BI GING MN K THUT SN XUT CHT DO GV SON: PHAN TH ANH

PHN 1 CNG NGH SN XUT MT S POLYMER TRNG HP CHNGI: SN XUT POLYETYLEN (PE) I.Nguyn liu Nguyn liu sn xut PE l etylen (C2H4), ch yu thu c t vic cracking du m. Tnh cht ca C2H4: + tonc = -169oC + tos = -103,8oC + Khi lng ring tosi: d(ts) = 0,57 g/cm3 Etylen khng phn cc ( o =0) nn kh trng hp. Lng nhit to ra khi trng hp cao. Monome C2H4 (kh) Stryren (lng) Lng nhit to ra (cal/g) 800 164

MMA (nh tng) 129 Etylen dng sn xut yu cu : C2H4 98% C2H6 1 2% N2 0,5 1% C2H2 0,1 0,3% II.L thuyt trng hp Phn ng trng hp etylen thnh PE c th thc hin theo c ch gc hoc ion. 1.Trng hp gc Peroxit, pesulfat, hp cht azo v cc dn xut alkyl ca cc kim loi khi un nng to ra gc t do. Cc gc t do mi ny d dng phn ng vi etylen: R + CH2=CH2 R-CH2-CH2 Gc ny tip tc pht trin :

R-(CH2-CH2-)CH2-CH2 R-CH2-CH2 + nCH2=CH2 Giai on ny nhit phn ng to ra rt ln do cn phi ly nhit ra khi hn hp phn ng. Nu khng do s tng cao nhit etylen khng phn ng b phn hu v thng km theo ting n. Phn ng pht trin mch ngng l do kt qu kh hot tnh gc polymer R-(CH2-CH2-)nCH2-CH2 + CH2=CH2

R-(CH2-CH2-)nCH=CH2 + CH3-CH2

Trong qu trnh phn ng, do s kt hp ca cc phn t etylen hoc gia monome vi i phn t polymer to ra nhnh. R-(CH2-CH2-)m C H-CH2-CH2-CH3 + nCH2=CH2
R-(CH2-CH2-)mCH-CH2 -CH2-CH3 (CH2-CH2)n-1-CH2- C H2

nCH2=CH2 + CH2=CH2 + mCH2=CH2

-(CH2-CH2-)nCH-(CH2 -CH2-)m CH3

2.Trng hp ion ng ch l trng hp etylen theo c ch trng hp ion c xc tc Xigle-Naptha, TiCl3 + Al(R1)3 R1: C2H5

TiCl3 + Al(R1)3 Ti Cl2Cl Al (R1)3 + C H2= C H2

TiCl2Cl Al (R1)3

t0

t0

CH - C H2

+u im: Trng hp etylen c xc tc Xigle-Naptha c nhiu u im nh polymer t nhnh, tnh c l cao. +Nhc im:

Xc tc t, d chy n Sau khi kt thc qu trnh phi tch xc tc ra khi polymer phc tp. III.Cc phng php sn xut PE Nha Polyetylen c nhiu loi: HDPE, LDPE, LLDPE, VLDPE, nhng trong th trng ph bin l 2 loi HDPE v LDPE. HDPE l PE c khi lng ring ln. C th sn xut theo 2 phng php: +p sut trung bnh (30 40 atm) +p sut thp (3 4 atm) LDPE l PE c khi lng ring b. Sn xut theo phng php p sut cao (1500 2500 atm). 1.Phng php p sut cao (P=1500 2500 atm) Phng php trng hp etylen trong pha kh p sut cao v nhit cao (180 200oC) c cht khi u l O2 l phng php c bn sn xut PE c t trng thp, trng lng phn t10.000 45.000. -Cc yu t nh hng n qu trnh trng hp: +Hm lng O2 trong kh
Hiu sut (%) 170 C
o

15 10 5

160 C

150 C

Hiu sut (%) 1350 atm 1150 atm 15 10 5 1000 atm 100 atm

0,01 0,02 0,03 0,04

% Oxi

0,01 0,02 0,03 0,04

% Oxi

Oxi l cht khi u trng hp, tc phn ng ph thuc vo lng O2 trong kh, nhng v nhit v p sut cng nh hng nhiu n n nn s ph thuc ny rt phc tp. Nu nng O2 qu cao, etylen s b phn hu thnh C, H v CH4. VD: 2000 at v 165oC phn hu xy ra ngay 0,075% O2 so vi lng monome. Trong 2 th trn ta thy tt c cc nhit v p sut u c hiu sut cc i v hng v pha O2 t. +Nhit : Tng nhit phn ng n gi tr nht nh s lm tng nhanh qu trnh trng hp v tng hiu sut polymer, trng lng phn t gim.

Tng nhit phn ng ph cng tng theo. +p sut: p sut tng th vn tc phn ng v hiu sut to thnh polymer ln.
Vp khi p= 1atm V
5000

4000

3000

2000

1000

300

1100

1500

2500

p (atm)

nh hng p sut n vn tc trng hp -Thit b phn ng loi ng c dng dtng=10 30mm -c im ca loi trng hp cao p: +C lin kt i cui mch nhiu (do chuyn mch, t mch) hm lng tinh th +C nhnh CH3, (-C2H5) ln hn cc phng php khc khng cao. K-(CH2-CH2-)x CH2- C H2 + CH2=CH2 K-(CH2-CH2-)x C H- C H2 + CH2=CH2

K-(CH2-CH2-)x CH2-CH2- C H-CH3

K (CH2 CH2)x CH CH2 CH2 C H2

-u, khuyt im: +u im: Sn phm sch (v khng dng cht khi u hu c), tnh cch in cao. +Khuyt im: V p sut cao: kch thc thit b b nn nng sut b. Nng lng tiu hao nhiu do qu trnh nn kh. Thit b t, lm t thp c bit, vn lm kn thit b, vn chuyn etylen p sut cao c nhiu kh khn. phng php cao p t sn xut. 2.Phng php sn xut trung bnh (30 40 atm) Trng hp etylen trn xc tc oxit crom c th tin hnh theo phng php gin on v lin tc trong dung mi hoc trong pha kh trng hp cation.

-Cc giai on chnh ca qu trnh: +Chun b xc tc: Trn CrO3 vi cht mang alumino silicat. Yu cu ca xc tc l phi c th tch t do v b mt ca mao qun phi ln Vtd= 1cm3/g F = 400 500m2/g Xc tc s dng dng huyn ph l 0,2-0,6%. +Chn dung mi: Dung mi ch ho tan C2H4 v khng ho tan polymer, ru metylic, xiclohecxan, xng tinh khitCH3OH l dung mi tt nhit no cng khng ho tan polymer nhng ho tan monome. +Tch xc tc ra khi hn hp sn phm: Mun tch xc tc th phi ho tan PE trong dung mi thch hp ri tch xc tc bng my li tm. Sau sy tch dung mi ta c PE em i to ht. -Cc yu t nh hng :
[] Lng PE (g/g xc tc)

1,8

110

0,6 10 10
PE (g/g xc tc)

20

30

40

10
[]

20

30

40

115-120 C o 125-130 C 135-140 o C 15 100-105 C

o

1,8

10

135-140 C 0,6

10

15

20

t(pht)

50

10

15

t op

p sut cng ln th [ ] cng ln

M P cng cao

Nhit phn ng cng ln [ ] cng gim

M P cng gim.

p sut cng tng, hiu sut to PE cng ln. Nhit thp th hiu sut phn ng thp, nhit cao th hiu sut cao nhng khi tng nhit ln na (125 130oC) th hiu sut gim v khi nhit (135 140oC) th hiu sut rt thp. Khi nhit cng cao th xy ra nhiu phn ng ph nh: ngt mch, oxi ho,.. nn hiu sut gim. -u, nhc im: So vi phng php p sut cao: +u im: -Khng dng cc thit b t tin -Th tch thit b ln nng sut cao gi thnh h. -% tinh th ln (>85%) do t phn nhnh -Khi lng ring d ln hn PEHD So vi phng php p sut thp: +u im: -Xc tc r, an ton khi s dng (t c, khng gy chy n) -D ti sinh dung mi. +Nhc im: -V xc tc l cht rn (CrO3) nn tch xc tc kh khn, mun tch phi ho tan PE ri lc, sau sy tch dung mi phc tp. 3.Phng php p sut thp (3-4 atm) Trng hp etylen trong dung mi c th thc hin c vi cc loi xc tc v cc cht khi u khc nhau, ph thuc vo h thng khi u m cc iu kin trng hp v tnh cht ca polymer thu c s thay i. Dung mi s dng c th ho tan hoc khng ho tan polymer, thng dng: ru metylic, xiclohecxan, n-hecxan, n-heptan, benzen,.. trong ru metylic l dung mi tt trng hp etylen v n ho tan etylen m khng ho tan PE. Xc tc c s dng rng ri trng hp etylen l Xigle-Naptha (TiCl4+Al(C2H5)3) Qu trnh tin hnh: Cho dung mi bezin + xc tc to thnh hn hp huyn ph, cho monome etylen p sut 3-4atm vo thit b phn ng. Nng nhit t t ln 75-80oC, gi to=80oC n khi kt thc phn ng, hiu sut 92 95% . nhit ny PE khng ho tan trong benzin, khi t hiu sut ngi ta tch PE ra khi huyn ph bng li tm. Sau ra sch bng

CH3OH ( tch cc xc tc cn ln li) ri ra li bng nc. Sau PE c sy kh vi hm m W=0,25 0,5%, c to ht, ng bao. Benzin c cha polyetylen t trng thp v hn hp benzin, rc c em i chng tch, lm sch, s dng li. u, nhc im: +u im: -Tin hnh p sut thp nn nng lng tiu hao b nht nng xut sn xut ln gi thnh thp. -Trng lng phn t ca PE ln nn bn c hc, bn nhit cao hn phng php p sut cao. +Nhc im: -Phi hon nguyn dung mi nn dy chuyn sn xut phc tp tn km. ra -PhI tch ht xc tc ra khi PE -Xc tc d chy n khi tip xc vi khng kh IV.Cu to, tnh cht v ng dng ca PE 1.Cu to Phn t polyetylen c cu to mch thng di gm nhng nhm etylen, ngoi ra cn c nhng mch nhnh. PE l polymer khng phn cc, monome lng cc 0 0 . Nu mch nhnh cng nhiu v cng di th kt tinh cng km. PE c kt tinh tng i cao v khc nhau i vi mi loi. Trong PE phn tinh th lm cho mch cng nn bn nhit , bn vi tc dng c hc, cn phn v nh hnh lm cho mch mm. Cu to ca PE ph thuc vo phng php sn xut. HDPE LDPE

S lng nhm -CH3 (nhnh) trong 1000 nguyn t C Tng lng Nhnh Loi cui mch nhnh CH3 PE cao p PE p sut thp 21,5 3,0 4,6 2,0 1,5 2,5 -

Nhnh C2H5 14,4 1 1

PE p sut trung bnh 2,5

Ta thy hai phng php sau nhnh t do c s iu chnh bi xc tc.

Lng nhm khng no tnh trn 1000 nguyn t C; Loi PE Tng lng ni i
H-C=CH2 R R1-C=CH2 R2 H R1 C=C R2 H

PE p sut trung 1,1 1,3 bnh PE p sut thp PE p sut cao 0,4 0,5 0,3 0,4

87% 52% 17%

7% 31% 71%

6% 17% 12%

2.Tnh cht ca PE n gin y ta nu ra mt s tnh cht quan trng ca 2 loi PE thng dng l HDPE v LDPE. LDPE HDPE +d=0,92 0,93 (g/cm3) +T trng d= 0,95 0,96 +Khng ht m, mc hp th nc trong +Khng ht m 24h<0,01% Mc hp th nc <0,02% + kt tinh 85 95% + kt tinh 60 70% Sn phm c m Sn phm trong hn PEHD. 110oC LDPE hon ton trng thi v nh hnh + ho mm thp (120oC), d gia cng +Chu ho cht tt trong sut. +Cch in tt +im ho mm thp (90oC), rt d gia cng. +Lc ko t 220 300 kg/cm2, c loi 2 tt cng ko t t 600kg/cm +Chu ho cht tt + dn di 200 400% +Cch in tt o +Nhit gin, gy: -80 C +Lc ko t 114 150kg/cm2 + gin di 400 600% +Nhit gin, gy: -80oC * HDPE +Lc un 170kg/cm2 + cng shore (theo phng php th ASTM-D2240): 60 65 + cng Brinel: 4 5kg/cm2 +Ch s chy MI: 0,1 20gr/10 pht +Tnh bm dnh km, d chy, khng mi, khng v, khng c * LDPE +Lc un 60kg/cm2 + cng shore (theo pp th ASTM-D2240): 30 35 + cng Brinel 1,8 2,5 kg/cm2 +Ch s chy MI: 0,1 60gr/10 pht

+Tnh bm dnh km, d chy, khng mi, khng v, khng c * ng dng ca PE: Ta ch quan tm n 2 loi nha PE thng l HDPE v LDPE HDPE +Sn xut loi mng (ti xp, ti ng ho cht, thc phm,..) sn xut mng , ch s chy (MI)<0,05 0,35gr/10 pht +Sn xut si dt, si n (Yarm v monofilament) lm bao dt, bao che ph (0,8 1,0) +Sn phm thi cc loi (thng cha, chai, l,..) (0,05 0,3) +Sn xut cc loi ng dn nc, ho cht. LDPE +Sn xut cc loi mng trong, mng che ph, mng co, mng che nh vn,.. sn xut mng, ch s chy 0,3 6gr/10 pht. +Sn phm thi cc loi nh chai, l, mng co (0,8 1) +Sn xut cc loi ng

CHNG II: SN XUT POLYPROPYLEN (PP) I.Nguyn liu Nguyn liu sn xut PP l propylen, c tch t kh cracking du m hoc t sn phm du m. Khng ch iu kin cracking (to, p, t, cht xc tc,) ta c th thu c propylen v etylen. Dng phng php lm lnh tch v lm sch propylen. Tnh cht ca propylen: CTCT: C3H6
CH 2 = CH CH3

Propylen l cht kh c ts= -47,7oC v tnc= -185,2oC. nhit si, t trng ca n 0,610g/cm3 Do nh hng ca nhm CH3 nn phn t Propylen c s phn cc, momen lng cc 0,35 debai. II.L thuyt trng hp propylen iu ch PP trng lng phn t cao tin hnh trong iu kin c xc tc d th. Cu to b mt kt tinh ca cht xc tc c vai tr quan trng trong vic iu ch phn t polymer c cu trc khng gian u n. Ngi ta cho rng, trc ht cc phn t monome b hp th ln b mt cht xc tc v nh hng, sau dnh vi mch ca polymer nh m ni i. Kt qu thu c polymer kt tinh c cu to thng, u n. Bng cch thay i h thng xc tc, c th loi tr tc dng khng gian ca cht xc tc v thu c polymer v nh hnh, c th thay i t l gia polymer c cu trc u n. Xc tc dng huyn ph cho polymer c cu trc khng u n. C ch:

Tu thuc vo iu kin trng hp, loi xc tc khc nhau m ta thu c polymer c cu trc khc nhau iu ho hay khng iu ho. V d: + PP c cu to khng gian khng cao c th thc hin trong h xc tc: dung dch TiCl4 + Al(C2H5)3 nhit 35 80oC, p = 3 5atm. + PP c cu to khng gian cao th dng h xc tc: TiCl4 nghin mn + dung dch dietylalumin clorit nhit 70 - 80oC, p = 5atm. + Hoc dng dung mi n-heptan, cc cacbuahydro khc c nhit si thp hn nhit nng chy ca polymer kt tinh n 50 80oC tch PP c kt tinh cao ra khi PP v nh hnh v PP c kt tinh thp. Nhit thp vn tc phn ng gim, thi gian phn ng tng, hiu sut gim, hm lng izotactic v trng lng phn t trung bnh tng. Nhit cao th ngc li v hu ht to ra atactic. 3. Cc phng php sn xut PP. 3.1. Phng php c p sut lm vic ca thit b phn ng l 4 6atm v nhit 50 55oC. Cho dung mi (benzin) v lng xc tc cn thit (TiCl3 + Al(C2H5)3) vo thit b phn ng. Sau cho propylen lc sch O2 vo, duy tr nhit 50 55oC cho n khi hiu sut t 95%, em lm lnh n 10oC tch PP dng huyn ph bng phng php ly tm ri em x l xc tc bng CH3OH trong dung dch HCl. Ra PP bng nc v sy trong iu kin chn khng nhit 60 - 70oC n m 0,25 0,5% ri em i to ht. 3.2. Phng php mi ( do Naphta ra) Dng hn hp propan (C3H8) propylen (C3H6) vi t l theo khi lng 30/70. H xc tc l TiCl3 + Al(C2H5)3 p sut phn ng 6 - 8atm v nhit phn ng 50 55oC. u tin C3H8 ho tan C3H6 ng vai tr nh l dung mi ca phn ng. Khi trng hp xong a v p sut thng hoc thp, C3H8 khng ho tan c PP c ho hi thu hi. Mt t C3H8 hp th vo PP ta dng hi nc qu nhit ko ra. Sau ra tch xc tc bng CH3OH trong dung dch HCl, ra li bng nc, sy chn khng v to ht. 3.3. Trong cng nghip Cho propylen vo trng hp trong ni phn ng p sut n 100atm v khuy u. Cht xc tc phn tn trong cacbuahydro lng. Duy tr nhit phn ng thp hn nhiu so vi nhit chy mm ca polymer. Sau khi c 40% hn hp phn ng chuyn thnh polymer th chuyn dung dch huyn ph cha: dung mi, polymer v cht xc tc vo thit b bc hi tch ( p sut thp ) propylen khng phn ng v hon nguyn n v sn xut. Sau nh my ly tm hoc my lc tch polymer dng bt v dung mi ra. Ra polymer bng CH3OH trong dung dch HCl long. Giai on ny phc tp i hi

thi gian khuy trn nhiu, sau mi ln ra phi dng my lc ly tm, dng nhiu ru v tiu hao nhiu dung mi. IV.Cu to, tnh cht v ng dng ca PP 1.Cu to Phn ln l isotactic, mt phn nh l syndiotactic v atactic. Khi nhit phn ng o t=50 C v dng xc tc TiCl3-Al(C2H5)3 th hm lng isotactic: 85 95% hm lng kt tinh ln. V mi mc xch c mt nhm CH3 nn mch cng hn PE v th bn c, bn nhit ln hn PE. Cng thc cu to: -(CH2-CH-)n
CH3

