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CHT TR VA P CAO PHN T

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CHT TR VA P CAO PHN T


I. GII THIU 1. Tnh nng ca cht tr va p bn va p l mt khuyt im ca mt s cht do cng nghip quan trng nh PVC, PS, PP c bit nhit thp, chng c bn va p c kha v khng kha qu thp cho nhiu lnh vc ng dng. Tuy nhin, khi thm cht tr va p (impact modifier) vo cc nha trn th bn va p tng ln r rt. Vn ci thin ny ch yu do cc yu t sau: Loi v t l cht bin tnh va p. iu kin kt hp cht bin tnh va p vo nha. iu kin gia cng to sn phm chng va p. Kh nng hp thu nng lng c hc tc dng vo vt liu m khng b nt v gi l tnh bn dai (toughness). ci thin tnh bn dai ca nha nhit do cng gin, c th thm cc cht ho do hay bng phng php ng trng hp, tuy nhin s dn n gim cng ng k. Nhng nu to ra c mt hn hp polymer (polyblend) ca nha nhit do v cht n hi, ngha l mt h nhiu pha gm hai polymer v c bn khng tng hp ln nhau, tnh do dai c th tng cao m khng gim nhiu cng. 2. L thuyt v ci thin bn va p

Khi sn phm lm t cc polymer bin tnh va p chu s va chm v ng sut va p, ban u nng lng c hc c pha cng (pha nn) hp th. Sau , nng lng c chuyn i, b lm trch hng n pha n hi vy quanh pha cng, v hin tng nt gy c ngn cn. Nu s truyn ny khng thc hin c, nng lng hp thu ny vn cn trong pha cng (pha lin tc) v c th dn n to ra cc mi ng sut ti cc v tr bt li v gy vt nt. Trong cc h ny, tnh dn dnh ng phn pha phi tt v y l ch chu cc ng sut khc nhau. II. POLYVINYL CHLORIDE BIN TNH VA P (PVC-I) 1. Hnh thi hc ca PVC c th gii thch c ch tc ng ca cc ph gia tr va p cao phn t trong PVC, cn xem xt hnh thi hc ca PVC chi tit hn: PVC trng hp bng phng php huyn ph (PVC-S) bao gm cc ht th cp (do kt t cc ht s cp m thnh) c c ht in hnh 100 150 m, c to thnh t cc ht s cp ng knh 0,2 1,5 m. Trong qu trnh gia cng (p n, cn trng, p phun) cc ht th cp b v ra di cc iu kin xc nh (nhit v lc trt). Tnh cht vt l ca sn phm cui s l tt nht nu cu trc ca cc ht s cp c gi li. i vi PVC bin tnh hay khng bin tnh, lc ct x v chuyn vt liu trong my gia cng vt qu hoc khng mc cn thit s lm gim ng k c tnh ca vt liu. Tng bn va p ca PVC cng bng cch kt hp mt pha n hi vo trong nn PVC, kt qu to ra cu trc hai pha do tnh khng tng hp ca cao su vi nha nhit do. u tin, nng lng va p c hp thu bi nn nha nhit do, ri sau chuyn n pha n hi nn trnh c s nn nt. Cc nghin cu bng knh hin vi in t vi cc cng thc PVC bin tnh va p khc nhau pht hin hai cu trc c bn khc bit ng k l: Cc cht bin tnh nh polyethylene clo ho (PE-C) v cc copolymer ethylene vinyl acetate (EVA) bao ly cc ht s cp PVC trong sut qu trnh gia cng do chng to mng li r t ong trong nn PVC. Cc cht bin tnh nh cc copolymer methyl methacrylate/butadiene/styrene (MBS) v cc polyacrylate (PAE) gi li hnh dng ring ca chng dng cc ht n hi hnh cu phn tn trong nn PVC.

