Preparation of poly(styrene-b-butyl acrylate-b-styrene) copolymers by single electron transfer-degenerative chain transfer living free radical miniemulsion polymerization

doi:10.11949/j.issn.0438-1157.20171005

Abstract

Abstract:

Iodine-terminated poly(butyl acrylate) (I-PBA-I) was prepared by single electron transfer-degenerative chain transfer (SET-DT) living free radical miniemulsion polymerization initiated by iodoform, catalyzed by sodium hydrosulfite/sodium bicarbonate and emulsified by dodecyl sodium sulfate/hexadecane. I-PBA-I was further employed as a macromolecular initiator to initiate styrene SET-DT seeded miniemulsion polymerization to prepare polystyrene-b-poly(butyl acrylate)-b-polystyrene (PS-b-PBA-b-PS) block copolymers. The structure and properties of PS-b-PBA-b-PS copolymers were characterized. Both butyl acrylate and styrene miniemulsion polymerizations exhibit great polymerization rates, and the dosage of initiator can be decreased, which is favor to preparing PBA and PS-b-PBA-b-PS copolymer with high molecular weights. PS-b-PBA-b-PS copolymers exhibit characteristics of micro-phase separation and thermoplastic elastomer. For PS-b-PBA-b-PS copolymer with PS mass fraction of 50%, the ultimate tensile strength and the elongation at break can reach 9.8 MPa and 660%, respectively.

Key words: polymer, emulsion, synthesis, single electron transfer-degenerative chain transfer, block copolymer

摘要：

以碘仿为引发剂、连二亚硫酸钠/碳酸氢钠为催化体系、十二烷基硫酸钠/十六烷为乳化体系，通过单电子转移-蜕化链转移（SET-DT）活性自由基细乳液聚合合成碘端基化聚丙烯酸丁酯（I-PBA-I），进而以其为大分子引发剂引发苯乙烯聚合，制备聚苯乙烯-b-聚丙烯酸丁酯-b-聚苯乙烯（PS-b-PBA-b-PS）三嵌段共聚物，并进行共聚物结构和性能表征。发现两个阶段的SET-DT细乳液聚合均具有大的反应速率，碘仿引发剂用量少，可获得高分子量PBA和PS-b-PBA-b-PS共聚物。PS-b-PBA-b-PS共聚物具有微相分离和热塑性弹性体特征，PS质量分数为50%的嵌段共聚物的拉伸强度达9.8 MPa，断裂伸长率为660%。

关键词: 聚合物, 乳液, 合成, 单电子转移-蜕化链转移, 嵌段共聚物

CLC Number:

TQ325.3

XU Jinchao, BAO Yongzhong. Preparation of poly(styrene-b-butyl acrylate-b-styrene) copolymers by single electron transfer-degenerative chain transfer living free radical miniemulsion polymerization[J]. CIESC Journal, 2018, 69(2): 840-847.

徐锦超, 包永忠. 单电子转移-蜕化链转移活性自由基细乳液聚合制备PS-b-PBA-b-PS共聚物[J]. 化工学报, 2018, 69(2): 840-847.

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