng cch gin tip hoc nh mng lin kt hoc bng cch phn phi su trong khi vt liu. Bt mu l thut ng ch yu ch cc hp cht v c c mu c dng trong lnh vc sn xut vt liu xy dng. Thuc nhum c dng ch yu nhum vt liu dt t x thin nhin (bng, lanh, gai, len, t tm...), x nhn to (vixco, axetat, polyno,...) v x tng hp (polyamit, polyeste, polyacrylonitrin, polyvinylic, polyolefin...). Ngoi ra chng cn c dng nhum cao su, cht do, cht bo, sp, x phng; ch to mc in trong cng nghip n lot, ch to vn phng phm, vt liu lm nh mu dng lm cht tng v gim nhy vi nh sng. nhum cc loi vt liu dt a nc ngi ta dng nhng lp thuc nhum ho tan trong nc, chng khuch tn v gn mu vo x si nh cc lc lin kt ho l, lin kt ion hoc lin kt ng ho tr vi thuc nhum hot tnh. nhum cc loi vt liu dt ght nc v nhit do (x axetat v x tng hp) ngi ta dng loi thuc nhum khng tan trong nc, sn xut dng bt mn phn tn cao gi l thuc nhum phn tn, n bt mu vo x si theo c ch ho tan (x si l dung dch rn) hoc phn b su trong h thng mao qun ca x. nhum cao su, cht do, ch mu, mc in, sn mu, ngi ta dng pigment v nhng loi thuc nhum khng tan trong nc. Trong trng hp ny pigment hay thuc nhum c gn vo vt liu hoc l nh cht to mng (khi nhum b mt) hoc l trn vi khi vt liu phn b chng su trong . Khi nhum cht bo, du, m, xng, vecni nitro ngi ta dng loi thuc nhum ho tan trong cc vt liu ny. 2. THUC NHUM THIN NHIN T thi thng c loi ngi bit s dng thuc nhum thin nhin ly t thc vt v ng vt: Bng cc mu vt khai qut c Kim T Thp Ai Cp, Trung Quc v n ngi ta xc nh rng trc cng nguyn 1500 nm ngi Ai Cp bit dng inigo (mu xanh chm) nhum vi v s dng ph bin alizarin ly t r cy marena nhum mu , s dng campec chit xut t g si nhum mu en cho len v la t tm. Ngoi ra ngi ta cn chit xut c cc mu vng, tm v - tm t mt s loi cy khc nhau. 5

Tr mu xanh chm v mu alizarin l c bn mu cao, nhn chung thuc nhum thin nhin c bn mu thp, nht l vi nh sng, cng lc mu nh do cha trong phn t h thng mang mu km bn. Hn na hiu sut khai thc thuc nhum t thc vt rt thp, phi dng nhiu tn nguyn liu mi thu c mt kilgam thuc nhum, nn gi thnh rt cao. V vy n nay hu ht thuc nhum thin nhin b thay th bng thuc nhum tng hp, s cn li ch yu c dng nhum thc phm hoc nhum vi ca cc dn tc t ngi theo phong tc c truyn. n nay ngi ta xc nh c cng thc cu to ca mt s thuc nhum thin nhin theo tng loi mu, t nh gi c tnh cht s dng ca chng. 2.1. Thuc nhum thin nhin mu vng Tt c thuc nhum thin nhin mu vng u c ngun gc thc vt. Mu vng quan trng hn c c dng trong nhiu th k qua l rezea. Khi phi n vi mu xanh chm s nhn c mu xanh lc gi l mu Lincon tuyt p. 2.2. Thuc nhum thin nhin mu Khc vi cc mu vng, ba trong s bn thuc nhum mu thin nhin (cecmec, cosenil, lac) c ngun gc ng vt, song mu quan trng nht vn l marena hay cn gi l alizarin thu c t thc vt. Tt c cc thuc nhum mu k trn u l dn xut hiroxy ca antraquinon. Cc dn xut khc nhau ca chng cn c ng dng n ngy nay do chng c mu ti nh, c bn mu rt cao vi nh sng. V vy c th ni rng thuc nhum thin nhin mu c bn mu vi cc ch tiu cao hn nhiu so vi cc mu vng. 2.3. Thuc nhum thin nhin mu ta Cu to ca thuc nhum thin nhin mu ta c Fridlender tm ra vo nm 1909, chnh l 6,6-ibrominigo (4). Gn y t thn l ca cy Dacathais orbita ngi ta xc nh c qu trnh to thnh mu ta ny. Hp cht ban u l tirinocxysunfat (1) c mu ghi, khi thy phn bng men n s chuyn thnh tirinocxyl (2), mt phn b oxy ho bng oxy ca khng kh n 6-brom-2-metyl-tioinoleninon (3). n lt mnh hp cht (3) ny li kt hp vi (2) thnh phc 1: 1 kiu quihiron (tiriverin), di tc dng ca nh sng mt tri n bin thnh 6,6-ibrominigo (4) l gc ca mu ta. Qu trnh nh sau:
OS3Me+ SMe Br N H
ln men

OH SMe Br N H
+ [O]

O SMe Br N H

(1)

(2)
O H N Br N H O

(3)
Br

(1)

(2)

nh sng mt tri

(4) 6

2.4. Thuc nhum thin nhin mu xanh chm Trong cc mu xanh thin nhin c mu xanh lam vaia v mu xanh chm c dng n ngy nay. Lc u ngi ta cho rng l hai mu khc nhau, v sau mi bit chng ging nhau v cu to ho hc v chnh l inigo tch c t cy h chm c tn khoa hc l Indigofera tinctoria L, c cng thc ho hc nh sau:
O H N N H O

Hin nay inigo l mt trong hai thuc nhum thin nhin vn cn c ngha thc t tuy n c tng hp v ch to phm vi cng nghip. 2.5. Thuc nhum thin nhin mu en Thuc nhum thin nhin mu en c ngha thc t duy nht l mu en campec, n c bit t nm 1500, nhng n nm 1812 mi thc s c ngha thc t khi mt nh ho hc Php tm thy n c kh nng to thnh phc khng tan vi mui kim loi c mu en. Khi mi tch t g campec ra, hp cht ban u c mu gi l hematein, khi kt hp vi mui crm n chuyn thnh mu en v th m g campec tr nn c gi tr. Hematein c cng thc nh sau:
OH HO O OH

HO O

Mc d cha bit c th cu to ca phc kim loi ny nhng ngi ta cho rng n c cu trc i phn t, trong ion crm lin kt vi cc phn t hematein to thnh phc. Cn nhn mnh rng a s thuc nhum tng hp mu en dng trong ngnh dt v mt s ngnh khc u l hn hp ca hai hoc nhiu hn na cc thuc nhum thnh phn, v thuc nhum tng hp mu en c mu khng ti khi dng ring. Mu en campec c dng nh l mt thuc nhum n, ring bit, nhum t tm, da v mt vi vt liu khc, vn c ngha n by gi. 2.6. S dng thuc nhum thin nhin Vit Nam Cha c ti liu no cho bit c th nin i ngi Vit Nam bit dng cc mu thin nhin, ch bit rng cng ng cc dn tc Vit Nam t thi thng c dng thuc nhum thin nhin trong i sng. Kinh nghim dng thuc nhum ly t tho mc truyn t i ny sang i khc cc min, cc vng c cc loi cy ny. n nay ng bo thiu s cc tnh min ni pha Bc vn cn dng l chm nhum mu xanh lam. Nhng thp k u ca th k ny mt s vng Bc B dng 7

nc chit t c nu nhum mu nu ti, khi nhng vo bn ao th mu nu ny chuyn thnh mu en rt bn v p (y cng l mt dng phc ca thuc nhum vi ion kim loi nng c trong bn). Ngoi ra nhum nu v en ngi ta cn dng l bng, v s, v vt v mt s v v l cy khc na. nhum en mt s vng Nam B cn dng nc chit t qu mc na nhum lt sau nhng vo bn sng Hu s to thnh mu en bn v p. Mt s loi l v qu c dng nhum thc phm nh: qu ginh ginh, bt ngh nhum mu vng, l cm si nhum xi mu v.v. n nay vn cha c c s t chc chit tch thuc nhum thin nhin dng vo mc ch k thut v dn sinh; vic s dng chng nc ta vn da vo kinh nghim dn gian ca tng min. 3. THUC NHUM TNG HP n nay vic nghin cu v ch to thuc nhum tng hp t n nh cao c v mt khoa hc v cng ngh. Cc hng ch to sn xut v bn ra trn th trng th gii hng trm mu ca trn mi lp thuc nhum khc nhau; chng khngnhng c mu sc p v rt a dng m cn c bn mu cao hoc rt cao vi nhiu ch tiu c l v ho l. t c nhng thnh tu nh vy, vic nghin cu v sn xut chng cng phi tri qua cc thi k pht trin t thp n cao, t n gin n phc tp. 3.1. Cc giai on pht trin Ngi c vinh d pht minh ra thuc nhum tng hp u tin pararoalinin t anilin (1855) l I. A. Natason, gio s Trng i hc tng hp Vacsava. Sau mt nm (1856) nh ho hc tr ngi Anh l V. G. Pekin tng hp c thuc nhum mu tm tn gi l movein thuc lp thuc nhum azin v l thuc nhum tng hp u tin c sn xut phm vi cng nghip. t nm sau, Lyon, mt trung tm t la ca Php, F. E. Vergen tng hp c thuc nhum baz u tin c gc triphenylmetan, l thuc nhum fucxin. C nhiu yu t nh hng n qu trnh nghin cu v ch to thuc nhum tng hp, trong vic pht trin ngnh ho hc hu c v vic ra i x si tng hp l nhng yu t c tm quan trng hng u. Qu trnh pht trin ca thuc nhum tng hp c th chia lm ba giai on. Giai on th nht (1855 - 1876) Giai on ny c nh du bng cc pht minh v ng dng vo sn xut thuc nhum lp azin v triphenylmetan (movein, fucxin, tm metyl, inulin, xanh metylen); mt s thuc nhum azo (vng anilin, nu bismac, crizoiin) v.v. a s nhng thuc nhum k trn thuc v lp thuc nhum baz, chng ch nhum mu cho t tm v len; cn khi dng nhum vi t x xellulo th phi dng hn hp tanin - antimoin lm cht hm mu (cm mu). Tt c nhng thuc nhum ny u c sn xut t anilin v cc dn xut ca n nn cn c tn gi lch s l thuc nhum anilin. Xut pht t nh to nn thuc nhum c bn mu cao trn x bng, nm 1863, J. Laifut tm ra quy trnh tng hp thuc nhum anilin en bng cch oxy ho trc tip anilin trn vi. Pht minh ra phn ng iazo ho ca P. Griss nm 1858 ng vai tr m ng v t nn mng cho vic sn xut thuc nhum azo l lp thuc nhum c phm vi ng

dng rt rng, vi c im chung l cha nhm azo trong phn t m cc thuc nhum khc khng c. Trong thi k ny nhiu nh khoa hc ch nghin cu bn cht ca mu sc v s lin quan gia cu to ca thuc nhum v mu sc. Nm 1876, O. Witt ra thuyt mang mu v tr mu, l thuyt mu u tin, tuy n cha i su vo bn cht m ch da vo hin tng v n nay n ch c gi tr lch s nhng n m ng cho s pht trin ca l thuyt mu. Nhng thuc nhum tng hp c pht minh v ch to giai on th nht khng ging nhng thuc nhum thin nhin ang dng thi by gi, v vy ny sinh nh nghin cu v ch to nhng thuc nhum tng hp c tnh cht tng t nh cc thuc nhum thin nhin c trng dng nht. Theo hng , nm 1868 K. Grebe v K. Libecman ch to c thuc nhum alizarin t 1,2-ibromantraquinon. Cng nm y, A. F. Bayer bt u nghin cu tng hp inigo v nm 1878 ng thnh cng trong vic ch to thuc nhum ny t izatin. Giai on th hai (1876 - 1893) Giai on ny c nh du bng vic bt u sn xut thuc nhum azo. Nhng thuc nhum azo c sn xut lot u tin hu ht l thuc nhum axit, thuc nhum cm mu (alizarin vng GG) v mt s thuc nhum nhum t tm v len, cha c thuc nhum no c kh nng bt mu trc tip vo x bng. n y lch s pht trin thuc nhum ghi nhn mt pht kin tuyt vi na, l vic tm ra thuc nhum cng, m u cho vic nghin cu v sn xut loi thuc nhum ho tan trong nc c kh nng t bt mu vo x xenlulo, v cng m u cho vic hnh thnh v hon chnh dn lp thuc nhum trc tip hay cn gi l thuc nhum supstantip. Vo nhng nm tm mi ca th k qua R. Holiday tm ra phng php tng hp thuc nhum azo khng tan (azoid) trn vi. Lc u ngi ta dng -naphtol cho kt hp vi p-nitroanilin iazo ho nhn c mu dng vo vic nhum v in hoa, v sau thay th -naphtol bng cc arylit ca axit -oxynaphtoic v gi l naphtol AS. Phng php tng hp thuc nhum azo khng tan trn vi c coi l c bn hon thin vo nm 1911. Giai on th ba (1893 - 1902) Giai on ny c nh du bng s pht trin sn xut thuc nhum lu hunh v hon thin cng ngh tng hp inigo. Nm 1893 ln u tin trn th trng th gii xut hin thuc nhum lu hunh mu en c tn gi thng phm l Vial en, sau ln lt ra i cc mu khc ca lp thuc nhum ny. Nm 1897 A. F. Bayer hon thin cng ngh sn xut inigo phm vi cng nghip, sau R. Bon tng hp c thuc nhum hon nguyn c mu xanh lam ging nh inigo gi l inantren xanh lam, tiu biu cho thuc nhum hon nguyn dy antraquinon c bn mu v nh rt cao. gim bt kh khn khi chun b dung dch nhum t thuc nhum hon nguyn khng tan, u th k XX ngi ta thnh cng trong vic ch to thuc nhum hon nguyn tan (inigosol, cubozol...). Cn nng cao bn mu ca thuc nhum trc tip, nm 1883 ngi ta dng mui ng, v dng mui crm tng bn mu cho mt s thuc nhum axit. n nm 1893 cc nh ho hc ch to c thuc nhum axit cm mu hay thuc nhum axit crm c bn mu rt cao vi git v nh sng. Mt khc khi cm mu bng mui kim loi th mu ban u s bin i kh khn cho vic thit 9

k cng ngh nhum. khc phc hin tng ny nm 1915 ngi ta tm ra qui trnh cng ngh tng hp thuc nhum axit cha kim loi 1 : 1 v n nm 1951 th tm ra thuc nhum cha kim loi 1 : 2 nhum len trong mi trng trung tnh. Vn nhum la axetat (loi x nhit do, ght nc) c nghin cu v gii quyt t nm 1921 - 1924, lc u ngi ta dng cc ch phm nhum azo khng tan, sau dng cc dn xut ca nitroiphenylamin v n gin hn l dng dn xut ca antraquinon gi l thuc nhum acet. Khi nhu cu nhum x tng hp cao th ra i lp thuc nhum phn tn trn c s ny. Pigment ftaloxianin c sn xut t nm 1934, do c nh v bn mu rt cao nn trn c s gc mu ny ngi ta sn xut c pigment xanh da tri v xanh lc, v sau dng gc mu ny sn xut mt s thuc nhum trc tip bn mu v thuc nhum hot tnh. Sau i chin th gii ln th hai cng nghip sn xut x si tng hp chuyn sang giai on bng n pht trin, nhiu loi x si mi ra i dn n yu cu ch to nhng thuc nhum thch hp cho cc loi x ny. Trong qu trnh tm kim ngoi vic hon chnh dn lp thuc nhum phn tn, mt trng hp khng mong i c gii quyt, l nhng thuc nhum thuc lp baz khng bn mu vi nh sng khi nhum cc loi x khc nhng li bt mu rt tt v c bn mu vi nh sng kh cao trn x polyacrylonitrin (PAN), iu ny dn n vic nghin cu v sn xut loi thuc nhum baz ring cho yu cu ny gi l thuc nhum cation. Mt trong nhng thnh qu tuyt vi trong 40 nm gn y ca ho hc thuc nhum l vic pht minh ra thuc nhum hot tnh, chng c kh nng to thnh mi lin kt ho tr vi x nn c bn mu cao vi gia cng t. Nm 1965 hng ICI (Anh) sn xut ra thuc nhum hot tnh u tin c tn gi l procion, tip theo nm 1957 hng Ciba (Thy S) sn xut ra thuc nhum hot tnh gi l Cibacron. T nhiu nc v nhiu hng c cng nghip ho hc pht trin nghin cu v sn xut thuc nhum hot tnh vi cht lng ngy cng nng cao, chng loi ngy cng m rng bo m t l lin kt ho hc vi x cao, t b thy phn, bn mu, ti mu v cng ngh nhum n gin.

10

Chng I

L THUYT V MU SC
1. LCH S PHT TRIN CA CC THUYT MU T lu cc nh khoa hc nghin cu v tm cch gii thch cu hi: ti sao th gii xung quanh ta li c mu v mu ca chng li khc nhau? y l vn rt hay nhng cng rt kh, tri qua nhiu th k cho n khi cc ngnh khoa hc v vt l v ho hc pht trin n mc cao mi tm c nhng li gii p tng i tho ng v xy dng c l thuyt. mu hin nay. Gii p vn mu sc ca mi vt theo quan im ca ho hu c c ngha l xc nh s ph thuc chung gia s hp th cc tia sng trong min thy c ca quang ph nh sng mt tri v cu to ho hc ca hp cht hu c ni chung v thuc nhum ni ring. n nay nh da vo l thuyt mu ngi ta nh hng cho vic tng hp nn nhng cht mu v thuc nhum mi rt phong ph v a dng. Di y l tm tt ni dung ca cc thuyt mu c s dng nhiu hn c. 1.1. Thuyt mang mu Da trn cc quan im ca Butlerov v Alektsev nm 1876 O. Witt lp nn thuyt mang mu ca hp cht hu c, c coi l thuyt mu u tin. Theo thuyt ny th hp cht hu c c mu do chng cha cc nhm mang mu trong phn t, l nhng nhm nguyn t cha bo ho ho tr. Nhng nhm mang mu quan trng hn c l: CH=CH N=N CH=N N=O NO2 C=O nhm etylen nhm azo nhm azo metyl nhm nitrozo nhm nitro nhm cacbonyl

Theo O. Witt th nhng hp cht hu c cha nhm mang mu c gi l cht mang. Ngoi cc nhm mang mu cn thit, khi a thm vo phn t ca cht mang mt nhm nguyn t gi l nhm tr mu th mu ca hp cht s su hn v s c kh nng nhum mu cho mt s vt liu thch hp. Trong s cc nhm tr mu th quan trng hn c l: OH, NH2, N(CH3)2, N(C2H5)2. Da vo thuyt mang mu ngi ta rt ra mt s kt lun c tnh cht quy lut nh sau: - khi lin kt ni i cch trong phn t ca hp cht hu c c ko di thm th mu s su hn; - tng s nhn thm trong hp cht t cu trc n gin thnh cu trc a nhn phc tp th mu s su hn; - tng s nhm cacbonyl lin kt trc tip vi nhau trong hp cht cng dn n su mu; - vic to thnh mi lin kt mi gia cc nguyn t cacbon trong tng phn phn t v khng ph v h thng mi lin kt ni i cch cng lm cho mu su hn; 11

- vic chuyn nhm tr mu thnh dng mui v alkyl ho nhm amin s dn n su mu; - khi alkyl ho nhm hiroxyl trong nhn thm hoc chuyn nhm tr mu vo lin kt vng th mu ca hp cht s nht i. Tuy cha c nhng gii thch tho mn v bn cht mu ca hp cht hu c, nhng kt lun rt ra ch da vo hin tng v kinh nghim, song thuyt mang mu lm c s cho cc thuyt mu sau ny tip tc nghin cu su hn, n gp phn khng nh vo vic tng hp cht mu v thuc nhum, mt s khi nim n nay vn cn c s dng. 1.2. Thuyt mu quinoit Thuyt mu ny c R. Nesaki xut nm 1888, theo ng th cc hp cht hu c c mu l do trong phn t ca chng c cha nhn thm dng quinoit. minh ho cho thuyt ny ngi ta dn ra th d sau y: parabenzoquinon (1) c mu vng do c cu to quinoit; khi b kh n 1,4-xyclohexanion (2) th b mt mu d vn cha hai nhm cacbonyl l hai nhm mang mu; khi b kh n hiroquinon (3) cng mt mu. Hin tng ny c gii thch rng cc hp cht (2) v (3) mt mu l do khng cn tn ti cu to quinoit.
O H2 H2 O (1) O (2) O H2 H2 OH (3) OH

Thuyt mang mu c s dng gii thch hin tng mu ca thuc nhum da vo cu to phn t ca chng; tuy nhin thuyt ny cha tm c cc quy lut chung, mt s trng hp ngoi l (hp cht c mu nhng khng vit c cu to quinoit) dng thuyt ny khng gii p c hin tng mu. 1.3. Thuyt nguyn t cha bo ho v thuyt to mu khi chuyn hp cht hu c v dng mui Nm 1902 Bayer tm ra hin tng gi l Galocromy, th hin cc hp cht hu c c cha nhm cacbonyl ( C=O), mu ca chng s su hn di tc dng ca axit hay mui kim loi. lm r hn hin tng ny nm 1910 Pfeifer tm thy rng cc axit hay mui kim loi c kh nng kt hp vi oxy ca nhm cacbonyl l do nguyn t oxy cha trong cc hp cht ny c cp in t cha chia nn chng c th lin kt vi axit hay mui ca kim loi lm cho mu su hn, v c cu to mui c th vit tng qut nh sau:
R R C O HX R R
+

OH

khng mu y R l cc gc hu c; HX l axit khong.

c mu

Nm 1928 inte - Vixinge cn nhn thy rng cc nhm mang mu l nhng nhm nguyn t cha bo ho ho tr, khi chuyn sang dng ion th mu s su hn. 12

1.4. Thuyt dao ng mu gii thch bn cht ca hin tng mu, nm 1910 Porai - Cosix (nh bc hc ngi Nga) ln u tin nghin cu su v thc cht ca hin tng mu, gn kh nng hp th cc tia sng vi qu trnh thay i cc mi lin kt gia cc nguyn t trong cc hp cht mu. Theo ng th trong phn t ca hp cht hu c cha bo ho lin tc xy ra bin i hoc dao ng cc lin kt, v gi thit rng s hp th chn lc cc tia sng l kt qu ca s giao thoa gia dao ng ca cc tia sng ng b vi dao ng ca cc lin kt ni phn t trong cc hp cht cha bo ho. Nu nh tc dao ng ca cc lin kt ca hp cht hu c mc ng b vi dao ng ca cc tia sng trong min quang ph nhn thy th im hp th cc i ca cc hp cht s chuyn n min ny lm cho hp cht c mu. Thuyt dao ng mu tin thm mt bc na trong vic gii thch bn cht ca mu sc. 1.5. Thuyt nhim sc Khi nghin cu v bn cht ca mu sc, nm 1915 nh bc hc ngi Nga l V. A. Izmanski ra thuyt nhim sc. Theo ng th kh nng hp th chn lc nh sng ca thuc nhum hu c khng ch do chng cha cc nhm mang mu m cn do chng c thay i cu to trong phn t nh s lin hp ca cc nhm mang mu ring bit v s tng tc ca cc in t trong h thng lin hp. ng gi trng thi ca phn t lc ny l trng thi nhim sc. Trng thi nhim sc ca mt hp cht s xut hin khi mt u ca h thng mi lin kt ni i cch cha nhm nhng in t nh: NH2, NR2, OH, OR, CH3, Cl; v u kia cha mt trong cc nhm thu in t nh: NO2, SO3H, COOH, CN. Do kt qu tng tc ca cc nhm ny qua h thng mi lin kt ni i cch lm pht sinh ra trng thi c bit ca phn t l s cnh tranh in tch ca cc nhm hai u h thng mi lin kt ni i cch, chuyn hp cht sang trng thi c mu. Thuyt nhim sc gp phn gii thch bn cht mu ca mt s thuc nhum hu c. Cc thuyt mu k trn ng vai tr nht nh trong vic nghin cu v gii thch hin tng mu, song do nhng hn ch v iu kin v phng tin nghin cu, cha c thuyt no c coi l hon ho, nht l cha gii thch c y bn cht ca mu sc. Bn cht ca mu sc gn y c nghin cu v gii thch y hn bng thuyt in t. 2. L THUYT MU HIN I 2.1. Bn cht ca mu sc trong t nhin Mu sc l mt hin tng ph thuc ch yu vo cc yu t sau y: 1- Cu to ca vt th c mu; 2- Thnh phn ca nh sng chiu vo vt th v gc quan st; 3- Tnh trng ca mt ngi quan st. Mu sc ca mi vt trong th gii t nhin xung quanh chng ta rt phong ph v a dng. Trc tin n ph thuc vo cu to ho hc ca vt th. Do c cu to ho hc khc nhau nn di tc dng ca nh sng mi vt s hp th v phn x li cc phn tia ti vi t l v cng khc nhau. Nhng tia phn x ny s tc ng vo h thng cm th th gic v truyn thng tin v h thng thn kinh trung ng hp thnh cm gic mu. Mu ca mi vt chnh l mu hp thnh ca cc tia phn x. 13

Do ph thuc vo mt ngi quan st nn mu sc ph thuc vo yu t ch quan ca con ngi. nh gi v phn bit mu sc mt cch khch quan ngi ta ch to ra nhng dng c v thit b o mu da vo bc sng v cc thng s khc na ca cc tia phn x. Hin nay mn khoa hc v mu sc ra i cng vi cc h thng o mu, cc phng php tnh ton mu. Khi nghin cu v mu sc ngi ta dng cc khi nim sau y. Mu quang ph l nhng mu nhn c khi phn tch nh sng trng ra thnh nhng tia mu hp thnh nh cc dng c quang hc, mi mu c c trng bng mt bc sng nht nh t 380 n 760 nm v gi l mu n sc, c im ca cc mu ny l ti v thun sc. Mu v sc (hay cn gi l mu tin sc, mu trung ho) l nhng mu c c trng bng cng mu nh nhau ca tt c cc bc sng. Do c phn x hn hp cc tia sng c bc sng khc nhau vi cng mt cng , khng c tia no tri hn nn chng trung ho ln nhau, nn mt con ngi khng cm th c sc thi ring ca mu. Th d, trong t nhin chng ta vn cm th c cc mu v sc nh: mu trng, mu ghi, mu en. Mu hu sc l nhng mu thin nhin th hin mi vt trong th gii xung quanh chng ta vi cc t: xanh lam, xanh lc, , tm, vng, da cam v.v. Mu hu sc l kt qu ca s hp th chn lc v phn x mt s tia sng c bc sng nht nh. Mu ca vt th l hiu ng mu phi hp ca cc tia phn x m mt ngi cm th c. Mu hu sc chia lm hai loi: mu n sc v mu a sc. Mu n sc chnh l mu quang ph, gp nhng trng hp vt th ch phn x mt tia ca quang ph nh sng trng, cn cc tia khc th hp th ht. Mu a sc l mu ca tp hp cc tia phn x ca mt vt no c bc sng khc nhau nhng cng v t l cc tia ny khng nh nhau. Mu ch o ca vt th s l mu ca tia phn x no chim t l ln nht c ho vi mu ca cc tia cn li theo quy lut phi mu. Trong t nhin ch mu a sc ngi ta dng cc tnh t kp nh: mu tm , lam nh , lc nh vng hoc dng cc mu c sn trong t nhin gi nh: vng chanh, vng kim, xanh da tri, xanh nc bin v.v. Theo l thuyt mu v cc php tnh mu, cc th mu th mu hu sc l mt i lng ba chiu c xc nh bng: tng mu, thun sc hay bo ho v sng hay nh. Tng mu l mt khi nim tng i tru tng nhng cng thng gp. Trong ngn ng thng thng n c hiu l sc iu ca mu v c biu th bng cc t: sc, sc thi, hoc nh mu, th d nh: sc xanh, sc vng hay nh vng. Trong k thut ngi ta hiu tng mu l s khc bit v cm gic mu ca mt mu hu sc no so vi mu ghi c cng sng. Sc hay tng mu c biu th bng bc sng tri ca mu. Nhng mu ging nhau v sc thng c xp vo loi c chung mt tng mu. thun sc hay bo ho l ch tiu xc nh mc ca sc thi trong mu. Nhng mu thun sc phi cha ng mt t l ln tia n sc thun khit, cn nhng mu km thun sc th t l ca tp hp cc tia khc s tri hn. thun sc ca mu c nh gi bng t l ca nh thnh phn n sc so vi nh chung ca mu (tnh ra phn trm) nh vy thun sc ca cc mu n sc hay mu quang ph s l 100%. sng cng l mt khi nim thng dng khi nh gi v phn tch mu sc. Trong php so mu ngi ta dng sng hay nh ng ngha vi phn chiu, c 14

nh gi bng phn trm cc tia phn chiu so vi tng ca chm tia ti. Trong thc t thng gp cc mu hunh quang c sng hay nh cao hn cc mu thng thng. 2.2. Tnh cht ca nh sng v s hp th nh sng ca vt th Nh trn trnh by, mu sc ca mi vt xung quanh ta c lin quan cht ch n ngun sng chiu vo n v kh nng hp th nh sng ca mi vt. 2.2.1. c im ca nh sng mt tri nh sng l yu t trc tip to cho c quan th gic ca mt cm th c mu sc. Trong bng ti mi vt s khng th hin c mu sc ca mnh v mt ngi cng khng cm th c g c. Cc ngun sng c cu to khc nhau khi chiu vo mt vt s lm cho vt th hin mu sc khc nhau. Di nh sng ban ngy khi tri p th mu sc ca mi vt trong thin nhin r rng, rc r v ti p, cn trong nh sng nhn to th mu sc ca chng khng th hin y , thng l ti sm, bin mu hoc m nht. C s sai khc mu nh vy l do cu to ca nh sng nhn to khc vi nh sng thin nhin hay nh sng mt tri. Trong s cc tia sng chiu t mt tri n tri t chng ta, mt ca con ngi ch cm th c phn nh sng trng, cn gi l min thy c ca quang ph nh sng mt tri. Cng ging nh cc loi sng pht thanh v truyn hnh, cc tia sng cng c dao ng sng in t v cng c o bng n v nanomet (theo quy c quc t 1 nm = 109 m). Dao ng sng ca nh sng c gi l bc sng v k hiu l . Bc sng ca cc tia trong quang ph nh sng mt tri c v tr nh trong bng 1.1. Bng 1.1 Tn tia sng Tia v tr Tia Tia X Tia t ngoi Tia thy c Tia hng ngoi Sng ngn ra a, radio, sng truyn hnh Bc sng m <1014 1014 1011 1011 108 108 4.107 4.107 8.107 8.107 103 nm

0,01 10 10 400 400 800 800 106 106 3.1012

Nh vy th phn thy c ch chim mt gii rt hp trong ton b quang ph nh sng mt tri. Phn thy c hay nh sng trng ny c hp thnh t mt s tia sng c bc sng khc nhau ng vi cc mu ca cu vng m ta vn gp trong t nhin. T lu chng ta bit trong cc th nghim ca Newton rng khi cho mt chm tia sng trng song song i qua mt lng knh th s nhn c by mu trn mn nh t sau lng knh, l: tm, xanh lam, xanh da tri, xanh lc, vng, da cam v . By mu ny chnh l mu n sc hay mu quang ph, chng c thun sc rt cao. Gia by mu chnh ny l cc mu trung gian do kt qu phi ghp ca hai mu ln cn, sc mu ca chng nh th no l do t l thnh phn ca cc tia hn hp v bc sng ca chng. Nh vy s c v s mu trung gian, nhng nhng mu chnh c trnh by trong bng 1.2.

15

Bng 1.2 Tn mu Cc tm Tm Tm lam Xanh lam Xanh da tri Xanh lc Vng lc Bc sng, nm 400 420 440 470 500 530 560 Tn mu Vng Vng cam Da cam cam Cc Bc sng, nm 580 590 600 610 650 780

2.2.2. Nng lng ca nh sng Theo thuyt photon th nh sng l kt qu ca hin tng bc x sng c truyn i km theo nng lng ca chng c tnh bng kilcalo. Cn theo cc thuyt cu to ho hc th nguyn t ca cc nguyn t c mt nhn gia v mt m my in t phn b thnh nhiu lp quay vi nhng qu o khc nhau xung quanh nhn. Song ch c nhng in t ca lp ngoi cng hay cn gi l in t ho tr mi c kh nng tham gia vo phn ng ho hc. Nhng in t ho tr ny cng to nn hin tng pht sng v c gi l in t quang hc. Khi mt nguyn t no c cp nng lng th cc in t ca n s chuyn sang trng thi b kch ng v c th nhy sang nhng qu o khc xa nhn hn, khi ngng kch ng th chng c th li tr v qu o c ca n. T sau cc cng trnh nghin cu ca Einstein, ngi ta tha nhn rng s pht ra v hp th ng sng c lin quan n s chuyn dch cc in t k trn. S chuyn dch ny s to ra hay lm bin i nhng ht khng c khi lng (tri vi cc in t) gi l photon lng t, chng nh th l vt cht ho nh sng, lm cho nh sng c ht v c sng. Mt photon c sinh ra khi mt in t vng ngoi nhy sang qu o khc gn nhn hn. Photon ny thot ra vi tc 300.000 km/s v ti i mt nng lng m nguyn t b mt di dng tia sng m bc sng t l nghch vi nng lng c truyn i. Tri li mt photon bin mt khi n va vo v y mt in t ngoi vi sang mt qu o xa nhn hn. Khi ny nng lng ca photon c thu ly v to nn trng thi kch thch c kh nng lm sinh ra mt photon khc. Nu nh nhng dch chuyn in t ny xy ra nhng tn s tng ng vi tn s ca cc bc x mu ca nh sng trong min thy c ca quang ph nh sng mt tri th s c mu. Theo thuyt ny, mt vt mun c mu th n phi c kh nng hp th c bc x trong min thy c chuyn t trng thi bnh thng sang trng thi kch ng, hai trng thi ny khc nhau bi mt nng lng nm trong khong 35 kcal (ca tia ) v 70 kcal (ca tia tm) tnh cho mi phn t lng. Theo nh lut lng t, khi vt th hp th mt tia sng, nng lng chuyn ti vt th c tnh theo phng trnh: h.c E = h = , kcal (1.1) trong - tn s dao ng; h - hng s Planck, bng 6,626.1027 erg/s (hay 6,626.1034 j.s); c - tc nh sng, bng 300000 km/s; - bc sng. 16

Nh vy nhng tia sng c bc sng cng nh cng c tn s dao ng ln hn v chng cng mang nng lng ln hn. 2.2.3. nh sng nhn to Khi quan st mu bng nh sng nhn to ngi ta nhn thy c s sai khc vi mu quan st hoc o trong nh sng ban ngy. Khc vi quang ph lin tc ca nh sng mt tri, nh sng nhn to c quang ph t qung, l nguyn nhn gy nn s sai lch mu khi quan st. khc phc hin tng ny v nhm chuyn cc tia bc x cc tm thnh cc bc x nhn thy c c quang ph lin tc, ngi ta ph ln bn trong cc loi n ng mt lp cht hunh quang c thnh phn khc nhau nhm to ra ngun sng gn vi nh sng trng. Cc tia bc x ca loi n ny phi hp quang ph vch ca hi thy ngn vi quang ph lin tc ca lp ph to thnh quang ph lin tc ca nh sng pht ra. Trn c s ny ngi ta ch to ra nhng loi n chuyn dng cho vic nh gi mu, trong s ny c n xenon c coi l ngun nh sng nhn to tiu chun dng quan st, nh gi v o mu. 2.2.4. S hp th chn lc nh sng ca vt th Nh nhng thnh tu nghin cu v nh sng v mu sc, vn ti sao mi vt ca th gii xung quanh ta li c mu khc nhau tm c li gii p khoa hc v y . Trong t nhin mi vt c mt mu vi sc thi, nh mu v cng mu khc nhau ch yu l do chng c cu to ho hc ring nn c kh nng hp th chn lc cc tia sng chiu vo chng. Kt qu l nhng vt khng c kh nng hp th cc tia ti, phn x li hon ton cc tia ny th chng s c mu trng hoc khng mu. Ngc li khi chng hp th hon ton cc tia sng chiu vo chng th chng s c mu en. Gia nhng vt c kh nng hp th hon ton v phn x hon ton cc tia ti, c v s nhng vt ch c kh nng hp th mt phn v phn x li mt phn cc tia ti, nhng vt ny c mu. Chng ta cm th c mu ca nhng vt ny nh tc dng ca cc tia phn x vo c quan th gic ca mt. Nh vy mu ca mt vt l do cc tia phn x to nn. Mi vt mun mu l do chng c kh nng hp th chn lc nhng phn nht nh ca nh sng v phn x li nhng phn nht nh. Nhng vt ch hp th mt phn cc tia ti v phn x phn cn li vi t l cc tia phn x gn bng nhau th chng s c mu ghi (xm). Nu nh trong s cc tia phn x c mt vi tia tri hn th vt s c mu a sc, nu nh chng hp th hu ht cc tia ti, ch phn x mt tia duy nht th vt s c mu n sc (hay mu quang ph). Nh vy mu ca mi vt phu thuc vo cu to ho hc, kh nng hp th chn lc nh sng, vo s lng v t l ca cc tia phn x. Trong thc t ngi ta thy rng khi mt vt hp th cc tia th nhng tia phn x s c mu xanh lam - lc, ngc li nu mt vt hp th cc tia xanh lam - lc th cc tia phn x s c mu . Cng nh vy khi mt vt hp th cc tia vng th n s c mu lam v ngc li. Mt khc trong thc nghim v vt l, bng cch phi hp cc tia hp th v cc tia phn x ngi ta c th ti to li c nh sng trng. Nh vy l cc tia phn x v cc tia hp th c tc dng b sung cho nhau nn chng c gi l cc tia mu b tr. Khi nghin cu v tnh cht ca mu sc, da vo kt qu khi phi hay hp nht quang hc cc tia mu vi nhau theo quy lut phi cng mu v phi tr mu, ngi ta 17

lp nn vng trn mu (hnh 1.1). Trong vng trn mu ny, theo chu vi ca n, mi mu c th xem l kt qu phi cng ca hai mu bn cnh to thnh mu trung gian, th d, mu da cam l kt qu phi hp ca mu vng v mu v.v. Bn cnh hiu ng phi cng to nn mu hu sc, khi phi hai tia mu nm i din vi nhau trong vng trn mu th s nhn c mu trung ho (mu trng). Nhng cp mu nh vy gi l mu b tr, tp hp tt c cc mu ny li cng to thnh mu trng tm vng trn. Theo vng trn mu, c nm cp mu b tr chnh l: xanh lam - vng, tm - vng lc, tm - xanh lc, - xanh lc - lam, v da cam - xanh da tri.

xanh lam xanh da tri xanh lc - lam xanh lc vng lc

tm tm da cam vng

Hnh 1.1. V tr ca cc cp mu b tr trong vng trn mu. Trong thc t cn gp nhng trng hp tuy vt th khng hp th phn no trong min thy c ca quang ph nh sng mt tri, nhng li hp th v phn x nhng tia nm min t ngoi hoc hng ngoi ca quang ph, nn chng khng c mu, thc ra l chng c mu nhng mu ngoi phm vi cm th ca mt. Khi vn dng tc dng b tr ca cc tia mu cn ch rng hn hp ca hai thuc nhum vi nhau s khng cho mu nh khi phi hai tia n sc. Chng hn nh khi phi hai thuc nhum mu vng v mu lam (cng lp) s khng nhn c mu trng nh khi phi hai tia mu ny, m s nhn c cc mu trung gian t xanh lc n vng lc. C hin tng nh vy v thuc nhum thng khng c kh nng phn x cc tia n sc m phn x tp hp cc tia ln cn, nn hiu qu b tr mu khng hon ton theo quy lut ca phi mu quang hc. 2.2.5. Thuyt in t v hp cht hu c c mu Nh nhng thnh tu ca cc ngnh vt l v ho hc ngi ta xc nh rng ch c nhng in t vng ngoi (in t ho tr) ca cht mu mi tham gia vo qu trnh hp th nh sng km theo s chuyn ng ca chng. Khi hp th nh sng th hp cht mu s tip nhn nng lng ca cc ht photon, lm cho cc in t vng ngoi b chuyn sang trng thi kch ng, sau phn nng lng ny c th chuyn sang cc dng: quang nng, ho nng, nhit nng v.v. v hp cht mu li tr v trng thi ban u nh vy s hp th nh sng l kt qu ca s tng tc ca cc in t vng ngoi ca cc nguyn t v phn t cc hp cht hu c vi photon nh sng. Nhng hp cht hu c no c lin kt cc in t vng ngoi vi nhn yu th ch cn nng lng ca cc tia c bc sng ln trong min thy c ca quang ph cng lm chuyn dch v hp th mt phn cc tia ny lm cho n c mu. Hp cht no c 18

in t vng ngoi lin kt vi nhn cng yu th cng cn t nng lng kch ng chng, cng d hp th cc tia c bc sng di hn v cho mu su hn. Bi vy cu to phn t ca hp cht mu hay thuc nhum phi nh th no nng lng ca cc tia sng trong min thy c ca quang ph cng lm thay i chuyn ng cc in t vng ngoi ca chng, lm cho chng c mu. Nguyn nhn lm cho cc in t vng ngoi lin kt vi nhn yu l: trong phn t cha h thng mi lin kt ni i cch di; trong h thng ny ngoi nguyn t cacbon cn c cc nguyn t khc nh oxy, nit, lu hunh v.v.; do nh hng ca cc nhm th; do hin tng ion ho phn t v cu to phng ca phn t. a. nh hng ca h thng lin kt ni i cch Trong cc hp cht hu c thng gp hai loi lin kt c bn: lin kt n v lin kt i. kch ng cc in t trong mi lin kt n cn c mt nng lng ln, tng ng vi nng lng ca cc tia sng ngn nn nhng hp cht ch cha mt loi lin kt ni n thng khng c mu. Ngc li, cc in t vng ngoi ca mi lin kt ni i do lin kt vi nhn yu, chng linh ng, nn ch cn mt nng lng nh cng kch ng, nn chng c kh nng hp th cc tia sng c bc sng ln hn trong min thy c ca quang ph v chng c mu. Nu nh cc mi lin kt ni n v ni i trong mt hp cht hu c c xp lin tc thnh mt h thng mt cch mt hay cn gi l ni i cch, ni i lin hp th cc in t vng ngoi s linh ng hn. linh ng ca cc in t vng ngoi trong h thng ny ph thuc vo cc yu t sau y: - di ca h thng; - bn cht cc nguyn t cha trong h thng; - cu to ca hp cht (mch thng hay mch vng). Hp cht hu c cha trong h thng mi lin kt ni i cch cng di th h thng in t vng ngoi cng linh ng, n cng d hp th cc tia sng c bc sng ln nn mu cng su. Mt khc d c cu to mch vng hay mch thng, hp cht hu c phi cha ng cc mi lin kt ni i cch lp thnh mt h thng lin tc th n mi c kh nng su mu. Trong bng 1.3 l mt vi th d minh ho nh hng ca di ca h thng lin kt ni i cch n nng lng kch ng v kh nng hp th nh sng ca mt s cht. Nu nh tng s mi lin kt ni i kh ln, nhng chng khng nm thnh mt h thng ni i cch lin tc trong phn t ca hp cht hu c th linh ng ca cc in t vng ngoi cng khng tng ln v hp cht khng c mu hoc mu khng su. Cao su l mt th d in hnh, phn t ca n cha trn mt trm mi lin kt ni i nhng ch hp th c cc tia sng c bc sng trong khong 200 nm nn c khng c mu. b. nh hng ca cc nguyn t khc ngoi cacbon Khi trong h thng mi lin kt ni i cch ca mt hp cht hu c no ngoi cacbon cn cha cc nguyn t khc nh: O, N, S v.v.; do cc nguyn t ny c in tch ht nhn v khong cch t nhn n cc in t vng ngoi khc nhau, khi nm chung trong h thng mi lin kt ni i cch th cc in t vng ngoi ny d dng chuyn dch t nguyn t ny sang nguyn t khc, ngha l chng linh ng hn, nn cc hp cht ny s hp th c cc tia sng c bc sng ln hn v c mu su hn. 19

Bng 1.3 Cng thc cu to Loi mch thng CH3CH=CHCOOH CH3(CH=CH)2COOH CH3(CH=CH)3COOH Loi mch vng benzen naphtaxen pentaxen Nng lng kch ng, kcal/mol 135 107 92 110 61 48 Kh nng hp th max, m 208 261 303 225 khng mu 460 da cam 580 mu tm

c. nh hng ca cc nhm th Cc phn t ca hp cht hu c khi trng thi kch ng lun lun khc vi trng thi bnh thng ca chng. Khi hp th nng lng ca cc tia sng th s phn b mt in t vng ngoi ca chng s thay i, mt in t s tng ln hoc gim i nhng v tr nht nh ca phn t. Trong phn t s c nhng v tr tch in dng v nhng v tr tch in m, ni khc i nh sng lm phn cc ho chng, y l tnh cht chung ca tt c cc hp cht hu c c mu. Nhng hp cht hu c cha trong phn t h thng mi lin kt ni i cch s c kh nng phn cc d hn cc hp cht khc; kh nng ny s tng ln mnh m khi u mch v cui mch c cha cc nhm th c kh nng thu v nhng in t. iu ny s lm cho cc in t vng ngoi linh ng hn v kt qu l hp cht s c th hp th c cc tia sng c bc sng ln hn v mu s su hn. d. nh hng ca s ion ho phn t Khi trong phn t ca hp cht hu c c mt ng thi cc nhm th thu v nhng in t, ngoi kh nng b phn cc n cn c kh nng b ion ho. Khi ny c th chuyn min hp th v pha cc tia sng c bc sng ngn hn hoc di hn, ngha l c th lm cho hp cht c mu nht i hoc su mu thm. Kh nng ny c tu thuc vo bn cht ca cc nhm th v v tr ca n trong h thng mi lin kt ni i cch. Trong lnh vc ho hc thuc nhum, s ion ho xy ra do tc dng ca mi trng i vi cc nhm nhng in t nh: OH, NH2 v cc nhm thu in t nh: C=O, C=NH c ngha hn c, mi trng hp c mt hiu ng mu ring. i vi hp cht hu c ch cha nhm th c kh nng thu in t, khi tng axit th ion H+ s lin kt vi nguyn t oxy hay nguyn t nit v s chuyn hp cht v dng tch in dng nh sau: C=O + H+ C=NH + H+ 20 C=OH C=NH2
+ +

S xut hin cc tm tch in dng lm cho tnh i in t tng ln dn n tng cng mu ca hp cht v mu su hn. Th d, benzaurin sunfoaxit c mu vng, trong mi trng axit c mu do b ion ho nh sau:
HO C SO3H O
+ H+ pH = 1,5

HO C

OH +

SO3H

mu vng

mu

Trng hp hp cht hu c ch cha nhm th c kh nng thu in t, trong mi trng kim nhm OH (c trong nhn thm) s tch ion H+ ra lm cho oxy c ba cp in t cha chia v mang in tch m, chng c kh nng nhng in t; kt qu l tr s hp th cc i ca hp cht s chuyn v pha c bc sng di hn, hp cht s c mu su hn. in hnh l alizarin c mu vng, trong mi trng kim s tch in m v c mu tm:
O OH OH
+ NaOH H
+

O O

alizarin c mu vng

dng anion ca alizarin c mu tm

Nhng khi nhm amin b ion ho th kt qu s ngc li, trong mi trng axit cp in t tha ca nit s lin kt vi H+ v lm gim kh nng nhng in t ca nit do tr s hp th cc i s chuyn v pha cc tia sng c bc sng ngn hn, hp cht s c mu nht i. e. nh hng ca cu to phn t Theo thuyt in t, cho phn t hp cht hu c c mu su th yu cu quan trng l phn t ca n phi c cu to phng nh m s tng tc ca cc in t khng b cn tr. Bt k yu t no ph v yu cu ny cng lm nh hng n mu ca hp cht. Nu nh cu to phng ca phn t cha b ph v hon ton th tc dng tng h gia cc in t cha b mt hn m ch gy ra s gin cch tng phn ca mch lin hp hai pha k t v tr ph hy trc song song ca m my in t. iu ny lm cho hp cht hp th cc tia sng c bc sng ngn hn v mu s nht i. nh hng ca cu to phn t n bn cht mu ca n c s dng khi nghin cu v tng hp cc thuc nhum vi cc gam mu khc nhau. Khi nghin cu v mu sc v thuc nhum ngi ta thng nht mt s quy c nh sau: Nu v mt nguyn nhn no m mu ca mt vt thay i, chuyn t vng n , n tm v.v.. ngha l chuyn min hp th cc i v pha cc tia mu c bc sng ln hn th ngi ta ni mu ca vt su hn; s thay i theo hng ngc li th gi l s nht mu. Hai khi nim ny ch dng vi ngha k trn, khng nn nhm 21

ln vi khi nim v cng mu ( m, nht). Th d khi nhum mt vt liu no bng thuc nhum mu vi nng thp s nhn c mu nht hay mu hng, nhng khi tng nng ln s nhn c mu m hay sm. Trng hp ny khng th ni l su mu c. Quy c v th t su mu v nht mu nh sau: mu trng mu vng - lc mu vng mu da cam mu mu tm mu xanh lam mu xanh da tri mu xanh lc mu en

Hng su mu

Hng nht mu

2.3. Nguyn l phi ghp mu Trong thc t t khi sn c mu ph hp vi mu ca cc mt hng theo th hiu hoc mt thi trang ca ngi tiu dng, v vy phi ghp to nn cc mu mi l cng vic thng xuyn ca cc nh k thut nhum, in hoa, hi ho v nghin cu mu sc. 2.3.1. Kh nng cm th mu ca mt Mu l mt hin tng phc tp mang c bn cht vt l v tnh cht tm l, cm gic; hay ni cch khc mu mang c im ca nng lng sng nh sng c cm th bng mt, khng c s tham gia ca mt th khng c nim v mu sc. Nhng ngi b m hay lon th t nh s khng c khi nim v mu sc, nhng ngi c tt v mt cng khng c kh nng nhn bit v nh gi ng v mu sc. Mt c th xem nh c cu to bng mt h thng quang hc rt tinh vi gm c: mt thu knh chnh l thy tinh th c che bi gic mc v thy dch ngn cn nhng tia cc tm c hi cho mt; mt mng ngn l trng en gip cho con ngi h m rng hay hp. Ging nh mi thu knh khc, thy tinh th to nn hnh nh cc vt tiu im ca n. Vi mt thng (mt lnh) tiu im ny cui nhn cu, pha trn vng mc ta nh knh hay phim nh. Khi nhn c thng tin mu di dng nng lng sng ca nh sng th h thng dy thn kinh th gic s truyn hnh nh v no, y no s tp hp v dng li cc yu t ca hnh nh. Nh vy nhn l mt cm gic c sinh ra v no. Trn c s ca thuyt ba mu ngi ta gii thch rng: mt cm th c mu, phn bit c cc sc thi khc nhau trong thin nhin l do s phi hp ca ba mu c bn. Vng mc ca mt c cu to t hai loi t bo hnh que v hnh nn, chng c kh nng cm th cc tia c bc sng nht nh ca nh sng trng. Nhng t bo hnh que lm nhim v phn bit s khc nhau v cng ca hnh nh sng to ra trn vng mc, khng tham gia vo vic cm nhn mu th gic. Cc t bo hnh nn c ba min nhy cm cc i tng ng vi bc sng ca cc mu: , xanh lc (ng ra l vng lc) v xanh lam, chng c chc nng chnh trong vic to nn cm gic mu. Mi khi nhn c 22

tn hiu mu t mi trng xung quanh, thng qua cc nn nhn cm ng vi ba mu trn, chng hi t li v truyn v thn kinh th gic, sau v v no. v no mu s c ti to v cho ta nhn bit y v sc thi ca n. Da trn nguyn tc t ba mu c bn c th phi ghp thnh cc gam mu khc nhau ca h thng thn kinh th gic v v no, ngi ta lm c nh mu, in nh v truyn hnh mu. Trong k thut nhum, in hoa, hi ho v n lot v.v. nm vng quy lut phi mu ny ngi ta c th to nn nhiu mu khc nhau. 2.3.2. S tng phn mu v s hi ho mu Trong in hoa cng nh trong may, an v ghp cc mu khc nhau to ra cc sn phm a dng v mu sc, cn phi c bit lu n nh hng qua li gia cc mu khi chng c sp xp gn nhau. S nh hng s biu hin s thay i sc thi, cng v sng ca cc mu. S thay i ny ph thuc vo s xp t v khng gian v din tch cc mu. S thay i sc thi mu phn nh nh hng qua li gia mu ny vi mu khc khi chng gn nhau, m nhng mu li c sc thi khc nhau. Trong trng hp xp cc mu cch xa nhau th sc thi ca cc mu mnh s lm thay i sc thi ca cc mu bn cnh theo hng mu b tr ca mu mnh. Th d, mu xm trn nn s c sc thi ca mu xanh lc, mu xm trn nn xanh l cy s c sc , mu xm trn nn xanh lam s c sc vng. Cc sc vng trn nn s c sc lc vng, cc sc vng trn nn xanh lc s c sc vng. Khi xp hai mu thuc cp mu b tr tc l hai mu c sc thi hon ton khc nhau th s nh hng qua li ca chng dng nh khng tn ti hay c th ni l s tng phn gia chng tr nn bo ho. Th d, mu vng trn nn xanh lam hoc mu trn nn xanh lc. S thay i v ti sng ca cc mu xp gn nhau s xy ra khi chng c ti sng khc xa nhau. Mt hnh vung mu xm trn nn trng s cho cm gic nh hnh b ti i. Cn khi n trn nn en th li sng ra. S tng phn v sc thi v ti sng ca cc mu thng xy ra r nt ranh gii gia chng. gim bt s tng phn ranh gii ngi ta thng tch bit cc hnh c mu sc khc nhau bng cc ng vch en, trng, xm hoc to nn c mu cng vi nh mu ca mu tng phn. Th d, mu vng lc trn nn xanh lc s cho cm gic nh mu vng thun sc. Din tch ca cc hnh mu cng c quan h qua li vi s nh hng ca mu sc, nu din tch ca mu cng ln th nh hng ca n cng mnh. ng thi sng v cng mu cng c nh hng n din tch ca cc hnh. Th d, din tch hnh mu s cho cm gic nh i khi n nm trn nn sng; hoc din tch hnh mu ti trn nn sng s cho cm gic nh hn hnh cng din tch c mu sng trn nn ti. iu ny c gii thch nh sau: nhng ng vin ca cc hnh sng qua vng mc mt ngi s b chy di ra hn l cc ng vin quanh hnh ti. Trong khi nim v mu sc, ngi ta cn chia chng thnh hai loi mu nng v mu mt. Mu nng gm cc mu gn vi mu ca cc vt pht nhit (nh mt tri, ngn la) - l cc mu mu da cam, mu vng. Mu mt l cc mu gn mu ca cc vt thu nhit, cho cm gic mt (nh nc, bu tri) - l cc mu xanh. Ring mu tm l mu trung gian n c th l mu nng hay mu mt l ty thuc vo nh mu. Ngi ta cng thy rng mt cp mu b tr trong vng trn mu thnh quy lut: mu ny l nng th mu b tr l mt, chng hn cc cp mu: 23

da cam xanh da tri xanh lc vng xanh lam Cc mu nng li c cng mnh v sng ln thng gy n tng mnh c coi l mu tri. Cn cc mu mt cng mu nh, sng km t gy n tng c coi l mu n. T nhng c im v tnh cht ca mu sc nu, cn p dng trong thc t to ra cc mt hng c mu sc hi ho hp vi th hiu ngi tiu dng. S phi mu hi ho l s kt hp p nht cc tnh cht ca mu sc sao cho ph hp vi th hiu ca tng dn tc, vi iu kin s dng mt hng v i khi cn ph hp vi mt ca tng nc, tng vng. Phng php phi mu hi ho ni chung c nhng nguyn tc c bn nh sau: c th kt hp hi ho gia mu a sc vi mu thun sc nu nh chng c sng nh nhau. Th d, mu xm c sng trung gian gia mu en v mu trng nn n c th kt hp vi hai mu mt cch hi ho. Mu xm sng c th kt hp hi ho vi cc mu hng sng, xanh sng hoc bt k mu n sc no c ti sng. Mu xm sm th phi kt hp vi cc mu ti sm. c bit nhng mu n sc c bo ho ln li l mu nng nh mu th phi kt hp vi mu en lm gim bo ho ca mu . Cng c th kt hp hi ho t cc mu tng phn nhng cn phi xem xt c th mt s yu t. T ba mu tng phn, s hi ho s t c nu s dng mt mu mt v hai mu nng. Nhng mu c cng bo ho ln s c s dng vi lng cng t i. Khi kt hp cc mu ng sc, c sng v nh mu gn nhau, tc l cc mu nm lin nhau trong vng trn mu th s hi ho v mu sc d dng t c khi sng ca chng dch chuyn theo phn cp. Th d, mu xanh da tri thun sc ti sng c th kt hp hi ho vi mu xanh da tri v mu xanh lam. 2.3.3. Phng php phi mu thuc nhum Phi hp thuc nhum cng da trn nguyn l ghp cng v ghp tr cc tia mu quang ph v nguyn l ghp t ba mu c bn. iu khc ch yu vi ghp mu quang hc l ch thuc nhum khng phi l cc sn phm tinh khit c mu n sc, li cha cc ph gia nn mu to thnh c sai lch so vi ghp quang hc. Phi ghp mu t thuc nhum k thut cn gi l ghp mu c hc c th thc hin bng bin php th cng hoc thit b x l bng my tnh in t. D dng phng php no cng phi da vo cp nguyn tc sau: 1- Phi dng thuc nhum cng lp theo phn lp k thut v c cc tnh cht k thut tng t nhau: cng iu kin nhum (nhit , tr s pH, xc tc, ph gia); cng c tc bt mu; cng c bn mu vi cc ch tiu khc nhau, v.v. 2- Khi phi thuc nhum thuc cc lp khc nhau nhum vi pha cn chn nhng loi khng tch in tri du, khng cha cc ph gia c tnh cht k nhau lm cho dung dch nhum b kt ta, sa lng hoc bin mu, kh ghp ng mu; 3- C th phi t hai thuc nhum k thut to nn mu mi cn thit nhng s mu mi to thnh s b hn ch. to nn nhiu gam mu khc nhau ngi ta dng thut phi ghp t ba mu c bn: , vng v xanh lam hoc , vng v xanh lc. th ghp mu c thit lp theo hnh tam gic u, mi mu c bn c t mt nh ca tam gic, t l phi ghp c chia u theo cc cnh, mu to thnh s theo quy lut sau:

24

- Theo mi cnh ca tam gic s nhn c mt dy cc mu trung gian do kt qu ghp t hai mu; - Theo cc ng cao ca tam gic s l dy mu do kt qu b tr nhau ca nhiu cp mu tng ng; - Tm ca tam gic v vng ph cn s l min c mu v sc (ghi, xm) do hiu qu trung ho ln nhau ca ba mu c bn c cng mu tng ng; - Cc im khc nm bn trong tam gic s l v s cc mu c phi ghp t ba mu c bn vi t l khc nhau, mu v nh mu ca chng ty thuc vo to trn tam gic. Tam gic mu c biu din nh sau:

tm

ghi

da cam

xanh lam

xanh lc

vng

Vic chn ba thuc nhum dng lm ba mu c bn ng vi yu cu ca l thuyt rt kh tho mn, trong thc t yu cu ny ch l tng i, nn mu v nh mu thu c do hiu qu phi ghp ph thuc nhiu vo ba mu ban u. Di y l mt s th d v kt qu ghp nhng mu thng gp: Mu phi ghp: Hng + vng Hng + ghi Vng + lc Xanh lam + tm Xanh lam + xanh lc Xanh lam + en Nu + en Kali + en Nu + vng Xanh lam + + en en + vng + xanh lc Vng + da cam + xanh lc Xanh lc + tm + vng + nu Mu nhn c: Lng tm Tm hoa c Vng chanh Xanh tm than (xanh cng nhn) Cm thch Ghi, xm Ghi, xm C a Be hng Nu Mu ximng Mu liu Xanh l m Vng nu da b

3. TNH TON MU V CNG NGH PHI GHP MU 3.1. Cc h thng phn nh mu sc 3.1.1. Cc i lng c trng cho s cm th mu sc thun li cho qu trnh tnh ton v so snh cc mu vi nhau, ngi ta tm cch th hin cc mu bng nhng con s v sp xp chng mt cch c h thng, trong mi 25

mu c mt v tr nht nh c xc nh bi ba i lng: tng mu hoc nh mu (H) (hue or metamerism); bo ho hoc thun sc (C) (saturation) v sng (L) (lightness). 3.1.2. Cc h thng biu din mu sc a. Bn mu CIE Hng nghn tng mu m mt ta cm nhn c t nh sng mu v cht mu c sp xp trong mt h thng chun ca y ban Chiu sng Quc t cn gi l bn mu CIE hay tam gic mu CIE. C s ca s th hin mu bng s lng trn bn mu CIE l mi mu c xem l hn hp cng ca b ba mu c bn. B ba mu c bn c chn da trn c s thuyt ba mu ca Young cho rng nh sng trng l tng hp ca ba mu c bn: (red), xanh lc (green) v xanh lam (blue). B ba mu c bn vi s lng tng ng l X, Y, Z, c th ti to v s mu khc nhau. iu kin t ra cho vic la chn ba mu c bn l khi phi hai trong s chng, ta khng th nhn c mu th ba. T l thnh phn ca ba mu c bn x, y, z s xc nh v tr ca mu (to mu ) trn bn mu: X Y Z x= ; y= ; z= X+Y+Z X+Y+Z X+Y+Z H thng CIE c trnh by bng th cc v tr mu trong tam gic cn hoc tam gic vung. Din tch bn trong phm vi th c dng mng nga l khng gian mu ca tt c cc mu thc (hnh 1.2). T tri sang phi trn ng cong bt u t bc sng 380 - 780 nm l cc mu trn dy ph t tm n . Gia din tch l im v sc (mu trng). y l ph dng mng nga c 24 tng mu c xc nh theo di bc sng. Cc tng mu trn ng cong c bo ho ln nht v thp dn ti im v sc (gm 15 bc). Bt k mu no nm trn ng bo ho u c cng tng vi mu ghi gi l mu cng tng.

