PHN 1 : EPOXY

I. Tng Quan Nha epoxy l nha nhit rn c s dng rng ri trn th gii. Nha epoxy c rt nhiu loi, nhng ph bin nht l epoxy c iu ch t phn ng gia nhm epichlorohydrin v bisphenol-A. Bng sng ch cho qu trnh tng hp epoxy t bisphenol-A c cp cho hai nh khoa hc Pierre Castan (Cng ty Ciba - Thy S, sau ny c bn cho Huntsman Corporation - M) v S.O. Greenlee (Cng ty Devoe Reynolds - M, sau ny c bn cho hng Shell Chemical) nm 1936. Cng vi Dow chemical company, Huntsman Corporation v Shell development company l hai cng ty ni ting v sn xut nha epoxy trn th gii ngy nay. Nha epoxy c nhiu ng dng rng ri nh lm cht kt dnh, vt liu composite v sn xut sn. Trong cng nghip sn xut cht kt dnh epoxy c s dng rt rng ri do c th bm dnh trn g, kim loi, thy tinh, , v mt s loi nha khc. Ta c th iu chnh c c loi keo epoxy mm do hay rt cng, trong sut hoc c mu, ng rn nhanh hoc rt chm,... Ngoi ra epoxy l cht kt dnh k thut dng trong cng nghip ch to my bay, xe hi, xe my, dng c th thao vi yu cu bn kt dnh. Trong cng nghip sn xut sn, sn epoxy c ng dng rng ri lm sn che ph cc ng thp thch hp s dng trong cng nghip du kh, ng dn nc v b tng nh kh nng bm dnh cao, kh nng chng n mn. Ngoi ra, ngi ta cn dng sn epoxy ph cc thng cha, lon hp chng r st do cc loi acid c trong thc phm. Mt ng dng na ca sn epoxy l lm sn sn nh vi tnh thm m cao, kh nng chng ha cht n mn, chng vi khun,... NHA EPOXY NN BISPHENOL A Cng thc ha hc :
CH3 CH2 CH CH2 O O C CH3 O CH2 CH CH2 O OH n CH3 C CH3 O CH2 CH CH2 O

Nha epoxy nn Bisphenol A l nha epoxy c sn xut t Bisphenol A v epichlorohydrin.

H3C HO C CH3 OH

H2C Cl

HC O

CH2

Nhm Bisphenol A

Nhm Epichlorohydrin

S c mt ca nhm Bisphenol A cung cp cho loi nha ny cc c tnh nh cng cao, chng c mi trng ha cht v nhit . Trong phn t khng cha nhm ester m ch c nhm ete v cc lin kt gia cc carbon, nh vy n li cng tng kh nng chng ha cht cho nha ny. Ngoi ra, cc nhm hydroxyl v cc nhm epoxy u mch gip nha c kh nng thm t v bm dnh tt cng nh c th tng tc v phn ng vi cc loi nha khc. Nhm epoxy c th phn ng vi cc nhm amine, thiols, methylol, cc acid carboxylic v c cc nhm cyanate v ester isocyanate. V vy, n c th phn ng vi cc amine mch thng v amine mch vng, cc amide, cc loi nha amino, polyester, carboxylated acrylic... Cc phn ng ny khng lm mt i cc nhm chc ca nha epoxy ban u m ch gn thm cc loi nhm chc mi vo mch nha, nh ta c th b sung thm cc tnh cht khc cho nha. NHA EPOXY NN BISPHENOL F Cng thc ha hc :
H2C CH CH2 O O CH2 O CH2 HC O CH2

Nha epoxy nn Bisphenol F c cu trc tng t nha epoxy nn Bisphenol A, tuy nhin ch c nhm methylene ni hai vng benzen thay cho nhm isopropylidene trong Bisphenol A, iu ny lm gim s thy tinh ha trong qu trnh lu tr v cung cp nht thp hn cho nha nn Bisphenol F. Nha epoxy nn Bisphenol F khi lng phn t thp c nht t 3000 8000 cps thp hn so vi nha epoxy nn Bisphenol A khi lng phn t thp nht t 11000 16000 cps. Vi cu ni methylene gia hai nhm phenolic thay cho nhm isopropylene trong nha epoxy nn Bisphenol A, nha epoxy nn Bisphenol F c kh nng kt mng cao hn, lm cho mng phim ca nha ny c nhit thy tinh ha, kh nng chu nhit v kh nng chng dung mi v ha cht cao hn.

