Tap chi Héa hoc, T. 45 (6), Tr. 666 - 670, 2007 PHG HONG NGOAI, CAU TRUC VA TINH CHAT NHIET CUA VAT LIEU POLYME BLEND TREN CO SG POLY AXIT LACTIC VA COPOYME ETYLEN-VINYLAXETAT Dén Téa soan 10-11-2006 THAI HOANG', DO VAN CONG', MASAO SUMITA* "Vien K5 thugt Nhigt déi, Vién Khoa hoc va Cong nghé Viet Nam *Khoa Héa hitu co va khoa hoe vat ligu, Hoc vign Cong nghé Tokyo, Nhat Ban SUMMARY Polylactic acid is one of the most popular bioplastics used in recent years and it is often mixed with other polymers or chemicals to form polymer blend because polytactic acid is able 10 accelerate biodegradation of polymer blends. This paper presents some results of study on polymer blend based on polylactic acid (PLA) and ethylene-co-vinylacetate copolymer (EVA). Fourier transform infrared spectroscopy of polymer blend PLAIEVA shows that position of peaks of C=O, C-O-C groups shifts to intermediate position characterized these groups in PLA and EVA due to their dipole-dipole interactions. These interactions make PLA and EVA disperse into each other more regularly. The presence of PLA increases slightly initial degradation temperature of polymer blend with PLA contents of:20 - 60 wt.%. EVA enhances oxidation thermostability of polymer blend at high temperatures. 1-MO DAU Cic chat déo c6 nguén géc dau mé da duge dua vao sit dung trén thé gidi khoing nhing nam 1950 va wo thanh vat ligu cia thé ky 20 trong nhiéu linh vuc nhu bao géi, vat ligu xay dung, giao théng van tai... va sé con dong vai tr quan trong trong tuong lai [1J. Tuy nhién do khé bén trong diéu kign méi wutng khi quyén, thi gian phan huy cita cdc chat déo thudng kéo dai nén ching t6n dong va gay 6 nhiém moi trudng. Dé han ché diéu nay, cdc nha khoa hoc da tién hanh nghién cttu va ché tao cde cdc chat déo mdi, cé nguén géc ty nhién, than thién véi moi trong va dé bi phan huy khi qua sit dung. Mét trong s6 cac chat déo d6 1a poly (axit lactic) (PLA), mot polyeste c6 céc tinh chat gdn giéng véi mot polyme c6 nguén géc déu md la polyetylen terephtalat (PET) nhu do cting cao, mhiét do néng chdy cao, modun dan héi cao va 666 do bén kéo ditt 16n [2]. Dac bigt, PLA co kha nang phan huy sinh hoc & diéu kién thuéng, dé tai sinh, do dé khong gay 6 nhiém méi trudng. Tuy nhien, PLA khé gidn va cé do dan dai khi dt thap nén han ché khi nang sit dung cia n6 [3,4]. Dé nang cao cic tinh chit cha PLA cing nhu cai thin kha nang phan hay sinh hoc cia céc polyme khdc, PLA dugc won hop (blend hod) véi cdc polyme cé ngudn géc tu nhién nhu tinh bot [5], polyme cé kha nang phan huy sinh hoc nhu polyvinylancol [6] hay ede polyme khong cé kha nang phan huy sinh hoc va cé nguén géc dau mé nh polyetylen, polypropylen [7]... Copolyme etylen-vinylaxetat (EVA) 1a mot polyeste c6 nhigu tinh chat t6t nhu do din dai khi ditt lon, mém déo, bén xé, trong sudt [8 - 12]... Tuy nhien, n6 khong c6 kha nang phan huy sinh hoc trong diéu kign thudng, Viée tron hgp EVA véi PLA cé thé cai thién dugc khanang phan huy sinh hoc cla EVA cing nhu cai thién mét s6 tinh chat co ly cho PLA. Bai nay trinh bay cdc két qua nghién ctu sv tuong tac cia PLA voi EVA bing phd héng ngoai bién ddi Fourier, cau tric hinh thai va do bén oxi héa nhiet cla vat ligu polyme blend PLA/EVA. Cfc két qua nghién citu cho thay, khi tron hop PLA véi EVA, céc pic hdp thy cia nhém C=O va C-O-C bi chuyén dich vé gid wi nim trung gian gita cdc gid tri cia ching trong PLA va EVA. Su phan tén cilia PLA va EVA vao nhau xay ra tot hon khi ham lueng PLA hay EVA In. Su cé mat cha PLA 1am tang nhiét do bat déu phan huy trong khi EVA cai thign do bén oxi héa nhiét 6 nhiét do cao cla vat liu polyme blend. I - THUC NGHIEM 1. Héa chat Nhua poly axit lactic (PLA) ¢6 tén thuong mai 1a Lacty # 5000, nhiét d6 thuy tinh héa T, = 61°C. nhiét do chiy mém T,, = 175°C, M, = 170.000, M, = 320.000 do Toyota Motor Company (Nhit Ban) sin xuat, EVA cé ham luong vinyl axetat 18%, nhiét dQ chay mém 95 — 99°C, khdi Ivgng riéng 0,93 g/cm’. Xylen tinh khiét do Trung Quéc san xuait. 