Cc cht bin tnh va p da trn PE-C v EVA, hiu qu khi to mt mng li, nhy vi bin dng trt hn nhiu so vi cc cht ny i t MBS hay PAE v c phm vi cc iu kin gia cng hp hn. t bn va p cao tho ng, lc trt trong qu trnh gia cng phi ln to ra mng li; nu lc trt vt qu, mng li ny s b ph hu, dn n gim ng k bn va p. Tc ng tng t khi vt qu gii hn nhit 185 - 190oC. Cu trc mng li ca cht bin tnh va p EVA cng b ph hu theo cch ny v sau EVA chuyn sang dng ht cu (s nghch chuyn pha). PVC bin tnh vi PAE t nhy trt hn v y l mt nguyn nhn m EVA dn dn b mt th phn cho cc ph gia tr va p cao phn t h polyarylate. 2. Cc cht bin tnh h polyacrylate cho PVC Cc cht bin tnh va p cho PVC polyacrylate chim u th trn th trng do cc tnh cht tuyt vi ca chng trong lnh vc p n tm v profile, c th l: Khng b s c khi gia cng khng thi tit v nh sng cao bn va p c kha cao To b mt tt Khng lo ha cao. Trong nhm ny, polybutyl acrylate (Tg -56oC) v poly(2-ethylhexyl acrylate) (Tg -70oC) c a dng cho PVC; nhng khi kt hp trc tip cc polymer ny vo nn nha gp kh khn do nhit phng chng c tnh cht ging nh cao su. Trong thc t c cc hng sn xut c bn nh sau: Sn xut trc tip PVC khng va p bng cch ghp vinyl chloride ln trn mt cht n hi acrylate ni mng ngang (trong cht lm phn tn) bng qu trnh trng hp huyn ph. (1) Sn xut cc cht bin tnh ring bit bng s ng trng hp ghp cc monomer acrylic nh butyl acrylate (BA) vi methyl methacrylate (MMA). (2) Qu trnh (2) to ra cc sn phm d kt hp vo trong PVC. bn va p c kha mong mun c th iu chnh bng lng dng, t 2 n 10% khi lng tng quan gia bn va p v hm lng ph gia theo t l thun.

H s gin n nhit ca polybutyl acrylate cao hn nhiu so vi PVC trong khong 56oC n nhit chuyn thy tinh ca PVC. Do vy, trong qu trnh lm lnh sn phm cui cng, cao su ny c co rt r rt hn nn nha bao quanh n, to ra cc ng sut ko gia nn v cc ht polybutyl acrylate. Cc ng sut ko ny v s to thnh cc khong trng l c s cho hiu qu cao ca cc cht bin tnh ny. Cc iu kin gia cng nh tc quay trc vt v nhit ci t t nh hng n bn va p c kha ca sn phm c bin tnh vi ph gia nn acrylate, do tnh n nh trt tt ca ph gia loi ny so vi cc cht bin tnh va p khc. Cn vi qu trnh (1), bng s trng hp vinyl chloride trong h phn tn ca polyacrylate ni mng ngang, thu c h hai pha PVC/cht bin tnh vi s phn tn cc ht n hi rt ng nht trong nn PVC. V cc ht n hi ny c tnh n nh cu trc rt tt ngay c di lc trt cao v di ng sut nhit cao nn loi PVC bin tnh ny c kh nng n nh gia cng cao. i vi c tnh ca sn phm to ra t PVC loi ny, bn va p c kha gn nh khng ph thuc nhit gia cng, nng sut my n v tc quay ca trc vt. Tng t nh PVC c thm cht bin tnh va p acrylate, loi PVC bin tnh va p ny cng c mi tng quan t l thun gia bn va p v hm lng cht bin tnh. Cc cht bin tnh h polyacrylate cho sn phm PVC trong sut Trong cc lnh vc p dng cn tnh trong sut nh lp ph ngoi khung g ca trm dng xe but v cc tng bn ca cc khu vn ma ng, vt liu yu cu l PVC khng thi tit, chu va p v trong sut. Cc cht bin tnh va p cao phn t khng p ng tt c cc yu cu ny. Mc d PVC c th t c tnh khng thi tit v chu va p cao vi cc polyacrylate nh ni trn nhng khng c tnh trong sut. Do , cc cht bin tnh cn phi c ch s khc x v s tn sc ging nh PVC nn. iu ny ch t c vi cc copolymer ghp ca styrene v butyl acrylate. PVC to polyblend vi cc vt liu ny c th sn xut sn phm c trong rt tt km theo bn va p v tnh khng thi tit cao. Cc cht bin tnh va p cho PVC i t cc polymer ABS

