Study on the Mechanism of a Side Coupling Reaction during the Living Anionic Copolymerization of Styrene and 1-(Ethoxydimethylsilyphenyl)-1-phenylethylene (DPE-SiOEt)

Pibo Liu; Hongwei Ma; Heyu Shen; Li Han; Shuang Chang; Long Zang; Yiyu Bian; Yu Bai; Yang Li

doi:10.3390/polym9050171

Study on the Mechanism of a Side Coupling Reaction during the Living Anionic Copolymerization of Styrene and 1-(Ethoxydimethylsilyphenyl)-1-phenylethylene (DPE-SiOEt)

Polymers (Basel). 2017 May 11;9(5):171. doi: 10.3390/polym9050171.

Authors

Pibo Liu¹, Hongwei Ma², Heyu Shen³, Li Han⁴, Shuang Chang⁵, Long Zang⁶, Yiyu Bian⁷, Yu Bai⁸, Yang Li⁹

Affiliations

¹ State Key Laboratory of Fine Chemicals, Liaoning Key Laboratory of Polymer Science and Engineering, Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China. ipoy@mail.dlut.edu.cn.
² State Key Laboratory of Fine Chemicals, Liaoning Key Laboratory of Polymer Science and Engineering, Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China. mahw@dlut.edu.cn.
³ State Key Laboratory of Fine Chemicals, Liaoning Key Laboratory of Polymer Science and Engineering, Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China. shy920218@mail.dlut.edu.cn.
⁴ State Key Laboratory of Fine Chemicals, Liaoning Key Laboratory of Polymer Science and Engineering, Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China. lili88882008@126.com.
⁵ State Key Laboratory of Fine Chemicals, Liaoning Key Laboratory of Polymer Science and Engineering, Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China. dlmuchang@163.com.
⁶ State Key Laboratory of Fine Chemicals, Liaoning Key Laboratory of Polymer Science and Engineering, Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China. 201549043@mail.dlut.edu.cn.
⁷ State Key Laboratory of Fine Chemicals, Liaoning Key Laboratory of Polymer Science and Engineering, Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China. 201449053@mail.dlut.edu.cn.
⁸ State Key Laboratory of Fine Chemicals, Liaoning Key Laboratory of Polymer Science and Engineering, Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China. 201549024@mail.dlut.edu.cn.
⁹ State Key Laboratory of Fine Chemicals, Liaoning Key Laboratory of Polymer Science and Engineering, Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China. liyang@dlut.edu.cn.

Abstract

A 1,1-diphenylethylene (DPE) derivative with an alkoxysilyl group (DPE-SiOEt) was synthesized. It was end-capped with poly(styryl)lithium (PSLi) and then copolymerized with styrene via living anionic polymerization (LAP) in a non-polar solvent at room temperature. The observed side coupling reaction was carefully investigated by end-capping the polymer. Changes in molecular weight support the plausibility of a mechanism involving living anionic species (PSLi or lithiated DPE-end-capped polystyrene, PSDLi) and the alkoxysilyl groups. Through a series of copolymerizations with different feed ratios, the kinetics of the side coupling reaction were also studied. The results showed that the side reactions could be controlled using an excess feed of DPE-SiOEt, a potentially useful strategy for the synthesis and application of well-defined alkoxysilyl-functionalized polymers via LAP.

Keywords: 1,1-Diphenylethylene-SiOEt; functionalized polymers; living anionic polymerization; side reaction.

Abstract

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