Ta thy cng thc ca PP c nguyn t H C bc 3 rt linh ng do PP d b oxi ha, lo ha. 2.Tnh cht Tnh cht l nhit ( bn nhit) +Nhit nng chy cao tnc= 160 170oC +n nh 150oC khi khng c ngoi lc +Chu c nc si lu, khng b bin dng. + 155oC, PP vn cn th rn, nhng n gn nhit nng chy PP chuyn sang trng thi mm cao (nh cao su). nhit kt tinh +Khi gim t nhit nng chy n 120oC, PP bt u kt tinh cao
dn di tng i (%)
1 150 4 100 2 3 5

50

50

100

150

Nhit (oC)

dn di ca cc vt liu khc nhau nhit cao 1 PE t trng thp 2 Polymetylmetaacrylat 3 PE t trng cao

4 PVC 5 PP +Cc tp cht v khi tip xc vi cc kim loi nh: Cu, Mn hoc cc hp kim cha kim loi , c nh hng ln n tnh chu nhit ca vt liu. Do phi ht sc trnh. Kh nng chu nh sng mt tri: Do c nguyn t H C bc 3 linh ng nn d b oxi ho, lo ho. +PP khng c cht n nh -Di nh sng khuyt tn vn n nh tnh cht trong 2 nm. -C nh sng trc tip th ch sau vi thng s b gin v ph hu ngay. +PP c cht n nh (hoc dng mui than 2%) di nh sng trc tip (tia cc tm) th sau 2 nm tnh cht khng thay i, bn trong 20 nm. bn ho hc + nhit thng, PP khng tan trong cc dung mi hu c, ngay c khi tip xc lu, m ch trng trong cc cacbuahydro thm v clo ho. Nhng nhit trn 80oC th PP bt u tan trong hai loi dung mi trn. +Polymer c kt tinh ln bn ho cht hn polymer c kt tinh b. +PP thc t xem nh khng ht nc, mc ht m <0,01% bn c hc +Trng lng phn t nm trong khong 80.000 200.000 +T trng thp d=0,9 0,92 ( dVLDPE =0,09 0,91) + bn ko t : k (KG/cm2) = 300 350

n (KG/cm2) = 600 700 u (KG/cm2) = 900 1200

cao hn PE + gin di : % = 300-800% (cao hn PE) + bn nhit (theo Vica) oC =105 110 +tg (106hex, to=25oC) : 0,0002 0,0003 +Nhit gin gy thp hn PE: (-5oC) (-15oC) + cng Brinel: 6 6,5 kg/cm2 +Tnh bm dnh km +Ch s chy t 2 60 gr/10pht 3. ng dng: Hon ton ging PE Loi thng thng sn xut cc loi vt dng thng thng. Loi trng hp khi: sn xut cc vt dng cht lng cao, chi tit cng nghip, cc loI van, v hp acqui, Loi tnh nng c l cao: dng sn xut cc vt dng cht lng cao. Loi c bit: chuyn dng cho chi tit sn phm cng nghip, chi tit nha trong xe my, t, in t, hp thc phm, my git,

Loi trong: nhiu pha v nh hnhdng cho bao b y t, bao b thc phm, xylanh tim, CD, VCD, sn phm loI c bit trong cho thc phm , khng mi, c bng b mt cao.

CHNG III: SN XUT POLYSTYREN (PS) I/ Nguyn liu -Nguyn liu sn xut PS l Styren c cng thc phn t C8H8 v cng thc cu to CH=CH2

-Cc tnh cht vt l ca Styren: Styren l mt cht lng trong sut, khng mu n hi vng c mi hc, khc x nh sng mnh. - Khi lng ring 25oC : d= 0,9045 (g/cm3) - nht (25oC) = 0,7 cp - Nhit si: ts = 145,2 oC - Nhit nng chy: tnc = -30,63oC - Nht bng chy: tbc = 34 oC - Nhit ho hi: 86,9 (kcal/mol) - Nhit trng hp: 16,5 (kcal/mol) - Gii hn chy n trong khng kh (%V): 1,1 6,1 - co th tch khi trng hp: 17% Styren tan trong cc dung mi khng phn cc hay phn cc yu: xtn, CS2, este, hydrocacbon mch h, vng no hp cht thm v dn xut halogel. Styren t tan trong nc v trong cc glycol khc. Styren c, gy kch thch nim mc mt, mi, phi, gy ng c thn kinh. Vi nng 0,2 mg/ lit c th lm h da, nim mc mt v c hng. -Tnh cht ho hc ca Styren: + Cng hydr: CH-CH3 CH=CH2 H2, Ni 25oC, 3at + Cng halogen: C6H5-CHBr-CH2Br C6H5-CH=CH2 + Br2 + Cng HA ( HOH, HX, H2SO4...) C6H5-CH-CH3 C6H5-CH=CH2 + HA A + Phn ng oxy ho: C6H5-COOH + CO2 + H2O C6H5-CH=CH2 + O2 Styren rt d trng hp v c ni i v vng thm, trong qu trnh bo qun nn hn ch cho tip xc vi nh sng, oxy, nhit . Thng thng khi bo qun ta cho 0,5 1,5 % khi lng hydroquinon vo lm cht c ch trng hp.

-iu ch Styren: Styren c th thu c t hai ngun: + T sn phm Cracking v chng ct du m, kh ho than cc. + Bng con ng tng hp: C2H6 + C2H4 C6H5-CH2-CH3
AlCl3 90-95oC dehydro ha ZnO, 500oC

C6H5-CH2-CH3 C6H5-CH=CH2 + H2

II/ L thuyt trng hp Styren Trong sn xut Styren ch trng hp theo c ch trng hp gc v thu c polymer c cu to ch yu l lin kt u - ui v dng v nh hnh. Trong nghin cu ngi ta c s dng trng hp ion to PS tinh th hu ht dng izotactic, mt phn dng syndiotactic, rt t dng atactic. Styren d trng hp khi, trng hp dung dch, trng hp nh tng v trng hp huyn ph. Mi phng php u c nhng u, nhc im ca n. 1/ Trng hp khi Trng hp Styren thnh khi c th tin hnh khi un nng c cht khi u hoc khng c cht khi u. Cht khi u thng l cc peroxit hu c. Benzoyl peroxit l cht khi u rt ph bin nhng khng thch hp khi trng hp styren v n lm vng sn phm. Tc trng hp tng theo nhit nhit di 50oC vn tc trng hp rt chm (c khi n hng nm), 150oC phn ng kt thc trong vi gi. Nhng khi chuyn ha c khong 90% th phn ng chm li v khi c 9899% th phn ng hu nh khng xy ra na. iu c ngha l polymer c trng lng phn t cao khng thu c vi hiu xut cao. Nu cn li nhiu monome th nhit chy mn ca PS s gim xung, vt phm tr nn c do monome chuyn ln b mt v bc hi t t i khi lm vng sn phm. thu c polymer c trng lng phn t trung bnh cao tng i v cha monome cn li t nht ta dng ch trng hp hai giai on: + Giai on u: to ra xirop (PS c trng lng phn t thp tan trong monome) vi hiu sut 3040%. + Giai on hai: vo khun ( c th tch nh 510 lt) sau trng hp tip tc cho n khi kt thc. Tho sn phm ra khi khun em p, nghin, sng hay to ht. 2/ Trng hp dung dch So vi trng hp khi th phn ng trng hp trong dung dch xy ra vi vn tc b ( iu kin khng c cht khi u) v polymer to ra c trng lng phn t thp hn. Gi tr trng lng phn t trung bnh ca PS ph thuc vo iu kin trng hp v

loi dung mi. Qua th nghim thy benzen, xiclohexan, toluen trng hp tt hn cc dung mi khc. iu ch polymer trong dung dch thun li lm sn, cn vi mc ch khc th thm cht lm lng kt ta polymer. 3. Trng hp nh tng Nh tng gm c: monome, nc, cht nh ha, cht khi u v cht iu chnh sc cng b mt. C ch trng hp nh tng: cht nh ha khi tan trong nc to thnh cc Mixen hnh cu m cc u khng a nc ca phn t nh ha s hng vo trong v cc u a nc hng ra ngoi. Cc phn t cht khi u tan trong nc to thnh cc gc t do nh phn a nc ca cht nh ha i vo Mixen v tip xc vi cc phn t monome xy ra cc phn ng trng hp. + Nc l mi trng phn tn cng l cht ti nhit iu chnh nhit phn ng ta ra. + Cht nh ha: gi monome v polymer mi trng thi phn tn trong pha nc. Cht nh ha thng dng l cc loi x phng nh: lat kali, natri, starat hay cc sunfoaxit ca ru cao bo, x phng nha thng, nkan Nu gim nng cht nh ha th vn tc phn ng gim, nhng thi gian trng hp v trng lng phn t trung bnh polymer tng. V vy mun iu chnh trng lng phn t trung bnh polymer trc ht nn thay i nng cht khi u ch ng thay i lng cht nh ha. V cht nh ha ch thay i M ca PS mt t nhng li tng thi gian trng hp ln rt nhiu. + Cht kch ng: l cc peroxit v hydroperoxit tan trong nc ( H2O2, pesulfat amn v kali..) vi hm lng 0,11% trng lng monome. Khi thnm cht xc tin ( cc mui kim loi c tnh axit: ion Ag+ ) lm phn hy cht kch ng vo hn hp phn ng th thi gian trng hp gim. Nu dng h thng oxi ha-kh: cht oxy ha ( cht kch ng ) v cht kh ( mui kim loi c ha tr thay i) th vn tc ca qu trnh trng hp c th tng v gim nhit phn ng xung. + Cht iu chnh: thng dng ru hay cc cht lm gim sc cng b mt ca h thng tc l c kh nng lm tng khuch tn ca nh tng. 4/ Trng hp huyn ph Huyn ph gm: monome, nc, cht kch ng, cht n nh v cht hot ng b mt. y cht kch ng peroxit hu c khng tan trong nc m tan trong monome. + Nc dng tch monome ra thnh tng ht ring ng thi cng l mi trng trao i nhit.

+ Cht n nh l cc polymer hu c tan trong nc nh ru polyvinilic, metyl xenluylochng phi hon ton khng tan trong monome. Vai tr ca n l lm tng nht ca nc v do ngn cn cc ht polymer dnh vo nhau. III/ Sn xut Polystyren (PS) 1/ Trng hp khi: + Phng php gin on Qu trnh gm hai giai on - Giai on 1: trng hp s b Styren p sut thng sau to chn khng 200-270 mmHg v un nng. Khi hiu sut phn ng t khong 30-40% tin hnh lm lnh n 70-80oC v rt vo khun c dung tch t 5-10 lt. - Giai on 2: trng hp xirp trong khun nh nh un nng. Sau tho sn phm ra ri em i p, nghin, sng v ng bao. Cc yu t nh hng n qu trnh trng hp khi: Vn tc ban u (% nht (Cp) Nhit trng hp o 2 MP trong 1 gi) (d 10% trong Toluen) ( C) 60 0,089 3.000 2.250.000 80 0,462 650 880.000 100 2,15 200 420.000 140 28,4 30 130.000 160 -14 83.000 50oC phn trm chuyn ho rt b, thi gian trng hp rt lu. 150 oC trng hp ch trong vi gi,

=100.000.

+ Phng php lin tc Hnh v ( xem sch ) -Styren t thng lng (1) t chy lin tc vo ni phn ng (3). Trn ng chy c b tr thit b lc (2) tch b cc tp cht c hc. Nhit phn ng duy tr ni (3) t 75-80oC, vn tc cnh khuy khong 50-60 vng/pht. Khi hiu sut phn ng t t 18-20% ta cho xirp chy vo thp trng hp c chiu cao 7.000 mm, ng knh 650 mm. Thit b (4) chia lm 4 khu vc, khu vc I ch c v bc ngoi un nng, cc khu vc khc c thm ng xon rut g bn trong un nng. Hi bay ra khi thit b phn ng (4) c ngng t thit b lm lnh (5). Sn phm PS nng chy t khu vc VI i vo phn hnh nn ca thp c nhit 235oC sau nh trc vt y lin tc ra thnh bng hay thi, ri em i lm ngui v thc hin qu trnh p, nghin, sng, ng bao. -Ch nhit trong thp phn ng (4): Nhit phn ng (oC) STT

Ch 1 Ch 2 Ch 3 I 100-110 100-110 100-110 II 100-110 120 145 III 150 145 165 IV 150 190 220 V 180 200 230 VI 180 215 235 2/ Trng hp dung dch - Phng php gin on c 3 giai on: trng hp trong ni phn ng, tch polymer khi dung dch, p nh polymer. - Phng php lin tc: cho Styren v dung mi t thng lng theo t l nht nh vo thp trng hp (gm nhiu thp ni tip nhau). Dung dch PS nht t cui thp trng hp chuyn vo thit b un nng nhit lm vic khong 225oC tch dung mi v mt phn monome khng phn ng. Sau PS dng nng chy cho qua my n trc vt to dng cho sn phm v lm ngui bng nc. 3/ Trng hp nh tng Nguyn liu I II III Styren 100 100 100 H2O 250 175 200 X phng du thu du (du ve) 3 0,4-1,2 K2S2O8 0,25 0,3 2 H2O2 (d 30%/H2O) 2,5 u tin cho nc v x phng du ve vo thit b phn ng tin hnh khuy trn. Sau cho styren v cht khi u vo, duy tr vn tc cnh khuy khong 120-160 vng/pht. un nng hn hp ln 65-70oC lc ny cht khi u bt u phn ly v to ra cc gc t do, phn ng xy ra theo c ch trng hp gc, phn ng to nhit nn nhit ca hn hp t tng ln 85-90oC. Gi nhit ny cho n khi hm lng monome d trong hn hp phn ng nh hn hoc bng 1%. Khng nn tng nhit ln na v khi cc ht PS va to ra s chy mm v dnh li vi nhau. Sau tin hnh ph nh tng ri em i lng, lc, ly tm tch polymer ht b v dung dch cht nh ho, cht khi u cn d...Monome t do c th c tch bng cch sc hi nc qu nhit vo hn hp polystyren nc thc hin qu trnh li cun hi nc. Vic ph nh tng c th thc hin bng nhiu cch khc nhau chng hn nh: - Dng nhit ph h nh tng - Dng c hc: khuy mnh vi vn tc khuy 3.000-6.000 vng/pht. - Dng in trng

Dng cht in ly: mui n, NH4Cl, ZnCl2, CH3COOH... Sn phm to ra em ra nhiu ln bng H2O lm sch ht cc cht nh ho cn li trn b mt cho n khi trung tnh. Cui cng em i sy kh n m nh hn 0,5 % v sng phn loi, ng bao. 4/ Trng hp huyn ph Cho nc, monome v cht khi u t t vo thit b phn ng ng thi m cnh khuy chy vi vn tc 80-120 vng/pht. Cho tip dung dch PVA vo. Ban u nng nhit ln 75-80oC trong vng 1,5h sau tng nhit ln 88-90oC trong vng 2h. Tng thi gian phn ng khong 4-5h, hiu sut t 95-98%. Hn hp huyn ph gm: ht PS, mi trng em ly tm v ra bng nc m o 45-50 C sau em i sy kh nhit 65-75oC trong chn khng n m nh hn 0,2-0,5%. IV/ Cu to, tnh cht, ng dng ca PS 1/ Cu to Qua nhiu phng php nghin cu khc nhau, c bit l phng php nhit phn PS th thy rng PS c cu to u ni ui
CH2 CH CH2 CH C H2 CH

