Cobalt-Mediated Radical Polymerization Routes to Poly(vinyl ester) Block Copolymers

被引：29
作者：
Bunck, David N. [1 ]
Sorenson, Gregory P. [1 ]
Mahanthappa, Mahesh K. [1 ]
机构：
[1] Univ Wisconsin, Dept Chem, Madison, WI 53706 USA
来源：
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY | 2011年 / 49卷 / 01期
基金：
美国国家科学基金会;
关键词：
biodegradable; block copolymers; cobalt-mediated radical polymerization (CMRP); degenerate transfer polymerization; radical polymerization; self-assembly; vinyl acetate; vinyl ester; VINYL-ACETATE; MOLECULAR-WEIGHT; CMRP; MONOMERS; ACRYLATE; STYRENE;
D O I：
10.1002/pola.24445
中图分类号：
O63 [高分子化学（高聚物）];
学科分类号：
070305 ; 080501 ; 081704 ;
摘要：
Cobalt-mediated radical polymerizations (CMRPs) utilizing redox initiation are demonstrated to produce poly(vinyl ester) homopolymers derived from vinyl pivalate (VPv) and vinyl benzoate (VBz), and their block copolymers with vinyl acetate (VAc). Combining anhydrous Co(acac)(2), lauroyl peroxide, citric acid trisodium salt, and VPv at 30 degrees C results in controlled polymerizations that yield homopolymers with M-n = 2.5-27 kg/mol with M-w/M-n = 1.20-1.30. Homopolymerizations of scrupulously purified VBz proceed with lower levels of control as evidenced by broader polydispersities over a range of molecular weights (M-n = 4-16 kg/mol; M-w/M-n = 1.34-1.65), which may be interpreted in terms of the decreased nucleophilicity of these less electron donating propagating polymer chain ends. Based on these results, we demonstrate that sequential CMRP reactions present a viable route to microphase separated poly(vinyl ester) block copolymers as shown by small-angle X-ray scattering analyses. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 242-249, 2011
引用
收藏
页码：242 / 249
页数：8
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