Chemoselective and Living/Controlled Polymerization of Alkenyl Methacrylates by the Phosphonium Ylide/Organoaluminum Lewis Pairs  

作　　者：Zhi-Kang Chen Wu-Chao Zhao Yi-Ling Zhao Cong-Lei Liu Liu-Yin Jiang Yue-Tao Zhang Hong-Ping Zhu 

机构地区：[1]State Key Laboratory of Physical Chemistry of Solid Surfaces,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen,361005,China [2]State Key Laboratory of Supramolecular Structure and Materials,College of Chemistry,Jilin University,Changchun,130012,China

出　　处：《Chinese Journal of Polymer Science》2024年第2期159-167,I0005,共10页高分子科学（英文版）

基　　金：financially supported by the National Natural Science Foundation of China (Nos. 21972112 and 22225104);China Postdoctoral Science Foundation (Nos. 2022TQ0115 and 2022M711297)。

摘　　要：Chemoselective,living/controlled polymerizations of allyl methacrylate(AMA) and vinyl methacrylate(VMA) with/without methyl methacrylate(MMA) by using the phosphonium ylide/organoaluminum based Lewis pairs(LPs) have been realized.The P-ylide-2/AIMe(BHT)_(2)(Pylide-2=Ph_(3)P=CHMe and BHT=2,6-iBu_(2)-4-MeC_(6)H_(2)O) was demonstrated to be superior by which homopolymers PAMAs(M_(n)=27.6-111.5kg/mol and ■=1.14-1.25) and PVMAs(M_(n)=28.4-78.4 kg/mol and ■=1.12-1.18) and block copolymers PMMA-b-PAMA,PAMA-b-PVMA,PAMA-bPMMA,PMMA-b-PAMA-b-PMMA,PAMA-b-PMMA-b-PAMA,and PAMA-b-PVMA-b-PAMA were synthesized.In the polymerizations,all of the monomers were reacted by the conjugated ester vinyl groups leaving intactly the nonconjugated acryloxy groups.The pendant acryloxy groups attached to the main chain enable further to post-functionalization by the AIBN-induced radical "thiol-ene" reaction using PhCH_(2)SH.The thiolether side group-containing polymers PAMA-SCH_(2)Ph and PAMA-SCH_(2)Ph-b-PMMA-b-PAMA-SCH_(2)Ph were thus prepared.

关 键 词：Phosphonium ylide Alkenyl methacrylate CHEMOSELECTIVITY Living/controlled polymerization Post-functionalization 

分 类 号：O631.5[理学—高分子化学]