Synthesis of dual thermoresponsive ABA triblock copolymers by both living cationic vinyl polymerization and RAFT polymerization using a dicarboxylic RAFT agent

被引:17
|
作者
Sugihara, Shinji [1 ,2 ]
Iwata, Keiji [1 ]
Miura, Soichiro [1 ]
Ma'Radzi, Akmal Hadi [1 ,3 ]
Maeda, Yasushi [1 ]
机构
[1] Univ Fukui, Grad Sch Engn, Dept Appl Chem & Biotechnol, Fukui 9108507, Japan
[2] Japan Sci & Technol Agcy, PRESTO, Kawaguchi, Saitama 3320012, Japan
[3] Univ Malaysia Perlis, Sch Bioproc Engn, Arau Perlis 02600, Malaysia
关键词
Living cationic polymerization; Reversible addition fragmentation chain; transfer (RAFT); Triblock copolymer; BLOCK-COPOLYMERS; RADICAL POLYMERIZATION; DIBLOCK COPOLYMERS; DISPERSION POLYMERIZATION; ALCOHOL/WATER MIXTURES; PHYSICAL GELATION; PHASE-SEPARATION; VESICLES; ETHERS; TRANSFORMATION;
D O I
10.1016/j.polymer.2012.12.039
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
To elucidate a difference of micelles formed from AB di- and ABA tri-block copolymers, PMOVE-PNIPAM PMOVE triblock copolymers were synthesized by both living cationic polymerization of MOVE and RAFT polymerization of NIPAM using a dicarboxylic RAFT agent, where MOVE is 2-methoxyethyl vinyl ether, NIPAM is N-isopropylactylamide. The ABA triblock copolymers consist of cationically polymerizable monomer (A), MOVE, and radically polymerizable monomer (B), NIPAM. The key to success in the triblock copolymerization is to utilize a dicarboxylic RAFT agent/SnBr4 initiation system for living cationic polymerization. The cationic polymerization was simultaneously initiated from two protons per one dicarboxylic RAFT agent. After the cationic polymerization, the polymerization was quenched and then the RAFT carboxylate counter anion was concurrently recovered at ca. 86% efficiency, followed by the RAFT polymerization. The resulting PMOVE-PNIPAM-PMOVE triblock copolymers contain two thermoresponsive blocks. The resulting block copolymers reversibly formed or deformed micellar assemblies in water. When the chain length of the core-forming block, PNIPAM, is increased, larger micelles were invariably obtained. The triblock micellar size was larger than that of the corresponding diblock micelle. The micelles at the concentrated solution formed physical gel, and the minimum gelation concentration of the triblock micelles was lower than that of the corresponding diblock micelles. (C) 2012 Elsevier Ltd. All rights reserved.
引用
收藏
页码:1043 / 1052
页数:10
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