Hnh 1.2. Bn mu CIEXYZ. Bng my o mu quang ph chuyn dng ngi ta xc nh cc to x, y ca mi mu. Khi bit to ca mi mu th ta c th bit ngay tng mu v bo ho ca mu . 26

b. Khng gian mu CIEXYZ Tam gic mu ch cho php biu din mu sc bng hai i lng nn cc to trn tam gic ch cho bit v bo ho v tng mu nhng li khng c sng. Nu mun quan tm n sng th phi a thm to th ba, qua mt phng mu s m rng thnh khng gian mu bng cch t thm to - sng Y thng gc vi mt phng mu. Nu in vo cc gi tr sng vi kh nng cc i c th c cho mi to mu trn mt phng mu th gi tr cc i Y = 100 ch dnh cho rt t to mu. Mt mu no cng km bo ho th sng ca n cng ln. xc nh mt mu trong khng gian mu CIEXYZ th u tin phi xc nh s lng mu X, Y, Z tham gia hn hp cng, sau l xc nh to mu x, y v Y c coi l sng. Bng cch ngi ta c th so snh s ging nhau hay khc nhau gia hai mu, tuy nhin s ging, khc nhau gia hai mu ln nh th no th cng khng th nh gi chnh xc c. ln khc nhau ca cc hnh elip l s khc bit mu sc gia cc vng mu khng bng nhau trong tam gic mu CIEXYZ. Cch trnh by khong cch mu khng bng nhau c Aam ln u tin nu ra, nn n c gi l elip Aam.

Hnh 1.3. Khng gian mu CIEXYZ. c th xc nh c mu sc khc nhau t s khc bit v to mu th cn phi bin i h thng sao cho khong cch gia cc to mu trong c ng vi s cm th th gic bng nhau. c mt bn mu vi khong cch th gic bng nhau th ngi ta tnh ton lm lch tam gic mu XYZ lm cho elip Aam thnh hnh trn c ng knh bng nhau. Tam gic mu b lm mo u tin vo nm 1960 l UCS (Uniform Chromaticity Scale: thang bng nhau ca cc loi mu). Mt trong nhng khng gian mu to ra t s UCS l khng gian mu CIELUV. c. H thng CIELAB thun li hn na cho vic tnh ton v so snh cc mu vi nhau, nm 1976 CIE gii thiu mt h thng sp xp mu sc, l h thng CIELAB. H thng CIELAB s dng ba tr s L*, a*, b*, trong : L* l sng ca mu; a* l to mu trn trc lc; b* l to mu trn trc vng - lam. Giao im ca hai trc a*, b* l im v sc (en, ghi, trng ty thuc vo sng). Trc sng L* c gi tr t 0 - ng vi mu en n 100 - ng vi mu trng. Nhng 27

mu cng mt tng mu trong mt phng a* b* nm trn on thng ko di t im trung tm ra pha ngoi. Thc cht, h thng CIELAB c cu to thng qua s bin i cc gi tr X, Y, Z t h thng CIEXYZ. S bin i ny da trn thuyt mu i lp nhau ca Hering: mt mu hn hp khng bao gi l nh lc hay vng nh lam, nhng mu nh vng hay mu lc nh vng th bao gi cng ng. Nh vy mi tr s mu cho php nh gi theo thnh phn tham gia ca hay lc, vng hay lam, theo mi mu c th cha ng nhng thnh phn sau: v vng, v lam, lc v vng, lc v lam.

Hnh 1.4. Khng gian mu CIELAB. 28

Da vo thuyt mu i nhau ca Hering, ngi ta to ra cc hiu s t cc gi tr X, Y, Z: XY=a YZ=b V X th hin b thu mu , Y th hin b thu mu lc ca mt ngi nn hiu s ny rt ra mt thang bc, trn cc gi tr a dng khi X > Y, ngha l mu tri hn, khi a m c ngha l mu lc tri hn. Hiu s Y Z to ra mt thang vng - lam trn gi tr dng ca b tng ng vi mu vng v gi tr m ca b tng ng vi mu lam. Mt khc mu sc cng c th c m t bi sng L*, tng mu Ho v bo ho C* trong h thng CIELCH. Khi bit cc gi tr a*, b* ca mt mu th d dng tnh c cc gi tr C*, Ho ca mu thng qua cng thc: H* = arctg (a*) 2 + ( b*) 2 3.2. S khc nhau gia cc mu. K hiu v tnh ton 3.2.1. So snh mu bng mt Trc y, ngi ta ch so snh s khc nhau gia cc mu bng cm nhn v tho thun vi nhau m khng da vo mt tiu chun no c. Tuy nhin, mu sc va mang bn cht vt l va mang bn cht tm l v cm gic, v vy s nh gi ca mi ngi nhiu lc l khc nhau, l nguyn nhn dn n s khng thng nht v sai lch mu sc. Trc nhng kh khn trn, ngi ta tm cch biu din mu sc trong mt h thng mu m trong , khong cch gia hai v tr mu tng ng vi s cm nhn bng th gic. C rt nhiu h thng mu khc nhau (CIEXYZ, CIExyY, CIEUCS, CIELUV, CIELAB...). S khc bit quan trng nht gia chng l khong cch sai lch gia cc mu. Mi quan tm ln nht trong cng nghip dt l nh gi c s sai lch mu sc gia cc sn phm nhum. Ngi ta tm cch to ra mi quan h gia s khc bit mu sc c nhn ra v khong cch sai lch mu trong mt h thng o. Khong cch ny trong mt h thng mu l khong cch hnh hc gia hai im m cc mu c sp xp trong h thng. Mc ch t ra l t v tr hai mu trong h thng mu c th suy ra ln ca s khc bit cm nhn. lm c iu ny trc ht phi nh ngha i lng E*, n cho bit khong cch hnh hc ca hai mu trong mt h thng, E* > 1 tng ng vi khong cch mu m mt c th phn bit c ngay. Khong cch mu nh hn theo quy nh ngha l mt khng th nhn ra. Song song vi khong cch hnh hc ca hai mu th s biu din cn ni ln hng ca s dch chuyn mu. Vic pht trin mt h thng mu ph hp chnh xc vi kh nng cm nhn s khc bit mu sc ca mt ngi l cc k kh khn. Trong thc t cho n nay cha tm c mt h thng mu no nh vy. 3.2.2. S sai lch mu trong h thng CIELAB H thng mu c khong cch th gic mu bng nhau ni ting nht, ph bin rng ri nht l h thng mu CIELAB. Mi mu c th hin bi ba gi tr: L*, a*, b*. Khi bit cc gi tr hnh hc ca hai mu trong khng gian mu th ngi ta tnh c s khc bit ca mu sc thng qua cc tr s a*, b*, C*, Ho v E. ln ca cc tr s ny s phn nh s khc bit gia hai mu mt cch r rt. 29

S khc nhau gia hai mu 1 v 2 trong h thng CIELAB c xc nh thng qua cc hiu s sau: L* = L*2 L*1: S khc nhau v sng gia hai mu. a* = a*2 a*1: S khc nhau v to trn trc - lc. b* = b*2 b*1: S khc nhau v to trn trc vng - lam. C* = C*2 C*1: S khc nhau v bo ho. Ho: S khc nhau v tng mu. E*: Khong cch hnh hc ca hai mu (tng gi tr sai lch gia hai mu) E*ab = E*ch =
( a*) 2 + ( b*) 2 + ( L*) 2
( C*) 2 + ( H o ) 2 + ( L*) 2

Nu L* mang du "+" ngha l s lch mu theo chiu hng sng ln, nu mang du "" th ngc li. Nu a* mang du "+" ngha l s lch mu theo chiu hng hn, nu mang du "" th s lch mu theo chiu hng lc hn. Nu b* mang du "+" ngha l vng hn, nu mang du "" th s lch mu theo chiu hng lam hn. 3.2.3. S sai lch mu CMC S khc bit v mu sc c nh gi bng gi tr E*ab cng khng hon ton ph hp vi thc t. Nhng mu trong phm vi v sc c E*ab < 1 nhng mt li d nhn ra, mt khc nhng mu hu sc c thun sc cao c E*ab > 1 th mt li rt kh nhn ra. T l do m ngi ta tip tc kho st tm ra cch tnh khong cch mu mi ph hp hn vi s cm nhn mu sc ca mt ngi. Mt phng php nh gi mi l s dng h thng CMC - nh gi s khc bit mu sc do y ban o mu thuc Hip hi cc nh Ho nhum v K thut mu Lin hp Anh xc lp (Committee Measurement of Society Dyers and Colourists in Britain Great). S khc nhau mu sc trong CMC k hiu l ECMC: ECMC = trong : SL = SC =
L * C * H o + 2S + L 2S C 2S H
2 2

0,040975L * . Nu L* < 16 th SL = 0,511 1 + 0,01765L * 0,0638C * . + 0,638 1 + 0,0131C *

(C*) 4 (C*) 4 + 1900

SH = (f.T + 1 f).SC f=

T = 0,36 + 0,4 cos(H + 35) Nu 164 <H < 345 th T = 0,56 + 0,2 cos(H + 168)

30

 c th tnh ton c cc gi tr ca mu trong cc h thng phn nh mu sc, ngi ta phi s dng mt thit b chuyn dng o mu gi l my o mu hay cn gi l u o quang ph. 3.3. o mu Mc ch ca o mu l tm ra ch s mu c lp vi nhau, cc gi tr ny khng khng nh g v cm nhn mu, nhng t cc gi tr ny ta c th tinh ra c cc c trng v s cm nhn mu nh : tng mu, bo ho v sng. C hai phng php o mu: - Phng php o ph. - Phng php ba khu vc. 3.3.1. Phng php o ph a. Nguyn l o mu v x l s liu bng phng php o ph Phng php o ph l phng php chnh xc nht v phc tp nht bao gm o ph v tnh ton s liu o. o ph l qu trnh thun vt l xc nh phn x theo di bc sng. phn x c tnh theo t l nh sng phn x t mu o so vi mu trng chun. Tp hp cc gi tr phn x theo di bc sng c th biu din thnh ng cong phn x (hoc hp th) trong vng nh sng thy c. ng cong gi l ng cong phn x ca mt mu (hnh 1.5). Thng qua phn x nh sng theo di bc sng, ngi ta c th tnh ton c cc to mu c th trong cc khng gian mu.
R,% 12 10 8 6 4 2 0 40 44 48 52 56 60 64 68 nn

H nh 1.5. ng cong phn x ca vt c mu vng. Nh vy, bc th nht l o c, bc th hai l t gi tr phn x tnh ra to mu trong h to xyY. Qu trnh tnh ton din ra nhanh chng nu thit b c t mt phn mm thch hp v c th cho ra kt qu o trn mn hnh hoc my in. Tnh ton mu l cng vic tn nhiu thi gian v cng vic ny do mt my tnh m nhim nhm tm ra cc tr s X, Y, Z t tnh ra to mu x, y, z: X = k S .R .x.d
400 700

31

Y = k S .R .y.d
400

700

Z = k S .R .z.d
400

700

n gin hn cho vic tnh ton, vic ly tch phn c thay bng php cng ln lt theo khong di bc sng: X = k S .R .x.
400 700

Y = k S .R .y.
400

700

Z = k S .R .z.
400

700

trong : SA - phn b nng lng ph theo di bc sng ca nh sng chun; RA - h s phn x theo di bc sng; - khong di bc sng; k - h s chun ho ph hp cho mi loi nh sng chun. T cc gi tr X, Y, Z, c th xc nh to mu trong cc khng gian mu theo cc cng thc sau: Trong khng gian mu CIExyY: X Y Z x= ; y= ; Z= X+Y+Z X+Y+Z X+Y+Z Trong h thng CIELAB:

Y L* = 116 Y n

1/ 3

16

1/ 3

X a* = 500 X n
Y b* = 200 Y n

Y Y n
Z Z n

1/ 3

1/ 3

1/ 3

trong : Xn, Yn, Zn - cc gi tr o mu ca vt trng l tng v thay i ty thuc vo loi nh sng chiu ti. b. Nguyn l cu to v hot ng ca my o mu theo phng php o ph My o mu c th chia lm hai phn: phn quang hc v phn o. Phn quang hc: Ngun sng (L), khe nh sng vo iu chnh c (E), ng knh chun trc (K), quang k h tn sc vi mt lng knh hay hai lng knh, knh lc nhiu x lin tc hay cch t nhiu x... to ra tia n sc (P), thu knh O, khe iu chnh nh sng thot ra (A). 32

 Phn o: B th quang in (F), khuch i (V), b vi x l v hin th kt qu o ni vi cc thit b ngoi vi nh mn hnh, my in. Tin hnh o mu: Bc x xut pht t trong quang ph k thng qua khc x, nhiu x tn x thnh mt di nh sng ton sc ng vi gc xoay ca lng knh P, s cho bc x n sc c bc sng xc nh i vo khe hp A. Khe A cho nh sng thot ra c iu chnh tng ng vi rng . Tia n sc s chiu ln mu o v mu trng chun. T l gia phn nh sng n sc tr li t mu o so vi nh sng n sc tr li t mu trng chun gi l phn x ti mt bc sng R. phn x c dn vo b thu quang in F, c x l cui cng cho ra s liu v nhng ng cong phn x.

Hnh 1.6. S nguyn l cu to v hot ng ca my o mu. 3.3.2. Phng php ba khu vc Phng php ba khu vc (trc y gi l phng php ba knh lc hay phng php Tristimulus) ngi ta dng ba knh lc khc nhau tng ng vi ng cong nhy ph ca mt (iu kin Luther) sao cho c th trc tip tm ra cc gi tr mu X, Y, Z, nu nh b thu bc x c tnh nhy ph tng ng. Tnh nhy ph ca b thu bc x cn phi ph hp vi ng cong nhy ph ca ngi quan st chun khi cc tia sng xuyn qua cc knh lc. Nu kt qu o thu c trc tip th xuyn qua ca cc knh lc phi tho mn iu kin sau y gi l iu kin Luther: D1 = C y y Cx x C z ; D2 = ; D3 = z S 2 S1 S 3

trong : D1, D2, D3 - o thu quang ca ba knh lc; Cx, Cy, Cz - hng s thit b khng ph thuc vo chiu di bc sng; Sl, S 2, S 3 - tnh nhy ph ca b thu bc x khng dng knh lc. Knh lc ca cc thit b c ghi cc h s phn x: 33

RX - knh lc ; RY - knh lc lc; RZ - knh lc lam. Cc gi tr X, Y, Z c tnh theo cng thc sau: X = a.RX + b.RY ; Y = RY; Z = C.RZ trong : a, b, c - hng s ph thuc vo iu kin chiu sng chun v gc quan st chun. 3.3.3. Nhng in kin o mu Kt qu o mu ph thuc vo cc iu kin sau: loi nh sng chiu ti; gc o hnh hc v gc nhn ca ngi quan st chun. a. iu kin chiu sng S khc nhau c bn ca mt ngun sng ny so vi ngun sng khc chnh l s phn b nng lng nh sng trn ton b di ph. Khi quan st vt th di cc ngun sng khc nhau th s cm nhn mu sc s khc nhau. Th d, di nh sng ca n trn th vt c v b vng hn so vi khi quan st vt di nh sng mt tri. Nguyn nhn ca hin tng ny chnh l s phn b nng lng ph khc nhau ca cc ngun sng khc nhau. b. Gc nhn ca ngi quan st chun Ngoi s khc nhau v ngun chiu sng, kh nng nhn mu to nh cng lm cho cm nhn th gic bin i tc l mu s c cm nhn khc nhau ngay c khi iu kin chiu sng v tnh cht b mt khng thay i. Thc t ny cn phi lu khi o mu, trong mi loi b thu i din cho c ln mu khc nhau v nhy khc nhau. Khi tin hnh o vi cc mu nh, ngi ta chn gc o 2o v vi cc mu c din tch ln th gc 10o l quan st chun.

1 m

10o (17,5 ) 2o (3,5 )

Hnh 1.7. Gc quan st chun 2o v 10o. c. Gc o hnh hc Nhm t c nhiu ng dng khc nhau ngi ta ch to ra thit b o mu c nhiu gc o hnh hc khc nhau. Khi chiu ln mu o nh sng thng gc nh hng 34

th c v khc hn khi chiu ln nh sng t mi hng. V vy gc o hnh hc ng vai tr quan trng trong o mu. Gc o hnh hc 45/0: Mu o c ri di gc 45o v quan st di gc Oo so vi phng thng ng. Gc o hnh hc 0/45: Mu o c ri di gc 0o v quan st di gc 45o so vi phng thng ng.
Ngun sng B thu B thu Ngun sng 1 m

45o

45o

Mu o

Mu o

Hnh 1.8. B tr b thu theo gc o hnh hc 45/0 v 0/45.

B thu

Ngun sng Qu cu Ubeicht

Hnh 1.9. B tr gc o d/0 trong qu cu. Ngoi cc gc o hnh hc trn, cc gc o hnh hc khc l trong qu cu Ulbeicht (quang k qu cu), mt trong ca n c bi trng m. Vi qu cu ny c th chiu cng nh bc x li bng nh sng khuch tn. Phn ln gc o hnh hc trong qu cu l d/0 (ngha l nh sng c chiu t mi hng v o gc 0o). Cc gc o trong qu cu cn quy nh: d/0, 8/d v d/8. Gc o hnh hc d/0: Mu o c ri bng nh sng khuch tn v quan st di gc 0 so vi phng thng ng.
o

Gc o hnh hc d/8: Mu o c ri bng nh sng khuch tn v quan st di gc 8 so vi phng thng ng.

o

d. B mt mu o B mt mu o nh hng rt nhiu n kt qu o. kt qu o c chnh xc th khi chun b mu o cn tho mn mt s yu cu sau: 35

- Kch thc ca mu o phi ln hn kch thc ca s o ca thit b. - Mu o phi gp thnh nhiu lp m bo nh sng khng xuyn qua. B mt mu o phi phng. Trong trng hp b mt khng th phng th cn phi ly kt qu trung bnh mt s im o. Ty theo loi nh sng, gc nhn ca ngi quan st chun v gc o hnh hc khc nhau m kt qu o cho ra khc nhau. Mun biu din mt mu no bng s th cn phi km theo cc iu kin o mu v s so snh gia cc php o phi c thc hin di cc iu kin o mu nh nhau. 3.4. Thc hnh phi mu thuc nhum bng my o mu Trong thc t, cc mu thuc nhum thng l hu hn trong khi nhu cu v mu sc ca sn phm dt lun thay i theo th hiu hoc mt thi trang ca ngi tiu dng. V vy cng vic phi ghp mu to nn mu mi l cng vic thng xuyn ca nh k thut nhum. Nguyn tc phi ghp mu t thuc nhum k thut c cp mc 2.3.3, chng 1 (trang 36). 3.4.1. Cc bc phi ghp mu Phi mu bng phng php th cng yu cu c rt nhiu kinh nghim v hiu bit v s tng tc gia vt liu, cht tr, thuc nhum v qu trnh nhum ca cc nh k thut nhum mu. Ngy nay, cng vi s pht trin tng i hon thin ca my o mu v kt hp vi phn mm tnh ton nng nhum cn thit cng nh hiu chnh n nhum mt cch t ng lm gim bt rt nhiu kh khn trong lnh vc phi mu. Tnh ton n nhum bng my o mu v phn mm phi mu c bt u t nhng nm by mi ca th k XX v ngy cng c ph bin rng ri nh nhng u vit ca n. c th s dng phn mm phi mu th cng vic u tin v khng th thiu l ngi s dng phi xy dng c s d liu mu. Tt c nhng thng s v thuc nhum, c th l s liu v phn x (hp th), bn mu, gi c... ca mt lot cc nng t thp n cao ca mi mt thuc nhum n c nhp lu gi trong my tnh. S chun b thng s cc thuc nhum n c gi l qu trnh chun b c s d liu. Mu mu chun c xc nh thng qua my so mu, kt qu cho ra l ng cong phn x theo bc sng v cc gi tr L*, a*, b*. Da vo c s d liu c sn, my tnh s tnh ton cc kh nng kt hp c th ca cc thuc nhum n vi mt t l nht nh ri cho ra kt qu ca mu m phng sao cho cc tr s L*, a*, b* ph hp vi mu chun. Cc kh nng kt hp s c biu din trong mt bng cng vi cc ch s v sai lch nh mu, lch v cng mu, gi c... Qua ngi s dng c th la chn n nhum ph hp nht ty thuc vo yu cu c th. a. Phng php chun b c s d liu Qu trnh chun b c s d liu (hay cn gi l ngn hng mu) l qu trnh nhum mt chui cc mu n ni tip nhau t nng thp n nng cao cho cng mt loi vt liu. Khi chn iu kin nhum cho cc mu n ny th yu cu cc iu kin nhum phi tht st so vi iu kin thc t sn xut. 36

S lng cc nng cho mi thuc nhum n thng l t 6 - 18 nng ty theo tng phn mm c th. Nng cao nht c chn ty thuc vo thc t sn xut v thay i theo tng loi thuc nhum khc nhau. Nng thp nht khng nn chn qu thp v mu ca vt liu c th khng thay i vi nng . Khi tnh ton n nhum, mt yu t nh hng n kt qu phi mu l vt liu nn v s hp th nh sng ca chng cng cn phi tnh n. Vt liu nn l mt mu c chun b cng vi qu trnh chun b ngn hng mu vi nng thuc nhum l 0%. Gi tr phn x ca mu trong vng t 400 - 700 nm c xc nh bi my o mu, lp thnh mt ng cong gi l ng cong phn x. Da vo s liu ca phn x R, h s K/S ca mu nhum c xc nh theo cng thc:
K (1 R) 2 = S 2R

b. Nguyn l xc nh n nhum cho mu phi bng my tnh Nguyn l xc nh n nhum bng my tnh da vo l thuyt ca Kubelka Munk. Theo nh lut Kubelka - Munk h s K/S ca vt liu c nhum tnh theo cng thc:
K (1 R) 2 = S 2R

(1.2)

trong : R - gi tr phn x; K - h s hp th ca vt liu; S - h s khuch tn - tn x. Trong trng hp vi c nhum ngi ta biu th K/S theo cng thc: K K K = VL + C S VL S S VL trong : KVL, SVL - h s hp th v tn x ca vt liu; K, C - h s hp th v nng ca thuc nhum. Theo cng thc trn, nu tr i gi tr K/S ca vt liu cha nhum th h s K/S ca ring thuc nhum trn vt liu c xc nh theo cng thc:
K K C = S TN S VL

(1.3)

(1.4)

Trong trng hp vt liu c nhum bi i thuc nhum n th h s hp th ca vt liu c xc nh theo cng thc: K K i C i K = VL + (1.5) S VL S VL S trong : Ki, Ci - h s hp th v nng ca thuc nhum i. Khi tnh ton n nhum u tin, my o mu s o cc gi tr phn x ca mu v chuyn vo lu gi trong phn mm. Trc khi phi mu, vt liu nn cng c o K xc nh gi tr VL ca vt liu. Sau , trn c s d liu cc thuc nhum s c kt S VL 37

K hp li vi nhau theo cc t l xc nh gi tr ca thuc nhum. Gi tr K/S S TN ca mu m phng trn my tnh c xc nh theo cng thc ( 1.5) v cc gi tr phn x ca mu m phng c tnh ton da vo cng thc (1.2). Cc gi tr phn x ca mu m phng, cc gi tr L*, a*, b* s c so snh vi mu chun. Nu sai lch, my tnh s thay i nng cc thuc nhum n cho n khi c c mt t l thuc nhum thch hp.
3.4.2. Cc loi my o mu My o mu quang ph s dng c th do nhiu hng ch to (Orintex, Datacolor Spectral Flash 600, X-Rite (CFS 57, SP, 68), GretagMachbet, Macbeth Color Eye (7000 A, 3.100), Minolta 3.700d, v.v. My c nhim v o mu v truyn kt qu o vo my vi tnh. Ngoi ra u o c kh nng phn tch, so snh mu sc v hin th kt qu c lp vi my tnh. Mt s c im chung ca my o mu: - Gc o hnh hc. - ng knh mt o. - Cc iu kin chiu sng. - Gc quan st: 2o v 10o. - Min quang ph: 380 - 760 nm. - Khong rng bng o. - Min o. - Thi gian o. - Thi gian s dng n chiu. - Nhit mi trng lm vic. - Nhit mi trng bo qun. - Kch thc. Sau khi o mu, u o chuyn tn hiu vo phn mm x l kt qu o. 3.4.3. Phn mm phi mu Chc nng quan trng nht ca phn mm l phi mu thuc nhum v hiu chnh n nhum gn vi cc ch tiu so snh gia mu chun v mu phi bng my nh thng qua gi tr E ch s v sai lch nh mu (metamerism), kh nng hiu chnh n nhum, gi c. C th kt ni vi cc my o mu bt k. Chng trnh phn mm phi giao din vi ngi s dng mt cch tin li, d hiu v d thao tc.. a. Xy dng c s d liu mu c th phi mu bng my tnh th bc u tin phi xy dng c s d liu mu. My tnh da trn c s d liu mu tnh ton n nhum. Do vy qu trnh xy dng ngn hng mu phi c tin hnh mt cch cn thn, sau mi mu phi kim tra bn mu v lp li ca mu nhum. 38

b. Phng php nh gi u mu Cc mu nhum sau khi sy kh trong mt khong thi gian nht nh phi c kim tra u mu. u mu c nh gi trn c s o gi tr E gia cc im trn mt mu mu. Mu u mu khi gi tr E < 1 v vi nhng mu c E > 1 th mu c coi l loang mu. i vi nhng mu nhum loang th phi tin hnh nhum li cho n khi gi tr E o t c theo quy nh. Khi kim tra u ca mu nhum cn ch nhng im sau: Chun b mu o: Mu c gp thnh nhiu lp v m bo b mt phi phng. Tin hnh o c ly gi tr chun ti ba im trn mu, cc gi tr so snh c so vi gi tr chun v ghi li gi tr E. Cc iu kin o mu c chn cho qu trnh o nh sau: - Loi nh sng chun: c nh. - Gc o hnh hc: c nh. - Gc quan st chun: c nh. Xin xem thm mc 4, chng IV.
Mu chun o mu ng cong phn x v cc gi tr L*, a*, b* C s d liu Kt hp Mu

E < 1 So snh

E < 1

T l thuc nhum ln 1

Nhum th E < 1 E > 1 n hiu chnh Nhum th E > 1 E < 1 n nhum

So snh

So snh

Hnh 1.10. S mu thuc nhum. 39

c. Kim tra lp li Sau khi kim tra ng u mu ca ln nhum th nht, tip tc nhum mu ln th hai kim tra lp li. Trong ln nhum th hai tin hnh kim tra lp li ti mt s nng thuc nhum. Qui trnh cng ngh ca ln nhum th hai ging ht nh qui trnh nhum mu ln th nht. Sau tin hnh kim tra u ca mu nhum ln th hai. lp li gia hai ln nhum tho mn khi gi tr E o c nh hn 1. Nu gi tr E ca mt mu no ln hn 1 th phi tin hnh nhum li ln th ba so snh vi hai ln trc. Chun b mu o v cc iu kin o mu khi kim tra lp li c chn ging nh khi nh gi u mu. d. Tnh ton t l thuc nhum cho mu phi Sau khi hon thnh vic xy dng c s d liu mu, c th s dng phn mm thit lp cc n cng ngh phi mu. Trong s cc n nhum m my a ra vi gi tr sai mu cho php, cn la chn da trn cc tiu ch ph hp v gi tr chi ph, cng thc nhum theo yu cu khch hng v.v. Xin xem thm mc b, 3.4.1, chng I. 3.4.4. Cc phng php nh gi s sai lch mu Mt ngi d nhn r trc tin l s sai khc v nh mu, sau l cng mu v cui cng mi l sng. Chnh v vy m cc h thng tnh ton mu s a ra nhng s sai lch khc nhau dn n s chp nhn ty theo yu cu c th. Qui c theo CIELAB: Th hin bi hnh hp vung; cc gi tr L, a, b c th c nhng s liu b ra ngoi s cm nhn ca mt ngi nn kh c th chp nhn. Qui c theo CIELCH: Th hin bi hnh hp p xung quanh im chun; n nm trong h to cc nn hp c th quay trong nh hng theo gc nh mu H, cc gi tr C, H, L xch gn hn ti s chp nhn ca quan st mt ngi. iu gim bt nhng bt ng gia ngi quan st v my o c cc gi tr chun. H (metamerism): = Hue H > 0 qui nh quay ngc chiu kim ng h, c ngha l khi nh mu dch chuyn t sang vng n lc, lam. H < 0 qui nh quay theo chiu kim ng h, c ngha l khi nh mu s dch chuyn t sang lam n lc, vng. Qui c theo CMC: y khng phi l khng gian mu nhng n l mt h thng cho php s sai lch mu da trn khng gian mu CIELCH. C s ca n da vo s tho thun cho php ty thuc vo s cn thit quan st sai lch mu. Trong c tnh n yu t thng mi C1, ngi ta qui nh nu C1 = 0,5 th hnh elip nh, nu C1 = 1 th hnh elip s ln hn m bo chnh xc cao hn, khi E nh hn 1 s chp nhn sai lch mu, nu E ln hn 1 s khng cho php. CMC (2:1): Th hin s sai khc v sng gp hai ln s sai khc v cng mu, iu ny cho php t kt qu tt nht trong nh gi so snh mu gia my v mt ngi. Qui c theo CIE1994 ging nh CMC, trong ngi s dng phi kim tra t l gi tr sng k1 v gi tr cng mu kc cng cc yu t thng mi cf nh CMC; s khc nhau c bn qui c ny chnh l b mt o. CMC thng s dng cho cc sn 40

phm c b mt th rp khng u, cn CIE1994 c s dng cho cc b mt nhn u v mn nh cc sn phm in hoc sn ph v.v. Kt lun Mt d c nhiu qui c v s sai lch mu nhng khng c mt h thng no hon ho, s chp nhn tt nht khi h thng m t s sai khc ging nh mt ngi cm nhn c. C th so snh cc phng php nh gi nh trong bng 1.4. Bng 1.4 Phng php nh gi CIELAB CIELCH CMC (2:1) CIE1994 T l sai khc so vi quan trc, % 75 85 95 95

Khi quyt nh tnh ton v s sai khc mu cn phi xem xt cc nguyn tc sau: - La chn phng php ph hp, n gin nht trong vic tnh ton v s dng chng mt cch c nh. - Lun lun xc nh mt cch chnh xc vic tnh ton c thc hin nh th no. Khng bao gi c sa i gia nhng s sai khc mu c tnh ton bng nhng sai s tng ng thng qua vic s dng cc yu t trung bnh. S dng cc s sai khc mu ch khi s xp x u tin c thit lp cho n khi chng c n nh bng s iu chnh bng th gic. Phi lun nh rng khng ai c th chp nhn hay phn i mu sc ch da vo cc con s v chng ch l cch nhn ra l n c tnh ton m thi.

41

Chng II

TNG HP THUC NHUM

l. PHN LOI THUC NHUM THEO CU TO HO HC Trc y thuc nhum c phn loi theo ngun gc ca chng nh: thuc nhum v c, thuc nhum hu c, thuc nhum t ngun thc vt, thuc nhum t ngun ng vt v.v. T khi ho hc hu c pht trin, cc hc thuyt v cu to ca cc hp cht hu c ra i v c bit l cc l thuyt v mu sc pht trin khng nh s lin quan gia cu to hp cht vi mu sc th s phn loi thuc nhum theo c trng ca cc h mang mu trong phn t thuc nhum cng c th hin r nt. S phn loi ny gip cho cc nh sn xut thuc nhum d dng nh hng phng php tng hp cc loi thuc nhum, mt khc n cn gip cho nhng ngi s dng thuc nhum nm vng cc tnh cht ho hc ca thuc nhum. Phng php phn loi ho hc chia thuc nhum hu c thnh cc lp thuc nhum nh sau. 1.1. Thuc nhum azo Trong phn t loi thuc nhum ny c mt hoc nhiu nhm azo (N=N). Da vo s nhm azo c trong h mang mu ca thuc nhum m ngi ta chia ra cc nhm thuc nhum: monoazo: ArN=NAr; iazo: ArN=NArN=NAr; tri v polyazo: ArN=NArN=NArN=NAr...; trong Ar, Ar, Ar... l nhng gc hu c nhn thm c cu to a vng, d vng rt khc nhau. Thuc nhum azo l lp thuc nhum quan trng nht v c lch s pht trin rt lu i. N bao gm hu ht cc loi thuc nhum theo phn lp k thut: thuc nhum hot tnh, thuc nhum trc tip, thuc nhum bazic, thuc nhum cation, thuc nhum axit, thuc nhum phn tn, thuc nhum cm mu, thuc nhum azo khng tan v pigment. Thuc nhum azo c sn xut nhiu nht, chim ti gn 50% tng sn lng thuc nhum. 1.2. Thuc nhum antraquinon Trong phn t loi thuc nhum ny c mt hoc nhiu nhn antraquinon hoc cc dn xut ca n. Nhng dn xut khc nhau cc v tr 1, 4, 5, 8 s cho cc loi thuc nhum tng ng nh sau: - thuc nhum amino antraquinon; - thuc nhum hyroxyl antraquinon; - thuc nhum axylamino antraquinon; - thuc nhum antrimit; 42

- thuc nhum antraquinon a vng. Thuc nhum antraquinon chim v tr th hai sau thuc nhum azo. N bao gm cc loi thuc nhum cm mu, thuc nhum phn tn, thuc nhum cation, thuc nhum axit, thuc nhum hot tnh, thuc nhum trc tip v thuc nhum hon nguyn a vng. 1.3. Thuc nhum inigoit
8 7 6 5 9

1 2 3 4

10

Loi thuc nhum ny trc y c ngun gc t thc vt, l mu xanh sm trch c t l cy chm. Khi ho hc thuc nhum pht trin, da trn gc thuc nhum inigo c trong l chm ngi ta tng hp c thuc nhum inigoit vi nhiu mu sc phong ph bng cch a thm cc nhm th vo phn t inigo. Gc mang mu ca loi thuc nhum ny c cng thc: O
C C X C C O Y

trong X, Y l O, S, Se, NH,... 1.4. Thuc nhum arylmetan Chng l nhng dn xut ca metan m trong nguyn t cacbon trung tm s tham gia vo mch lin hp ca h mang mu: ArC=Ar R Nu R l nguyn t hyro hoc gc hyrocacbon mch thng th s c thuc nhum iarylmetan, nu R l Ar th s c thuc nhum triarylmetan. Theo cu to phn t, thuc nhum arylmetan c chia thnh cc phn nhm sau: - thuc nhum xanten: nu gia gc thm c ni vi nhau bng nguyn t oxy cc v tr o, o i vi cacbon trung tm O O Ar Ar' Ar Ar' CH CH2 Ar" - thuc nhum acryin: nu cc gc thm ni vi nhau qua cu ni NH NH NH Ar Ar' Ar Ar' CH CH2 Ar" Phm vi cu to ca h thuc nhum arylmetan rt rng, ngoi nhng gc chnh, chng cn tn ti cc dng dn xut nh: iamino, triamino, hyroxyl, ihyroxyl. N bao gm cc loi thuc nhum bazic, thuc nhum axit v mt s cht tng nhy quang hc. 43

1.5. Thuc nhum nitro Thuc nhum nitro c cu to n gin nht v cng c ngha khng ln. Phn t thuc nhum c t hai hoc nhiu nhn thm (benzen, naphtalen), c t nht l mt nhm nitro (NO2) v mt nhm cho in t (NH2, OH). Th d,
NH NO2 NO2

Thuc nhum loi ny ch bao gm mt s thuc nhum phn tn. 1.6. Thuc nhum nitrozo Trong phn t ca thuc nhum ny c nhm nitrozo (NO), thuc nhum -naphtolnitrozo c kh nng to phc ni phn t vi st c mu xanh lc thng c s dng lm pigment.
N O OH N OH O FeSO4
N O O Fe O O

O O N
Na+

Nu tin hnh to phc vi Cr3+ s cho mu gch, vi Ni2+ v Zn2+ cho mu vng. Nhn chung lp thuc nhum ny t c ngha thc t. 1.7. Thuc nhum polymetyn Chng c cng thc tng qut l Ar(CH=CH)nCH=Ar, trong Ar, Ar tng ng phi c nhm cho v nhm nhn in t, chng c th l cc vng thm nh benzen, naphtalen hoc cc gc d vng nh quinolin, piriin, inol. Mu ca thuc nhum ph thuc ch yu vo hai nhm cho v nhm nhn in t trong h mang mu nhng nhn chung chng u c mu ti, thun sc. Trong lp thuc nhum ny phn ln l cc thuc nhum bazic, thuc nhum cation, c mt s l thuc nhum phn tn. 1.8. Thuc nhum lu hunh Chng l nhng thuc nhum m trong phn t c nhiu nguyn t lu hunh. Gc mang mu ca thuc nhum thng l cc nhm c cu to nh sau:
H N S
HC HC S N CH

S S
S

N N

S N

thiazin

thiazol

thiantren

dibenzenthiophen

azin

Nhng gc trn quyt nh mu sc ca thuc nhum v trong lp thuc nhum ny khng c mu v mu tm. 44

1.9. Thuc nhum arylamin Trong phn t thuc nhum arylamin c h mang mu l mch ni cc gc thm vi nhau qua nguyn t nit trung tm ArN=Ar, trong Ar l gc thm cha nhm cho in t, Ar l gc thm cha nhm nhn in t. Theo cu to, lp thuc nhum ny c th chia thnh cc phn nhm: iarylamin Ar NHAr:
O
osazin Ar

S Ar' ;
thiazin Ar

Ar' ; NH

NH Ar azin Ar NH

NH

Lp thuc nhum ny bao gm cc loi thuc nhum trc tip thuc nhum bazic, thuc nhum lu hunh, thuc nhum axit, thuc nhum hon nguyn, pigment, thuc nhum lng th, thuc nhum in nh mu. 1.10. Thuc nhum azometyn Trong phn t ca chng c cha h mang mu l ArCH=NAr. Lp thuc nhum ny t c sn xut v ch c s dng nhum x axetat, x si tng hp v in nh mu. 1.11. Thuc nhum hon nguyn a vng Trong phn t ca chng c h mang mu l cc hp cht a t gia antraquinon (hoc dn xut) vi cc vng d th khc, to nn cc mch a vng. Hp cht a t ca lp thuc nhum ny gm cc nhm sau:
O O N O O
1,2-antraquinonoxazol

O N

N O N

2,3-antraquinonaxazol
O

antraquinonpirazin

N N O HN

NH

O
phlavantren
indantron

NH CO Ar

O
axylaminoantraquinon

O
antantren

O
benzantren

45

1.12. Thuc nhum phtaloxianin Chng l lp thuc nhum tng i mi; h thng mang mu trong phn t ca chng l mt h lin hp khp kn. Th d:

N N N

N H H N

N N N

N N N

N H H N

N N N

tetrazaporphin

phtaloxianin

c im chung ca lp thuc nhum ny l: nhng nguyn t hyro trong nhm imin d dng b thay th bi cc ion kim loi; cn cc nguyn t nit khc th li tham gia to phc vi kim loi lm cho mu sc ca thuc nhum thay i. S thay i ny ph thuc vo bn cht ca ion kim loi. Nhng thuc nhum c gc phtaloxianin c bn mu vi nh sng rt cao. Lp thuc nhum ny gm cc loi thuc nhum pigment, thuc nhum hon nguyn, thuc nhum axit, thuc nhum hot tnh v mt s azotol. 2. TNG HP PHM VT TRUNG GIAN Phn ln cc loi thuc nhum hu c u c tng hp t cc hp cht trung gian. Nhng hp cht trung gian thng l nhng hp cht vng thm, chng c tng hp t cc nguyn liu nh: benzen, naphtalen, antraxen. Cc nguyn liu ny chnh l sn phm quan trng ca cng nghip ch bin than v cng nghip du m. T nhng nguyn liu ban u ngi ta c th thu c hng trm phm vt trung gian bng cc phn ng ho hc c bn sau: - Phn ng th nguyn t hyro trong nhn thm: phn ng sunfo ho, phn ng nitro ho, phn ng nitrozo ho v phn ng halogen ho; - Phn ng bin i nhm th nhn thm nhm a mt s nhm th khc vo nhn thm m bng phng php trc tip khng th thc hin. - Phn ng ng vng nhm to ra cc hp cht a nhn v cc dn xut a vng hoc cc hp cht d vng. 2.1. Phn ng th vo nhn thm Phn ng ny c ngha rt quan trng nhm a cc nhm th nh: nhm sunfonic, nhm nitro, nhm nitrozo v nguyn t halogen vo nhn thm. Nhng hp cht ny c vai tr quyt nh n nhiu tnh cht ca thuc nhum. Cc nguyn liu ban u ca phn ng th l: benzen, naphtalen, antraquinon. Nhng hp cht vng thm ny u l cc h thng giu cc in t linh ng nn rt d tham gia cc phn ng th electrophin, cn vi cc tc nhn nucleophin chng ch tham gia phn ng trong nhng iu kin khc nghit. 46

2.1.1. Phn ng th electrophin (th i in t) Cc tc nhn electrophin thng l cc cation E+ hoc cc phn t phn cc X Y . C ch ca phn ng th electrophin ph thuc vo nhiu yu t. Sau y l mt s trng hp c th. a. Qui lut th vo nhn benzen Benzen c cu to su cnh ng phng, cc electron ri u trn ton b vng thm khin cho phn t benzen c bit bn vng. Benzen c khuynh hng tham gia cc phn ng th mnh hn l phn ng cng hp nhm bo ton h thng lin hp trong vng. C ch ca phn ng th electrophin vo nhn benzen c th biu din nh sau:
H + E
+
+

E
H
+

phc

Trong phc l mt cation khng bn v bn in t ri u trn nm nguyn t cacbon nn n c xu th tch proton to li h thng electron ca nhn thm. Cc tc nhn electrophin c th l cc cation nh NO2, HSO3 ... hoc c th l phn t phn cc nh ClCl, ClSO3H, RCOCl, RBr. Khi trong nhn benzen cha c nhm th th tc nhn electrophin c th tn cng vo bt k v tr no. Nhng khi trong nhn c mt nhm th th s tn cng s c tnh chn lc. Nu trong nhn benzen c sn mt nhm th loi I - l nhm th c kh nng lm tng mt in t ca nhn thm - th tc nhn electrophin s tn cng vo v tr octo v para so vi nhm th c. Nhm th loi I gm: OH, O, OR, OC6H5, NH2, NR2, NHCOCH3, CH3, C(CH3)3, C6H5, Cl, Br, CH2Cl, CH=CHNO2. Nu trong nhn c sn mt nhm th loi II - l cc nhm th c kh nng ko in t ra khi nhn thm - th chng s gy kh khn cho phn ng th electrophin v s nh hng tc nhn electrophin vo v tr meta so vi nhm th c. Nhm th loi II gm: NO2, NH3+, +NR3, CF3, COOH, COOR, CONH2, CN, CHO, COR, SO3H, SO2R. Qui lut th vo nhn thm ni chung da vo mt s yu t sau: l- mt in t nguyn t cacbon trong nhn thm; 2- s bn vng ca cc phc trung gian; 3- s cn tr ca khng gian; 4- hot ca tc nhn th. Da vo cc yu t trn c th gii thch s nh hng ca cc nhm th l do chng nh hng n nng lng hot ho ca cc phn ng dn ti tc ca chng khc nhau v to ra cc sn phm khc nhau cc v tr nh hng. Nhm th loi I c sn trong nhn benzen s c tc dng b tr phn in tch dng phc khi c tc nhn electrophin tn cng vo nhn benzen. V d, phn ng th electrophin vo nhn anilin v nitrobenzen xy ra nh sau:

47

NH2

+

NH2
+

NH2
+

NH2 E
E H
+

E+

NH2
+ + +

NH2
+

NH2
+

E
+

E
+

H
NO2
o + m + p
+

E
NO2
+ + +

o + m

NO2
+

NO2 E
+

E+
+

E H

+ , + + m < o p

Xt yu t th nht v s phn b mt in t nh trn nhn thy: trong nhn anilin ti cc v tr octo v para c in tch m nn chc chn tc nhn electrophin E+ phi tn cng vo . Cn trong nhn nitrobenzen, in tch dng cc v tr meta nh hn ti cc v tr octo v para nn tc nhn E+ tn cng vo v tr meta. Xt yu t th hai: cc nhm th c tc dng b tr phn in tch dng trong phc trung gian. S b tr ny cng c hiu qu khi nhm th loi I cng gn mt trong cc in tch dng +. Nh vy trong trng hp anilin (c nhm th loi I) th tc nhn electrophin v tr octo v para lm cho in tch dng + c b tr ln hn hn cc v tr meta. Ngc li trong nitrobenzen (c nhm th loi II), nhm th cng lm tng in tch dng + khi n cng gn in tch ny v lm cho phc trung gian khng tn ti. Ch c cc v tr meta th nh hng ca nhm th ti + mi gim i lm cho phc n nh. Trong trng hp nhn benzen c sn hai nhm th th c hai nhm ny u c nh hng n hot ca nhn v s nh hng nhm th tip theo s tun theo cc qui lut sau: - nu hai nhm th c cng nh hng nhm th ba th phn ng xy ra d dng, th d:
Cl
+ H2SO4

Cl SO3H

NO2

NO2

- nu hai nhm th nh hng nhm th ba vo cc v tr khc nhau th v tr ca n thng c quyt nh bi nhm c nh hng mnh hn, th d: 48

CH3 + NO2 NO2 O2N

+

CH3

NO2

b. Qui lut th vo nhn naphtalen Naphtalen c trong nha than vi hm lng khong 5 - 6% v trc y n ch thu c t ngun ny. Ngy nay, naphtalen c sn xut nhiu hn t du m. Cu to ca naphtalen gm 10 nguyn t cacbon phn b thnh hai vng su cnh cng vi 8 nguyn t hyro. Phn t naphtalen c cu to ng mt phng v cc electron c phn b mt cch i xng. Nh vy, hai vng su ca naphtalen hon ton c gi tr nh nhau to nn mt h thng thng nht vi 10 electron . biu din 8 1 phn t naphtalen ngi ta thng dng hai vng benzen gip nhau. 9 2 7 Tuy nhin, s phn b cc electron trong h thng naphtalen khng 3 6 c u n nh benzen. Cc bc lin kt trong phn t naphtalen 10 5 4 khng nh nhau. Ngi ta quy c cc v tr 1, 4, 5, 8 l v tr , cn 2, 3, 6, 7 l v tr . Nhn chung, kh nng tham gia phn ng ca naphtalen mnh hn nhiu so vi benzen; phn ng vo cc v tr mnh hn vo cc v tr v lin kt hot ng hn nhiu so vi cc lin kt . Khi trong nhn naphtalen cha c nhm th th phn ng th nguyn t hyro s xy ra cc v tr nhiu hn. Tuy nhin, s ng phn ca cc dn xut th naphtalen thng tn ti nhiu hn v ng phn c bn nhit ng cao hn ng phn . Th d, sn phm th mt ln naphtalen bng tc nhn sunfo ho s c hai ng phn:
H2SO4 40 - 60oC

160oC H2SO4 160oC

SO3H

SO3H

Trong trng hp th ln hai th nhm th tip theo c th vo nhn thm th cng nh nhn cha b th. S nh hng s tun theo mt s qui tc sau: - nu trong nhn c nhm th loi I th tc nhn electrophin s nh hng vo v tr octo hay para chnh nhn c nhm th
SO3H
OH
+ H2SO4

OH

- nu trong nhn c nhm th loi II th tc nhn electrophin s nh hng vo nhn cha b th

SO3H
+ HNO3

SO3H

NO2

SO3H

v
NO2

49

- khi trong nhn naphtalen c hai nhm th th v tr th tip theo c xc nh bi kh nng nh hng ca cc nhm th v cc v tr cn t do. c. Qui lut th vo nhn antraquinon Antraquinon c iu ch thng cng nghip bng hai phng php: - phng php oxy ho antraxen (antraxen c ch bin t nha than ):
O
oxy ho HNO3 + H2CrO4

- phng php i t cc nguyn liu du m:

O
CO O CO
anhiric phtalic benzen

O
H2SO4

AlCl3

COOH

O antraquinon

Antraquinon c s dng nhiu trong sn xut cc loi thuc nhum. Cu to ca phn t antraquinon c coi l hp cht a nhn ngng t. Phn t cu to t hai vng benzen ni vi nhau bi hai nhm xeton: Cc v tr 1, 4, 5, 8 c coi l v tr . Cc v tr 2, 3, 6, 7 l v tr .
7 8

1 2

3 Khi tc nhn electrophin tn cng vo nhn antraquinon th 6 5 4 phn ng xy ra cc v tr mnh hn v ti cc v tr O nguyn t hyro linh ng hn. Tuy nhin, trong thc t phn ng th electrophin vo nhn antraquinon li theo mt qui lut khc bit: trong mt s phn ng (phn ng sunfo ho khng c xc tc) ch thu c sn phm ng phn do ng phn ny c bn nhit ng cao hn ng phn . Cc phn ng nitro ho v halogen ho cho sn phm l ng phn .

Khi trong nhn antraquinon c mt nhm th loi I th phn ng electrophin s xy ra cc v tr octo hoc para so vi nhm th c ca chnh vng . Cn khi trong nhn antraquinon c mt nhm th loi II th vng benzen th hai vn gi nguyn kh nng tham gia phn ng v tc nhn electrophin s vo cc v tr ca vng benzen , v vy sn phm thng c hai ng phn. 2.1.2. Phn ng th nucleophin (th i nhn) Nh trnh by trn, cc hp cht vng thm giu in t, khi cha cha cc nhm th s kh tham gia vo phn ng th nucleophin. Tuy nhin, nhm th loi II c sn trong nhn thm tc l lm cho nhn thm tch in dng to kh nng cho chng tham gia phn ng th nucleophin:
NO2 + KOH NO2 OH

50

S nh hng tc nhn nucleophin (Nu) thng vo cc v tr octo v para c gii thch nh sau:
NO2
+ o + m p
+

SO3H
+ o + m + o + m + p + o + m

+ + trong o > + p > m , v vy tc nhn nucleophin s vo v tr c in tch d ng ln

nht. Cc tc nhn nucleophin gm: NH2, ArS, RO, R2NH, ArO, OH, ArNH2, cc anion halogen, H2O, ROH. Nhn chung phn ng th nucleophin trong nhn thm thay th nguyn t hyro t xy ra. Trong thc t, phn ng th nucleophin thay th cc nhm th khc thng gp nhiu hn v c nhiu ngha trong lnh tng hp phm vt trung gian. 2.2. Phn ng bin i nhm th Trong cng nghip sn xut phm vt trung gian, c mt s hp cht khng th iu ch bng cch thay th trc tip nguyn t hyro trong nhn thm m phi bng phng php bin i nhm th - tc l thay nhng nhm th c sn trong nhn thm bng nhng nhm th khc m ta mong mun. Phn ng bin i nhm th c th thc hin bng mt s phn ng c trng sau. 2.2.1. Phn ng th nucleophin Chng gm cc phn ng to nhm hyroxyl bng cch thay th nhm sunfonic, nhm amin, hoc nguyn t halogen v.v.:
X
X Nu

Nu

+ Nu

trong X l SO3H, NH2, Cl, Br; Nu l OH, NH3. 2.2.2. Cc phn ng bin i khc Phn ng kh nhm nitro: ArNO2
[H]

ArNH2 ArNHR

Phn ng alkyl ho nhm amin: ArNH2 + RX trong X l OH, halogen. Phn ng axyl ho: O ArNH2 + RC O ArOH + C ArNHC R O ArOCR 51 O

Phn ng aramin ho: ArNH2 + RNH2 Phn ng iazo ho ArNH2

+

ArNHR.

NaNO2 HCl

{ArNN}Cl

Phn ng th nhm iazo: {Ar N N}Cl + Z Z = OH, Cl, CN, NO2, OR 2.3. Phn ng bin i vng thm y l loi phn ng ngng t c km theo s ng vng hp cht ban u hoc to nn cc vng d th. Trong cng nghip sn xut thuc nhum, ngi ta s dng rt nhiu cc hp cht trung gian c vng d th hoc cc hp cht a vng thm. S a dng ho phm vt trung gian cho ra i nhiu loi thuc nhum c cc mu sc phong ph v cc tnh cht qu bu. Phn ng iu ch cc dn xut ca antraquinon:
O
CO O CO OH + OH OH
AlCl3

ArZ + N2

OH OH OH

Phn ng to vng d th:

CH3 CO CH2 COOC2H5 CH3 CO CH2 COOC2H5
+ + H2 N

CH3
NH C 6H 5

H2C O C N

C CH3 N

C N NHC6H5 CH2 COOC2H5

C6H5
1-phenyl-3-metylparazolon-5

NH2 CO CH2 NH
O

CH2

N R

OH

R Nhng phm vt trung gian trn c s dng tng hp thuc nhum azo.

Phn ng to gc triazin tng hp thuc nhum hot tnh:

Cl C
4

Cl2 + HCN

3ClCN
Cl

N5

3N

6 2 C 1

Cl

2,4,5-triclo-1,3,5-triazin

52

Phn ng a tr to cc hp cht a vng:

O
O
KOH + NaOH CH3COONa

NH O HN

NH2 O

KNO2 + KOH 250oC

O
inantron - thuc nhum hon nguyn mu xanh lam

2.4. Mt s qui trnh cng ngh tng hp phm vt trung gian 2.4.1. Sunfo ho a. Mc ch - Sunfo ho cc hp cht thm to nn cc axit arensunfonic lm tng tnh axit ca hp cht v c dng trong tng hp thuc nhum axit. - Lm tng tnh tan ca hp cht khi chuyn nhm sunfonic thnh natri sunfonat gip cho cc sn phm ho tan c trong nc thun tin cho vic s dng. - Thng qua nhm sunfonic a mt s nhm th khc vo nhn thm m bng phng php trc tip kh hoc khng th a chng vo c. b. Tc nhn sunfo ho tin hnh sunfo ho ngi ta thng dng cc tc nhn: - axit sunfuric vi cc nng khc nhau: H2SO4 92 - 93% gi l du sunfat, H2SO4 98 - 100% gi l monohyrat; - oleum: H2SO4 bc khi cha SO3 t do vi nng 25% hoc 65% SO3; - axit closunfonic: ClSO3H. c. C ch ca phn ng Phn ng sunfo ho c coi l phn ng th electrophin. Tc nhn electrophin s c th hin qua cc tc nhn sunfo ho nh sau: - axit sunfuric nhit thng s phn ly theo phn ng: H2SO4 H2S2 O7 khi nhit nng cao 2H2SO4 H3SO4+ H3SO4+ + HSO4 HSO3+ + H2O H3O+ + H2S2O7 + HSO4 H2SO4 + SO3

- oleum l H2SO4 + SO3; - closunfonic l ClSO2OH. 53

Nh vy, tc nhn electrophin trong phn ng sunfo ho s l HSO3+, SO3 v + SO2Cl. Nhng tc nhn trn s tn cng vo cc nhn thm giu in t
H + HSO3
+

HSO3
+

SO3H
H2SO4

H + SO3
+

SO3

SO3H

SO2Cl + ClSO2OH
H2O

SO3H

C ch ca phn ng sunfo ho vo cc nhn thm v vo cc nhn c nhm th u tun theo cc qui lut nh trnh by phn 2.1.1, chng II. d. Cc yu t nh hng n qu trnh sunfo ho Cc iu kin phn ng sunfo ho ph thuc vo bn cht ca hp cht thm, ca tc nhn phn ng v vo s nhm sunfonic cn a vo. Khi cc yu t trn khng thay i th cc yu t ca iu kin phn ng s c nh hng n tc phn ng. Khc vi a s phn ng th electrophin nhn thm, phn ng sunfo ho l mt phn ng thun nghch. ArH + H2SO4 ArSO3H + H2O Axit arensunfonic to thnh d b thy phn bng hi nc qu nhit (180oC). Bng thc nghim, nhiu cng trnh nghin cu chng minh c tc ca phn ng sunfo ho tun theo phng trnh: v = k [ArH] [H2SO4] trong k - hng s tc phn ng, n tng khi tng nng H2SO4. Song s bin i ny ch th hin mt gii hn nht nh ca nng H2SO4. Nu tng qu nng H2SO4 s c phn ng ph xy ra; nu gim thp hn gii hn th phn ng s b ngng. Nng gii hn c xc nh da vo tnh cht ca hp cht thm, vo s nhm sunfonic cn a vo nhn thm v vo nhit ca phn ng. Nhit v thi gian phn ng sunfo ho c gii hn ti u i vi tng phn ng cc hp cht c th. Nu tng nhit v ko di thi gian so vi gii hn ti u s xy ra phn ng ph ngoi mc ch. Tng nhit cao qu gii hn s lm cho phn ng xy ra phc tp v c cc phn ng ph km theo nh: phn ng oxy ho, phn ng ngng t, phn ng to hp cht sunfon. Tc dng ca xc tc: khi thc hin phn ng sunfo ho benzen v naphtalen (v cc dn xut ca chng) th khng cn n xc tc. Ch c phn ng sunfo ho antraquinon l cn xc tc nh hng vo v tr . 54

O
+ H2SO4 + SO3

SO3H

khng xc tc

O O

SO3H

+ H2SO4 + SO3 xc tc HgSO4

C ch tc dng ca xc tc chnh l s to thnh sn phm trung gian bn ca phc .