Ph thuc s kt hp c th ca tng loi copolymer ghp ABS, chng thch hp cho c cc cng thc trong sut v m c ca PVC cng v bn cng. C th vi PVC bn cng, p dng ch yu lm ci chn bn cho xe hi. Trong cc loi sn phm ca cht bin tnh ny, sn phm c hiu qu bin tnh va p t hn th thch hp hn cho cc sn phm trong sut, cn loi ABS hiu qu cao ch yu cho cc sn phm PVC m. Cc cht bin tnh va p ABS cho PVC c sn xut bng vic ghp acrylonitrile v styrene (SAN) trn cao su butadiene. Vic ghp ny c mc ch ci thin lin kt ca pha n hi phn tn vi pha PVC cng. Cht bin tnh va p ABS do tnh tng hp tt nn PVC bin tnh ABS c bn va p cao. Trong mt copolymer ghp ABS, styrene lm cho gia cng d dng hn do kh nng ci thin dng chy, acrylonitrile ci thin tnh khng ho cht v nhit, v ngoi ra tng cng ca vt liu, v cui cng, butadiene lm tng bn va p. Tu thay i c mong mun trong mt tnh cht, cc monomer kt hp khc cng c th c dng, v d thay styrene bng -methylstyrene s ci thin tnh n nh kch thc nhit cao. Cc cht bin tnh va p cho PVC i t cc terpolymer methyl methacrylate/ butadiene/styrene (MBS) Polymer MBS cng l copolymer ghp v c cu trc tng t ABS. S ng gp ca cc thnh phn monomer ring bit trong cht bin tnh MBS tng t ABS. MBS c vai tr rt quan trng trong cc cng thc PVC trong sut, c th cho s sn xut chai nc khong. ci thin tnh tng thch vi PVC, cc loi MBS c thm lng nh acrylonitrile. Cc loi PVC bin tnh va p vi MBS v ABS thng khng thch hp cho cc p dng ngoi tri, v thnh phn polybutadiene d b phn hu quang. 3. S dng cht tr va p cho PVC. Tn vit tt S dng ngoi tri Cht tr va p

EVA EVA/VC PAE/VC ACE

Ethylene-vinyl acetate copolymer graft Ethylene-vinyl acetate/vinyl chloride graft copolymer Polyacrylate/vinyl chloride graft polymer Acrylate/methyl methacrylate graft polymer cho PVC polyblend. Chlorinated polyethylene cho PVC polyblend.

CPE Ch dng trong nh MBS ABS

Methyl methacrylate-butadiene-styrene graft polymer Acrylonitrile-butadiene-styrene terpolymer Cht tr va p cho PVC c s dng nhiu dng:

Trn kh: PVC v cht n hi c trn dng bt to thnh polyblend, hn To hn hp nng chy: PVC, cht n hi v cc ph gia khc c gia nhit Trng hp graft: cht n hi c ho tan trong mono vinyl chloride v c

hp ny c dng gia cng trc tip. v trn trong Banbury hoc my cn, sau em to ht. chuyn thnh polymer PVC graft. 4. Mt s ng dng v cng thc ngh cho PVC bin tnh va p Cng nghip bao gi PVC bin tnh vi MBS c trong sut tuyt vi, bn va p cao v tnh chy tt nn n c chn c thi cc sn phm rng c cc tnh cht sau: cao Khng to vt trng khi ko cng (quan trng i vi thit k chai l) S phn tn cao trong sng ca sn phm cao bn va p ca sn phm khi th nghim th ri t mt cao nht nh

