Block Copolymerization of Vinyl Acetate and Vinyl neo-Decanoate Mediated by Dithionodisulfide

被引：24
作者：
Gu, Yuankai
He, Junpo [1 ]
Li, Changxi
Zhou, Changming
Song, Shijie
Yang, Yuliang
机构：
[1] Fudan Univ, Dept Macromol Sci, Shanghai 200433, Peoples R China
来源：
MACROMOLECULES | 2010年 / 43卷 / 10期
关键词：
FRAGMENTATION CHAIN-TRANSFER; LIVING RADICAL POLYMERIZATION; POLY(VINYL ALCOHOL); RAFT POLYMERIZATION; STAR POLYMERS; MADIX/RAFT POLYMERIZATION; MACROMOLECULAR DESIGN; LEAVING GROUPS; AGENTS; XANTHATES;
D O I：
10.1021/ma1000139
中图分类号：
O63 [高分子化学（高聚物）];
学科分类号：
070305 ; 080501 ; 081704 ;
摘要：
Block copolymerization of vinyl acetate (VAc) and vinyl nee-decanoate (VNDc) is carried out in the presence of a disulfide, isopropylxanthic disulfide (DIP), using 2,2'-azoisobutyronitrile (AIBN) as the radical initiator. The polymerization proceeds in a controlled/"living" style, as illustrated by stepwise increase in molecular weight and relatively narrow molecular weight distribution of the final product. The reaction mechanism is investigated in detail for the system of VAc homopolymerization in the presence of DIP. The results of chromatography, NMR. and mass spectra reveal that there exists two kinds of RAFT agents, that is, S-(cyano)isopropyl O-isopropyl xanthate and diisopropyl dithiocarbonate, the former coming from the reaction of 2-cyano-isopropyl radical with DIP and the latter being formed in situ during a series of radical process participated by the monomer. High efficiency of the cross initiation is achieved for the sequential polymerization. The block lengths are well controlled by the ratio of monomer to RAFT agents. The resulting block copolymer, PVAc-b-PVNDc, is hydrolyzed to prepare PVOH-b-PVNDc. These block copolymers, before and after hydrolysis, undergo self-assembly in solution and phase separation in bulk state.
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页码：4500 / 4510
页数：11
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