RAFT ab initio emulsion copolymerization of γ-methyl-α-methylene-γ-butyrolactone and styrene

被引：25
作者：
Xu, Shaohong [1 ]
Huang, Jie [1 ]
Xu, Song [1 ]
Luo, Yingwu [1 ]
机构：
[1] Zhejiang Univ, State Key Lab Chem Engn, Dept Chem & Biol Engn, Hangzhou 310027, Peoples R China
来源：
POLYMER | 2013年 / 54卷 / 07期
基金：
美国国家科学基金会;
关键词：
Gradient copolymer; RAFT polymerization; Emulsion polymerization; FREE-RADICAL COPOLYMERIZATION; FRAGMENTATION CHAIN TRANSFER; MINIEMULSION POLYMERIZATION; KINETICS; COMPARTMENTALIZATION; METHACRYLATE; VALEROLACTONE; AGENT;
D O I：
10.1016/j.polymer.2013.02.007
中图分类号：
O63 [高分子化学（高聚物）];
学科分类号：
070305 ; 080501 ; 081704 ;
摘要：
RAFT ab initio emulsion copolymerization of gamma-methyl-alpha-methylene-gamma-butyrolactone (MeMBL) and styrene with various monomer ratios was investigated with PAA(20)-PS5 trithiocarbonate being mediator and surfactant at 70 degrees C. The polymerization was fully controlled as evidenced by stable latexes, well predicted molecular weights and low PDIs about 1.2 when [MeMBL]:[St] <= 1:2. However, in the case of [MeMBL]:[St] = 1:1, the molecular weight became out of control due to gel effect of RAFT reactions. The relatively water-soluble MeMBL was found to dramatically influence the polymerization kinetics and copolymer properties, as evidenced by (I) No inhibition period was observed; (2) The copolymer compositions in the early stage of polymerization were much higher than those predicted by the Mayo-Lewis equation in the case of [MeMBL]:[St] = 1:2, leading to the formation of linear gradient copolymer. (3) T(g)s of the copolymers from emulsion copolymerization were higher than those from bulk copolymerization. It was concluded that we could synthesize the gradient copolymer with preset molecular weight and low PDI in RAFT emulsion polymerization, T-g of which should be much higher than 100 degrees C. (C) 2013 Elsevier Ltd. All rights reserved.
引用
收藏
页码：1779 / 1785
页数：7
相关论文
共 48 条
[21]   Effect of reversible addition-fragmentation transfer (RAFT) reactions on (mini)emulsion polymerization kinetics and estimate of RAFT equilibrium constant [J].
Luo, YW ;
Wang, R ;
Yang, L ;
Yu, B ;
Li, BG ;
Zhu, SP .
MACROMOLECULES, 2006, 39 (04) :1328-1337
[22]   Compartmentalization in TEMPO-mediated styrene miniemulsion polymerization [J].
Maehata, Hideo ;
Buragina, Catherine ;
Cunningham, Michael ;
Keoshkerian, Barkev .
MACROMOLECULES, 2007, 40 (20) :7126-7131
[23]   Catalytic synthesis of α-methylene-γ-valerolactone:: a biomass-derived acrylic monomer [J].
Manzer, LE .
APPLIED CATALYSIS A-GENERAL, 2004, 272 (1-2) :249-256
[24]   Atom transfer radical polymerization [J].
Matyjaszewski, K ;
Xia, JH .
CHEMICAL REVIEWS, 2001, 101 (09) :2921-2990
[25]  
McGraw W. J., 1953, [No title captured], Patent No. [US2624723A, 2624723]
[26]   Coordination polymerization of renewable butyrolactone-based vinyl monomers by lanthanide and early metal catalysts [J].
Miyake, Garret M. ;
Newton, Stacie E. ;
Mariott, Wesley R. ;
Chen, Eugene Y. -X. .
DALTON TRANSACTIONS, 2010, 39 (29) :6710-6718
[27]   Living Polymerization of Naturally Renewable Butyrolactone-Based Vinylidene Monomers by Ambiphilic Silicon Propagators [J].
Miyake, Garret M. ;
Zhang, Yuetao ;
Chen, Eugene Y. -X .
MACROMOLECULES, 2010, 43 (11) :4902-4908
[28]   Free-radical polymerization of styrene in emulsion using a reversible addition-fragmentation chain transfer agent with a low transfer constant: Effect on rate, particle size, and molecular weight [J].
Monteiro, MJ ;
de Barbeyrac, J .
MACROMOLECULES, 2001, 34 (13) :4416-4423
[29]   Copolymers with controlled distribution of comonomers along the chain .1. Structure, thermodynamics and dynamic properties of gradient copolymers. Computer simulation [J].
Pakula, T ;
Matyjaszewski, K .
MACROMOLECULAR THEORY AND SIMULATIONS, 1996, 5 (05) :987-1006
[30]   RAFT-Mediated Emulsion Polymerization of Styrene with Low Reactive Xanthate Agents: Microemulsion-like Behavior [J].
Pepels, Mark P. F. ;
Holdsworth, Clovia I. ;
Pascual, Sagrario ;
Monteiro, Michael J. .
MACROMOLECULES, 2010, 43 (18) :7565-7576
12345