O
H2SO4 HgSO4

O H

HgSO4
SO3 HgSO4

SO3H

Ngoi tc dng i vi antraquinon, HgSO4 cn c tc dng lm tng ng phn para v octo khi sunfo ho cc hp cht dn xut thm c nh hng meta. e. Tnh cht ca cc axit arensunfonic Tch sn phm. C mt s axit arensunfonic t ho tan trong dung dch H2SO4 long nn c th tch chng ra dng axit bng cch pha long dung dch phn ng (dng nc thng hoc nc ). Cn li phn ln cc axit arensunfonic phi tch ra dng mui natri (ArSO3Na). Trong khi phn ng cn c H2SO4 nn khi ho mui s c c lng natri sunfat: ArSO3H + NaCl ArSO3Na + HCl H2SO4 + NaCl Na2SO4 + HCl Nh vy, c th dng mui n tch sn phm va r tin d kim nhng li to ra axit trong khi phn ng. Trong sn xut tt nht nn dng hn hp mui Na2SO4 + Na2SO3: ArSO3H + Na2SO4 + Na2SO3 ArSO3Na + NaHSO4 + H2O + SO2 Ring i vi axit -antraquinon sunfonic, ngi ta dng kali clorua kt ta tch sn phm. Tnh cht l hc. Nhng axit arensunfonic thng tn ti dng bt trng kh ho tan trong nc lnh, d ho tan trong nc nng v mt vi dung mi hu c. Nhng mui natri sunfonat d ho tan trong nc v thun tin cho vic s dng. Nhng axit arensunfonic thng c chuyn v dng mui axit v mui ny s kh ho tan hn mui trung tnh. Tnh cht ho hc - Cc axit arensunfonic l nhng axit mnh, chng c kh nng chim cation ca cc mui bn nn chng tham gia phn ng trao i vi cc loi mui trung tnh: ArSO3H + NaCl ArSO3Na + HCl ArSO3H + Na2SO4 ArSO3Na + H2SO4 ArSO3H + Na2CO3 ArSO3Na + H2O + CO2 55

Chng cng c kh nng to mui vi cc baz hu c ni chung v amoniac ni ring. - Nhm sunfonic trong nhn thm d b thay th bi cc nhm th hoc nguyn t khc: ArSO3Na + 2NaOH ArSO3Na + NaCN ArSO3Na + PCl5 ArSO3H + H2O Dy benzen:
SO3H
H2SO4 oleum 80oC

nung chy

ArONa + Na2SO3 + H2O

ArCN + Na2SO3 ArSO2Cl + POCl3 + NaCl ArH + H2SO4

g. S sunfo ho mt s hp cht thm

SO3H

SO3H

benzen
NH2

axit benzenmonosunfonic
NH.H2SO4
H2SO4

axit benzen meta-disunfonic

NH2

anilin

anilinsunfat

SO3H axit sunfanilic

NO2
oleum

NO2

SO3H

nitrobenzen

axit meta-nitrobenzensunfonic
Cl
oleum

Cl

clobenzen

SO3H
axit clobenzensunfonic

CH3
H2SO4

CH3

CH3

CH3 SO3H
oleum

,
SO3H

SO3H SO3H

toluen

85%

10%
OH + SO3H

OH
H2SO4

OH

phenol

SO3H

56

Dy naphtalen:
H2SO4 35 - 60oC H2SO4 160oC

SO3H
SO3H
H2SO4 + SO3 35 - 60 C
o

H2SO4 + SO3 50 - 90 C
o

H2SO4 + SO3 160 - 170 C

o

H2SO4 + SO3 160 - 170oC

HO3S
50 - 90oC

SO3H
SO3H HO3S
SO3H

SO3H HO3S

SO3H

HO3S
H2SO4 + SO3 150 - 250oC

H2SO4 + SO3 95oC

H2SO4 + SO3 160oC

SO3H SO3H HO3S SO3H

H2SO4 + SO3 150 - 250oC

SO3H HO3S HO3S SO3H

SO3H
SO3H

SO3H

-Naphtylamin:
H2SO4 nung

NH2

NH.H2SO4

NH2

-Naphtylamin:
SO3H

NH2

H2SO4 + SO3 35 - 90oC

HO3S

NH2
thu phn

HO3S

NH2

SO3H

SO3H
axit I

-Naphtol:
OH

H2SO4 10oC

H2SO4 90oC

H2SO4 120oC

H2SO4 70 - 80oC

SO3H OH

SO3H
OH HO3S
HO3S OH SO3H

OH HO3S

57

Dy antraquinon:
O

oleum HgSO4

oleum NaCl

SO3H

O SO3H HO3S O HO3S

HO3S

HO3S O O
SO3H

HO3S

O O

O
HO3S O SO3H

O
Hg

SO3H HO3S

SO3H

HO3S O O NH2
H2SO4

O O NH.H2SO4
nung

NH2 SO3H

O -aminoantraquinon O OH

OH SO3H

HO3S OH O OH O
1,5-ihyroxy antraquinon

2.2.2. Nitro ho Nitro ho l mt trong nhng phn ng quan trng tng hp phm vt trung gian v thuc nhum. Chnh nhm nitro l mt nhm mang mu trong thuc nhum; n cng c s dng chuyn ho thnh nhm amin l nhm tr mu quan trng trong thuc nhum. a. Tc nhn nitro ho v c ch phn ng Nhn chung, phn ng nitro ho c xp vo loi phn ng th electrophin, nhng c nhng trng hp ngoi l ph thuc vo bn cht tc nhn nitro ho. Phn ng nitro ho l mt phn ng khng thun nghch: ArH + HNO3 58 ArNO2 + H2O

Dng hn hp axit nitric m c v H2SO4 90 - 100%, cn c gi l hn hp axit nitro ho lm tc nhn nitro ho. S hnh thnh tc nhn phn ng l do HNO3 b proton ho v tch i mt phn t nc to ra cation nitroni: HONO2 + H+ H2+ONO2
H2O

NO2+

Nh vy, s to thnh cation nitroni trong tng trng hp s dng cc axit mnh khc nhau s c chung bn cht: 2HNO3 NO2+ + NO3 + H2O H3O+ + 2HSO4 HNO3 + 2H2SO4

Ngoi H2SO4 cn c th s dng cc axit mnh nh HClO4, HF, BF3. Trong trng hp ny tc nhn phn ng l electrophin NO2+ v c ch phn ng l c ch th electrophin:
H
NO2
+

NO2
+

NO2
H+

Dng axit nitric long: khi dng axit nitric long th phi dng c HNO2 hoc c mt kh NO. Phn ng nitro ho s xy ra theo mt c ch khc nh sau: HNO3 + HNO3 N2 O4 gc: ArH + NO2 Ar + NO2 HNO2 + HNO3

N2 O4 + H2 O 2NO2

Tc nhn tn cng vo nhn thm l gc NO2 v phn ng chui xy ra theo c ch Ar + HNO2 ArNO2 H2O + 2NO2

Phn ng loi ny ch c th dng cho cc hp cht thm c trong nhn nhm th loi I nh: nhm hyroxyl hoc nhm amin. Th d, phenol, crezol, clophenol v.v. Dng mui nitrat: NaNO3, KNO3, NH4NO3. Phn ng nitro ho c tin hnh trong H2SO4 m c, n tng ng nh khi dng HNO3 100%: NaNO3 + H2SO4 NaHSO4 + HNO3 Ch s dng tc nhn ny khi tin hnh nitro ho cc hp cht thm kh nitro ho v sn xut nhng hp cht polynitro. Dng nit ioxyt NO2 (N2O4) c cht xc tc l AlCl3 hoc FeCl3 hoc PCl5: N2O4 + AlCl3
H

AlCl3.NO2.NO2+
NO2
+

NO2

+ AlCl3.NO2.NO2+ 2AlCl3 + 3HNO2

. AlCl3.NO2
3NOCl + Al2Cl3(OH)3

+ AlCl3 + HNO2

Ngoi ra cn c th dng NO2 trong pha hi c xc tc l silicagen:

+ NO2
310oC silicagen

NO2

59

b. Cc yu t nh hng n qu trnh nitro ho Trc ht phi xem xt bn cht ca cc hp cht thm khi nitro ho. D phn ng nitro ho theo c ch th electrophin hay th gc th mt in t trong nhn thm cng nh hng rt nhiu n phn ng. Nu trong nhn thm c mt nhm nitro th vic nitro ho tip theo s xy ra kh khn hn. Nu trong nhn thm c cha nhm th loi I th qu trnh nitro ho xy ra d dng. Th t ca cc nhm th nh hng n phn ng c th xp nh sau: NO2 > SO3H > COOH > Cl < CH3 < OCH3 < OC2H5 < OH Tc gim Tc tng Nng HNO3 v H2SO4 phi lun m bo gii hn ti u cho mi hp cht, lng HNO3 phi ly d 1 - 10% so vi tnh ton l thuyt, d qu s to sn phm ph do b oxy ho. Lng H2SO4 cng phi ly d v lun m bo nng 90 - 100%, nu nh hn 90% phn ng phn ly to NO2+ s xy ra kh khn, cn nu ln hn 100% th phn ng phn ly HSO4 s kh khn. Nhit lun phi m bo lm lnh thit b phn ng v nitro ho l mt phn ng ta nhit. c. Tnh cht ca hp cht nitro - Cc hp cht nitroaren u l nhng cht c, mt s cht d gy chy da, cay mt, ngt th, nhiu hp cht khi b va chm mnh hoc t nng s gy n nguy him. - Nhiu hp cht nitro c kh nng tan trong kim to thnh dung dch c mu vng, mu da cam hoc mu . Hp cht nitro khng bn nhit cao cho nn khng cho php tin hnh phn ng nung chy kim. d. S nitro ho mt s hp cht Dy benzen:
HNO3 40 - 50 C
o

NO2
HNO3 90oC

NO2

NO2

Dy antraquinon:

NO2

NO2

NO2 O
O

O
NO2 O NO2

O SO3H

O SO3H
+

NO2 O SO3H

NO2 O

60

OH

OH

OH NO2

O O CH3

NO2

NO2

NO2 CH3

2.2.3. Halogen ho Halogen ho l phn ng th mt hay nhiu nguyn t hyro hoc ca nhn thm hoc ca mch nhnh bng mt hoc nhiu nguyn t halogen. Mc ch ca phn ng halogen ho l tng hp ra mt s loi dung mi hu c nh clobenzen..., nhng quan trng nht l tng hp cc phm vt trung gian (anilin, phenol, axit hu c) v thuc nhum. Nhng thuc nhum c cha nguyn t halogen thng c bn mu cao vi nh sng, mu ti v thun sc hn. a. Tc nhn halogen ho C th s dng Cl2, Br2, I2, ring F2 c tnh hot ng qu cao nn khng th dng trc tip v s kh nhn c sn phm th ng nht v F2 kh iu ch. a nguyn t flo vo nhn thm ngi ta phi dng phng php gin tip nh thay th nguyn t clo hoc phn ng vi hp cht iazo thm. Phn ng halogen ho ch yu l tin hnh bng tc nhn Cl2 v Br2, chng va r, d kim li c sn xut vi qui m ln. Trong mt vi trng hp c th dng cc tc nhn khc nh NaClO, NaClO3, SO2Cl2, HCl vi khng kh. b. C ch phn ng xc nh c ch ca phn ng halogen ho cn phi xem xt tng trng hp c th v phn ng ny c th xy ra c nhn thm v c mch nhnh vi nhng ankylaren. Phn ng halogen ho nhn thm. Nu iu kin phn ng nhit cao ngoi nh sng v khng c xc tc th cc halogen d tham gia phn ng cng hp vo cc ni i ca nhn thm. Mun phn ng th xy ra phi tin hnh trong bng ti v c mt xc tc l cc axit Lewis: FeCl3, AlCl3, FeBr3, ZnCl2. Tc dng ca xc tc l hot ho phn t halogen to cc ion electrophin: FeCl3 + Cl2
+ Cl+

[FeCl4]Cl+
H Cl
+

Cl
FeCl4

FeCl4

Khi trong nhn benzen c mt nhm th loi II th kh nng halogen ho s gim i, nu cha mt nguyn t halogen th kh nng halogen ho gim i cht t, cn nu cha nhm th loi I th kh nng halogen ho s tng ln, phn ng xy ra d dng hn (thm ch c trng hp khng cn xc tc). Phn ng halogen ho mch nhnh. C rt nhiu phm vt trung gian c dng tng hp thuc nhum l cc dn xut halogenua mch nhnh ca nhn thm, th d benzyl clorua c s dng trong qu trnh benzyl ho dng sn xut thuc nhum axit 61

triarylmetan. iu kin phn ng halogen ho mch nhnh l nhit cao (gn bng nhit si ca cc hyrocacbon) khng cn c xc tc v cn tc dng ca cc tia tm hoc tia t ngoi vi bc sng > 300 nm. C ch phn ng l c ch gc t do: X2 ArCH3 + X ArCH2 + X2 ArCH2X + X ArCHX + X2
h

2X ArCH2 + HX ArCH2X + X ArCHX + HX ArCHX2 + X

Cc cht tham gia phn ng ny phi c kh nng to gc. Phn ng halogen ho vo mch nhnh khng c tin hnh trong cc thit b kim loi. Halogen ho naphtalen v antraquinon. Dn xut clo ca naphtalen t c ngha nn t c xem xt. Phn ng clo ho antraquinon xy ra kh khn v sn phm t c s dng, c ngha hn c l 1-clo-2-metylantraquinon dng iu ch thuc nhum hon nguyn. C trng hp halogen ho thuc nhum a nhn antraquinon to cc mu p hn. c. S clo ho mt s hp cht thm
Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl

Cl Cl

Cl Cl Cl

CH3

CH2Cl

CHCl2

CCl3

CH3 Cl

CH3

CH3 Cl +

CH3

+
Cl
CCl3 Cl

Cl Cl CHCl2 CCl3 Cl Cl

Cl

Cl

d. Tnh cht ca hp cht halogenaren Nhng sn phm halogen mch nhnh c tnh cht tng t cc dn xut halogen mch thng ngha l nguyn t halogen d dng b thay th bi cc nhm amin v nhm hyroxyl. 62

Nhng sn phm c nguyn t halogen nhn thm thng km hot ng ho hc hn. Mun th chng bng cc nhm amin v hyroxyl phi tin hnh phn ng nhit cao, p sut cao v i khi phi dng c xc tc. 2.2.4. To nhm hyroxyl trong nhn thm Vic a nhm hyroxyl vo nhn thm c mt ngha quan trng trong tng hp phm vt trung gian v thuc nhum. Cc nhm hyroxyl lm hot ho cc hp cht thm trong cc phn ng ho hc tip theo v to cho thuc nhum c nhng tnh cht cn thit. Vic a trc tip nhm hyroxyl vo nhn thm rt t gp m ch yu l thng qua cc nhm khc (SO3Na, Cl, Br, NH2...) bng phn ng th nucleophin. a. Phn ng nung chy kim l phn ng thay th nhm sunfonat bng nhm hyroxyl:
o ArSO3Na + NaOH 160 - 320 C

ArONa + Na2SO3 + H2O.

ON a 3Na C ch phn ng l thSO nucleophin tc l tc nhn nucleophin s tn cng vo nhng + + + + + SO H2O Na 2 v tr tch in dng ln nht. Trong axit benzensunfonic th o ,4 + p > m nn phn

ng cn c th xy ra cc v tr octo. Tc nhn ca phn ng nung chy kim c th l NaOH, hn hp KOH + NaOH, Ca(OH)2... Trong NaOH c s dng nhiu hn c v r tin, d kim; hn hp KOH + NaOH lm tng kh nng phn ng, gim nhit ; Ca(OH)2 ch s dng cho phn ng th mt nhm hyroxyl. iu kin ca phn ng ph thuc vo bn cht ca hp cht cha nhm sunfonic, vo loi tc nhn kim v thun khit ca chng. Mt s hp cht c iu ch theo phng php ny:
SO3Na
2NaOH 300oC

ONa +
OH +
phenol

Na2SO3

H2O

ONa

+ SO2 + H2O

Na2SO3

NaO3S

NH2
2NaOH

6 - 7 at, 178 - 180 C

ONa NH2
dung dch H2SO4 long

OH

NH2

NaO3S

SO3H

NaO3S

SO3H

NaO3S

SO3H

axit H

SO3Na

2NaOH

ONa

+ SO2

OH

-naphtol
SO3Na NH2 NaO3S NaO3S ONa NH2 NaO3S OH NH2

axit

63

SO3Na

OH

NaO3S

NH2

NaO3S

NH2

O SO3H

OH OH

O alizarin

b. Phn ng th nguyn t halogen ArX + NaOH ArONa + NaX. - Thy phn bng kim: iu ch phenol v alizarin.
Cl +
O Cl + O 3NaOH O

2NaOH

300oC 100 - 200 at

ONa + NaCl
O ONa ONa + NaCl + H2O

H2O

- Thy phn bng nc trong pha hi: iu ch phenol

Cl + H2O
500 - 600oC silicagen

OH + HCl

- Phng php thy phn Rasi

+ HCl +
Cl + H2O

1 O 2 2

Cl +
OH + HCl

H2O

Phn ng tng qut

+ 1 O 2 2 OH

Khi trong nhn thm c nhm th nhn in t cc v tr octo v para so vi nguyn t clo th phn ng thy phn xy ra d dng hn. Phn ng thy phn halogen i vi dy naphtalen xy ra kh khn nn t c ngha thc t. c. Phn ng thy phn nhm amin bc nht ArNH2 + H2O ArOH + NH3 Phng php ny c s dng cho dy naphtalen, s thy phn c th tin hnh trong mi trng kim hoc mi trng axit: 64

NH2 + NaOH
dung dch 3 - 10% 150 - 180oC

OH

NH2 + H2O + H2SO4

OH

HO3S

SO3H

HO3S

SO3H

2.2.5. To nhm amin trong nhn thm Vic to nhm amin trong nhn thm c ngha rt ln trong cng nghip sn xut thuc nhum. Nhm amin khng nhng c vai tr chuyn ho hp cht trung gian (iazo thnh phn trong tng hp thuc nhum azo) m n cn l mt nhm tr mu quan trng trong thuc nhum. Trong h thng mang mu - h lin hp ca cht mu th nhm amin l mt nhm nhng in t, n lm tng kh nng dch chuyn in t trong h lm cho cht mu hot ho hn, tng kh nng hp th nh sng lm thay i mu v tnh cht nhum mu. Ngoi ra nhng hp cht amin thm cn c s dng rng ri trong cc lnh vc cng nghip khc nh dc phm, hng liu v.v. to nhm amin trong nhn thm, khng th s dng phng php th trc tip nguyn t hyro trong nhn thm m phi bin i cc nhm th khc c sn trong nhn. Sau y l mt s phng php c s dng trong cng nghip sn xut phm vt trung gian v thuc nhum a. Kh nhm nitro v cc nhm cha nit Phn ng tng qut: ArNO2
[H] [H] [H]

ArN=O

ArNHOH

ArNH2

y l mt phn ng oxy ho kh, qu trnh xy ra qua mt s giai on trung gian, kt qu cui cng s ph thuc vo bn cht ca tc nhn kh v vo mi trng phn ng. Tc nhn kh l Fe, Zn, Sn. Dng phoi st trong mi trng axit 2ArNO2 + 5Fe + 4H2O
axit

2ArNH2 + Fe3O4 + 2Fe(OH)2

Phng php ny c th iu ch hng lot cc amin thm bc nht:

NO2 NH2

nitrobenzen

anilin

NO2 CH3
nitrotoluen

NH2 CH3
2-toluiin

65

NO2

NH2

NO2
1,3-nitrobenzen
OH OH

NH2
1,3-phenileniamin

NO2

p-nitrophenol
NO2

NH2 p-aminophenol
NH2

NH2
-nitronaphtalen

NHOH + 3Zn + 3H2O -naphtylamin + 2Zn(OH)2

- Dng phoi km trong cc mi trng khc nhau:

NH2 + 2Zn + 3H2O NHOH + 2Zn(OH)2
OH

NH2

Hp cht hyroxylamin rt hot ng, di tc dng ca axit khong, n chuyn nhm ni phn t to thnh aminophenol. Phn ng c th tin hnh ngay trong axit m c cng s to ra sn phm trn:
NH2 + Zn
HCl c

NH2

OH

Trong mi trng kim s to ra sn phm khc nhau: ArNO2 + Zn NaOH ArN=O nitrozo ArNO2 + Zn
NaOH

ArNHOH hyroxylamin ArN=N+=Ar O azoxi

ArN=O + ArNHOH

ArN=N+=Ar O 66

2[H]

ArN=NAr

2[H]

ArNHNHAr hydrazo

hp cht azo

Hp cht hyrazo l sn phm c bn ca phn ng kh trn, nhng n l hp cht c kh nng chuyn nhm ni phn t khi c tc dng ca axit v c to nn cc hp cht ia min thm. phn ng to ra hp cht hyrazo th iu kin phn ng phi c khng ch cht ch: nhit , mi trng kim, kch thc v hm lng phoi km thch hp. Nu tng qu nhit v mi trng kim th phn ng s to ra amin bc nht: ArN=N+Ar O

+6[H] H2O

2ArNH2

Phn ng iu ch cc dn xut ca benziin cng tng t nh trn. Dng cc mui sunfua kim Khi dng NaHSO3 trong mi trng axit va kh c nhm nitro va a c nhm sunfonic vo nhn thm:
NO2 + NaHSO3
nhit p sut

NH2 SO3Na

SO3Na NO2 OH
+ NaHSO3

NH2 OH

SO3H

Dng sunfua kim Na2S2 v NaHS kh chn lc nhm nitro m khng nh hng n cc nhm khc. Tc nhn loi ny c s dng kh cc hp cht sau:
NO2
+ NaHS 74 - 99oC

NO2 + NH2 Na2S2O3

NO2

NO2 OCH3 O2N

O NO2
+ Na2S 90 - 120oC + NaHS

NH2 OCH3 O2N

O NH2

NO2 O

NH2 O

Ngoi ra ngi ta cn s dng natri hyrosunfit Na2S2O4 kh nhm nitro v nhm azo ca thuc nhum thnh nhm amin nhng phn ng ny khng s dng trong cng nghip m ch tin hnh trong phng th nghim nhm xc nh cu to v thnh phn ca mt s loi thuc nhum. 67

b. Phn ng thay th cc nhm khc Thng thng nhm amin c to trong nhn thm bng phn ng th nucleophin cc nhm sunfonic, nhm hiroxyl hoc nguyn t halogen c sn. - Khi trong nhn thm c nguyn t halogen m khng c mt nhm hot ho khc th phn ng th xy ra iu kin khc nghit:.
Cl +
Cl + 2NH3
[Cu(NH3)2]2SO4 250 - 270oC, 110 at

NH2 2NH3
CuCl2 , 200oC 60 - 100 at

NH4Cl
NH2

O Cl + NH3 O
200 - 210 at

O NH2

- Khi trong nhn thm c cc nhm th loi II cc v tr octo v para so vi nhm halogen th kh nng phn ng ca nguyn t halogen tng ln v iu kin ca phn ng th nucleophin s m du hn.
Cl + NO2
Cl + SO3H 2NH3
170oC

NH2 2NH3
170 - 200oC 30 - 45 at

+ NO2
NH2

NH4Cl

SO3H

Phng php thay th halogen c s dng iu ch cc amin bc hai:

Cl + H2N
CuO 250oC

HN

HCl

- To nhm amin bng phng php thay th nhm hyroxyl. Hp cht thm c cha nhm amin v hp cht cha nhm hyroxyl lun lun c th chuyn ho cho nhau theo s : ArNO2 ArNH2 ArOH ArSO3H Phng php to nhm amin bng cch thay th nhm hyroxyl thc s c ngha i vi nhng amin khng th iu ch bng phng php khc nh cc dn xut ca dy naphtalen (khng th tin hnh nitro ho chng, ri kh v amin):
OH
+ (NH4)2SO4 150oC, 15 at

NH2

68

SO3H OH
+ (NH4)2SO4

SO3H NH2

OH HO3S + (NH4)2SO4 HO3S

NH2

OH + COOH NH3

200oC

NH2 COOH

SO3H OH

SO3H NH2

SO3H OH HO3S HO3S

SO3H NH2

Vi dy benzen, phn ng th nucleophin nhm hyroxyl bng nhm amin xy ra rt kh khn v hiu sut phn ng thp. Ch khi trong nhn thm c cha nhm nhn in t v tr octo hoc para so vi nhm hyroxyl th phn ng mi xy ra d dng hn:
OH + N O NH3
nhit si

NH2 HO N N O NH

Vi dy antraquinon, th phn ng c s dng iu ch 1,4-iaminoantraquinon t xinizarin:

O OH + NH3 (Na2S2O4) O OH
90oC 2 - 3 at

NH2

NH2

Ngoi cc phng php a cc nhm chc quan trng vo nhn thm trnh by trn, cn c mt s cc phn ng khc na (nitrozo ho, ankyl ho, aryl ho,oxy ho, axyl ho, phn ng ngng t v chuyn nhm) m trong phm vi gio trnh khng th cp n. Cc iu kin v phng php c th ca nhng phn ng c th tham kho trong cc ti liu khc. c. Mt s phn ng in hnh

NH2

NHSO3Na

CH3

NHCH3

SO3Na

69

OH

NH2 + COCl HO3S

OH

NH CO

HO3S

SO3H

SO3H

NH2 + COCl CO NH

NH

CO

NH2 O

O
O2 V2O5

antraxen

O antraquinon

N(CH3)2 + H C O H2O

(CH3)2N

CH

N(CH3)2

2.2.6. Tng hp cc cht vng d th Trc y trong cng nghip sn xut thuc nhum phn ln s dng cc hp cht trung gian l cc dn xut ca benzen v naphtalen. Nhng xu th pht trin sn xut thuc nhum ngy cng tng i hi nhng loi thuc nhum mi c cc tnh cht s dng cao hn, p ng nhu cu pht trin ca vt liu dt. S c mt trong vng thm cc nguyn t d th nh nit, oxy, lu hunh v.v. cho php to nn cc loi thuc nhum c nhng tnh cht tt hn nh ti mu, su mu bn mu v thun sc v.v. a. Tng hp hp cht pizolon Ngoi nhm phenyl c th s dng cc gc aryl c cha cc nhm th halogen hoc sunfonic to ra dn xut ca pirazolon.
CH3 C O CH2 C O O
H2C
un nng C2H5OH

CH3 + H2N NH C6H5

H2O

C CH2

NH

C6H5

C2H5

C O O
C N N C6H5 CH3
HO

C2H5

HC HO C N

C N C6H5

CH3

1-phenyl-3-metyl pirazolon-5

70

CH2

b. Cc hp cht inol C nhiu phng php tng hp inol, th d:

C6H5NH2 C6H 5N 2
CH3 C6H5 NH N CH3
CH2 NH CH3 NH3
+

CH3 NH2
+

NH

NaHSO3

C6H5NHNH2

+ CH3COCH3

C6H5

NH

C CH3

CH3

H3O

CH3
+

CH3

H CH2 NH
CH

C NH2

CH3

NH NH2
CH2 N

CH3

C NH

CH3

c. Aminothiazol Phng php tng hp aminothiazol n gin nht l phn ng a t:

H C O CH2 Cl + H2 N C S NH2 HC HC N C NH2

-cloaxetalehyt

thioure

S aminothiazol

Ngoi ra cn c th to ra cc dn xut ca aminothiazol bng cch a cc nhm th vo vng thiazol. Nhng hp cht ny thng c s dng lm iazo thnh phn tng hp cc loi thuc nhum azo c mu m. d. Aminobenzothiazol Chng c iu ch t hp cht amin nh sau:
NH2 CH3 O
Br2 / KSCN

N CH3 O S C NH2

hoc t anilin:
H NH2 N + KCNS S C NH2
+ Br2

N C NH2 S 2-aminobenzothiazol

SCN + NH2
+ Na2S (CH3)2SO4

(SCN)2 NH2

N SCN NCS S C NH2

N (CH3)2S S C NH2

[O]

N CH3O2S S C NH2

Cc loi thuc nhum i t cc hp cht trn s rt a dng, chng c s dng cho nhiu loi vt liu dt: thuc nhum cho si polyamit, thuc nhum azo cation cho polyacrylonitrin, thuc nhum phn tn cho polyeste. 71

e. Dn xut thiophen Trong thi gian gn y ngi ta bt u s dng cc dn xut thiophen tng hp mt s thuc nhum hu c. Nhng loi thuc ny c mu su m, bn mu cao v mt s tnh cht c bit khc khi nhum vi pha. Nm 1977 hng ICI (anh) sn xut loi thuc nhum phn tn c cha gc thiophen theo s sau:
S ClCH2CHO + NaHS HSCH2CHO HO S OH

CO2H
+ NCCH2CO2H (axyl)2O

NH-axyl

NH-axyl

0oC nitro ho

0oC nitro ho

CO2H O2N S NH-axyl

0
o C,

NO2
o oh

O2N

n it

NH-axyl NO2

O2 N

NH-axyl

O2N

NH2

2-aminoinitrothiophen

g. Cc dn xut ca piriin Piriin rt t c s dng tng hp thuc nhum, nhng cc dn.xut ca n nh: 2,6-ihyroxyl priin, 2,6-iamino piriin gn y li c s dng nhiu tng hp cc loi thuc nhum azo mu vng v mu . Cc dn xut pinin c iu ch theo mt s s sau: - dn xut 2,6-ihyroxyl piriin: CH3 C CH2 C O C2H5 O O
CH3 CN O N R OH
HO N

+ H2C C N O C O C2H5

+ R NH2

CH3 CN OH

nu R = H
CH3 X + X CH2 C NH R O R CN O N R OH

hoc
CH3 C CH2 C O C2H5 O O

hoc
R C O CH2 C O O C2H5 + CN CH2 CN

N H

OH

72

- dn xut 2,6-iamino piriin:

R X
+

R X POCl3 O N R'
R X Cl N Cl
R3NHR4

R X O PCl2 O
R X R3 N R4 N N R3 R4

N R'

OH

N R'

Cl

h. Tng hp gc triazin Gc triazin c s dng rt rng ri trong lnh vc tng hp hng lot thuc nhum hot tnh; gc triazin khng ng vai tr cht mang mu m n c gi tr to kh nng lin kt bn vng vi x si; n c coi l nhm hot tnh ca thuc nhum. Phng php n gin nht iu ch gc ny l iu ch 2,4,6-triclotriazin:
Cl C N

6 HCN

3 Cl2

6 ClCN

2 Cl

N C

N C Cl

2,4,6-triclotriazin

3. QU TRNH TNG HP THUC NHUM Thuc nhum d l ly t thin nhin chng cng u c nhng tnh cht c bn l kh nng hp th chn lc nh sng v bin i nng lng nh sng hp th trong vng quang ph nht nh ca nh sng: vng nh sng thy c, vng gn t ngoi v vng gn hng ngoi. c tnh bin i nng lng ca thuc nhum theo ngha rng s nh hng n c th s dng chng. Da vo c tnh ny c th chia thuc nhum thnh ba loi: - Thuc nhum (theo ngha hp) thc s c kh nng nhum mu cho cc loi vt liu khc. l nhng hp cht c kh nng bin i nng lng nh sng hp th thnh nhit nng v chuyn nhng vo mi trng xung quanh dng nhit. Kt qu l trong quang ph ca nh sng phn x xut hin cc vt, cc vt ny tc ng ln vng mc mt ngi gy cm gic mu; - Cc cht pht hunh quang gm cc cht tng trng quang hc v cc cht pht quang. l cc hp cht c kh nng ch bin i mt phn nng lng nh sng hp th thnh nhit nng, phn nng lng cn li s c pht ra dng tia sng c bc sng ln hn. - Cc cht tng (hoc gim) nhy nh sng. l cc hp cht c kh nng bin i nng lng hp th thnh nng lng ho hc to qu trnh chuyn ho cc cht lm chng hin hnh. Trong mi trng hp, vic nghin cu thuc nhum theo ngha rng chnh l i tng ca l thuyt mu ca cc hp cht hu c c trnh by c th trong chng I. 73

Trong phm vi ca cun sch ny ch c th a ra cc nguyn tc c bn tng hp nhng thuc nhum dng cho cc loi vt liu dt. Nhng thuc nhum ny cn p ng cc yu cu v mu sc, kh nng nhum mu, bn mu di tc dng ca cc tc nhn ho hc, nh sng, nhit v.v. Qu trnh tng hp thuc nhum l mt giai on tip theo ca cng ngh tng hp phm vt trung gian nhm a cc nhm mang mu vo mt h thng mu - h thng ni i lin hp trong cc nhn thm. Tuy nhin, giai on tng hp thuc nhum c nhng c im ring vi nhng nguyn tc khoa hc c lp. Bn cnh s ph thuc ca mu sc vo cu to ho hc ca hp cht hu c th mt s tnh cht ca thuc nhum cn ph thuc vo cng ngh sn xut chng. Da vo cu to ho hc ca cc nhm mang mu c trong phn t thuc nhum m c th ra nhng phng php chung nht tng hp cc loi thuc nhum cng phn lp ho hc. 3.1. Tng hp thuc nhum azo Thuc nhum azo l lp thuc nhum c sn xut nhiu nht, trn 50% tng sn lng thuc nhum. Loi thuc nhum ny bao gm hu ht cc loi thuc nhum theo phn lp k thut nh: thuc nhum hot tnh, thuc nhum trc tip, cht tng trng quang hc, thuc nhum baz, thuc nhum axit, thuc nhum phn tn, thuc nhum cm mu, thuc nhum azo khng tan v pigment. H thng mang mu ca thuc nhum azo l mt h thng ni i lin hp m trong c cha mt hoc nhiu nhm azo N=N. S tham gia ca nhm azo vo trong h thng lin hp ca thuc nhum dn n kh nng linh ng ca mch in t do cc nguyn t nit c nhng i in t cha chia tham gia mnh vo s chuyn dch in t ca ton mch. to nhm azo, qu trnh tng hp thuc nhum phi tin hnh qua hai giai on lin tc vi hai loi phn ng ho hc: phn ng iazo ho cc min thm bc nht v phn ng kt hp azo (phn ng azo ho).
ArNH2 ArN2
+

+ ArH

ArN=NAr

+ H+

3.1.1. Phn ng iazo ho Thc cht qu trnh ny bao gm chui phn ng: nitrozo ho amin bc nht, phn ng tch proton v phn ng kh nc.
ArNH2
nhanh

O Z

chm

ArNH2N

O Z

nhanh Z

ArNH2N=O [ArNN}X
+

nhanh H+

ArNHN=O

ArN=NOH

HX H2O

Trong cc phn ng trn th giai on phn ng nitrozo ho amin bc nht l giai on quyt nh. C ch ca phn ng l c ch th electrophin; tc nhn ca phn ng c axit nitr to ra khi tc dng vi cc cht khc trong mi trng phn ng. Trong mi trng axit sunfuric c: HNO2 + 2H2SO4 Trong mi trng axit clohiric: HNO2 + HCl 74 NOCl + H2O NO + H3O + 2HSO4
+ +

Trong mi trng axit bromhiric: HNO2 + HBr Trong mi trng nc: 2HNO2 + H2O 2HNO2
+

NOBr + H2O ONNO2 + 2H2O N2 O3 + H2 O

Theo hot electrophin ca cc tc nhn iazo ho, c th xp chng theo th t sau: NO > NOBr > NOCl > ONNO2 Nh vy khi tin hnh iazo ho amin trong mi trng nc th N2O3 lun lun l mt trong nhng tc nhn nitrozo ho; s tham gia ca cc tc nhn khc ty thuc vo mi trng phn ng. Mc tham gia phn ng ca chng cn ty thuc vo bn cht ca amin v cc iu kin tin hnh phn ng nh pHmi trng, nhit v nng cc cht. S la chn tc nhn phn ng ph thuc vo tnh baz ca amin: nhng amin c tnh baz yu phi tin hnh iazo ho trong mi trng pH < 1, nhng amin c tnh baz trung bnh v mnh s tin hnh iazo ho trong mi trng pH = 1 - 3. Khi tin hnh phn ng iazo ho cc amin thm bc nht ngi ta thng s dng mui natri nitrit vi axit v c trong mi trng nc: 2NANO2 + H2SO4 + H2O ONNO2 + Na2SO4 + 2H2O Tt nht l s dng axit sunfuric hoc hn hp n vi axit axetic bng hoc vi axit photphoric. Khng nn s dng axit nitric v d gy n nguy him v xy ra cc phn ng ph nh nitro ho, oxy ho. Axit clohydric cng t c s dng v n d b axit nitr oxy ho to ra clo; ch nn s dng axit clohiric dng dung dch long. V phn ng iazo ho tin hnh trong mi trng nc nn cn quan tm n kh nng ho tan ca cc amin v cc mui ca chng trong dung dch axit. Nhng amin ho tan tt th phn ng tin hnh nhanh. Nhng amin kh ho tan s phi un nng sau lm lnh chuyn chng v dng ht nh l lng, ri tin hnh iazo ho theo phng php thun tc l nh t t dung dch NaNO2 vo dung dch ho tan trn. Ring mt s amin khng c kh nng ho tan trong dung dch axit nhng li c kh nng to cc mui tan nh mui natri, mui amoni th phi tin hnh iazo ho chng theo phng php nghch: ho amin vo dung dch natri cacbonat hay dung dch amoniac, cho natri nitrit vo v trn u ri t t vo dung dch axit. chn iu kin phn ng sao cho ph hp cn phi xem xt n bn ca hp cht iazo c to thnh. Phn ln cc hp cht ny u khng bn, chng d b phn hy, nht l khi tng nhit . Phn ng iazo ho l mt phn ng ta nhit (hiu ng nhit 20 - 30 kcal/mol). V th trc khi phn ng phi lm lnh hn hp 0oC - 10oC v trong qu trnh phn ng phi s dng tc nhn lm lnh trc tip hoc gin tip. Ch c mt s amin c cha cc nhm th loi II th hp cht iazo s n nh hn, nn c th tin hnh iazo ho nhit cao hn. Th d, iazo ho aminantraquinon 30 - 40oC, axit sunfanilic 15 - 20oC. m bo cho bn ca hp cht iazo, cn phi gi cho khi phn ng lun lun c mt lng d axit (0,4 - 1 mol cho mt mol amin). Lng axit v c d s trnh c cc phn ng ph xy ra trong khi phn ng. Th d, c mt s hp cht iazo c kh nng kt hp vi amin t do cha kp iazo ho trong khi phn ng to nn hp cht ph iazoamino (ArN=NNHAr). Lng natri nitrit c s dng theo tnh ton l thuyt v c pha thnh dung dch c nng 25 - 30%. Kt thc phn ng iazo ho, cn phi kh ht lng HNO2 cn d trnh cc phn ng ph xy ra trong phn ng kt 75

hp azo sau ny. Cc cht kh HNO2 thng dng l axit sunfamic hoc ur v chng c tc dng theo phn ng sau: HNO2 + NH2SO3H HNO2 + NH2CONH2 N2 + H2SO4 + H2O N2 + CO2 + H2O

3.1.2. Cu to v s bin i ca hp cht iazo Phn ng iazo ho gm mt s giai on to ra cc dng cu to ca hp cht iazo ph thuc vo mi trng v bn cht cc nhm th c trong hp cht. S bin i ca hp cht iazo c th biu din theo s sau: ArNHN=O
nitrozamin

ArN=NOH
H+

OH H+ Z H+

ArN2O
iazotat

H+ OH

iazohirat

ArN=NOH
iazohirat

OH

ArN2
iazoni

ArN=NZ
hp cht azo

Trong anion iazotat ArN2O l anion ca axit trung bnh ArN=NOH, n c to nn khi pH mi trng tng tc l trong mi trng kim mnh. Anion iazotat c th tn ti hai dng ng phn lp th nh sau: ArN=N
OH , to

O Ar N=N

sin-iazotat

anti-iazotat

Dng siniazotat khng bn, di tc dng ca axit chng d chuyn thnh cation iazoni ArN+N. Dng antiiazotat ngc li rt bn, chng ch c th thay i v tr v dng sin di tc dng ca cc tia sng t ngoi v th c th s dng dng antiiazotat chuyn hp cht iazo v dng cc hp cht n nh. iazohirat trong phn ng c to thnh s chuyn ho thnh cation iazoni khi mi trng l axit, tc l pH gim: ArN=NOH
H+ OH

ArNN

Cation iazoni l sn phm chnh ca phn ng iazo ho, n thng tn ti dng mui. Cc mui iazoni phn ln d gy n nn khng tch ra khi phn ng m c s dng ngay cho qu trnh phn ng kt hp azo tip theo to nn thuc nhum. 3.1.3. Phn ng kt hp azo Phn ng kt hp azo l phn ng tc dng gia hp cht iazoni vi cc cht c kh nng b thay th mt nguyn t hyro hoc mt nhm th nguyn t cacbon trong nhn thm v to nn hp cht azo: ArN2X + RY
+ +

ArN=NR + Y+ + X

ArN2X l mui iazoni dng hot ng trong cation iazoni ArN2 l tc nhn electrophin ca phn ng th electrophin. RY l cht th ng gi l azo thnh phn. Cc azo thnh phn l nhng hp cht cha nguyn t cacbon c mt in t cao do trong phn t ca chng c cha cc nhm th cho in t nh nhm amin hoc nhm hyroxyl. Trong phn ng kt hp azo nguyn t hyro cc v tr cacbon giu in t s b thay th bng cation iazoni. S thay th xy ra khc nhau trong cc trng hp c th sau y. 76

a. i vi cc hp cht amin thm Nhm amin ch c kh nng lm giu mt in t cho nhn thm khi chng tn ti dng t do (cha b ion ho). m bo s tn ti ny th phn ng kt hp azo ho phi thc hin trong mi trng trung tnh hoc kim yu.
+

Ar N

N +

.. N +

R1 R2

Ar N N H

N R2

R1

Ar

N N

N R2

R1 + H+

R c th l gc akyl hoc hyro. Tuy nhin trong phn ng th electrophin ny th tc nhn electrophin l cation iazoni li hot ng mnh trong mi trng axit. Trong mi trng kim yu, mt s amin phn ng vi hp cht iazo theo mt c ch khc, khng to ra thuc nhum azo m to ra sn phm iazoamino ngoi mc ch mong mun: Ar N NX + H2NR
+

ArN=NNHR + HX.

Vy vic la chn sao cho ph hp phn ng t hiu qu cao l ht sc cn thit. Phn ln cc amin thm tham gia phn ng kt hp azo trong iu kin mi trng axit yu v mi trng trung tnh (pH = 3,5 - 7). Trong iu kin ny cation iazoni vn tn ti dng hot ng m cc amin thm th cha b ion ho, nn tham gia mnh vo phn ng kt hp azo ch khng hoc kh to thnh hp cht iazoamino. to ra mi trng axit yu cho phn ng trn, cn cho vo khi phn ng dung dch azo thnh phn mt lng natri axetat v soa. Phn ng c tin hnh theo phng php nghch tc l dung dch azo thnh phn c cha natri axetat v soa s c vo dung dch iazo thnh phn (mi trng axit). Nh vy c qu trnh phn ng kt hp azo s lun xy ra trong mi trng axit. Nhit phn ng trong khong 15 - 25oC, v vy cn lm lnh cc dung dch trc khi phn ng bng cch gin tip hoc cho nc trc tip. Phn ng kt hp azo vo cc v tr nh du sao ca cc amin thm nh sau:
NH2 H3C
*

NH2 H3CO
*

NH2

NH2
*

CH3

CH3

m-toluiin
NH2 H3C
* **

p-xiliin
NH2
*

kreziin
NH2
* * *

CH3

SO3H
NH2
*

NH2

SO3H

NH2

m-toluileniamin

m-phenileniamin

SO3H

b. i vi cc azo thnh phn c cha nhm hyroxyl Cc hp cht c cha nhm hyroxyl c th tham gia vo phn ng kt hp azo dng t do cng nh dng b ion ho. Tuy nhin dng ion ho c hot cao gp nhiu ln so vi dng t do v anion O c kh nng cho in t vo nhn thm gp nhiu ln nhm hyroxyl. Phn ng kt hp azo l mt phn ng th electrophin nn n s xy ra cc v tr c mt in t cao nht trong nhn thm: 77

Ar

N N +

Ar O

N N O H

Ar N N

+ H+

Hoc vi cc hp cht d vng:

H3C Ar N N
+

N N Ar'

H3C Ar N N O

N N Ar'

H+

Tuy nhin cn lu l hp cht iazo s b gim hot phn ng trong mi trng kim. Vic la chn iu kin phn ng phi m bo sao cho cc cht tham gia phn ng u phi tn ti dng hot ng v trnh cc phn ng ph xy ra. V vy phn ng kt hp azo trong trng hp ny cn phi tin hnh trong mi trng hoc trung tnh hoc kim yu pH = 7 - 9. Ch c mt s hp cht c hot cc mnh nh -naphtol c th thc hin phn ng mi trng axit yu pH = 5 - 6. Phn ng kt hp azo trong mi trng kim s c tin hnh theo phng php thun tc l dung dch iazo thnh phn vo dung dch azo thnh phn c cha soa m bo mi trng kim n nh trong qu trnh phn ng. Nhit ca phn ng phi thp, lun gi trong khong 0 10oC, v nhit cao hp cht iazo trong mi trng kim rt km bn, d b bin i. Trong mt s trng hp, phn ng xy ra qu chm th cn phi s dng xc tc l cc baz hu c nh piriin. Hot ca cc cht tham gia phn ng kt hp azo cng nh hng nhiu n tc ca phn ng. Nu trong nhn thm ca hp cht iazo thnh phn c cha cc nhm th nhn in t th s lm tng kh nng i in t ca cation iazoni v tc phn ng kt hp azo cng s tng ln. V tr phn ng kt hp azo ca mt s hp cht cha nhm hyroxyl c nh du sao nh sau:
OH
** * * *

OH COOH
**

OH
** *

OH
** *

OH
OH

OH OH
*

* *

SO3H

SO3H

c. i vi cc azo thnh phn c cha ng thi c nhm amin v nhm hyroxyl Trong nhng hp cht azo thnh phn c cha ng thi c hai nhm cho in t th s gy nn s cnh tranh v tr kt hp. Xt v kh nng cho in t ca chng s thy s khc nhau th hin theo th t sau: OH < NH2 < O. Nh vy trong mi trng axit yu v trung tnh th nhm amin s c xu th quyt nh v tr kt hp. Cn trong mi trng kim th nhm hyroxyl s quyt nh v tr kt hp do n b ion ho. 78

Nhng hp cht azo thnh phn kiu ny s c kh nng to ra hai nhm azo tc l chng c th tham gia phn ng kt hp hai ln. Tuy nhin th t phn ng s ph thuc vo s iu chnh mi trng. Thng thng nhng hp cht c cha ng thi c hai nhm amin v hyroxyl l nhng dn xut ca dy naphtalen:
NH2 OH
HO3S NH2
H2N SO3H

HO3S
axit H

SO3H

OH axit I

OH axit

Nhng hp cht ny rt c ngha sn xut ra hng lot thuc nhum azo c gi tr. Phn ng kt hp azo ln mt thng c tin hnh trong mi trng axit tc l phn ng th electrophin s xy ra nhn c cha nhm amin. Phn ng kt hp azo ln hai tin hnh trong mi trng kim tc l phn ng th vo nhn c cha nhm hyroxyl. Nu tin hnh phn ng theo th t ngc li th s khng t c hiu qu mong mun. Nguyn nhn ca hin tng l: phn ng th electrophin trong mi trng axit thng xy ra (tc l nh hng nhm amin km hn nh hng nhm enolat). Hn na, sau khi hp cht azo thnh phn l mt thuc nhum monoazo (sau bc 1), n s c kch thc phn t ln hn v linh ng ca phn t s km i lm nh hng n ng hc phn ng. 3.1.4. Tnh cht ho hc ca thuc nhum azo a. Tc dng ca cc cht kh. Nhng cht kh yu nh Na2S, FeCl2 khng th kh c nhm azo trong thuc nhum:
HO N N NO2
+ Na2S

HO

NH2

Nhng cc cht kh mnh nh Na2Sx, Sn, Zn, Fe (trong axit HCl); SnCl2, TiCl3 + HCl, VSO4 + H2SO4, Na2S2O4 + NaOH u kh nhm azo trong phn t thuc nhum to thnh cc amin: ArN=NArN=NAr
[H]

ArNH2 + NH2ArNH2 + ArNH2

Phn ng trn c s dng xc nh cu to ca thuc nhum azo, phn tch nh lng thuc nhum v c bit c s dng trong phng php in ph gn. b. Tc dng ca nhit. un si dung dch thuc nhum azo trong thi gian di s ph hy phn t thuc nhum, c bit nu trong dung dch c mt axit hoc kim. c. Tc dng ca axit. Axit sunfuric m c s sunfo ho mt s thuc nhum azo nhit thp, nhng nu tng nhit cao hn th axit s ph hy thuc nhum. Axit nitric bc khi s phn hy thuc nhum azo ngay nhit thp, to nn cation iazoni ban u v sn phm azo thnh phn b nitro ho:
NO2 HO3S N N N CH3 CH3
+ HNO3
+

O3S

N2 + O3N

N CH3 CH3

Tnh cht ny c s dng xc nh cu to ca thuc nhum azo. 79

d. Tc dng ca halogen. Brom v clo u c tc dng phn hy thuc nhum azo:

Cl N N OH
+ Cl2

N Cl

Cl Cl

OH

e. Nhng hp cht azo ca cc nhn n gin cha c nhm th nh azobenzen l nhng baz yu. Khi a vo phn t trn cc nhm amin v nhm amino-alkyl th s lm tng tnh baz ca thuc nhum azo. Nhng thuc nhum azo loi ny nu ho tan trong nc th c s dng nh cc thuc nhum baz. g. Trong phn t thuc nhum azo c nhm hyroxyl th chng vn cha c tnh axit do nh hng ca nhm azo. Ch khi a vo phn t cc nhm th lm tng kh nng ion ho nhm hyroxyl (th d, nhm nitro, sunfonic) th thuc nhum azo mi c tnh axit. h. Nhng thuc nhum azo khng ho tan trong nc c s dng lm pigment v thuc nhum phn tn. i. Khi a vo phn t thuc nhum azo nhng nhm sunfonic hoc nhm cacboxylic s lm tng kh nng ho tan ca thuc nhum. V nu s nhm trn p o tnh baz ca nhm azo v cc nhm amin c trong phn t thuc nhum th thuc nhum s c tnh axit. k. Khi trong phn t thuc nhum azo c cha cc nhm c kh nng to phc vi kim loi th chng c s dng lm thuc nhum cm mu hoc thuc nhum cha kim loi. l. Khi trong phn t thuc nhum azo c cha cc nhm amin t do c kh nng tip tc c iazo ho th sau khi nhum vi c th tin hnh iazo ho v cho kt hp vi mt azo thnh phn khc na to nn bn mu cao hn. m. Tnh cht s dng. Thuc nhum azo c kh nng nhum mu cao (gp gn hai ln kh nng nhum mu ca thuc nhum antraquinon). Thuc nhum c sn xut n gin t cc nguyn liu r tin d kim nn gi thnh thp. Thuc nhum azo c gam mu v bn mu cao. Tuy nhin thuc nhum c nh mu xn v bn mu nh sng khng cao (c bit l cc mu xanh). 3.1.5. An ton trong sn xut thuc nhum azo Trong sn xut thuc nhum azo cng nh cc azotol v cc azoamin u c s dng v thu c cc ho cht c, d chy v d n. Cc cht c l nhng amin thm nh anilin, toluiin, benziin, ianiziin, ioxibenziin, aminoazobenzen v.v., trong c mt s cht gy ung th. Khi lm vic vi cc cht cn trnh rt vo c th v qun o, khng cho nhim vo ni lm vic. Vn chuyn cc cht phi bng cc ng ng kn, c gii ho cc thao tc sn xut. C h thng ht cht c mnh mi thit b, cn thng gi tt ni lm vic v lun lun gi gn ni lm vic sch s, nng cc cht c phi l nh nht di gii hn cho php. Cc cht d gy n l nhng hp cht iazo trng thi kh khi b un nng, va chm mnh, b rung lc mnh, b tia la in v v. Cn ht sc trnh khng cho dung 80

dch hoc dng nho ca hp cht iazo ri vo bt c ch no s b sy kh nh thnh, np thit b, nn, tng nh... Cc hp cht iazo n nh (iazol, nitrozamin, iazoamino...) tuy t gy n hn nhng nhit cao chng vn c th b n. Khi lm vic hoc bo qun chng cn trnh lm nng cc thit b. Nhng thuc nhum azo khng c cha nhm sunfonic rt d chy, c bit hn hp bi thuc nhum vi khng kh s gy n. c bit nguy him i vi cc thuc nhum azo khng ho tan trong nc c cha nhm nitro. Khi lm vic vi chng, c bit l khi sy cn trnh qu nhit, trnh pht tia la v trnh to bi. Trong qu trnh sn xut thuc nhum azo trc tip, i khi phi s dng photgen (COCl2) l mt ho cht rt c!! Photgen nng hn khng kh nn c th tch t lu di trong ni lm vic, cn phi ui ht photgen cng vi cc kh thi ra khi ni lm vic. Tc dng c hi, tnh cht nguy him cng nh nng cho php ca chng ni lm vic c th xem xt c th trong cc ti liu khc. 3.2. Tng hp thuc nhum antraquinon Thuc nhum antraquinon chim mt v tr th hai sau thuc nhum azo. y l loi thuc nhum c gc mang mu phc tp nn to c bn mu cao, c bit l bn nh sng. Cng ngh sn xut loi thuc nhum ny kh khn phc tp hn cng ngh sn xut thuc nhum azo nn gi thnh cng cao hn. Bn cnh kh nng nhum mu ca loi thuc nhum ny li km thuc nhum azo. Hai loi thuc nhum quan trng ny lun lun tc dng b sung cho nhau v gi tr s dng. Nu nh cc thuc nhum azo mu vng, da cam v chim u th v chng c bn mu cao m gi thnh li thp, th nhng thuc nhum antraquinon mu xanh s vt hn thuc nhum azo v bn mu cao hn. Nhng thuc nhum antraquinon c gc mang mu l cc nhn antraquinon. Nhn ny c cu to t hai nhn benzen v ni vi nhau qua hai nhm cacbonyl, nn mch lin hp ca nhn b phn cch. Khi a vo nhn antraquinon nhng nhm th s c tc dng lm cho mch lin hp ni i ko di v h thng in t linh ng hn) to cho hp cht c kh nng hp th nhng tia sng c bc sng ln hn, nn mu sc s su hn. Th d, antraquinon c mu vng l,4-iaminoantranquinon c mu tm. Nhng nhm th cho in t v tr s ko di mch lin hp hn l v tr . Th d:
O X

O X

X l OH X l NH2

= 410 nm hp cht c mu da cam = 375 nm hp cht c mu vng = 480 nm hp cht c mu = 450 nm hp cht c mu da cam

81

Khi a thm nhm th cho in t vo cng nhn c nhm th th s lm thay i mu sc ty thuc vo v tr th v bn cht ca nhm th. Nhng nu a vo nhn bn cnh th s thay i mu xy ra khng ng k do cu to c bit ca nhn antraquinon. Th d:
O NH2 O NH2 NH2 O NH2

O mu da cam

NH2 O mu da cam

O mu d

Da vo bn cht cc nhm th trong cc dn xut ca antraquinon m c th chia thuc nhum antranquinon thnh cc phn nhm sau: - thuc nhum hyroxyantraquinon; - thuc nhum aminoantraquinon; - thuc nhum axylaminoantraquinon; - thuc nhum antrimit 3.2.1. Tng hp thuc nhum hyroxyantraquinon Tiu biu cho nhm ny l hai loi thuc nhum alizarin v thuc nhum axit cm mu.
O Cl
+ NaOH 235oC

O ONa
+ 2NaOH 235oC

ONa ONa ONa

O O
[O] + H2O KNO3, 235oC

O ONa ONa
H2SO4

ONa O OH OH

Phng php tng hp thuc nhum alizarin i t -cloantraquinon Hp cht alizarin l bt mu vng nhng khi to phc vi kim loi nhm - canxi th tr thnh mu ti, cn vi kim loi crom cho mu gch, vi st cho mu tm. Trong ch c phc vi kim loi nhm - canxi l c s dng trong hi ho v n lot cht lng cao. Thuc nhum axit cm mu c iu ch t alizarin bng cch sunfo ho:
O OH OH
oleum 170oC

OH OH SO3H

Thuc nhum ny nhum mu thm cho len ri cm mu bng mui crm thnh mu booc; bn mu vi nh sng, git v ma st rt cao. 82

3.2.2. Tng hp thuc nhum aminoantraquinon Nhm thuc nhum ny c mu su hn nhm thuc nhum trn do nhm amin c kh nng cho in t mnh hn nhm hyroxyl. Tc dng cc v tr th trong nhn vn tun theo qui lut chung: nhm amin v tr s lm cho hp cht su mu hn l v tr ; hai nhm amin mt nhn benzen s c tc dng mnh hn hai nhn benzen khc nhau. Thuc nhum aminoantraquinon c tng hp bng cch kh nhm nitro hoc thay th nhm hyroxyl, halogen, nhm sunfonic c sn trong nhn bng nhm amin. Phng php thay th c ngha thc t hn do cc nguyn nhn sau: - S thay th trong nhn antraquinon tun theo mt nguyn tc chn lc: cc nhm th v tr linh ng hn v tr nn chng d b thay th hn. iu ny cho php iu khin c phn ng theo mc ch; - Trong nhn antraquinon cc nhm th khc nhau cng cc v tr ( hoc ) nhng s b thay th mc khc nhau do linh ng ca chng khc nhau theo dy sau: Br > Cl > NO2 > OH > NH2. iu ny cho php ch thc hin phn ng thay nhm th ny v gi nguyn c nhm th khc:
O NH2
+ anilin + NaOH CuSO4 , 140oC

OH

Br

NH

- Cc nhm th ging nhau cc v tr ging nhau s tham gia phn ng lin tip ch khng ng thi nn cho php thu c nhng sn phm khng i xng theo nhng iu kin phn ng c th. Nhm thuc nhum ny bao gm nhiu loi thuc nhum theo phn lp k thut: thuc nhum phn tn, thuc nhum cation, thuc nhum axit, thuc nhum hot tnh, thuc nhum trc tip. Phng php iu ch c th nhng thuc nhum c th tham kho trong ti liu. 3.2.3. Tng hp thuc nhum axylaminoantraquinon s dng thuc nhum aminoantraquinon lm thuc nhum hon nguyn a vng thng phi nng cao i lc ca thuc nhum vi xenlulo bng cch a thm vo phn t thuc nhum nhm th axylamino NHCOR. Phng php n gin nht l tin hnh phn ng axyl ho aminoantraquinon. Nhng thuc nhum c ngha thc t phi c cha trong phn t t nht l hai nhm axylamino v chng khng b phn hy trong mi trng kim mnh nhit cao (80 - 90oC). Phn ng axyl ho aminoantraquinon thng c thc hin bng cc tc nhn cloanhyrit trong cc dung mi hu c (o-iclobenzen, nitrobenzen, clobenzen). trung ho lng kh axit clohiric thot ra phi dng soa hoc cc cht khc, cng c th ui trc tip kh HCl v khng c nc n khng n mn thit b. tng i lc ca thuc nhum hon nguyn vi xenlulo thng lm tng kch thc phn t thuc nhum bng cch s dng tc nhn axyl ho l icloanhyrit 83

NH2 +

COCl O COCl

OC HN

CO NH O

O O O
thuc nhum hon nguyn mu vng 23X

Mt iu ng ch l c th axyl ho aminoantraquinon bng xianogen clorua v to ra loi thuc nhum qu mu c bn mu cao. c bit mt hng pht trin mi trong ho hc thuc nhum l tng hp nhng loi thuc nhum hon nguyn c cha nhm sunfonic. Mc ch nhm tng kh nng ho tan ca hp cht lyc v gim i lc ca n vi xenlulo (v trong mi trng kim n tch in m) lm chm qu trnh hp th thuc nhum ng thi lm cho thuc nhum thm su vo li x si, kt qu mu nhum u v bn mu cao hn. 3.2.4. Tng hp thuc nhum antrimit Trong phn t ca loi thuc nhum ny c cha hai hoc nhiu nhn antraquinon, chng lin kt vi nhau qua nhm imin NH. Nhm imin lm phn cch h lin hp gia cc nhn antraquinon v mi nhn antraquinon l mt nhm th b aryl ho i vi nhm amin nhn kia, v th mu ca hp cht s su hn so vi aminoantraquinon. Antrimit khng ho tan trong nc v c s dng nh mt thuc nhum hon nguyn khng tan. Thuc nhum hon nguyn nhm ny c bn nh sng v bn vi cc tc nhn khc rt cao. Phng php chung iu ch thuc nhum antrimit l cho aminoantraquinon tc dng vi cloantraquinon trong dung mi c nhit si cao (nitrobenzen, naphtalen) vi s c mt cc cht kim trung ho axit clohiric thot ra (soa, natri axetat, magie oxyt) v bt ng hoc mui ng lm xc tc, nhit cao (> 200oC). Ngoi vic s dng antrimit lm thuc nhum, chng cn c s dng nh hp cht trung gian tng hp cc thuc nhum hon nguyn a nng phc tp hn - cc dn xut cacbazol. S to ra vng khp kn xy ra trong iu kin tch nguyn t hyro cc v tr octo so vi nhm imin. 3.2.5. An ton trong sn xut thuc nhum antraquinon Trong sn.xut thuc nhum antraquinon, c s dng hng lot cc cht c v d chy nn khng c cho chng ri vo c th hay qun o ngi lao ng. Qu trnh phn ng xy ra nhit cao c thot ra cc kh c nn cn c h thng thng gi tt. Mt s bt thuc nhum d chy v d n, nn cn c bo qun tt nhng ni thong mt. 3.3. Tng hp thuc nhum polymetyn y l lp thuc nhum c mu ti v thun sc, ch yu l loi thuc nhum baz v thuc nhum cation. Nhng thuc nhum baz c bn mu nh sng thp nn thc t t c s dng. Ring thuc nhum cation nhum x polyacrylonitrin cho bn mu cao nn ngy cng c pht trin. 84

Mt lnh vc quan trng s dng thuc nhum polymetyn l sn xut vt liu phim nh. Nhng thuc nhum cation ch yu l xianin khng i xng phng php tng hp l ngng t hai hp cht d vng. Phn ng ngng t amin thm vi focmalehit
N(CH3)2 + CH2O
H2SO4, H2O, 65oC axit sunfanilic

(CH3)2N CH2

N(CH3)2

+ MnO2 + H2SO4 0 -10oC

(CH3)2N CH OH
N(CH3)2 CH CH3

N(CH3)2

H 3C

NO2

H2SO4 , 98oC
+

(CH3)2N

(CH3)2N C

N(CH3)2 Cl

+ MnO2 + HCl 0 - 10oC

O2N

thuc nhum baz mu bch dng

cho thuc nhum c mu su hn c th thay th nhn benzen bng nhn naphtalen. Thuc nhum meroxiamin l nhng thuc nhum pigment v phn tn:
(C2H5)2N C O H
+ CH2

COOC2H5

H2O

(C2H5)2N

CH

COOC2H5

CN

C N thuc nhum phn tn vng

Thuc nhum ny trn x axetat cho bn mu nh sng cao, cn trn x PA th km bn hn. 3.4. Tng hp thuc nhum arylmetan Nhm thuc nhum iarylmetan c iu ch t cc dn xut ca benzophenon (nh xeton Miclera). Nhm triarylmetan c iu ch bng hai phng php: 1- Phng php benzalehit: phn ng ngng t benzalehit vi cc amin thm bc hai hoc bc ba (c cc cht ht nc nh ZnCl2, H2SO4, axit oxalic khan); 2- Phng php iu ch da trn c s l to ra trong phn t thuc nhum nhng nhm axit (sunfonic, cacbonyl) t nht phi c t hai nhm ny v trong mt nhm phi lm nhim v trung ho nhm amin mang in tch dng cn nhng nhm khc to tnh axit cho thuc nhum. Phng php iu ch n gin nht l sunfo ho cc thuc nhum baz tng ng:
CH3 H2N C CH3 NH2 Cl
oleum
+

H2N HO3S C

NH2 SO3 SO3H NH2 thuc nhum axit fucxin

CH3 NH2

85

Tuy nhin phng php sunfo ho trc tip ny b hn ch i vi mt s loi thuc nhum nn phi tin hnh iu ch chng t cc hp cht amin c cha sn nhm sunfonic ri mi ngng t vi benzalehit. Nhm thuc nhum xanten c iu ch bng phng php ngng t anhirit phtalic vi cc hp cht amin thm.
O (C2H5)2N OH
+