2. Ché tao cde polyme blend PLA/EVA bing phuong phap tao mang trong dung dich Can 0,5 g hén hop PLA va EVA theo ty Ie da tinh ton vao 25 ml xylen, dun héi-luu, cé Khudy tir vi gia niet & 80°C. Khi 2 polyme da tan hoan toin, mau duge trai ra cde tim thuy tinh phang va cho dung moi bay hoi wr nhién, thu duge c&e polyme blend & dang mang mong véi chigu day khoang 50 pm. Sdy mang & 60°C trong ti hit chan khong t6i khi khOi Iuong khong déi. 3. Cée phuong phap nghién citu - Nehién citu tvong téc gitfa PLA va EVA. bang phé héng ngoai bién déi Fourier (FTIR): Mang polyme blend dugc chup pho héng ngoai trén thiét bi Nexus 670 cia hang Nicolet (M¥) tai Vien Ky thuat Nhiét déi, Vien Khoa hoc va Cong nghé Viet Nam. - Cu tric clia polyme blend duge quan sat tren anh hign vi dién tir quét (SEM) cia mau, chup trén thiét bj JEOL $300 (Nhat Bin) tai Vien Ky thuat Niet di véi do phéng dai 1000 in, mau duge phi lép bac méng trudc khi chup. - Phan tich nbiét-khéi Iuong (TGA) duge thyc hign tren may Universal V3.8BTA (Nhat Ban) tai Khoa Vat ly trudng Dai hoc Khoa hoc Tu nhien HA Noi, t6c dO gia nhiét 5°C/phit trong méi trudng khong khi, tir nhiét do phong én 500°C. Il - KET QUA VA THAO LUAN 1. Tuong tac cia 2 polyme thanh phdn trong polyme blend PLA/EVA Hinh | biéu dién phd héng ngoai bién ddi Fourier cba céc polyme PLA, EVA va polyme blend PLA/EVA cho thay vi ti hap thu dac trung ciia mot s6 nhém chttc trong PLA va EVA da thay déi khi 2 polyme nay duge tron lin véi nhau. Bang 1 tinh bay chi tiét sy thay déi cia cdc pic dac trung d6. C6 thé nban thay vi ui nhém C=O, C-O-C trong polyme biend nam trung gian gitfa vi wi cla cdc nhém wén trong PLA va EVA (bang 1). Diéu nay cho thay gitta cdc nhém chite cia PLA va EVA cé sy tuong téc véi nhau. Méi twong téc giia chting, ngoai luc Van der Waals thong thudng, cdn c6 tong tac dipol-dipol (tuong tdc luéng cuc) xay ra gitta cc nhém cacbonyl C=O cia EVA véi nguyén tO trong nhém C-O-C cia PLA va nguge lai, gitta nhém C=O cia PLA véi nguyén tir O trong C-O-C cia EVA. Ngoai ra, con c6 lien két hydro gitta nhém COOH trong PLA véi nhom C=O trong EVA. Chinh cdc tuong tac nay gitip cho 2 polyme c6 thé tron In véi nhau. 2. Cau tric hinh thai cia polyme blend PLA/EVA ‘Tren hinh 2 ta thy, wong polyme blend PLA/EVA cé thanh phan EVA chiém uu thé (& ty 1e 20/80, hinh 2c), 2 polyme nay phan tin kha t6t vio nhau (kich thuée pha phan tn khé nho, khodng 2 - 10 wm). RO rang Ia gitta cde polyme thanh phan da cé su tuong t4c, bam dinh kha 16t v6i nhau. Trong polyme blend PLA/EVA cé thinh phin PLA chiém wu thé (6 ty le 80/20, 667hinh 2a), sy phan tan cia cdc polyme kha t6t tue kich thudc hat khé lén (8 - 20 um). Diéu nay hung khong lien tuc, tao ra cdc Khuyét t€t trong cho thay sy phan tén va bim dinh cia PLA véi cu tric cia mau, V6i cdc polyme blend c6 t¥ 1é EVA 819 Ie tuong duong khong tt bang 6 1y 1¢ 2 polyme thanh phdn gn tong duong nhau ma mot tong 2 polyme chiém uu thé, (hinh 2b), cdc pha phan tan vio nhau khong lien Dé truyén qua, % 1758.76 1743.36 173746 : 1900 36 séng v, om! Hinh 1: Ph6 héng ngoai cia PLA (duvng 1), EVA (dung 3) va potyme blend PLA/EVA 60/40 (dung 2) & ving 900 — 2200 em" Bang 1: Su thay d6i pic dc trung tren phé FTIR ciia cdc nhém chttc trong polyme blend PLA/EVA. ‘Thanh phan Su thay d6i céc pic dic trung trén phé héng ngoai FTIR (cm'') PLA/EVA Dao dong héa tri cia C=O Dao dong héa tri cla nhém C-O-C 100/0 1758,76. 