PS nhit phn ng khng cao th t to nhnh v nhnh b. 2/ Tnh cht PS l cht do trong sut , cng chc, khng mi, khng v, khi chy c nhiu khi, gi thnh r, d gia cng bng phng php p v c di p sut, chu ho cht v nc cao... V c nguyn t H C bc 3 linh ng nn H ny d tham gia phn ng oxi ho v th PS nhanh b lo ho trong khng kh khi c nh sng trc tip. Vng bezen c th tham gia phn ng sunfo ha, nitro ho,...dng sn xut nha trao i ion nh cationit axit mnh. PS khng phn cc do bn vi cc ho cht phn cc v phn cc mnh. PS c trng lng phn t thp rt gin v c bn khi ko cng b. dn di tng i ca PS tng vt sau 80oC v tr nn mm do nh cao su v dnh. -Khi lng ring d=1,05-1,1 g/cm3 -Ch s chy MI: 1-8 g/10pht - bn ko t: 400-450 kg/cm2 Tnh cht PS huyn ph Dung dch Khi Nh tng 2 Gii hn bn un [KG/cm ] 816 875 800 900 2 bn va p [KG/cm/cm ] 14,7 15 15 180

 bn nhit (Mactanh) [oC] 80 80 80 80 2,6 2,6 2,6 2,6 thm in mi (in th 6 xuyn thng) (10 hex) tg (106 hex) 0,0004 0,0006 0,0004 0,0008 3/ ng dng -PS c lm vt liu cch in (iu kin khng ti hoc ti trng b v tnh) -Lm cc sn phm khc dng trong dn dng v cng nghip, phi bin tnh bng cch ho do hoc ng trng hp vi cc monome khc. -PS xp dng lm v ng my khi vn chuyn, cch m v nhit thp trong xy dng

CHNG IV:

CHT DO TRN C S CC POLYMER CA RU VINYLIC V CC DN XUT A- SN XUT PVAx

I/ Nguyn liu Nguyn liu chnh sn xut polyvinyaxetat l vinyaxetat Tnh cht: l mt cht lng trong sut, khng mi, t tan trong nc, tan trong dung mi hu c, c: + Nhit si ts= 73oC + Nhit ng bng t= -84oC + Nhit bc la tl = -5 -8oC + Khi lng ring 20oC 20= 0,934 (g/ml) + nht 20oC = 0,432 Cp + n nhit bc hi: 7,8 ( Kcal/mol) + ho tan trong nc 20oC : 2,5 % + Cng thc cu to:
CH2 CH

OCO

CH3

Tnh khng no: do trong mch c ni i nn VA c kh nng tham gia cc phn ng cng, ng vng, oxi ho. C lin kt este nn tham gia phn ng thu phn vi nc, ancol
CH2 CH OCO CH3

C4H9OH

CH3 C OH O

CH2 CH O C4H9

* iu ch: C hai phng php + Sn xut VA trong pha lng theo phng php gin on hoc lin tc. Cho axetylen (C2H2) qua hn hp CH3COOH m c v anhydrit axetic c cha sunfat thu ngn hoc phtphat thu ngn. Phn ng xy ra nhit 75-80oC, kt thc phn ng C2H2 tha c tch ra v mt lng nh VA c a i x l. Vi phng php gin on cui qu trnh ta lm chm vn tc hp th C2H2 gim lng VA b tht thot v i xc tc mi. Cn i vi phng php lin tc th lin tc cho C2H2, CH3COOH v cht xc tc mi vo thp phn ng ng thi lin tc tho xc tc phn ng ra. Sn xut VA theo phng php pha kh th ngi ta tin hnh theo phng php lin tc. Cht xc tc thng dng l axetat km (CH3COO)2Zn hoc (CH3COO)2Cd c ph ln b mt than hot tnh sau sy kh. Nhit phn ng 170oC 240oC. Lc u nhit phn ng 170oC nhng sau do hot tnh ca xc tc gim nn tng

vn tc phn ng th nhit phi nng ln 210oC 220oC. hiu sut phn ng cao th dng t l C2H2 : CH3COOH = 9 : 1 khi hiu sut t c l 80 85%.
HC CH

Xc tc

CH3 C OH O

CH2 CH OCO CH3

+ Phng php mi sn xut VA l phn gii diaxetat-etyl theo phng trnh phn ng cho hiu sut cao
o H3C CO Xc tc,t O H3C H3C CHO + H3C CO

Xc tc,to

CH (OCO CH3)2

CH2 CH

+ CH3 COOH

OCO CH3

II/ L thuyt trng hp VA Vinylaxetat d b trng hp di tc dng ca nh sng, nhit , cht kch ng v cht xc tc. Nhit to ra do trng hp kh ln + VA : 21,3 Kcal/mol + MMA :13 - 13,6 Kcal/mol + Styren : 16 17,5 Kcal/mol + Etylen : 25 26 Kcal/mol V vy khi trng hp VA cn mt nng lng kch ng kh ln, gy kh khn cho qu trnh iu chnh. Cc monome c cha nguyn t C bc 3 c khuynh hng to ra polymer nhnh ln do phn ng chuyn mch. + Chuyn mch qua monome
R

+ CH2

CH

xt, tO

RH

+ CH2

C OCO CH3

OCO CH3

Hoc
R

CH2 CH

xt, tO

RH

+ CH2

OCO CH3

H OCO C H

CH

R : gc polymer ang pht trin. Nu trng hp tip tc th sinh ra nhnh.

CH 2 C OCO

xt, t O CH 3 xt, t O

CH 2 C OCO CH 3

(a)

CH 2 CH OCO

H C H

CH 2 CH OCO CH 2

(b)

C ch to nhnh theo kiu (a) nhiu hn (b) + Chuyn mch cho phn t polymer khng hot ng . , ,. RH + R R + RH Mun lm gim s nhnh trong polymer hoc ta cho ngng phn ng trng hp mc chuyn ho thp. Hoc cho tin hnh phn ng trong dung mi hoc cho thm cht iu chnh (mecaptan, aldehyt...) c nguyn t H linh ng. S chuyn mch t polymer ang pht trin sang dung mi c m t nh sau: . . RH + A (km hot ng) R + HA III/ Sn xut PVAx C 4 phng php trng hp VA: trng hp khi, trng hp dung dch, trng hp huyn ph v trng hp nh tng. Trong phng php trng hp khi t c s dng v to thnh khi PVAx gy kh khn cho cc cng on x l tip theo (Tg = 28oC). Trng hp huyn ph cng t c s dng, phng php c s dng ph bin nht l trng hp nh tng. 1/ Trng hp dung dch Sn phm thu c dng lm sn, vecni, keo dn, sn xut PVA Thnh phn hn hp phn ng + Monome 100 PKL + Dung mi 70 100 PKL + Cht khi u [ (C6H5COO)2 ] 0,2 0,5 % + Cht iu chnh ( C2H5CHO ) 0,01 0,1 % iu kin tin hnh phn ng + Dung mi ho tan c monome v + Nhit phn ng ban u 75 80oC sau tng ln 85oC, hiu sut phn ng t 98% + Thi gian phn ng 4 6h Khi c mt ca dung mi th s phn tn nhit c ng u hn. Nhng nng monome trong trng hp dung dch nh hn nng monome trong trng hp khi nn

vn tc phn ng khng cao v trng lng phn t b hn so vi trng hp khi v c s chuyn mch, ngt mch vi dung mi. Vinylaxetat tan tt trong cc dung mi etylaxetat, axeton, benzen, toluen, ru tuyt i. Bn cht v nng dung mi khc nhau th dn n hiu sut v trng lng phn t ca polymer cng khc nhau c th. Nguyn Axeton Toluen Ru tuyt Etylaxetat Benzen liu i 28 22,6 89,3 55 Hiu sut 68,5 to Po (%) nht 3 2,9 5,6 8,2 18,2 (Cp) Ta thy ru tuyt i, benzen v toluen lm chm qu trnh trng hp VA, tc phn ng ln nht l tin hnh trng hp trong dung mi etylaxetat v axeton. Cn trong dung mi benzen th polymer thu c c trng lng phn t cao nht, nu dng toluen th trng lng phn t rt thp mc d nhng tnh cht ca hai dung mi gn ging nhau. Trong k thut dung mi thng dng trng hp VA l etylaxetat, axeton v benzen. Ru etanol v metanol ch dng khi sn xut polymer tip tc x l thnh PVR v polyvinylaxetal. 2/ Trng hp nh tng C 2 loi nh tng : nh tng mn ht = 0,05 0,5 m nh tng th ht = 0,5 10 m Thnh phn nh tng mn: + VA : 100 PKL 100 120 PKL + H 2O : 0,1 0,5 ( dung dch 10 15%) + Cht nh ho C17H33COOK: 0,5 1,5% + Cht khi u H2O2 : 0,01 0,1% + Cht iu chnh C2H5CHO : Chun b: + Ho tan cht nh ha trong nc + Ho tan cht khi u trong t nc + Ho tan dung dch cht iu chnh vo nc Cc bc tin hnh trng hp: + Cho ht dung dch nc v cht khi u vo thit b phn ng, cho cht nh ho vo khuy u. + Cho t t monome vo khuy u

+ un nng n nhit 65 70oC gi trong khong 1h, do phn ng to nhit nn nhit t nng ln 90oC, tip tc duy tr nhit ny trong khong 1,5 2h. Cho cht iu chnh vo gn cui qu trnh, kt thc phn ng hiu sut chuyn ho t 98% + Lm lnh hn hp phn ng n 40oC, thm cc cht khc nu cn thit. + Hm lng cht kh trong nh tng khong 50% 3/ Trng hp huyn ph Thnh phn nguyn liu: + VA: 100 PKL 100 PKL + H2O: 0,5 1 PKL + (C6H5COO)2: + Cht n nh huyn ph : 0,1 0,2 PKL ( dung dch PVA c 8 20 % nhm axetat) S dy chuyn cng ngh Hnh v: (xem sch) Cc bc tin hnh + Chun b nguyn liu: -Ho tan cht khi u vo monome -Ho tan PVA trong H2O -Trn hn hp dung dch cht khi u vo ht monome cn li + Tin hnh phn ng u tin cho ht phn nc vo thit b phn ng (6), cho dung dch PVA ho tan trong nc vo ng thi tin hnh khuy trn. Ri cho t t hn hp VA v cht khi u vo thit b phn ng. Thit b phn ng c v bc bn ngoi gia nhit cho hn hp phn ng. Dng hi nc bo ho nng nhit ln khong 70 80oC ng thi khuy u lin tc to c cc git lng monome c dung dch PVA bao bc xung quanh. PVA c nht tng i ln nn ngn cng khng cho cc git monome dnh li vi nhau. Khi un nng phn ng xy ra v to nhit nn nhit ca hn hp t tng ln 80 90oC, khi ta ng van hi nc li v m van nc lnh gi nhit ny trong vng 45 60 pht. Tip tc nng nhit ln n 90 95oC trong thi gian 30 35 pht. Tng thi gian phn ng ny mt khong 2h. Trong qu trnh phn ng hi monome v nc bay ra c cho vo thit b ngng t lm lnh bng nc (7) ri cho hi lu tr li thit b phn ng. Hiu sut chuyn ho ca qu trnh khong 98 99%. Khng kh nn hoc N2 (nu dng khng kh nn th phi lc) c tc dng ngn khng cho khng kh bn ngoi vo trong thit b phn ng, ng thi khng cho hn hp bn trong thit b phn ng b trn. Khi cho kh nn vo th phi ng tt c cc van khc li. Hn hp phn to ra trong thit b (6) c chuyn sang thit b cha (9), ti y hn hp c duy tr nhit 50oC gim nht, v trnh sa

lng th thit b phi c cnh khuy hot ng lin tc. Sau hn hp c chuyn sang my ly tm (10), y dung dch nc thi em i x l cn cc ht polymer c chuyn sang xe gong (11) v theo h thng nng (12) i vo thit b sy (13). Ti thit b sy (13) nhit sy c duy tr 65 70oC trong iu kin chn khng vi thi gian khong 15-20 pht ( y ch c tc dng lm kh nc ch khng sy kh trit , cc ht polymer to ra c th ht m tr li). Sau khi sy xong a vo my sng phn loi ht th em i nghin nh ri trn li vi sn phm ht nh. IV/ Cu to, tnh cht v ng dng ca PVAx 1/ Cu to Ngi ta dng phn ng x phng ha PVAx to thnh PVA nghin cu cu trc ca PVAx. Cc monome VA kt hp vi nhau to thnh polymer PVAx theo nguyn tc u ni ui. Cc phng php nghin cu: + Khi oxi ho PVA bng HNO3 ta thy c to ra acid oxalic:
CH2 CH CH2 CH OCO CH3 CH2 CH OH CH2 CH OH HOOC COOH OCO CH3

+ Xt ph hp th th thy PVA c vch hp th ging 2,4-pentadiol

CH 3 CH CH2 CH CH3 OH OH

+ Phn tch Rnghen ta thy PVA c cu trc -glycol. + Dng phn ng oxi ho PVA bng HIO4 chng minh PVA c cha nhm glycol hay -glycol. Nu PVA c cha nhm -glycol tc l mch phn t PVA c cu trc u ni u khi PVA d b oxi ho bng HIO4. Nu ta un nng PVA vi HIO4 th thy nht gim nhng khng ng k, chng t lc u c phn ng t mch xy ra nhng sau nht khng gim c ngha phn ng khng xy ra na. Phn ng t mch PVA nh sau:
CH 2 CH OH CH 2 CH OH CH2 CH CH OH OH CH 2 CHO CH 2 CH CH2 CH OH OH CH2 CH HIO 4

CH CH2 CH OH OH

H2 O

Phn ng t mch xy ra mt s v tr u ni u, ui ni ui nhng v tr ny rt t nn nht gim t. PVAx l mt polymer v nh hnh, nu mc ko cng ln (nh hng) cng khng kt tinh v bn cht ca n khng nh hng c do nhiu nhnh v nhnh ln. Polymer phn cc trung bnh yu = 2,3.10-18 debay, do vy tan tt trong cc dung mi phn cc tng ng.

2/ Tnh cht a/ Tnh cht nhit: + PVAx c Tg = 28oC khi trng lng phn t trung bnh ln hn 30.000, nu trng lng phn t trung bnh thp 15.000 th Tg = 17oC + PVAx c th chy lnh( mu PVAx chu tc dng ca ti trng no y nhit thng khng un nng, mu cng b bin dng chy) + Khi un nng 170oC tr ln th PVAx b phn gii to CH3COOH
170OC

CH2 CH

CH2

CH OCO CH3

CH

CH

CH2 CH

+ CH3

COOH

OCO CH3

OCO CH3

Do lm cho polymer b vng, c th to polymer mng li khng gian khng nng chy, khng ho tan trong bt k dung mi no. Kh nng to mng li khng gian l do m lin kt i trong mch. b/ Tnh cht ho hc + PVAx bn oxi ho, lo ho, nh sng + PVAx tan trong cc dung mi: xton, este, dn xut ca HC, HC thm. + PVAx phn cc trung bnh nn khng tan trong xng, du ho, HC bo mch thng no, cc cht c phn cc ln: glycol, glyxerin. + PVAx b trng trong nc v c th bn vi cc mui. + PVAx b thu phn to PVA trong mi trng kim hoc axt + Trn ln tt vi cc polymer: nitro xenlulo, cc dn xut khc ca xenlulo, cao su clo ho, mt s polyeste, nha epoxy, phenolformaldehyt nhng khng trn ln vi cc nha alkyd, ure-formaldehyt v melamin-formaldehyt. c/ Tnh cht c hc Ph thuc vo trng lng phn t trung bnh v phng php sn xut + Khi lng ring d= 1,18 1,19 g/cm3 + Gii hn bn ko (KG/cm3): -10oC 600 10oC 400 20oC 350 30oC 150 180 37 + bn nhit (Vica, oC): o o 3% + ht nc (24h, t =20 C): + thm in mi (60 hex): 6,1 + tg (60 hex): 0,025 3/ ng dng + sn xut PVA + Lm sn, vecni, keo dn thng thng trn vi polymer khc

+ Dng PVAx nh tng dng trong xy dng tng Mac ca va ximng v ximng btng, tng chng thm + Dng PVAx nh tng dng lm sn trong trang tr ni tht B- SN XUT POLYVINYLALCOL (PVA) I/ Sn xut PVA Phng php c bn sn xut PVA l thu phn (x phng ho ) PVAx nh kim v axit ( NaOH, HCl, H2SO4l...) thng thng thu phn trong mi trng kim vi dung mi l CH3OH. Trng kp dng NaOH lm xc tc th cho PVAx tan trong CH3OH khan nc v sau x l bng mt lng nh (0,2 0,4%) dung dch NaOH trong CH3OH khan nc. Gi hn hp nhit phng, PVA tch ra dng gel, dng phng php gn tch cht lng gm: CH3OH tha, axetat v nati axetat, cn PVA tan trong nc. Rt dung dch ny vo axeton (lng tha) kt ta PVA dng nguyn liu si trng, sch. iu chnh lng nc, nng PVAx v lng cht xc tc c th khng ch c mc thu phn bt k. Sau em ly tm, ra, sy chn khng nhit 80 90oC n m 2 3% ( sy bay hi axeton i, cn ht vn m do PVA tan tt trong nc c th ht m tr li). Trng hp dng HCl lm xc tc th nht ca PVA gim, c khi PVA khng tan trong nc v trong axit long. iu c l do PVA b mt mt s nhm hydroxyl trong qu trnh thu phn hoc trong thi gian sy. Rt kh kh vt axit c bit l axit H2SO4 ra khi PVA, v th axit cn li c th xc tin qu trnh kh hydro
CH3OH, NaOH

CH2 CH CH2 CH to=30 - 40oC O C CH O C CH3

3

CH2 CH CH2 CH OH OH

CH3COONa

+ CH3COOCH3

II/ Cu to v tnh cht ca PVA 1/ Cu to Dng polyvinylfocmiat th PVA to ra dng syndiotactic