(C2H5)2N
155 - 160oC 4h

OH HO C O C O
(C2H5)2N
HCl

N(C2H5)2

C C O

(C2H5)2N

O C O C O

N(C2H5)2
NaOH 30 - 35oC

O C HO

O C

N(C2H5)2 Cl

COONa

COOH

roamin C

y l thuc nhum baz mu c nh pht quang, nhum c cho len, t tm trong mi trng trung tnh, nhum vi bng c cm mu bng tanin. bn mu khng cao, c th s dng nhum da, giy, x phng v cc loi sn (dung mi l cn). Nu a nhm sunfonic vo phn t thuc nhum roamin s thu c thuc nhum axit cho len mu p. Nu thay cc nhm ankyl bng cc nhm aryl th mu ca thuc nhum s su hn. 3.5. Tng hp thuc nhum inigoit Trong nhm thuc nhum ny c rt nhiu cu to mch vng d th khc nhau v c cc nhm th cc v tr khc nhau to nn h thuc nhum inigoit tng hp vi nhiu mu phong ph. 3.5.1. Phng php tng lp thuc nhum inigo Phng php ny c th i t anilin hoc naphtylamin. S tng hp t anilin nh sau:
COOFe1/2 NH2
ClCH2COOH + Fe(OH)2 95oC

C
KOH

CH2 NH

OK CH2 NH

OK KO C OK
KOH 185 - 200oC

OK NaO C
NaNH2 200oC

OK
200 C
o

NaO

CH2 NH

CH2 NH

C NH

OK CH2
200oC

ONa C CH NH
4'

O
+ O2 + CO2
5' 6' 7'

C 3' NH

C
1'

2'

C
3C 4

NH

7 6 5

inigo xanh

86

Khi tin hnh halogen ho trc tip inigo s thu c sn phm cui cng l 6,6-ibrom inigo c mu tm nh . Khi sunfo ho bng monohyrat hoc axit sunfuric m c c un nng s to ra 5,5-isunfonic inigo mu xanh
O HO3S C C NH C C O NH SO3H

y chnh l thuc nhum axit inigocacmin nhum cho len t bn mu nh sng km, n c s dng nhum mu chun cp 1 l cp thp nht ca tm cp bn nh sng. N ch c dng lm mc xanh v nhum thc phm. Vic halogen ho inigo c mt ngha ng k l to ra nhng thuc nhum c mu p ti, bn mu vi tc dng clo tng, bn mu vi gia cng t v ma st cng tng, c bit cn tng i lc ca thuc nhum vi x si. S lng nguyn t halogen ch nn a vo l t 1 n 3, nu qu 3 nguyn t halogen s lm cho bn mu t ngt h xung. Clo ho v brom ho inigo tin hnh trong axit sunfuric m c hoc axit axetic bng hoc trong nitrobenzen. iu ch thuc nhum 5,5,7,7-tetrabrominigon:
O C C NH C C O NH
+ Br2 + NaNO2 H2SO4 0 - 70oC

O Br Br C C NH C C O NH

Br Br

3.5.2. Phng php tng hp thuc nhum thioinigo V nguyn tc chung th phng php ny ging nh phng php tng hp inigo, ch khc l nguyn liu ban u c cha nguyn t lu hunh. Nguyn t lu hunh thay nit lm cho mu ca thuc nhum thay i t mu xanh sang mu .
O C 2 S CH2
4

O
+ [O]
5 6 7

1'

C3 S

C
1

2'

7' 6' 5' 4'

3' C

O thioinigo

Nu nguyn liu l axit antranilic th s tng hp s nh sau:

COOH NH2
+ NaNO2 + HCl 5 - 10oC

COO + N2

+ Na2S 0 - 5o C

axit antranilic

COONa NaOOC N2 S S N2

15oC N2

COONa S

NaOOC S

87

+ Na2S + NaOH 90 C
o

COONa SNa

+ ClCH2COOH + NaOH Na2S2O4 , 40 C

o

COONa S CH2

COONa

OH
dung dch c KOH, NaOH 60 - 170oC

CO CH COONa S

C C COONa S

O
+ S + NaOH 95oC

C C S C

S C O thioinigo

Ngoi nhng thuc nhum i xng k trn cn c nhng thuc nhum indigoit khng i xng, chng cu to t cc nhn thm khc nhau:
O O C C C NH O
thioinigo xanh lc

S C O

C C S C C

O thioinigo thm

3.6. Tng hp thuc nhum phtaloxianin 3.6.1. Tng hp pigment Loi thuc nhum phtaloxanin quan trng l bt mu thi thanh lam. Phng php n gin nht l i t anhiric phltalic, ur v ng clorua vi t l tng ng 4:14:1. Phn ng c thc hin trong mi trng triclobenzen v c AS2O5 lm xc tc 200oC trong vi gi

N
CO O CO
Cu2Cl2 , NH2CONH2 As2O5 , 200oC triclobenzen

N Cu N N

N N

thi thanh lam

Cc tinh th thuc nhum lc u kt tinh dng c kh nng nhum mu km nn phi chuyn chng v dng bng cch kt tinh li trong axit sunfuric m c. Qu trnh thc hin sau khi va kt thc phn ng nh sau: khi phn ng c pha long v lm lnh n nhit 100oC ri vo axit sunfuric m c. Sau tch thuc nhum, lm lnh n l00oC, ri li tip tc cho lng axit khc cng vi mt lng du thng, sau c khi dung dch trn vo nc 90oC. Cui cng thuc nhum c tch ra dng phn tn cao, gn lc, ra li nhiu ln bng nc si, nc nng, lc v sy kh. 88

Phng php tng hp c th n gin hn nu s dng phtalonitryl. Phtalonitryl c iu ch bng cch thi kh amoniac vo anhiric phtalic nung chy (340oC):
CO O CO
+ 2NH3 bocxit 340 C
o

C C

N N

phtalonitrin

N C N C N
+ CuCl2 410oC

N Cu N N

N N

thi thanh lam

Bt mu xanh khng tan trong nc, trong ru, trong du v cc dung mi hu c khc, c bn nh sng rt cao, bn nhit, bn axit v bn kim, khng b phn hy 500oC, khng b phn hy bi kim nung chy hay axit si. N c s dng nhiu trong n lot, sn ph my mc v nhiu lnh vc cng nghip khc. Bt mu xanh lc c iu ch bng cch clo ho bt mu xanh. Tc nhn clo ho l mui nhm clorua v natri clorua nng chy ( 180 - 190oC, trong 20 h). Sau phn ng khi nng chy vo nc c cha axit clohiric, khuy trn ri lc ra thuc nhum v sy kh. Cng c th tin hnh kt tinh li trong axit sunfuric m c nh loi bt mu thi thanh lam. 3.6.2. Tng hp loi thuc nhum tan trong nc Khi tin hnh sunfo ho phtaloxianin - ng bng oleum 25% 60oC s to nn thuc nhum ho tan trong nc [CuF(SO3Na)2] (F l gc phtaloxianin). Thuc nhum ny c i lc vi xenlulo nn l loi thuc nhum trc tip, c th nhum cho vi bng, la t tm, visc, vi pha len cho mu xanh cm thch. Nu tc dng ln phc phtaloxianin - ng tc nhn axit closunfonic 130 - 135oC s to ra CuF(SO2Cl4). Sau gia cng vi amoniac s thu c sn phm [CuF(SO2NH2)(SO3H)2] l thuc nhum trc tip c mu xanh ti thun sc, v bn mu vi nh sng cao. Thuc nhum hot tnh. Khi a vo phc phlaloxianin - ng cc nhm hot tnh c kh nng lin kt ng ho tr vi vt liu dt s nhn c thuc nhum hot tnh mu xanh lam v mu cm thch.
Cu F(SO2Cl)4 + H2N NHCOCH3 Cu F(SO2Cl)3SO2NH NHCOCH3

Cl
+ H2 O

Cu F(SO2Cl)3SO2NH

NH2

+ N3C3Cl

N Cu F(SO2Cl)3SO2NH NH N N Cl

89

S iu ch thuc nhum hot tnh mu cm thch:

CuF
+ ClSO3H

130 - 135oC

CuF(SO2Cl)4

ClH3N(CH)2Cl 20 - 25oC

CuF(SO3Na)2(SO3NHCH2CH2Cl)2

3.7. Tng hp thuc nhum lu hunh Trong cc loi thuc nhum hu c th thuc nhum lu hunh c gi thnh r nht v cng ngh tng hp chng rt n gin m nguyn liu li d kim, r tin. Phng php chung nht l cc hp cht hu c tc dng vi lu hunh hoc natri polysunfua to ra cc phn t thuc nhum c cha nhiu nguyn t lu hunh. Ty thuc vo tc nhn phn ng m c th tin hnh tng hp theo cc phng php c th sau. 3.7.1. Phng php nu Phng php ny c dng tng hp cc thuc nhum mu en mu xanh lam, mu lc. Phn ng thc hin trong mi trng nc hoc ru vi tc nhn l natri polysunfua. Trong thc t, ngi ta ho lu hunh vo dung dch natri polysunfua hoc dung dch xt to thnh natri polysunfua theo cc phn ng sau: Na2S + nS 6NaOH + nS Na2S(n+l) 2Na2S(n-2)/2 + Na2S2O3

Qu trnh phn ng thc hin 100 - 150oC trong 1 - 48 h. Kt thc phn ng cho thm Na2S ho tan ht thuc nhum. Sau lc b cn ri un nng dung dch v oxy ho tch thuc nhum dng bt khng tan. 3.7.2. Phng php nung Phng php ny c s dng tng hp cc thuc nhum lu hunh mu nu, mu vng, mu da cam. Cc hp cht hu c thm c trn vi lu hunh v t nng trong mt thi gian nht nh. Sau khi phn ng c a vo thit b nung v gia cng 200 - 300oC trong 10 - 15 h. Kt thc phn ng, dng dung dch ca hn hp Na2S + NaOH ho tan thuc nhum trong khi phn ng. Sau lc b cn, ri axit ho dung dch lc kt ta thuc nhum. Thuc nhum lu hunh c sy kh 60 - 70oC. 3.8. Hon tt sn phm thuc nhum Sau mi qu trnh tng hp thuc nhum l cc qu trnh ho l, c l cn thit nhm hon tt sn phm thuc nhum. Cht lng mu sc v cc tnh cht s dng ca thuc nhum khng nhng ph thuc vo cu to ho hc phn t thuc nhum m cn ph thuc vo trng thi ca thuc nhum. Trng thi ny li ph thuc rt nhiu vo cc qu trnh tch lc, sy kh v nghin nh thuc nhum. 3.8.1. Tch lc v lm sch thuc nhum Kt. thc qu trnh phn ng ho hc thuc nhum thng tn ti trong dung dch hoc trng thi huyn ph. Trong mi trng hp, thuc nhum c cha cc tp cht v c v hu c cho nn cn phi loi b chng bng cc cch tch, ra thi b. Sau cn phi kt ta thuc nhum bng cch ho mui hoc axit ho dung dch. Nu kt ta thuc nhum bng phng php ho mui th khi lc phi dng dung dch mui ra sch thuc nhum, cn kt ta thuc nhum bng phng php axit ho th phi dng dung dch axit ra thuc nhum. Cn lu l nng dung dch mui hoc dung dch axit 90

cn phi m bo sao cho t li tp cht v c trong thuc nhum. Ngoi ra cc iu kin tch lc thuc nhum t dung dch phn ng (nhit , pH mi trng, nng dung dch, bn cht v lng cht in ly cng hng lot cc nhn t khc cng c nh hng rt nhiu n kh nng ho tan ca thuc nhum. nng cao mt s tnh cht s dng ca thuc nhum i khi ngi ta cn cho vo qu trnh lc cc cht hot ng b mt nh cht phn tn) cht ngm... 3.8.2. Sy thuc nhum Giai on sy thuc nhum khng nhng nh hng n cc tnh cht ho l ca thuc nhum m n cn c th lm thay i c cu to ho hc ca thuc nhum. chn ch sy sao cho ph hp cn phi xem xt cu to ca tng loi thuc nhum. Nhng thuc nhum nitro, nitrozo, azo, lu ho, triarylmetan... s b thay i ho hc khi sy. Trong khi thuc nhum antraquinon li rt bn nhit, c th sy nhit cao thm ch c mt c kim hoc axit. Mt s thuc nhum li c th d dng bc chy hoc gy n nn phi ht sc thn trng khi chn phng php sy. C th s dng cc phng php sy khc nhau nh: sy trong chn khng, sy trong dng kh tr, sy nhit khng cao qu. Trong qu trnh sy cng c th cho thm cc cht n, cht hot ng b mt, cht n nh... nhm gi cho thuc nhum khng b phn hy khi sy hoc khng b ehyro ho hay keo t cc ht thuc nhum. Ch sy thuc nhum cn nh hng n iu kin chun b dung dch mng nhum trong qu trnh s dng sau ny. Trong mt s trng hp sy kh thuc nhum cn l mt phng php to ra cho chng nhng tnh cht mi, th d, sy thuc nhum lu hunh c cho thm natri bisunfit NaHSO3 s to ra thuc nhum hon nguyn tan. Qu trnh sy kh thuc nhum chim mt t l thi gian v chi ph nng lng kh ln (hn c chi ph cho c qu trnh tng hp thuc nhum). 3.8.3. Nghin mn thuc nhum. nh hay mn ca thuc nhum c nh hng nhiu n s ho tan ca thuc nhum, n tc bt mu mc nhum mu v cc tnh cht khc v.v. mn ca thuc nhum ph thuc vo thit b nghin v cc cht ph gia khc c cho vo trong qu trnh nghin. c bit cn lu l khi nghin phi trnh lm nng cc ht thuc nhum v c th khng m bo cht lng thuc nhum. 3.8.4. Hiu chnh thuc nhum v mu chun c c mt loi thuc nhum n nh vi cc tnh cht mu sc xc nh nh: kh nng nhum mu, nh mu... cn phi iu chnh nng , nh mu ca l thuc nhum v ng cc ch tiu ca mu chun. Vic xc nh nng thuc nhum c tin hnh bng cch nhum so snh vi mu chun ri so snh ch khng phi xc nh hm lng ca cht mu thun khit c trong thuc nhum thnh phm. Nng mu chun c coi l 100%, nhng mu xc nh c th l 150%, 200%, khng th chp nhn thuc nhum c nng nh hn 100%. iu chnh thuc nhum v ng mu, ngi ta thng trn cc l thuc nhum ln vi nhau (c th chng c nng khc nhau, nh mu khc nhau). Sau b sung thm cc cht ph gia (mui, extrin) hoc cc cht khc pha long mu, phi mu v.v. 91

Tuy nhin cn lu s nh hng ca cc cht ph gia n tnh cht ca thuc nhum. Th d, thm mui natri clorua hay natri sunfat vo thuc nhum axit s lm chm qu trnh nhum, trong khi thm cc mui trn vo thuc nhum trc tip th li lm tng nhanh qu trnh nhum. Thm mui natri thiosunfat NaS2O3 vo thuc nhum lu ho s lm tng tnh cht nhum mu v s n nh ca dung dch thuc nhum. Sau khi phi trn cc cht ph gia th vic la chn trng thi thuc nhum cng v cng cn thit, c bit i vi nhng thuc nhum khng ho tan trong nc. Hai trng thi c bn nht ca cc thuc nhum chuyn dng l bt th v bt nho. Bt th thun li cho vn chuyn v bo qun; cn bt nho thun tin cho vic s dng, khng cn sy va tit kim nng lng va khng lm nh hng xu n cc tnh cht ca thuc nhum. Dng thuc nhum bt nho thng gp cc hoi thuc nhum hon nguyn khng tan. thuc nhum phn tn v pigment dng cho in hoa. Trong thnh phn ca nhng thuc nhum dng bt nho thng cha thuc nhum vi hm lng thp, cn li ch yu l cc cht dung mi, cc cht gi m (glyxerin, polyetylenglycol, glyxerogen, hexantriol...). Cc cht chng thi, chng mc (axit salixilic, triclophenol...), cc cht xc tc, cc cht phn tn v cc cht hot ng b mt khc nhm lm tng tnh cht s dng ca thuc nhum. Tt c nhng cht ph gia cng vi thuc nhum phi c trn k ri tin hnh nghin trn my sao cho bt nho phi tr thnh dng ng nht tuyt i, khi cn, c th phi tin hnh lc qua sng nh. Yu cu ca thuc nhum bt nho l phi n nh trong qu trnh bo qun: khng b kh, khng b vn cc, khng b phn lp, khng b ng c nhit thp. Dng thuc nhum bt th hay bt mn thng c nhc im l d bc bi nn cn phi cho thm cht phu gia hn ch hin tng (cc cht ph gia c th s dng l silicon hoc cc loi du khong vi t l l 1 - 2%). Ngoi hai trng thi trn, ngy nay cn c thm loi thuc nhum tn ti dng lng. Loi ny s thun tin cho vic nh lng v pha long khi s dng, d nhum u mu.

92

Chng III

THUC NHUM THEO PHN LP K THUT

l. PHN LOI THUC NHUM THEO PHM VI S DNG Hin nay s lng thuc nhum m cc nc v cc hng sn xut ra ln n con s hng nghn mu khc nhau v tn thng phm khc nhau. D tin cho vic tra cu v s dng ngi ta lp nn t in thuc nhum, ting Anh gi l Color Index, vit tt l CI c dng rng ri trn th gii. Trong Color Index mi thuc nhum c ch dn v phng php ch to, cu to ho hc, c im v mu sc v phm vi ng dng. Nhng thuc nhum c cng cc tnh cht k thut c xp chung thnh tng lp nh: trc tip, axit, hot tnh v.v. Trong mi lp li xp theo th t gam mu ln lt t: vng. da cam, , tm, xanh lam, xanh lc, nu v cui cng l en. d tra cu, u tn gi ca mi thuc nhum u c ch CI, sau l tn lp thuc nhum, cui cng l mu v s th t ca mu. Th d, CI vat blue 4 (CI hon nguyn xanh lam 4). CI acid yellow 1 (CI axit vng 1)... nh m c th i chiu tn cc thuc nhum thng phm ca cc hng ch to bit kh nng s dng thay th khi cn. phn loi thuc nhum, ngoi phng php phn loi ho hc trnh by chng 2, ngi ta cn dng phng php phn lp k thut da vo tnh cht cng ngh s dng chng nhum in hoa cc sn phm dt, da, giy, vt liu cao phn t v cc vt liu khc. Theo cch phn lp ny th nhng thuc nhum tuy c xp cng mt lp theo phn lp ho hc c th nm cc lp khc nhau theo phn lp k thut. Nhng lp thuc nhum theo phn lp k thut gm: - thuc nhum trc tip; - thuc nhum axit; - thuc nhum hot tnh; - thuc nhum baz - cation; - thuc nhum cm mu; - thuc nhum hon nguyn tan v khng tan; - thuc nhum lu hunh; - thuc nhum azo khng tan; - thuc nhum phn tn; - thuc nhum oxi ho (anilin en); - thuc nhum pigment. 2. TN GI CA THUC NHUM Nc ta hin nay cha c cng nghip sn xut thuc nhum, tt c thuc nhum dng cho ngnh dt v mt s ngnh khc u phi nhp ngoi nn cha c qui nh gi tn thuc nhum ring ca nc ta, chng ta phi dng tn gi ca cc nc v hng sn xut thuc nhum th gii. V th vic nm vng tn gi ca thuc nhum v cc k hiu v tnh nng ca chng s dng cho ng l iu rt quan trng. Vn ny cn phc tp thm na do s pht trin nhanh chng ca cng nghip sn xut thuc nhum, bn cnh nhng mu c tn gi lch s li xut hin thm cc 93

thuc nhum mi vi cc tn ring ca mi hng c quyn sn xut, qung co v cnh tranh. Nhiu thuc nhum tuy cng thuc v nhm phn lp k thut nhng li c tn gi khc nhau. Nhn chung tn gi ca thuc nhum gm ba phn: - Phn th nht: vit c ch, ch tn lp thuc nhum theo phn lp k thut nh: trc tip, axit, hot tnh... Nu nh khng dng cc t trn m dng tn ring ca hng sn xut th phi hiu n thuc v lp thuc nhum no. Th d: procion, cibacron (hot tnh), terasil (phn tn); - Phn th hai: vit c ch, thng l cc tnh t ch mu ca thuc nhum, c th l mu n nh: xanh lam (blue), (red), vng (yellow) hoc mt tp hp t ch cc mu kp nh: gold orange (da cam - vng kim) red - violet (tm ), jade - green (xanh lc sm); - Phn th ba: c vit bng ch ci v ch s ch sc v cng ca sc. Ngi ta cng dng mt s ch ci ch tnh cht s dng ring ca mi thuc nhum. Mt s ch ci l u ca cc t c ngha ging nhau trong tn gi bng ting la tinh ca mt s nc c dng chung, tha nhn nh quc t ho, l: B: ch sc xanh lam (t ch blue (Anh), bleu (Php), blau (c); R: ch sc (cng t ch red (Anh), rouge (Php), rot (c); G: ch sc vng (gelb (c)). ch cng ca sc mu ngi ta thng dng hai ch ci lin nhau nh: BB, RR, GG, hoc t ch s trc cc ch ci nh: 2B, 3B, 6B, 2R, 5R... Ch s cng to cho bit sc mu cng mnh. Nhng sc trung gian c k hiu bng hai ch ci lin nhau. Nhng ch ci ch sc hay tnh cht s dng ring do cc hng k hiu rt a dng, cn thn trng s dng trnh nhm ln. Di y l nhng trng hp thng gp: A: ch rng thuc nhum inigosol c sn xut t thuc nhum algol (do hng Durand ca Thu S sn xut) c bn mu km hn inanthrene, th d, indigosol green AB; D: ch rng thuc nhum c kh nng b bc mu, ph mu t ch dischargeable (dng cho thuc nhum trc tip, hot tnh, azo khng tan v inigo). Khi c ch D ng sau tn gi ca thuc nhum hon nguyn th c ngha l sn phm dng bt mn phn tn cao; E: ch thuc nhum c bn mu cao do hng Bayer dng cho nhng thuc nhum ca hng ny ch to t sau nm 1945, ly t ch Echt, th d, indanthrene brilliant green E3G; F: l k hiu ca nhiu hng sn xut thuc nhum Chu u ch thuc nhum hon nguyn c bn mu cao vi nhiu ch tiu nh: bn vi git, nh sng v kh quyn (t ch fast), th d, durindone rose FF; FA: l k hiu ch nhng thuc nhum hon nguyn bn mu, sn xut dng nho in hoa theo phng php hai pha v hp nhanh, th d, Durindone rose FFFA (hng ICI ch to), Solanthrene noir BLFA (hng Francolor ch to); FD: l k hiu dng ch nhng thuc nhum c sn xut dng bt mn phn tn cao (fine disperse) do hng ICI dng v c t trc tn gi ca thuc nhum, th d, FD - caledon jade green XBN; FDN: ch loi thuc nhum bt mn phn tn cao mi c sn xut (t ch fine disperse new) do hng ICI dng. Th d, FDN Caledon gold - yelow GK; 94

GF: ch thuc nhum bn vi kh thot ra t ng khi (t ch gaz - fast); GFL: ch thuc nhum bn vi khi l v nh sng (t cc ch gaz - fast - light); H: C nhiu ngha khc nhau khi ng sau tn gi ca thuc nhum, cn phn bit trnh nhm ln; - Nu l thuc nhum indigosol th c ngha rng n l dn xut ca helidon, th d. indigosol orange HR; - Nu l thuc nhum hon nguyn khng tan cng ch rng n thuc nhm helidon, th d, indanthrene rot - violet RH; - Nu l thuc nhum hot tnh th ch rng n c th nhum nhit cao (t ch hot), th d, procion brillian sky - blue H5S; - Nu l thuc nhum phn tn th c ngha l n bn v nhit, th d, Selisol red brown HWL; I: Khi ng sau tn gi ca thuc nhum cng c ngha cn lu hiu cho ng nh: - ch nhng thuc nhum indigosol v indanthrene c bn mu cao do hng Duland sn xut, th d, Indigosol Sky blue, IB; - ch rng thuc nhum c dng in hoa do hng Francolor sn xut t u ch Impression, th d, solanthrene gris 4BI; ITR: Tp hp ba ch ny ch rng mu alizarin ca thuc nhum naphtol c bn mu ngang thuc nhum hon nguyn (indanthrene Turkish rot), th d, naphtol AS ITR. J: ch sc vng (t ch Jaune theo ting Php) do hng Francolor (Php) t tn; K: l k hiu ch nhng thuc nhum hon nguyn v hot tnh phi nhum nhit thp (t ch "kalt" ca ting c), th d, indanthrene gold - yellow GK; L: l k hiu ch thuc nhum c bn mu cao vi nh sng, tng ng vi ch u t ca ting Anh, Php, c u ng ngha l nh sng: light, lumire, licht, th d, Terasil orange 5 GL; LL: l k hiu nhng thuc nhum c bn mu c bit cao vi nh sng hoc ch thuc nhum c ho tan cao (t ch loslich); LSW: l k hiu tp hp ca cc tnh cht: bn vi nh sng, bn vi thng hoa v bn vi git (t cc ch: light - sublimathion, washing), th d, Eastman polyester rose RLSW; M: l k hiu ch nhng thuc nhum hot tnh cn nhum trong iu kin m du (t ch mild) nh: nhit thp, nng kim trong mng thp; N: l k hiu nhng thuc nhum mi c sn xut t u cc ch new, nouveau, nu ca ting Anh - Php - c u ng ngha l mi, th d, Solanthrne red N4B; O: ch rng thuc nhum inigosol c sn xut t thuc nhum inigo, ngha l t gc ban u (t ch origin); P: l k hiu ch rng thuc nhum dng nhum giy (t ch paper, papier), th d, Solanthrene Violet 4RP; - ch thuc nhum c th nhum cho x polyamit, do hng Bayer v Geigy sn xut; 95

S: l k hiu c nhiu ngha cng cn phn bit chnh xc nh sau: - ch thuc nhum c hm lng bng hm lng mu nguyn cht ca mu chun (t ch standard brand) do hng ICI dng, ch rng thuc nhum bn vi m hi (t ch schweiss) do hng Geigy sn xut; - i vi thuc nhum axit neolan do hng Ciba sn xut ch rng thuc nhum c th nhum c t tm (t ch silk, seike); - ch rng thuc nhum d ho tan trong nc (t ch soluble); - i vi thuc nhum phn tn ch rng n bn vi thng hoa; SF: ch rng thuc nhum siu bn (t ch super-fast); SE: l k hiu ch thuc nhum bn vi mui (t ch salz-echt), SQ: ch loi thuc nhum c nghin rt mn, c cht lng cao do hng ICI k hiu (t ch super fine quality); T: ch thuc nhum c sn xut nhum x terilen; TR: ch cc mu ca thuc nhum naphtol c bn mu cao (t ch Turkish roi), th d, naphtol AS-TR; W: l k hiu c cc ngha sau: - ch thuc nhum c bn vi nc (water); - ch thuc nhum bn vi git (washing); - ch rng mt s thuc nhum trc tip c th dng nhum hn hp len - bng (wool - cotton); X, XX: l k hiu ch nhng thuc nhum c bn mu rt cao (extra), th d, caledon jade green XBNS; Y: l k hiu ch thuc nhum c sc pht vng (t ch yellow), th d, durindone red Y; Z: ch nhng thuc nhum inigosol c cu trc i xng. Ngoi nhng trng hp k trn nu nh sau tn gi ca thuc nhum cn c cc con s nh: 150%, 200%, 300% th c ngha rng nhng sn phm ny c hm lng thuc nhum nguyn cht cao hn mu chun l 1,5, 2 v 3 ln. Cn nm vng k hiu ny tnh ton mu khi thit k cng ngh nhum. Trng hp gp nhng tn thuc nhum vit nh sau: CI disperse red 60 hay CI disperse blue 79 v.v., th nhng ch s 60, 79 l s hiu mu ca n trong Color Index ca mc thuc nhum phn tn. Trong tp sch ny chng ti kt hp dch tn thuc nhum sang ting Vit, gi nguyn k hiu ca ch ci v ghi ch bng ting nc ngoi tin cho vic hc tp v tham kho. 3. C CH LIN KT THUC NHUM VI VT LIU Khi tip xc vi vt liu (si dt, da, lng th, giy, g, chiu ci, nha cao phn t v.v.) hoc trong mi trng nc hoc dng kh phn tn cao vi nhit thch hp, thuc nhum s thc hin lin kt vi vt liu lm cho n c gi li bn vng trn vt liu vi nhiu ch tiu khc nhau (x l t, nh sng, khi l, ma st). Qu trnh lin kt ny khng ch xy ra mt ngoi ca vt liu m ch yu trn mt cc thnh mao qun. 96

cc khoang trng bn trong gia cc chm i phn t ca vt liu. Qu trnh ny cng khng n thun ch l cc lc lin kt ho l (lc lin kt phn t v lc hp ph) m c trng hp cn l qu trnh ho hc, thuc nhum thc hin lin kt ion hay lin kt ho tr vi vt liu. Tu thuc vo mi lp thuc nhum, mi loi vt liu m lin kt no s tri hn s l ch o, nhng thng th thuc nhum c gn hay c gi trn vt liu bng nhiu lc lin kt cng thc hin ng thi. Trong cng ngh nhum, in hoa qu trnh to iu kin cho thuc nhum lin kt vi vt liu gi l gn mu, hm mu, c nh, nh hnh v.v. tu theo mi trng hp c th. Di y l cc lc lin kt ca thuc nhum vi vt liu thng gp. 3.1. Lin kt ion Lin kt ny c thc hin gia cc gc mang mu tch in m ca thuc nhum (axit, trc tip) v cc tm tch in dng ca vt liu. Nhng vt liu trong iu kin nhum (mi trng axit) c kh nng tch in dng l: len, t tm, x polyamit, da, lng th; chng cu to t cc mch polypeptit, cha nhiu nhm amin t do, trong mi trng axit cc nhm ny chuyn thnh mui v phn ly lm cho vt liu tch in dng, c th minh ho nh sau: HOOCPNH2 + HCl HOOCPNH3Cl y P l k hiu mch polypeptit. Mt khc trong nc phn t thuc nhum cng phn ly v ion mang mu tch in m nh sau: ArSO3Na ArSO3 + Na+ Ar - gc thuc nhum axit, thuc nhum trc tip. Trong qu trnh nhum, khi tip cn vi vt liu, ion m ca thuc nhum s b thu ht v cc tm tch in dng ny v thc hin lin kt ion hay cn gi l lin kt mui nh sau: HOOCPNH3 + O3SAr

HOOCPNH3Cl HOOCPNH3 + Cl
+

HOOCPNH3 O3SAr

Nh c nng lng ln nn thuc nhum lin kt vi vt liu kh mnh, tc bt mu nhanh, phi iu chnh tc nhum bng cch iu chnh tr s pH ca dung dch nhum. 3.2. Lin kt ng ho tr Lin kt ny c thc hin ch yu thuc nhum hot tnh vi cc loi vt liu c cha cc nhm hyroxyl v nhm amin (x xenlulo, len, t tm, x polyamit, da v lng th). Do thuc nhum hot tnh cha cc nguyn t cacbon hot ng nn trong iu kin nhum chng c th tham gia phn ng ho hc vi vt liu theo c ch th i nhn hoc kt hp i nhn to nn mi lin kt ng ho tr gia thuc nhum v vt liu. Nh c lin kt ng ho tr nn mu ca vt liu nhum bng thuc nhum hot tnh c bn cao vi nhiu ch tiu, trc ht l vi x l t. 3.3. Lin kt hyro Lin kt hyro c thc hin gia cc nhm nh chc ca x v thuc nhum 97

nh: nhm hyroxyl, nhm amin, nhm amit v nhm cacboxyl. Khi phn t thuc nhum tip cn vi vt liu khong cch cn thit th lc lin kt hyro s pht sinh do tng tc ca cc nhm nh chc vi nhau. Nng lng ca mt mi lin kt hyro khng ln nhng tng nng lng ca nhiu lin kt hyro ca c phn t thuc nhum vi vt liu th ng k. Lin kt hyro c vai tr quan trng trong mt s trng hp c nh thuc nhum trn vt liu. Th d, thuc nhum trc tip gn mu vo x xenlulo v t tm ch yu bng lc lin kt hyro. 3.4. Lin kt Van der Waals Lin kt Van der Waals c thc hin hu ht cc lp thuc nhum khi tng tc vi vt liu. Tu theo loi thuc nhum (c cc hay khng c cc) v loi vt liu (a nc hay k nc) v tu theo mc tip cn gia phn t thuc nhum v vt liu m lc lin kt phn t s l chnh hay ch c ngha nht nh. Th d, thuc nhum hon nguyn v azo khng tan, ngoi yu t nm trn vt liu dng khng tan, chng c gi li trn x xenlulo ch yu bng lc Van der Waals v lin kt hy ro. Lin kt Van der Waals c coi l t hp ca cc lc ht: lng cc, phn cc cm ng v lc phn tn London. 3.5. Lc tng tc k nc Lc ny pht sinh gia cc gc hyrocacbon ca thuc nhum v vt liu khng c cc khi tip cn vi nhau, do chng khng y nhau, d ho ng vo nhau, bm dnh vo nhau. C th coi trng hp nhum cc x tng hp ky nc bng thuc nhum phn tn l th d in hnh. Thuc nhum phn tn khng tan trong nc c sn xut dng bt mn phn tn cao, iu kin nhum hoc l nhit cao p sut cao hoc l gia nhit kh, thuc nhum s tan vo cc x k nc v nhit do ny. X tng hp c xem l dung dch rn ca thuc nhum phn tn. Nh c lin kt ny m thuc nhum c bn mu cao vi git. 4. CC LOI THUC NHUM C TH 4.1. Thuc nhum trc tip 4.1.1. c im v cu to Thuc nhum trc tip hay cn gi l thuc nhum t bt mu (supstantip) l nhng hp cht mu ho tan trong nc, c kh nng t bt mu vo mt s vt liu nh: cc x xenlulo, giy, t tm, da v x polyamit mt cch trc tip nh cc lc hp ph trong mi trng trung tnh hoc kim. Hu ht thuc nhum trc tip thuc v nhm azo, s t hn l dn xut ca ioxazin v phtaloxianin, tt c c sn xut di dng mui natri ca axit sunfonic hay cacboxylic hu c, mt vi trng hp c sn xut di dng mui amoni v kali, nn c vit di dng tng qut l ArSO3Na (Ar l gc hu c mang mu ca thuc nhum). Khi ho vo nc thuc nhum phn ly nh sau: ArSO3Na ArSO3 + Na+. ion ArSO3 l ion mang mu, tch in m. Kh nng t bt mu ca thuc nhum trc tip ph thuc vo ba yu t di y: 1- Phn t thuc nhum phi cha mt h thng mi lin kt ni i cch khng di 8 k t u nhm tr mu ny n u nhm tr mu kia, nh vy phn t thuc 98

nhum s lun trng thi cha bo ho ho tr v c kh nng thc hin cc lin kt Van der Waals v lin kt hyro vi vt liu; 2- Phn t thuc nhum phi thng, v x xenlulo ni ring v nhng vt liu m thuc nhum c kh nng bt mu u c cu to phn t mch thng, c nh vy phn t thuc nhum mi d tip cn vi vt liu v thc hin cc lin kt; 3- Phn t thuc nhum phi c cu to phng, cc nhn thm hoc cc nhm chc ca thuc nhum phi nm trn cng mt mt phng n c th tip cn cao nht vi mt phng ca phn t vt liu cng l yu t quan trng cho vic pht sinh v duy tr cc lc lin kt ca n vi vt liu. Ngoi ba yu t k trn phn t thuc nhum trc tip cn phi cha mt s nhm chc nht nh, ch yu l nhm hydroxyl v nhm amin (OH, NH2), nhng nhm ny va lm nhim v tr mu va to cho thuc nhum thc hin lin kt hyro vi vt liu. Theo cu to ho hc thuc nhum trc tip c chia thnh cc nhm sau y: - Thuc nhum trc tip azo, trong phn t cha mt hoc nhiu nhm azo (N=N), nhm ny chim i b phn cc thuc nhum trc tip v xp thnh bn loi: loi thng thng, loi c bn mu cao, loi cha hoc c kh nng kt hp vi ion kim loi thnh phc khng tan v loi c kh nng iazo ho sau khi nhum; - Thuc nhum trc tip l dn xut ca ioxazin; - Thuc nhum trc tip l dn xut ca phtaloxianin. Ngoi ra trong phn t thuc nhum cn cha vng triazin va ng vai tr phn t ngn cch va cha cc nguyn t bo ho ho tr nn cng lm tng kh nng bt mu ca n vo vt liu. Trong phn t thuc nhum cn cha gc ca axit xalixilic nn n c th to phc vi cc ion kim loi nng tng thm bn mu. Thuc nhum trc tip iazo c nhm amin bc nht v tr para hay meta so vi nhm azo c th iazo ho v kt hp vi thnh phn azo mi (thng l -naphtol) tng bn mu. d nhn bit khi s dng, trong tn gi ca loi thuc nhum ny c ch iazo. Cc mt hng thng phm ca thuc nhum trc tip. Da vo cc ch tiu v bn mu v phng php s dng thuc nhum trc tip c chia lm bn nhm: 1- Gm nhng mu c bn vi nh sng di cp 4 (theo thang 8 cp), cn bn vi x l t di cp 3 (theo thang 5 cp); 2- Gm nhng thuc nhum trc tip c bn nh sng trn cp 4, bn vi x l t mc trung bnh, sau khi cm mu bn s tng ln; 3- Gm nhng thuc nhum cn x l cm mu vi mui ng nn trong tn gi c ch cupro, bn mu vi git t trn cp 3, cn vi nh sng khng di cp 5. 4- Gm nhng thuc nhum c th iazo ho trn vi v kt hp tip vi mt thnh phn azo na tng bn mu vi git ln n cp 4. Tn thng phm ca cc thuc nhum trc tip ca cc hng ni ting th gii c th xem ti liu tham kho. 99

Bng 3.1 Nc sn xut Anh Ba Lan c Hng sn xut ICI Bayer Hochst BASF Wolfen M Du-Pont Tn nhm thuc nhum 2 3 Durazol, fixazol Durazol cupro Helion Sirius bn Sirius supra Remastral Lurantin Solamin Pontamine Sec v Slovackia Chemapol Thu S Ciba Direct Pontamine fast Resotix Saturn Chlorantine Polytex, Rigan Ciba-geigy Sandoz Diphenyl Chloramin Solophenyl Pirazol Solar Benzo cuprol Bbenzo cuper Cupracon Solamin - fau Pontamine Cuper Ribantin Copratin Neooupran Cupranon Cuprophenyl Cuprofix Reofix Diazophenyl Diazophenyl Diazoamin Diazo Benzamin Benzo para Dianil Naphtogen Zambenzi Pontamine diazo Azogen Diazo Rosantren

1 Chlorazol Benzo nh Columbia

4 Chlorazol

Chemicolor Direct

Tnh cht m thut ca thuc nhum trc tip tin cho vic s dng, cc hng ch to thuc nhum u c ti liu ch dn v tnh cht sn phm ca mnh, tuy nhin gia cc l hng khc nhau v sn phm ca cc hng khc nhau vn c sai lch, khi dng cn th nghim li nhm bo m kt qu nhum trng lp. Khi chun b dung dch nhum vi nhng thuc nhum trc tip kh tan cn phi thm natri cacbonat vo mng to mi trng kim yu. Nhit nhum v hp ph ti u. Ch tiu ny c xc nh theo mc hp ph ti a ca vi bng trong cc dung dch thuc nhum c nng khc nhau nhn c mu c cng trung bnh. Nhit nhum ti u ca thuc nhum trc tip trong khong t 75oC n 95oC tu thuc vo mi mu v mi loi vt liu. hp ph ti u c xc nh khi nhum si bng lm bng nhit ti u vi dung t bng 40 khi c mt 15% mui n. S liu hay th hp ph ti u ca mi thuc nhum c s dng khi ghp mu vi cc thuc nhum khc. bn mu v s bin sc. Thuc nhum trc tip c u im l c gam mu t vng n en, mu tng i ti, song nhiu thuc nhum trc tip km bn mu vi 100

git v nh sng. bn mu v nh mu ca nhiu thuc nhum trc tip s thay i khi nhum cho cc vt liu khc nhau.Th d mt s thuc nhum km bn mu khi nhum cho x bng nhng li rt bn mu khi nhum cho la t tm. nng cao bn mu (cm mu, hm mu) cho vt liu nhum bng thuc nhum trc tip ngi ta dng cc bin php khc nhau nhng ph bin hn c l dng cc ch phm t nha cao phn t tch in tri du vi thuc nhum hoc mui kim loi nng. Sau khi cm mu bng cc ch phm ny bn vi git v nh sng c th tng ln 1 - 2 cp nhng mu s km ti (b bin sc). Cc ch phm cm mu cho vt liu nhum bng thuc nhum trc tip c cc hng sn xut v s dng ph bin trong ngnh dt gm c: mui copratin II, mui copratin TS, coprantex B, Sapamin, Sapamin A, Sapamin CH, Sapamin BCH, Sapamin MS Sapamin KW, Liofix EW, Liofix SB (do hng Ciba sn xut), Solidogen B, Solidogen BSE, Solidogen BS (hng Cassella sn xut); fixanol PN (hng ICI sn xut); Cuprofix S v SL, Resofix BV, Sandofix B (hng Sandoz sn xut); Tinofix B, Tinofix LW (hng Geigy sn xut); Levogen WW v FW (hng Bayer sn xut); Sintefix v Sintefix S (Sec v Slovackia sn xut); DCU v DCM (do Lin X (c) sn xut). 4.1.2. Phm vi s dng Do c kh nng t bt mu, cng ngh nhum n gin v r nn thuc nhum trc tip c s dng trong nhiu lnh vc khc nhau nh: nhum trong ngnh dt (vi, si bng, hng dt kim t bng, la, vixco, la t tm, si polyamit, si ay v cc si libe); nhum giy, nhum cc sn phm t tre na, mnh trc; nhum da thuc v ch mc vit. Mt s thuc nhum trc tip c bn mu cao vn c dng nhum mt s loi vi v si bng k c hng dt kim t si bng hoc thnh phn bng trong vi pha. Khi nhum theo phng php tn trch thnh phn mng nhum gm c: thuc nhum (1 - 4% so vi vt liu), natri cacbonat (2 - 4 g/l), cht ngm (1 - 2 g/l), dung t nhum t 5 - 8 tu loi thit b. Qu trnh nhum c thc hin 85 - 95oC trong thi gian 60 - 90 ph. Mui n vi hm lng 15 - 20 g/l c ho thnh dung dch v a vo my nhum sau khi tin hnh nhum c 45 - 50 ph. Kt thc qu trnh nhum vi c cm mu bng mt trong cc ch phm thch hp 60 - 70oC trong 15 ph. Thuc nhum trc tip cng c dng ph bin nhum la vixc k c thnh phn vixc trong vi pha. Do x vixc c cu trc xp nn n d bt mu bng loi thuc nhum ny, mu bn hn v ti hn so vi khi nhum vi bng. Thnh phn dung dch nhum v cng ngh nhum tng t nh khi nhum vi bng, ch khc l nhiu trng hp khng phi dng mui n v khng cn hm mu. t c u mu cao mt s hng sn xut cc mt hng thuc nhum trc tip dng ring cho la vixc nh: benzo vixc (hng Bayer), rigan (hng Ciba), vixc (hng Sandoz), isil (hng ICI) solamin - fau (hng Wolfen). T tm l mt hng dt qu him cng c nhum nhiu bng thuc nhum trc tip. Thnh phn nhum v cng ngh nhum cng tng t nh khi nhum vi bng, iu khc ch yu l phi khng ch tr s pH khng nh hng n bn ca t (pH = 8 - 8,5), t phi dng mui n v khng cn hm mu. Nhng thuc nhum trc tip c ch nh dng ring cho t tm gm: Benzyl, Chlorantine (hng Ciba-Geigy); Colozol (hng Colourtex); Atul (hng Atul); Solar (hng Sandoz); Rono sunfast (hng IDI) Incomine (hng INDOKEM) v.v. 101

Thuc nhum trc tip cng c dng nhum mt s sn phm dt t x polyamit vi cc gam mu nht. c bit n c dng nhum vi lanh, si ay v cc si t x libe cho mu bn v ti. Trong cng nghip giy thuc nhum trc tip c dng nhum giy hoc bng cch a ngay vo b cha bt giy trc khi xeo hoc nhum ph b mt bng cch cn p hoc qut dung dch thuc nhum ln mt giy. Trong cng nghip thuc da mt s thuc nhum trc tip c dng nhum da nht l cc mu en, nu v mt s mu xanh. Mt s thuc nhum trc tip c ho tan tt c dng ch to mc vit. nc ta thuc nhum trc tip cn c dng nhum hng my tre, mnh trc, cc dng an t tre na, tm hng v nhum g trc khi ph vecni. 4.2. Thuc nhum axit Cc loi thuc nhum axit c c im chung l ho tan trong nc, c phm vi s dng rng, ngoi mc ch nhum len, t tm v x polyamit, mt s c dng nhum lng th v nhum da. Lp thuc nhum ny c tn gi l axit v chng bt mu vo x trong mi trng axit, cn bn thn thuc nhum th c phn ng trung tnh. Theo cu to ho hc, a s thuc nhum axit nhum v nhm azo, s t hn l dn xut ca antraquinon, triarylmetan, xanten, azin v quinophtalic; mt s c th to phc vi ion kim loi. Theo tnh cht k thut thuc nhum axit c chia thnh ba nhm: - thuc nhum axit thng thng; - thuc nhum axit cm mu; - thuc nhum axit cha kim loi. Ba nhm thuc nhum ny c c im chung l mu, mu ca chng ti v thun sc. a s chng l mui ca cc axit mnh v baz mnh nn khi ho tan trong nc th phn ly thnh cc ion nh sau: ArSO3Na ArSO3 + Na+. Cc ion mang mu ca thuc nhum tch in m (ArSO3) s hp ph vo cc tm tch in dng ca vt liu. Nh m n c gn mu hay gi li trn vt liu bng mi lin kt ion hay lin kt mui, l c im ring ca thuc nhum axit. Ngoi ra chng cng c lin kt vi vt liu bng lc Van der Waals, lin kt hyro v lin kt phi tr, nhng nhng lc lin kt ny khng mnh. 4.2.1. Thuc nhum axit thng thng Loi thuc nhum ny c gam mu rt rng, mu thun sc v ti, bn mu vi gia cng t cao nhng bn mu vi nh sng ch t cp trung bnh. Theo cu to ho hc th a s thuc nhum axit thng thng l dn xut azo; dn xut ca antraquinon chim t l thp hn, cc dn xut khc cn t na. Thuc nhum azo axit Trong s cc thuc nhum azo axit ch c loi monoazo v iazo l c ngha thc tin, loi polyazo t gp v phn t ca chng qu ln. Thuc nhum monoazo axit do c phn t nh nn c ch yu cc gam mu vng, mu da cam v mu ; a s chng l dn xut ca azobenzen, benzonaphtalen, azonaphtalen, pirazolon. Khi a thm nguyn t halogen vo nhn benzen ca gc phenylpirazolon th bn mu vi nh sng ca thuc nhum s tng ln. nng cao ho tan ca thuc 102

nhum ngi ta a thm vo phn t ca chng cc nhm natri sunfonat (SO3Na), iu ny s lm tng u mu nhng s lm gim i lc ca thuc nhum. duy tr u mu cao, bn mu cao vi nh sng v bn mu cao vi iu kin cn mn, ngi ta thay mt phn trong s cc nhm natri sunfonat bng nhm sunfamit (SO2NH2) hoc nhm ny c th bng cc gc arylankyl. tng thm bn mu vi nh sng v gia cng t, tng thm u mu, hng ICI sn xut ra loi thuc nhum axit c cha vng pirazolon v gc hidrocacbon thng di. Thuc nhum iazoaxit chim t l ln trong s cc thuc nhum azoaxit, chng c cc gam mu vng, da cam, nhng ch yu l cc mu xanh v en. Thuc nhum axit antraquinon V l dn xut ca antraquinon nn thuc nhum axit loi ny c bn mu cao hoc rt cao vi git v nh sng, mu ti v thun sc. Ngoi nhm natri sunfonat trong nhn antraquinon cn cha cc nhm khc nh: OH, NH2. Khi cc nhm ny nm v tr thch hp th thuc nhum c th to phc vi ion kim loi lm cho mu bn hn. Th d, alzarin , l hn hp ca hai ng phn c cng thc nh sau:
O OH SO3H O

OH OH

HO O

SO3Na

Len hay t tm nhum bng thuc nhum ny lc u c mu khi to phc vi mui crm th chuyn thnh mu lu, bn mu vi nh sng, gia cng t v cn mn. Hng ICI sn xut ra loi thuc nhum axit antraquinon c cha nhm alkyl di (c s nguyn t cacbon n 20) gi l cacbolan. Nhng mt hng thuc nhum ny c cc gam mu vng, tm, xanh lam, xanh lc v nu. Chng c bn mu cao vi nh sng v git, d u mu v c th bt mu vo x len trong mi trng trung tnh nn c dng nhum vi len pha x xenlulo. Cacbolan tm 2R l thuc nhum tiu biu c cng thc sau:
O NH2 O (CH2) n CH3

O HN SO3H

Thuc nhum axit l dn xut ca triarylmetan Thuc nhum axit thuc v loi ny khng nhiu, ch c cc mu xanh lam, xanh lc v mu tm l c ngha hn c, chng cha t nht hai nhm natri sunfonat. Cc nhm amin nm v tr para so vi nguyn t cacbon trung tm chnh l cc nhm tr mu. Cc mt hng thng phm c im ca thuc nhum axit thng thng l khc nhau kh nhiu v kh nng bt mu vo vt liu, kh nng u mu, bn mu vi git v nh sng. Nhng thuc nhum l dn xut ca hp cht azo v arylmetan thng km bn mu vi nh sng; 103

nhng mu l dn xut ca antraquinon thng c mu ti, c bn mu cao vi nhiu ch tiu gia cng t v nh sng, li c th nhum trong mi trng axit yu hoc trung tnh nn chng c s dng nhiu hn trong thc t. Theo tnh cht k thut thuc nhum axit thng thng chia lm ba nhm: d u mu (bt mu vo vt liu trong mi trng axit mnh), kh u mu (bt mu vo vt liu trong mi trng axit yu) v u mu trung bnh chim v tr trung gian ca hai nhm trn. c im ca mi nhm thuc nhum ny c thng k trong bng 3.2. Bng 3.2 Tn ch tiu bn vi gia cng t Tr s pH khi nhum Tc nhn axit dng c im ca thuc nhum: khi lng phn t ho tan i lc vi vt liu tc khuch tn Loi thuc nhum axit u mu kh u mu kh cao 4-6 6-7 CH3COOH CH3COONH4 trung bnh thp cao thp ln rt thp cao rt thp

d u mu thp 2-4 H2SO4 nh cao thp cao

Tuy cng ngh nhum phc tp nhng nhng thuc nhum kh u mu s t c bn mu cao vi gia cng t v nh sng, hn na li c th nhum trong mi trng axit yu v trung tnh nn c th thit lp cng ngh nhum cc loi vi pha t x len hoc t tm, x polyamit vi x xenlulo bng hn hp thuc nhum thch hp. Hin nay cc loi vi len c sn xut rt a dng gm c: vi thun len, vi len pha bng, len pha x vixc, len pha x polyamit, len pha x polyeste v len pha x acrylic v.v., v vy ngi ta cng sn xut ra cc hn hp thuc nhum phi sn dng cho cc loi vi k trn. Di y l tn gi thng phm ca thuc nhum axit thng thng ca mt s hng trn th gii sn xut (bng 3.3). Bng 3.3 Tn nc Anh Ba Lan c Lin X (c) M Nht Bn Php Sec v Slovakia Thu S Tn hng ICI Bayer Du-Pont KKK Francolor Chemapol Cba-Geigy Sandoz Tn thuc nhum thng phm Cumassi, lissamine, carbolan Acid, metanin Acilan, supramine, supracen, cupranol, telenfast Kitlotni, acid Pontasil, metanil, litocol Kayacil, kayanol Sulphacid, supracid, acide Egaoid, midlon, ribacid Erio, eriosin, irganol, erionil Sandolan

104

X polyamit cng c nhum bng thuc nhum axit nhng kh nng bt mu yu hn so vi len v t tm nn ngi ta sn xut mt s thuc nhum axit dng ring cho x polyamit, tn thng phm ca cc mt hng ny c trnh by trong bng 3.4. Bng 3.4 Tn nc Anh c Tn hng ICI BASF Bayer Cassella Hoechst Sec v Slovackia Thu S Chemapol Ciba-Geigy Sandoz Basolan Supramine, supranol, telon lightfast Perlamin, perlaminfast Lanoperl, antralan Midlon, alizarin-asurol, ribacid Elanyl, benzyl, neonyl, erionil, eriofast, enosolid, polar, textilon Nylocan, lanasin, sandolan, nylosan, alizarin Tn thuc nhum thng phm Carbolan, nylamin

Thuc nhum axit thng thng v hn hp ca chng vi thuc nhum trc tip c s dng theo truyn thng nhum da thuc, lng th, da nguyn lng v cc sn phm bng lng khc nhau. Nhng mt hng ny rt phong ph v a dng, cn tm hiu thm trong cc ti liu chuyn kho. 4.2.2. Thuc nhum axit crom Mt s thuc nhum va c cc tnh cht nh thuc nhum axit thng thng va c kh nng to phc vi mui kim loi, ch yu l mui crom, nn c xp ring thnh mt nhm gi l thuc nhum axit crom hay thuc nhum axit cm mu. Chng c s dng nhum len nht l cc mt hng cn c bn mu cao vi ma st v nh sng), nhum da thuc, lng th v cn c dng nhum b mt kim loi (nhm) trang tr. cm mu ngi ta thng dng mui kali bicromat, cn cc mui khc ca crom th t dng hn. Vic cm mu c th thc hin trc khi nhum, sau khi nhum hoc nhum v crom ho ng thi nn cng xut hin cng ngh v s la chn thuc nhum cho ph hp vi cc iu kin cng ngh ny. Gam mu ca thuc nhum axit crom rt rng nhng a s sau khi cm mu tr nn km ti hoc bin sc. Sau khi to phc vi ion kim loi mu ca chng s bn vi gia cng t, nh sng, ma st v iu kin cn mn, nh to thnh phc khng tan gia thuc nhum v kim loi, xut hin thm cc vng ph lm tng lc lin kt ca thuc nhum vi x. Nhng thuc nhum axit crom c ngha thc tin hn c u l dn xut azo, s t hn l dn xut ca antitraquinon v mt vi dn xut khc. Tu theo v tr ca cc nhm nh chc c th lin kt vi ion kim loi, thuc nhum axit crom gc azo c cc loi tiu biu di y: 0,0-ihyroxiazo; 0,0-hyroxicacboxylazo; 0,0-hyroxiaminoazo; dn xut ca axit cromotropic v 8-hyroxiquinolin dn xut ca axit xalixilic. Khi gia cng vi mui crom ho tr ba nhng thuc nhum ny c th to thnh ba loi phc: 1:1, 1:2 v 2:3 ngha l mt ion kim loi c th lin kt vi mt hay hai phn t thuc nhum hoc hai nguyn t kim loi vi ba phn t thuc nhum, theo cc dng tng qut nh sau: 105

Kiu phc 1:1 (mt ion crom, mt phn t thuc nhum)

+

N O Cr

N
+

Kiu phc 1:2 (mt ion crom, hai phn t thuc nhum)
N O Cr O N O N N O
Na
+

hoc
N N

H2O

H2O N N

O C O C O O O C O

Na

Kiu phc 2:3 l ghp ca hai kiu phc trn:

N
+

N O Cr O N

N O Cr

N O

O O N

Cc kiu phc k trn c to thnh dng no l tu thuc vo qu trnh crom ho v mi trng; cc phc 1:1 v 1:2 c ngha thc tin hn phc 2:3, song nhng phc c hm lng crom thp hn (1:2 v 2:3) s c mu su hn phc 1:1. Ngoi ra cc phc 1:2 khng c cu to phng, hai phn t thuc nhum thng nm trong cc mt phng gc vi nhau, cc phn t nc lin kt vi phc ny ch b tch ra khi sy trn 120oC. Khi phc c to thnh trn vt liu (len, da thuc, lng th) th phn t nc s tch ra, nhng ch cho cc nhm chc ca vt liu lin kt vi crom. Lin kt gia vt liu, thuc nhum v crom c m hnh ho nh sau:
mch keratin, gelatin
+

COO

NH2
O N

Cr O N SO3

NH2

NH3

106

Cc mt hng thng phm Thuc nhum axit crom cng c nhiu hng sn xut vi cc tn gi thng phm khc nhau dng cho cc phng php nhum khc nhau. Trong bng 3.5 trnh by mt s thuc nhum thng gp trn th trng th gii. Bng 3.5 Tn thuc nhum thng phm Tn nc Anh n Ba Lan c Tn hng ICI dng cho cc phng php nhum dng cho nhum v crom ho ng thi Colochrome, colochromat

M Php Sec v Slovackia Thu S

Colochrome, Omegachrome Ksa, tula, esgi, chromic Acid chrome Bayer Diamant, telen chromic BASF Basolan, chromic Hoechst Saldinchrome, saliclicinchromic Du-Pont Prontachrome Francolor Francolan, chromic Chenapol Alizarin Ciba-Geigy Fastchrome, eriochrome Sandoz Omegachrome, alizarin

Orthochrome Monochrome, chromogen Metachrome Chromat Crinolan Alizarinchrome Sintochromat, eriochromal Metomegachrome

4.2.3. Thuc nhum axit cha kim loi n gin ho qu trnh chun b v nhum vt liu, ngi ta ch to ra loi thuc nhum cha sn nguyn t kim loi trong phn t ca chng, gm thuc nhum cha kim loi 1:1 v 1:2. to phc vi phn t thuc nhum ngi ta dng cc ion kim loi c in t vng ngoi cha bo ho, thng l cation ca cc kim loi chuyn tip thuc chu k th nht ca bng tun hon cc nguyn t Mendeleev nh: crom, niken, coban, ng. Vic la chn kim loi to phc ph thuc vo cu to ho hc ca thuc nhum; to phc kiu 1:1 ngi ta dng ch yu crom ho tr ba v n to phc bn vi mi trng axit mnh, thun tin cho vic nhum mt s vt liu trong mi trng axit v c c tr s pH trong khong 3 - 3,5. Vi loi phc 1:2, ngoi crom ngi ta cn dng coban, ho tr ba. Thuc nhum axit cha kim loi 1:1 ln u tin c hng Ciba ca Thu S sn xut vo nm 1924 vi tn gi l neolan, sau hng BASF sn xut vi tn gi l palatin; chng c c im chung l d ho tan trong nc, d u mu, mu ti v bt mu vo vt liu trong mi trng axit mnh. Palatin xanh lam bn mu GGN l mt trong nhng thuc nhum tiu biu cho nhm ny, c cng thc sau:
H2O O NaO3S N Cr N
+

H2O O SO3

107

Khi thuc nhum ny lin kt vi vt liu th cc phn t nc s tch ra nhng ch cho cc nhm chc ca vt liu lin kt vi crom. Thuc nhum axit cha kim loi l:2 cng c nhiu hng quan tm sn xut. to cho thuc nhum c ho tan cn thit ngi ta a vo phn t ca chng cc nhm a nc nh: sunfamit (SO2NH2), metylsunfon (SO2CH3); ch gi li mt phn nhm natri sunfonat. V nguyn t kim loi (thng l crom) c bo ho bng cc lin kt phi tr ni phn t, chng khng cn kh nng lin kt phi tr vi vt liu na. Chng lin kt vi cc vt liu t protein (len, t tm, da thuc, lng th) bng lin kt ion, lin kt hidro v lin kt Van der Waals trong mi trng axit yu (pH = 5 - 6) v ngay c mi trng trung tnh na. Irgalan mu ghi BL l mt trong nhng thuc nhum tiu biu ca nhm ny, c cng thc nh sau:
H3C CO SO2CH3 N O Cr O N N H N O H N N O
Na
+

OC CH3

Do c mu ti, bn mu cao vi nhiu ch tiu gia cng t v nh sng, cng ngh nhum li n gin nn thuc nhum axit cha kim loi c dng nhiu nhum vi, x len, nhum lng th, nhum cc loi vi len pha vi cc x khc, nhum vi t x polyamit v nhum da. Ring thuc nhum cha kim loi l:2 do c th nhum trong mi trng axit yu nn ngoi cc sn phm dt t len hay len pha n cn c dng nhiu nhum t tm, c bit l c s dng in hoa cho la t tm, in hoa vi t x polyamit v nhum cc tm da nguyn lng. Thuc nhum axit cha kim loi 1:1 thuc loi d ho tan trong nc ( ho tan ti a n 400 g/l) v s u mu; cn thuc nhum axit cha kim loi 1:2 th kh ho tan trong nc hn v thuc loi kh u mu nn phi dng cc cht tr nhum cn thit mi c th t c u mu cao. C hai loi thuc nhum ny u t nhy cm vi nc cng v cc ion kim loi c trong nc nh: ng st, crom v.v. Bng 3.6 dn ra cc mt hng thuc nhum axit cha kim loi thng gp. 4.3. Thuc nhum hot tnh Thuc nhum hot tnh l nhng hp cht mu m trong phn t ca chng c cha cc nhm nguyn t c th thc hin mi lin kt ho tr vi vt liu ni chung v x dt ni ring trong qu trnh nhum. Nh vy m chng c bn mu cao vi gia cng t, ma st v nhiu ch tiu khc na. Thuc nhum hot tnh c gam mu, mu ti v thun sc, cng ngh nhum a dng v khng qu phc tp, v vy nn tuy mi ra i nm 1 956 n nay c sn xut vi khi lng ln v s dng kh ph bin. Chng c s dng nhum v in hoa cho cc vt liu xenlulo, t tm, len, vt liu t x polyamit. Ti liu tham kho v thuc nhum hot tnh rt phong ph. 108

