DOI: 10.3724/SP.J.1105.2014.13217

Acta Polymerica Sinica (高分子学报) 2014/014:2 PP.248-254

Photo-induced Synthesis of PVC Macroinitiators and Preparation of Amphiphilic Graft Copolymers

To increase number of labile sites on PVC and thus facilitate grafting from PVC by aids of free radical polymerization (FRP) under mild conditions, self-initiated, or bi-isopropyl thioxanthone (BIITX) and isopropylthioxanthone (ITX) initiated FRP of vinyl chloride (VC) in THF at 0 ℃ or 20 ℃ was carried out under UV irradiation.Influences of monomer concentration,incident light intensity, reaction time and temperature on monomer conversion, polymer molecular weight and its distribution were investigated. Radical ITX· produced by dissociation of BIITX or by H abstraction of ITX from monomer could combine with a macroradical. This allowed ITX residues to be incorporated onto PVC via weak C—C bonds which could be cleaved easily to regenerate radicals under UV light or heat stimuli, and thus yielded new labile sites on PVC for initiation. UV-Vis,1H-NMR and FTIR spectra analyses demonstrated the presence of labile chlorines and ITX residues on the resultant PVC, and indicated that PVC resulted from self-initiated or ITX initiated FRP contained great labile sites. Using the PVC as a macroinitiator, grafting polymerization of N,N-dimethylaminoethyl methacrylate (DMAEMA) in THF at 50 ℃ was started, and PVC-based graft copolymer (PVC-g-PDMAEMA) was synthesized. Compared with the initial PVC used, the graft copolymer achieved an increased molecular weight and narrowed molecular weight distribution.1H-NMR and FTIR analyses further confirmed the formation of PVC-based graft copolymer, and revealed that more labile chlorines or ITX residues on PVC favored initiation of graft polymerization. SEM and TEM observations showed that the graft copolymers containing more than 15 mol% (analyzed by 1H-NMR) of PDMAEMA segments could assemble into stable core-shell micelles in water (pH 3).The grafted hydrophilic PDMAEMA stretched towards aqueous media,forming the shell, while hydrophobic PVC portion coiled up to the core. This phenomenon suggested an amphiphilicity of the graft copolymers. In contrast, the copolymer with less content (only 0.15%) of grafted PDMAEMA could not form micelles due to its insufficient amphiphilicity.

Key words:Photopolymerization, PVC, Macroinitiator, Graft copolymer, Amphiphilicity

ReleaseDate:2014-07-21 17:05:30

1 Endo K.Prog Polym Sci,2002,27(10):2021~2054

2 Starnes Jr W H.Polym Sci,Part A:Polym Chem,2005,43(12):2451~2467

3 Starnes Jr W H.Polym Degrad Stab,2012,97(9):1815~1821

4 Percec V,Popov A V,Ramirez-Castillo E,Coelho J F J,Hinojosa-Falcon L A.J Polym Sci,Part A:Polym Chem,2004,42(24):6267~6282

5 Abreu C M R,Mendonca P V,Serra A C,Coelho J F J,Popov A V,Gryn’ova G,Coote M L,Guliashvili T.Macromolecules,2012,45(5):2200~2208

6 Rosen B M,Percec V.Chem Rev,2009,109(11):5069~5119

7 Jorge F J Coelho,Fonseca A C,Gois J R,Goncalves Pedro MOF,Popovc Anatoliy V,Gil M H.Chem Eng J,2011,169:399~413

8 Piette Y,Debuigne A,Bodart V,Willet N,Duwez A S,Jérome C,Detrembleur C.Polym Chem 2013,4:1685~1693

9 Zhang Ming(张明),Chen Xiaosong(陈晓松),Yan Changhao(严长浩),Chen Haiyan(陈海燕),Zhou Lanxiang(周兰香),Qiu Guanming(邱关明),Okamoto Hiroshi(冈本弘).J Chin Rare Earth Soc(中国稀土学报),2003,21(2):143~146

10 Li Kanshe(李侃社),Huang Hu(黄虎),Li Jin(李锦),Niu Hongmei(牛红梅),Yan Lanying(闫兰英).Acta Polymerica Sinica(高分子学报),2013,(3):335~340

11 Percec V,Asgarzadeh F.J Polym Sci,Part A:Polym Chem,2001,39(7):1120~1135

12 Bicak N,Ozlem M.J Polym Sci,Part A:Polym Chem,2003,41:3457~3462

13 Bicak N,Karagoz B,Emre D.J Polym Sci,Part A:Polym Chem,2006,44:1900~1907

14 Koh J H,Lee K J,Seo J A,Kim J H.J Polym Sci,Part B:Polym Phys,2009,47(15):1443~1451

15 Wang Jinming(王金明),Dong Jianguo(董建国),Bi Xiaohong(毕晓红).Polyvinyl Chloride(聚氯乙烯),2012,40(5):16~21

16 Pi Z J,Kennedy J P,Summers J W.J Polym Sci,Part A:Polym Chem,2002,40:3644~3651

17 Jindra P,Kim F D P,Wendy Z,Eltjo J V,Arend J S,Michelle L C.Macromolecules,2005,38(15):6352~6366

18 Valentine L.J Polym Sci,1957,24:439~443

19 Manson J A,Iobst S A,Acosta R.J Polym Sci,A-1 Polym Chem,1972,10:179~186

20 Torikai A,Hasegawa H.Polym Degrad Stab,1999,63:441~445

21 Deng J P,Wang L F,Liu L Y,Yang W T.Prog Polym Sci,2009,34:156~193

22 MaY H,Liu L Y,Yang W T.Polymer,2011,52(19):4159~4173

23 Liu L Y,Ren M W,Yang W T.Langmuir,2009,25(18):11048~11053

24 Bai H D,Huang Z H,Yang W T.J Polym Sci,Part A:Polym Chem,2009,47(24):6852~6862

25 Meng H,Liu L Y,Yang W T.J Macromol Sci,Part A-Pure Appl Chem,2009,46(9):921~927

26 Tonokura K,Daniels L B,Suzuki T,Yamashita K.J Phys Chem A,1997,101:7754~7764

27 Wu Y J,Yang X M,Lee Y P.J Chem Phys,2004,120(3):1168~1171

28 Zheng X F,Yue M,Yang P,Li Q,Yang W T.Polym Chem,2012,3(8):1982~1986

29 Dietrich B.Macromol Symp,1996,111:63~71

30 Ma Wenguang(马文光),Zhang Zhengbo(张正柏),Wei Chunming(魏春鸣),Hang Guopei(杭国培),Xia Xulin(夏旭林).J Hefei University Tech(合肥工业大学学报(自然科学版)),1991,14(l):130~135

31 Purmova J,Pauwels K F D,Zoelen W,Vorenkamp E J,Schouten A J.Macromolecules,2005,38(15):6352~6366

32 Shen Deyan(沈德言),Hu Xingzhou(胡兴洲),Ying Xinfang(英新芳),Qi Juying(齐菊英),Zhou Xiaoshu(周小蜀).Acta Polymerica Sinica(高分子学报),1997,(2):183~187