NHA NN NOVOLAC Cng hc :

EPOXY

thc ha

Nha epoxy nn novolac c kh nng chng ha cht rt tt v n c cu trc rt cht ch. Khi nhit cao 500oF (260oC) v p sut 10.000psi (69Mpa) nha ny vn c kh nng chng ha cht tt. Nha epoxy nn novolac c nht kh cao (30.000 500.000 cps). Trong cng nghip sn, nha epoxy nn novolac thng c dng lm sn bt (powder coating). Khi c ng rn bi cc amin bo, nha ny c kh nng chu c hu ht cc loi dung mi nh : ketone, chlorinated hydrocarbon, acid v c (HCL, HF, H 2SO4), dung dch kim ngay c khi phi ngm trong cc dung dch ny hng thng. Ngoi ra, n c th chu c nhit cao, trong mi trng kh hoc m t, mi trng kim hoc acid v chu mi mn cao

II. Tng hp epoxy Nha epoxy ph bin v quan trng nht l nha c to thnh t phn ng trng ngng gia bisphenol A v epychlohydrine. Phn ng xy ra gm hai giai on: Giai on 1 : l phn ng kt hp vng epoxy ca epychlohydrine vi nguyn t hydro ca bisphenol A, phn ng xy ra nhanh nhit 60 70 oC, ta nhit mnh (H = -17.09 Kcal/mol).

2Cl CH2

H C

CH2

+ HO
CH3 C CH3

O Cl CH2
CH HO CH2 O

CH3 C CH3

OH

NaOH

CH2

H C OH

CH2

Cl

Sn phm to ra nhm -OH bc 2 v tr so vi nguyn t clo. v tr ny trong mi trng kim s xy ra phn ng tch loi kh HCl v to ra nhm epoxy mi. Giai on 2: l giai on tch HCl, phn ng thu nhit ( H = 17.09 Kcal/mol), phn ng xy ra chm:

Cl CH2

CH HO

CH2

CH3 C CH3

CH2

H C OH

CH2

Cl

NaOH

H2C O

H C

CH2

CH3 C CH3

CH2

H C

CH2

2HCl

Trng hp tng bc vi s loi tr HCl to ra mt chui cht a phn t c cng thc tng qut:
H H 2C C O CH3 CH2 O C CH3 H O CH2 C OH CH3 CH2 O n C CH3 H O CH2 C CH2 O

Nha epoxy c trng lng phn t tu thuc vo t l mol gia bisphenol A v epychlohydrine, nhit v thi gian phn ng, nng NaOH s dng v phng thc tin hnh tng hp. Ngoi ra khi mun tng cng thm cc tnh cht mong mun ngi ta c th to ra thm nhiu loi nha epoxy vi cc loi sn khc nhau. V d nh : +Nha epoxy-novolac
O
O CH2 C H CH2 CH2

O
O CH2 C H CH2 CH2 * O CH2 C H

O
CH2

Kh nng chu nhit ca nha tng ln, chu c nhiu loi mi trng nh mi trng oxi ho, axit, kim,Tuy nhin n rt gin, cng, nht cao gy kh khn trong qu trnh gia cng. +a vo sn bisphenol A cc dn xut halogel : Nha to thnh s tng kh nng chu nhit, kh nng chng chy, chu mi mn v chu mi trng.
Br O Br CH3 C CH3 Br Br O

+Thay sn bisphenol A : Thay sn bisphenol A bng cc dng mch thng ( aliphatic ), cao su (to cao suepoxy ho) hay c th thay bng silicon-epoxy, du u nnh epoxy ho,s lm tng kh nng mm do ca nha, tng bn un, chu va p, tuy nhin bn ko li gim.
III. Tnh cht : a. Tnh cht vt l