Xc tc, to

polyvinylformiat CH=CH + HCOOH CH2=CH-OOC-H Dng polyvinylbenzoat to PVA dng izotactic Dng PVAx to hn hp 3 loi: izotactic, syndiotactic v atactic, trong atactic chim ch yu nn PVAx l mt polymer v nh hnh. V c nhm OH phn cc v c lin kt H gia cc mch phn t nn Tg cao, Tg = o 85 C v th gy kh khn cho qu trnh gia cng. 2/ Tnh cht:

C kh nng to ete, phn ng vi cc aldehyt to polyvinylaxetal

CH2 CH OH CH2 CH OH

CH2O

CH2 CH O

CH2 CH2

CH O

polyvinylformal (form-va)
CH2 CH OH CH2 CH OH

C3H7CHO

CH2 CH O

CH2 CH
C3H7

CH O

but-va Hai phn ng ny c ngha quan trng Khi un nng nhit cao (>200 250) th tch nc, to ni i. PVA tan trong H2O ph thuc vo nhit v phn trm nhm CH3COO- c trong PVA + Nu %CH3COO- < 5 th khng tan trong nc lnh m ch tan trong nc nng (65 70oC) dung dch t nng ti a 10 12 %. + Nu %CH3COO- = 20 th ho tan trong nc, khi un n nhit 30 35oC ri lm lnh th Po s lng xung. + Nu %CH3COO- = 50 th khng tan trong nc lnh v nng m ch trng nhng tan trong hn hp ru v nc ( thng dng CH3OH ) + Ngoi nc PVA cn c th tan trong glycol thng, glyxerin, phenol, ure ( khi un nng ) Dung dch PVA bm dnh tt trng thi kh v khng b thi ra bi vi sinh vt nn dng lm keo dn giy, phong b. III/ ng dng Nu PVA cha 15 20% nhm CH3COO- th dng lm keo dn. Dung dch PVA cho thm mt lng nh formalin dng lm keo dn giy, vi, da. bn c hc ca PVA nh hn polyamid-6, polyamid 6-6, axetat xenlulo, phenol formaldehyt, ure formaldehyt... Si PVA x l bng dung dch CH2O c dng lm si cu, li nh c. Ngm si PVA c x l bng CH2O trong nc bin trong vng 95 thng th bn thay i khng ng k. Si PVA x l ho hc bng CH2O kt hp vi si Visco dit vi may mc, mt s ni gi l si vinylong

CHT DO I T CC DN XUT CA AXIT ACRYLIC V AXIT METAACRYLIC Axit polyacrylic v polymetaacrylic ng trng hp vi divinyl benzen ( 10 15% khi lng ) dng lm nha trao i ion loi cationit
* CH2 CH COOH CH CH2 n CH2 CH

CHNG V:

Polyacylat v polymetyl-metaacrylat, polyacrylonitril, polybutylmetaacrylat l cc loi nha thng thng. Polyacrylonitril c Tg > nhit phn hu do phi dng dng ng trng hp ch khng dng dng n trng hp, n khng tan trong bt c dung mi no. I/ Nguyn liu chnh 1/ Axit acrylic ( CH2=CH-COOH ) l axit hu c khng no, n gin nht, c kh nng trng hp v ng trng hp. C nhiu phng php sn xut axit acrylic. + Phng php tng hp Reppe iu ch trc tip t C2H2, CO, H2O ( CO c iu ch t ttracacbonyl niken ho tan trong HCl )
CH CH

H2O

1/2 HCl

+ 1/4 Ni(CO)4

CH2 CH COOH

+ 1/4 NiCl2 +

1/4CH2

+ Phng php c in: oxi ha acrolin bng khng kh trong mi trng CH3COOH m c 20 40oC c oxit bc hoc oxit vanadi + Nhng tin nht l:
H2C CH2 O

+ HCN

CH2 CH2 CN OH

etylenxianhydril
CH2 CH2 CN OH

H2O + H2SO4

95OC

CH2 CH COOH

+ (NH4)HSO4

Axit acrylic l cht lng khng mu, c mi hc tan trong nc v cc dung mi hu c theo bt c t l no. Khi khng c peroxit, trong mi trng N2 v nhit n 180oC vn khng b trng hp. Ngc li nu c mt lng nh oxi hoc peroxit vo th d to ra Po. 2/ Este ca axit acrylic ( CH2=CH-COOR ) Trong cc este ca axit acrylic th metyl, etyl, butyl acrylat c dng nhiu nht Ngi ta tng hp este acrylic t etylenxianhydrin

CH2 CH2 CN OH

ROH

H2SO4

CH2 CH COOR

+ (NH4)HSO4

Este tinh khit d b trng hp ngay nhit phng. 3/ Axit metaacrylic

CH2 C COOH CH3

Nhn axeton xianhydrin t axeton v HCN

CH3 CO CH3

HCN

CH3 C(CH3) CN OH

Kh H2O v x phng ha axeton xianhydrin bng H2SO4.

CH3 C(CH3) CN OH CH2 C COOH CH3

Axit metaacrylic l cht lng, khng mu, si 160oC. 4/ Este ca axit metaacrylic ( CH2=C(CH3)-COOR ) Metyl metaacrylat v butyl metaacrylat c dng nhiu nht. Phng php chung l kh H2O, x phng ho v ete ho axeton xianhydrin bng ru tng ng.
CH3 C(CH3) CN OH

+ ROH +

H2SO4

CH2 C(CH3) COOR

(NH4)HSO4

Tn Nhit si (oC) Khi lng ring (g/ml) CH2=CH-COOH 141 1,0487 (20oC) CH2=C(CH3)-COOH 160 1,015 (20oC) CH2=CH-COO-CH3 80 0,952 CH2=CH-COO-C2H5 99,5 100 0,919 CH2=C(CH3)-COO-CH3 100,3 0,937 CH2=C(CH3)-COO-C2H5 117 0,911 * Nhn xt: Thay H linh ng (1) bng CH3- tr thnh (2) th nhit si cao hn do s cn tr chuyn ng quay ca nhm CH3, ng thi khi lng ring ca (2) cng nh hn do cng knh v mt sp xp khng gian ca mch i phn t. Nhit si thp nht l metylacrylat v khi lng ring thp nht l etyl metaacrylat. Quy lut trng hp ca monome ny cng ging nh cc monome ca dn xut vinyl, ch khc v iu kin trng hp. * Xt MMA MMA c nhit trng hp thp ( nh hn Styren ) nn MMA d trng hp. MMA trong qu trnh bo qun nu tip xc vi nh sng c bc sng ngn, oxi khng kh th n t

trng hp. Do trong qu trnh bo qun cn phi cho thm cc cht c ch (hay hm trng hp) l cc cht c H linh ng, ph bin nht l hydroquinon. V vy trc khi tin hnh trng hp th tch lng hydroquinon ny ra khi monome bng dung dch NaOH nhng hm lng ch nhiu hn mt t so vi hydroquinon v nng xt phi long.
CH3 CH2 C COOCH3 CH3

NaOH

CH2 C COONa

CH3OH

II/ Nguyn tc trng hp C th trng hp theo mt trong 4 phng php: trng hp khi, trng hp dung dch, trng hp nh tng , trng hp huyn ph. 1/ Trng hp khi Thnh phn nguyn liu: + MMA: 100 PKL + Hn hp cht khi u ( peroxit benzoic:azodiizo butyronitril = 2:1 ): 0,02 1% S dng hn hp cht khi u gim tc oxi ho ca peroxit benzoic. Qu trnh phn ng: + Chun b nguyn liu: trn cht khi u vi mt t MMA ri sau cho hn hp ny trn vi lng MMA cn li. + Tin hnh gia nhit cho hn hp phn ng, ban u duy tr nht 70 80oC, phn ng to nhit nn s t nmg ln 80 -90oC. Khi hiu xut chuyn ho ca hn hp t 30 40% tin hnh vo cc khun nh c dung tch 5 10 lt v vn gi nhit 80 90oC, tip tc trng hp trong l sy vi thi gian 4 6 ngy. Nhit sy trong l c iu chnh nh sau: 80 - 90oC trong 1 2 ngy. 90 95oC trong 1 ngy. 95 110oC trong 1,5 ngy. 110 120oC trong 1 ngy. co ngt th tch khi trng hp khi l 20,1% Trong qu trnh sy nng nhit t t trnh hin tng monome bc hi to l xp v hm lng monome cn li trong sn phm cui cng 0,5 1%. Trng hp khi c ng dng nhiu nht trong sn xut PMMA. nng cao hiu xut ng thi gim co ngt ca sn phm ngi ta tin hnh trng hp MMA theo mt phng php khc: trn MMA vi mt lng xirp ca PMMA v cht khi u ri tin hnh trng hp theo trnh t cc bc nh trn. 2/ Trng hp dung dch

Bn cht v hm lng dung mi nh hng n trng lng phn t trung bnh ca Po, vn tc ca phn ng. Dung mi tt nht dng trng hp l benzen do hng s chuyn mch, ngt mch b nht. Trong dung mi khng phn cc phn ln polmer c cu to izotactic, trong dung mi c cc th to ra polymer c cu to syndiotactic. 3/ Trng hp nh tng Phng php ny rt c hiu qu sn xut nhiu polymer ca ete axit acrylic v metaacrylic. Dng nhiu nht l latex ca polyetyl v polymetylacrylat ph ln b mt da, giy... tuy nhin mng nhn t phng php ny km bn hn mng nhn t dung dch trong cc dung mi hu c. X phng natri v amn l cc cht nh ho tt nhng khi dng chng th mi trng kim to ra v monome nhiu hay t cng b x phng ho. V vy nn tin hnh phn ng trong mi trng trung tnh hoc axit yu. C ch trng hp ging vi trng hp styren. 4/ Trng hp huyn ph Phng php ny c dng ph bin gn nh trng hp khi - T l th tch: H2O/MMA = 2/1 n ti a 4/1. - Cht n nh huyn ph: jelatin, metylxenlulo, PVA (8 -12% nhm axetat t do): 0,05 0,2% so vi monome. Cht n nh tan tt trong nc, khng tan trong monome, dung dch c nht ln. Nng cht n nh trong mi trng nc 15 20%. - Cht khi u: hn hp peroxit benzoic v azodiizobutyronitril vi hm lng: 0,01 1%. - Cht mu hu c tan trong monome, bn mu, khng c nh hng n qu trnh phn ng. Qu trnh tin hnh: Ban u duy tr nhit 80oC sau nng dn nhit ln 90, 95, 98oC trong khong thi gian 2,5 3h. Nhit cui ca qu trnh duy tr 100 110oC trong vng 30 pht v kt thc. Tng thi gian phn ng 4,5 5h. Hm lng monome t do cn li trong hn hp sau phn ng nh hn 1%. Sau tin hnh ly tm, ra bng nc nhit 65 70oC ngay trong thit b ly tm. Ra bng nc m tch cc cht n nh huyn ph, cht iu chnh... c trit . em sy nhit 75 80oC trong thi gian 30 pht ri tin hnh to ht, ng bao. III/ Cu to, tnh cht v ng dng ca PMMA 1/ Cu to Nghin cu cc dn xut ca polyacrylic thy rng cu trc ca chng c th u ni ui v u ni u. Tt c cc polymer ca ete acrylic v meta acrylic l nhng

sn phm khng mu, trong sut, cng, n hi, chng u l nhng nha nhit do d gia cng theo nhiu phng php khc nhau. 2/ Tnh cht a/ Tnh cht ho hc - PMMA bn vi cc ho cht iu kin thng nh: dung dch nc mui, dung dch kim long, dung dch axit long... - PMMA t ht nc, khng tc dng vi ru, cht bo v du khong. b/ Tnh cht nhit PMMA c nhit ho thu tinh Tg = 80oC
80 Tg(oC)

(1) (2)

0 -20 -60 1

Nhn xt: (1) : khi gc R c 1C th Tg = 80oC, khi tng s nguyn t C th Tg gim n 12C th Tg bt u tng tr li. (2) : khi R c 1C th Tg = 0oC, khi tng s nguyn t C th Tg gim n 8C th Tg tng nhanh hn so vi ng (1) Gii thch:
CH3 * CH2 C COO R
n

12

16 S nguyn t C trong gc R

Khi tng R th n c tc dng che chn nhm phn cc C O R lm Tg gim. Khi tng R n ln hn 12C th tc dng che chn khng cn na ( ti 12C th hiu ng che chn t ti hn ) m khi s sinh ra s cn tr khng gian ln lm nh hng n chuyn ng nhit ca cc mc xch, v th Tg tng tr li. Xt ng (2) c Tg thp hn v khng c nhm CH3- nn mch phn t mm hn so vi (1). PMMA khi nhit ln hn 180oC th bt u b phn hu, khi nhit cao hn 250oC th qu trnh phn hu xy ra nhanh hn ( hiu sut phn hu t 75 80%) c/ Tnh cht quang hc

PMMA cho qua 91 -92% tia trong thy, 75% tia t ngoi, cho qua hu ht tia hng ngoi. PMMA rt trong sut, khi dy tm 6,5 m th trong sut gim 50%. d/ Tnh cht c hc Xt polyalkyl metaacrylat -C2H5 n-C3H7- n-C4H9- Izobutyl Tnh cht -CH3 3 d (g/cm ) 1,19 1,11 1,06 1,05 1,02 2 ko(KG/cm ) 630 350 280 70 240 2 bn va p(KG.cm/cm ) 10,5 7,1 6,5 11,5 1,6 o Nhit chy mm( C) 125 65 38 30 70

CHNG VI:

CHT DO I T CC POLYMER CA DN XUT HALOGEN ETYLEN SN XUT PVC

I/ Nguyn liu Nguyn liu sn xut PVC l vinylclorua C2H3Cl

CH2 CH Cl

L cht kh khng mu, c mi ete nh, khng tan trong nc nhng tan trong cc dung mi hu c nh axeton, ru etylic, HC thm, HC mch thng. PVC c cc thng s vt l nh sau: + Nhit si ts= -13,9oC + Nhit nng chy tnc= -159oC + Khi lng ring -12,96oC d= 0,9692 g/cm3 + nht -20oC = 2,81 Cp + n nhit ho hi: 85,7 Kcal/kg + To hn hp n vi khng kh: 4 21,7% th tch + Nng VC cho php trong 1 lt khng kh: 1mg/l Vinylclorua c th ng trng hp vi nhiu cht khc nhau * Sn xut vinylclorua Kh hydro v clo ca diclotan bng dung dch ru kim
CH2 Cl CH2 Cl

NaOH

CH2

CH Cl

NaCl

H2O

Phng php ny khng kinh t tn nhiu NaOH, ru v thit b phi ln + Clo ho etylen nhit cao

CH2

CH2

+ Cl2 (450-600 C)
O

FeCl3

CH2 CHCl

+ HCl

Phng php ny cha dng trong cng nghip v cha c phng php ly nhit phn ng ra. + Nhit phn dicloetan
CH2 Cl CH2 Cl
(Al2O3 , C hot tnh) 500-590oC

CH2 CHCl

HCl

Phng php ny rt kinh t, dy chuyn sn xut n gin nhng xc tc khng bn, khng ti sinh c v nhit cao to ra sn phm ph nh C2H2, dien... + Hidro v clo ho C2H2 p= 4 - 6atm, to= 200oC
CH CH

HCl

Xtc HgCl2/cht mang aluminosilicat

CH2 CHCl

Phng php ny cng c dng ph bin trn th gii: qu trnh thc hin lin tc trong thit b tip xc loi ng 160 200oC. Xc tc l clorua thu ngn ph ln b mt than hot tnh mt lng 10 - 15%. Kh C2H2 v HCl lm sch, sy kh cho vo thit b phn ng. Cho cht xc tc vo trong cc ng ca thit b phn ng v khong cch gia cc ng cho du tun hon nhit 70 130oC. Khi nhit t 70oC xc tc bt u lm vic th nhit ca phn ng t n 160oC. Hn hp sau phn ng gm: vinylclorua to ra, dicloetan, axetaldehyt, axetilen, HCl c a qua thit b phun dng nc v dung dch kim 10% ra kh mc ch l hp th kh HCl. Sau cho vo thp sy bng KOH rn ri qua thit b lm lnh n 40oC ngng t VC v hp cht c nhit si cao hn. Sau qu trnh ngng t cho qua thp tinh luyn hot ng lin tc ui sch axetaldehyt, dicloetan v cc sn phm ph khc. Sau VC c tch ra khi C2H2 ho tan trong thit b chng ct khc. II/ L thuyt trng hp vinylclorua Nu khng c oxi v cht khi u ch c nhit th vn tc phn ng b. Khi c mt cht khi u (C6H5COO)2, cat-19 v cat-29 (dng hn hp 2 cat th iu chnh trng lng phn t trung bnh v vn tc phn ng c d dng) th tc phn ng ln. Tp cht nh hng ln n phn ng trng hp: C2H2, CH3OH, C2H5OH, HCl th lm chm tc phn ng cn Styren, hidroquinon, rezoxin, anilin, phenol...lm ngng hn qu trnh. Khi trng hp VC th rt nhy vi nhit c bit trong dung mi. Trong trng hp nh tng, huyn ph, dung dch th nhit trng hp 35 55oC khi nhit ln hn 75oC th % Cl trong sn phm gim xung do kh to HCl ng thi hnh thnh lin kt i lm cho sn phm c mu. Nghin cu trng hp VC trong khi c cht kch ng th thy rng trng hp xy ra theo c ch chui gc bnh thng nhng c nt c bit: + Vn tc trng hp tng t lc bt u phn ng n khi hiu sut chuyn ho t gn 50% th chm li, hin tng gi l hiu ng gel. + Vn tc chuyn mch c gi tr ln hn rt nhiu so vi trng hp nhng hp cht vinyl khc. nh hng ca dung mi v nhit n mc trng hp v % Clo trong sn phm. Dung mi Nhit phn ng Mc trng hp Hm lng clo (n) trong PVC (%) (oC) CH3OH 80 310 55,98 Toluen 85 87 53,3 n-hexan 80 295 55,75 Diocxan 80 100 55,52

