Synthesis of PEVE-b-P(CTFE-alt-EVE) block copolymers by sequential cationic and radical RAFT polymerization

被引:34
作者
Guerre, Marc [1 ]
Uchiyama, Mineto [2 ]
Lopez, Gerald [1 ]
Ameduri, Bruno [1 ]
Satoh, Kotaro [2 ,3 ,4 ]
Kamigaito, Masami [2 ]
Ladmiral, Vincent [1 ]
机构
[1] Univ Montpellier, ICGM, CNRS, ENSCM, 240 Av Prof Emile Jeanbrau, F-34296 Montpellier 5, France
[2] Nagoya Univ, Grad Sch Engn, Dept Mol & Macromol Chem, Chikusa Ku, Furo Cho, Nagoya, Aichi 4648603, Japan
[3] Japan Sci & Technol Agcy, Precursory Res Embryon Sci & Technol, 4-1-8 Honcho, Kawaguchi, Saitama 3320012, Japan
[4] Univ Ghent, Dept Organ & Macromol Chem, Polymer Chem Res Grp, Krijgslaan 281, B-9000 Ghent, Belgium
基金
日本学术振兴会;
关键词
VINYLIDENE FLUORIDE; POLY(VINYLIDENE FLUORIDE); CHLOROTRIFLUOROETHYLENE; POLYMERS; ETHERS; ROUTE; EPOXY; ATRP;
D O I
10.1039/c7py01924f
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 copolymers containing chlorotrifluoroethylene (CTFE) are relatively rare. This article presents the synthesis of unprecedented CTFE-containing block copolymers (PEVE-b-P(CTFE-alt-EVE)), where EVE stands for ethyl vinyl ether, via sequential cationic and radical Reversible Addition-Fragmentation chain Transfer (RAFT) polymerizations. Two synthetic pathways were followed and compared: (1) synthesis of a PEVE block by cationic RAFT polymerization from a P(CTFE-alt-EVE) macromolecular Chain Transfer Agent (macroCTA) prepared by radical RAFT copolymerization, and (2) synthesis of a P(CTFE-alt-EVE) block by radical RAFT copolymerization from a PEVE macroCTA prepared by cationic RAFT polymerization. Careful chain-end analysis using H-1 and F-19 NMR spectroscopies revealed that irreversible transfer reactions severely affected the chain-end fidelity of the P(CTFE-alt-EVE) macroCTA. In addition, the penultimate CTFE unit of these macroCTAs seemed to adversely alter the reactivity of the -CH2-CH (OEt)-XA end-group under cationic RAFT conditions. The chain extension of these macroCTAs by cationic RAFT polymerization thus led to poorly defined block copolymers. Nevertheless, both xanthate and dithiocarbamate RAFT agents were shown to provide efficient control over the radical RAFT copolymerization of CTFE and EVE. In contrast, the cationic RAFT polymerization of EVE afforded PEVE macroCTAs with high chain-end fidelity and chain extension reactions resulting in well-defined PEVE-b-P(CTFE-alt-EVE) block copolymers with low dispersities (D < 1.35).
引用
收藏
页码:352 / 361
页数:10
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