Bng 3.6 Tn nc Anh n Tn hng ICI IDI Atul LEL Bayer BASF Hoechst Du-Pont KKK Francolor Chemapol Ciba Geigy Sandoz Ciba-Geigy Tn thuc nhum thng phm loi phc 1 : 1 loi phc 1 : 2 Ultralan Varilan Navilan Metalan, neolan Crestalan Isolan, levalan Fast palatine Fast via lon, ortolan Fast remalan Chromasil Capranil Kayacolan Supracid, inocchrome Chromoilan Ostala, ostalan F Erio, eriosin, neolan, Cibalan textilon, erionil Glycolan Irgalan, irganol Vitrolan Lanasin, sandolan Lanaset

M Nht Bn Php Sec v Slovackia Thu S

4.3.1. Cu to ho hc v tnh cht chung Cc loi thuc nhum hot tnh tuy c khc nhau v cu to phn t, phm vi s dng v hot nhng u c th trnh by di dng tng qut l: S R T X Th d, procion M 2BS c cng thc sau:
Cl N SO3Na N N NaO3S
SR

NH N

N Cl SO3Na
TX

y: S - nhm to cho phn t thuc nhum c ho tan cn thit trong nc, thng gp hn c l cc nhm: SO3Na, COONa, SO2CH3. Ring thuc nhum phn tn hot tnh th phn t ca n khng c nhm cho tnh tan; R - phn mang mu ca phn t thuc nhum, n khng nh hng n mi lin kt gia thuc nhum v x, n quyt nh v mu sc, v bn mu vi nh sng v cng c tc ng n cc ch tiu v bn mu khc, nn vic chn gc R phi tho mn c cc yu cu k trn. Nhng gc mu c chn vo mc ch ny l: mono v iazo, phc cht ca thuc nhum azo vi ion kim loi, gc thuc nhum axit antraquinon, hon nguyn a vng, dn xut ca phtaloxianin...; TX - nhm hot tnh c cu to khc nhau, c a vo cc h thng mang mu khc nhau; 109

X - nguyn t (hay nhm) phn ng, trong iu kin nhum n s tch khi phn t thuc nhum, to kh nng cho thuc nhum thc hin phn ng ho hc vi x. X khng c nh hng g n mu sc nhng i khi cng c nh hng n ho tan ca thuc nhum. Nhng nguyn t ny thng l: Cl, SO2, OSO3H, NR3, CH=CH2, ... T - nhm mang nguyn t (hay nhm) phn ng, n lm nhim v lin kt gia thuc nhum vi x v c nh hng quyt nh n bn ca mi lin kt ny, trc ht l bn mu ca thuc nhum vi gia cng t. Khng nhng th, hu ht cc trng hp, s tng tc ca thuc nhum hot tnh vi x l phn ng nucleophin, nhm T s ng vai tr quyt nh tc phn ng nn vic la chn nhm T cho ph hp l mt yu t quan trng. Khi chuyn t vng triazin cn i sang cc vng pirimiin v quinoxalin bt i lm gc T th kh nng phn ng ca thuc nhum s gim i (bng 3.7). Da vo c s l thuyt ny ngi ta chn cc gc T khc nhau tng hp nn nhng thuc nhum c hot mong mun. Ngoi cc yu t k trn th nhm cu ni gia phn SR v TX ca thuc nhum cng c ngha quan trng. Ngi ta thng dng cc nhm: NH, NHCH, SO2N lm cu ni. Tuy khng c tnh quyt nh nhng cu ni cng c tc ng n mu sc ca thuc nhum, n cng nh hng n hot v bn ca mi lin kt gia thuc nhum v x. Di y l nhng loi nhm phn ng c dng nhiu sn xut thuc nhum hot tnh. Bng 3.7 Cu to ho hc
N N Cl N Cl

Nhm TX Tn gi, nhum cho loi x Diclotriazin (xenlulo)

Tn thng phm Procion M Ostazin C Mikacion Helactil F Procion H Cibacron Ostazin H Helactin D Drinmaren Reacton

Ni, hng sn xut ICI Sec v Slovackia Nht Bn Ba Lan ICI Ciba Sec v Slovackia Ba Lan Sandor Geigy

N N N

Cl

Monoclotriazin (xenlulo, len)

NH R
Cl N Cl N
N N

Cl NH R

Triclopirimidin (xenlulo)

Cl Cl

Dicloquinoxalin

Levafix E

Bayer

N Cl Cl O N Cl

Diclopiridazol (xenlulo)

Primazin P

BASF

110

Bng 3.7. (tip theo) Nhm TX Cu to ho hc Tn gi, nhum cho loi x Phtalazin (xenlulo) Cl
N N Cl

Tn thng phm Reateco

Ni, hng sn xut Bayer

NHCOCH2Cl COCl (xenlulo) SO2CH2CH2OSO3Na

Axylhalogen Vinylsunfon (xenlulo, len)

Cibalan

Ciba

SO2NH(CH2)2OSO3Na NHCOCH=CH2 CH2CHCH2 O NHCH2CHCH2Cl OH

Vinylsunfamit (xenlulo) Acrylamit (len) Epoxy hay epyclohidrin (polyamit) Diclohidrin (polyamit)

Ostazin Remazol Remalan Genafix Levafix Primasin Cibacrolan Priocinyl

Sec v Slovackia Hoechst M M Bayer BASF Ciba ICI

Trong iu kin nhum, khi tip xc vi vt liu thuc nhum hot tnh s tham gia ng thi vo hai phn ng: vi vt liu v phn ng thy phn. Phn ng vi vt liu (x) l phn ng chnh c dng tng qut: SArTX + HOX SArTOX + HX. Phn ng thy phn l phn ng ph lm gim hiu sut s dng ca thuc nhum, c dng tng qut: SArTX + HOH SArTOH + HX. Thuc nhum b thy phn khng c kh nng lin kt ho hc vi vt liu na, ch bm vo mt ngoi bng lc hp ph khng mnh nn khng bn mu cn thit, cn phi git sch phn thuc nhum ny t bn mu ca thuc nhum. Khi tng hp thuc nhum hot tnh ngi ta phi chn cc yu t v cu to ho hc sao cho phn ng chnh t c t l ti a v hn ch n mc thp nht phn ng thy phn. t c yu cu ny cc loi thuc nhum hot tnh cn t cc yu cu cng ngh di y: - phi bn khi bo qun trng thi kh v trong dung dch; - c kh nng phn ng cao trong iu kin nhum m du v phi t yu cu tc cao ca sn xut. - bn ca mi lin kt gia thuc nhum v vt liu khng nh hng n iu kin x l ho hc v s dng sn phm; 111

- c i lc cao i vi x si khi nhum tn trch bo m mc hp ph cn thit trc khi n thc hin lin kt ho tr vi x ng thi c kh nng d git ra khi vt liu phn thuc nhum b thy phn. Nhng thng s k thut cn thit khi nhum bng thuc nhum hot tnh l: nhit , tr s pH, thi gian nhum, nng cht in ly, nng cht tr v cht xc tc. Ch khi no la chn ng cc thng s k thut ny th mi c th t c hiu sut s dng thuc nhum ti a. n nay c hng nghn mu khc nhau ca thuc nhum hot tnh c sn xut, khng c nhm phn ng khc nhau, hot , mu sc v tc phn ng khc nhau, th hin cc ch tiu: - khc nhau v i lc vi x v vi nc; - khc nhau v mt c im phn ng vi nhm nh chc ca vt liu; - khc nhau v i lng nng lng to thnh mi lin h ho tr; - khc nhau v bn mu vi git, m hi, dung dch kim, clo nh sng v khi l. c im chung ca thuc nhum hot tnh l mu ti v c bo ho mu cao. phn loi thuc nhum hot tnh, ngi ta dng cc ch tiu chnh sau y: - theo cu to ho hc (ch yu l theo nhm phn ng); - theo c ch nhum: th nucleophin hay kt hp nucleophin; - theo cng ngh nhum: nhum ngui, nhum nng (phng php tn trch), nhum cun (bn lin tc), nhum ngm hp hoc gia nhit kh (phng php lin tc) - theo mc git sch phn thuc nhum b thy phn. 4.3.2. Nhng thuc nhum hot tnh thng thng Thuc nhum hot tnh c gii thiu trong cc ti liu khoa hc cng nh thng gp trn th trng th gii c sp xp theo cu to ho hc, sau y l nhng loi chnh. a. Thuc nhum iclotriazin Thuc nhum iclotriazin c nhiu hng sn xut vi tn gi thng phm khc nhau, ch kh nng phn ng cao v cn nhum trong iu kin m du cui tn gi ca mi mu thng c ch M, ch K hoc ch X. Phn mang mu (R) ca thuc nhum iclotriazin thng l gc mu azo, antraquinon v gc phtaloxianin. Cu ni gia gc SR v TX thng l nhm NH, ch khi dng phtaloxianin lm gc mang mu th mi dng cu ni l nhm SO2 hoc nhm NH(CH2)2NH v mt vi nhm khc. Do trong vng triazin c hai nguyn t clo cha b thay th nn thuc nhum c hot cao. Khi nhum nhit thng (30oC) trong mi trng kim yu (NaHCO3) th mt nguyn t clo tham gia phn ng vi x, cn khi tng kim th c hai nguyn t clo s lin kt vi x. Nu nh chng tham gia phn ng vi hai nhm nh chc ca hai mch phn t xenlulo hay protein th s to nn nhng cu bc ngang, lm cho x c cu trc mt li. b. Thuc nhum monoclotriazin C th xem thuc nhum loi ny nh l thuc nhum iclotriazin trong mt nguyn t clo b th bi cc nhm th c kh nng nhng in t nn hot ca chng gim i, chng tham gia phn ng vi cc nhm nh chc ca x nhit cao (80oC), hoc nu nhit thp hn th phi tin hnh trong mi trng kim mnh, v vy trong tn gi thng c thm ch H ngha l nng (heat). 112

Hot ca thuc nhum monoclotriazin ph thuc nhiu vo bn cht ca nhm th c kh nng nhng in t trong vng triazin, cn kh nng ho tan v i lc ca chng th ph thuc vo gc thuc nhum. Cng nh cc trng hp khc, nhit cao i lc ca thuc nhum gim, nhng kh nng khuch tn li tng ln. V vy khi dng thuc nhum hot tnh loi ny nhum theo phng php tn trch nhit cao, mun nhn c hiu sut s dng thuc nhum cao th gc mang mu ca chng phi c i lc cao hp ph mnh vo x. Nhng gc mang mu p ng c yu cu ny l: gc mu azo, gc mu azo cha kim loi v gc mu phtaloxianin. c. Thuc nhum hot tnh l dn xut ca pirimiin Nhng thuc nhum thuc nhm ny thng l dn xut ca i- v triclopirimiin c cu to chung nh sau:
N S R NH C
4 3 5 2

C C
6

Cl N1

C Cl

Cl

Vng pirimiin c th xem nh vng triazin trong mt nguyn t nit b thay th bi mt nguyn t cacbon nn cc nguyn t cacbon km hot ng hn v loi thuc nhum ny c th nhum nhit cao hn. Trong ba nguyn t clo c trong vng piriin th nguyn t cacbon v tr s 2 hot ng hn nguyn t clo v tr cacbon s 5 v s 6. Vic tng hp thuc nhum hot tnh nhm ny c thc hin bng cch ngng t tetraclopirimiin vi gc mu antraquinon hoc gc mu nitro c cha nhm cacbonyl v cha t nht l mt nhm amin t do. d. Thuc nhum hot tnh vinylsunfon Khc vi cc nhm k trn, thuc nhum hot tnh vinylsunfon thc hin phn ng kt hp vi x si. Nhm phn ng ca thuc nhum l este ca axit sunfuric v hyroxyletylsunfon c dng tng qut nh sau: SRSO2CH2CH2OSO3Na Dng ny cha hot ng, sau khi hp ph vo x, trong mi trng kim yu, thuc nhum s chuyn v dng vinylsunfon, lm cho phn cc ca nguyn t cacbon tng ln, n tr nn hot ng. Dng hot ng mi to thnh s tham gia vo phn ng kt hp vi cc nhm nh chc ca x dng ion ho to thnh lin kt ete gia thuc nhum v x. Th d qu trnh kt hp ca thuc nhum vi x xenlulo c trnh by nh sau: SRSO2CH2CH2OSO3Na + NaOH SRSO2CH
+ CH2 + Oxen

SRSO2CH

CH2 + Na2SO4 + H2O

SRSO2CH2CH2Oxen

Thuc nhum vinylsunfon c nhiu hng sn xut vi cc tn thng phm nh remazol (Hoechst), primazin (BASF), sumifix (Sumitomo), v.v. tng hp thuc nhum hot tnh vinylsunfon ngi ta dng gc mang mu azo, gc mu antraquinon v phtaloxianin. Nhng thuc nhum dng cho len nh remalan c gc mang mu l thuc nhum axit cha kim loi. Mt hng ca vinylsunfon tng i mu t vng, , tm, xanh da tri n xanh lam v en. Hot ca thuc nhum vinylsunfon ln hn thuc nhum monoclotriazin nhng 113

li thp hn hot ca thuc nhum iclotriazin, nn n tng i bn trong mi trng trung tnh, km bn trong mi trng kim, c kh nng nhum nhit cao. Tuy c u im l mi lin kt vi x bn vng, t l lin kt ho hc vi x cao, nhng do c i lc nh nn tn trch thp; khi nhum gin on phi dng cc bin php cng ngh nh: thm cht in ly vo mng, gim dung t nhum. hn ch nhc im ny ca thuc nhum vinylsunfon ngi ta dng phng php nhum lin tc hoc c hiu qu hn na l dng phng php bn lin tc (ngm p cun ). e. Thuc nhum hot tnh c nhm phn ng l 2,3-icloquinoxalin Nhm thuc nhum ny c hng Bayer sn xut vi tn gi thng phm l levafix E, chng c kh nng phn ng tng t nh thuc nhum iclotriazin, nhng thng ch c mt nguyn t clo trong d vng tham gia phn ng nn khng c kh nng to thnh cu bc ngang gia cc mch x si. i lc ca thuc nhum vi x tng t nh thuc nhum triazin. - Thuc nhum hot tnh l dn xut ca epiclohyrin Nhng thuc nhum nhm ny c coi l thuc nhum hot tnh phn tn do hng ICI sn xut vi tn gi l procinyl dng cho x polyamit. Chng l dn xut ca epiclohyrin, trong mi trng kim s chuyn v dng epoxy c kh nng phn ng vi x. Qu trnh phn ng ca thuc nhum vi x nylon (polyamit) c trnh by nh sau: RNHCH2CHCH2 OH Cl O y: R - gc mang mu khng tan trong nc; Nyl - x nylon. Cu ni gia gc mang mu R v nhm mang nguyn t phn ng c th l mt trong cc nhm: NH, O, S, SO2. g. Thuc nhum hot tnh chc vng etylenimin Loi thuc nhum ny c tn thng phm l levafix, c cu to ho hc gn ging thuc nhum remazol. Trong qu trnh nhum trong phn t thuc nhum xut hin vng etylenimin km bn, d tham gia phn ng vi nhm chc ca x. C ch phn ng ca n vi x xenlulo c trnh by nh sau: RSO2NHCH2CH2OSO3Na
CH2 CH2
+ OH NaHSO4 + NaOH H2O NaCl

RNHCH2CHCH2 O RNHCH2CHOHCH2NHNyl

RNHCH2CHCH2 + H2NNyl

R SO2 N

CH2 CH2

R SO2 N

+ HOXen

RSO2NHCH2CH2OXen

y R - gc mang mu khng tan; HO-Xen - Xenlulo. h. Thuc nhum hot tnh l dn xut ca 2-clobenthiazol Nhm phn ng ca thuc nhum loi ny l 2-clobenthiazol c cng thc chung nh sau:

114

4 5 6 7

N S
1

Cl

Trong mch d vng ny, ngoi nguyn t cacbon v nit cn c nguyn t lu hunh. Trong mi trng kim nguyn t cao s tch ra v thuc nhum s lin kt vi x theo c ch th nucleophin. Hng Francolor sn xut loi thuc nhum ny vi tn thng phm l reatex. 4.3.3. Cc mt hng v phm vi s dng n nay c trn 1000 mu ca thuc nhum hot tnh c sn xut v ang s dng trong cng nghip dt vi gam mu rt rng t vng n en. Theo phm vi s dng, thuc nhum hot tnh c chia lm hai loi: loi nhum x xenlulo, len, t tm v loi nhum x polyamit. Theo tnh cht k thut loi th nht li chia lm ba nhm: - nhm nhum ngui, trong tn gi c ch M hay ch X, a s thuc v thuc nhum iclotriazin, chng c kh nng phn ng cao, phi nhum trong mi trng kim yu v nhit thp (25 - 30oC); - nhm nhum nng, trong tn gi thng c ch H, a s thuc v nhm vinylsunfon, mt s l thuc nhum monoclotriazin, khi nhum tn trch tr s pH ca dung dch c th trong khong 10 - 11, nhit 60oC; - nhm nhum nhit cao trong tn gi khng c k hiu g c bit hoc c ch HT, a s thuc v nhm monoclotriazin, chng c kh nng phn ng thp so vi hai nhm trn nn c th nhum tn trch 70 - 90oC trong mi trng kim mnh hn. Theo mc gim kh nng phn ng, cc mt hng thuc nhum hot tnh c th xp theo th t di y: Procion M, X c kh nng phn ng cao nht; Drimaren K, R Levafix E-A Cibacron F Levafix E Remazol Cibacron Bazilen E P Cibacron E, A, P Procion H, H-E Cibacron (reacton) T Drimaren X v Z c kh nng phn ng thp nht. Mi loi thuc nhum k trn cng c nhng mu c kh nng phn ng cao hn hoc thp hn t nhiu; th t sp xp ny ch l tng i, c dng ch yu khi thit lp cng ngh nhum. Da vo kh nng git sch phn thuc nhum b thy phn cn bm li trn vi, thuc nhum hot tnh c chia lm bn nhm: - nhm I: d git sch, khng dy mu sang nn trng; - nhm II: c mc git sch trung bnh, dy mu cht t sang nn trng; - nhm III: kh git sch, y mu sang nn trng nhiu; 115

- nhm IV: rt kh git sch, bt mu mnh sang nn trng (loi ny khng thch hp in hoa). Do c nhng u im ni bt v ti mu, bn mu v gam mu nn tuy mi ra i cha y 40 nm, thuc nhum hot tnh c cc hng ch to thuc nhum ln ca th gii sn xut. Nhp iu sn xut v s dng chng tng ln rt nhanh; thuc nhum hot tnh chim v tr hng u v tng s mu v khi lng sn phm trong s cc lp thuc nhum tng hp c s dng hin nay. Phn ln thuc nhum hot tnh c dng cho x xenlulo, phn nhum len, t tm v x polyamit ch chim 4,5 - 5% tng s thuc nhum hot tnh. Nhng u im v nhc im ch yu ca thuc nhum hot tnh c dn ra trong bng 3.8. Bng 3.8 u i m C gam mu rng Mu ti v thun sc C bn mu cao vi gia cng t Phng php nhum a dng D ti lp li mu D lm sch nc thi Gi thnh va phi Nhc im Kh git sch phn thuc nhum b thy phn Chu k nhum di Tn nhiu ho cht bn mu vi nh sng khng cao nht l cc mu v da cam

4.3.4. Thuc nhum hot tnh mi sn xut Cc mt hng chnh ca thuc nhum hot tnh c bn hnh thnh xong vo u nhng nm by mi, sau n khng ngng c hon thin v b sung thm cc mu mi v ngng sn xut cc mu khng p ng c yu cu s dng. Th d, hng CibaGeigy sn xut thuc nhum cibacron F c nhm hot tnh l flotriazin, s dng c hiu qu cao khi nhum trch vi dung t thp (1:10, 1:12). n nay c khong 300 h thng hot tnh c ng k paten ch to thuc nhum hot tnh, song cc dn xut ca triazin vn chim con s ln nht trong cc mu thng dng. Trong s ny th loi monoclotriazin chim t l cao hn v s lng mu c sn xut, chng c s dng nhum theo phng php ngm p v in hoa, ch c mt s t c dng nhum tn trch v chng c i lc nh vi x xenlulo. m rng phm vi s dng ca thuc nhum kiu monoclotriazin, nht l nhum tn trch v in hoa ngi ta bin tnh loi thuc nhum ny bng cch a vo phn t ca chng cc nhm hot tnh mi, nht l a thm nhm phn ng th hai vo phn t thuc nhum. Khi c mt nhm hot tnh th hai trong phn t th mc s dng ca thuc nhum monoclotriazin s tng 15 - 20%, gim t l thuc nhum khng lin kt vi x phi git sch. Thuc nhum loi ny cn bn mu vi cht oxy ho v vi clo, vt hn loi ch c mt nhm phn ng, iu ny cho php thit lp cng ngh ty - nhum ng thi. Theo hng ny nm 1971 hng ICI sn xut ra thuc nhum procion HE nhum tn trch, chng cha hai nhm mang mu v hai nhm hot tnh monoclotriazin. Mt hng loi ny pht trin kh nhanh, ch sau 10 nm c 25 mu c sn xut di cc tn gi: cibacron E (Ciba-Geigy), bazilen E (BASF), helanthrene D-E (Ba Lan), v.v. 116

Cng theo hng bin tnh nhng thuc nhum hot tnh thuc th h trc, t 1980 hng Sumitomo (Nht Bn) v sau l hng Glo-tex (M) v mt vi hng khc ch to ra loi thuc nhum hot tnh chromozol cha hai nhm mang mu khc nhau: nhm monoclotriazin v nhm vinylsunfon dng nhum tn trch v in hoa. c im ca loi thuc nhum hai chc nng ny l cho php nhn c mu bo ho ngay c trn vt liu xenlulo cha lm bng. Ngoi ra do c hai nhm phn ng khc nhau nn m rng c khong nhit ti u, nng cao c kh nng nhum ti lp mu, nng cao n nh vi kim, d nhum, c tn trch cao, d ghp t ba mu c bn, t nhy cm vi nhit v vi cc dung dch mui, c u mu v bn mu cao, t l lin kt ho hc vi x cao v nhiu tnh u vit khc. Thuc nhum hot tnh thng c sn xut dng bt v c n nh bng cht m ngn nga chng t ng thy phn nhm hot tnh khi bo qun. Hin nay trnh hin tng bc bi khi sn xut v s dng ngi ta a vo thuc nhum thnh phm cht chng bc bi nh: dng cc loi du khong thch hp, nh tng ca polyetylsiloxan. Gn y ngi ta thnh cng trong vic sn xut thuc nhum hot tnh cc dng khc nh: hng ICI v Sandoz sn xut thuc nhum hot tnh dng ht v dng lng. Tt c thuc nhum remazol do hng Hoechst sn xut cng dng lng. Vic nghin cu hon thin cc mt hng thuc nhum hot tnh p ng yu cu ca ngi tiu dng vn cn tip tc n gin ho quy trnh cng ngh nhum; t bn mu cao; gim nh iu kin lao ng bo v mi trng, t ng ho qu trnh nhum v.v. 4. 4. Thuc nhum baz - cation 4.4.1. Thuc nhum baz Thuc nhum baz l nhng hp cht mu c cu to khc nhau, hu ht chng l cc mui clorua, oxalat hoc mui kp ca baz hu c. Thng gp hn c trong nhm thuc nhum ny l cc dn xut ca i- v triphenylmetan, mono v iazo, polymetyl, azometyl, antraquinon v phtaloxianin. c im ni bt ca thuc nhum baz l c gam mu, mu ti thun sc v cng mu rt mnh. Song nhc im ca thuc nhum baz l cho mu km bn vi git v nh sng nn chng c dng nhum mt s sn phm dt t x xenlulo, nhum la t tm trang tr, nhum giy v dng lm mc in trong cng nghip in n. nc ta thuc nhum baz c dng rng ri nhum v in chiu ci, cc mt hng my tre v g cho mu tng i bn v p. Do i lc ca thuc nhum baz vi xenlulo rt thp mun s dng chng nhum vi may mc th phi cm mu, nhng khi cm mu (bng tanin v mui antimoan) th ti mu li gim i. Tt c thuc nhum baz u d ho tan trong nc, khi ho tan chng phn ly thnh hai ion: cation l ion mang mu, anion khng mang mu. Nh vy theo tnh cht in ho th thuc nhum baz i cc vi thuc nhum axit. Nhng thuc nhum baz thng nh sau: a. Loi iaminotriarylmetan Tiu biu ca loi ny l xanh metylen, c cng thc nh sau: 117

(C2H5)2 C

N(C2H5)2 Cl

thuc nhum ny c mu xanh lc ti, c tc dng dit khun nn c dng trong y hc thay cho iot. b. Loi triaminoiphenylmetan Tiu biu ca loi ny l auramin (cn gi l vng b), c mu vng, c dng nhum vi si bng v cm mu bng tanin, nhum t tm, nhum giy, chiu ci, g v da. Cng thc cu to ca auramin nh sau:
(CH3)2N
+

C NH2Cl

N(CH3)2

c. Loi triaminotriarylmetan Tiu biu cho nhng thuc nhum baz loi ny l thuc nhum fucsin, n l hn hp ca fucsin v parafucsin c cng thc nh sau:
CH3 H2N C NH2Cl
+

H2N C

NH2Cl

NH2

fucsin

NH2

parafucsin

Fucsin c mu ti nhng km bn mu vi nh sng nn ngi ta dng n ch to cc thuc nhum khc bng cch alkyl ho cc nhm amin t do cn li. d. Thuc nhum baz l dn xut ca xanten Tiu biu cho nhm ny l nhng thuc nhum thuc gc roamin, chng c tnh baz yu nn c th dng nhum x ng vt v c cho x bng nhng phi cm mu. Roamin c mu ti, rt thun sc ( th trng quen gi l phm cnh sen hay cnh qu) c cng thc nh sau:
(C2H5)2N O C COOH N(C2H5)2Cl
+

Nhng dn xut ca roamin m trong phn t ca n nhm cacboxyl b este ho s c tnh baz mnh hn, c bn mu vi gia cng t cao hn, mu vn ti v thun sc. 118

4.4.2. Thuc nhum cation Sau khi tng hp c x polyacrylonitrin (PAN) ngi ta tm thy mt s thuc nhum c cu to ging thuc nhum baz nhng li bt mu mnh vo x PAN, c bn mu cao vi nhiu ch tiu gi l thuc nhum cation. Chng c th xem nh cc mui amoni bc bn vi dng tng qut l R1NR3Cl, y R1, R3 l cc gc alkyl hay aryl khc nhau. Phn mang mu ca thuc nhum c th l cc gc triphenylmetan, thuc nhum metin v azo, dn xut antraquinon v phc ca ng-phtaloxianin. in tch dng ca nguyn t nit bc bn c th nm mch nhnh hoc nm trong d vng. Trong s cc anion, thng gp hn c l ion Cl v CH3SO4, chng t nh hng n tnh cht mu ca thuc nhum, nhng ng vai tr quan trng trong qu trnh ho tan thuc nhum trong nc. Nhng loi chnh nh sau. a. Thuc nhum cation mang in tch dng mch nhnh V cu to nhng thuc nhum ny gn ging nh thuc nhum phn tn, nhng khc ch chng c mch nhnh cha nhm amoni bc bn, nh m thuc nhum ho tan trong nc v c tnh baz cn thit. Nhng mui amoni bc bn ny n nh trong mt khong pH rng, chng c bn mu cao vi nh sng, nhng khng ti v thun sc bng mu ca cc nhm khc. b. Thuc nhum cation mang in tch dng nhm mang mu Nhm thuc nhum ny c mu ti hn c v c kh nng nhum mu rt cao. C nhiu kiu thuc nhum cation loi ny nhng qu hn c l nhng thuc nhum c gc oxazin, xianin polymetin v triarylmetan, cn nhng gc khc th cho mu km bn vi nh sng hoc d b thy phn. c. Thuc nhum cation to thnh in tch dng khi nhum Nhng thuc nhum loi ny khng tch in dng trong mi trng trung tnh v kim yu, n ging nh thuc nhum phn tn. Khi c mt axit cn thit trong dung dch nhum x PAN th phn t thuc nhum s kt hp proton v tr nn tch in dng nn n li c nhng tnh cht ca thuc nhum cation. Khc vi cc nhm trn, thuc nhum cation nhm ny coi nh thuc nhum phn tn nn bt mu vo x PAN kh u. 4.4.3. Cc mt hng thuc nhum cation Thuc nhum cation c sn xut dng bt v dng lng. Dng bt kh thm nc, c ho tan hn ch trong nc, li d bc bi nn ngi ta sn xut mt s mt hng thuc nhum ny dng lng cho d s dng v cn o. Vn c ngha thc t l nng cao ho tan, n nh v bn nhit ca thuc nhum ny nht l khi bo qun lu trong kho. Cng nh cc thuc nhum ho tan khc, trong nc, thuc nhum cation phn ly thnh ion. S thay i mc phn ly ca n l mt yu t quan trng iu chnh qu trnh nhum. Khi gim mc phn ly s gim lng thuc nhum hp ph vo x, nhng khi tng phn ly th c nguy c loang mu do thuc nhum bt vo x qu nhanh. Khi tng nhit nhum, mc phn ly ca thuc nhum cng tng ln, t 80 85oC tr ln thuc nhum bt vo x rt nhanh, 95 - 98oC khng quan st thy cc phn t thuc nhum cation lin hp. Khi gim tr s pH ca dung dch nhum s gim mc phn ly thuc nhum v lm chm tc bt mu. 119

Thuc nhum cation c tc bt mu khc nhau, thng c chia lm ba nhm: bt mu nhanh, bt mu chm v bt mu trung bnh. Tc bt mu vo x PAN ca chng khc nhau l do chng khc nhau v: cu to ho hc, tnh baz, phn cc ca phn t thuc nhum v c im ca anion. Nhng thuc nhum cation c sn xut trn c s cc dn xut ca antraquinon c tc bt mu vo x PAN khng cao v kh nng nhum mu ca chng cng khng cao. u im ch yu ca loi ny l c bn vi x l bng hi (hp) cao hn so vi nhng thuc nhum cation cng c gam mu xanh nhng li c gc mang mu t cc hp cht khc. Loi thuc nhum ny rt thch hp in hoa, nhum lin tc hoc nhum mt s ch phm t x PAN c yu cu phi x l hi trong quy trnh cng ngh nhum. Thuc nhum cation c u im l d phi t ba mu c bn: vng, xanh lam v , bo m nhn c u mu, c th to c cc gam mu rng. dng lng thuc nhum cation rt thun tin cho cng ngh nhum lin tc, dung dch thuc nhum n nh nhit cao. Trong mi trng axit axetic hay axit focmic v c mt cht hot ng b mt dng lng ca thuc nhum cation kh n nh. Mt hng ca thuc nhum cation mu t vng n en v c sn xut di cc tn thng phm khc nhau: Bng 3.9 Tn thuc nhum Cation Astrasol Bazacryl Maxilon. Diorlin Sandocryl Catilon, Diacryl, Daito-acryl Anylan Melacryl Lircamin Sevron Acrolon Synacryi 4.5. Thuc nhum hon nguyn 4.5.1. c im chung Thuc nhum hon nguyn l nhng hp cht mu hu c khng ho tan trong nc. Tuy c cu to ho hc v mu sc khc nhau nhng chng c chung mt tnh cht, l tt c u cha cc nhm xeton trong phn t v c dng tng qut l R=C=O. Khi b kh dng khng tan ny s chuyn v dng lyc axit, n cha tan trong nc nhng tan trong kim v chuyn thnh dng lyc baz. Do c i lc ln vi x v ho tan trong nc nn n hp ph rt mnh vo x xenlulo, mt khc n li d b thy phn v oxi ho v dng khng tan ban u. Ton b qu trnh ny c trnh by nh sau:
R C O
+ [H] + [O]

Tn nc v hng sn xut Lin X (c) v nhiu nc khc Bayer BASF Ciba-Geigy Sandoz Nht Bn Ba Lan Rumani Francolor Du-Pont ICI

OH

+ NaOH + H2O

R C

ONa

lyc axit

lyc baz

120

Do c i lc vi x xenlulo nn hp cht lyc baz bt mnh vo x, sau khi ra bt kim th li d b thy phn v dng lyc axit v oxi ho bng oxi ca khng kh v dng khng tan nguyn thy. Nh c trng quan trng k trn m lp thuc nhum ny c tn gi rt thch hp l hon nguyn. Tt c thuc nhum hon nguyn cn c cc tnh cht qu khc nh: c mu; mu ti nh: c bn mu cao vi gia cng t, vi nh sng v kh quyn; ch c bn mu vi ma st l khng cao lm. Chng c bn mu cao vi nhiu ch tiu mt mt do khi nm trn x dng khng ho tan, mt khc do phn t ca chng nhiu nhn thm nn c kh nng pht sinh cc lc lin kt mnh. Thuc nhum hon nguyn c dng ch yu nhum cc ch phm t x xenlulo hoc thnh phn xenlulo trong cc loi vi pha; chng khng c dng nhum len v t tm v qu trnh nhum phi tin hnh trong mi trng kim, nhng loi x ny s b ph hy. Mt s t thuc nhum hon nguyn cng c dng nh thuc nhum phn tn (dng khng tan nghin mn) nhum x tng hp hoc lm pigment in hoa. Trc nhng nm 70 ca th k XX thuc nhum hon nguyn chim t l kh ln trong tng s thuc nhum tng hp sn xut trn th gii (n 23%) nhng hin nay n ch chim khong 17% v gi thnh kh cao v cng ngh nhum phc tp. Theo cu to ho hc thuc nhum hon nguyn c chia thnh hai phn nhm: - thuc nhum inigoit gm inigo v dn xut ca n; - thuc nhum hon nguyn a vng. Bn cnh dng khng ho tan, d dng cho qu trnh nhum ngi ta cn sn xut ra loi hon nguyn tan. Nu nh mi n cui th k XIX ngi ta ch bit c mt thuc nhum hon nguyn duy nht l inigo tch t l chm c trng thnh n in cc nc nhit i th n nm 1940 hu ht cc thuc nhum hon nguyn quan trng c tng hp, b sung v hon thin cc phn nhm ca lp thuc nhum ny. n nay vic sn xut cc loi thuc nhum hon nguyn chng li, xu hng chung l tm cch bin tnh hoc phi ch nhng mu c cht lng cao cho d s dng. 4.5.2. Thuc nhum hon nguyn inigoit a. Inigo thc vt nhum mu xanh lam sm t nhiu th k trc y loi ngi bit dng inigo thc vt tch c t cy chm v mt s cy thuc h ny. Th k th XII Trung Quc, n , Innxia v nhiu o khc vng nhit i c cc n in trng cy chm. Sut trong th k XIX ngun nguyn liu ch yu sn xut inigo u t nguyn liu thc vt. Thnh phn ch yu ca cht mu cha trong cc loi cy h chm l Inican, n l dn xut glucozit ca inoxin. tch inigo ra t thn v l chm ngi ta thng dng phng php vi sinh di hnh thc cho ln men. Khi , di tc dng ca men, inican s b thy phn to thnh inoxin v glucoza. Di tc dng ca oxi khng kh, inoxin s chuyn thnh inigo nh sau: 121

O C6H11O5 C CH N H
inican
+

OH C H2O N H
inoxin
O H N C N H
inigo

CH

C6H12O6

OH C CH N H
+2O 2 H2O

C C

C O

Nhiu cng trnh nghin cu chng minh rng inigo c hai dng ng phn nh sau:
O C C N H C C H N

H N C C O C

H N C O
cis-indigo

O trans-indigo

Inigo l mt hp cht ho hc c th tch ra dng thun khit c mu xanh sm, khng tan trong nc, ru, ete v benzen, kh tan trong axeton v axit axetic, nhng tan c trong phenol, nitrobenzen v anilin nhit si. 290oC inigo bt u bc hi v c mu tm, 390 - 392oC n b nng chy v nhit hy. Khi b oxi ho qu mnh, inigo s b ph v cu trc phn t ban u, chuyn thnh izalin, sau chuyn thnh benzen axit picric, axit xalixilic... v mt mu. Li dng tnh cht ny ngi ta thng in ph gn trn nn inigo. b. Inigo tng hp v dn xut ca n Sau khi tm c cng thc ho hc ca inigo ngi ta tng hp c n bng nhiu phng php khc nhau, nhng v inigo ch c mt mu lam sm, m rng gam mu ngi ta tng hp cc dn xut ca inigo hay gi l inigoit. Bng cch a nhm th khc nhau vo phn t inigo s nhn c cc mu khc nhau. Inigo T c mu xanh lam nh lc; inigo xanh lc brominigo c mu tm . Trong cc ng ng ca inigo c nhiu hp cht cha nguyn t lu hunh trong phn t gi l thioinigo. Nhng thuc nhum kiu ny rt phong ph v mu sc v c chia lm hai loi: thioinigo i xng c mu v thioinigo khng i xng c mu tm. Tt c thuc nhum hon nguyn l dn xut ca inigo c c im chung l d b kh hn cc thuc nhum hon nguyn a vng. Dung dch nhum ca chng cng yu cu nng kim thp hn so vi thuc nhum hon nguyn a vng. 4.5.3. Thuc nhum hon nguyn a vng Hon nguyn a vng l loi thuc nhum c cu to phn t phc tp, cha nhiu nhn thm, nhiu nhm mch vng, a s l dn xut ca antraquinon. 122

Khc vi thuc nhum hon nguyn l dn xut ca inigo, nhng thuc nhum thuc phn nhm ny i hi iu kin kh mnh hn, nhum trong mi trng kim mnh hn v dung dch lyc baz km n nh hn, d b thy phn v oxi ho v dng khng tan ban u hn. C th xem antraquinon nh mt thuc nhum hon nguyn n gin nht din t qu trnh kh v oxi ho ca nhm thuc nhum ny. Thuc nhum hon nguyn a vng c gam mu, mu ca chng ti, c bn mu cao vi gia cng t v nh sng, ring bn mu vi ma st khng cao lm. Theo cu to ho hc thuc nhum hon nguyn a vng gm cc phn nhm di y. a. Thuc nhum l dn xut ca oxylaminoantraquinon Mu ca thuc nhum loi ny c trong di t vng n tm. Khi s dng cn lu l nhit v kim cao th nhm axyl c th b x phng ho lm cho thuc nhum b bin cht. b. Thuc nhum l dn xut ca antrimit (antraquinonimin) Nhng thuc nhum loi ny c ngha thc t hn c trong phn t ca chng cha t hai gc antraquinon tr ln, lin kt vi nhau qua nhm imin (NH) nn c tn gi nh trn. Algol booc RT l mt trong s nhng thuc nhum tiu biu ca nhm ny, c cng thc nh sau:
O

NH O

NH O

Cl O O

Cl

Do trong phn t c cha hai nguyn t clo nn mu ca n su hn v bn hn vi nh sng so vi dn xut khng cha clo. c. Thuc nhum hon nguyn l dn xut ca inantron Thuc nhum nhm ny cha cc nhn antraquinon lin kt vi nhau qua hai nhm imin hp thnh mt vng khp kn tiu biu l hon nguyn xanh lam RSN c cng thc hai dng sau:
O O H NH O HN O O H O O N N O

(1)

(2)

Thuc nhum ny c mu xanh lam ti, nhng d b qu kh. dng cu to (2) phn t ca n c thm hai vng ph nn nu c bn nhm xeton u b kh th cc vng ph ny s b ph v, thuc nhum chuyn mu v khng c kh nng oxi ho tr v 123

dng nguyn thy na. V vy khi chun b dung dch nhum phi ly lng cht kh va sao cho ch c hai nhm xeton b kh v chuyn thnh dng mui inatri trong dung dch. d. Thuc nhum hon nguyn l dn xut ca antantron Mt s dn xut ca antantron c dng lm thuc nhum hon nguyn, phn t ca chng c th xem nh gm hai nhn antraquinon ghp li. a s chng l nhng thuc nhum qu, c bn mu cao v mu ti nn c nhiu hng ch to, tiu biu l hon nguyn da cam RK c cng thc nh sau:
O Cl

Cl O

e. Thuc nhum hon nguyn l dn xut ca benzantron Nhng thuc nhum loi ny c tng hp t benzantron, c cu trc phn t a vng vng chc nn c bn mu rt cao vi git v snh sng, tiu biu l thuc nhum hon nguyn xanh lam sm O, c cng thc sau:

Dng cu to ny cn c tn gi l violantron, c mu tm m bn mu vi nh sng v clo. trng thi m mu ca vi nhum bng thuc nhum ny s c nh do n lin kt vi nc, khi sy kh mu li tr v dng ban u. Di tc dng ca nhit (v d nh sy hoc l) mu ca hu ht thuc nhum nhm ny u bin sc. Hin tng ny ch yu do cc cp in t cha dng n ca phn t thuc nhum lin kt vi nc, nhit cao nc b tch i lm cho mu b bin sc. g. Thuc nhum hon nguyn l dn xut ca antraquinonacryon Antraquinonacryon c th coi l hp cht c to thnh khi thay th mt hoc c hai nhn benzen ca acrydon bng cc nhn antraquinon. Nhng thuc nhum loi ny c bn mu cao vi git, nh sng, clo v ma st, tiu biu l hon nguyn da cam R c cng thc nh sau:
O

CO O HN

124

4.5.4. Cc mt hng ca thuc nhum hon nguyn Thuc nhum hon nguyn vn chim v tr quan trng trong s cc thuc nhum c sn xut trn th gii. Tuy gi thnh cao nhng chng c bn mu cao vi nhiu ch tiu ho l nn vn c quan tm sn xut v hon thin cng ngh nhum. Bng 3.10 dn ra cc ch tiu quan trng ca thuc nhum hon nguyn khng tan. Bng 3.10 Hm lng cht mu, % 35 - 60 phn tn t l ht ch yu, % 60 - 80 kch thc ht, m Ht ch yu Ht ln hp Ht lin hp ln nht Ht ch yu di Ht lin hp di Ht lin hp ln nht di Ht ch yu di Ht lin hp Ht ch yu Ht lin hp Ht lin hp ln nht Ht ch yu di Ht cn li 3-6 0 - 15 25 - 50 2 10 15 - 20 1 5 1 10 - 15 25 - 30 1 5

Dng sn xut Bt th nhm

Bt mn nhum huyn ph (D) Bt nho nhum huyn ph (P) Bt nho in hoa

30 - 50

90 - 93

10 - 20 10 - 12

93 - 95 khng xc nh 97 - 98

Bt nhum vixc dng khi

30 - 40

Mt s thuc nhum hon nguyn mi ch to c cha cc nhm silic hu c (Si(CH3)3, Si(C6H5)3 c bn mu cao vi clo, mt s thuc nhum hon nguyn c kh nng lin kt ho hc vi x (cubogen) cng c ch to. Thuc nhum hon nguyn khng tan thng c sn xut dng bt th nhum theo phng php lyc baz, dng bt mn phn tn cao nhum theo phng php huyn ph (k hiu D) v dng lt nho (k hiu P). Bng 3.11 trnh by tn thng phm ca thuc nhum hon nguyn do mt s hng ln trn th gii sn xut. Bng 3.11 Tn nc Anh Ba Lan CHLB c Tn hng ICI Ciech BASF Bayer Hoechst AKHA Du-Pont Mitsui Francolor Ciba-Geigy Sandoz Chemapol Dng khng ho tan Caledon, durindone Helanthrene Indanthrene Indanthrene Indanthrene Romanthrene Cubovi Sulfanthrene, ponsol Mikethren Nihonthren Solanthrene Cibanone, Ciba, tina Sandothrene Ostanthren Dng ho tan Soiedon Helaso

Italia Lin X (c) M Nht Bn Php Thu S Sec v Slovackia

Anthrasol Solindol Cubosol Potosol

Solasol, hbliasol Cibantin, tinosol Sandosol

125

Bng 3.12 Tn gi Natri hyrosunfit Rongalit C Decrolin Rongalit H Rongal A Rongal P Rongal HT Rongalit Cng thc ho hc Na2S2O4 NaHSO2.CH2O.2H2O (HOCH2SO2)2ZnO (HOCH2SO2)2Ca NaHSO2 n nh bng axetaldehit Dn xut ca axit sunfonic Rongal A + cht hot ho Hn h p c a N(CH2SO2Na)3 v NH(CH2SO2Na)2 (NH2)2C=SO2 NaBH4, KBH4 ArCCHAr (RCH2OH)SO2Na R = CH3C2H5, C3H7 Phm vi s dng Nhum v in hoa In hoa In hoa theo phng php hai pha In vi t x tng hp Nhum huyn ph hai pha v in hoa hai pha Nhum huyn ph Nhum nhit cao In hoa theo phng php ongalit potat Nhum huyn ph hai pha nhit cao lyc axit, in hoa Nhum v in hoa in hoa theo phng php hai pha in hoa

Thioure dioxit Borohydrit (hydrotex) Reductor v reductonat Dn xut ca axit oxialkylsunfonic

Do khng ho tan trong nc (dng khng tan) nn thuc nhum hon nguyn khng bt mu trc tip vo vt liu dt. Khi b kh v chuyn v dng lyc baz th n mi c i lc v bt mu vo x si. Qu trnh kh v ho tan thuc nhum hon nguyn thuc loi phn ng d th; tc ca phn ng ny ph thuc nhiu vo cht kh, nhit , tr s pH v c bit l kch thc ht thuc nhum. Kch thc ht cng nh, thuc nhum c nghin cng mn, phn tn ht cng cao th n cng c kh nhanh v hon ton. Tu theo yu cu cng ngh nhum v in hoa, ngi ta dng cc cht kh c tnh nng khc nhau. Bng 3.12 cho bit nhng cht kh thng c dng vo mc ch ny. 4.5.5. Thuc nhum hon nguyn tan Khi nhum vt liu dt bng thuc nhum hon nguyn dng khng tan (inigoit, a vng) vic chun b dung dch nhum rt phc tp, hn na dng lyc baz ca thuc nhum c i lc ln vi x bt vo x qu mnh gy nn loang mu v kh thm su vo bn trong x. n gin qu trnh chun b dung dch nhum, thun tin cho vic s dng thuc nhum nht l khi in hoa, ngi ta sn xut ra loi thuc nhum hon nguyn tan, gi nh vy v n tan trong nc. Mt khc dng thuc nhum c i lc nh vi x nn c kh nng iu chnh u mu khi nhum. Tu theo hng ch to v ngun gc chuyn ho t loi thuc nhum hon nguyn khng tan no m chng c cc tn gi khc nhau. Th d, inigozol t inigoit, solazol t solanthrene, antrazol t indanthrene v.v. Tuy khc nhau v cu to ho hc v tn gi nhng tt c thuc nhum hon nguyn tan u c th vit dng tng qut: R COSO3Na, y R - gc thuc nhum. 126

Dng ny l este sunfonat ca hp cht lyc axit ca thuc nhum hon nguyn khng tan, c mu n, ho tan trong nc. c tnh quan trng ca n l trong mi trng axit lin kt este b ph v, gii phng ra hp cht lyc axit nh sau: R COSO3Na
[H+] + H2O

R COH + NaHSO3

Hp cht lyc axit do km bn, di tc dng ca cht oxi ho k c oxi ca khng khi n chuyn v dng khng tan ban u: R COH + [O] R=C=O + H2O. k hiu thuc nhum hon nguyn tan c sn xut t loi khng tan tng ng no ngi ta dng cc ch ci sau: O - ch sn xut t inigo (origin); A - ch sn xut t thuc nhum algol, H - ch sn xut t helidon; I - ch sn xut t indanthrenel; T - ch sn xut t thioindigo. Do qu trnh nhum c thc hin trong mi trng trung tnh, hin mu trong mi trng axit v c mt cht oxi ho nn thuc nhum hon nguyn tan khng nhng c dng nhum cc loi vi, si t x xenlulo m cn c dng nhum t tm, len, x polyamit v mt vi loi x khc bng cng ngh thch hp. Do c mu ti v cng ngh n gin nn thuc nhum hon nguyn tan c dng ph bin in hoa. Nhc im ch yu ca loi thuc nhum ny l kh nhum c mu m v gi thnh cao. 4.6. Thuc nhum lu hunh Thuc nhum lu hunh l nhng hp cht mu khng tan trong nc v mt so dung mi hu c, nhng trong dung dch kim ca natri sunfua Na2S th n b kh chuyn v dng lyc baz ho tan trong nc. Ging nh thuc nhum hon nguyn dng lyc baz ca thuc nhum lu hunh c i lc vi xenlulo, c kh nng bt mu vo x, ng.thi cng d dng b thy phn v oxi ho v dng khng tan ban u. Li dng tnh cht ny ngi ta thit k nn cng ngh nhum thch hp. Sau khi nhum thuc nhum nm trn vi dng khng tan nn n c bn mu vi gia cng t t loi kh. Thuc nhum lu hunh tng i mu tr mu tm v mu thun khit th cha tng hp c; n c s dng ch yu nhum vi bng. Mc d lp thuc nhum ny c mu km ti bn mu vi nh sng v kh quyn ch t loi trung bnh, nc thi t xng nhum c mi hi v lm bn ngun nc. Song v cng ngh tng hp thuc nhum lu hunh khng qu phc tp, gi thnh r, cng ngh nhum n gin nn n vn cn l lp thuc nhum chim t l tng i cao trong tng s thuc nhum sn xut trn th gii. 4.6.1. Cu to chung Bng nhiu cng trnh v phng php nghin cu hin i ngi ta xc nh rng thuc nhum lu hunh khng phi l mt hp cht ho hc thun khit, khng c cc hng s vt l, khng th tch ring v lm sch bng cc phng php ho hc. Tuy nhin ngi ta cng i n nht tr chung l: - Nguyn t lu hunh nm trong phn t thuc nhum cc dng: S, SH, SS, SO, Sn. Trong nhiu trng hp n nm trong cc d vng nh: thiazol, thiazin, thiantren v vng azin. Vng thiazol cha ch yu trong cc thuc nhum mu 127

vng, mu da cam v mu nu. Vng thiazin ch yu cha trong cc thuc nhum mu en v xanh lc. Vng azin cha trong cc thuc nhum v nu (xem chng 2). Nhn chung, cu to ca thuc nhum lu hunh rt phc tp, n nay ngi ta vn cha xc nh c cu to ca chng mt cch chnh xc. 4.6.2. Thuc nhum lu hunh ho tan trong nc lm d dng cho vic chun v dung dch thuc nhum lu hunh khi nhum, nhiu hng trn th gii sn xut ra loi thuc nhum lu hunh ho tan trong nc. c loi thuc nhum ny gi l leuco-immedial, ho tan c trong nc lnh, khi nhum khng cn thm natri sunfua v c th nhum cho x bng, x vixc, v thuc nhum thnh phm cha sn cht kh. Hng IG ca c cn sn xut ra loi thuc nhum c tn l immedial-zol, n l hn hp ca thuc nhum lu hunh, natri cacbonat v rongalit. Anh loi thuc nhum ny c sn xut di nhn hiu Thionol M, cn Thu S th c sn xut di tn gi l neozol, elipzol. Nga gi l Thiozol BS, l dn zut bisunfit ca thuc nhum lu hunh. 4.6.3. Cc mt hng thuc nhum lu hunh Mc d c nhc im l mu km ti v bn mu vi nh sng khng cao nhng do gi thnh sn xut thp nn thuc nhum lu hunh vn khng ngng c hon thin quy trnh cng ngh v mt hng. khc phc hin tng bc bi v thun tin cho s dng ngi ta sn xut thuc nhum dng lng cng cha sn cht kh v cc cht ph tr khc na khi nhum c d dng. Trong bng 3.13 l nhng mt hng thuc nhum lu hunh c cc hng ln trn th gii sn xut. Bng 3.13 Tn nc Anh Ba Lan c Lin X (c) M Php Sec v Slovackia Thu S Tn hng ICI Ciech Cassetla Wolfen Du-Pont Francolor Chemapol Ciba-Geigy Sandoz Tn thuc nhum Thionone Sulphur Immedial, hydron sulphur Sernhicti, thiozol BS Sulfogene Sulphanol Sulphogene Pyrogene, Ciba, eklips thiotinone Thional, sandon

4.7. Thuc nhum phn tn 4.7.1. c im chung v cu to ho hc Trc y, khi mi ra i thuc nhum phn tn c tn gi l thuc nhum t axetat, l nhng hp cht mu khng tan trong nc do khng cha cc nhm cho tnh tan nh SO3Na, COONa. Nhng thuc nhum phn tn lot u sn xut vo nhng nm hai mi ca th k ny hu ht l cc hp cht mu gc azo v antraquinon. Tn gi ca lp thuc nhum ny ch rng chng c ho tan rt thp trong nc v phi s 128

dng dng huyn ph hay phn tn vi kch thc ht trong khong 0,2 - 2 m, c dng nhum loi x nhn to ght nc duy nht by gi l x axetat. Theo hng ny khi cc x tng hp ra i v dn tr thnh nguyn liu quan trng ca ngnh dt th nhng thuc nhum phn tn kiu mi c tng hp p ng nhu cu nhum cho cc x: polyamit, polyeste, polyaclylonitrin, polyvinylic v cc x tng hp khc na. V trong phn t ca thuc nhum phn tn c cha cc nhm amin t do hoc b alkyl ho (NH2, NHR, NR2 ...) c bit l c cha cc nhm amin b th bng cc gc alkyl hidroxyl (NHCH2CH2OH) nn nhng thuc nhum ny d dng phn tn trong nc hn. Theo phn lp k thut thuc nhum phn tn c th chia thnh ba phn nhm sau: - loi thng thng v c th iazo ho sau nhum; - loi cha trong phn t nguyn t kim loi; - loi phn tn hot tnh, c th lin kt vi x bng lin kt ho tr. ho tan ca thuc nhum phn tn trong nc rt thp, 25oC ch tiu ny ca a s thuc nhum ch vo khong 0,2 - 8 mg/l, cn 80oC ho tan ca chng cng ch t ti 50 - 350 mg/l l ti a. i vi nhng x tng hp ght nc th ho tan ca thuc nhum trong nc cng thp, thuc nhum cng d bt mu vo x theo c ch dung dch rn. Song t c yu cu phn b tht u, lc u l mt ngoi v sau l trong x th thuc nhum loi ny phi c nghin n dng cc mn v phn b u trong dung dch nc dng phn tn cao chng c th d dng i vo x iu kin nhum. gii quyt yu cu ny, ngoi dng bt mn phn tn cao ngi ta cn sn xut ra loi thuc nhum phn tn tan tm thi trong nc c tn thng phm l solacet. Trong qu trnh nhum, nhit cao nhm cho tnh tan tm thi ny s tch ra, gii phng phn t thuc nhum khng ho tan trong nc, phn b u trong dung dch dng n phn t v cng bt mu vo cc x nhit do ght nc nh l loi khng tan trong nc. 4.7.2. Thuc nhum phn tn loi thng thng v loi c th iazo ho sau nhum Tu theo cu to ho hc v theo mu nhng thuc nhum loi ny c chia thnh cc nhm: gc azo, gc antraquinon, gc nitroiphenylamin v cc dn xut ca naphtoquinon. Trong s nhng thuc nhum phn tn bit r cu to ho hc th 35% c gc azo, ch yu l monoazo; 27% l cc dn xut ca antraquinon; 5% l dn xut ca nitrophenylamin. Phn cn li l nhng thuc nhum cha c ch dn cu to ho hc trong Color index. Mt hng ca thuc nhum phn tn nhm ny chim tt c cc gam mu, t vng cho n en. a. Thuc nhum phn tn gc azo Trong s cc thuc nhum azo th cc dn xut monoazo aminobenzen c i lc vi axetyl xenlulo v x tng hp ln hn c, dng tng qut ca n nh sau:
A N N B N R1 R2

y R1, R2 c th l H, CH3, C2H5, C2H4OH, alkyl-OH... 129

Aminoazobenzen c mu vng, khi a vo nhn A cc nhm th m tnh nh: NO2, Cl v Br v tr octo hay para so vi nhm azo th s to cho thuc nhum c y gam mu: da cam, ti, sm, nu , cm thch v xanh lam. Nhng thuc nhum ph cp rng ri ca nhm ny c cu to nh sau: - Phn tn ta G:
O2N N N N C2H5 C2H4OH

- Phn tn R bn mu:
O2N N N N C2H4OH C2H4OH

Nhng thuc nhum ny cha nhm nitro nhn A, khng c tnh hng quang nhng sc mu su hn. Khi nhm amin nhn B b th bi cc gc alkyl hay alkylhiroxyl th tnh baz ca thuc nhum gim i, loi tr c hin tng lm su mu v tnh hng quang. Nhng thuc nhum c cu to khc s khng c hin tng k trn. Mt s thuc nhum phn tn azo cha nhm amin t do trong phn t, sau khi nhum c th iazo ho v kt hp vi mt thnh phn azo na tng thm bn mu ca thuc nhum. b. Thuc nhum phn tn l dn xut ca antraquinon Mu ca thuc nhum nhm ny ph thuc vo chng loi, s lng v v tr ca cc nhm th trong phn t antraquinon. Nhng nhm th v tr s lm cho thuc nhum bt mu vo sn phm dt mnh hn so vi khi nhm th c v tr . Nhng nhm th v tr 1,4 s lm cho mu ca thuc nhum su hn so vi khi chng v tr 1,5 hay 1,8. Theo th t lm tng mu ca thuc nhum cc nhm th c sp xp nh sau: NO < Cl < Br < OH < NH2 Nhm thuc nhum ny c cc mu da cam, mu , mu tm v a s cc mu xanh thng gp. Nhng nm gn y thuc nhum phn tn gc antraquinon c b sung thm nhiu mu mi c bn mu cao hn nhum x polyamit v polyeste. c. Nhng thuc nhum phn tn c cu to khc Thuc v loi thuc nhum ny c cc dn xut ca nitroiphenylamin, v cc thuc nhum monoarylmetin. Thuc nhum l dn xut ca nitroiphenylamin c mu vng sc xanh lc (t G n 7G), hay mu (R, 2R), chng khc vi cc thuc nhum azo c cu to tng t l c bn mu cao v khng c hin tng hng quang. Cc thuc nhum monoarylmetin c bn mu cao vi nh sng trn x axetat, nhng km bn mu khi dng cho x polyamit. Ngoi ra khi nhit cao mt s nhm nh chc c th b thy phn. 4.7.3. Thuc nhum phn tn cha kim loi Thuc nhum phn tn cha kim loi 1:2 dng nhum x polyamit c cu to gn ging nh thuc nhum axit cha kim loi 1:2 (nh ostalan, wofalan, cibalan, irgalan...). Song thuc nhum phn tn loi ny khc vi thuc nhum axit ch chng khng cha cc nhm to cho thuc nhum tnh tan. 130

Thuc nhum phn tn cha kim loi 1:1 cng ho tan trong nc, c sn xut dng bt mn phn tn cao. Chng km thuc nhum phn tn loi thng thng kh nng u mu v kh nng che ph cu trc khng u ca x polyamit, nhng vt hn chng v bn vi gia cng t, nh sng, bn vi ma st rt kh. Nhng thuc nhum loi ny c cc hng sn xut di cc tn gi thng phm nh: vialon (Bayer), avilon (Ciba-Geigy), amichrome (Francolor) v.v. 4.7.4. Thuc nhum phn tn hot tnh Nh trnh by chng thuc nhum hot tnh, a s thuc nhum lp ny c dng nhum x xenlulo, s t nhum len, t tm, nhng cng c mt vi loi dng nhum x polyamit. c im chung ca thuc nhum phn tn hot tnh l khng cha nhm cho tnh tan phn mang mu, cng c sn xut dng bt mn phn tn cao, nhng c cha nhm phn ng. Trong iu kin nhum chng s thc hin lin kt ho tr vi x v nm li trn x va dng khng tan trong nc va lin kt ho tr vi x. Nhng loi thuc nhum kiu ny chia lm cc nhm sau y: - Loi cha nhm epoxy nhum polyamit c cng thc tng qut: RCH2CHCH2 O - Loi procinylon (do hng ICI sn xut) c mt trong cc cng thc tng qut sau: RCH2CHCH2 OH Cl - Loi levafix (do hng Bayer sn xut) c dng tng qut: RSO2NHCH2CH2OSO3Na. Lc u thuc nhum ny ho tan trong nc nh cha cc nhm este sunfonat. Trong qu trnh nhum nhm ny s tch ra lin kt vi x va theo c ch ca thuc nhum hot tnh va theo c ch ca thuc nhum phn tn. 4.7.5. Mi quan h gia cu to ho hc v tnh cht ca thuc nhum phn tn Thuc nhum phn tn bao gm nhiu hp cht c cu to ho hc khc nhau nhng c c im chung l: Khng cha cc nhm to tnh tan. Trong phn t cha cc nhm: NH2, NHR2, NR1R2, OH, OR (R c th l gc alkyk, aryl, alkylhiroxyl); - Trung tnh hoc c tnh baz yu. C khi lng phn t khng ln (250 - 300), kch thc phn t nh v cu to khng phc tp. Cc tnh cht ho l ca thuc nhum phn tn cng c nhng im chung l: - phn cc ca phn t dao ng trong khong 1,5 - 7,7 debai; - ho tan trong nc rt thp (t 0,2 - 8 mg/l 25oC). Tng nhit , ho tan ca chng c tng cht t nhng khng vt qu 0,5 g/l; - Nhit nng chy ca thuc nhum tng i cao (150 - 300oC); - Cc ht thuc nhum c cu trc tinh th (i khi l v nh hnh). dng huyn ph phn tn c kch thc ht ch yu t 0,2 - 2 m, trong qu trnh nhum chng khng chu bt k mt bin i no. 131

 bn mu ca thuc nhum phn tn vi nhiu ch tiu cng l nhng tnh cht quan trng cn ch . 4.7.5.1. bn mu ca thuc nhum phn tn trn x axetat a. bn vi nh sng Ch tiu ny ph thuc vo cc yu t nh: thnh phn ca chm tia sng, hm lng oxi ca kh quyn xung quanh, m v nhit ca khng kh v loi x. Th d, c trng hp cng mt thuc nhum nhng khi nhum cho x polyamit mu s km bn hn so vi khi nhum x axetat. Tnh cht phc tp ca qu trnh ph hy thuc nhum bng nh sng khng cho php ta tm ra nhng quy lut chung, v th vic xc nh cu trc ti u ca thuc nhum b hn ch bng cc ti liu kinh nghim. Th d, nh hng ca nhm th n tnh cht ca thuc nhum c th nh sau: - cc dn xut 1-amino-4-hyroxylantraquinon khi th mt nguyn t hyro ca nhm amin bng gc dng tnh (CH3) s lm gim bn mu vi nh sng; cn khi a vo v tr 2 cc nhm th dng tnh (CH3, OCH3, OCH2CH2OCH3) bn vi nh sng s tng ln; - Trong cc thuc nhum azo, khi a vo cc nhm th m tnh v tr octo hay para so vi nhm azo hoc a vo v tr beta hay gama mch nhnh c th bng nhm amin s lm tng bn mu vi nh sng. Trong s cc nhm th m tnh th thng gp hn c l nhm nitrin (CN); - Cc dn xut mononitroiphenylamin, c bit l cc dn xut 2-nitroiphenylamin-4-sunfonamit c bn mu cao vi nh sng. b. bn mu vi git v gia cng t Thng thng th nhng thuc nhum c x hp ph d dng s c bn mu thp vi git, l trng hp nhng thuc nhum c cu to n gin, khi lng phn t thp, in hnh l cc thuc nhum mu vng. nng cao bn mu ca chng phi tng khi lng phn t bng cch a cc nhm th vo thuc nhum vi iu kin khng lm thay i i lc v sc mu ca chng. Cng v th trong cc thuc nhum monoazo khng gp nhng mu vng bn vi git, cn cc dn xut nitroiphenylamin c bn kh cao vi git. c. bn vi khi l cc vng cng nghip, mc d khng chu tc dng ca nh sng, mt s thuc nhum phn tn khi nm trn x axetat vn b bc mu. Hin tng ny thng gp cc thuc nhum mu xanh lam, cc dn xut ca antraquinon cha cc nhm amin hay nhm alkylamino v tr 1 v 4. c im ny cng c cc thuc nhum antraquinon mu , mu tm v mt s thuc nhum azo mu cha cc nhm th tng t c tnh baz. Hin tng phai mu xy ra trong cc trng hp k trn c gii thch l do tc dng ca cc kh c axit tnh cha ch yu nit oxit thot ra t khi l v cc ng c t trong. Khi ny cc nhm amin bc nht ca thuc nhum s b iazo ho, cc nhm amin bc hai s b nitro ho, cc phn t thuc nhum s b oxi ho, lm cho chng mt mu. Tnh nhy cm ca.thuc nhum phn tn vi khi l ch th hin ch yu x iv triaxetat; hin tng ny t thy hn x polyamit, polyeste v polyacrylonitrin. 132

hn ch nhc im ny ca nhng thuc nhum phn tn dng cho x axetat, ngi ta nghin cu bin i cc nhm th ca thuc nhum. 4.7.5.2. bn mu ca thuc nhum phn tn trn x tng hp a. bn mu vi nh sng bn mu ca thuc nhum phn tn trn x tng hp vi tc dng ca nh sng khng ch ph thuc vo thuc nhum m cn ph thuc vo cu to ho hc v tnh cht l hc ca x si, v th nn cng mt thuc nhum s c bn mu khc nhau khi nhum cho cc x khc nhau. Nhn chung nhng thuc nhum phn tn c in, cc dn xut ca aminoazobenzen cha t nhm th s c bn mu vi nh sng trn x tng hp vo loi trung bnh; cn cc thuc nhum phn tn c gc iazo, dn xut ca nitroiphenylamin v antraquinon th c bn mu cao vi nh sng. Khi a vo phn t thuc nhum cc nguyn t halogen th bn mu vi nh sng ca thuc nhum tng ln. b. bn mu vi git bn mu vi git ca thuc nhum phn tn trn x tng hp ph thuc vo tnh ght nc ca x nhiu hn l ph thuc vo cu to ca thuc nhum. Chng hn khi cng nhum bng mt thuc nhum phn tn ging nhau cho cc x: iaxetat, polyamit v polyeste th thy rng hai trng hp u mu ch t c bn trung bnh, cn trng hp cui th mu c bn rt cao. c. bn mu vi khi l Khi l t c kh nng lm bc mu thuc nhum phn tn trn x tng hp, iu ny c gii thch l do n khng c kh nng thm su vo bn trong x. d. bn mu vi thng hoa Nhng thuc nhum monoazo c cu to n gin bt u thng hoa ngay nhit 135 - 170oC, ngha l bn ca chng vi thng hoa khng t yu cu v khi nhum vi polyeste bng thuc nhum phn tn phi gia nhit kh nhit trn 180oC. Cc thuc nhum iazo c khi lng phn t ln hn nn bt u thng hoa 160 - 180oC. nng cao bn mu vi thng hoa ngi ta a vo phn t thuc nhum phn tn cc nhm th c kh nng ch nhit nhng khng lm gim i lc ca thuc nhum. Nhng nhm th c hiu ng ny l: SO2NH2; CONH; CN; OH; CHF2; CF3. 4.7.6. Cc mt hng thuc nhum phn tn Hin nay thuc nhum phn tn c sn xut dng bt mn phn tn cao v siu mn cha t 15 - 50% cht mu tu mt hng ca mi hng, phn cn li l cht phn tn, cht ngm v ph gia khc. Ngi ta cng sn xut loi bt nho phn tn cao cha l0 20% cht mu, phn cn li l cht phn tn, cht ngm, nc v cht chng vn cc. Bt nho c c im l mc nghin mn v phn tn ca cc ht rt cao, c n 85% s ht c kch thc di 0,5 - 2 m chng rt thch hp nhum theo phng php gia nhit kh. Cc mt hng thuc nhum phn tn c cc hng v cc nc trn th gii sn xut c trnh by trong bng 3.14.