Nhn xt: trng hp trong toluen th nhit phn ng cao hn nn trng lng phn t trung bnh nh. Tt c hm lng clo u b hn theo l thuyt l 56,8% ngha l c 1 mc xch th c 1 nguyn t clo. Ba dung mi u ch ho tan VC khng ho tan PVC cn diocxan ho tan t PVC. Trng hp VC c peroxit benzoic th trng lng phn t trung bnh ca polymer: + Thc t khng ph thuc vo nng cht khi u trong gii hn di 2%, nu nng cao hn th trng lng phn t trung bnh gim nhanh. + Trng lng phn t trung bnh khng ph thuc vo mc chuyn ho monome + Trng lng phn t trung bnh gim khi tng nhit trng hp. III/ Cc phng php trng hp VC 1/ Trng hp VC trong khi Phng php ny t c s dng v polymer thu c dng khi gy kh khn cho cng on gia cng sau ny. Qu trnh phn ng kh ly nhit ra lm phn hu polymer to kh HCl v lm cho polymer c mu. 2/ Trng hp VC trong dung mi C th dng hai loi dung mi: - Dung mi khng ho tan polymer ( hay dng ru ): trong trng hp ny sn phm cui cng ca phn ng l polymer dn dn tch ra dng bt mn. - Dung mi ho tan c monome v ( hay dng dicloetan, axeton...) sn phm thu c dng dung dch, mun tch ra th phi tin hnh kt ta hoc chng ct loi b ht dung mi. Phng php ny t dng trong thc t do qu trnh trng hp lu v tn nhiu nhiu dung mi. 3/ Trng hp VC trong nh tng Cht khi u thng dng l H2O2, pesulfat kim loi kim. Cht nh ho l cc loi x phng ncal ( mui natri ca axit izobutyl sulfonaphtalenic ) dng vi lng 0,1 0,5% trng lng nc. Dng thm mui m gi nguyn pH, thng thng pH = 4 9. Mui m hay dng l axetat kim loi nng, phtphat, cacbonat kim loi kim... Vinylclorua trc khi trng hp nn cho qua than hot tnh nhit 70 80oC hoc sc qua dung dch NaOH hay KOH nng 25 60% 4/ Trng hp VC trong huyn ph Thnh phn nguyn liu Nguyn liu I II Vinylclorua 100 100 H2O 150 20 100

Cht n nh huyn ph

PVA (15% nhm CH3-) Jelatin: 0,5 2% dung dch 5% trong nc Cht khi u (peroxit benzoic) 0,04 0,04 0,6% Ngoi ra c th thm cht ngt mch phn ng AD-3 ( diphenylol propan)
CH3 HO C CH3 OH

Cht n nh nhit AD-5: C35H50O3

C(CH3)3 HO C(CH3)3 CH2 CH2 CO O C17H37

S dy chuyn cng ngh Hnh v: (xem sch) u tin phi chun b kn ca thit b phn ng (1) bng cch cho nn N2 p sut p= 4 5atm trong thi gian 5 -10 pht sau tho v p sut thng. Chun b dung dch cht n nh huyn ph, lc (3) vo (2) cha ri vo (1). Cho H2O tnh vo thit b, cho tip dung dch n nh huyn ph v tin hnh khuy trn vi vn tc cnh khuy 60 80 vng/pht trong thi gian 2 3pht ri ngng khuy. Tip tc cho kh N2 vo ui ht khng kh trong thit b phn ng ( khng cn p sut cao). Cho t t VC vo ri cho dung dch cht khi u vo gi p sut 7 8atm ng thi tin hnh khuy trn trong thi gian 30 pht, khi to ra cc git monome c bao bc bi dung dch cht n nh huyn ph. Nhit ban u ca phn ng 40 55oC thi gian cui c th nng ln 60oC ngt mch. Ra khi thit b phn ng hn hp qua thng cha (7) lm vic p sut thng, trc tin cho xt vo o pH ng thi sc hi nc qu nhit vo nhm ui VC t do v kh khc. Hi nc qu nhit sc vo trong 30 pht, VC khng phn ng b hp th bi PVC bay ra theo ng hn hp kh ra. Hoc y ht VC v kh khc th sc kh N2 vo p sut khng ln. Trong thit b (7) phi tin hnh khuy lin tc PVC khng b sa lng. Sau khi tch ht VC t do, hn hp PVC c a qua thit b ly tm. Cht lng tch ra ban u cn nhiu NaOH nn cho vo thng (9), nc m dng ra nha sau khi ly tm c cho vo thit b (10) ri em i x l. PVC bt mn lng xung y ca thit b (9), (10) c tch ra v thu hi. Ly tm xong bt PVC c hm m tng i ln nn cho qua thit b sy (11). Bt PVC c th sy theo nhiu phng php khc nhau: sy pht bng khng kh nng (thi gian sy 30 45 pht, nhit ca khng

kh nng 95 105oC), sy tng sibt PVC sau khi sy c hm m W 0,5%. Cui cng chuyn sang cng on sng, ng bao. IV/ Cu to, tnh cht v ng dng PVC 1/ Cu to ca PVC Trng hp VC theo c ch gc t do l s kt cc phn t theo u ni ui thnh mch pht trin.
CH2 CH Cl CH2 CH Cl CH2 CH Cl

Ngi ta dng nhiu phng php ho hc, Rnghen v quang hc chng minh cu to ca PVC: + Cho tia phng x xuyn vo PVC th xy ra qu trnh kh HCl v to thnh ni i cch mt trong polymer. + Quang ph t ngoi hp th PVC cng tng ng vi quang ph hp th 2,4diclobutan hoc nhiu hn l vi quang ph hp th 2,3-diclobutan. + Cho KI tc dng vi dung dch PVC th khng thy I2 t do thot ra ( I2 t do thot ra khi KI tc dng vi cc cht m cc nguyn t Cl ni lin vi hai nguyn t C cnh nhau) PVC cng c cu to nhnh nhng rt t, t 50 100 mc xch mi c mt nhnh. PVC l mt polymer phn cc mnh. trng thi khng ko cng PVC hon ton v nh hnh, ch khi no ko cng tht mnh mi c kh nng nh hng mt phn. 2/ Tnh cht a/ ha tan: polymer phn t thp vi n=300 500 tng i d tan trong axeton, kton, este, xiclohexanol...Khi trng lng phn t trung bnh cao th PVC rt kh ho tan (1 10%) tan trong: dicloetan, clo benzen, diocxan, tetrahidrofuran. iu kin ngui PVC khng tan trong cc cht ho do nhng nhit cao th b trng nhiu v c trng hp li tan. Polymer dng nh tng c ho tan km hn polymer huyn ph, polymer dung dch. b/ Tnh cht nhit Nhit chy mm ca PVC cao hn mt t so vi nhit phn hu ca n. PVC khng bn nhit, ngay 140oC bt u phn hu chm v 170oC th nhanh hn khi HCl b tch ra lm bin mu sn phm v mt tnh tan. Mt tnh tan ca PVC l do to ra lin kt ngang
Cl CH2 CH Cl CH2 CH Cl CH2 CH Cl CH2 CH Cl
-2HCl

CH2

CH

CH

CH2 CH

CH2 CH Cl

Bin mu ca PVC l do to ra lin kt i

CH2 CH Cl CH2 CH Cl CH2 CH Cl
-HCl

CH

CH

CH

CH

CH

CH

n nh nhit ca PVC ta thm cht n nh vo theo 4 nhm: hp th kh HCl, cht trung ho HCl, cht ngn chn tc dng ca O2 v cht hp th tia t ngoi. c/ bn ho hc PVC l mt polymer bn ha hc cao lm cc thng cha, ng dn ho cht (axit, kim, mui...) d/ Tnh cht c hc - Tg = 78 80oC - d = 1,38 1,4 (g/cm3) - k = 400 600 (KG/cm2) - u = 900 1200 (KG/cm2) - n = 800 1600 (KG/cm2) - = 10 25% - bn va p = 70 160 (KG/cm2) - bn nhit (Mactanh) = 65 70oC - Nhit gin = -10oC + Kh nng trn ln vi cc cht khc Vi polymer: PVC trn c vi phenolformaldehyt, epoxy... Vi cht ho do: PVC trn c vi hu ht cht ho do loi este phn t thp nh: DOP, DBP, tricrezylphotphat... 3/ ng dng PVC cng ( khng c cht ho do) lm tm, ng dn, vt liu cch in PVC mm: ng dn mm, bc dy in, mng mng, da gi

PHN II CNG NGH SN XUT MT S POLYMER TRNG NGNG CHNG VII: SN XUT NHA PHENOL-FORMALDEHYT I/ Nguyn liu 1/ Cc phenol a/ Phenol C6H5OH Phenol tn ti dng tinh th hnh kim, khng mu v c mi hc c trng. lu trong khng kh phenol c mu hng, nu c mt ng, st, amoniac th phenol d bin mu nhanh hn v chuyn sang mu nu nht. + d (45oC) = 1,0545 g/cm3 + tnc = 40,9oC + ts = 182,2oC Phenol l cht ht m, nhit thng tan n 27% trong nc to thnh dung dch ng nht. Phenol rt c, gy bng da v kch thch nim mc. Nng gii hn cho php trong khng kh l 0,005 mg/l. * Tnh cht ho hc Phn ng to mui phenolat C6H5ONa + H2O C6H5OH + NaOH Phn ng th SE v nhm OH- l nhm th loi mt nn n nh hng ch yu vo v tr octo hay para. Phn ng halogen ho
OH Br OH Br

Br 2 Br

* iu ch phenol Phng php i t than : khi cc ho than thu c nha than , sau chng nha ny ta c du nh ( hydrocacbon thm ), du trung ( phenol, crezol, xylenol, naphtalen) v du nng. Phng php tng hp: + Phng php benzosunfonat: cho sunfo ho benzen ri trung ho benzosunfonic axit bng cch un nng chy n vi kim, phn gii phenolat v chng phenol. + Phng php clobenzen: cho clo ha benzen, sau cho clobenzen tc dng vi dung dch NaOH 10% theo t l 1 :1,25 vi iu kin phn ng nhit 400oC. + Phng php Rasic: cho benzen tc dng vi HCl v khng kh nhit 200 o 230 C vi xc tc l mui nhm, st hoc ng. Tch clobenzen v thu phn trong mi trng kim nhit 350oC vi xc tc l SiO2 hay Ca3(PO4)2. Sau ra phenol bng nc, tin hnh chng ct cui cng thu c phenol.

+ Phng php Cumen: iu ch izopropylbenzen khi c xc tc, sau oxy ho izopropylbenzen bng oxi khng kh c thm cht nh ho 85oC. Tip tc thu phn sn phm va mi to ra bng dung dch H2SO4 10% thnh phenol v axeton. Sau dng phng php chng ct tch phenol. b/ Mt s phenol khc + Crezol ( CH3C6H4OH )
OH CH3 CH3 o-crezol(35%) m-crezol(37-49%) CH3 p-crezo(25%) OH OH

+ Xilenol (CH3)2C6H3OH c tch ra t phn c nhit si cao nht ca du trung ( 210 25oC) c 6 ng phn
OH CH3 CH3 CH3 1,2,3 Xilenol OH CH3 CH3 CH3 CH3 1,2,6 Xilenol 1,3,4 Xilenol H3C CH3 1,2,4 Xilenol OH OH CH3 H3C 1,2,5 Xilenol OH OH CH3

1,3,5 Xilenol

+ Rezorsin: C6H4(OH)2
OH

OH

Rezorsin c 3 v tr hot ng rt mnh hn phenol 2/ Cc andehyt a/ Formaldehyt (andehyt formic) CH2O

H C H O

* Tnh cht vt l iu kin thng formaldehyt l mt cht kh khng mu, c mi hc, gy kch thch nim mc.

+ d = 0,8153 g/cm3 + tnc = -92oC + ts = -21oC Formaldehyt dng ch yu dng dung dch nc gi l formalin. Formalin cha 33 40% th tch formaldehyt tng ng vi 33 37% theo khi lng. * Tnh cht ho hc Formaldehyt c kh nng t trng hp nhit thp to thnh nha polyformaldehyt (parafoc) v khi un nng th phn hu cho ra li formaldehyt.
n HCHO * CH2O * CH2O n
Vi n= 3 -5

n HCHO n

Parafoc l polymer v nh hnh c mu trng. V d trng hp nhit thng nn khi bo qun ta cho vo 7 12% ru metylic. Formaldehyt d tan trong nc khi trong nc n dng hydrat ho (metylenglycol) HO CH2 OH HCOH + H2O Dng hydrat ho ny d bt c nng no cng to ra polyoxymetylglycol HO CH2 O CH2 OH + H2O 2 HO CH2 OH HO-(-CH2O-)n+1CH2OH + H2O HO CH2 O CH2 OH + n HO CH2 OH * iu ch formaldehyt Oxy ho ru metylic: 2 HCHO + H2O + 36,8 Kcal/mol 2CH3OH + O2 HCHO + H2 - 28,8 Kcal/mol CH3OH Phng php oxy ho kh metan HCHO + H2O (phn ng chnh) CH4 + O2 2CH3OH (phn ng ph) 2 CH4 + O2 b/ Cc andehyt khc Furfurol C5H4O2
CH CH O CH C CHO
Xt, 400-600oC

Urtrpin (CH2)6N4 II/ L thuyt trng ngng phenol vi formaldehyt * Phn loi

Tu thuc vo xc tc v t l cu t m chia nha PF ra lm 2 loi: nha novolac v nha rezolic. Nha novolac: dng xc tc ion H+ ( cc axit thng dng l HCl, c khi dng H2SO4) t l C6H5OH/CH2O = 6/5 hoc 7/6 Nha rezolic xc tc l OH- ( hay dng NaOH, NH4OH, Ba(OH)2...). Dng xt lm xc tc th nha to ra tan trong nc thnh h nh tng. Dng NH4OH lm xc tc th nha to ra khng tan trong nc m tan trong cn. T l C6H5OH/CH2O = 5/6 hoc 6/7. * Cc yu t nh hng n qu trnh trng ngng + Cu to ho hc ca nguyn liu Cu to khc nhau th nh chc khc nhau dn n kh nng phn ng khc nhau. Nha nhit rn c iu ch t cc nguyn liu cha phenol c 3 v tr hot ng nh phenol, m-crezol, 1,3,5-xylenol, v rezorsin. Cn cc andehyt th ch c formaldehyt v furfurol l to nha nhit rn. Nha nhit do c th iu ch t nguyn liu cha cc phenol c 2 v tr hot ng nh octo v para-crezol; 1,2,3 hay 1,3,4-xylenol. Do ch c hai v tr hot ng tc l nhm metyl khng lm hot ho cc nguyn t hydro bn cnh nhn thm nn khng c kh nng to nha nhit rn. Cc nhm hydroxyl ca phenol khng tham gia phn ng a t. + T l mol C6H5OH/CH2O Nu t l mol P:F = 1:1 th ch yu to ra cc octo v para monometylol phenol. T cc ru phenol ny tip tc a t to thnh nha nhit do. Nu t l mol P:F = 1:2 hoc cao hn th ch yu to ra cc di v tri metylol phenol. T cc ru phenol ny tip tc ngng t to thnh nha PF khng nng chy, khng ho ho tan. + pH ca mi trng pH < 7 th cc ru phenol to thnh khng bn, n nhanh chng ngng t vi nhau hoc vi phenol to nha nhit do. pH > 7 th cc ru phenol to thnh rt bn, cc di, tri metylol tip tc trng ngng vi nhau hoc vi phenol to thnh polymer nhit rn. * Nguyn tc trng ngng + Novolac
OH OH CH2 OH

CH2O

monometylol phenol Rt t dimetylol phenol c to:

OH CH2 OH

dimetylol phenol V trong mi trng axit nn tc phn ng cu nhm metylol ln. Phn ng trng ngng to nha c th c vit nh sau:
OH CH2 OH OH CH2 OH CH2 OH OH OH H
+

CH2OH

OH CH2

OH

OH

OH H
+

OH CH2 CH2 OH CH2 O CH2

OH

+ +

HOCH2 OH

OH H
+

HOCH2

cu ni metylen ete Cu ni metylen ete khi p, gia cng nhit cao th b phn hu to ra CH2O. - CH2 - + CH2O - CH2 O CH2 Cng thc tng qut ca nha Novolac:
OH CH2
n

OH CH2

OH

+ Rezolic Xc tc l OH- (NaOH, Ba(OH)2, NH4OH...) - NaOH l xc tc mnh, lm mu nha ti ( nu sm), tan c trong nc kh tch lp tc l dng nh tng trong nc. - Ba(OH)2 cho nha mu sng hn - NH4OH l xc tc yu, nha c mu sng v phn lp mnh Phn ng to nha
OH OH OH CH2 OH CH2 OH CH2OH HOCH2 OH CH2 OH CH2OH

CH2O

OH-

Trong mi trng OH- th cc nhm metylol c vn tc phn ng b.