Nha epoxy l loi nha nhit rn, c mu t vng sng n trong sut, dng lng (M<450), c (450<M<800) v rn (M>1000) ty thuc khi lng phn t ca nha. Tan tt trong cc dung mi hu c nh : xeton, axetat, hydrocacbon clo ho,khng tan trong cc dung mi hydrocacbon mch thng : ete du m, xng Nha dng lng v d dng chuyn sang trng thi ng rn, to mng li khng gian ba chiu khng nng chy, khng ha tan khi s dng cc cht ng rn c km theo hin tng co rt.
b. Tnh cht ha hc

Nha epoxy trn sn bisphenol A c 2 nhm cha hot ng l nhm epoxy vi nhm hydroxyl. Tu theo khi lng phn t ca nha m th hin tnh cht theo nhm chc tri hn. Phn ng ca nhm epoxy Phn ng c trng ca nhm epoxy l phn ng cng m vng epoxy. Kh nng phn ng ca nhm epoxy ty thuc vo tng loi cht xc tc. Vi tc nhn i nhn (nucleophin): HX, phn ng xy ra theo c ch SN , tc nhn i nhn tn cng vo cacbon c t nhm th hn ca vng. C 3 gi thit v c ch phn ng sau:
2

CH2
O

+ _

CH

HX

CH2
X

CH OH

Khi c mt cc cht cho proton H nh axit, phenol, ru, phn ng xy ra thun li hn v cc cht ny thng c s dng lm xc tc cho nha epoxy. Phn ng ny c xc tc bi ion H :
+

CH2
O

CH

HX

H2C

CH

O
H

H2C CH2
X OH

Kh nng phn ng ca nhm hydroxyl

So vi nhm chc ca vng epoxy nhm chc hydroxyl trong nha c hot tnh yu hn, phn ng thng xy ra nhit cao, c xc tc. Nhm hydroxyl c th tham gia vo cc phn ng ester ho, ete ho, Vi tc nhn i in t : phn ng xy ra khi c mt proton H : R-OH + H
+
+

R H
+

O+

R+ + H2O H

H C

H C

H C R

H C

R+

O
H

R+

O
H

O+
H

O
H

H+

Vi tc nhn i nhn Khi khng c xc tc : phn ng xy ra nhit cao

H C

OH +

R-C

-H2O HC
O H

R C OH O-

OH

HC

Khi c mt ca xc tc : vi xc tc acid mnh nh cc acid v c phn ng thng xy ra khng cn nhit cao.

H C OH

+
OH

H C OH R

O C OH

H OH

-H2O

H C O R C H OH

IV. Cht ng rn cho nha epoxy Cc cht ng rn cho nha epoxy thng c cha hai hoc nhiu nhm chc c nguyn t H linh ng, v d nh cc amin bc 1, 2, 3, nha UF, PF, cc axit, cc anhydric, Nhit ca phn ng ng rn ph thuc vo tc nhn ng rn.
Cht ng rn loi amin
+

ng rn bng aliphatic amin khng bin tnh: cc amin c s dng sm nht nh l cc cht ng rn cho nha epoxy l alkylene amin khng bin tnh: DETA (dietylen triamin), TETA (trietylen tetramin), TEPA (tetraetylen pentamin) Cng thc chung:

NH2

CH2

CH2

NH

CH2

CH2

NH2

Cc amin ny phn ng vi nha epoxy nhit phng v hm lng ng rn c dng theo ng lng ca nhm epoxy v ng lng ca nhm hydro hot ng. [ph lc 2] Khi cc amin tc dng vi nha epoxy th phn ng m vng epoxy to ra lin kt NH-CH2- ng thi khng to ra sn phm ph nn co ngt nh. C ch ng rn ca amin bc 1, 2
OH R - NH2 + CH2 O R - NH - CH2 - CH OH + CH2 O CH CH2 NR CH2 CH OH CH CH R - NH - CH2 - CH -

Bn cnh , khi ng rn bng cc amin ny th gp nhng kh khn nh sau :