133

Bng 3.14 Tn nc Tn hng sn xut Anh ICI Tn thuc nhum thng phm Duranol T Dispersol Serizol Serilen Synten P Rozolin, Vialon fast Palanil, cottesthrene celliton fast, perliton Polysisthrene Samorone Acetamine, celatren latil, easman, istone easman-polyester emichrome fast Sumlkaron Acetosol, esteroquinone esterophyl, amichrome fast Loi x nhum c axetat poly este poly amit + + + + + + + + + + + + + + ++ + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + +

Ba Lan Ciech CHL c bayer BASF Casselle Hoechst Du-Pont

Nht Bn Php

Sumitomo Francolor

Sec v Slovackia Chemapol Ostacet Thu S Ciba-Geigy Terasil, cibacet, efanin setaron, setasyl, avilon Sandoz Terindosol Foron Artizin Italia AKHA Tersetil
Ghi ch: du + : bt mu tt; du : bt mu khng tt.

Trn y l nhng mt hng thuc nhum phn tn ca mt s hng ln sn xut v khi qut v phm vi s dng ca chng. Khi t mua hoc thit k cng ngh nhum cn tham kho y cc ti liu ch dn phm vi s dng c th ca mi loi thuc nhum v mi mu thu c hiu qu mong mun. Cng vi s pht trin cc mt hng x tng hp v a dng ho cc loi vi pha t x tng hp v x thin nhin ngi ta sn xut cc loi thuc nhum phn tn c ch dn nhum ring cho x axetat, polyamit. polyeste, polyacrylonitrin v cc hn hp phi sn nhum cho mi loi vi pha km theo quy trnh cng ngh thch hp. Th d hng Ciba-Geigy sn xut ra thuc nhum teracoton, n l hn hp ca thuc nhum phn tn kiu terasil v thuc nhum hon nguyn khng tan dng bt mn kiu cibanone, c dng nhum cho vi polyeste pha bng theo quy trnh cng ngh thch hp. 4.8. Thuc nhum azo khng tan Thuc nhum azo khng tan cn c tn gi khc nh: thuc nhum lnh, thuc nhum v thuc nhum naphtol; chng l nhng hp cht c cha nhm azo trong 134

phn t nhng khng cha cc nhm c tnh tan nh SO3Na, COONa nn chng khng ho tan trong nc. nhum vt liu dt ngi ta phi tng hp chng trc tip trn vi t hai loi hp cht trung gian c tn gi l thnh phn azo (ROH) v thnh phn iazo (R1NNCl) theo phn ng kt hp c dng tng qut nh sau:
R ONa + R1 N Cl N
+

[OH ] 0 5oC

R1

OH + NaCl

Phn ng kt hp azo thng phi tin hnh nhit thp (0 - 5oC) bng cch lm lnh dung dch nhum hoc thm nc vo mng nhum nn thuc nhum c tn l nhum lnh, nhum . Do nm trn vi dng khng tan trong nc nn thuc nhum loi ny c bn mu cao vi gia cng t, cn bn mu vi nh sng v ma st th khng cao lm. Tuy nhin lp thuc nhum ny vn c s dng rng ri v cng ngh nhum n gin, gi thnh thp, mu ca thuc nhum ti. Kh khn thng gp phi khi chun b dung dch hin mu (thnh phn iazo) c khc phc bng cch ch sn cc hn hp n nh ca cc bn thnh phm, trong iu kin nhum hay in hoa chng mi th hin kh nng phn ng. Nh cha trong phn t nhm azo, nhm ny c th b ph v di tc dng ca cht kh lm cho thuc nhum b mt mu, nn chng c s dng nhiu in hoa theo phng php in ph gn mu. Theo cc s liu mi nht th hin nay ngi ta s dng gn 80 hp cht lm thnh phn iazo v 60 hp cht lm thnh phn azo tng hp gn 5000 mu khc nhau (theo l thuyt) trong cc gam mu t vng n en, song s mu c ng dng rng ri th khng n nh vy v ch yu nhum, in hoa vi t x xenlulo. 4.8.1. Thnh phn azo lm thnh phn azo khi nhum lnh trc y ngi ta dng -naphtol nhng v mu ca thuc nhum c to thnh t n s km bn vi nh sng cho v ma st, dung dch -naphtol li khng bn d b oxi ho. Ngoi ra kh nng hp ph ca -naphtol vo x rt thp nn sau ny ngi ta dng cc dn xut ca n. Trong k thut nhum thnh phn azo c cc tn gi khc nhau nhng ph bin hn c vn gi l naphtol, c cng thc tng qut nh sau:
OH CO NH R

y R l cc gc alkyl khc nhau. Nh vy naphtol c th xem nh dn xut aniziit ca axit naphtoic. Tu theo cu to ca gc R m chng c tn gi v cho mu cng nh sc mu khc nhau. Naphtol khng ho tan trong nc nhng ho tan trong kim gi l naphtolat hai dng nh sau:
ONa

ONa

v
CO NH R

C N R
mui inatri

mui mononatri

ONa

135

 dng naphtolat khng nhng chng ho tan trong nc m cn c i lc vi x nn c th hp ph vo x xenlulo, bo m thun li cho giai on nhum nn. Trong bng 3.15 l tn gi tng ng ca cc naphtol sn xut trn th gii. Bng 3.15 Tn nc Anh n Ba Lan CHLB c M Tn gi Brentol Amartol Naphtoelan Azonaphtol Naphtol Naphtanil Naphtazol Naphtolat Azoto Naphtoid Diatoz Dragotoi Mits Nipponaphtol Naphtazol Antonaphtol Ultrazol Naphtanllid Cibanaphtol Celcot Irganaphtol Naphto AS AS A A AS AS AS AS A AS AS AS AS AS AS AS I-AS RC RF RF RF C Tn k hiu ca thnh phn azo AN AS-BO BO A AS-BO BO BO BO ANF BO BO N3B M3B BO RN RN RN F FO AS-BG AS-BG DMA XII-BG BG RDM BG BT LB AS-LB K RM MH AB-B BS MNA AS-BS BS BS AS-BS MNA BS AS-BS AS-BS BS NB AS-BS IV-BS BS RM M LTR LTR AS-LTR O NITR

Nga Nht Bn

Php Sec v Slovackia Thu S

ITR SS

Iltalia

4.8.2. Thnh phn iazo Cu t th hai hp thnh thuc nhum azo khng tan l thnh phn iazo, c chuyn ho t cc amin thm bc nht nh phn ng iazo ho. Qu trnh iazo ho c th thc hin trong xng nhum mi khi c nhu cu s dng, song v hp cht iazo khng bn. khng th bo qun c lu nn ngi ta chuyn hp cht iazo v cc dng bn vng (dng th ng), khi nhum hoc in hoa mi chuyn n v dng hot ng tham gia vo phn ng to mu. Amin bc nht dng vo mc ch ny gi l azoamin hay baz, ch tip theo l ch mu, v ch ci ch sc s nhn c khi kt hp vi naphtol. Amin thm mun s dng vo mc ch ny cn phi c phn t nh, c kh nng iazo ho v kt hp azo cao, c kh nng to thnh mu bn v ti, khng cha cc nhm c tnh tan. Bng 3.16 l cc azo amin thng gp.

136

Bng 3.16 Tn azoamin Azoamin da cam O

O2 N

Cng thc ho hc
NO2 NH2

Azoamin da cam R
Cl

NH2

Azoamin ta 2G
Cl

NH2

Azoamin G

O2N

NH2 CH3

Azoamin 2G

O2N

NH2
CH3

Azo amin B
Cl

NH2

Azoamin hng O

O2N
OC2H5

NH2 OCH3

Azoamin xanh lam 2B

H2N

NH OC2H5

CO

Azoamin xanh lam O Azoamin ta R

H2N

NH
NH2 O2N OCH3

OCH3

a. Tnh cht chung ca cc mui iazo Cc mui iazo thu c khi iazo ho amin thm ch tng i bn trong dung dch nhit thp (0 - 5oC), nhit cao hn chng t phn hy, v vy mi khi chun b ra phi s dng ngay, trng hp mun bo qun lu hn phi chuyn chng v dng th ng ho. trng thi rn khi cha b th ng n c th gy n nu gp va chm mnh v cng khng bn, nhit cao n cng t hy. b. Cc dng n nh ca hp cht iazo thun tin cho vic s dng khi nhum v in hoa cng nh d dng cho vic bo qun, chuyn ch ngi ta sn xut hp cht iazo mt s dng th ng, nhng dng thng gp l: 137

- Mui iazol. C th n nh hp cht iazo bng cch to thnh cc mui kp c tn k thut l iazol, c thc hin bng cch a vo dung dch mui iazo cc mui v c khan nh: Na2SO4, ZnCl2 ..., sau lm kh bng cch sy chn khng s to thnh cc mui kp n nh, dng tng qut nh sau:
R N N
+

Cl ZnCl2

Ngoi cc mui v c k trn ngi ta cng dng cc mui sunfonat hu c hoc mui floborat n nh hp cht iazo. Khi s dng, iazol c ho vo nc, dng mui kp s b ph v, gii phng ra hp cht iazo dng hot ng c th tham gia vo phn ng kt hp azo. Mui iazol c dng ch yu nhum, dng trong vic in chp bn v trn giy. c. Cc dng n nh ca hp cht iazo dng cho in hoa gim nh vic chun b h in ngi ta sn xut ra cc hn hp ca hp cht iazo dng th ng v naphtol theo kiu hn hp ch sn. Sau khi in v sy vi c chng hp trong mi trng hi thch hp, khi ny hp cht iazo s chuyn v dng hot ng tham gia ngay vo phn ng kt hp vi naphtol hin mu. Nhng ch phm thng gp: iazoaminol (rapidogen), rapidozol, iazotol. Chng l hn hp ca hp cht iazo th ng ho v naphtol c n nh cao. Sau khi in ln vi, trong qu trnh chng hp c mt hi axit chng s b phn gii thot ra hp cht iazo dng hot ng v kt hp ngay vi naphtol hin mu mong mun. Nhc im chung ca cc hn hp bn vng k trn l phi hin mu trong mi trng axit, gy kh khn cho vic bo v thit b chng n mn, v vy ngi ta sn xut ra cc hn hp c th hin mu c trong mi trng trung tnh nh: neutrogen, neocotone... 4.8.3. Cc mt hng thuc nhum azo khng tan Thuc nhum azo khng tan l lp thuc nhum ra i sm hn so vi nhiu lp thuc nhum khc nn cc mt hng ca n tng i y v n nh. a. Thnh phn azo Cc sn phm dng lm thnh phn azo a dng, c nhiu hng sn xut c trnh by trong bng 3.16. Theo tng dn ca i lc i vi x bng, ngi ta o mc hp ph vo x bng (%) trong nhng iu kin nh nhau ca mt s naphtol v xp nh sau: -naphtol (8%) naphtol AS (12%) naphtol AS-D (12%) naphtol AS-OL (14%) naphtol AS-PA (16%) naphtol AS-BS (16%) naphtol AS-ITR (19%) naphtol AS-BO (21%) naphtol AS-LB (44%) naphtol AS-RL (90%) naphtol AS-S (95%). Nhng nm gn y trn th trng th gii xut hin mt s naphtol mi nh: naphtol AS-KN; naphtol AS-fau L, chng c kh nng tn trch cao nn thun tin cho vi c nhu m lin t c cc mu nu. C ng c m t s naphtol m i v i tn g i l naphtol AS-ultra, chng rt d thm t v ho tan trong dung dch kim nng cho dung dch trong sut. 138

Cng c mt s thnh phn azo khng thuc loi naphtol, l mt s thuc nhum trc tip c nhm amin hay nhm hiroxyl t do nm v tr octo so vi nhm azo, c th xem nh thnh phn azo chng tham gia phn ng kt hp vi cc hp cht iazo. b. Thnh phn iazo Cng vi vic tm kim v sn xut cc mu naphtol mi ngi ta ch to hng lot amin c kh nng bin i thnh hp cht iazo v cc mui iazo bn kt hp vi thnh phn azo trn x to thnh nhng mu ti v bn. Hin nay c khong 100 azoamin khng cha cc nhm c tnh tan c dng lm thnh phn iazo. Vic a mt vi loi nhm th c bit vo v tr meta so vi nhm amin, th d nh nhm CF3 s lm tng bn mu vi nh sng v thun sc ca thuc nhum, cn nhm sunfonamit ch lm tng bn mu vi cc ch tiu ho l. Nhng nm gn y xut hin mt s azoamin mi, trong ng ch hn c l mui nhum cc mu: ta bn AFA, RL, booc OL v BRH v mui nu nhum mu ghi bn mu BR. Gam mu xanh lam cng c b sung bng cc azoamin mi nhum mu lam sm bn mu RA v GRA. Cc tng mu tm c hon thin khi cho naphtol AS-BS kt hp vi azoamin. Gn y xut hin mt s thuc nhum azo khng tan cha kim loi, trong phn t ca nhng thuc nhum ny cha cc nhm hiroxyl, cacboxyl v alkylhiroxyl v tr octo so vi nhm amin, chng c kh nng to phc vi ion kim loi, trc ht l vi ion ng v crm. Cc hng nc ngoi sn xut azoamin dng anmin t do, dng mui iazol v dng hn hp bn vng in hoa vi cc tn thng phm khc nhau. Nhng azoamin thng gp c dn ra trong bng 3.l7. Bng 3.17 Tn nc Anh Ba Lan CHLB c Tn hng ICI Ciech Bayer Hoechst AKHA Azoamin Francolor Chemapol Ciba-Geigy Sandoz Azoamin v iazol Brentamine Fast base Fast base variogen Fast base diazol Fast base Fast base Base ciba, salt ciba base irgra Devol iazotol Rapld fast fast salt Sitazin iazotol Cibagen, thinogen Momentogen iazoaminol Brentogen Pologene Rapldogen Sitasol, neutrogen iazoaminol Naphtasogene Cibanogen, irgatral Santogen, brentogen

Italia Nga Php Sec v Slovackia Thu S

c. Nhng vn phi gii quyt khi nhum azo khng tan u im ca vic nhum azo khng tan l c th nhum t cc bn thnh phm, khng cn ch to n dng thuc nhum hon chnh nn gi thnh thp hn so vi cc loi thuc nhum khc. Song vn phc tp l ch phi chn c loi bn thnh phm ph hp p ng hng lot cc i hi phc tp nh: 139

- d hp ph ln mt x v khuch tn su vo x; - c tc phn ng cao hin mu, tho mn cc iu kin cng ngh nhum gin on, lin tc v in hoa; - iu kin phn ng va phi, khng lm tn thng n x si... V vy ngoi nhng bn thnh phm tng hp thuc nhum azo khng tan truyn thng, bt u s dng nhng loi khc nh: phtaloxiamin, aroyleniminazol. Gam mu ca thuc nhum azo khng tan thiu mu vng, xanh lam thun khit v xanh a tri. Mu ca chng ch t cp trung bnh v kh vi tc dng ca gia cng t, ma st v nh sng; thua cc chi tiu ny ca thuc nhum hot tnh v hon nguyn. Mt trong nhng bin php nng cao bn mu ca thuc nhum azo khng tan vi git v ma st l dng cc bn ch phm c kh nng tng tc ho hc vi x, v vy thay cho cc azoamin thng thng (thnh phn iazo) ngi ta dng cc este ca 4--hydroxyletylsunfonyl-2-aminoanizol sunfonat c cng thc H2NRSO2CH2CH2OSO3Na tn dng kh nng phn ng vi x ca nhm vinylsunfon (H2NRSO2CH= CH2) khi x l trong mi trng kim. 4.9. Thuc nhum pigment 4.9.1. c im chung Pigment l nhng hp cht mu c cu to ho hc khc nhau c c im chung l khng tan trong nc do trong phn t khng cha cc nhm cho tnh tan (SO3H, COOH), hoc cc nhm ny b chuyn v dng mui bari, canxi khng tan trong nc. Mt s pigment hu c tuy khng tan trong nc nhng ho tan trong mt s dung mi hu c c dng nhum du m, xng, sp. a s pigment c bn mu cao vi nh sng v bn vi nhit cao: khng b di tn bt mu sang phn vt liu trng, c kh nng bao ph cao v thun sc, ti mu. Pigment cc loi u c nghin siu mn, c kch thc ht nh hn 1 m, c sn xut dng phn tn cao hoc bt nho cha 15 - 25% pigment nguyn cht, phn cn li l cc ph gia. Pigment c s dng nhiu trang tr b mt (nhum v c bit l in hoa) cc sn phm dt v mt s sn phm khc (giy, da cao su, cht do), n cn c dng nhiu trong cng nghip sn, n lot v nhum cht do dng khi. Di y l mt s loi pigment hu c thng gp. 4.9.2. Pigment azo L nhng pigment cha nhm azo trong phn t, a s l mono azo, c cc gam mu vng, da cam v , cn cc mu khc t gp hn. Theo cu to ho hc pigment azo c chia lm cc loi sau. a. Loi dng cho nhum v in hoa b mt vt liu Khi ch to loi pigment ny ngi ta thng dng -naphtol v naphtol lm thnh phn azo kt hp vi cc thnh phn iazo c cu to khc nhau. Tu theo loi nhm th v v tr nhm th c trong thnh phn iazo m pigment s c mu sc v bn mu khc nhau. Sau y l mt vi pigment tiu biu. Pigment da cam bn mu, ch to t 2,4-initroanilin v 2-naphtol c cng thc sau: 140

HO O2N N NO2 N

Pigment ti 4G, ch to t 2-5-icloanilin v aniziit ca xit 2-oxi-8-naphtoic c cng thc sau:

HO Cl Cl N N CO NH OCH3

Pigment vng bn mu nh sng ch to t 3-nitro-4-toluiin cho kt hp vi anilin ca axit axetoaxetic, c cng thc sau:
NO2 H3C N N CO CH3 CH CO NH

b. Pigment azo dng nhum cht bo, cao su v cht do Mt s pigment azo ho tan tt trong mt s dung mi hu c, du, m v sp c dng nhum cc vt liu ny. ho tan trong dung mi hu c ca chng s tng khi trong phn t cha nhiu nhm alkyl v cc gc aryl hiro ho. Nhng thuc nhum ho tan trong cht bo th yu cu chung l phn t ca chng phi cha mt hoc mt s nhm chc c tnh baz (nhm amin t do hoc b th). Mt s pigment iazo c mu ti, bn nhit, bn nh sng, t b di tn, khng ho tan trong dung mi hu c, c dng nhiu nhum cao su v nhum cht do dng khi (polyvinylclorua, polystirol, nha amin...). Di y l nhng mu tiu biu. Mu nu R
N N NH2 NH2

Mu sm

OH N

H3C N N

H3C N

Thuc nhum ny cn c dng trong cng ngh thuc sng to khi mu tm. Mu en
N N N N NH NH C CH3 CH3

c s dng nhum cht do. 141

4.9.3. Pigment l mui khng tan ca thuc nhum tan trong nc Mt s pigment c th ch to t nhng thuc nhum ho tan trong nc nh thuc nhum baz v thuc nhum axit bng cch chuyn chng v dng mui khng tan. Chng c ch to hoc bng cch x l thuc nhum thnh phm vi cc mui bari, canxi, molipen, vonfram... hoc bng cch a cc mui ny vo khi phn ng kt ta thuc nhum thnh pigment. a. Trng hp ch to t thuc nhum axit Pigment ch to t thuc nhum axit ch yu l loi monoazo, tu theo cu to ho hc v cu trc tinh th ca n. Nhng thuc nhum cha nhm sunfonat (SO3Na) v tr octo so vi nhm azo th s to thnh vi ion bari v canxi km ho tan trong nc hn c, khng ho tan trong dung mi hu c v cht bo. nhn c mu da cam v mu ngi ta dng thnh phn azo l -naphtol (nu thnh phn iazo c cha nhm SO3H), -naphtolsunfonic (mui P, mui G, axit -hyroxynaphtoic, dn xut benzoyl ca axit K). lm thnh phn iazo thng dng dn xut ca anilin cha nhm metyl halogen. bn mu v sc mu ca pigment s tng ln khi trong thnh phn iazo c cha nhm metoxi, nhm nitro v nhm halogen, chng hn khi kt hp cc thnh phn iazo tng ng vi axit P th s nhn c pigment ca bari bn vi nc v sc mu rt ti. Th d: Pigment tm B
SO3Ca1/2 H3C N N HO COOCa1/2

Mu ca pigment ny bn vi nh sng, bn vi nhit cao, kh ho tan trong nc v trong dung mi hu c. b. Pigment t thuc nhum baz gc arylmetan Trong nhiu trng hp thuc nhum baz gc arylmetan km bn mu vi nh sng c th chuyn thnh dng kt ta khng tan ch to pigment c bn mu nh sng rt cao. kt ta loi thuc nhum ny ngi ta dng cc axit d th a chc. Pigment thu c khng tan trong nc v dung mi hu c, c bn mu cao vi nh sng, c dng nhiu trong cng nghip in n, in trn tn v st ty, v trn knh, lm thuc mu trong hi ho, lm bt ch mu, in giy, ba v nhiu mc ch khc. u im ca loi pigment ny l mu rt ti. Trong s cc axit d th ngi ta thng dng: axit photphomolipenic: axit photphovonframic: axit photphovonfram molipenic: H7[P(Mo2O7)6] H7[P(W2O7)6] H7[P(W2O7)4(Mo2O7)2].

Khi tng tc thuc nhum baz vi cc axit ny s nhn c kt ta khng tan trong ch c bn nguyn t hyro ca axit b th bi gc thuc nhum, nn pigment thu c l mui axit tnh. Di y l nhng mu thng gp. Pigment xanh lc: t thuc nhum baz xanh lc ti v axit photphovonfram molipenic c cng thc nh sau: 142

(C2H5)2N C

N(C2H5)2
H3 P(W2O7)4(Mo2O7)2

Tng t nh vy ngi ta cng ch to: Pigment xanh lam R t thuc nhum baz xanh lam R Pigment hng G Pigment Pigment tm t roamin G t roamin 3B t thuc nhum baz tm R.

4.9.4. Pigment t thuc nhum hon nguyn khng tan Thuc nhum hon nguyn khng tan do c nhng tnh cht u vit nh: c mu ti, bn mu cao vi nh sng. khng ho tan trong nc v nhiu dung mi hu c, bn nhit nn cng c s dng ch to pigment. Nhng mu c dng nhiu phn ln l nhng mu ti nh: hon nguyn da cam nh: hon nguyn da cam nh RK, hon nguyn da tri O hoc thioinigo RK, thioinigo nu G, thioinigo tm B... (xem (thng thuc nhum hon nguyn). Do gi thnh ca thuc nhum hon nguyn t hn so vi cc loi pigment khc nn vic s dng lp thuc nhum ny lm pigment ch hn ch trong mt s mu p. 4.9.5. Pigment phtaloxiamin Phtaloxiamin l hp ch t mu c phm vi s dng rt rng, dng vo nhiu mc ch khc nhau. Loi pigment phtaloxianin khng ho tan trong nc dng ch to mc in dng cho cng nghip in n, thuc mu trong hi ho, sn du, nhum cao su, cht do v hin nay ch to pigment dng cho in hoa ln hng dt. u im ni bt ca pigment phtaloxianin l c mu ti, nhun sc, cng mu cao, cc ch tiu bn mu vi nh sng, kim, axit u t cao v tri hn hn cc lp thuc nhum khc. bn nhit cng rt cao. 4.9.6. S dng pigment trong cng nghip dt Trong cng nghip dt cc loi pigment azo, phtaloxianin v hon nguyn c s dng nhiu nhum, in hoa vi v cc sn phm dt. u im ca vic s dng pigment l cng ngh tng i n gin, c th dng cho tt c cc loi vi, c th phi trn cc loi pigment vi bt k t l no nn cho php m rng gam mu. Ngoi ra hu ht cc loi pigment u c kh nng nhum mu cao, mu ca chng bn vi git r v nh sng. Mt hng nhum v in hoa rt rng bao gm vi v cc sn phm may mc, trang tr v vi cng nghip. Nhc im ca phng php nhum v in pigment l mu km bn vi ma st kh v t, vi t nhiu b cng. a. Trng hp s dng pigment nhum V pigment khng c i lc vi x si nn khi s dng n nhum cng nh in hoa phi dng mng cao phn t gn n vo vi, y l im c trng ca phng php 143

nhum ny. Thnh phn mang nhum gm c: pigment dng siu mn, cht to mng, cht to lin kt ngang, xc tc v cht lm mm. Cht to mng v cht to lin kt ngang phi d thm vo x trc khi a t, c kh nng to thnh mng bn gn cht pigment vo vi: cn trong sut, mm do, bn vi cc tc dng ho l, khng b bin i khi bo qun. Nhng cht bn a t c dng vo mc ny thuc dn xut ca vinylic, ankit, cacbamit v acrylic. Cc dn xut ca acrylic c s dng rng ri hn c. Th d nh latex CKC-65GP v emulcryl (do Nga sn xut). Cu t lm nhim v to cu to mt li gia cc x si thng dng loi dn xut metylol ca ur v melamin. Sau khi ngm p (n mc ch cha 60 - 80% m) vi c sy kh (60 - 90oC) v i ngay vo gia nhit 140oC (2 - 3 ph), 180oC (1 ph) v 200oC (30 s). Trong iu kin ny hp cht bn a t s chuyn thnh mng cc mng gn pigment vo vi, sau khng cn git sn phm. Cht to mng trong nhiu trng hp c s dng kt hp h chng nhu, chng co, gi np v vy vic nhum pignent thng kt hp vi h hon tt. b. Trng hp s dng pigment in hoa Hin nay phng php in pigment c s dng rt ph bin in hoa vi v nhiu loi sn phm dt v cng ngh n gin v c th in cho bt k loi vi v sn phm dt no: Cng ging nh khi nhum pigment, h in gm c: pigment c nghin siu mn nho, cht to mng v to cu trc mt li c tn gi thng phm l bin (binder) hay fix (fixer). Th d nh: metazin, latex DMMA-65-1GP, sandye binder OL, ryudye binder 450... Cht lm mm nh luprimol SIG, ibutylphtalat... Thnh phn quan trng ca h in pigment l h. V dng cht to mng gn thuc nhum vo vi nn khng th dng cc loi h thng thng t cao phn t thin nhin v cao phn t tng hp nh khi in bng cc lp thuc nhum khc. Loi h thch hp cho in pigment l h nh tng du trong nc hoc nc trong du (OW, WO). Sau khi in v sy nc v du u bay hi. khng li mng h trn vi, khng lm cho vi cng. Song khi dng loi h ny c th gy ho hon nn gn y ngi ta s dng h tng hp c hm lng cht kh rt nh vi tn thng phm l lutexal HP v HSD. Hm lng cc loi h ny trong dung dch ch chim 2 - 5% khi lng chung ca h cng c cn thit. 4.9.7. Cc mt hng ca thuc nhum pigment Thuc nhum pigment ca mt s hng sn xut v bn trn th trng th gii c tn gi nh trong bng 3.18. Bng 3.18 Tn nc Ba Lan CHLB c Tn hng Ciech BASF Bayer Hochst ACNA Lamberti Mineva Tn thng phm Pigment poloprint Helizarin Acramin Imperon Pigment Velesta Lifbond Mineprint

CHLB Nga Itatlia

144

Bng 3.18 (tip theo) Tn nc M Tn hng Inmont Hilton-Davis Roma Verona CFMC Ciba Tn thng phm Hlfast (type O v type W) Lifebond. seabond Questrol Acramm Oritex, ryudye pigment Neopralac Versaprint Microfix, Orema Oremasin

Nht Bn Php Sec v Slovakia Thu S

Ngoi loi pigment thng thng ngi ta cn sn xut ra mt s mt hng pigment c tnh hunh quang, khi nhum v in ln vi di tc dng ca nh sng mt tri n s pht ra cc tia hunh quang lnh cho mu ti v rc r. 4.9.8. S dng pigment vo cc lnh vc khc Ngoi vic s dng nhum v in hoa trong cng nghip dt, s dng nhum cht bo, cht do v cao su nh trnh by trn, pigment cn c s dng vo nhiu lnh vc khc na. Nhng loi pigment c mu ti, c bn mu cao vi nh sng nh: pigment phtaloxianin, pigment ca thuc nhum hon nguyn v mt s pigment gc azo bn mu c dng ch to thuc v dng trong hi ho. Nhng loi pigment c bn mu cao vi nh sng: pigment ca mt s thuc nhum axit, pigment phtaloxianin, pigment ca thuc nhum hon nguyn, c dng sn xut bt mu cao cp trong xy dng. Nh chng c kh nng ph b mt cao, cng mu cao hn rt nhiu so vi bt mu t oxit kim loi nn liu lng dng thp hn nhiu so vi bt mu v c. Chng c s dng lm bt mu v sn mu qut tng, men mu ca vt liu trang tr khng nung (gch bng). Nhng loi pigment c mu ti, c nh hunh quang cao nh pigment l mui bari ca thuc nhum baz v nhng pigment khc c cht lng tng t c s dng ch to cc loi mc mu dng trong cng nghip in vn ho phm, ch mu, mc in trn bao b bng giy v bng cc loi mng PE, PP, PVC, mc in ln kim loi. Nhng loi pigment c mu ti, c bn mu cao vi nh sng v dung mi hu c c dng pha sn mu. Mt s loi pigment c mu ti, lm sch tp cht, khng c v khng gy d ng cho da c s dng ch to m phm nh: son mi, phn mu, kem mu trang im. 4.10. Cht tng trng quang hc 4.10.1. Gii thiu chung Trong cng nghip dt ty trng vi si ngi ta dng bin php ho hc, ch yu l dng tc dng ty ca cc cht oxi ho nh: natri clorit NaClO2, natri hipoclorit NaClO, hyroperoxit H2O2, axit peroxiaxetic CH3COOOH. Nh phn ng oxi ho xy ra trong qu trnh ty m cht mu c trn vi si b ph hy thnh phm vt khng mu, trng ca vi c nng ln. 145

Nhng sau khi ty trng ho hc trng ca vi cao nht cng ch t 82 - 85% so vi trng tiu chun (100%), trn mt vi v sn phm dt hy cn sc vng nht (pht vng) hoc pht vng nu, lm cho vi c cm gic trng c. kh sc vng cn li v nng trng ca vi ln na, trc y ngi ta vn dng bin php l bng cch x l vi hay qun o trng vi dung dch thuc nhum axit c mu xanh lam hoc mu tm lam nht, nhng sc mu ny c tc dng lm trit tiu sc vng cn li trn vi lm cho vi c cm gic trng bic. Song bin php ny khng cho hiu qu cao v khng bn vi nh sng, khng bn vi git, sau mt vi ln git li phi l li. 4.10.2. Cu to v tnh cht Nhng nm gn y nng cao trng ca vi ngi ta s dng ph bin loi hp cht gi l cht tng trng quang hc, chng l cc hp cht hu c trung tnh, khng mu hoc c mu vng nht, c i lc vi x si. c im c bit ca chng l khi nm trn x si chng c kh nng hp ph mt s tia trong min t ngoi ca quang ph v phn x ra nhng tia c bc sng di hn ch yu l tia xanh lam v tia tm trong min thy c ca quang ph mt tri. Nhng tia ny chnh l tia b tr ca tia vng cn li trn vi thnh tia trng theo quy lut b tr mu. V vy cc loi vi, si sau khi l bng cht tng trng quang hc c trng rt cao (gn 100%) v c nh hunh quang xanh bic. V qu trnh tng trng da vo tc dng quang hc nn hiu qu ca n ch c pht huy y di tc dng ca nh sng mt tri. Trong nh sng nhn to hiu qu ca n b hn ch. Cht tng trng quang hc u tin c Krais (ngi c) tm ra vo nm 1929, c tn gi l resculin (1) trch t cy d di, c tc dng tng trng nhng khng c i lc vi x si nn khng tr thnh thng phm. Mi nm sau Meyer (ngi Anh) s dng -metylumbelliferon (2) lm cht tng trng cho hng dt, cng thc cu to ca chng nh sau:
H HO HO C O C H C O

CH3 C HO O C H C O

(1)

(2)

Tuy cha xc nh c mi lin quan gia cu to ho hc v kh nng pht hunh quang ca cht tng trng quang hc nhng ngi ta khng nh tng trng cc hp cht ny phi cha khng di bn mi lin kt ni i cch (C=CC=CC=CC=C) v khng c mt nhng nhm c trng to mu nh thuc nhum. Hin nay nhiu cht tng trng quang hc c tng hp t cc dn xut ca stinben (3) benziin (4) v pirazol (5):
HC CH N NH

CH

CH

H2N

NH2

HC

(3)

(4)

(5)

c th dng vo mc ch tng trng cho hng dt, cht tng trng quang hc cn phi c i lc vi x si, ngha l phi c kh nng lin kt vi x v c th coi nh thuc nhum trng. iu ny i hi phn t cht tng trng quang hc (loi dng cho 146

x xenlulo) cng phi c phn t thng, phng v c chiu di nht nh d tip cn vi cc mch phn t ca xenlulo v pht sinh ra cc lc lin kt mnh gi chng li trn x ging nh thuc nhum trc tip. Loi cht tng trng quang hc dng cho cc x protein c tnh axit hay tnh baz khi tip cn vi mch keratin, mch fibroin th c kh nng to thnh mi lin kt ion vi nhm cacboxyl hay nhm amin ca x si. Ring loi cht tng trng dng cho x tng hp th phi chn loi khng ho tan trong nc, c nghin siu mn v phn tn cao ging nh thuc nhum phn tn. Di y l mt s cht tng trng quang hc thng gp. Blancophor P (CI-30) (do hng Bayer sn xut) c ch to bng cch cho arylizoxianat tc dng vi iaminostinben-isunfoaxit v sau chuyn thnh dng mui natri. Sn phm s cha hai gc ure th hai nguyn t hyro nh sau:
NH CO NH CH SO3Na CH NaO3S NH CO NH

Blancophor B (do hng Bayer sn xut) c ch to bng cch ngng t iaminostinbenisunfoaxit vi hai phn t clorua xianua, sn phm thu c cho tc dng vi hai phn t anilin v chuyn v dng mui tan, c cng thc cui cng nh sau:
NH C N N C OH C N NH CH SO3Na CH NaO3S NH C N N C OH C N NH

Blancophor B tng trng cho vi bng, c nh xanh lam ti, rt bn mu vi nh sng. Tng t nh vy, khi trong phn t cht tng trng quang hc c cha vng triazol th n s bn vi cho v cho php va ty trng ho hc bng dung dch natri hipoclorit va tng trng quang hc. Th d, blancophor c cng thc sau:
N NaO3S N N CH CH N N N SO3Na

Blancophor WT (CI-18) c ch to bng cch ngng t ure vi benzoin v sau sunfo ho, c cng thc cui cng nh sau:
NaO3S C NH CO C NH SO3Na

Blancophor WT c dng tng trng quang hc cho len v t tm, n bt vo x tng t nh thuc nhum axit. 4.10.3. Cc mt hng cht tng trng quang hc v phm vi ng dng Cht tng trng quang hc hin nay c s dng kh rng ri, l cc ch phm dt, tng trng cho x nhn to, x tng hp, dng trong cng nghip giy, dng trong 147

cng nghip sn xut bt git v x phng, trong cng nghip da v cng c s dng trong cng nghip sn xut cht do. Khi s dng chng cn nm vng tnh nng v iu kin cng ngh l pht huy y hiu lc ca n. a. Cht tng trng quang hc dng cho cc loi vi v vt liu t xenlulo Blancophor P, R, B, RG Leucophor R, S Svitex R, RBS, SI Tinopal B, SP Mikephor BX (hng Bayer sn xut (hng Sandoz sn xut.) (hng Ciba sn xut) (hng Geigy sn xut) (hng Mitsui sn xut) v cc loi tng t.

Khi dng nhng cht tng trng quang hc ny ch cn ly 0,05 - 0,5% so vi vt liu, nhit 40 - 50oC v tt hn c l a vo dung dch 5 g/l mui n. C th thc hin trong mi trng kim yu hoc trung tnh. Qu trnh tng trng quang hc cho cc loi vi xenlulo c th thc hin sau khi ty trng ho hc, hoc kt hp vi ty trng ho hc dng cho nhng cht bn vi tc dng oxy ho) hoc kt hp vi qu trnh h hon tt. Di y l nhng cht tng trng quang hc bn vi tc dng ca cht oxy ho, c th a vo dung dch ty trng ho hc. Bn vi natri hipoclorit: CI-fluorescent brightrner 41 47 59 Bn vi hyro peroxit: CI-fluorescent brightener 19 23 30 42 47 49 54 59 104 142 Bn vi natri clorit: CI-fluorescent brightener 41 47 59 Trong cng nghip giy, cht tng trng quang hc c a vo trong b cha bt trc khi xeo. b. Cht tng trng quang hc dng cho len, t lm v da Blancophor WT (hng Bayer sn xut) Leucophor W (hng Sandoz sn xut) Tinopal WR (hng Geigy sn xut) 148

Ultraphor WT Svitex WS

(hng BASF sn xut) (hng Ciba sn xut)

Qu trnh tng trng cc loi vt liu t protein ny c thc hin 40 - 50oC vi hm lng cht tng trng quang hc trong khong 0,25 n 2,5% so vi vt liu, trong dung dch 5% axit fomic 85% hay axit axetic 80%. Vi cc vt liu t x polyamit cng tin hnh tng t nh vy. c. Cht tng trng dng cho x tng hp X tng hp c trng nht nh, nhng cc sn phm dt t loi x ny mun t c trng cao vn cn phi l quang hc. Cc cht tng trng quang hc dng cho loi x ny khng ho tan trong nc c sn xut dng bt mn phn tn cao vi cc tn gi nh: Uvitex EBF Uvitex ERN-P (hng Ciba-Geigy) (hng Ciba-Geigy)

Qu trnh tng trng quang hc cc loi vi t si tng hp c thc hin hoc l nhit cao, p sut cao (130 - 150oC, 2 - 8 at) hoc l bng phng php gia nhit kh 180 - 200oC trong thi gian 2 - 3 ph, hoc kt hp vi qu trnh h chng nhu, chng co. d. Cht lng ca cht tng trng quang hc Cht lng ca cht tng trng quang hc c nh gi ch yu bng kh nng pht hunh quang t trng cao v nh cao. Ngoi ra chng cn phi bn vi git nh sng, bn vi tc dng ca nhit, vi dung dch axit v nhiu tc nhn ho hc khc na Mt s cht tng trng quang hc dng cho vi xenlulo km bn vi git v nh sng (ch t cp 2 - 3 trong thang nm cp) nn ngi ta a vo trong x phng bt, x phng kem mt lng nht nh loi cht ty trng ny, nh vy mi ln git qun o li c gia tng trng t dung dch git. 4.11. Thuc nhum dng cho cc ngnh khc Ngoi vic s dng cho ngnh dt, thuc nhum cn c dng cho cc ngnh khc nh: nhum lng th, nhum da, nhum cao su, nhum cht do, nhum x dng khi, ch to mc in v.v. Di y l khi qut v tnh cht v phm vi ng dng ca thuc nhum vo cc mc ch trn. 4.11.1. Nhum lng th Lng th thng c nhum dng cc tm da nguyn lng, y l loi nguyn liu qu t, c thnh phn ho hc v cu to ging nh keratin len nn vic nhum chng cng dng cc loi thuc nhum len. Lng th thng c cc mu thin nhin khng p, km bn mu, khng ti v khng ng u trn ton tm, nh qu trnh nhum m ngi ta c c nhng tm lng bn mu, mu ti theo s thch ca ngi tiu dng, tng v p bn ngoi, tng gi tr sn phm. Qu trnh nhum lng th d bng loi thuc nhum no cng phi bo m khng nh hng.n bn ca lng v da nn thng c tin hnh nhit thp (30 - 35oC) v khng vt qu 55 - 60oC trong mi trng trung tnh, axit yu hoc kim yu. Vic nhum tc cng c yu cu tng t nh vy. Trc khi nhum lng th cn qua cc bc x l sau y: - git sch m v cht bo bng dung dch cht hot ng b mt v Na2CO3; - ty sch mu thin nhin bng tc nhn kh hoc oxi ho; - clo ho lng mm mi v tng kh nng hp ph thuc nhum; 149

- x l vi dung dch mui kim loi nng (tu loi thuc nhum) to thnh phc khng tan vi thuc nhum trn lng. nhum lng th c th dng thuc nhum trc tip thuc nhum axit (loi thng thng v loi axit crom), thuc nhum hot tnh v thuc nhum oxy ho. Di y l nguyn tc s dng cc loi thuc nhum ny. a. Dng thuc nhum trc tip Thuc nhum trc tip t c s dng nhum lng th do chng c phn t ln, kh khuch tn su vo trong li lng. Nhng nm gn y ngi ta c s dng mt s thuc nhum trc tip c bn mu cao vi nh sng v dng cc cht tng cng qu trnh nhum c hiu gy trng n lng v dn thuc nhum vo su li lng nh: trietanolamin, propylen cacbonat, syntamin DT-18, Syntanol DC-10 v.v. Khi nhum loi vt liu ny cn phi chn nhng thuc nhum trc tip c ch dn dng ring cho lng th. Qu trnh nhum c thc hin trong mi trng axit yu nhit 50 - 55oC. nhum cc mu en c th x l lng vi dung dch nhm etylen iamin tetraaxetat trc v sau nhum bng thuc nhum trc tip mu en. b. Dng thuc nhum axit (loi thng thng) C ch gn mu ca thuc nhum axit vo lng th tng t nh khi n gn mu vo len v t tm (bng lin kt ion), nhng qui trnh nhum th c mt s im khc. l trong qu trnh nhum khng c tng nhit qu 60oC bo v cht lng ca phn da. cho thuc nhum d khuch tn vo x, trc khi nhum, lng thng c clo ho: Lng qua clo ho d bt mu bng thuc nhm axit hn, mu bn v p hn, c th nhum nhit 40 - 60oC. Qu trnh nhum c thc hin trong mi trng axit yu (axit axetic, axit fomic) vi tr s pH khng di 4,5. c. Dng thuc nhum axit crom v axit cha kim loi Thuc nhum axit crom do c bn mu cao nn c s dng nhiu nhum lng th cc gam mu nu, be hng v mu en. Qu trnh nhum c thc hin theo phng php nhum trc, crom ho sau hoc nhum v crom ho ng thi trong mi trng axit yu. Thuc nhum axit cha kim loi 1: 1 v 1: 2 c dng nhum lng th nhiu hn so vi loi thuc nhum axit crom, qu trnh nhum c thc hin trong mi trng trung tnh hoc axit yu. d. Dng thuc nhum hoi tnh nhum nhng tm da lng t bn mu cao vi git, nh sng v c ti mu cao ngi ta cng dng thuc nhum hot tnh loi c ch dn dng cho len. Qu trnh nhum c thc hin trng mi trng axit vi pH = 4,5 v nhit 40oC. e. Dng thuc nhum oxi ho Loi thuc nhum ny cha c mu hon chnh, chng l nhng hp cht thm khng mu hoc c mu nht, c th xem nh chng cn l phm vt trung gian. Vic tng hp thnh mu mong mun c thc hin ngay trn tm lng hoc trn tc nh qu trnh oxi ho nn c tn gi l thuc nhum oxi ho v c sn xut vi cc tn thng phm nh: ursol, furol, vulfurol, furein v ursatin v.v. Cc hp cht thm c dng nhiu nhum lng th v nhum tc l p-phenyleniamin (nhum mu en), 2,4 iaminotoluen (nhum mu nu), 4-nitro-1,2-phenyleniamin v cc hp cht tng t. c im chung ca cc hp cht ny l d b oxy ho 150

 to thnh hp cht c cu to quinoit, khi b oxy ho mnh hn bng hyroperoxit th chuyn thnh hp cht c mu. Th d, khi oxi ho o-, p-phenyleniamin v o-, p-aminophenol th giai on u s to thnh quinonmonoimin v quinoniimin theo s sau:
OH NH2
OH
+ O2 H2O

+ O2 H2O

O NH
O

NH2

;
NH2
NH2

+ O2 H 2O

NH NH
NH

;
NH

+ O2 H 2O

NH2

NH2

NH

Quinonmonoimin v quinoniimin l nhng hp cht khng bn c kh nng phn ng cao, d t trng hp to thnh thuc nhum thuc nhm azin, c dng tng qut nh sau:
O
3

O N
N N

N O
N N

NH
NH 3 NH

Khi oxi ho ng thi cc amin thm vi amin thm cha nhm phenol th xy ra qu trnh a t v thuc nhum s c to thnh, gn cht vo vt liu. Cc amin thm thng dng l inamin (l), inophenol (2) v inoanilin (8), chng u thuc v loi hp cht quinonimin c cng thc sau:
N

;
HN NH2

;
O OH
O NH2

(1)

(2)

(3)

Qu trnh to thnh thuc nhum t inophenol v inoanilin thng xy ra nhit thp (35 - 38oC) trong mi trng trung tnh hoc kim yu. nh vy qu trnh nhum tc v lng th cng l qu trnh tng hp thuc nhum ngay trn vt liu. Cng thc cui cng ca nhiu mu trong lp thuc nhum ny cha c xc nh chnh xc, song c im chung ca chng l cha a vng, khng ho tan trong nc, bn vi nhiu tc dng ho l, c cc gam mu t vng n nu, ghi v en. bn mu ca thuc nhum oxi ho trn tc v lng th s tng ln rt nhiu khi cm mu bng mui kim loi nng to thnh phc khng tan bn vng. t c yu cu ny, trc khi nhum, cc tm lng hoc tc c x l bng mui kim loi (ng, crom hoc st) sau mi nhum. Khi dng cc mui kim loi khc nhau s nhn c mu khc nhau. Vic nhum c th thc hin bng cch nhng tm da lng vo dung dch nhum hoc bng cch bi pht dung dch nhum ch vo phn lng hay tc, hoc dng bin php in li, in phun. Tt c u thc hin nhit thp trong mi trng trung tnh hoc kim yu. 4.11.2. Nhum da Nhum l mt khu quan trng trong qu trnh thuc da. Da c th nhum bng cc 151

thuc nhum ho tan trong nc hoc bng cch ph mu. Khi nhum bng cc thuc nhum ho tan trong nc thng tin hnh trong cc thit b thng quay. Lp thuc nhum s dng tu thuc vo: loi da, yu cu mu sc ca sn phm v cng ngh thuc. Th d, da thuc bng thuc thuc crom th nn dng thuc nhum trc tip v nhum sau khi thuc. Bn cht thin nhin ca mi lin kt gia colagen da vi thuc nhum c nh hng quyt nh n bn mu ca sn phm, ngoi ra s tng tc ca thuc nhum vi cht thuc cng l yu t quan trng phi k n. Trong qu trnh nhum da, thuc nhum cng khuch tn t mt ngoi, qua cc mao qun vo su trong thn da v thc hin lin kt vi thnh mao qun ca cc si colagen. Do kch thc cc mao qun ca da ln hn ca x dt (mao qun ca da trng thi kh l 100 nm, trng thi t l 140 160 nm, kch thc phn t thuc nhum trc tip l 60 nm) nn thuc nhum d khuch tn vo da hn vo x dt. bo m cho thuc nhum lin kt tt vi da, trc khi nhum da cn c trung ho gim axit cn li trong qu trnh chun b. Tu thuc vo loi thuc nhum c dng, tr s pH cn li ca da thuc crm m chn tr s pH ca mng nhum cho thch hp. Tr s ti u ca mng nhum nh sau: Tn thuc nhum Trc tip Axit Axit cha kim loi 1:l Axit cha kim loi 1:2 pH cn li trn da 5 - 5,5 4,5 - 5 4 - 4,5 5 - 5,5 pH ca mng nhum 6 - 6,5 4,5 - 5 4,5 - 5 4,5 - 5

Khi nhum da, lng thuc nhum tiu th chim 1,5 - 4% so vi khi lng da kh, ring mu en ln n 7%. a. Dng thuc nhum trc tip Ngoi nhng thuc nhum trc tip c ch nh dng ring cho da, c th dng mt s thuc nhum trc tip dng cho si dt nhum da. Yu cu ca thuc nhum trc tip dng vo mc ch ny l phi bn vi nc, bn vi nh sng v du m. C th nhum da bng thuc nhum trc tip theo hai phng php: kh v t Khi nhum kh, thuc nhum dng bt c phun vo cc tm da kh ang quay trong thng nhum, x l 20 ph khng gia nhit, sau thm 20 - 30% nc (so vi da) v nhum 60oC trong 80 pht n 1 gi. Cui qu trnh nhum c th thm axit fomic vo dung dch nhum cho thuc nhum bt su vo da hn. Theo phng php t, thuc nhum kh c phun vo da t trong thng quay. Nc s t da thot ra ho tan thuc nhum thm vo da. Do c phn t ln nn a s thuc nhum trc tip ch nhum lp ngoi ca da. nhn c mu su ngi ta thng phi trn thuc nhum trc tip vi thuc nhum axit. b. Dng thuc nhum axit Cc loi thuc nhum axit u c dng nhum da, ngoi nhng mu c ch nh ring cho da c th dng nhng mu dng cho hng dt nhng phi la chn iu kin ti u t hiu qu mu cao nht. Khi nhum bng hn hp thuc nhum axit v thuc nhum trc tip nn a thuc nhum axit vo mng trc, ch khi thuc nhum axit bt mu ht mi a thuc nhum trc tip vo mng nhum.