OH CH2 OH OH OH CH2 OH CH2OH OH CH2 OH CH2 O CH2 CH2OH OH CH2
n

HOCH2

CH2 OH CH2OH OH CH2 OH CH2OH

OH-

Nha rezolic c metylol t do v tr para ca phenol nn c kh nng ng rn nhit thch hp to nhnh mng li khng gian khng nng chy, khng ho tan. III/ Quy trnh sn xut nha phenol-formaldehyt 1/ Nha Novolac Thnh phn nguyn liu 100 PKL C6H5OH 26,5 27,5 PKL CH2O HCl (d= 1,19) ln 1: n pH = 1,6 2,3 ln 2: 0,056 PKL Axit oleic: 1,5 2 PKL Cho ht formaldehyt ( C%=37%) v phenol vo thit b phn ng ri khuy u, sau cho axit ln 1 vo trong lc cnh khuy vn hot ng. Mc ch ca vic cho axit ln 1 l h pH ca formaldehyt v ng thi lm mi trng xc tc. Tin hnh un nng n nhit 80 85oC phn ng to nhit nn nhit ca hn hp t tng ln 95 98oC, lc ny hn hp bc u si. Duy tr nhit ny trong khong thi gian 30 pht. Tin hnh cho axit ln hai v gi nhit si ts=98oC trong thi gian 45 50pht, cng trong thi gian ny ngi ta ly mu th xc nh d = 1,17 1,2 g/ml. Khi phn ng kt thc tin hnh sy nha tch loi nc v hm lng phenol t do cn li trong nha. Sy trong mi trng chn khng p=350 410 mmHg nhng trc khi ht chn khng phi tin hnh lm lnh hn hp nha xung 75 78oC. Sau khi sy tnh cht ca nha phi m bo cc ch tiu sau: - Nha c mu vng rm hoc vng hi nu - Nhit nh git : 95 105oC - nht dung dch 50% trong ru C2H5OH: 75 160Cp - Hm lng phenol t do < 9% Trong qu trnh sy giai on cui dng chng ct bng hi nc qu nhit nhm mc ch gim hm lng phenol t do trong nha.

Biu tng hp nha

T(oC) 110 100 80 b a 1 23 45 6 7 Thi gian (h) c d e

20

2/ Nha rezolic Nhit ban u 75 80oC un nng trong thi gian 35 45 pht, phn ng to nhit nn t nng ln 95 98oC ( c th ln n 100oC ). Gi nhit ny trong khong thi gian 100 pht v nht t 150 250Cp. Nu nha dng dng nh tng th ch lng, tch bt nc v em i x dng ( tm ph gia dng si, vi, giy, hoc dng bt, lm keo dn...). Nu dng dng rn th h thp nhit sn phm xung 70 80oC sau sy chn khng 300 mmHg, sy n khi t c nht 800 1000Cp nha ra khun v ngui. Tnh cht ca nha sau khi sy: mu hi nu, hm lng phenol t do khng qu 9%, vn tc ng rn 150oC: 75 90 giy/1mm chiu dy sn phm Nha rezolic thc t c 3 trng thi: + Nha rezol l nha cha ng rn n l mt sn phm c phn t thp mch thng v nhnh + Nha rezitol l nha bt u ng rn nhng c mt mng li khng gian t,c th ho tan hon ton trong mt s dung mi nh:xilohexanol,phenol,dioxan....vi iu kin nhit ca cc dung dch >100oC, lc ny ni ngang b gy + Nha rezit l nha ng rn hon ton to thnh polime c mng li dy c, trng thi khng nng chy, khng ho tan trong bt k dung mi no. Mng li khng gian to ra do lin kt nhm metylen v lin kt hydro . c/ Sn xut bt p t nha novolac Thnh phn nguyn liu: - Novolac 42,8 PKL - Ph gia bt g l kim ( g chc, t tp cht, cha nhiu xenlulo, khng cn dng xenlulo trc tip do sn phm bn thn c mu ti cn xenlulo c mu trng) 43,6 PKL - Cht ng rn (urotropin) 6,5 PKL

- Cht lm trn, bng (stearat Zn, Ca...) 0,7 PKL - Cht tr ng rn (CaO, MgO...) 0,9 PKL - Cht mu (ch l mu sm) 4 4,5 PKL * Chun b nguyn liu: Nghin mn nha Novolac Nghin mn v sng bt g ( 960 l/1cm2) * Tin hnh: - Trn 1 t nha nghin mn vi urotropin (m nh) - Trn 1 t nha nghin mn vi cht mu v cc ho cht khc - Trn nha v ph gia (ph gia c cho vo t t). Sau cho hn hp cht ng rn v hn hp cht mu chun b trn vo. u tin trn trong my hai trc nm ngang c cnh khuy hnh ch Z, tip tc trn trn my cn nng 2 trc c t tc nhit < 105oC hoc trn trong my trc vt lin tc. Thi gian trn trn my cn 2 3,5 pht/m, nu trn trong thi gian di s xy ra phn ng ng rn hay b chy ra v dnh vo trc. Sau lm ngui v p, nghin trn my nghin bi ri sng ng bao. * Qu trnh p, gia cng sn phm Nhit p 160 165oC ph thuc vo chiu dy sn phm. p sut p 300 350 KG/cm2. Khi p c kh NH3, N2, H2O, CH2O thot ra nn phi nng chy p ln 1,2 ln trnh hin tng xut hin l xp do kh thot ra trong qu trnh p. Thi gian p 1,5 2 pht/1mm chiu dy sn phm. Trong qu trnh ng rn + Phenol kt hp vi urotropin to nha novolac trc ri sau to rezol -> rezitol -> rezit. + Nha novolac kt hp vi urotropin to rezol -> rezitol -> rezit - CH2 - + CH2O - CH2 O CH2 - CH2 - + 2 N2 (NH3) (CH2)6N4 + Nha ng rn c mng li khng gian tng i dy c nn sn phm hi dn, v vy khi thm ph gia vo th gim c tnh dn ca nha. + Khi qu trnh ng rn kt thc th trong cu to ca nha vn cn mt s nhm CH2OH t do hay ti nhn phenol vn cn v tr hot ng.

OH CH2 CH2 CH2 OH

OH CH2 CH2OH

OH CH2

OH CH2 OH CH2OH OH

CH2 HO CH2 CH2 OH CH2

CH2 OH CH2OH

+ CaO ngoi tc dng tr ng rn cn tham gia vo qu trnh phn ng nh:

O Ca O

* Tnh cht ca sn phm p: + Khi lng ring d = 1,25 1,4 g/cm3 + Gii hn bn ko k= 400 600 KG/cm2 + Gii hn bn nn n= 1000 1600 KG/cm2 + dn di %= 0,3 0,7% + cng Brinel 25 40 KG/mm + ht nc tng 0,2 0,6% + bn ho hc: bn axit (tr axit c tnh oxi ha mnh), dung dch mui v cc ho cht, khng bn vi kim (do c OH- ca phenol) IV/ Tnh cht, ng dng ca nha phenol-formaldehyt * Tnh cht : Nha rezolic l mt hn hp sn phm phn t thng v nhnh, trng lng phn t t 400 1000. Nha rezolic c tnh n nh cao, cha t phenol t do, bn ha hc v cch in cao .

Nha rezolic nhit thng vn mt tnh chy nht, nng chy v ha tan, ngha l khi bo qun tnh cht ca chng thay i theo chiu hng to thnh polimer mng li v rezolic chuyn dn sang trng thi rezitol. Hm lng phenol t do cao hoc thp cn ph thuc vo t l ca cc cu t, c im v lng xc tc, chiu su ngng t v thi gian sy. Nha rezolic rn thng cha 8 12% phenol t do, nha rezolic lng cha 20 hoc cao hn. Lng phenol t do nhiu n s lm gim tc ng rn v tnh cht c l ca sn phm. Nhng c mt s trng hp cn cha mt t phenol t do trong nha v n lm cho nha d nng chy hn v to mng sau khi ng rn c n hi hn . Hm lng oxy trong nha rezolic (khi iu ch dng xc tc NaOH) c mt s lin kt ete( -CH2-O-CH2-)v khi un nng nha th thy c CH2O ta ra. Trong trng hp dng xc tc NH4OH khng c lin kt ete v un nng nha n 200oC th khng thy CH2O to ra. Nha rezolic c th ha tan hon ton trong nhiu dung mi nh: xilohexanol, phenol, dioxan, butanol... nhng vi iu kin l nhit si ca dung mi trn 100OC lc th cc ni ngang u b ph hy. Tc tng nhit nh hng n ha tan ca rezolic .Nu tng nhit nhanh th lc nha cha kp trng trong dung mi, lng ni ngang tng ln v ngng hn qu trnh ha tan nha. Nu un nng lu th c th lm rezolic tan hon ton. Nha rezolic b ng rn (rezit) : trong giai on rezit mng li tham gia to ra khng nhng ch do lin kt ha hc m cn do lin kt l hc. nhit cao lin kt l hc b ph hy do xut hin mt t tnh n hi, khi lm lnh tnh n hi mt i. Trong nhng iu kin xc nh ( nhit cao v un nng lu) nu dng mt lng phenol tha x l rezit nghin nh th nha ny c th bin thnh nha novolac trong trng hp ny xy ra hin tng t lin kt ha hc gia cc phn t v to ra lin kt vi phenol. *ng dng ca nha rezolic: Nha rezolic lng (khng c nc) p dng rng ri tm vi, si, dng lm bt p, dng lm vt liu p tng, keo dn v sn. +Bt p :

Vt liu p dng bt l hn hp cu t phc tp ch yu t nha novolac v rezolic .Bt p dng lm dng c k thut v sinh hot, dng lm vt liu cch in, chu tc dng ca dng in 20kV to =200oC. +Vt liu p tng: Tectolit l cht do lp, c dng ch to t ca nhng tm vi c tm nha rezolic, vi dng c th l vi thy tinh, vi dt cho, vi tng hp. Tnh cht ca Tectolit: C bn nn, va p cao nhng km bn nc, chu xng du tt nn dng trong cng nghip ch to my. + Keo dn v sn: Nha phenol - formaldehyt c ngha quan trng dng sn xut keo dn v sn. Keo phenol - formaldehyt c bn mi ni cao, chu m v vi khun nhng c nhc im l mng dn gin. Nha phenol - formaldehyt l loi nha tng hp dng sn xut sn. Ngoi nha v ru cn thm 5 10% colophan vo sn. Sn du cao cp iu ch t nha 100%. Sn du Copan l loi sn c iu ch t Copan trn vi du lanh nhit cao t 230 280oC. Sn t nha rezolic tan tt trong cn. Ngoi ra nha rezolic cn dng lm cht dobt.

CHNG VIII: SN XUT NHA URE-FORMALDEHYT I/ Nguyn liu 1/ Ure CO(NH2)2 d = 1,335 g/cm3 tnc= 132,7oC + Cu trc tinh th hnh kim di khng mu hoc hnh lng knh trng. Ure ho tan tt trong nc, trong ru v trong amoniac lng, nhng ho tan t trong este v khng tan trong cloroform. Ure c c tnh kim yu v khi t nng dung dch nc ca ure n 80oC to ra mui amon ca axit cacbamit NH3COOH, khi t cao hn 130oC ure b phn hu thnh CO2 v NH3. + iu ch: NH3 tc dng vi CO2 to thnh cacbamat amon, sau tch nc t cacbamat rn hoc dng chy lng bng cch un nng n nhit 135 150oC v p sut 55 60atm trong autoclave NH2COONH4 CO(NH2)2 + H2O CO2 + 2NH3 2/ Formaldehyt ( CH2O) phn trc II/ L thuyt trng ngng ure vi formaldehyt v cu to ca nha 1/Qu trnh to ra cc sn phm ban u Nhiu kin cho rng mono v dimetylol ure l nhng sn phm u tin ca phn ng ure vi formaldehyt. Ph thuc vo cc iu kin sau: + T l xc nh gia ure v formaldehyt + Mi trng trung tnh hoc kim yu + Nhit phn ng thp Trong mi trng kim yu pH = 7,5 8 v t l ure : formaldehyt = 1 : 1,6 2 th ban u to ra monometylol v dimetylol ure.
O C NH2 NH2

CH2O

to

NH CO NH2

CH2OH

monometylol ure (tinh th)

O C NH2 NH2

+ 2 CH2O

to

NH CO NH

CH2OH CH2OH

Dimetylol ure (tinh th) Monometylol ure c nhit nng chy tnc=111 113oC, cn dimetylol ure khong 121 122oC, chng tan tt trong nc, trong ru metylic, etylic, khng tan trong ete. Trong mi trng axit pH = 1 5 vi t l ure:formaldehyt = 1 : 2 hoc 1 : 1 th to ra sn phm v nh hnh khng trong sut, khng tan.

N CH2 CO NH2

N CH2 CO N CH2

monometylen ure dimetylen ure 2/ Qu trnh to nha v cu to ca nha ure-formaldehyt T monometylol ure to ra nha mch thng qu trnh xy ra theo tng bc
NH CH2OH CO NH2 HO CH2 NH2 NH CH2OH CO

CO NH2

H2O

NH CH2 NH CO NH2 NH CH2OH CO NH CH2OH CO

Hoc

H2O

NH CH2 O CH2 NH

Tng qut: H2N-CO-NH-CH2-[-NH-CO-NH-CH2-]n-NH-CO-NH-CH2OH T dimetylol ure c th to ra nha mch thng v vng

NH CH2OH

(n+2) CO
NH CH2OH

HOCH2 NH CO NH CH2 N CO NH CH N CO NH CH2OH 2 ` CH2OH nCH2OH

+
Hoc:
CH2OH N CO CH2 NH CO CH2OH N CO CH2 NH CO
n

H2O
CH2OH N CO CH2 NH CO CH2OH

NH CH2 N CH2 N CH2 N CH2

N CH2 N

3/ Qu trnh ng rn ng rn nha UF ch xy ra trong trng hp nha cha cc nhm metylol t do. Lng nhm metylol trong nha cng ln nu lng CH2O ly dng cho phn ng cng nhiu. Nhit v xc tc c nh hng n tc ng rn ca nha. Cht xc tc ng rn nha ure-formaldehyt l cc axit hu c (axit oxalic, axit leic, axit formic....) axit v c (HCl, H3PO4...) mt s mui (clorua amn, clorua km...). III/ Sn xut nha ure-formaldehyt

T l ure/formaldehyt = 1/1,6 2, pH = 7,5 8 (dng dung dch xt nng C%=10% trung ho). Cho axit oxalic hoc axit formic cui qu trnh 0,01 0,02 phn so vi ure Th t cho vo: cho formaldehyt vo thit b phn ng ri dng dung dch NaOH 10% khmg ch pH=7,5 8 sau cho ure vo tin hnh khuy trn. Nhit ban u ca phn ng 40 50oC, trong giai on ny to dn xut mono nn khng nng nhit cao, duy tr nhit ny trong vng 30 45pht. Sau tng nhit ln 80 85oC trong thi gian 20 pht v bo m pH khng thay i. Lm ngui xung 60 65oC, cho thm dung dch axit oxalic nng 10 15% vo nhm mc ch to nha phn t ln hn v xc tc ng rn. Tng thi gian phn ng 4 5 gi/1m. * Sn xut bt p ure-formaldehyt Thnh phn: + Nha (dung dch keo trong nc): 45 PKL + Sunfit-xenlulo: 55 PKL + Cht lm trn: 0,8% so vi nha + Cht xc tc ng rn ( cc mui c tnh axit nh ZnCl2, NH4Cl hoc mui sunfua axit) + Cht mu (mu sng) Qu trnh phi trn tng t nh qu trnh chun b bt p phenol-formaldehyt nhng phi ch nhit v thi gian. Tin hnh sy nhit thp v trong mi trng chn khng. S dng my nghin bi pha ngoi my phi c b phn lm lnh bng nc. * iu kin p: p sut p: 250 280 KG/cm2 Nhit p: 135 145oC Thi gian p: 70 110 giy/1mm chiu dy sn phm Trong qu trnh ng rn c to ra nc Nhn xt: Mng li khng gian tha, cn mt lng nh nhm CH2OH- v NH2 t do. + Nha bt p ure-formaldehyt bn nhit cao nhng km bn vi nc c bit l nc nng Khi lng ring d = 1,35 1,45 g/cm3 ko = 350 500 KG/cm2 nn = 1200 1500 KG/cm2 u = 600 900 KG/cm2 bn nhit (Martens) 100 120oC ht m ( 25oC, thi gian 3 ngy m) 1 1,5% IV/ Tnh cht v ng dng ca ure-formaldehyt.