- Cc amin ny c tc bay hi cao, c cao s gy kch thch ln da v mt. - Lng cht ng rn s dng qu t, cn phi cn tht chnh xc, gy kh khn cho thao tc gia cng. - Cc amin ny c xu hng to trn b mt ca sn phm ng rn mt lp m c, nht do hin tng cc amin tri ln b mt s tc dng vi hi m trong khng kh v kh CO 2 to cacbamate,iu ny s lm gim bng ca b mt sn phm, lm d b mt, gy kh khn cho vic gia cng cc mng nhiu lp. Nhit thp, m cao s lm tng s hnh thnh lp m c trn b mt. S hnh thnh hin tng Carbamate do Amin kt hp vi khng kh m t nh sau:

H2O H2CO3

+ +

CO2 NH2

H2CO3 NHCOOH Carbamic acid + H2 O

NHCOOH

NH2

- Trng lng phn t thp ca cc amin ny khi ng rn s to nn mt lin kt dy c nn sn phm c kh nng chu nhit, chu dung mi v ho cht rt tt. Tuy nhin, mm do v kh nng chu va p li thp. V nhng l do nu trn, ngy nay cc aliphatic amin t khi s dng nh mt cht ng rn m thng kt hp vi cc cht khc to nn cc hp cht ng rn nh amido-amin, amin Adduct, mannich basenhm ci thin tnh cht ca sn phm sau ng rn, gia cng d dng nn ngy cng c m rng phm vi ng dng.
ng rn bng amin bc 3

NH3OCONH Carbamate

Cc amin bc 3 khi ng rn cho nha epoxy chng c tc dng nh cht xc tin qu trnh trng hp nha epoxy thng qua nhm epoxy. Do sn phm cui cng sau ng rn l nhng cu ni eter. Chng thng c dng xc tin qu trnh ng rn khi ng rn bng poliamit. C ch :

R3 - N

CH2 O

CH

+ R3 - N - CH2 - CH O + R3 - N - CH2 - CH O CH O CH2

+ R3 - N - CH2 - CH O

CH2 O

CH

ng rn bng nha Ure-formadehyt (UF), Phenol-formadehyt (PF)

Nha epoxy c th ng rn bng cc loi nha novolac, resole hoc cc sn phm trung gian cha nhn phenol trong phn t ( dioxidiphenyl propan ) Sn phm sau khi ng rn c mu sc p hn ng rn bng nha PF. Kh nng chu ho cht v mi trng kh cao.
ng rn bng poliamit

Nha poliamit lm tc nhn ng rn cho nha epoxy thng c dng cho h ng rn ca mng sn. Sn phm sau khi ng rn c kh nng chu mi trng kim v dung mi km nhng mm do hn khi b lo ho v kh nng khng n mn cng tng ln. Khi ng rn bng cc poliamit th t gy kch ng da so vi cc tc nhn ng rn l amin v Adduct amin. Ngoi ra cc khuyt tt trn b mt cng gim.
ng rn bng Anhydric phtalic (AP), Anhydric maleic (AM)

Phn ng ng rn xy ra chm v cn nhit cao, do tng tc qu trnh ng rn th dng thm xc tc. Cht xc tc thng s dng m vng anhydric l cc amine bc 3. Hn hp nha anhydric c nht thp, thi gian sng ca hn hp di. Sn phm sau khi ng rn c co ngt thp, tnh cht c l cao, tnh cht in tt bn nhit cao hn mt s sn phm ng rn bng amine.

V. ng dng

Vi nhng tnh cht nu trn, nha epoxy ngy cng c ng dng rng ri trong nhiu lnh vc k thut cng nh trong i sng nh : - Cng nghip sn v cht bao ph chng n mn. - Cng nghip in v vt liu cch in do kh nng cch in v chu nhit cao. - Ch to vt liu composite : dng cho cc sn phm c yu cu c tnh nng c l cao. - Cng ngh ch to khun c, dng c. - L cht kt dnh kt cu btng, chng thm, bt trt trong xy dng nh ca v ng cao tc