152

Khi dng thuc nhum axit crom nhum da thuc crom th khng cn phi crom ho bng mui crom na, mu nhn c c bn rt cao v thuc nhum to phc ng thi vi crom v colagen ca da. Thuc nhum axit cha kim loi 1 : 1 v 1 : 2 cng c s dng kh ph bin nhum da, chng c i lc vi da thuc crom, da thuc tanin v da thuc bng thuc thuc hn hp. Da nhum bng thuc nhum cha kim loi 1: 1 v 1:2 c bn mu cao vi nh sng, gia cng t v ma st. Cng ngh nhum da bng thuc nhum cha kim loi l : 2 rt n gin v nhum trong mi trng trung tnh v axit yu, cn dng thuc nhum cha kim loi 1 : 1 th kh u mu hn, cn chn tr s pH cho thch hp. c. Dng thuc nhum hot tnh Cc loi thuc nhum hot tnh dng nhum x xenlulo v polyamit cng c s dng nhum da. Do thuc nhum c lin kt ho tr vi colagen da nn mu c bn cao vi gia cng t, ma st, nh sng v cc tc ng mt ngoi khc na. Qu trnh nhum da bng thuc nhum hot tnh cng chia lm hai giai on. Trong giai on u da c nhum 60oC vi pH = 4,5 - 5 trong 60 ph. Giai on sau nhum 40oC vi pH = 8 - 8,5 trong 15 - 20 ph, giai on ny thuc nhum lin kt ho hc vi da. ngha ca vic s dng thuc nhum hot tnh nhum da ngy cng tng ln v cc loi da dng may qun o, gng, m... cn phi c bn mu cao vi lm sch ho hc (git bng dung mi hu c). Mu ca da khng ch phi bn mt ct (mt ngoi) m c mt tht (mt trong) na, c nh vy n mi khng phai sang qun o mc lt bn trong. d. Dng thuc nhum baz Thuc nhum baz bt mu vo colagen da tng t nh khi n bt mu vo keratin len, nhng t c bn mu cao vi x l t nh sng v cc ch tiu khc phi tin hnh nhum sau khi x l da vi tanin hoc cc hp cht polyphenol hc hin yu cu cm mu. Trong thc t t khi ngi ta dng ring thuc nhum baz nhum da m thng dng n nhum trng sau khi nhum bng thuc nhum axit hay thuc nhum trc tip cho mu ti hn. Do thuc nhum baz s to thnh kt ta vi mui kim loi nng, vi thuc nhum axit v thuc nhum trc tip nn khng th tin hnh nhum ng thi hn hp cc thuc nhum ny trong cng mt mng m phi chia thnh cc giai on ring. e. Dng cch ph mng mu Khi nhum da bng cch ph mng mu, pigment c gn ln mt da bng bin php c hc nh mt mng mng cao phn t. Thnh phn ca hn hp mu ph bao gm c: - Cht mu thng l pigment v c v hu c mu lc, lam, mu ), pigment t cc thuc nhum axit, azo khng tan; - Cht to mng, thng dng l cc este xenlulo (nitroxenlulo), cazein, nha acrylic, nha t m cao su. Yu cu chung ca mng dng vo mc ch ny l d tan trong dung mi, bn c hc, do, co gin, trong sut; - Dung mi thng dng l amyl axetat, butyl axetat, xenlozonv; - Cht ho do (du thu du, ibutyl phtalat); 153

- Cc cht lm mm lm bng, chng mc. Da lm sch thot tin c ph mu lt bng cch dng bn chi mm qut u ln mt da, hong cho kh trong khng kh, cui cng phun lp mu ngoi bo m ng u trn c tm da. 4.11.3. Nhum caosu nhum cao su c th dng nhiu lp thuc nhum khng tan khc nhau, nhiu mu l mui bari v canxi ca thuc nhum azo. Nhng mu c s dng rng ri l: - Pigment booc B l mui canxi ca thuc nhum iu ch bng cch kt hp axit azurinic iazo ho vi 1-naphtylamin; - Pigment da cam l mui bari ca thuc nhum azo iu ch t axit anilin sunfonic iazo ho v -naphtol; - Pigment xanh lc l mui st ca nitrozo -naphtol; - Pigment xanh lam R ch to t ianiziin iazo ho v kt hp vi anizit ca axit -oxinaphtoic. Ngoi pigment gc azo ngi ta cn dng cc loi thuc nhum v piment khc nh: thuc nhum hon nguyn khng tan k c dn xut ca inigo v chng c mu ti v bn vi iu kin lu ho: phc ca phtaloxianin vi ng v cc kim loi khc. Thuc nhum v pigment dng nhum caosu c sn xut dng bt mn bt nho hoc dng phn tn, chng phi t cc yu cu k thut di y: - Bn nhit (n 160oC) bn vi tc dng ca hi nc, khng kh nng. nc nng, kim, lu hunh, cht tng tc v cht ho do; - Bn vi tc dng ca nh sng; - Khng di chuyn gia cc lp cao su v ra lp ngoi; - Khng c tc dng xc tc qu trnh lo ho cao su. Cao su c th c nhum trong khi hoc nhum mt ngoi. Khi nhum trong khi th pigment c trn v cn gia cc lp cao su ng thi vi vic gia cc ph liu khc. Lng pigment ly trong khong 1 - 4% so vi khi lng cao su. Khi nhum mt ngoi ngi ta dng hn hp pigment v cht to mng qut, in hay phun, v ln mt sn phm cao su. Cc hng nc ngoi sn xut pigment dng cho cng nghip caosu vi cc tn gi thng phm nh: vulcal, vulcal fast (CHLB c), vulcaphor (ICI), Irgaphor (Geigy) v.v. 4.11.4. Nhum cht do (nha ho hc) Cht do c nhiu loi v rt khc nhau v cu to ho hc, khng c s dng rng ri trong lnh vc sinh hot v trong k thut. Nhng loi cht do thng gp l: polyetylen. polypropylen, polyvinylclorua, polystiron, polymetylmetacrylat, polyeste v.v. Ngi ta cng sn xut cc loi nha khc nh: Urefomaldehit, phenolfomaldehit. polyuretan bt, nha amin, nha epocxy v cc dn sut ca este xenlulo. Do cht do khc nhau v cu to ho hc nn s tng tc ca thuc nhum vi chng cng khc nhau. Khi chn phng php nhum cht do ngi ta khng da vo bn cht ho l xy ra gia thuc nhum v vt liu nhum nh khi nhum vt liu dt, da vo cc iu kin cng ngh gia cng cht do thnh bn sn phm hay sn phm cui 154

cng. Nhum cht do l thut ng ch chung cc qu trnh bin nha bn thnh phm hoc thnh phm thnh dng c mu bng cc bin php: nhum trong khi, nhum mt ngoi, v hoc in hoa ln sn phm. Tu tng loi cht do v sn phm c th dng pigment cc loi, thuc nhum ho tan trong cht bo, thuc nhum ho tan trong dung mi hu c, thuc nhum hon nguyn khng tn v thuc nhum phn tn nhum chng. Yu cu chung ca pigment hay thuc nhum dng vo mc ch ny l phi c mn cao, chu c s tng tc ho hc vi cc cu t c trong thnh phn cht do k c cc sn phm do s nhit hy sinh ra, s tng tc l hc xy ra khi gia cng cht do. Ngoi ra pigment v thuc nhum dng cho cht do cn phi thun khit, ti mu, c kh nng nhum mu cao; khng b bin sc di tc dng ca nh sng, kh quyn v nhit ca mi trng; khng di chuyn t bn trong ra mt ngoi sn phm; d dng phn b trong khi cht do nhn c mu ng nht. nhum cc loi cht do ght nc (khng cha cc nhm chc a nc) th nguyn l chung l dng pigment v thuc nhum khng tan trong nc, nhit cao chng s tan vo cht do, hay cht do l dung dch rn ca thuc nhum. a. Nhum cht do trong khi Phng php ny c dng ph bin hn c v n c kh nng nhum u v m, thc hin n gin v c coi l vn nng. nhum ngi ta a pigment hay thuc nhum vo khi phn ng cui giai on tng hp khi nha cn trng thi nng chy nh m thuc nhum c dp phn b su v ng u trong ton khi. giai on ny cn khuy trn tht mnh v u nhn c mu ng nht. Kt thc qu trnh phn ng v nhum, nha c lm ngui, ra, chuyn thnh dng ht hoc bt gia cng thnh sn phm nha mu. b. Nhum b mt cht do Phng php ny c th thc hin bng cc bin php sau: - Nhng sn phm vo dung dch thuc nhum ho tan trong nc hay trong dung mi hu c; - In vn hoa mu ln sn phm; - V thuc mu ln sn phm; - Phun thuc mu ln sn phm. Cc bn php ny c s dng cho nhng loi cht do t polyamit; polymetylmetacrylat; polystiron, este xenlulo; uremelamin v phenolfomaldehit. Nhc im chung ca phng php ny l nng sut thp, ch thch hp vi cc l sn phm nh, bn mu ca sn phm thp hn so vi khi nhum trong khi. Ring phng php nhum bng cch nhng sn phm vo dung dch thuc nhum, ngoi vic phi la chn loi thuc nhum hay pigment cho ph hp vi loi cht do cn phi bo m cc yu cu nh: nhit nhum phi thp hn nhit mm ca nha, gi cho sn phm khng b mo, cong vnh. rn mt v c, phi dng thit b thch hp v phi ra sn phm trc khi nhum. Phng php in, v v phun to mu trn sn phm t cht do c u im l c th dng mt loi pigment hay thuc nhum cho tt c cc loi cht do nhng nhc im l phi dng cht to mng ho tan trong dung mi hu c d bay hi gn pigment ln mt sn phm. 155

c. Nhum kh cht do Phng php ny c dng nhum cht do dng ht. Loi thuc nhum hay pigment s dng c chn t y theo loi cht do v kch thc ca chng. Khi nhum nha c trn u vi bt thuc nhum kh trong my trn, hiu qu nhum mu s tng ln khi a thm vo hn hp cc cht tr thch hp. Sau khi trn u th gia nhit hn hp n nhit di nhit chy mm ca nha, trong iu kin ny thuc nhum kh s khuch tn hay ho tan vo nha theo c ch dung dch rn. Phng php ny c dng nhum polyetylen, polyamit, polyaxetal v nha ng trng hp t stirol v acrylonitrin. Cc loi pigment azo, pigment l mui bari v canxi ca thuc nhum baz, pigment phtaloxianin, thuc nhum ho tan trong cht bo u c th dng nhum cc loi nha k trn theo phng php ny. 4.11.5. Nhum giy Giy c th c nhum ngay trong khi bt giy trc khi xeo hoc nhum dng t giy thnh phm bng cch nhng n vo dung dch mu hay qut ph, lng dch mu ln mt mt giy. sn xut giy trang tr ngi ta cn s dng rng ri phng php in, k c in li. nhum v in giy ngi ta dng ch yu cc loi pigment, i khi cng dng loi thuc nhum ho tan trong nc nh thuc nhum baz, thuc nhum trc tip v thuc nhum axit. Pigment hu c dng nhum giy c chia lm hai loi sau: - Loi th nht l hn hp ca pigment hu c mu v cht v c tr dng lm cht nn. Pigment hu c thng dng l thuc nhum azo, iazo v nitrozo khng tan trong nc; chng c che ph cao, bn vi nc. bn vi mi trng kim v ch yu l bn vi nh sng, chng c s dng nhiu sn xut giy mu, cactng v ba mu giy trang in; - Loi th hai l pigment ca mt s thuc nhum hu c tan trong nc c chuyn thnh dng khng tan bng cch kt ta v hp ph ln cht nn v c, cht nn thng dng trong trng hp ny l nhm hidrat oxit, spat barit, blanfix, cao lanh, bt trng (barit, ch cacbonat, km oxit) pigment loi ny c s dng rng ri nhum ba v cc tng v chng c bn mu cao, ti mu v gam mu. a. Nhum ph b mt giy Phng php ny c tn gi nh vy v khi nhum, thuc nhum hay pigment cng vi cht nn ch nm mt ngoi ca t giy va to mu va lm nhim v che ph. Thnh phn ca dung dch nhum gm c: - Thuc nhum hay pigment dng ho tan hay huyn ph; - Cht nn chun b dng huyn ph; - H lm nhim v cht to mng gn pigment vo mt giy v tng nht ca dung dch nhum. Thnh phn ca dung dch nhum rt a dng tu theo loi giy, yu cu nhum v cht lng mu. lm cht to mng c th dng cc loi keo thin nhin hoc keo tng hp. Trong s cc keo thin nhin ngi ta thng dng keo gelatin (t xng v da ng vt. H gelatin c nu nhit di 70oC. n gin v r hn c l h t tinh bt sn, tinh bt khoai ty, tinh bt ng v tinh bt bin tnh. Tuy nhin nhng loi h ny to mng km bn vi m t nn ch dng cho nhng loi giy mu thng dng v cp thp. 156

Hin nay ngi ta s dng ngy cng rng ri cc loi h tng hp nhum v in giy. Dng cc loi h ny giy s c bng cao hn, tng mm do v co gin, tng kh nng khng mi mn v nhiu u im khc na. Nhng h tng hp c dng nhiu l: hn hp ca stirol (60 phn) v butaien (40 phn) cho hiu qu tt, gi thnh khng cao; h t dn xut ca acrylic c trong sut cao, t b vng khi bo qun, khng c mi, c bng cao, t phi cn bng. H tng hp thng c chun b dng bn a t, sau khi ph ln mt giy phi kh hoc cn n s a t thnh mng mng gn vo giy. Dung dch mu k trn c th a ln giy bng cch qut th cng tng t hoc bng cch cn p c cun vi bin php phi sy thch hp sao cho gy khng b co v nhn dm. b. Nhum khi bt giy Giy c th c nhum ngay trong khi bt trc khi xeo; c th dng c loi thuc nhum ho tan trong nc v pigment. Khi dng cc loi thuc nhum baz phi ho tan thnh dung dch, lc, a vo b cha bt t t v khuy o lin tc. Do c i lc vi x xenlulo nn thuc nhum s bt mu vo x, sau khi xeo s c giy mu. Khi dng pigment v c hay pigment hu c th cn ho chng thnh dung dch huyn ph, a vo b cha bt cng vi cao lanh sau khi gia nha v phn. Khi xeo, pigment s c gi li trong cc khoang trng gia cc th si. Phng php nhum ny dng cho cc loi giy mu nht. 4.11.6. Thuc nhum trong cng nghip sn v n lot ch to sn mu trong cng nghip sn v mc in trong cng nghip n lot ngi ta dng ch yu cc loi pigment c nghin cc mn vi cc gam mu khc nhau. Nhng loi pigment c s dng vo mc ch ny gm c: - Pigment v c gm cc mui v oxit c mu, khng tan ca nhiu kim loi khc nhau; - Pigment hu c gm cc thuc nhum khng tan nh: monoazo, phtaloxianin, hon nguyn khng tan; thuc nhum nitro v nitrozo. - Pigment l phc khng tan ca mt s thuc nhum axit, thuc nhum baz, thuc nhum axit - crom v thuc nhum cm mu vi cc mui ca bari, canxi, nhm, crom v mt vi kim loi khc na. a. S dng pigment trong cng nghip sn Trong cng nghip sn ngi ta s dng nhiu cc loi pigment hu c v chng c mu ti, gam mu, c bn mu cao vi nh sng. iu quan trng l trc khi phi ch vi cc thnh phn khc phi trn pigment vi cht n (cc loi bt trng) thnh hn hp mu v cc l do sau y: - Pigment nguyn cht c mu qu m, nu em trn ln ngay vi cc thnh phn khc s kh u, ngoi ra nhiu loi pigment nguyn cht thng c nh , kh quan st v i chiu mu; - Cht n to cho sn kh nng che ph ngha l c kh nng lm y n nn mu; - Cht n c tc dng lm tng ti mu, khi nghin v trn pigment vi cht n phn tn ca pigment s tng ln; - Trong nhiu trng hp cht n ng thi cng l cht hp ph v phn tn pigment. 157

 lm cht n trong cng nghip sn ngi ta thng dng cao lanh, thch cao, spat barit, nhm hirat oxit, bari sunfat, ch sunfat, ch oxit, titan ioxit, litopon v nhiu cht khc. gn pigment vo vt liu ngi ta cn a vo thnh phn sn cht lin kt hay cht to mng. Loi cht ny cng a dng, c th dng cc hp cht thin nhin v nha tng hp nh: du trng hp (du sn), du ankit, nha epoxy, polyuretan, nha melamin v urefomaldehit, peclovinyl v nhiu nha khc. Chn loi cht to mng no cn tu thuc vo phm vi s dng ca sn phm. Trong thnh phn ca sn ngoi pigment, cht n, cht to mng cn c dung mi. cht ho do v cht lm kh nhanh. b. Pigment trong cong nghip n lot Pigment dng trong cng nghip n lot cn c cht lng cao hn so vi loi dng pha sn. Nhng yu cu l pigment phi nguyn cht: mu ti, bn mu vi nh sng, c nghin mn cao v phn tn cao, bn vi nc, c kh nng phi trn ng u vi cht to mng. lm cht to mng trong ch to mc in ngi ta cng dng cc loi du trng hp, du ankit (chng l cc loi du thc vt cha no nh du lanh, du tru, du ht qu cao su trng hp s b) v cc loi nha ng hp khc na. lm cht n hay cht y nn ngi ta cng dng cc loi bt trng (bari sunfat, canxi cacbonat, nhm hidratoxit). Ngoi ra trong thnh phn mc in cng c dung mi hu c ( ho tan cht to mng) v cht lm kh nhanh nh coban naphtenat hay mangan naphtenat. 4.11.7. Nhum g v chiu ci Trc khi sn vecni hoc quang du, nhum mu lt cho mt s mt hng g ngi ta cng dng bin php nhum. Thuc nhum c dng vo mc ch ny ch yu l hai lp trc tip v baz. Do c i lc vi xenlulo v nht l cc thnh phn c trong nha cy nn cc loi thuc nhum ny bt vo g tng i bn. Thuc nhum baz v thuc nhum trc tip cn c s dng nhiu nhum hng my tre an, mnh trc v cc mt hng khc t tre na, cho mu bn v p. Chiu ci l mt hng c sn ca nc ta c nhum ch yu bng thuc nhum baz. Do c mu, mu ti v c kh nng bt mnh vo chiu ci nn lp thuc nhum ny c s dng nhum ci si dng an v dt, dng in hoa chiu v cc sn phm t ci. 4.11.8. Thuc nhm tc Nh trnh by mc 1 ca phn ny, mt s thuc nhum dng nhum lng th cng c th dng nhum tc, tuy nhin khi dng thuc nhum v ho cht nhum tc ngoi yu cu k thut cn phi quan tm n yu cu y sinh na. nh nhum tc c t u th k XX v vic ch to thuc nhum tc cng c nhiu nh khoa hc ch . Ch ring trong 40 nm (1930 - 1970) c hng trm bng pht minh v cc ho cht nhum tc. Ho cht hay thuc nhum dng vo mc ch ny u phi bo m t yu cu v mu sc, khng gy d ng cho da v an ton v y hc. n nay cc phng php nhum tc tng i n nh, chng khc nhau v phng php s dng, bn, tnh cht mu sc v ho tnh thin nhin ca thuc nhum. C bn loi cht nhum tc di y: 158

a) Cht kh mu tc l loi dung dch ch sn bn trn th trng dng dung dch khng mu rt d nhn bit. N c dng theo ch dn ca thang i mu v dng ty mu thin nhin ca tc trc khi nhum mu mi. Nhng ch phm ny cha ch axetat v i khi l mui bitmut. C th nhn bit nh tnh bng cch dng dung dch H2S, nu c kt ta en l ch axetat, cn kt ta en nu l mui bitmut. b) Thuc nhum tc c bn thp c s dng nhum mu cho tc trong thi gian ngn, chng c th l thuc nhum hon chnh hay cht lng c mu c sn xut dng dung dch cha mt lng nh nha tng hp. Hiu qu nhum mu s t c khi chi tc bng dung dch ny. Do c bn thp nn sau mt vi ln gi, mu mi nhum s mt hn. Loi thuc nhum ny cng c sn xut dng bt, c ch dn cch ho tan mi khi dng. Thuc nhum dng trong trng hp ny thng l loi c khi lng phn t ln, kh thm su vo cc lp bn trong ca si tc gm c: thuc nhum nhum vt liu dt, thuc nhum nhum thc phm, dc phm v m phm. Chng c th l thuc nhum axit. thuc nhum baz v thuc nhum phn tn c cu to ho hc khc nhau k c thuc nhum l phc ca kim loi. Loi thuc nhum tc ny c dng nhiu ho trang trong biu din ngh thut, in nh v nhng trng hp c nhu cu thay i mu tc thng xuyn. c) Thuc nhum tc c bn trung bnh. Loi thuc nhum ny c sn xut v bn dng lng ng trong l, dng bng cch chi hoc phun, c kh nng gi mu sau 4 - 6 ln gi. Thnh phn ca thuc nhum tc ny gm c: thuc nhum loi c khi lng phn t nh, cht ty ra tng hp hay cht nh ho. Thuc nhum pha ch thng l: nitroanilin, nitrophenyleniamin, niotroaminophenol v aminohyroxiantraquinon. Nhm ny c mu vng, da cam, mu v mu tm. T nhng mu ny khi phi ch vi thuc nhum antraquinon mu lam th c th to c cc gam mu thin nhin khc nhau. Trrong cc sn phm ch sn dng nhum tc loi ny thng cha 2 - 20 thuc nhum khc nhau. Nhng thuc nhum chnh ca nhm ny l: Tn thuc nhum 2-Nitro-p-phenyleniamin (NPD) 4-Nitro-o-phenyleniamin (NOD) 4-Nitro-m-phenyleniamin NPD th N1 (bng nhm metyl hay 2-hyroxietyl) NPD th N4 (bng nhm metyl hay 2-hyroxietyl) NPD th 3 ln N1, N4, N4 (bng nhm metyl hay 2-hyroxietyl) NOD th N1 (bng nhm metyl hay 2-hyroxietyl) 2-Nitro-4-aminophenol Axit picraminic Axit picraminic mbtyl ho N 1,4-Diaminoantraquinon 1,4,5,8-Tetraminoantraquinon Mu da cam vng da cam vng lc tm hay tm da cam da cam - vng vng tm xanh lam xanh lam

d) Thuc nhum tc c bn vnh cu hay thuc nhum oxi ho. Loi thuc nhum ny l ch phm gm hn hp ca mt s phm vt trung gian (tu theo mu nh nhum cha c mu cui cng c ch to dng lng. Thnh phn chnh l cc hp cht kiu iaminobenzen, aminophenol, polyhyroxiphenol c ho tan trong dung dch 159

amonioleat hay dn xut amoni ca cht hot ng b mt tng hp. Cht oxy ha c chun b ring, khi no dng mi trn vi dung dch nhum trn. Cc cht oxy ho thng dng l hyroperoxit dng lng, hay mt s cht th rn nh ureperoxit, melaminperoxit v natri peborat. Cc iamin v aminophenol iu kin nhum (nhit thp v mi trng trung tnh hay kim yu) s b oxy ho n dng quinoimin su trong thn tc, sau hp cht ny tip tc phn ng vi cc amin v phenol khc c trong hn hp to thnh thuc nhum h inoanilin v iniamin. Cu to phn t ca thuc nhum v mu to thnh tu thuc vo thnh phn cc phm vt trung gian c trong ch phm. Mu ca loi thuc nhum ny c bn cao vi gi v nh sng l do chng c phn t ln v c tng hp su trong thn tc nn kh b tch khi khi gi. Mc d c nhiu hp cht trung gian c ngh dng lm thuc nhum oxy ho nhum tc nhng M cng nh mt s nc khc ch c trn 20 cht c dng vo mc ch ny. Khi phi trn vi t l thch hp cc vt trung gian khc nhau s nhn c thuc nhum tc c mu nu, nu lc, tm, tm, xanh lam, xanh en v en. Khi mun ch to thuc nhum tc mu vng v mu ht d th phi dng cc dn xut ca nitrophenyl iamin. Trong cc loi thuc nhum tc trn th trng dng lng th hm lng cc phm vt trung gian ( to mu) ch chim 20 - 30%, phn cn li l cc cht ph gia. Di y l nhng phm vt trung gian c dng nhiu pha ch thuc nhum tc oxy ho. Tn phm vt trung gian p-Phenylendiamin Cng thc ho hc
H2N
H2N

NH2

m-Phenyleniamin N-Phenyl-p-phenylendiamin 2,4-iamino anizol

H2N
NH

NH2

NH2

OCH3 NH2

2-Nitro-p-phenyleniamin

H2N

NH2 NO2

4-Nitro-o-phenyleniamin

O2N

NH2 NH2

2,5-iaminotoluen

H2N

CH3 NH2

160

2,4-iaminophenol

H2N

OH NH2

p-Aminophenol o-Aminophenol

H2 N

OH

OH NH2
H2N

m-Aminophenol
O2N

OH

5-Nitro-2-aminophenol

OH NH2

2-Nitro-4-aminophenol

H2N

OH NO2

Rezocxin
HO

OH

Hydroquinon

HO

OH

OH

Pirogalon
OH

OH

OH

1-Naphtol
OH

1,5-ihyroxinaphtalen
OH

Trn y l nhng phm vt trung gian c s dng nhiu hn c, khi khng c hoc mun chuyn nh mu th phi thay i t l phi liu hoc dng cc cht tng ng. 4.11.9. Thuc nhum ng cho thc phm, dc phm v m phm Trong cc nhu cu v mu sc ca i sng x hi c nhu cu nhum thc phm (thc n v ung), nhum dc phm (thuc ung v bi ngoi da) v m phm son..phn...). C mu sc p v ph hp cc sn phm k trn s tng tnh hp dn, d tiu th v tng gi tr s dng. Song cc loi thuc nhum v cht mu dng vo mc 161

ch ny c yu cu chung l phi khng c vi c th hoc c khng ng k, khng li cc di chng v y hc, y l tiu chun hng u. nhng nc cng nghip pht trin ngi ta ban hnh cc lut v s dng thuc nhum cho thc phm, dc phm v m phm. Th d nh M t nm 1906 c lut quy nh rng ch nhng loi thuc nhum no khng c mi c dng vo cc mc ch k trn. Sau lut ny lin tc c b sung vo cc nm 1916, 1929, 1939 v n nm 1960 - 1964 th coi nh tng i hon chnh, trong c nhng iu quy nh c th nh sau: - Tt c thuc nhum (thin nhin v tng hp) trc khi a vo thc phm, dc phm v m phm u phi lm sch tp cht v c kim nghim cht ch; - Sau khi nhum cn phi kim tra li an ton ca thuc nhum a vo cc sn phm k trn. Nh vy r rng l khng th tu tin s dng thuc nhum hay bt mu (pigment) loi k thut nhum thc phm, dc phm v m phm v cc ch phm ny c th c vi c th, cha nhiu ph gia v tp cht. S dng khng ng thuc nhum v bt mu vo cc mc ch k trn s gy nguy hi v sc khe trc mt cng nh lu di cho ngi dng. Thuc nhum dng cho nhum thc phm, dc phm v m phm c chia lm cc loi sau y: - Loi khng cn kim nghim: loi ny ch yu l cc cht mu thin nhin chit sut hay ch to c t mt s loi khong vt ng vt v thc vt c mu. Do kinh nghim s dng lu truyn t nhiu th h c tha nhn l chng khng c, khng cn kim nghim. Nhc im ca'chng l t mu, v mu khng p; - Loi cn phi kim nghim v cho php s dng: loi ny gm cc thuc nhum hu c c lm sch tp cht hoc kt ta vi mui kim loi chuyn v dng khng tan, c cc c s y t xc nhn l khng c hoc khng cha cc nguyn t gy c cho c th, gy d ng ngoi da v cc phn ng khc na vi c th. Tu theo phm vi s dng (ung, n, bi ngoi da) ngi ta li chia ra lm ba nhm: a) thuc nhum dng cho thc phm, dc phm v m phm; b) thuc nhum ch dng cho dc phm v m phm; c) thuc nhum dng cho dc phm v m phm bi ngoi da. Theo cu to ho hc thuc nhum hu c dng vo mc ch ny cng chia ra lm cc nhm sau y: - thuc nhum azo tiu biu l mu vng No6 pirazolon tiu biu l mu vng No5 dng cho nhm a;
(*)

dng cho nhm thuc nhum

- thuc nhum triphenylmetan tiu biu l mu lam No1 dng cho nhm a; - thuc nhum inigoit tiu biu l mu lam No2 dng cho nhm a; - thuc nhum antraquionon tiu biu l mu lc No5 dng cho nhm b; - thuc nhum xan ten tiu biu l mu da cam No5 dng cho nhm b; - thuc nhum quinolin tiu biu l mu vng No10 dng cho nhm b. Tu theo loi nhm th c trong phn t m ho tan thuc nhum s dao ng trong khong t rt tt n khng tan.
(*)

Con s l s mu trong Color Index.

162

Tu theo loi nhm th c trong phn t m ho tan thuc nhum s dao ng trong khong t rt tt n khng tan. Tng s nhm SO3H hay COOH s tng ho tan ca thuc nhum trong nc. Khi a vo phn t thuc nhum cc nguyn t hay nhm th nh: Cl, NO2 v CH3 s lm tng ho tan ca thuc nhum trong dung mi hu c. Cc mui ca thuc nhum vi kim loi kim th khng ho tan c trong nc v trong dung mi hu c. Trong bng 3.19 l danh mc mt s thuc nhum tng hp c dng nhum thc phm mt s nc trn th gii. Bng 3.19
Tn nc Italia Php Anh c M B S Cl Thu in Nht Bn Thu S o o o o o o o o Canaa Ba Lan n Tn thuc nhum thc phm theo Vng 4 Vng 8 Vng 13 Vng 2 Vng 5 Vng 3 Da cam 2 Da cam 3 Da cam 4 3 9 7 2 8 14 4 1 10 11 13 17 Xanh lam 4 Xanh lam 5 Xanh lam 1 Xanh lam 2 Xanh lc 4 Xanh lc 3 en 1 en 2 Nu 3 Tm 3 Tm 2

19140 14270 47005 13015 18965 15985 15980 11920 16230 14720 16185 16255 14815 16290 45430 16045 14700 18050 18055 14780 16035 69800 42051 73015 42090 44090 42053 28440 27755 20285 42580 42640

o o

o o

Ghi ch: - cho php dng; o - ch s dng hn ch; khng c du ngha l khng c dng.

163

Chng IV

PHN TCH V NH GI THUC NHUM

1. CC TNH CHT CHUNG CA THUC NHUM Vic nh gi cht lng s dng ca mi thuc nhum phi thng qua cc tnh cht v gi tr s dng chng. Tnh cht thuc nhum hoc ph thuc vo cu to ho hc phn t hoc ph thuc vo cng ngh sn xut thuc nhum. C nhng tnh cht ch ph thuc vo cng ngh sn xut, nhng c nhng tnh cht khc li ch ph thuc vo cu to ho hc m t ph thuc hoc khng ph thuc vo cng ngh sn xut. Phn ln cc tnh cht ca thuc nhum c nh gi nh lng bng cc n v qui nh. Tuy nhin, vic nh gi thng da vo cc mu chun. C hai loi mu chun: 1- mu chun c nh khi qu trnh sn xut thuc nhum n nh, cht lng thuc nhum khng b sai lch t l ny n l khc v n c xc nhn trong sut c thi gian di nh trc cho tng loi thuc nhum. 2- mu chun khng c nh khi sn xut mu thuc nhum, chng c iu chnh v thng xc nhn cho mt phn thi gian nh trc. Cc tnh cht biu th cht lng ca thuc nhum gm c nhng c trng sau. 1.1. Nng thuc nhum Khi nim nng c th hin hai mc qui nh: nng tuyt i v nng tng i. Nng tuyt i l nng thc s ca thuc nhum (cht mu tinh khit) c trong thuc nhum thnh phm. Loi nng ny ch gp trong cc loi thuc nhum khng ho tan trong nc nh: thuc nhum phn tn, thuc nhum hon nguyn bt nho, pigment bt nho v.v. Loi nng ny khng bao gi t ti 100% v cng vi thuc nhum cn c nhng cht ph gia khc. Nng tng i l nng khi so snh vi mu chun theo qui nh (cn c gi l nng qui c). Mu chun thng c xc nh bng cch: ly mu thuc nhum t cc l sn xut ti nh my thuc nhum em th nghim ti cc vin nghin cu, sau tho thun vi cc c quan s dng thuc nhum, cui cng c c quan nh nc c thm quyn ph chun v thng qua. Mu chun c coi l c nng qui c 100%. Tt c cc mu thuc nhum cng loi khi sn xut ra s c xc nh bng cch so snh vi mu chun. Trong thc t thng gp nhng loi thuc nhum vi nng 120%, 150%, 200% v.v., c ngha l thuc nhum mi sn xut c nng ln hn mu chun (gp 1,2; 1,5; 2,0 ln). Khng cho php sn xut loi thuc nhum c nng tng i nh hn 100%. Nng tng i thng gp nhng loi thuc nhum c in nh: thuc nhum axit, thuc nhum trc tip, thuc nhum lu hunh. Khi nim nng tng i thng lin quan n ngi t hng v c quan t k hoch nh gi thuc nhum vi ngi s dng thuc nhum, khng nn dng n v ny tnh ton thnh phn dung dch nhum hay t l ln mu. 1.2. Cc dng thuc nhum thng phm Tu theo tng loi thuc nhum m yu cu sn xut chng cc dng khc nhau. Thuc nhum dng bt th c kch thc ht 0,5 - 10 m, gm cc loi thuc nhum 164

ho tan trong nc, thuc nhum lu hunh v thuc nhum hon nguyn khng tan nhum theo phng php kim kh (lyc/baz). Thuc nhum dng bt mn c kch thc ht 0,2 - 0,5 (1) m, gm cc loi thuc nhum phn tn. thuc nhum hon nguyn khng tan nhum theo phng php huyn ph, hon nguyn bt mn phn tn cao. Thucnhum dng bt nho: sau qu trnh tng hp, thuc nhum c lc ra ri phi trn vi cc ph gia (cht gi m, cht phn tn, cht chng thi, cht chng vn cc, cht xc tc v.v.) v em nghin n mn t yu cu, khng cn sy. Loi ny bao gm cc thuc nhum pigment dng cho in hoa v hon nguyn bt nho. Thuc nhum dng lng: gn y hng Sandoz gii thiu loi thuc nhum sodyesul lng l thuc nhum lu hunh c kh trc v dng lyc n nh trong dung dch. 1.3. n nh ca thuc nhum trong thi gian bo qun Tnh cht ny th hin bn ca cht mu c trong thuc nhum thnh phm. Trong sut thi gian bo hnh, cc tnh cht ca thuc nhum cha b thay i th thuc nhum cn hiu lc s dng v gi l thi gian ti hn s dng. Khi cc tnh cht ca thuc nhum b thay i th thuc nhum ht thi hn s dng. Ch c mt vi thuc nhum cn quan tm n ch tiu ny nh: thuc nhum hot tnh, thuc nhum lu hunh v thuc nhum hon nguyn tan. Cn hu ht cc loi thuc nhum khc nu bo qun tt trong nhng iu kin bnh thng th chng c nhng thi gian s dng l v hn. Khi cn so snh n nh ca cc loi thuc nhum khc nhau hoc ca cc hng sn xut (cng loi thuc nhum) khc nhau, ngi ta s dng cc ch dn v thi hn bo qun ca mu chun cho. 1.4. ho tan ca thuc nhum Tnh cht ny th hin kh nng ho tan ti a ca thuc nhum trong mt lt nc hoc mt lt dung dch (c cha cc cht tr nhum khc). n v tnh l s gam thuc nhum ti a ho tan trong mt lt nc (hoc mt lt dung dch). ho tan ca thuc nhum c nh hng n nng ti hn cho php ca thuc nhum v cc cht.in ly; n qui nh nhit nhum, mun nhum v cc thng s khc ca qu trnh nhum. 1.5. phn tn ca thuc nhum Chi tiu ny cn phi xc nh i vi nhng loi thuc nhum khng ho tan trong nc nh: thuc nhum phn tn, thuc nhum hon nguyn bt mn v pigment. Thc cht vic nh gi phn tn chnh l xc nh mn ca cc ht thuc nhum. Ht thuc nhum cng nh th kh nng phn tn ca chng cng cao. 1.6. Kh nng t nhum Tnh cht ny th hin kh nng ca thuc nhum chuyn t dung dch nhum vo vt liu nhum sau mt thi gian nht nh. Ch tiu ny c nh gi bng phn trm lng thuc nhum hp ph ln vt liu nhum so vi lng thuc nhum pha trong dung dch nhum. 1.7. Kh nng u mu ca thuc nhum y l kh nng phn b u ca thuc nhum ln vt liu nhum. Kh nng ny c lin quan n cng ln mu ca thuc nhum sau khong thi gian nht nh. Da trn ch tiu ny c th phn thuc nhum thnh ba nhm: thuc nhum kh u mu 165

(thuc nhum c i lc ln vi vt liu nhum); thuc nhum u mu trung bnh v thuc nhum d u mu (i lc nh). 1.8. n nh ca dung dch thuc nhum Ch tiu ny c xc nh bng khong thi gian m dung dch thuc nhum cha b thay i; n cho bit kh nng cho php pha ch mt lng ln dung dch nhum trc khi tin hnh nhum. Nhng dung dch thuc nhum khng n nh ch c php pha trc khi s dung. 1.9. bn ca thuc nhum trong dung dch Ch tiu ny xc nh bn ca thuc nhum trong dung dch mt s cht nh mui, cht in ly, cht oxi ho. N th hin kh nng chu c ca thuc nhum khi gia cng chng trong cc qui trnh kt hp nh: ty v nhum ng thi hoc thit lp qui trnh nhum c mt cc cht trn nhit cao. nh gi tnh cht ny c th nhum so snh iu kin c th vi mu nhum iu kin ti u cho. 1.10. bn ca thuc nhum trong h in Ch tiu ny c xc nh bng khong thi gian n nh (tnh theo ngy hoc theo gi) ca cc loi h in. S n nh k t khi bt u pha ch thuc nhum vo h in cho n khi tnh cht ln mu v nh v thuc nhum trn vt liu bt u b gim i. 1.11. nhy ca thuc nhum vi mt s ion kim loi nng Ch tiu ny xc nh iu kin nhum cng nh yu cu khi pha ch dung dch nhum. nh gi ch tiu ny theo cc cp qui nh sau khi nhum so snh mu trong iu kin c mui kim loi nng (ng, st, crm) v iu kin khng c chng. 1.12. Kh nng di tn thuc nhum Tnh cht ny c trng cho s dy mu t vt liu nhum sang vt liu trng khi x l trong cng dung dch, c ngha l thuc nhum c kh nng di chuyn t vt liu nhum ra dung dch trong khi nhum. Ch tiu ny c xc nh bng s sai khc v cng mu ca vi nhum v vi trng dy mu sau khi x l chng trong cng dung dch. nh gi ch tiu ny bng cp mn qui nh hoc bng phn trm lng thuc nhum dy t vi mu sang vi trng. 1.13. Mc s dng thuc nhum Ch tiu ny c trng cho hiu qu s dng thuc nhum khi nhum v in. N c nh gi bng t l lng thuc nhum c bt mu trn vt liu vi lng thuc nhum cn s dng trong n nhum v in. 1.14. Mc git sch thuc nhum Sau khi nhum v in, nhng phn thuc nhum khng c nh v trn vt liu s phi git sch. Mc d git sch cng cao th bn mu vi gia cng t trong qu trnh s dng sau ny cng cao. 1.15. nhy ca mu thuc nhum vi cc ch phm hon tt Tnh cht ny c trng cho nhng loi thuc nhum c kh nng tng bn mu khi tin hnh cm mu sau khi nhum hoc gia cng vi cc ch phm hon tt tng

166

gi tr s dng. nh hng ny c nh gi bng s so snh cng mu, nh mu, trc v sau khi gia cng. 1.16. bn mu y l mt trong nhng tnh cht quan trng nht ca thuc nhum, n xc nh phng php nhum cng nh cng dng ca mi thuc nhum. bn mu c chia lm hai loi: 1- bn mu cng ngh l ch tiu bn mu trong cc qu trnh gia cng tip theo sau nhum; 2- bn mu s dng l ch tiu bn mu di tc dng ca cc iu kin s dng nh: git, l, c xt, m hi, nh sng, thi tit v.v. V nguyn tc, hai ch tiu trn khng c s khc bit, v l tt t cc tc nhn ho l tc dng ln vt liu nhum trong qu trnh sn xut v s dng. 2. PHN TCH NH LNG THUC NHUM Phng php phn tch nh lng thuc nhum rt c ngha khoa hc cng nh trong sn xut. nh lng thuc nhum trong dng bt thnh phm, trong dung dch, trong bt nho, huyn ph hay trn vt liu nhum mu u rt cn thit nh gi cht lng thuc nhum, thit lp cc qui trnh cng ngh nhum ph hp, nghin cu c ch nhum v nh gi bn mu ca thuc nhum. Trong sn xut thuc nhum, vic phn tch nh lng l cn hit khng ch nng cht mu trong thuc nhum sn phm. Bi v hu ht cc thuc nhum xut xng khng phi l thuc nhum thun khit m chng thng b pha long bi cc cht ph tr khc nhm lm tng tnh cht s dng ca thuc nhum. Trong vic s dng thuc nhum, phn tch nh lng cng quan trng khng ch nng thuc nhum trong qu trnh nhum, kim tra cht lng sn phm nhum v c bit n phc v cho qu trnh t ng ho trong sn xut. Vi ni dung trn, phn tch nh lng c nhiu phng php. 2.1. Xc inh nng thuc nhum bng phng php nhum so snh Phng php ny c s dng khi c mu chun so snh i chng. Mi loi thuc nhum c th vi cng loi vt liu nhum v tin hnh trong cng iu kin vi cc mu nht, trung bnh v m. Ngoi ra, c th nhum thm hai mu vi gii hn nng trn v di (t l tng gim t 5 - 10% so vi hm lng thuc nhum ti u theo ch dn). Ring i vi cc mu vng, cn phi cho thm mt lng thuc nhum mu xanh lam tng cng mu v d so snh. Lng thuc nhum mu xanh ch c ly khng cao hn 20% so vi thuc nhum mu vng v cn thng nht trong tt c cc th nghim. S dng nc ct pha thuc nhum v cc ho cht khc. Cc iu kin th nghim nh: t l gia dung dch nhum v khi lng mu (moun); nhit , thi gian v qui trnh thao tc phi thc hin ging nhau cho tt c cc mu th nghim. Cc bc th nghim c th nh sau. 2.1.1. Chun b dung dch nhum Cc cht rn cn vi chnh xc 0,01g, cc cht lng ong vi chnh xc 0,1 ml. i vi hu ht cc loi thuc nhum mu th nghim c dng 0,5 - 1 g, ring thuc nhum lu hunh dng 2,5 g. Thuc nhum c ho tan trong bnh nh mc (loi 500 167

ml), nhit ho tan ca tng loi thuc nhum c khc nhau: thuc nhum trc tip, thuc nhum axit, thuc nhum hot tnh (nhm nhum nng) ho tan nhit 80 90oC; thuc nhum hot tnh nhm m ho tan nhit 40 - 50oC. Thuc nhum hon nguyn v thuc nhum lu hunh ch c kh v ho tan trc khi th nghim nhum. Tt c cc dung dch thuc nhum cn c kim tra ho tan bng cch nh git dung dch thuc nhum ln giy lc. 2.1.2. Chun b mu vt liu nhum C th nhum si, nhum vi dt thoi, vi dt kim v.v. Cht liu mu la chn sao cho ph hp vi phm vi s dng ca thuc nhum. Cc mu vi si bng, lanh, vixco phi qua x l lm sch iu kin sn xut v c mao dn 10 cm/h. Mu th nghim cn vi khi lng khng nh hn 5 g. Mu vi, si len, len pha phi c lm sch iu kin sn xut nhng cn gia cng thm trong dung dch gm: cht hot ng b mt 2 g/l nhit 80oC, thi gian 30 ph, moun 40. Sau git nng git lnh. T tm sau khi qua x l lm sch iu kin sn xut cng phi x l thm trong dung dch: NH4OH 25%; 3 m/l, natri hexametaphotphat: 2 g/l, nhit 50oC, thi gian 20 ph, sau git nng ri git lnh. Cc mu len v t tm ch cn vi khi lng khng nh hn 2 g. Nu cc mu si th phi cun vo a thy tinh hnh ch U. 2.1.3. Nhum mu Trc khi nhum cc mu vi hoc si phi c thm nc u v vt n lng m 120 - 150% (tc l 1 g vi em theo 1,5 - 2 g nc). Cho mu ngp trong dung dch nhum v trong 15 ph u phi khuy o lin tc, sau gim dn 3 - 4 ph khuy mt ln, khng c mu vi ni ln trn dung dch. Nhit nhum v thi gian nhum cho tng loi thuc nhum thc hin theo cc ch dn c th. Kt thc mu nhum u, nc lu c gi li ri b sung nc n mc c v nhum tip mu sau (lng vt liu ly gim i 5 ln so vi ln trc). Cc iu kin nhum gi nguyn cho tt c cc ln th nghim. Cc mu nhum c git sch v sy kh nhit khng qu 70 - 80oC. 2.1.4. nh gi kt qu nhum mu Cc mu nhum sau khi sy kh c gi trong bng ti t nht 2 h ri em so snh v ch s dng cc mu nhum u mu khng b loang. Vic quan st so snh c thc hin trong nh sng t nhin hoc di nh sng n non, khng dng n mu ni th nghim. n chiu sng vo mu vi phi t cch b mt mu 50 cm v nghing mt gc 40 - 50o. Hng quan st phi vung gc vi b mt mu nhum. Cc mu vi phi cng trn mt phng v cng chiu si nh nhau. trnh b la khi quan st cn xp cc mu thnh 2 - 4 lp, v thay i ch ca cc mu 2 - 3 ln. i vi cc mu si phi cun chng li vi nhau thnh cc con si c b dy t nht 15 mm trng thi t do v d chi. Cc con si c xp song song vi nhau, i ch cho nhau ba ln so snh, ln cui cng xp mt phn ca con si ny ln gia hai u ca con si kia v quan st. Kt qu nh gi trong cc ln quan st cho php sai s nh hn 5%. xc nh nng v nh mu ca thuc nhum cn phi tnh c cc mu nhum trong nc lu. Phng php xc nh nng thuc nhum bng cch so snh s ch cho kt qu tng i v ch thc hin c khi ngi lm th nghim c nhiu kinh nghim trong lnh vc ny. 168

2.2. Phng php quang trc ph C s ca phng php ny l da trn tnh cht hp th nh sng c chn lc ca thuc nhum trong vng quang ph thy c (c bc sng = 400 - 760 nm). Mi thuc nhum tng ng vi mt dng ng cong hp th nht nh, da vo ng cong m thit lp phng php phn tch nh lng v nh tnh thuc nhum. nh tnh th hin mu sc v thun sc ca mi thuc nhum. nh lng thuc nhum ch c th c xc nh theo nh lut Lambert Bera: I D = lg o = .C.l I trong : Io - cng nh sng trc khi i qua dung dch; I - cng nh sng sau khi i qua dung dch; D - cho trc; - h s phn t hp th; C - nng ca dung dch thuc nhum (mol/l, mg/l, %); l - b dy ca lp dung dch. Khi o c D, bit C, l s xc nh c h s phn t hp th: D = C.l trong : D - mt quang hc im hp thu cc i. Khi hai thuc nhum: mu th v mu chun ng nht th chng s c h s phn t hp th ging nhau: Dt Dc C .l .D c = t = = Ct = c c t C t .l t C c .l c l t .D c So snh Dc (ca dung dch thuc nhum chun) v Dt (ca dung dch mu th) s cho php tnh c nng thuc nhum ca mu th Ct. Khi xc nh c Ct s tnh c hm lng cht mu thc trong thuc nhum. chnh xc ca phng php cn ph thuc vo nhiu yu t, trong phng php pha dung dch thuc nhum cn c bit lu . pha dung dch thuc nhum: vic u tin cn tnh ton l la chn nng dung dch thuc nhum ti u. c c nng , trc tin cn pha dung dch thuc nhum vi nng 0,05 g/l, ri o mt quang hc ca dung dch bc sng cc i max. Nng ti u s c tnh ton theo cng thc: 1.0,05.10 G= , g/l D max trong : 1- mt quang hc cho trc cc i; 0,05 - nng dung dch thuc nhum, g/l; 10 - h s pha long dung dch, g/l; Dmax - mt quang hc o c. Bit c G, cn lng thuc nhum ti u pha trong mt lt nc. Sau ly 10 ml dung dch thuc nhum pha long vo bnh nh mc 100 ml (h s pha long l 10). Nu nhit thng thuc nhum ho tan cha tt th cn phi un dung dch thuc nhum n 80 - 90oC. Nhng thuc nhum khng ho tan trong nc phi s dng cc dung mi khc nh cn, benzen, piriin, H2SO4 hoc phi thm vo dung dch cc cht tr khc nh: cht hot ng b mt Na2CO3, NH4OH v.v. Trong mi trng hp cn c c dung dch thuc nhum khng c, trong sut, khng cha tp cht. Vic o mt quang hc c thc hin ngay sau khi pha dung dch thuc nhum (tr khi c ch dn th mi pha trc).

169

 m bo chnh xc cn phi o mt quang hc ca cc mu trong cng mt iu kin: kch thc hnh dng, cht liu ca cc o (cuvet) phi hon ton ging nhau v c b dy 1 cm. Trc khi o cn kim tra v iu chnh cc thang chnh bc sng cng nh thang ch mt quang hc. Nhng thuc nhum km bn vi nh sng th khi pha dung dch cng nh khi o cn trnh tip xc vi nh sng. Nhng thuc nhum c kh nng hp ph ln thch anh hoc thy tinh th trc khi th nghim cn ngm ra cc cuvet trong dung dch thuc nhum. Nu thuc nhum nhy thay i theo mi trng th cn n nh tr s pH ca mi trng trong qu trnh o bng cc dung dch m. My quang trc ph hot ng trong iu kin nhit 18 - 25oC. u tin cho dng nh sng i qua cuvet cha dung mi, sau qua cuvet cha dung dch thuc nhum. Vi khong bc sng 400 - 760 nm s thc hin o mt quang hc sau mi on 20 nm. Ring nhng im un v im cc i s phi o nhiu hn, phi o cch on 10 nm hoc ngn hn c c nhiu im cc tr v im un r rng. Mi mu thuc nhum cn pha ba loi dung dch c nng khc nhau nhng sai s khi o mt quang hc (trung bnh ca ba ln o) khng c vt qu gii hn cho php. Thng thng D sai s khng vt qu 0,01; nu ln hn 0,04 th php o khng hp l. Sai s trung bnh c tnh ton nh sau: Vi mi bc sng xc nh, o c cc gi tr D; gi tr trung bnh: D Dtb = n trong gi tr n - s lng im ph o c cho mi loi dung dch thuc nhum. Gi tr sai s tuyt i ca mt quang hc i = Dtb Di, i l s dung dch c pha ra o. Gi tr sai s trung bnh:
i = n

itb
trong khng ly cc im c D < 0,2.

T cc gi tr thu c xy dng th c trc honh l bc sng (10 mm tng ng 20 nm) v trc tung l mt quang hc trung bnh Dtb ( 10 mm tng ng 0,1 n v D). Khi nng dung dch thuc nhum c tnh theo nng dung dch mu chun: b Ct = 100% a trong : a - tng trc tung ca mt quang hc ca mu chun; b - tng trc tung ca mt quang hc mu th. Vi nhng thuc nhum c kh nng hp th chn lc th ng cong ca chng c cc im cc i r rt, trong tnh ton ch cng nhng gi tr gia hai im cc i v trong khong = 30 nm. c bit i vi nhng thuc nhum c thun khit cao, c th tnh nng theo kt qu o trong phm vi bc sng hp v cng tt c cc im trc tung trn ng cong ch tr nhng im c D < 0,2. Cc thuc nhum c ng cong vi cc im cc i khng r rt (thuc nhum mu ghi, mu en, mu gch, mu liu...) th phi tnh nng theo tt c cc im ca cc ph. Cc sai s tnh ton nng ca mu th so vi mu chun cho php cc gii hn sau: 170

itb
0,005 - 0,01 0,011 - 0,02 0,021 - 0,03 0,031 - 0,04

sai s nng cho php % 2 3 4 5

Da vo ng cong hp th trn th cn c th tnh ton mc sai khc v nh mu gia mu th v mu chun. Vi mi bc sng tng ng trn th c th tnh c hiu s mt quang hc q1 = Dc1 Dt1 q2 = Dc2 Dt2 qn = Dcn Dtn Mc phn tn nh mu: qo =

q1 + q 2 + ... + q n n

trong : n - s ln tnh ton; Dc - mt quang hc ca dung dch chun; Dt - mt quang hc dung dch th. Nu qo 0,03 th hai thuc nhum c nh mu hon ton ging nhau. Tuy nhin gii hn qo cng c th cao hn khi thc hin o mt quang hc ca dung dch thuc nhum c nhy km. 2.3. Phng php trc quang (so mu quang in) C s ca phng php ny cng ging nh phng php trn, nhng n n gin hn v c s dng rng ri trong nhiu lnh vc. Nguyn tc chung ca phng php ny l so snh mt quang hc ca dung dch thuc nhum mu th vi mu chun. Th nghim c tin hnh trn my so mu quang in vi cng cc iu kin ging nhau: chiu sng, knh lc v cuvet v.v. Khi vi mt cht ho tan trong dung mi, mt quang hc s t l thun vi nng ca dung dch. T quan h ny c th xy dng th m trc tung l mt quang hc D v trc honh l nng thuc nhum trong dung dch C. Nhng dung dch hon ton tun theo nh lut Lambert Bera th th D C l tuyn tnh, cn nu khng hon ton tun theo nh lut th th D C s l ng cong. Khi xy dng th mu chun, cn phi pha dung dch theo cc khong nng sao cho n bao gm cc nng c th ca dung dch mu th. Nu khng ch dn c th loi knh lc cho tng thuc nhum th cn phi chn knh lc sao cho t c Dmax i vi dung dch. Sau khi c th chun D C, tin hnh o mt quang hc Dy ca dung dch th trong cng iu kin (ngun sng, knh lc, cuvet) nh khi xc nh mu chun. Theo th chun s xc nh c nng Cy qua Dy ca dung dch th. Bng cch o ny c th xc nh c hm lng thuc nhum cn li trong dung dch sau cc khong thi gian nhum. Trng hp cn so snh t l thuc nhum gia mu th v mu chun cng loi th sau khi tm c nng Ct, trn th D C ca mu chun c th tnh ton theo cng thc: C.100 ,% Xl = G trong : C - nng ca dung dch mu th tm c trn th mu chun, g/l; G - lng thuc nhum ca mu th pha trong dung dch, g/l. 171

Nu bit c hm lng cht mu tuyt i trong mu chun th s xc nh c hm lng trong mu th theo cng thc: C.B X2 = ,% G trong : B - hm lng cht mu tuyt i trong mu chun, %. Ngoi ra cn c th xc nh nng thuc nhum bng phng php c coi l n gin nht nh sau: cn lng thuc nhum ca mu chun v mu th nh nhau pha trong lng dung dch nh nhau, ri tin hnh o mt quang hc ca hai dung dch trong cng iu kin ging nhau: knh lc, cuvet. Thng qua mt quang hc c th xc nh nng thuc nhum: D .100 X3 = t ,% Dc trong : Dc - mt quang hc ca dung dch mu chun; Dt - mt quang hc ca dung dch mu th. 2.4. Phng php phn tch ho hc Phng php ny c tc dng b sung cho cc phng php trn v n c kh nng xc nh c th cc nhm chc c trong cu to phn t thuc nhum. Phng php kh c s dng phn tch cc loi thuc nhum azo, nitro, nitrozo, cc loi thuc nhum c cu to quinoit v mt s thuc nhum khc. C s ca phng php phn tch ho hc l phn hy cc phn t thuc nhum to ra cc hp cht n gin c th bit cu to v nh phn chng bng cc ho cht thng thng. Nu trong phn t thuc nhum c cha mt loi lin kt nhm chc nh
O O R O th vic phn hy xy ra d dng bng cc phn ng kh, thu phn, oxy ho hoc nhit hy. Nhng nu phn t thuc c mt s nhm chc khc nhau th phi thc hin mt lot phn ng.
N N ;

NH

Th d, ANHO2SArN=NArCONHB 3 1- phn ng kh; 2- phn ng thy phn bng kim; 3- phn ng thy phn bng axit. i vi cc loi thuc nhum c cha nhm azo, vic phn hy thnh sn phm n gin xy ra nhm azo nh cc cht kh. i vi cc loi thuc nhum azo trc tip, axit, hot tnh c th s dng cc cht kh VSO4, SnCl2 ; bt km trong CH3COOH long. Thuc nhum azo phn tn kh bng bt km trong CH3COOH dng bng, pigment kh bng SnCl2 v bt km trong hn hp HCl + CH3COOH bng. Sau khi ph t mch chnh, to cc hp cht n gin, c th s dng phng php nh phn ho hc hoc phng php sc k xc nh hm lng cc cht. Th d, phng php nh phn ho hc thuc nhum azo v nitro theo phn ng: 172 1 2

ArNO2 + 6VSO4 + 3H2SO4 ArN=NAr + 4VSO4 + 2H2SO4

A1NH2 + 3V2(SO4)3 + 2H2O ArNH2 + ArNH2 + 2V2(SO4)3

Lng d ca VSO4 trong cc phn ng trn c nh phn bng dung dch [Fe(NH3)6]SO4. Cc bc phn tch v tnh ton c th tham kho trong ti liu. 3. CC PHNG PHP KIM NGHIM TNH CHT THUC NHUM 3.1. Xc nh kh nng ho tan i vi cc loi thuc nhum ho tan trong nc cn xc nh kh nng ho tan ti a ca chng. Phng php c tin hnh nh sau: Cn 5 g thuc nhum (chnh xc ti 0,01 g) ho tan trong 100 ml nc ct; un si dung dch trong 2 pht, ri lc trn phu c t nng khng di 90oC. Nu lng thuc nhum khng ho tan ht th s c cn trn giy lc. Khi phi lm li th nghim vi lng thuc nhum gim dn: 4 g; 3 g; 2 g; 1 g. Nu 5 g thuc nhum ho tan ht hon ton th li tng lng thuc nhum 6 g; 7 g; 8 g, 9 g v hn na cho n khi c dung dch bo ho (tc l lng cn trn giy lc cn t nht). Sau cc th nghim s b trn s tin hnh xc nh chnh xc kh nng ho tan ca thuc nhum bng phng php so mu quang in. Dung dch so mu l dung dch bo ho c lc b cn ri pha long n th tch cn thit. Cn c vo mt quang hc o c, i chiu vi th chun s tm c nng ca dung dch C (g/l). Kh nng ho tan ca thuc nhum tnh theo cng thc: P = C.K, g/l K - mc pha long. Trong trng hp c mu chun i chng, nu lng thuc nhum ca mu th bng lng thuc nhum mu chun nh bit trc m ho tan hon ton th kh nng ho tan ca chng nh nhau v khng cn xc nh na. Kh nng ho tan ca thuc nhum c nh gi theo cc cp qui nh nh sau: ho tan, g/l 10 11- 20 21 - 30 31 - 40 > 40 C p 1 2 3 4 5

Ring vi thuc nhum hot tnh, khi ho tan cc mu th phi tin hnh trong mt s dung ch khc nhau. i vi thuc nhum hot tnh thuc nhm nhum lnh th phi xc nh trong hai dung dch: a) Nc ct nhit 20oC; b) Dung dch NaCl (30 g/l) nhit 20oC; i vi nhm nhum m, ngoi hai loi dung dch trn cn ho tan trong hai dung dch: c) Nc ct c nhit 50oC. 173

d) Dung dch NaCl (30 g/l) c nhit 50oC. i vi nhm nhum nng cn ho tan thm trong dung dch sau: e) Dung dch Na2CO3 (20 g/l) nhit 50oC. xc nh khi lng mu cn ti u, u tin cn 12,5 g thuc nhum ho tan trong 250 ml cc dung dch cn thit trn. Sau cc dung dch c gi nhit ti u v khuy nh trong thi gian 15 ph, ri lc dung dch. Nu 12,5 g thuc nhum khng ho tan ht, tc l cn li lng cn trn giy lc th phi cn lng thuc nhum t i: 10 g; 7,5 g; 5 g... Nu 12,5 g ho tan ht hon ton th cn lng thuc tng ln: 15 g; 17,5 g; 20 g. Lng thuc nhum ti u s tng ng vi mu ho tan cn li t cn nht trn giy lc. i lng chnh xc ca ho tan s xc nh tng t nh trn bng phng php so mu dung dch ca mu ti u. 3.2. Xc nh phn tn ca thuc nhum khng tan C nhiu phng php xc nh phn tn nh sau: 3.2.1. Phng php hin vi Phng php ny cho php va quan st va xc nh kch thc ca cc ht thuc nhum. Thuc nhum khng tan cn c chuyn v dng huyn ph bng cch cn 0,01g thuc nhum trn vi mt t nc ct to dng huyn ph sao cho khi soi di knh hin vi c th quan st c cc ht thuc nhum ring r. o kch thc cc ht thuc nhum cn tng t l phng i ln 600 ln. Nh git huyn ph ln knh, dn u, ri di chuyn sao cho nhng phn ht cn o c nm gia cc vch chia ca ng th knh. Gi tr ca mi vch chia trn ng th knh c xc nh trc cho mi h s phng i bng cch so snh gia cc vch chia ca thc o th knh vi vch chia ca thc o vt knh. 3.2.2. Phng php nh git Cn 0,25 g thuc nhum, trn vi mt t nc ct c huyn ph ng nht, sau cho nc n 50 ml khuy u v dng pipet (0,5 ml) ht ly mt lng huyn ph ri nh git ln giy lc v nh gi phn tn bng cch quan st trc quan theo cc cp qui nh sau: - cp 1: git huyn ph lp tc tch lp nc ngay sau khi nh git ln giy, thuc nhum nm trong trung tm git; - cp 2: vt mu nho t; - cp 3: vt mu m r rt; - cp 4:.vt mu yu i, mt phn giy lc nhum u; - cp 5: ton b vt mu r u. Trong cp 5 l cp c phn tn tt nht. 3.2.3. Phng php lng Xc nh phn tn bng cch so snh gia mu chun v mu th. Cn 0,5g thuc nhum ( chnh xc ti 0,0002 g) trn u vi 250 ml nc ct nng (80 - 90oC) v to dung dch huyn ph ng nht. Chuyn dung dch sang ng ong v gi yn trong 8 - 4 h vi nhit 85 2oC. Sau dng ng xiphng ht phn trn dung dch cho 190 ml (khng khuy ng phn di). T dung dch ht c ly ra 174

5 ml (mi mu) a vo bnh nh mc (100 ml) v pha long bng axeton n vch bnh. Tng t nh vy chun b dung dch thuc nhum t huyn ph cha sa lng. Hai mu dung dch c em o mt quang hc v xc nh phn tn theo cng thc: D D= 2 D1 trong : D2 - mt quang hc dung dch thuc nhum sau qu trnh sa lng; D1 - mt quang hc dung dch thuc nhum khng sa lng. Kt qu trung bnh ca cc mu khng sai khc qu 10% s c coi l kt qu th nghim. Theo phng php ny c th tin hnh bng cch pha dung dch huyn ph nh sau: Cn 2 g thuc nhum trn vi mt t nc ct ri pha long bng nc nng (80 85 C) n th tch mt lt. Chuyn dung dch sang ng ong mt lt. T dung ch huyn ph ny ly ra hai mu 5 ml, ri ng ong trong bnh n nhit ( 85 2oC), gi yn trong 3 h. Sau dng xiphng ht ra 750 ml dung dch, t dung dch ny ly ra hai mu 5 ml. Mi mu dung dch ny cng vi mu ly trc khi lng, cho vo cc 50 ml ri ho tan bng 10 ml axit H2SO4 m c. Sau rt c dung dch ny sang bnh mt lt c cht hot ng b mt khng mang ion (4 g/l) pha sn. Dung dch pha long n mt lt c s dng o mt quang hc cng vi dung dch thuc nhum (pha ch tng t) trc khi sa lng.
o

Kt qu tnh ton ging phng php trn. 3.2.4. Phng php sc k C th s dng sc k giy xc nh phn tn ca thuc nhum khng tan. Cch tin hnh nh sau: dng loi giy chuyn cho sc k ct thnh hnh ch nht chiu di 90 mm, rng 70 mm ri cun li thnh hnh tr. Mu thuc nhum c pha thnh dung dch huyn ph 1%. Ly 10 ml mi mu cho vo cc (50 ml) v 10 ml nc cho vo mt cc ring lm mu i chng. Nhng ng giy sc k trn vo cc cc dung dch. Quan st (ng giy nhng trong cc nc, khi thy nc thm u pha trn st mp ng giy th b tt c cc ng giy cc mu ra v sy trong khng kh. Tip theo ngi ta xc nh cao ca vt dung dch trn ng giy cng mu ca vt v cc ht bm trn phn ng giy tip xc vi b mt dung dch s th hin mc phn tn ca thuc nhum. Thng thng ngi ta tin hnh bng cch so snh mu th vi mu chun. 3.3. Xc nh kh nng hp ph ca thuc nhum ln vt liu nhum Mu vt liu phi qua x l lm sch, cn mi mu 1 g, nhum vi moun 40. i vi mi loi thuc nhum phi s dng cc mu vi si cho ph hp. Cc mu th nghim c nhum trong cng iu kin ging nhau: nhit , dng c nhum, n cng ngh. Mi loi thuc nhum c pha ch theo cc n s dng hoc ch dn trong ti liu cng ngh. xc nh tc hp ph thuc nhum ch thay i thi gian nhum trong su mu ng thi: 1 ph; 5 ph; 10 ph; 15 ph; 30 ph; 60 ph. Ly dung dch sau nhum o mt quang hc v so snh vi dung dch trc khi nhum. cho nng thuc nhum t b sai lch, cn nhum trong bnh c lp sinh hn, khi vt mu vi si ra cn b sung cho lng dung dch nh ban u v thng nht trong tt c cc mu. Lng thuc nhum cn li trong dung dch c tnh theo cng thc: 175