Nha ure c ng dng rng ri sn xut vt liu p, cht do lp, cht do bt, keo dn, mng ph... - Vt phm t bt p ure formaldehyt dng lm cc dng c in ( chp n, cng tc, cu dao...), chi tit my in thoi, v my thu thanh, hng tiu dng (chu, cc o, vn p...). un nng nhanh th vt phm t nha ure formaldehyt chu nhit 100 118oC, nu un lu th chu c nhit di 75oC. - Cht do lp dng lm bn, trang hong phng, bung li my bay, tu thu, toa tu ho, dng c m nhc... - Cht do bt mipo l loi vt liu nh cch nhit, cch m ch yu i t nha ure formaldehyt. u im c bn ca mipo l nh, dn nhit khng ln vo khng chy nu thm photphat amon vo. Mipo c c im rt qu l ht th m thanh mnh, c bit t tn s trung bnh n cao nn dng n truyn m rt tt khi xy dng nh ht, rp chiu bng... - Keo t ure formaldehyt c s dng nhiu trong cng nghip sn xut vn p, c khi dng lm keo dn snh s, kim loi - Nha ure formaldehyt khng tan trong ru v du, sau khi ng rn th n nh trong dung dch km v chu nc khng m bo. Do tnh a nc ca nha nn mng nha to ra d b m v nt ng thi khng t do cn thit. V vy mun s dng nha ure formaldehyt lm sn th phi bin tnh nha.

CHNG IX: SN XUT NHA MELAMIN-FORMALDEHYT I/ Nguyn liu: 1/ Melamin: (2,4,6 triamino-1,3,5 triasin) dng tinh th melamin l bt tinh th mu trng, c tnh kim yu nhng mnh hn ure, tan trong amoniac lng v dung dch NaOH, KOH, tan km trong nc v dung mi hu c. Melamin c cng thc cu to c biu din nh sau:
NH2 N C H2N C N N C NH2

2/ Formaldehyt: xem phn trc II/ L thuyt a t melamin vi formaldehyt Thng thng th t l gia melamin v formaldehyt l: 1/ 2,8 1/3 c dng lm bt p, cn nu 1/3 1/4 dng lm sn. iu kin phn ng: phn ng thc hin trong mi trng trung tnh hoc kim yu pH = 7,5 8 v nhit t 90 98oC. C ch phn ng: tng t nh ure-formaldehyt hay phenol-formaldehyt ban u to ra cc dn xut metylol melamin sau cc dn xut ny lin kt li vi nhau to ra sn phm nha melamin-formaldehyt.
C N

N C

N C

l R
NH CH2OH NH CH2OH HOCH2 NH R NH CH2OH HOCH2 NH R NH CH2OH NH2

NH2 H2N R NH2

CH2O

OH-,to

H2N

NH2

u tip tc un nng mnh hn th to ra:

NH CH2OH H2N R NH2 NH CH2OH H2N R NH2 NH CH2 NH R NH CH2 NH R NH NH CH2OH

H2N

NH CH2OH

H2N

R NH2

NH CH2OH

OH-,to

NH CH2OH

Nhng nhm CH2OH t do v NH2 t do c kh nng tham gia phn ng tip tc thc hin qu trnh ng rn to thnh mng li khng gian dy c trong mi trng axit v nhit 130 150oC.
NH CH2 NH R NH CH2 NH NH R NH CH2 NH R CH2 NH NH CH2 NH R NH CH2 NH R NH CH2 NH NH CH2 NH R NH CH2OH NH

Do melamin c nhiu nhm inh chc hn nn trong nha c nhiu ni ngang. V vy nha melamin-formaldehyt c chu nc, chu nhit, cng v bng hn so vi nha ure-formaldehyt. III/ Sn xut nha melamin-formaldehyt Cho formaldehyt vo thit b phn ng, iu chnh pH cho n khi pH = 7,5 8. Sau ta cho melamin vo ng thi tin hnh khuy trn, lc ny ta thu c hn hp huyn ph ng nht. Tin hnh gia nhit n nhit 75 80oC do phn ng ta nhit nn hn hp s t nng ln 90 98oC. Gi nhit ny trong khong thi gian 40 60 pht ta thu c nha nh tng trong nc. Khi mun tch nc th h nhit xung v nc s tch thnh lp pha trn hn hp cn li vn l nh tng nhng nht cao hn. * Qu trnh sn xut bt p tng t nh PF v UF Tnh cht ca bt p: + Khi lng ring d = 1,45 1,55 g/cm3 + Gii hn bn ko k 620 750 KG/cm2 + Gii hn bn nn u 650 KG/cm2 + ht m (3 ngy m 25oC) = 0,1 0,15% + bn nhit (Martens) > 120oC IV/ Tnh cht v ng dng ca nha melamin-formaldehyt Cng nh nha ure formaldehyt, nha melamin formaldehyt dng sn xut bt p, cht do tm, keo dn - Vt liu p c sn xut khng nhng t nha melamin formaldehyt n cn t nha melamin ure formaldehyt. iu ch nha c n hi cao ta thm vo cc polymer khc nh: polyamid, phenol formaldehyt, polyvinyl butyral

- Nha tm melamin c bit l nha tm t vi thy tinh v vi thu tinh c gi tr rt ln v mt k thut v n rt bn. Nha tm melamin t vi xenlulo v giy dng sn xut vt liu trang hong ( bc tng nh, lm mt bn gh), vt liu xy dng. - Keo t nha melamin formaldehyt c dng nhiu trong ngnh g. So vi mi dn t nha ure formaldehyt th mi dn t nha melamin formaldehyt c kh nng chu nc si trong thi gian di v gi thnh cng t hn keo ure formaldehyt. - Nha melamin formaldehyt khng bin tnh th khng trn vi cc cu t khc trong sn c. n c th tan vo trong cc dung mi hu c v trn tt vi cc loi nha khc th phi bin tnh nha. Khc vi nha ure formaldehyt bin tnh nha ny c bn nc v bn kh quyn cao, trn tt vi nha polyester, mng sn chu tc dng ca cc cht n mn, chu nhit v bn mu, tnh cht in mi tt. Sn l sn phm trn dung dch nha ete ho vi dung dch nha polyester trong du thu du v sau khi sy 120oC th mng sn c bn cao v bng

CHNG X: SN XUT NHA EPOXY I/Nguyn liu: 1/ Difenylonlpropan (hay 4,4- dioxy aiphenyl propan hay tn thng mi l bisphenolA, dian )
CH3 HO C CH3 OH

iu ch: -Bisphenol-A iu ch bng cch cho phenol tc dng vi axeton trong mi tng axit mnh nhit 40-50oC. Axit thng dng l H2SO4, HCl. Thi gian phn ng khong 15-20h.
2
OH

CH3 C O

CH3

Xt, to

CH3 HO C CH3 OH

H2O

-Bisphenol-A c Tnc =155oC, cu trc tinh th mu trng c th lm bng da, khng tan trong nc. 2> Epiclohidrin.
H2C CH CH2 Cl O iu ch: -i t glyxeryl u tin cho hai kh HCl tc dng vi glixerin nhit 110-115oC trong mi trng axit c c un nng.
CH2 OH CH OH CH2 OH

HCl

CH3COOH CH 2

to

CH Cl

CH2 OH

Cl

Diclohydrin glyxeryl Sau cho xt c c un nng vo

CH2 Cl CH Cl CH2 OH

to
H2C CH Cl O CH2

NaOH

NaCl

H2O

-i t propylene: Clo ho propylen p sut 18 kg/cm2 v nhit 800oC to ra clorua allil, sau cho clohydrin tc dng ln ni i v cui cng dng kim kh HCl ca iclohydrin to ra piclohydrin. CH2 = CH CH3 + Cl2
800oC, 18at

CH2 = CH CH2 Cl + HCl

CH2 = CH CH2 Cl + HOCl

CH2 CH Cl
CH2 Cl CH OH CH2 Cl

CH2 Cl
CH2 + NaCl

OH

NaOH

H2C CH Cl O

H2O

Epiclohydrin l mt cht lng khng mu, khng tan trong nc nhng tan trong cc dung mi hu c (C6H6, xeton,). Nhit si ts=118oC, d20oC ( g/cm3 ) = 1,1751,180. II/ L thuyt to nha epoxy: 1> Phn ng a t nha epoxy Nu tha piclohidrin th c th thu c te diglixit dioxi difenyl propan. phn ng xy ra trong mi trng NaOH:
CH3 H2C CH Cl H2C O O CH CH2 O CH2

HO

C CH3 CH3 C CH3

OH

NaOH

O CH2

CH O

CH2

+ 2 NaCl +2 H2O

C ch: +piclohidrin theo nhm epoxy tc dng vi hydro ca dioxydifenyl propan:

CH 3 H2C Cl CH O CH 3 H2 C CH CH 2 O C CH 3
C H3 H2C CH C H2 O C C H3 CH 3 H2C O CH C H2 O C CH 3 O CH 2 CH O CH 2 O CH 2 C H OH C H 2 Cl Cl O H

CH 2

HO

C CH 3

OH

CH 2 CH CH 2 Cl OH

Cl OH

+To ra nhm epoxy mi do t HCl:

NaO H

+ 2 N aCl + 2 H 2 O

+Cc sn phm ban u tip tc ngng t vi ioxdifenil propan:

CH3 H2C O NaOH CH CH2 O C CH3 CH3 H2C O CH CH2 O C CH3 O CH2 CH OH CH2 O O CH2 CH O CH2

CH3

+ HO

C CH3 CH3 C CH3

OH

OH

Cng thc tng qut:

CH3 H2C O CH CH2 O C CH3 O CH2 CH CH2 O OH
n

CH3 C CH3 O CH2 CH O CH2

Ta thy nha epoxy trng thi khng ng rn l nhng mch polyete di, trong nhm hydroxyl t do nm cch nhau mt khong cch tng i xa. Hai u mch l nhm epoxy. Nhm epoxy v hydroxyl c kh nng phn ng vi nhiu cht v ph thuc vo nh chc ca cc chc m c th thu c hoc nha nhit do bin tnh hoc nha ng rn khng nng chy v khng tan. Qu trnh xy ra chu nh hng ca t l cu t: T l mol E/D T l mol Mp ng lng Nhit mm, o NaOH/E C epoxy 2 1,1 451 314 43 1,4 1,3 791 592 84 1,25 1,3 1133 862 100 1,2 1,3 1420 1176 112 T l E/D cng thp th KLPT cng cao, ng lng epoxy cng tng, nhit mm tng. Cho xt t t, 2-3 ln bi v -Cl c th b thu phn trong mi trng kim to thnh OH lm bin i nguyn liu ban u. III/ C ch mg rn nha epoxy 1/ ng rn bng amin -Thng thng ngi ta dng di hoc tri hoc polyamin, khng dng monoamin v s khng to mng li khng gian. -Cc cht ng rn thng dng nht l: etylen diamin (ng rn ngui hoc di 60oC ), dietylen diamin, dietylen triamin (ng rn nhit cao ), trietylen triamin c tc dng gn ging vi polyamin. -Phn ng ng rn:

CH3 H2C CH O CH2 O C CH3 R1 " NH2 CH3 H2C CH O CH2 O C CH3 O CH2 CH CH2 O OH
n

CH3 O CH2 CH CH2 O OH

n

C CH3

O CH2 CH CH2 O

+ H2N

CH3 C CH3 O CH2 CH CH2NH R1" NH2 OH

NH2 t do cn li tip tc tn cng vo u epoxy ca mch diepoxy khc lm ko di mch -Cc phn ng ph xy ra: nhit cao nhm OH phn ng vi u NH2 ca cht ng rn amin.
CH OH CH NH R1 " NH2

+
NH2 R1 " NH2
CH OH

H2 O

Hoc nhit cao nhm OH phn ng vi u epoxy ca mch:

CH O CH3 CH O CH2 O C CH3 O CH2 CH OH CH2 O CH3 C CH3 O

+
H2C

+u im : cht ng rn ny c th ng rn cc chi tit ln hoc dn gch p tng. +Nhc im : amin c v kh iu chnh thi gian chun b . 1> ng rn bng axit hai chc: (cht ng rn nng ), ng rn bng anhidric. -Thng dng l cc anhidric ca axit dicacboxilic, anhidric malic, anhidric phetalic -Phn ng ng rn vi axit hai chc:
CH3 H2C O CH CH2 O C CH3 140-180oC R2 CH2 COOH CH3 H2C O CH O C CH3 O CH2 CH CH2 O OH n CH3 C CH3 O CH2 CH CH2 OOC OH R2 " COOH O CH2 CH CH2 O OH n CH3 C CH3 O CH2 CH O CH2

+ HOOC

V xy ra phn ng ng rn khc. To ra sn phm ph l nc khc vi loi cht ng rn amin, nc to ra bay hi li l xp nn cht ng rn axit t dng -Phn ng ng rn vi anhidric

V d: anhidric phtalic Phn ng tin hnh nhit cao t 180-220oC v qua cc giai on sau: Trc tin:
CH OH
CO

CO O

CH O CO

COOH

Sau :
CH O CO CH O CO

+
COOH

H2C CH O
COO CH2 CH

OH

2/ ng rn bng nhng cht ng rn khc -Ngoi hai cht ng rn trn ta cn dng cc hp cht c hai hay nhiu nhm nh chc d ng rn nha epoxy nh: nha phenol-formaldehyl, polyamine (-NH-CO-) , ure(melamin)-formaldehyl. -ng rn bng hai cht ng rn trn th nha sau ng rn c nhiu vng thm trong mch, c cng lm tng bn c hc, bn nhit , trong nha c lin kt ete, este lm cho mch mm, trong nha c nhm OH t do to nn bm dnh tt, trong nha c s lin kt ngang khng nhiu ( khng qu tha nh UF) lm mch khng qu cng. Do nha epoxy va bn nhit , bn c hc, bm dnh tt vi hu ht cc vt liu khc. IV/ Sn xut nha epoxy 1/ Sn xut nha epoxy phn t thp:(M=370-600 vC) Sn xut to ra c hai loi : ED-5: ti a 500 vC; ED-6: ti a 600 vC hoc tng t T l mol: Dian 1 Epi 2 NaOH 2 (dung dch 15% ) u tin nhit thng cho epiclohidrin vo TB phn ng, ri cho dian vo khuy u vi s vng 300 vng/pht, to huyn ph ng nht. Sau cho 65% lng NaOH vo, un nng 60-65oC, gi trong mt gi. Chop tip 22% lng NaOH vo nng nhit ln 65-70oC gi trong 2 gi . Cui cng cho ht 13% lng NaOH cn li , nng nhit ln 70-75oC gi trong 45 pht.

n y qu trnh iu ch nha epoxy xem nh kt thc. Tin hnh ra nha mc ch l tch ht mui NaCl v NaOH d (nu c), ra t 3-5 ln bng nc nng 50-60oC. Nu ch ra bng nc nng th nha khng tan trong nc do NaCl v NaOH pha trong nha khng tan ra ht. C th kt hp ra bng nc nng v toluen. Ra bng khuy trn cho nha tan trong toluen to ra nht thp. Mui v NaOH d ni ln trn c ht ra. C th tch NaCl v NaOH d bng cch sau: -Chng tch nc (trc khi chng phi cho toluen vo v khuy u nha tan trong toluen ). Sy nhit cao 75-85oC v p sut chn khng ( 600-650mmHg ). Hn hp ng ph toluen v H2O bc ln c lm lnh s phn lp, nc c tch ra v toluen quay tr li thit b. Khi nc c tch gn ht th mui trong nha bt u kt tinh. Ta tin hnh lc nha di li lc kch thc l nh. -Sau tin hnh chng ct toluene p sut chn khng v nhit ( nhit si ca toluen 112oC ) p sut <= 600 mmHg v nhit 75-85oC. n khi chng ct ht toluen, tin hnh lc vi li c kch thc l ln hn v c un nng ( 40-45oC) 2/ Sn xut nha epoxy phn t cao ( M=1500-3500 ) iu ch bng cch lm nng chy nha phn t thp vi dian nhit 200oC trong 1,5 2 gi, vi cch ny th nha phn t thp phi sch v vy khng to ra sn phm ph no v khng cn ra nha. Trng lng phn t trung bnh ca polymer to ra ph thuc vo t l dian.
H2C O H2C O CH CH CH O CH OH
OH
C H2

CH2

+ HO

OH + H2C O

CH

CH O CH

CH2

CH2 O

CH2 O

CH O

CH2

3/ Nha polyepoxy
OH

OH C H2

H2C CH Cl
CH2 CH O O CH2

CH2

O CH2
CH2 CH O O

CH2 CH2 CH
O O

CH2

C H2

V/ Tnh cht v ng dng 1> Tnh cht:

Tnh cht 30% anhydric maleic 1000 8,65 100

un [KG/cm2] va p [KG.cm/cm2] bn nhit (Martens) ht m (7 ngy m, to phng)

ED-6 ED-5 65% 7% 10% 40% polyetylen hexametylen polyetylen anhydric polyamin diamin polyamin maleic 1000 750 --7,1 100 7,0 100 0,04 0,05% -100 -100

2> ng dng: -Sn, vecni, keo dn -Lm vt liu compozit ( vi si vi thu tinh , si cacbon ) -Trn vi nhiu polymer khc lm vt liu p (vi PVC, phenolformaldehyt)