Cc tnh cht cm quan tt: khng di hnh mi v v t bao gi n sn phm

cha trong n. Cc sn phm c thi lm bng PVC bin tnh MBS thng s dng cha nc khong, du n, m phm v cht ty gia dng. Ngoi MBS ra, cn dng ABS ch yu cho sn xut cc mng v tm trong sut hay m, p dng chnh: mng kh ln, mng bc th tn dng, khay n lm bng phng php to hnh chn khng, mng co rt v cc bao gi thi phng ln. Cng nghip xy dng y l lnh vc p dng quan trng nht ca cc ph gia bin tnh va p cho PVC h acrylate cao phn t. Hn hp blend PVC/polyacrylate phn ln c dng cho sn xut cc profile ca s c mu, khung ca ra vo, cc thnh phn trong sn ph, tm chn chi mt trn ng cao tc v hng ro vn. Cc cht bin tnh va p cao phn t khng thi tit v c truyn sut cao da trn polybutyl acrylate a dng hn cho cc tm tng v trn nh c thit k ly sng trong nh thi u th thao v cc nh xng; vt liu lp mi cc khu vn ma ng, cc sn vn ng v nh ch xe but; lp ph ngoi ca cc h thng lnh v nh knh. Cc cng thc ngh vi PVC bin tnh va p nh sau: Tng v trn nh c thit k ly sng trong nh thi Profile ca s, khung ca ra vo, p dng cc thnh phn trong sn ph, tm chn chi mt trn ng cao tc v hng ro vn u th thao v cc nh xng; vt liu lp mi cc khu vn ma ng v nh ch xe but; lp ph ngoi ca cc h thng lnh v nh knh S n nh Pb Sn Ca/Zn Sn

Cc thnh phn trong cng thc % S-PVC K = 64 - 70 bin tnh va p cao Cht n nh Pb (Pb phosphite) Cht n nh Sn (thic maleate bin tnh) Cht n nh Ca/Zn Cht ha do epoxy Cht bi trn Cht tr gia cng da trn PMMA Cht hp thu UV Canxi carbonate Titan dioxide 2,0 - 4,0 2,0 - 4,0 III. 2,0 - 4,0 2,0 - 4,0 2,0 - 4,0 3,0 - 5,0 0,4 - 2,5 1,0 - 2,5 1,0 - 2,5 1,0 - 2,5 1,0 - 2,5 3,5 - 4,5 0,8 - 2,0 1,0 - 1,5 0,5 - 1,0 1,5 - 2,0 1,0 - 2,0 2,5 - 3,0 2,0 - 3,0 3,5 - 4,0 -

100

100

100

100

POLYPROPYLENE BIN TNH VA P (PP-I) Phng php ch yu ci thin bn va p ca polypropylene l s dng

cao su ethylene/propylene (EPM hay EPDM). Blend ca polypropylene vi cao su ethylene/propylene (PP/EPDM) c s dng ph bin, khi yu cu bn va p kha V cao nhit xung n -20oC v thp hn. Nhng polyblend ny l hn hp