1207.43 80/20 1758,19 1208,13 60/40 1743,36 1239.06 40/60 1741.17 1241,05 20/80 1739.76 1241.40 0/100 1737.46 1243,45 3. Tinh chat nhiét cita polyme blend PLA/EVA Hinh 3 biéu dign céc dung phan tich nhigt-kh6i lugng (TGA) cita PLA, EVA va cée polyme blend & cdc thanh phiin khéc nhau, Noi chung, ti 310°C 6 di, do déc du’ng TGA cia cae polyme blend nim trung gian git d6 déc cita cdc dubng TGA cia 2 polyme ban dau. 668Hinh 2: Anh hién vi dign tit quét (SEM) ciia cdc polyme blend PLA/EVA 6 cdc ty Ie 80/20 (a), 60/40 (b) va 20/80 (c) 120 J PLA PLAVEVA 80/20 PLAEVA 60/40 20 PLAVEVA 40/60 PLAEVA 20/80 0 EVA 0 100 200 300 400 500 600 Nhiét d6,°C Hinh 3: Cac duromg nhiet- khoi lugng cia PLA, EVA va polyme blend cla ching 6 cdc ty 1e khdc nhau Bang 2: Céc dac trtmg TGA cha PLA, EVA va polyme blend PLA/EVA ‘Thanh phén | Nhiet do bit dau phan % Khoi lvgng con Iai 6 PLA/EVA huy, 7, sz0c | 370¢ | aoc | aoc 100/0 310,59 75,53 a3 294 2,89 80720 22128 69,69 70,60 615 157 60/40 225.23 76,54 18,78 12.73 760 060 223,76 70,42) 3300) 23,10 353 20/80 234.10 6641 | 4813 | 32,88 322 07100 222,14 10,24 | 58.51 3137 2,10 Bang 2 tinh bay cée dac tung TGA cia cia PLA cao hon nhiéu so vi EVA. Céc PLA, EVA va cée polyme blend PLA/EVA. Dé polyme blend PLA/EVA @ cae ti Ie tit 60/40 dén dang nhgn thdy nhigt do bat ddu phan huy (T,) 20/80 c6 T, cao hon BVA mor ft. Tuy nhien mau 669polyme blend PLA/EVA 80/20 c6 Tj, tham chi cdn thap hon T, ciia EVA. Co thé 6 ti 1é tren, 2 polyme tuong téc va bém dinh véi nhau khong t6t, cfu tric vat ligu kém chat ché, dé bi tac dong cla nhiét do cao va oxi khong khi, gay phan huy oxi héa nhiét polyme blend. Két hop bang 2 va hinh 3 ta thay PLA cé T, cao hon EVA nbung qué trinh phan huy Jai dién ra rat nhanh va xay ra theo I giai doan, trong khi EVA cé T, thap hon nhung qué trinh phan buy kéo dai va trai qua 2 giai doan vi qué trinh phan huy oxi héa nhiét cla EVA dién ra tan w, phan este cia polyvinylaxetat trong EVA sé bi phan huy trude, sau dé dén phan hydrocacbon cita EVA [13]. Kha nang bén oxI héa nhiét cla EVA & ving nhiet do cao (tir khoang 350°C wo len) lon hon so voi PLA. Chinh vi vay, Zokhdi lygng con lai cita cic polyme blend c6 thanh phan EVA I6n déu cao hon so véi cita polyme blend cé thanh phan EVA thap (so sinh & ving nhi¢t 46 tit 370°C wu len). Tham chi polyme blend PLA/EVA 20/80 6 % khéi luong con Iai & 420°C con cao hon cla EVA. Nhu vay, su c6 mat cia PLA lam tang gid tri T, cho polyme blend trong khi sy cé mat cla EVA lai lam tang do bén nhiét cho polyme blend & ving nhiét do cao hon. Diéu nay duge thé hign 13 6 cdc polyme blend giau thanh phin EVA ( ti lé PLA/EVA 40/60, 20/80) (bang 2). IV - KET LUAN 1. Sut chuyén dich mot sé vi tri pic dac trumg cia céc nhém C=O, C-O-C tren phd FTIR cla polyme blend PLA/EVA ching to PLA va EVA 6 su tuong tc véi nhau. 2. Cic pha PLA va EVA phan tin vao nhau tt hon 6 cc mau gidu PLA hay EVA, Trong d6, PLA phan tan vao EVA déu hon so véi EVA phan t4n vio PLA, 3. 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