CHNG XI: SN XUT NHA POLYESTE I/ Phn loi nha: Cch 1: + PEs no: l PEs iu ch t axit v ru a chc no + PEs khng no: l PEs iu ch t hoc axit hoc ru a chc khng no Cch 2: + PEs nhit do: thu c t axit v ru 2 chc + PE nhit rn: thu c t hoc axit hoc ru 3 chc tr ln (thng l ru 3 chc) II/ Nguyn liu 1/ Cc ru: d20(g/ml) Tn Nhit si Nhit ng c o o ( C) ( C) Etylen glycol (EG) 197,5 -13 1,1155 Dietylen glycol (DEG) 245,8 -8 1,1184 1,2-propylen glycol (PG) 187,4 -1,0381 Glyxeryl 290 17,9 1,2638 Pentaeritric -260 -Ru alylic (C2H3-CH2OH) 96,7 -129 0,845 2/ Cc axit: Dng axit 2 chc hoc anhydric ca axit 2 chc - Axit phtalic (izophtalic, metaphtalic, terephtalic)
COOH COOH COOH

COOH

COOH COOH

Nhng ch c anhydricphtalic t axit izophtalic - Axit maleic

HOOC C C H H COOH

anhydric maleic
O CO C H CO C H

ng phn trans gi l axit fumaric - HOOC-(CH2)-COOH n = 2: axit succinic n = 3: axit glytalic n = 4: axit adipic n = 7: axit azelaic

n = 8: axit xebacic III/ L thuyt to nha polyeste im c bit ca qu trnh polyeste ho l phn ng cn bng v thun nghch. Nhng do hng s cn bng khng ln nn phn ng ph thuc nhiu vo iu kin chuyn dch cn bng v pha to ra polymer
HO R1 " OH

HOOC R COOH

xt, to

HO R1" OOC R CO
n

O R1" OCO R

2n H2O

COOH

Mun chuyn dch cn bng v pha phi th tch nc v dng xc tc c tnh ht nc. Cc phn ng ph: + Ru phn:
HO HO R1 " OOC R R1 " O CO
n

O R1 " OCO R COOH

+ HO
y

R1 " OH COOH

R1 "x OH

HOOC *

R CO

R1 " OCOR

Phn ng ru phn do tc dng ca ru n este, t mch ti este to mt cu ni ete v mt axit a chc. + Axit phn:
HO R1 " OOC R CO
n

O R1" OCO R COOH R CO

+
y

HOOC R1 " COOH R1 " OCOR COOH

HO

R1 " OOC
x

R COOH HOOC + *

Do phn ng thun nghch v c phn ng ph nn trng lng phn t trung bnh khng cao thng nh hn 30.000 Qu trnh to polyeste xy ra thao tng bc
Xt, 98 110oC

HO R1 " OH

HOOC

R COOH

HO

R1 " OOC R COOH

+ H2O

monoeste
HO R1" OOC R COOH + HO R1 " OH HO R1" OOC R COOH + HOOC R COOH HO R1" OOC R COO " R1 OH

+ H2O

HOOC R COO R1" OCO R COOH

Vn tc phn ng v tnh cht ca polyeste ph thuc vo cu to ho hc ca cc nguyn liu: + Nu ru 2 chc v axit 2 chc th to polyeste nhit do + Nu ru 3 chc tr ln v axit 2 chc th to polyeste nhit rn

+ Ru bc 2 v bc 3 kh phn ng hn ru bc 1 (tc l vn tc phn ng b hn ru bc 1) + cng ca polyeste (ca mng sn) - Theo th t gim dn ca axit Axit maleic > phtaleic > adipic > xebacis > limonic - Theo th t gim dn ca ru Pentaeritric > glyxerin > EG > DEG + Cc polyeste mch thng c kt tinh cao do c th ko si
HO CH2 CH2 OH

+ HOOC

COOH

HO

CH2 CH2 OOC

CO
n

OH

PET c cng ln, khng dng ko si m lm v chai nc do nhit thng th trong sut, cn khi un nng th c mu c. Nu dng axit metaphtalic th to ra PEs c kt tinh thp + Nu thay axit fumaric bng axit xebacis mch thng th kt tinh tng. Nu thay EG bng DEG th kt tinh gim do DEG c lin kt O+ Vn tc phn ng v trng lng phn t trung bnh ph thuc vo cu to v ng lng chc ca nguyn liu ban u. IV/ Sn xut nha polyeste Trc y ngi ta dng phng php 1 giai on tc l un nng hn hp nhit cao. u im l tng thi gian phn ng gim cn nhc im l tn tht nguyn liu nhiu ( nht l cc anhydric v axit thng hoa). V vy phng php ny t s dng. Phng php 2 giai on: + Giai on u: un nng hn hp nhit thp 98 120oC phn ln l to ra cc monoeste, gi thi gian thch hp + Giai on sau: nng nhit ln n 260 280oC v gi nhit ny n khi CA cn 1 25 th ngng phn ng. Cui cng lm lnh n nhit 150 180oC, nu dng polyeste lng th em ng thng cn nu dng polyeste rn th rt ra bng ti kim loi, lm ngui, em p, nghin, sng. CA: s mg KOH phn ng trung ho cc axit t do trong polyeste. gim CA th phi un nng v phi dng hi ca hn hp diphenyl mi to c nhit cao. giai on u c nhit thp th dng hi p sut nh. Hn hp hi bay ln ch yu l ru, ngoi ra c anhydric hoc axit do ru ko theo v nc. thit b phn ly: ru, anhydric v nc phn thnh hai lp; nc trn, ru v anhydric di. Ru v anhydric ngng t cho quay tr li thit b phn ng cn nc tch ra ngoi. * Polyeste khng no (PEsKN) ch yu i t axit khng no, ru phn ln l ru no 2 chc.

a/ Phn loi - PEsKN loi maleat

O CO C H O CH COO

PEsKN loi acrylat PEsKN loi thng (EG + AP + AM)

C C

OH OCO CH CH2

- PEsKN loi do: thay mt phn AP bng axit 2 chc mch thng hoc thay mt phn EG bng glycol mch di (DEG,DPG) - PEsKN bn mi trng: thm cht n nh quang ( nh benzophenol hoc thay mt phn styren bng MMA) - PEsKN bn ho hc: dng nguyn liu c vng thm (thay mt phn EG bng bisphenol-A) - PEsKN bn nhit: thay mt phn AP bng dn xut halogen ca axit 2 chc (axit tetraclophtalic hoc axit tetrabromphtalic)
Cl Cl Cl Cl COOH COOH

- PEsKN loi thng: EG-AP-EG-AM-EG-AP... b/ ng dng chnh ca PEsKN Lm vt liu composite + Nha nn (cht lin kt) + Ph gia ( cc loi si, vi...) + Cht ng rn ( styren, MMA) dng 20 30 PKL so vi PEsKN + Cht khi u (i vi PEsKN-styren): MEKP
H3C C2H5 O C OH HOOC O C CH3 C2H5 H3C C2H5 O O C COOH HOOC C CH3 C2H5

Lm vt liu composite c th dng tay, my, chn khng. Khi lm vt liu composite th cht nn ( hay cht lin kt ) l nha trn vi ph gia. Cht nn gip to hn hp vi ph gia thnh mi trng lin tc. Khi tc dng lc (nu ch c nha th dn, nu ch c ph gia th ri rc v th lc phn b khng u) ln mi trng lin tc th lc phn b u nn kh nng chu lc tt.

Si thu tinh dng lm vt liu composite c x l cht lin kt b mt. Nu si khng x l th si v nha khng bm dnh tt v si l hp cht v c v nha l hp cht hu c bm dnh vi nhau km. Cht lin din: RMX R: gc hydrocacbon khng no lin kt vi ni i ca nha hoc vi cht ng rn (styren) X: halogen hoc ete b thu phn to lin kt OH (lin kt vi si) M: Si, Cr S lin kt gia nha nn v ph gia xy ra + Giai on 1: thu phn
CH2 CH Cl Si Cl Cl H2C C O C CH3 O CrCl2 CH2 CH

3 H2O

HO Si OH OH H2C C

3 HCl

CH3 O Cr(OH)2

O 4 H2O (HO)2Cr

4 HCl

CrCl2 OH

OH

+ Giai on 2: to lin kt CH2 CH CH2 CH HO Si OH HO Si OH

O H O H O H O H

CH2 CH CH2 CH O Si O O Si O O

M M M M //////////////////////////////////////////////////// b mt si /////////////////////////////////////// //////////////////////////////////////////////////// ////////////////////////////////////// Ni i s tham gia trng hp vi hydrocacbon khng no ca nha hoc styrene. Si c x l bn hn si thng rt nhiu 20 30 ln.

H2C C CH3 O HOCr OH O H O HH O O H C O CrOH

H2C C CH3 O HOCr OH O H O HH O O H C O CrOH to

H2C C CH3 O -OCr OH O O C O Cr O

H2C C CH3 O Cr OH O O C O CrO--

M M M M M M M M ////////////////////////////////////////////////////////// ///////////////////////////////////////////////// V/ Tnh cht, ng dng Tnh cht ca nha polyeste khng no ph thuc vo thnh phn nguyn liu ban u v iu kin tng hp. trng thi khng ng rn nha c th c nht thp, trung bnh hoc cao. trng thi ng rn cc polyeste ny l vt liu rn, trong sut hoc khng trong sut. Vt liu trong sut cho nh sng i qua n 92% khi tip xc vi nh sng c bc sng ngn th nha s b vng. Polyeste ng rn bn axit, dung dch mui axit v trung tnh, cc dung mi c cc, nhng khng bn kim, kton, anilin, CS2 Nhc im ca polyeste khng no l co ngt ln, chu nhit khng cao, bn va p khng t Polyeste khng no c dng ph bin sn xut cht kt dnh ( ph gia cho xi mng), mng ph, vt liu composite, vt liu p v cht do thy tinh

CHNG XII:

SN XUT NHA POLYAMID, POLYURETAN, POLYCACBONAT, SILICON

I/Nha polyamid 1/ Nguyn liu a/ Caprolactam Caprolactam tinh khit si 262,5oC hoc 120oC (10mmHg) nng chy i nhit 68,5 69oC, d ha tan trong nc v trong a s dung mi. b/ Axit 11-aminoundecanic Axit 11-aminoundecanic nng chy 188 190oC. Phn ng iu ch n t axit rixinolic nh sau:
CH3 (CH2)5 CH CH2 CH CH (CH2)7 COOH 2CH2 CH (CH2)8 COOH Br (CH2)10 COOH CH3 (CH2)5 CHO + CH2 CH (CH2)8 COOH

HBr

Br

(CH2)10 COOH H2N

CH3 CH (CH2)8COOH Br

NH3

(CH2)10 COOH

HBr

c/ Axit adipic C th iu ch axit ny t cc sn phm ha hc khc nhau: phenol, furfurol, xiclohexan, axetylen, andehytTng hp axit adipic t phenol tin hnh qua cc giai on:
OH OH

+
OH

3 H2

HNO3

HOOC

(CH2)4 COOH

NO2

H2O

Nhit nng chy ca axit adipic l 151oC d/ Hexametylen diamin c tng hp t axit adipic, nhit si 14mmHg l 90 92oC
HOOC NC (CH2)4 COOH

+
4 H2

NH3

-4 H2O (300 375oC)

NC

(CH2)4 CN

(CH2)4 CN

H2N

(CH2)6 NH2

2/ L thuyt to thnh nha polyamid Ph thuc vo nguyn liu ban u m nhm amid trong polyamid c th nh hng theo cc chiu khc nhau + Polyamid c to ra t axit a chc (2) v amin 2 chc:

CH2 NH2 CH2 NH2

COOH COOH

-2 H2O

H2C H2C

H N N H

C O C O

+ Polyamid c to ra t aminno axit (hoc lactam ca amino axit 5 10% H2O)

n H2N n (CH2)4 CH2

(CH2)5 COOH CO NH

NH (CH2)5 CO
n

OH

+
n

(n-1) H2O OH

H2O

NH (CH2)5 CO

i vi lactam ch dng nc trong thi gian u v trong qu trnh trng ngng to ra nc th nc tham gia phn ng thy phn lactam Mun nhn c polyamid th c th dng cc axit 2 gc nhng vi iu kin s nhm metylen trong phn t khng c di 4, c ngha dng axit adipic v cc ng ng cao hn n. Phn ng to polyamid l phn ng thun nghch theo tng bc v to ra sn phm ph l nc. V vy tng hiu sut to ra polymer th phi tch bt nc. Nu tha mt trong cc tc nhn phn ng th c kh nng to ra mch polymer m u mch c cha nhm ca tc nhn tha v do lm ngng phn ng pht trin mch.
n HOOC (CH2)4 COOH

+ (n+1) H2N
H

(CH2)6 NH2 NH (CH2)6 NH2

n

NH (CH2)6 NHCO (CH2)4 CO

+ 2n H2O

3/ Tnh cht, ng dng Tnh cht ca polyamid ph thuc vo trng lng phn t trung bnh ca polymer, cu to ca cc monome ban u v s lin kt hydro Loi nha Nhit nng chy (oC) Polyamid-6 210 215 Polyamid-7 220 225 Polyamid-9 Polyamid-11 Polyamid-6-6 Polyamid-6-10 204 210 186 187 255 264 215 223

Khi tng s nguyn t C t 6 7 th c kt tinh ln hon mch c s nguyn t C t 9 11 nn c nhit nng chy cao hn. Polyamid 6-6 gm 6 nguyn t C v 6 nhm amin c nhit nng chy tng do s lin kt H tng. Polyamid-6
O NH CH2 CH2 NH CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 O C NH CH2 CH2 CH2 CH2 CH2 C O
O

C NH

CH2 CH2

CH2 CH2

CH2 C O

C O C O

NH

Polyamid 6-6
CH2 CH2
CH2 C O NH CH2 CH2 CH2 CH2 CH2 CH2 NH O CH2 CH2 CH2 CH2 CH2 CH2 NH C CH2 CH2 CH3 C CH2 CH2 CH3

CH2 CH2

CH2 C O

NH

Polyamid 6-6 c lin kt hydro ln hn polyamid-6 nn nhit nng chy cao hn. Polyamid c nhit nng chy cao nn c tnh cht c l cao, bn nhit ln, vt liu c ma st b v th c dng lm vt liu bi trn. Polyamid Tnh cht 6 11 6-6 3 Khi lng ring d (g/cm ) 1,14 1,04 1,14 k[KG/cm2] 500 800 500 700 800 1100 2 -u[KG/cm ] 700 1000 1000 1100 n[KG/cm2] Modun n hi E ( KG/cm2) -5000 600 1100 1000 2000 1000 1200 16000

II/ Polyuretan L polymer c to ra t polyizocyanat vi polyol -[-OCNH R NH COO R1 O -]nnOC = N R N = CO + n HO R1 OH + Cc cyanat thng dng: Hexametylen diizocyanat: OCN (-CH2-)6-NCO 2,4-Toluen diizocyanat:

CH3 NCO NCO

+ Cc phn ng ph: R NCO + H2O R1 NH2 + R NCO 2R NCO + H2O R NCO + R1OH R NCO + R2COOH ng dng: - Nha xp polyuretan - Vt liu composite III/ Polycacbonat iu ch t Dian v fosgen
CH3 HO C CH3 OH

RNH2 + CO2 R1 NH CONH R RNH CONH R + CO2 RNHCO CO R1 RNHCO R2 + CO2

NaOH, to COCl2 H

O O R O C

OH

+ 2n NaCl

bn nhit ln do mch c vng v nhm + Khi lng ring d = 1,2 g/cm3 + Gii hn bn ko k= 650 750 KG/cm2 + Gii hn bn nn n= 790 900 KG/cm2 + Gii hn bn un u= 800 1200 KG/cm2 + bn nhit (Martens): 115 125oC Polycacbonat cng, trong sut, d trn mu, khng c, c th thay th cho melamin-formaldehyt chu nhit cao, bn ln IV/ Silicon Nng lng lin kt gia Si, C vi cc nguyn t khc Lin kt Si Si Si C Si H Si F Si Cl Nng lng lin kt E(Kcal/mol) 42,5 58 75 143 85 Khong cch gia 2 nguyn t (Ao) 1,9 1,93 1,64 1,54 2,0

O O C

Si O C-C CH CF C Cl CO

89 58,6 87,3 104 70 75

-1,54 1,54 1,35 1,42 1,69 1,77 1,43

Si bn ha hc, bn nhit do c nng lng lin kt vi cc nguyn t khc ln hn C lin kt vi cc nguyn t . * Phng php iu ch
RSi 2 RSi O C2H5 O C2H5
3

+
2

H2O

RSi

O C2H5

OH

C2H5OH

OH

R(C2H5O)2Si O Si(OC2H5)2R

+H2O + C2H5OH

R(C2H5O)2Si R(C2H5O)2Si

O Si(OC2H5)2R

H2O

R(C2H5O)2Si

O Si(OC2H5)R OH

O Si(OC2H5)R OH + HO Si(OC2H5)2R R(C2H5O)2Si O Si(OC2H5)R O Si(OC2H5)2R

+ H2O

Tip tc phn ng cho n khi to ra polymer

R (C2H5O)2Si O Si(OC2H5)R O
n

Si(OC2H5)2R

* Tnh cht ca Silicon + Khi lng ring d = 1,9 g/cm3 + Gii hn bn un u > 500 KG/cm2 + bn nhit (Martens): > 200oC + ht m (trong 24 ngy m nhit thng): 0,25g/dm2