trn vt l ca cc copolymer n hi ethylene/propylene (diene) v polypropylene (PP). PP s dng c dng homopolymer PP isotactic cao v copolymer khi ca propylene v ethylene. Trong nhng blend ny, ni chung cht n hi c th trn vi nha nhit do tt c cc t l: Nu pha n hi chim phn ln, dng thut ng cht n hi nhit do (thermoplastic elastomer: TPE) hay cao su nhit do. Nu pha PP chim phn ln, dng trong bi ny, gi l polypropylene bin tnh va p (PP-I). 1. Cc tnh cht ca polyproplylene bin tnh va p Nu cc cao su EPDM trn vi t l khi lng 10 - 40% trong hn hp vi polypropylene dng homopolymer hay dng copolymer block, vt liu nha nhit do mi c gi thnh khng cao, c cng (modulus n hi) 600 N/mm2 ( 40%) n 1200 N/mm2 (ti 10%), ph thuc hm lng EPDM c th, v bn va p tt khi nhit xung n -50oC. Mt s tnh cht c trng ca cc blend ny theo t l ca EPDM cho trong bng 2, bn va p c kha cao i km cng thp v cng cng nhit vng xung di ti ca PP gim khi kt hp vi EPDM. Cc tnh cht ca blend PP/EPDM trong thc t chu nh hng nhiu ca k thut trn dng sn xut n. Cc tnh cht quan trng khi la chn cao su EPDM thch hp blend vi PP nh sau: Tnh tng hp Tnh cht hi dnh Tnh n nh nhit Kh nng gia cng. Bng 2. Cc tnh cht vt l ca blend PP theo hm lng EPDM Tnh cht ASTM n v Hm lng EPDM, % khi lng

10 bn ko t 23oC Modul n hi 23oC bn va p c kha +23oC 0o C -20oC D 638 84 D 790 86 D 256 84 J/m 40 - 800 20 - 120 20 - 60 N/mm2 1000 1200 N/mm2 24 - 28

20 22 - 25 850 950

30 18 - 20 700 800

40 15 - 17 600 650

70 800 30 150 40 - 90

200 800 100 500 80 160 130 134

400 800 200 500 120 500 112 115

Nhit mm Vicat

D 1525 82

oC

142 147

138 140

2. S dng PP bin tnh va p Cao su dng mu vn hay ht d kt hp v khi c trn trc vi PP c th n trc tip hay gia cng bng cng ngh p phun. Nguyn tc chung cho trn hp loi ny l cn bng gia modul n hi v bn va p cao nht nhit thp, hiu qu nht khi blend c to ra t PP khi lng phn t cao v EPDM v nh hnh. EPDM kt tinh mt phn, khi lng phn t cao cng c dng ph bin v blend ca n c tnh bn v k thut tt. Khi s dng PP homopolymer c ch s nng chy cao, t bn va p nhit thp tng t nh vi PP copolymer block, cn t l cao su cao hn v phi chp nhn gi tr modul n hi thp hn. PP bin tnh bng EPDM s dng ch yu trong cng nghip xe hi, n nh rt tt bng cc cht n nh quang amine c cu trc khng gian cng knh (HALS). Hn 90% sn lng PP bin tnh va p dng sn xut ci hm xung, phn u xe, cnh ca, cc profile gia cng khng va chm, tm chn bn v tm chn bnh xe.

IV.

POLYSTYRENE (PS) V CC COPOLYMER BIN TNH VA P Ngi ta ci thin tnh va p km ca PS bng cch ng trng hp ghp

styrene v polybutadiene, copolymer block butadiene/styrene (SBS). 1. Cc loi bin tnh a. PS bin tnh va p trong sut
y l nhng copolymer block cng i t styrene v butadiene nhng cc pha polybutadiene v polystyrene cc mn n mc ng knh ht ca tng pha nh hn bc sng nh sng nhn thy. Kt qu l nh sng khng ta ra v khng b cn tr bng qua, ngha l polymer truyn sut. PS bin tnh va p khng thi tit