B=

D2 100% D1

trong : D1 - mt quang hc ca dung dch thuc nhum trc khi nhum; D2 - mt quang hc ca dung dch sau mt thi gian nhum. Lng thuc nhum c hp ph ln vt liu nhum: A = 100 B Vi cc thi gian nhum khc nhau s tnh c A tng ng v s xy dng c th v kh nng hp ph ca thuc nhum. 3.4. Xc nh nhy ca thuc nhum vi nc cng Mi loi thuc nhum c nhy nht nh vi nc cng ty theo tnh cht ca n, v vy cn xc nh bit tnh nng ca mi loi. Phng php thc hin c th nh sau: i vi thuc nhum trc tip, vic xc nh c tin hnh khi nhum trong hai loi nc: nc c cng xc nh: 3,57 mlg/l (khng cho thm soa) v nc ct. Quy trnh nhum tin hnh nh nhau v kt thc qu trnh nhum, mu c em so snh nh gi kt qu theo cc tiu chun qui nh nh sau: - cp 1: rt nhy khi cng ln mu ca mu th yu hn hn mu nhum trong nc ct, - cp 2: nhy, khi cng mu ca mu th km hn cht t so vi mu nhum nc ct; - cp 3: t nhy khi cng mu t sai lch so vi mu chun; - cp 4: khng nhy khi cng mu ca hai mu bng nhau (thm ch c khi hn). Thuc nhum hon nguyn khng tan v thuc nhum lu hunh c kim tra vi bn loi nc: - nc ct coi l mu chun; - nc cng c cng 3,57 mlg/l; - nc cng c cng 7,13 mlg/l; - nc cng c cng 10,70 mlg/1. Cc mu nhum trong cng mt iu kin theo n cng ngh cho tng loi thuc nhum. Sau nhum cc mu c sy kh v nh gi theo cc cp qui nh trong thang chun mu ghi, mu chun l mu nhum trong nc ct. Thuc nhum axit v thuc nhum cm mu s c tin hnh nhum trong ba loi nc: - nc ct; - nc cng c cng 5,34 mlg/l; - nc cng c cng 8,91 mlg/l; Cch tin hnh Cn mi mu thuc nhum 0,25 g ( chnh xc n 0,0002 g). Ho tan thuc nhum vi tng loi nc cho mi mu: u tin cho 5 ml nc nh nhuyn ri mi pha long bng nc nng khuy cho tan u, ri chuyn sang bnh nh mc (250 ml) v lm lnh dung dch n 20oC; b sung nc n vch bnh s c dung dch thuc nhum vi nng 1 g/l. S dng vi len lm sch nhum; t l thuc nhum ly t 3 - 6% so 176

vi vi, moun nhum: 50. Cc iu kin nhum c thc hin ging nhau vi tt c cc mu, cc mu vi sau khi nhum c so mu theo thang chun mu ghi. Cc chi tiu c nh gi theo cc qui nh sau: - cng ln mu v nh mu; - bn mu vi dung dch x phng, m hi v c xt; - kh nng u mu. Hai ch tiu trn nh gi bng cc cp qui nh sau: - cp 1: nu s sai khc gia mu chun v mu th rt ln; - cp 2: s sai khc tng i r; - cp 3: s sai khc trung bnh; - cp 4: s sai khc khng ng k; - cp 5: khng c s sai khc. 3.5. Xc nh kh nng u mu ca thuc nhum i vi thuc nhum trc tip, kh nng u mu c xc nh bng s khng u mu ca giai on nhum u v s di tn thuc nhum t vi mu sang vi trng. Xc nh s khng u mu ca giai on nhum u bng cch sau y: pha dung dch nhum, khng ch nhit nhum ti u, dng hai mnh vi phin bng gi h, nhng cha ty trng th nghim. Bt u nhum mnh vi th nht v tnh gi, sau 2 ph nhum mnh vi th hai, sau 3 ph na th vt c hai mnh vi ra, git sch v sy kh. Vic nh gi s khng u mu c thc hin bng cch so mu mu nhum th hai vi mu nhum th nht v tnh theo phn trm. Mu th nht c coi l 100%, mu th hai s l A%. Xc nh s dy mu c thc hin bng cch gia cng hai mu vi phin (mu th nht nhum mu chun, mu th hai trng) trong dung dch cha cc cht ph tr. Gi nhit , moun v hm lng cc cht ph tr ging nh khi nhum mu chun. Thi gian gia cng l mt gi. Sau ly mu em git, sy v tin hnh so mu. Mu chun c coi l 100% th s dy mu sang vi trng c nh gi l B%. Kh nng u mu ca thuc nhum c tnh bng tng A v B v c nh gi nh sau: Gi tr A + B, % < 40 41 - 55 56 - 75 > 75 a - kh nng khng u mu ban u;. b - kh nng san bng mu trong qu trnh nhum; c - mc di tn thuc nhum. Th nghim xc nh a: ly cc mu vi phin bng ty trng ging nhau v c khi lng 2,5 g. Nhum mu vi th nht trong dung dch nhum c chun b theo n cng ngh chun, cha c mui; sau 2 ph nhum nhit ti u th cho tip mnh 177 kh nng u mu km trung bnh tt rt tt

i vi thuc nhum hon nguyn th kh nng u mu c xc nh bng ba ch s:

vi th hai vo nhum, sau 3 ph th vt c hai mnh vi ra, oxy ho v git sch. Th nghim xc nh b: phng php tin hnh tng t nh trn, ch khc l sau khi cho mnh vi th hai s phi nhum trong 40 ph mi c vt ra, oxy ho v git sch. Th nghim xc nh c: ly mt mu vi nhum mu trn nhng cha nu x phng em x l trong dung dch kim kh vi mt mnh vi trng tng t. Thnh phn dung dch kim kh c chun b theo nh n kh cho mi thuc nhum. u tin x l nhit kh ca Na2SO4 (50 - 60oC) trong thi gian 15 - 20 ph. Sau x l tip nhit ti u cho mi nhm thuc nhum (nhm nhum lnh: 20 - 30oC; nhm nhum m: 40 - 50oC; nhm nhum nng: 60 - 80oC) trong khong thi gian 30 - 35 ph (i vi nhm nhum m v nng), trong 45 - 50 ph i vi nhm nhum lnh). Cc mu vi sau khi nhum cng nh sau khi x l c s dng so mu. C th so mu trn vi v cng c th trch ly thuc nhum ra dung dch ri tin hnh phng php so mu quang in. Phng php trch ly thuc nhum hon nguyn a vng c th thc hin nh sau: mu vi nhum mu (vi khi lng 0,5 g) x l trong dung dch gm: NaOH (dung dch 32,5%): 12 ml/l; Na2S2O4: 10 g/l; etylxenlozol: 500 ml/l; nc: 488 ml/l. Qu trnh trch ly thuc nhum bt u nhit thng trong 10 ph, sau nng nhit n 60 70oC v x l trong 30 ph. Vic trch ly c lp i lp li nhiu ln v mi ln ch s dng vi mililit dung dch m bo m c cn thit. Sau khi trch ly ht thuc nhum khi vi, hp nht tt c dung dch lm mt o mt quang hc cho tng mu. Nu thuc nhum hon nguyn thuc h inigoit v tioinigo th c th trch ly theo phng php nhanh hn: ly mu vi mu (0,2 g) nghin mn v ho tan trong 10 ml H2SO4 m c (d = 1,84); thi gian ho tan 15 - 30 ph. Sau dung dch vo bnh nh mc cha 70 ml H2O v 5 ml dung dch 8% cht hot ng b mt khng ion. Lc dung dch cho tan u v b sung nc cho 100 ml tin hnh so mu. Sau khi o c mt quang hc ca cc dung dch trn c th xc nh cc ch s nh sau: D D D a= 1 ; b= 3 ; c= 5 D2 D4 D6 D1, D2 - mt quang hc ca dung dch trch ly t mu nhum 3 ph v 5 ph th nghim 1. D3, D4 - mt quang hc ca dung dch trch ly t mu nhum 2 ph v 42 ph th nghim xc nh b; D5, D6 - mt quang hc ca dung dch trch ly t mu vi nhum mu v vi b dy mu th nghim xc nh c. a+b+c Gi tr trung bnh s cho bit kh nng u mu ca thuc nhum theo cc 3 ch tiu c quy nh nh sau: Gi tr trung bnh, % > 75 65 - 75 50 - 65 < 50 178 nh gi Thuc nhum c kh nng u mu rt tt Thuc nhum c kh nng u mu tt Kh nng u mu trung bnh Kh nng u mu km C p 4-5 3-4 2-3 <2

i vi thuc nhum axit kh nng u mu c xc nh bng s chnh lch cng ln mu ca cc mu nhum cch nhau trong khong thi gian 5 ph. Mu nhum l loi vi len (1 g) dung tch nhum c chun b nh sau: lng thuc nhum: 1% so vi khi lng vi; Na2SO4: 10% so vi vi; dung dch CH3COOH: 30%: 3 - 5% so vi vi. Dung dch un n si th cho mu vi th nht vo nhum, sau 5 ph cho mu th hai v c cch 5 ph li cho tip cc mu khc cho n ht. Nhum cc mu trong thi gian 1 h k t mu u. Kt thc qu trnh nhum cc mu c vt ra, git sch, sy kh. Xc nh cng nhum mu ca cc mu vi bng cch o h s phn x trn my quang k. xc nh nng thuc nhum trn mu vi thng qua h s phn x, cn phi c th chun gia nng thuc nhum v h s phn x. Xy dng th chun bng cch nhum mu vi trong cc dung dch c nng chun: 0,3%; 0,6%; 0,9%; 1,2%; 1,5% thuc nhum so vi khi lng vi ri o h s phn x c c ng cong ph thuc gia h s phn x v nng thuc nhum. Sau khi tnh c nng thuc nhum trn mu u v cc mu sau l A v B s c c t s B/A; gi tr ca t s ny s qui nh cc cp u mu cho thuc nhum. B/A < 0,20 0,21 - 0,40 0,41 - 0,60 0,61 - 0,80 0,81 - 1,0 Cp 1 2 8 4 5

T s cng thp, tc l A cng ln, c ngha l thuc nhum axit c i lc vi len cng ln th u mu cng km (cp 1). Kh nng u mu ca thuc nhum phn tn c xc nh bng cch so snh cng ln mu ca hai mu nhum cch nhau 5 ph. Mu vi nhum l polyamit, mi mu cn 0,5 g vi c git sch. Dung dch nhum gm: 1 g/l cht hot ng b mt (c th loi anion, c th loi khng mang ion); lng thuc nhum 0,2 - 3% so vi vt liu nhum; moun nhum: 50. Dung dch nhum c un n nhit 90 95oC th cho mnh vi th nht vo nhum, sau 5 ph cho mnh vi th hai, ri nhum nhit trn trong thi gian 1 h 30 ph. Kt thc qu trnh nhum mu vi c vt ra, git nng, git lnh v sy kh. nh gi bn mu bng cch so snh cng ln mu ca hai mu nhum theo thang so mu ghi ri nh gi cp ca n. 3.6. Xc nh kh nng git sch phn thuc nhum hot tnh cha nh hnh S dng mu vi si va mi nhum bng thuc nhum hot tnh, p n mc p 100%, git mu trong nc lnh 10 ph, sau git trong nc ct 70oC trong 10 ph v cui cng git trong dung dch cht hot ng b mt khng mang ion (hm lng 2 g/l) nhit 95oC vi thi gian 15 ph. Moun trong cc ln git trn l 100. Sau mi ln git u p mu v cc dung dch p ra c tp trung li em so mu v xc nh hm lng thuc nhum b git ra khi vt liu nhum. Nu vi in hoa th quan st s di chuyn thuc nhum ln cc vn hay nn trng. Da vo kt qu nh gi, c th chia thuc nhum hot tnh thnh bn nhm sau: 1- thuc nhum c kh nng git sch tt v khng b dy mu sang vn trng khi git mnh; 179

2- thuc nhum c kh nng git sch mc trung bnh; c mt lng nh thuc nhum dy mu sang vn trng khi git mnh; 3- thuc nhum c kh nng git sch km: dy mu sang vn trng trong mi iu kin git bnh thng; 4- thuc nhum c kh nng git sch rt km: chng dy mu rt mnh sang vn trng nn khng th s dng cho in hoa c. 3.7. Xc nh mc lin kt ca thuc nhum hot tnh vi x Mu vi si ty trng (nhng khng qua lm bng) c nhum bng thuc nhum hot tnh. Sau khi nhum, vt mu ra em git iu kin ging nh phn 2.6, chng IV. Nc lu sau khi nhum v nc git c em so mu xc nh lng thuc nhum cn li trong dung dch (B) v lng thuc nhum phai ra khi git (C). Mc lin kt ca thuc nhum tnh theo cng thc: ABC X= 100% A A - lng thuc nhum s dng khi nhum. 3.8. Xc nh bn ca thuc nhum lu hunh trong qu trnh bo qun Cn su mu thuc nhum, mi mu 1 g trong chn cn ri t chng trong bnh ht m. Di y bnh cha nc v mt lng nh phenol. yn bnh nhit trong phng (20 - 30oC) chn thi im sao cho trong 10 ngy th nghim, nhit khng b chnh lch qu (20 - 30oC 1o), c th cho khng kh lu thng trong bnh. Sau thi gian th nghim xc nh kh nng nhum mu ca cc mu v so snh vi mu thuc nhum khng qua th nghim. bn ca thuc nhum lu hunh c phn ra ba nhm: 1- thuc nhum gi c kh nng nhum mu; 2- thuc nhum gim mt phn kh nng nhum mu (10%); 3- thuc nhum gim kh nng nhum mu rt mnh (>20%). 3.9. Xc nh s ph hp ca thuc nhum trc tip khi gia cng nhit cao S dng phng php so snh s thay i mu v nh mu gia cc mu nhum iu kin tiu chun v iu kin nhit cao (120oC v 140oC). Ba mu vi bng c nhum trong dung dch ging nhau ba iu kin nhit : 1- nhum theo quy trnh cng ngh thng thng; 2- nhum nhit 120oC; 3- nhum nhit 140oC. Mu th nht c nhum theo quy trnh cng ngh thng thng dung dch mt. Mu th hai v mu th ba c nhum theo quy trnh sau: Dung dch hai c un nng n 120oC trong 20 ph, dung dch ba c un nng n 140oC trong 30 ph. Nhum mu th hai v mu th ba trong dung dch nhit tng ng trn trong 60 ph. Sau khi nhum, h t t nhit cc dung dch nhum trong 20 ph, ri lm ngui cc dung dch nhum bng nc lnh n nhit thng trong 10 ph, sau git mu trong 15 ph. Cc mu nhum c so mu v nh gi theo thang so mu ghi v nh gi theo cp qui nh. Nhng thuc nhum t c cp 4 tr ln c coi l ph hp vi nhit cao v thng c k hiu du cng (+). Cn thuc nhum t di cp 4 coi l khng ph 180

hp v c du tr (). Nhng nhn chung th d t hay nhiu thuc nhum trc tip cng b thay i nh mu khi gia cng nhit cao trn 100oC. 3.10. Xc nh bn ca dung dch thuc nhum hon nguyn sau khi kh th nghim cn pha 100 ml dung dch kim kh m c: 20 g thuc nhum 17 - 20 NaOH 10 - 60 g Na2S2O4 (pha thnh dung dch 32,5%) (ty theo tng thuc nhum

Thuc nhum dng bt em trn vi mt t nc, nh nhuyn thnh dng nho. Tip thm nc, dung dch xt v nng nhit ca dung dch n nhit kh (50 60oC), khuy o u v gi cho nhit khng i. Thm vo dung dch lng Na2S2O4 cn thit.Trn u v gi hn hp yn trong 15 - 20 pht thc hin qu trnh kh. Dung dch lyc baz c vo bnh c cao nh (11 cm). t bnh vo thit b n nhit gi cho nhit n nh. xc nh n nh ca dung dch lyc baz trong qu trnh bo qun cn tin hnh nh sau: dng pipet ly 0,5 ml dung dch t bnh trn v chuyn vo bnh nh mc (100 ml) c cha sn dung dch gm: 5 ml dung dch 3% cht hot ng b mt khng mang ion v 94,5 ml dung dch kim kh (gm 6 g Na2S2O4 v 15 ml dung dch NaOH 32,5% trong 1 lt dung dch. Cc mu th nghim c chun b theo cc khong thi gian 10 ph; 20 ph; 30 ph; 40 ph; 60 ph; 90 ph; 120 ph; 180 ph; 300 ph sau khi pha dung dch lyc baz m c. Mu chun c coi l mu sau khi pha dung dch. Tt c cc mu c em so mu xc nh nng ca hp cht lyc baz. Thi gian (tnh theo pht) m nng hp cht lyc baz tng ng nh mu chun s xc nh tnh cht bn n nh ca dung dch lyc baz. Ngoi ra cn c th xc nh bn ca dung dch thuc nhum bng cch nhum mu sau cc thi gian v nh gi s thay i cng mu cng nh nh mu ca mu nhum. T pha trn lp dung dch ly ra 0,5 ml cho vo cc nh (50 ml) c cha sn 40 ml dung dch gm: 2 - 4 g/l Na2S2O4; 6 - 8 ml/l dung dch NaOH 32,5%; 5 - 30 g/l NaCl. Ly 1 g vi phin trng thm t bng dung dch gm 1,5 ml/l dung dch NaOH 32,5%; 1 g/l Na2S2O4 v nhum trong 45 - 60 ph nhit ti u cho mi thuc nhum. Cc mu nhum th nghim sau cc khong thi gian khc nhau c nh gi theo cp qui nh v bn ca dung dch lyc baz c coi l khong thi gian khi nh mu v cng mu nhum cha b thay i so vi mu nhum ngay sau khi kh. 3.11. Xc nh nh hng ca cc cht oxy ho n mu nhum ca thuc nhum hon nguyn Nhum tm mu vi phin trng bng thuc nhum hon nguyn theo phng php kim kh. Sau nhum, cc mu vi c nhng vo nc lnh trong 30 s ri tin hnh th nghim qu trnh oxy ho trong cc dung dch sau: 1- ngoi khng kh; 2- Cho qua dng nc lnh; 3- Ngm trong dung dch gm 1 g/l K2Cr2O7; 3 ml/l dung dch CH3COOH 30%; 4- Dung dch gm: 3 ml/l H2O v 3 ml/l dung dch CH3COOH 30%; 5- Dung dch gm: 3 ml/l H2O2 v 3 ml/l NH4OH 25%; 181

6- Dung dch 3 ml/l H2O2; 7- Dung dch gm: 2 g/l NaNO2 v 5 ml/l H2SO4; 8- Dung dch cha natri perborat 3 g/l. Qu trnh oxy ho tin hnh nhit 50oC trong 10 ph, moun l 40. Sau nu x phng (dung dch cha 5 g/l x phng), git nng, git lnh v sy kh mu vi. so snh nh mu, coi mu th hai l mu chun. Nhng mu no c nh mu ging mu chun th cht oxy ho l ph hp, c nh du cng (+); mu no c nh mu km i th cht oxy ho khng ph hp v nh du tr (). 3.12. Xc nh nh hng ca cc ch phm hon tt n mu nhum ca thuc nhum hon nguyn Ly cc mu vi c nhum trong iu kin chun (mi mu 10 g) ct mt phn mu lm i chng, cn li tin hnh th vi cc ch phm hon tt nh: chng nhu, chng co, chng thm nc, lm mm v.v. Cc ch phm hon tt v cc cht tr khc c pha ch thnh dung dch theo tng ch dn c th. Mu vi mu kh ngm dung dch trong 1 ph, nhit 20 - 25oC; sau vt p n hm m 100% ri sy s b nhit 60 - 80oC. Sau vi c gia nhit trong 5 ph nhit quy nh cho mi loi ch phm. Tr mu lm mm s khng git, cn cc mu khc phi tin hnh git bng dung dch x phng cacbonat (1 - 2 g/l Na2CO3 v 1 - 2 g/l x phng) trong 10 ph nhit 40 60oC, moun l 40. Cui cng mu c git nng, git lnh v phi kh. Cc mu c so mu vi mu i chng, s thay i nh mu v cng mu nh gi theo cp so mu trong thang so mu ghi. S thay i nh mu s nh gi v k hiu bng cc ch ci tng ng mu chuyn nh. S thay i bn mu vi nh sng th hin bng cc du sau: ++: tng bn mu ln mt cp; + : tng bn mu ln 0,5 cp; = : bn mu khng thay i; : bn mu gim i. 4. NH GI BN MU CA VT LIU NHUM Vic xc nh bn mu ca vt liu nhum l rt cn thit nh gi ton b tnh cht ca bt k thuc nhum no. thng nht gia vic kim tra v nh gi cc kt qu thu c, T chc tiu chun quc t (International Standard Organisation - ISO) cho thnh lp y ban kim tra bn mu ca thuc nhum vo nm 1947. Tiu chun quc t c chp thun, cng b v coi nh tiu chun Anh (British Standard - BS). Tt c cc tiu chun nh gi ngy nay u c trong BS. bn mu vi mi tc nhn c nh gi bng s thay i mu ban u (phai mu) cng nh mc dy mu sang vi trng cng gia cng. Cc ch tiu nh gi theo cc cp qui nh trong hai bng mu tiu chun. Bng chun mu xanh gm tm mu vi len c nhum bng cc loi thuc nhum mu xanh chuyn dng v chng c bn nh sng khc nhau t cp 1 n cp 8. Bng chun ny dng nh gi bn mu vi nh sng v thi tit. Bng chun mu ghi gm c hai bng, trong thang 1 xc nh s thay i mu (phai mu) gm c nm cp mu vi mu ghi vi s tng phn khc nhau, cp 1 l cp c s tng phn ln nht, cp 5 c s tng phn bng khng. Thang 2 xc nh kh nng dy mu sang vi trng, n gm nm cp mu l cc vi mu vi cc mc khc nhau: t mu trng n 182

ghi v vi mu trng, cp 1 c s tng phn ln nht v cp 5 s tng phn bng khng tc l khng b dy mu. Bng chun mu ghi dng nh gi ch tiu bn mu vi cc tc nhn c l v ho l. nh gi chnh xc hn cc ch tiu bn mu c th s dng cc cp mu trung gian nh 5 - 4 (hn 4 km 5) 4 - 3; 3 - 2; 2 - 1. Khi s c 9 cp phn loi. Ngoi cc cp qui nh trn cn s dng cc ch th hin s bin i nh mu xanh hn (B), hn (R), vng hn (Y) ti hn (B), xn hn (D). 4.1. Th t xc nh bn mu Mu n gin. Ct cc mnh vi mu vi kch thc 10 4 cm nu l si mu th phi cun si vo tm nha mng trong sut c kch thc 10 4 cm hoc an li thnh tm 10 4 cm. Nu l x cng phi chi thnh mng x c kch thc 10 4 cm. Mu phc tp. Ct mu vi mu kch thc 10 4 cm, kp bn pha mt phi ca mu th mt ming vi trng cng loi (cng kch thc, cn mt kia kp ming vi trng khc loi c kch thc bng na mu mu. Mnh vi trng khc loi s dng vt liu theo qui c sau: nu vi th l bng, lanh, la t tm, axetat th ming vi trng l vixc, nu vi th l len, vixc th vi km l bng. Nu vi th l PA, Pe, Pan, Pop th vi km l bng (vixc) hoc len. Mu vi pha. Khi vi mu th gm hai thnh phn th mnh vi trng km th nht s ly cng cht liu vi thnh phn tri trong vi pha, ming th hai s l thnh phn cn li. Mu vi in. C hai mnh vi trng km ch ly bng mt na kch thc vi mu v khu c v pha mt phi ca mu th. Yu cu ca vi km. Vi trng dng kim tra dy mu phi m bo cc iu kin sau: - Nu l vi bng th phi dt theo kiu dt vn im; khi lng trung bnh 100 g/m , khng c h, khng cn li cc ho cht sau tin x l.
2

- Cc loi vi khc dt theo kiu dt vn cho hoc vn im, vixc c khi lng 135 - 140 g/m2, len: 185 - 190 g/m2. Vi c lm sch, khng c h v cc ho cht khc. Tt c cc mu vi phi dng ch trng khu xung quanh chng li vi nhau. 4.2. nh gi bn mu Sau khi th nghim vi cc tc nhn ho l cn phi git, sy mu v t nht l mt gi mi c em so snh. Vi mu trc v sau th nghim c so snh theo thang th nht ca bng chun mu ghi; vi trng trc v sau khi th nghim cng vi mu so snh theo thang th hai ca bng chun mu ghi. Cc mu so snh cn gn trc tip vi bng mu chun trn cng mt mt phng c nn mu ghi ging mu tng ng cp 3 trong bng chun. Khi so snh mu c th vi lp mu chng ln nhau quan st. ngun nh sng tiu chun nh sau: nh sng t nhin vo lc 9 - 11 h hoc 14 - 16 h, hng v pha bc vi gc nghing 45o; ngun sng nhn to phi m bo chiu sng 250 lux. Khi nh gi kt qu bn mu ca cc mu phc hp th cch vit s theo th t: cp phai mu/dy mu sang vi trng cng loi/dy mu sang vi trng khc loi. Th d: 3/2/3-4 c ngha phai mu t cp 3, dy mu sang vi cng loi t cp 2 v dy mu sang vi khc loi t cp trung gian hn 3 km 4. 183

 xc nh y c tnh bn mu ca thuc nhum trn vt liu cn tin hnh nhum th nghim vi ba loi t l thuc nhum: mt t l theo ng cng chun trong ch dn v hai t l khc c cng mu ty theo tnh cht thuc nhum v thc t s dng. 4.3. Kim tra bn mu vi git Mu kim tra c chun b nh phn trn, sau tin hnh git mu trong dung dch gm: x phng Na2CO3 M = 50 Cc mu git c th tin hnh theo cc quy trnh cng ngh sau: - git m nhit 35 - 40oC, trong thi gian 30 ph. - git nng nhit 50 - 60oC trong thi gian 45 ph. - git si nhit 93 - 100oC trong thi gian 30 ph. Sau khi git ly mu ra, gi sch v vt; g ch khu ba mp, cn li mt mp ngang, m chng ra v sy kh ngoi khng kh hoc sy nhit khng ln hn 60oC. 4.4. Kim tra bn mu vi dung dch x phng nhit 40oC Dung dch x phng 5 g/l, mu th c x l trong ung dch vi M = 50 40oC trong 30 pht, khuy o v c hai pht li p mu vo thnh cc. Sau ly mu ra vt, git nc m (40 - 50oC), ri git lnh chy trn. Cui cng vt, tho ba mp khu v sy vi trong khng kh, ch khng cho ba mnh vi b dnh vo nhau tr ch c ng khu. nh gi phai mu v dy mu theo bng chun mu ghi. Kim tra bn mu vi dung dch x phng - cacbonat nhit si Mu th trong dung dch gm: 5 g/l x phng v Na2CO3, 3 g/l 95 2oC trong thi gian 30 pht, sau dung dch ra cc, lm ngui n 40oC, ly mu ra vt nh bng tay, ri li ngm chm trong dung dch ri li vi ra vt. Lp li qu trnh ny 10 ln lin tc. Kt thc em git mu bng nc m (40oC), ri git lnh v vt, g ba mp khu, sy kh, nh gi kt qu. 4.5. Kim tra bn mu vi m hi Dung dch th gm: 5 g/l NaCl; dung dch NH4OH 25% 6 ml/l; cho mu th vo dung dch nhit 37 2oC v gi nhit 30 ph. Sau ly mu ra, vt nh, dung dch vo cc s, nhng mu vo ri li ly ra vt nh, lp i lp li nh vy 10 ln. Cho thm vo dung dch 7 ml/l axit axetic bng (pH = 5,5) ri li cho mu vo x l nhit 37 2oC trong 30 pht v lp li th nghim nh trn 10 ln. Cui cng ly mu ra t gia hai tm knh p v yn trong 4 gi, ri g ba mp khu mu khng git, phi kh hoc sy nhit thp hn 60oC. nh gi phai mu v dy mu theo bng chun mu ghi. 4.6. Kim tra bn mu vi nc bin Dung dch NaCl 80 g/1. Nhng t mu hn hp trong dung dch trn ri khng vt vo gia hai tm knh c kch thc bng hoc ln hn mu (11,5 6 cm). Dng lc 4,5 kG p mu 37 2oC trong 4 h. Sau g mu ra ch li mt ng khu v phi 184 4 - 5 g/l 2 - 3 g/l

kh hoc sy nhit thp hn 60oC. nh gi phai mu v dy mu theo bng chun mu ghi. 4.7. Kim tra bn mu vi clo Mu th l mu n gin, c thm t bng nc ct sau vt nh v cho vo dung dch na tri hyproclorit vi nng 1 - 2 g/l clo hot ng. Gi yn mu nhit mi trng trong thi gian mt gi. Sau ly mu ra git bng nc ct ri x l trong dung dch Na2SO3 3 - 5 g/l nhit mi trng trong 10 ph. Cui cng git mu v phi kh. nh gi s phai mu ca mu th theo bng chun mu ghi. bn mu vi clo c th c nh gi khi dng nc kh trng bng clo. Dung dch th ny ch cha 20 mg/l clo hot ng. Mu th c nhng vo dung dch trong 4 gi 20 2oC. Sau ly mu ra vt lng dung dch cho n khi cn li t nht ri phi kh mu v nh gi kt qu. 4.8. Kim tra bn mu vi l nng Ct bn mu vi mu vi kch thc 10 4 cm, gi li mt mnh vi i chng, cn ba mnh vi em th nghim. Nu l si th an thnh mnh kch thc 10 4 cm hoc cun ln tm ba catng 14 4 cm. Cc mnh vi mu xp ln mnh vi phin trng sao cho mt phi vi mu s tip xc vi bn l. Nu l t th mnh vi mu v vi trng phi nhng t ri vt n hm m 100%. t chng ln nhau theo ln lt: mnh vi trng t ln trn mnh vi mu t gia mnh vi trng kh di cng. Nu tin hnh l hi th xp mnh vi trng thm t (100%) ln mnh vi mu kh ri n mnh vi trng kh. Tt c cc mu u l trong 15 s, nu vt liu th l bng, lanh th nhit bn l l90 - 210oC; nu vi len, la t tm vixc, polyeste, polycorylonitrin nhit l 140 - 160oC; nu vi polyamit, axetat, pop th nhit l 115 - 120oC. nh gi kt qu theo s thay i mu ngay sau khi th nghim l sau 4 h bo qun trong iu kin chun (nhit 20 2oC, hm m 65%), phn cp bn mu theo bng chun mu ghi v th t vit: cp mu sau khi l/cp mu sau 4 h; nu l t v l hi th thm cp dy mu sang vi trng th d: 3/4/4. 4.9. Kim tra bn mu vi c xt Nguyn tc chung l cho vi mu chuyn ng c xt vi vi trng di tc dng ca lc 1 kG (lc tc dng ln u hnh tr ln vi l 1 kg). Mu vi mu thng c ct vi kch thc 18 8 cm tri trn mt c xt. Vi trng th km l vi phin ty trng khng c h vi kch thc 5 5 cm (hoc hnh trn c ng knh 6,5 cm). Vi trng c bc (hoc kp) vo u hnh tr, vi mu tri trn mt phng. Khi c xt cn tin hnh theo c chiu si dc v si ngang, mi chiu cn tin hnh c xt 10 ln trong 10 s. Nu th bn vi ma st t th phi nhng t vi mu v vi trng trong nc ct ri vt n hm m 100%. Mu t sau khi th nghim cn phi phi kh. nh gi bn mu bng s thay i mu ban u (phai mu) v dy mu sang vi trng theo bng chun mu ghi. 4.10. Kim tra bn mu vi H2O2 Mu th c chun b theo mu phc hp, ri cun li theo chiu ngang 4 cm, cho mu vo ng nghim (sao cho m bo cha c lng dung dch theo M = 80) ri 185

dung dch ty vo tin hnh th nghim. iu kin v thnh phn dung dch ty cho cc loi vt liu khc nhau nh trong bng 4.1. Bng 4.1 Loi vi si Nhit , oC H2O2 (30%), ml/l Na2SiO3 1,32, ml/l Na2CO3, g/l NaOH, g/l Cht tr, g/l Na4P2O7.10H2O, g/l MgCl2, g/l pH Thi gian La t t m 70 2 20 5 0,1 10,0 2h Vixc 82 2 6,6 4 2,5 1 0,1 10,5 1h Bng v lanh 92 2 6,6 5 2 1 0,1 11,5 1h Len v axetat 50 2 20 5 9,3 2h

Sau th nghim, ly mu ra , git 10 ph trong nc sch ri g vi em sy nhit thp hn 60oC hoc phi kh. 4.11. Kim tra bn mu vi nh sng Da vo bng chun mu xanh gm tm mu len c nhum bng cc loi thuc nhum c bn nh sng khc nhau do Vin nghin cu tiu chun Anh xc nh: BS 1006 (1978) Cp 1: thuc nhum acid blue 104 Cp 2: thuc nhum acid blue 109 Cp 8: thuc nhum acid blue 83 Cp 4: thuc nhum acid blue 121 Cp 5: thuc nhum acid blue 47 Cp 6: thuc nhum acid blue 23 Cp 7: thuc nhum solvat blue 5 Cp 8: thuc nhum solvat blue 8 Cc mu chun c kch thc 6 1 cm v mu th cng phi ct vi kch thc nh mu chun. Cc mu th v tp hp mu chun c xp nh hnh. Cc mu th c c nh ln bng sao cho chng lun c ko cng. Bng mu c a vo hm g trn c y tm knh trong sut c b dy t nht 3 mm. Khong cch t knh ti mu l 5 - 7,5 cm. Hm mu c t ra ngoi nh sng mt tri hng v pha nam vi mt gc nghing 45o. Cc mu phi c nh sng chiu vo hon ton, khng c vt no che khut, khng b bng che lp, trnh nhng ni c khi hoc kh c. tin hnh th nghim, u tin che 1/5 cc mu vi bng ba catng, trn b mt c che thm mt tm nhm v phi mu ra ngoi sng. Phi sng cc mu trong mt s ngy cho n khi nhn thy c s phai mu u tin mu chun cp 3 (bng cch phi so snh cc phn l sng v phn che khut ca mu ny). S phai mu cht t ban u th hin c su mu v nh mu. Sau che tip 1/5 cc mu v l sng cho n khi nhn thy s phai mu mu chun cp 4 v tip tc th nghim cho n khi phai mu mu chun cp 6. Tip tc phi nng cc phn b che v 1/5 phn l sng cho n khi nhn thy s phai mu mu 186

chun cp 7 t c s tng phn vi mu ban u ging nh cp 4 trong bng chun mu ghi. Khi kt thc th nghim v nh gi s phai mu ca mu th sau 24 h so vi cc mu chun cng phi nng.
A x C E A

Cc mu th

Cc mu chun Cp 1 Cp 2 Cp 3 Cp 4 Cp 5 Cp 6 Cp 7 Cp 8 F B D 1 2 3

Mu th c s phai mu trng vi mu chun no th chng t cp mu ; nu khng hon ton trng lp th c th ly cp trung gian, th d, 3 - 4 c ngha mu th c bn mu nh sng hn cp 3, km cp 4. Trong trng hp khi mu chun cp 3 bt u phai mu th mu th cng phai mu nhng sau chng khng b phai mu na cho n cp 6 th phi nh gi bn mu ca mu vi cp b sung, th d 6(3) c ngha rng bn mu gim t cp 3 sau khng b thay i v li thay i t cp 6. Vic nh gi bn mu nh sng c tnh n c s thay i cng mu, nh mu v sng. Nu mu b thay i nh (xanh hn, vng hn, hn) th phi t k hiu bn cnh cp mu. 4.12. Kim tra bn mu vi nh sng v thi tit Cc mu th c ct vi kch thc 1,1 1,5 cm ri li chia nh thnh nm phn bng nhau 2,2 1,5 cm; mu si th phi cun ln tm ba catng trng c kch thc 2,2 1,5 cm. Trong nm phn mu s gi li mt phn trong bng ti, cn li bn phn c dn ln mt vi hoc giy cng, cc mu c c nh ln bng trng thi ko cng. Cc mu chun mu xanh c t trong hm g c knh che ging nh th nghim trn. Bng mu v hm g mu chun c t ra ngoi tri, hng v pha nam vi gc nghing 45o. Cc mu th v mu chun che c phi sng qua cc ngy cho n khi c s thay i mu mu chun cp 3. Khi ly mt bng mu th ct i, che tip 1/5 mu chun v th nghim tng t cho n khi t cp 4, cp 6. Khi ny ch cn li mt mu 187

th v 1/5 mu chun li phi sng tip tc cho n khi s phai mu mu chun cp 7 t s tng phn tng ng cp 4 trong bng chun mu ghi (so vi mu ban u) th th nghim kt thc. Ngay khi c s phai mu cp 3 m mu th phai mu t ti mc bng hoc hn s tng phn mu chun th khng cn th nghim tip. Sau th nghim, nh gi kt qu ging nh phn trn. Thng thng ngi ta tin hnh kim tra ng thi bn mu vi nh sng; vi nh sng v thi tit vi cng mt b mu chun. C nhng thit b chuyn dng kim tra bn mu vi nh sng, vi nh sng v thi tit cho kt qu nhanh v chnh xc. 5. PHN TCH NH TNH THUC NHUM i vi ngi s dng thuc nhum, vic nhn bit mt loi thuc nhum c th no l rt cn thit. Xc nh thuc nhum c th sau khi chng nhum mu cho mt loi vt liu no hoc vn dng thuc nhum thnh phm. 5.1. Xc nh thuc nhum trn vt liu dt i vi cc loi vi si mu, trc tin c th nhn bit s b lp thuc nhum c s dng. Da vo ngun gc vt liu vi si v phm vi ng dng ca thuc nhum cho php nhng phn on ban u. Bng 4.2 Cht liu vi si Bng Vixc Len T t m Polyeste, axetat Polyamit PAN (acrylic) Thuc nhum c th s dng Trc tip, hot tnh, hon nguyn, lu hunh, azo khng tan Trc tip, hot tnh Thuc nhum axit, hot tnh Thuc nhum axlt, hot tnh, trc tip, baz Pigment (nhum khi), phn tn Phn tn, axit, trc tip, hot tnh, pigment (nhum khi) Pigment (nhum khi), phn tn, thuc nhum cation

Sau khi nhn bit cht liu vi si, phn on thuc nhum, tip theo s da vo bn cht mu sc, nh mu, cng mu ca mi thuc nhum nh hng phn tch. Chng hn, mu ca thuc nhum hot tnh rt ti, c cc gam mu, thuc nhum lu hunh v thuc nhum trc tip c mu xn v thuc nhum lu hunh khng c mu , mu tm thun sc, thuc nhum azo khng tan t c mu en v mu xanh l cy; thuc nhum hon nguyn tan thng c cc mu nht n trung bnh t c mu sm; thuc nhum hon nguyn khng tan c mu ti bn thng nhum cho cc mt hng cao cp; thuc nhum trc tip v thuc nhum lu hunh rt t dng cho in hoa vi. xc nh chnh xc loi thuc nhum cn tin hnh theo cc bc sau. 5.1.1. Chun b mu Cho vi si mu vo nc ct un si loi b nhng cht h v tp cht c hc trong thi gian 2 - 3 ph. Nu vi c cc si dc v si ngang nhum mu khc nhau th phi tch ring chng ra; mu hoa nhiu mu cng phi ct tng vn hoa ring r. Mi mu vi th nghim ch cn ct kch thc bng 1 cm2 hoc hn mt cht, th nghim tin hnh trong ng nghim, mi ln th nghim phi dng mu vi mi. Sau y l iu kin tin hnh mt s phn ng xc nh cc lp thuc nhum. 188

5.1.2. Phn on cc loi thuc nhum Gia cng vi si mu trong dung dch x phng 5 g/l v natri cacbonat 3 g/l cng vi vi phin trng. Vi trng c kch thc 1 cm2, kch thc vi mu gp hai ln (nu vi mu m) v gp bn ln (nu vi mu nht). Cc mu vi mu trng c xp v cun trn cho vo ng nghim. 3 - 5 ml dung dch x phng + cacbonat vo ng nghim, ri un si mu trong 2 - 3 ph. Cui cng git, g mu v quan st s i mu. Nu mu b phai ra v dy sang vi trng th thuc nhum c th l trc tip hoc hot tnh cha git sch ht cc phn thuc nhum bm bn ngoi li x. Nu ngc li thuc nhum khng phai, dy sang vi trng th chng t mu vi si c nhum bng cc loi thuc nhum hon nguyn, lu hunh, azo khng tan, phn tn v cc thuc nhum khc cho bn mu cao trn vt liu. 5.1.3. Xc nh c th loi thuc nhum a. Thuc nhum trc tip Mu ca thuc nhum ny s b mt khi gia cng mu vi si mu trong dung dch cha 3 - 5 g clo hot ng hoc x l mu trong dung dch kim hirosunfit cng s lm mt mu thuc nhum. Mt s thuc nhum trc tip b tch ra khi vi si khi un si mu trong dung dch NaOH 5%. Thi gian 2 ph. Thuc nhum trc tip b thay i mu khi un si mu vi si trong dung dch axit v b trch ra khi ngm trong axit H2SO4 80%. b. Thuc nhum hot tnh Khi c lin kt tt vi x si th lc lin kt ca chng l ng ho tr nn rt bn vng. Thuc nhum s khng b mt mu trong cc x l ho hc vi si mu vi cc dung dch sau: - un si si vi mu trong dung dch cht hot ng b mt khng mang ion, thi gian x l 15 ph; - un si trong hn hp axit axetic bng vi cn etylic theo t l th tch 1 : 2 trong thi gian 4 ph. - un si trong hn hp imetylformamit v nc vi t l th tch 1 : 1, trong thi gian 4 ph. - un si trong fomamit m c, trong thi gian 4 ph. c. Thuc nhum baz Nu mu vi si mu c cm mu bng tamin th khi nh mt git st clorua ln vi s lp tc to thnh vt en, tip theo nh dung dch HCl long ln vt en s bin mt. Thuc nhum baz b trch ly ra khi vi si bng axit axetic, cn etylic, axit formic v dung dch amoniac nhit si trong thi gian 2 ph. d. Thuc nhum lu hunh Thuc nhum lu hunh b mt mu khi x l mu vi si mu trong dung dch cha 3 - 5 g/l clo hot ng. Thuc nhum c phn ng c trng vi ch axetat cho mu en. Mu vi si mu vi kch thc 2 - 3 cm2 cho vo ng nghim un si trong dung dch thic clorua v HCl, ming ng nghim c y mt t giy lc tm dung dch ch axetat. Khi th nghim, cn tin hnh mu i chng vi trng loi tr kh nng trong cc ho cht dng c tn ti lu hunh. Thuc nhum lu hunh khng b ho tan khi ngm mu vi si mu vo paraphin lng. 189

e. Thuc nhum hon nguyn Thuc nhum hon nguyn b trch ly khi vi si mu bng cloroform khi un si, hoc bng o-clophenol si trong vi gi hoc bng imetylformamit v 1% CH3COOH. Ly mt vi si ch mu nhng vo chn s c cha paraphin nng chy; un chn s trong mt pht, sau lm ngui v quan st mu ca paraphin. Nu parafin c mu th vi si c nhum bng thuc nhum hon nguyn hoc azo khng tan. Nhng thuc nhum khc khng b chuyn mu vo parafin. phn bit thuc nhum hon nguyn a vng vi h inigoit c th th nghim kim chng: un mu vi si mu trong ng nghim cho bc hi (thuc nhum b thng hoa), hi c mu tm l thuc nhum h inigoit. Hoc x l mu vi mu trong dung dch gm: 1% NaOH v mt lng nh Na2S2O4 nhit 65oC th thuc nhum inigoit chuyn t vi vo dung dch. g. Thuc nhum azo khng tan Thuc nhum ny b trch ly ra khi vi si khi un si trong dung dch 15 - 25% piriin v cloroform; thuc nhum bn vi dung dch clorua vi. Khc vi thuc nhum hon nguyn, thuc nhum azo khng tan s b mt mu t t khi un si mu vi si mu trong dung dch cht kh itionit v NaOH v khng th hi mu khi oxy ho tr li. Cng vi qu trnh ny th thuc nhum hon nguyn hi mu tr li ngay c khi ch phi ngoi khng kh. h. Thuc nhum axit Thuc nhum axit c th b mt mu hoc thay i mu di tc dng ca cc cht kh. Mt s thuc nhum axit b chuyn mu di tc dng ca axit clohiric m c. phn bit cc loi thuc nhum axit cn tin hnh th nghim un si mu len mu trong imetylformamit vi thi gian 2 ph (c cho len trng km trong dung dch). Nu thuc nhum b tch ra v li bt mu sang len trng th thuc nhum axit thng. Cc thuc nhum axit cm mu v thuc nhum axit cha kim loi khng xy ra hin tng trn. Kim chng cc loi ny phi tin hnh un si mu len trong dung dch EDTA 4% (dung mi glyxerol) 140oC trong thi gian 20 ph. Thuc nhum axit cha kim loi 1 : 1 s i mu rt nhanh; thuc nhum axit cha kim loi 1 : 2 thay i mu t t sau 20 ph, c khi cn nng nhit n 160oC; cn thuc nhum axit cm mu s khng b thay i mu. i. Thuc nhum phn tn Thuc nhum phn tn thng b trch ra mt phn khi un si mu vi mu (Pe, PA, PAN, Axetat) trong cn tuyt i hoc paraphin lng ng thi li bt ngay mu sang vi trng axetat cng gia cng. k. Thuc nhum cation X l mu vi si mu acrylic trong dung dch axit focmic 85% v nc (t l 50 : 50), nhit si, trong thi gian 1 - 2 ph cng vi vi si acrylic trng. Thuc nhum cation s b tch ra khi vi si mu v li nhum mu cho vi si acrylic trng. 5.2. Phn tch thuc nhum dng bt Trong trng hp cha bit r mt loi thuc nhum no , cn phi xc nh nh tnh chng nm vng cc tnh nng v phm vi s dng. Vic th nghim c tin hnh theo mt trnh t c h thng. 5.2.1. Xc nh kh nng ho tan ca thuc nhum Ly mt lng nh thuc nhum ho tan trong nc ct, un si trong 1 ph (nng 190

tng ng 1 g/l). Sau quan st: nu thuc nhum ho tan hon ton th c th phn on l cc loi thuc nhum sau: trc tip, hot tnh, baz, axit, cation, cubozol v inigozol. Nu thuc nhum khng ho tan th l nhng thuc nhum hon nguyn khng tan, thuc nhum lu hunh, thuc nhum phn tn. 5.2.2. Xc nh chnh xc nhng thuc nhum ho tan trong nc Sau khi xc nh l thuc nhum ho tan c trong nc th tin hnh nhum cc mu nh t cc loi vt liu khc nhau: dung dch thuc nhum pha vi nng 1 g/l v s dng nhum mu nh trong cc ng nghim, mu vi si bng v len ly khong 2 g. Tin hnh nhum chng trong cc iu kin khc nhau: trung tnh, kim tnh v axit. Cc n cng ngh c th tham kho trong [15]. Kt qu nhum mu cc mu s cho php xc nh loi thuc nhum. Tip theo cn tin hnh cc phn ng kim chng: - Phn bit thuc nhum hon nguyn tan bng cch nh vo dung dch thuc nhum 5 ml H2SO4 10% v 0,5 ml NaNO2 10%, un nng dung dch n 60 - 70oC; thuc nhum s b kt ta v i mu. Khc vi thuc nhum trc tip (cng b kt ta phn ng trn) l khi cho vo kt ta trn mt lng dung dch kim kh (NaOH + Na2S2O4) th thuc nhum hon nguyn tan li tan ra tr v dng dung dch ban u; cn kt ta ca thuc nhum trc tip khng thay i; - Phn ng kim chng ca thuc nhum trc tip vi thuc nhum hot tnh bng cch x l mu nhum trong dung dch cht hot ng b mt khng mang ion v xt. Thuc nhum trc tip s b phai mu, cn thuc nhum hot tnh bn khng phai. Hoc c th dng bin php trch ly trong dung dch piriin (15 - 25%); thuc nhum trc tip b trch ra khi vi, thuc nhum hot tnh khng b trch ly; - Phn bit cc loi thuc nhum axit: sau khi mu len c nhum mu, chia mu len lm hai phn: mt phn sy kh v mt phn gia cng cm mu bng dung dch K2Cr2O7 1% v H2SO4 2% (so vi lng vi len). Th nghim nhit si trong thi gian 30 ph. Sau git sch, sy kh v so snh mu. Nu mu khng thay i th thuc nhum l loi thng, nu mu thay i v tng bn th l thuc nhum axit cm mu; - Phn bit thuc nhum baz: un nng 1 ml dung dch thuc nhum vi 1 ml dung dch NaOH 10N, thuc nhum s i mu hoc mt mu. C th trch ly thuc nhum ra khi vi si bng cn tuyt i. 5.2.3. Xc nh nhng thuc nhum khng ho tan trong nc Trc tin kh thuc nhum bng cch pha dung dch kim kh gm: 20 ml dung dch NaOH 1N; 2 g Na2S2O4; 18 ml H2O. Ly 8 ml dung dch trn trn vi 0,1 g thuc nhum ri un nng n 60 - 70oC. Nu thuc nhum tan hon ton th l thuc nhum hon nguyn khng tan hoc thuc nhum lu hunh. khng nh chnh xc, phi tin hnh nhum mu vi bng 10 ph nhit 60 - 70oC, git lnh, oxy ho. Nu vi nhum mu th thuc nhum trn l thuc nhum hon nguyn hoc thuc nhum lu hunh. phn bit thuc nhum lu hunh vi thuc nhum hon nguyn bng phn ng vi ch axetat ( nu phn trn). Nu thuc nhum khng ho tan trong dung dch kim kh th s l thuc nhum phn tn. Thuc nhum phn tn c c im l phn tn cao, c th kim chng bng cch bng mt t thuc nhum ln giy lc t s thy thuc nhum loang rng ra khp giy. Khng nh thuc nhum bng cch nhum mu vi Pe hoc vi axetat theo phng php nhum thng thng. 191

TI LIU THAM KHO

1. P. F Gordon, Pgregory. Organic chemistry in colour. Moxkva, 1987. 2. K. Venkataraman. The analytical chemistry of synthetic dyes. Leningrad, 1979.. 3. E. R. Trotman. Dyeing and chemical technology of textile fibres. Sixth edition, 1984. 4. Textile printing with caledon, durindone and soleon dyes. Imperial chemical industries limited, dyestuff division, 1961. 5. International Standard Organation, Textiles - Tests for colour fastness. First eition 1978 - 12 - 15. 6. JIS. L0848, 1978 Testing metho for colour fastness (Sapanese Industrial Standard). Traslated and published by Japanese Standarods Association. 7. S tay tra cu thuc nhum. Vin cng nghip dt si, H Ni, 1993. 8. VF. Androxov, I. N. Petrova. Sintetitrexkie kraxiteli v legkoi promslennoxti. Legprombizat, Maxkva, 1989 (ting Nga). 9. V F. Androxov, L:M. Golomb. Sintetitrexkie kraxiteli v tekctilnoi promslenoxti. Legkaia induxtria, Moxkva, 1968 (ting Nga). 10. I. M. Kogan. Khimia kraxiteli. Goskhimizat, Maxkva, 1956 (ting Nga). 11. B. A. Porai - Kosix. Azokraxiteli. Izatelxtvo khimia, 1972 (ting Nga). 12. G.E. Kritrevxki. Aktivne kraxiteli. Legkaia induxtria, Maxkva, 1968 (ting Nga). 13. A. A. Khakharov, I. IA. Kalantarov. Aktivne kraxiteli i ikh primenenie v tekctilnoi promslenoxti. Rostekhizat 1961 (ting Nga). 14. A. G. Emelianov. Priame kraxiteli i ikh primeneniei v teketilnoi promlenoxti. Rostekhizdat, 1963 (ting Nga). 15. B. N. Menicov. Laboratorni praktikum po primeneniei kraxitelay. Leykaia induxtria, Maxkva, 1972 (ting Nga). 16. Kraxiteli dlya tekxtilnoi promislemoxti xpravotsnik. Maxkva, 1973 (ting Nga). 17. B. I. Xtepanov. Vedenie v khimiu i tekhnologiu organitsexkii kraxitelei. Maxkva, 1971 (ting Nga). 18. N. N. Voroftsov. Oxnov sinteza promejytotsnkh produktov i kraxitelei. Goxkhimizgat, 1955 (ting Nga). 19. Ti liu k thut ca hng Sumitomo. 20. Nguyn Qun. Ting ni ca hnh v sc. NXB Vn ho, H Ni, 1986. 21. Nguyn Duy Lm. Mu sc. Trng i hc M thut cng nghip, H Ni, 1994. 22. Dr. K. C. Lan. Datacolor International, 1995. 23. Colorimetry. 1990 Herbert NAF, Datacolor Ltd. 24. Integrated color line by Orintex Italia. 25. Gretagmacheth. Coloreye XTH Spectrophotometer. Technichal publication, 1999. 26. X- Rite (U.S.A). A guide to Understanding Color Comunication, 1993, 2001. 192

MC LC
Li ni u ...................................................................................................................... 3 M u.............................................................................................................................. 5 1. S lc v thuc nhum ............................................................................................... 5 2. Thuc nhum thin nhin ............................................................................................. 5 2.1. Thuc nhum thin nhin mu vng ...................................................................... 6 2.2. Thuc nhum thin nhin mu .......................................................................... 6 2.3. Thuc nhum thin nhin mu ta..................................................................... 6 2.4. Thuc nhum thin nhin mu xanh chm............................................................. 7 2.5. Thuc nhum thin nhin mu en ........................................................................ 7 2.6. S dng thuc nhum thin nhin Vit Nam ...................................................... 7 3. Thuc nhum tng hp ................................................................................................. 8 3.1. Cc giai on pht trin ......................................................................................... 8 Chng 1. L THUYT V SC MU 1. Lch s pht trin ca cc thuyt mu.......................................................................... 11 1.1. Thuyt mang mu ................................................................................................. 11 1.2. Thuyt mu quinoit............................................................................................... 12 1.3. Thuyt nguyn t cha bo ho v thuyt to mu khi chuyn hp cht hu c v dng mui............................................................................................ 12 1.4. Thuyt dao ng mu ........................................................................................... 13 1.5. Thuyt nhim sc.................................................................................................. 13 2. L thuyt mu hin i ................................................................................................ 13 2.1. Bn cht mu sc trong t nhin .......................................................................... 13 2.2. Tnh cht ca nh sng v s hp th nh sng ca vt th .................................. 15 2.3. Nguyn l phi ghp mu..................................................................................... 22 3. Tnh ton mu v cng ngh phi ghp mu ................................................................ 25 3.1. Cc h thng phn nh mu sc .......................................................................... 25 3.2. S khc nhau gia cc mu. K hiu v tnh ton................................................ 27 3.3. o mu................................................................................................................. 31 3.4. Thc hnh phi mu thuc nhum bng my o mu .......................................... 36 Chng 2. TNG HP THUC NHUM 1. Phn loi thuc nhum theo cu to ho hc ............................................................... 42 1.1. Thuc nhum azo ................................................................................................. 42 1.2. Thuc nhum antraquinon .................................................................................... 42 193

1.3. Thuc nhum inigoit .......................................................................................... 43 1.4. Thuc nhum arylmetan ....................................................................................... 44 1.5. Thuc nhum nitro ............................................................................................... 44 1.6. Thuc nhum nitrozo............................................................................................ 44 1.7. Thuc nhum polymetyn ...................................................................................... 44 1.8. Thuc nhum lu hunh....................................................................................... 44 1.9. Thuc nhum arylamin......................................................................................... 45 1.10 Thuc nhum azometyn....................................................................................... 45 1.11. Thuc nhum hon nguyn a vng ................................................................... 45 1.12. Thuc nhum phtaloxianin ................................................................................. 46 2. Tng hp phm vt trung gian ..................................................................................... 46 2.1. Phn ng th vo nhn thm ................................................................................ 46 2.2. Phn ng bin i nhm th ................................................................................. 51 2.3. Phn ng bin i vng thm .............................................................................. 52 2.4. Mt s qui trnh cng ngh tng hp phm vt trung gian ................................... 53 3. Qu trnh tng hp thuc nhum ................................................................................. 73 3.1. Qu trnh tng hp thuc nhum azo ................................................................... 74 3.2. Tng hp thuc nhum antraquinon..................................................................... 81 3.3. Tng hp thuc nhum polymetyn....................................................................... 84 3.4. Tng hp thuc nhum arylmetan........................................................................ 85 3.5. Tng hp thuc nhum inigoit ........................................................................... 86 3.6. Tng hp thuc nhum phtaloxianin.................................................................... 88 3.7. Tng hp thuc nhum lu hunh ....................................................................... 89 3.8. Hon tt sn phm thuc nhum .......................................................................... 90 Chng 3. THUC NHUM THEO PHN LP K THUT 1. Phn loi thuc nhum theo phm vi s dng.............................................................. 93 2. Tn gi ca thuc nhum............................................................................................. 93 3. C ch lin kt thuc nhum vi vt liu..................................................................... 96 3.1. Lin kt ion .......................................................................................................... 97 3.2. Lin kt ng ho tr ............................................................................................ 97 3.3. Lin kt hyro ...................................................................................................... 97 3.4. Lin kt Van der Waals........................................................................................ 98 3.5. Lc tng tc k nc ......................................................................................... 98 4. Cc loi thuc nhum c th ........................................................................................ 98 4.1. Thuc nhum trc tip ......................................................................................... 98 4.2. Thuc nhum axit................................................................................................ 102 4.3. Thuc nhum hot tnh....................................................................................... 108 4.4. Thuc nhum baz - cation ................................................................................. 117 194

4.5. Thuc nhum hon nguyn.................................................................................. 120 4.6. Thuc nhum lu hunh...................................................................................... 127 4.7. Thuc nhum phn tn ........................................................................................ 128 4.8. Thuc nhum azo khng tan................................................................................ 134 4.9. Thuc nhum pigment ......................................................................................... 140 4.10. Cht tng trng quang hc ................................................................................. 145 4.11. Thuc nhum dng cho cc ngnh khc ............................................................ 149 Chng 4. PHN TCH V NH GI THUC NHUM 1. Cc tnh cht chung ca thuc nhum......................................................................... 164 1.1. Nng thuc nhum ......................................................................................... 164 1.2. Cc dng thuc nhum thng phm .................................................................. 164 1.3. n nh ca thuc nhum trong thi gian bo qun ....................................... 165 1.4. ho tan ca thuc nhum ............................................................................... 165 1.5. phn tn ca thuc nhum ............................................................................. 165 1.6. Kh nng t nhum ............................................................................................. 165 1.7. Kh nng u mu ca thuc nhum ................................................................... 165 1.8. n nh ca dung dch thuc nhum .............................................................. 166 1.9. bn ca thuc nhum trong dung dch ........................................................... 166 1.10. bn ca thuc nhum trong h in ................................................................. 166 1.11. nhy ca thuc nhum i vi mt s ion kim loi nng ............................. 166 1.12. Kh nng di tn thuc nhum ............................................................................ 166 1.13. Mc s dng thuc nhum ........................................................................... 166 1.14. Mc git sch thuc nhum .......................................................................... 166 1.15. nhy ca mu thuc nhum vi cc ch phm hon tt................................ 166 1.16. bn mu ....................................................................................................... 167 2. Phn tch nh lng thuc nhum ............................................................................. 167 2.1. Xc nh nng thuc nhum bng phng php nhum so snh .................... 167 2.2. Phng php quang trc ph ............................................................................... 169 2.3. Phng php trc quang (so mu quang in) ..................................................... 171 2.4. Phng php phn tch ho hc ........................................................................... 172 3. Cc phng php kim nghim tnh cht thuc nhum .......................................... 173 3.1. Xc nh kh nng ho tan................................................................................... 173 3.2. Xc nh phn tn ca thuc nhum khng tan .............................................. 175 3.3. Xc nh kh nng hp ph ca thuc nhum ln vt liu nhum ....................... 176 3.4. Xc nh nhy ca thuc nhum vi nc cng ............................................. 177 3.5. Xc nh kh nng u mu ca thuc nhum..................................................... 177 3.6. Xc nh kh nng git sch phn thuc nhum hot tnh cha nh hnh........... 179 8.7. Xc nh mc lin kt ca thuc nhum hot tnh vi x ............................... 180 195

3.8. Xc nh bn ca thuc nhum lu hunh trong qu trnh bo qun .............. 180 3.9. Xc nh s ph hp ca thuc nhum trc tip khi gia cng nhit cao ...... 180 3.10. Xc nh bn ca dung dch nhum hon nguyn sau khi kh...................... 181 8.11. Xc nh nh hng ca cc cht oxy ho n mu nhum ca thuc nhum hon nguyn ................................................................................. 181 3.12. Xc nh nh hng ca cc ch phm hon tt n mu nhum ca thuc nhum hon nguyn ................................................................................. 182 4. nh gi bn mu ca vt liu nhum ................................................................... 182 4.1. Th t xc nh bn mu ................................................................................ 183 4.2. nh gi bn mu ........................................................................................... 183 4.3. Kim tra bn mu vi git............................................................................... 184 4.4. Kim tra bn mu vi dung dch x phng nhit 40oC ............................ 184 4.5. Kim tra bn mu vi m hi.......................................................................... 184 4.6. Kim tra bn mu vi nc bin ..................................................................... 184 4.7. Kim tra bn mu vi clo................................................................................ 185 4.8. Kim tra bn mu vi l nng ......................................................................... 185 4.9. Kim tra bn mu vi c xt ........................................................................... 185 4.10. Kim tra bn mu vi H2O2 .......................................................................... 185 4.11. Kim tra bn mu vi nh sng..................................................................... 186 4.12. Kim tra bn mu vi nh sng v thi tit................................................... 187 5. Phn tch nh tnh thuc nhum ................................................................................ 188 5.1. Xc nh thuc nhum trn vt liu dt ................................................................ 188 5.2. Phn tch thuc nhum dng bt........................................................................... 190 TI LIU THAM KHO ............................................................................................. 192

196