PS bin tnh vi EPDM c kh nng khng thi tit ln hn 5 - 20 ln so vi PS khng va p thng thng v ABS, do thnh phn n hi EPDM lm gim xu hng gin di nh hng ca bc x UV v nhit , v loi PS ny c dng trong cc p dng ngoi tri. b. Cht do ABS y l nhng loi nha nhit do dng cho cng ngh c khun, v nh hnh i t qu trnh ng trng hp khi cc monomer acrylonitrile (A), butadiene (B) v styrene (S), tuy nhin chng khng lin kt vi nhau thnh mt pha ng nht, ng hn ABS l h hai pha trong c mt cc polymer khc nhau v mt ha hc. Ni cch khc, tt c cc polymer ABS gm mt copolymer ca styrene hay alkylstyrene vi acrylonitrile (pha lin tc, cng hay pha kt dnh) v mt pha phn tn (pha cao su, pha n hi). Cao su polybutadiene (BR) hay styrene/butadiene (SBS) c mt kch c ht no ng vai tr pha phn tn, s phn tn c ht ph thuc qu trnh sn xut. Pha n hi ny ghp vi cc monomer cu to nn pha cng, ngha l vi styrene v acrylonitrile, ci thin lin kt vi pha lin tc. Nu pha polybutadiene trong cc polymer ghp ny c thay th bng mt cht n hi h acrylate, ta c polymer ASA.

Khi s dng nh mt ph gia bin tnh va p, ABS c u im l lm tng im bin mm Vicat ca nha nhit do c bin tnh bng n, v d nh PVC; cc nha nhit do khc c th kt hp vi ABS ci thin bn va p l polymethyl methacrylate, polycarbonate v polyurethane nhit do. ASA c dng thay ABS khi mt nha nhit do nh PVC dng cho cc sn phm ngoi tri v ASA c tnh khng thi tit cao hn v kh nng n nh nhit tt hn, v s kt hp ca cht bin tnh va p i km vi ng sut nhit cao trong sut qu trnh gia cng. 2. Cc ng dng cho PS bin tnh va p v ABS PS khng va p c cho l chim mt t l ng k trong cc nha nhit do dng sn xut cc ngn bn trong v cnh ca t lnh. Khi dng kt hp cht khng chy thch hp, PS khng va p lm phn sau ca v my thu hnh. Cng nghip xe hi l mt lnh vc p dng quan trng cho ABS: ch to cc phn thn xe, hp cp cu, thit b li v li ca l si, trong n c s dng nh mt loi nha nhit do v c nh ph gia bin tnh va p lm tng im mm Vicat ca cc nha nhit do khc. V. CC POLYAMIDE BIN TNH VA P Cc polyamide bo (mt loi nha k thut) c th c ci thin bn va p bng cch kt hp thnh phn c nhit chuyn thy tinh thp hn ng vai tr pha phn tn, n hp th p sut, khng nt gy. EPDM c hot ha, l dng polymer ghp vi acid acrylic, acid maleic hay maleic anhydride, l cht bin tnh va p c bit thch hp cho polyamide. Trong qu trnh sn xut polyblend, thnh phn kt hp dng polyolefin ny c ghp nh vi vt liu nn trong my p n, bng phn ng ca nhm carboxyl ca cht bin tnh vi nhm amino cui cng ca polyamide. Cc tnh cht ca PA 6 v PA 66 cha bin tnh v cc polyamide ny c bin tnh EPDM trong bng 3. Bng 3. So snh cc tnh cht vt l ca cc polyamide bin tnh va p v khng bin tnh

Tnh cht

Tiu chun

n v

PA khng bin tnh (uPA) uPA 6 uPA 66 PA 6/PE

PA bin tnh PA 66 bin tnh cht n hi PA 6 bin tnh cht n hi 1,087 50 - 60

T trng c (+23oC) bn va p izod (+23oC) kha

DIN 53479

g/cm3 kJ/m2

1,14 3,2

1,14 4

1,10 9

1,09 50

bn va p DIN 53453

ASTM D 256 ISO 180

J/m

50

910

1000

im Vicat cng

mm DIN 53460 ISO 306 DIN 53456

oC

> 200

> 200

191

185 190

N/m2

130

150

110

90

90

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