Organic Brønsted Acid-Catalyzed Stereoselective Cationic RAFT Polymerization:The Effect of RAFT Agents

作     者：Zheng-Yi Zhang Zan Yang Yun Liao Sai-Hu Liao Zheng-Yi Zhang;Zan Yang;Yun Liao;Sai-Hu Liao

作者机构：Key Laboratory of Molecule Synthesis and Function Discovery(Fujian Province University)College of ChemistryFuzhou UniversityFuzhou350108China State Key Laboratory of Physical Chemistry of Solid SurfacesCollege of Chemistry and Chemical EngineeringXiamen UniversityXiamen361005China Beijing National Laboratory for Molecular SciencesBeijing100190China 

出 版 物：《Chinese Journal of Polymer Science》 (高分子科学（英文版）)

年 卷 期：2024年第42卷第6期

页      面：711-717页

核心收录：

学科分类：081705[工学-工业催化] 08[工学] 0817[工学-化学工程与技术] 0805[工学-材料科学与工程（可授工学、理学学位）] 0703[理学-化学] 

基　　金：supported by the Recruitment Program of Global Experts of China,the National Natural Science Foundation of China(Nos.21602028 and 22371240) Beijing National Laboratory for Molecular Sciences(No.BNLMS201913) 100-Talent program of Fujian,Fuzhou University and Xiamen University. 

主　　题：Bronsted acid catalysis Stereoselective cationic polymerization RAFT polymerization Chain transfer agents Tacticity 

摘      要：The tacticity of vinyl polymers is a key factor affecting the properties of materials.Recently,organic Brønsted acids have been demonstrated as effective catalysts for the development of highly stereoselective cationic reversible addition-fragmentation chain transfer(RAFT)polymerizations of vinyl ethers,in which the use of RAFT agents could allow the control the molecular weight and tacticity of polymer products simultaneously.However,the effect of RAFT agents on the tacticity-regulation remains elusive and lacks of investigation.In this study,we synthesized four types of RAFT agents and evaluated their influence in the stereoselective cationic polymerization of isobutyl vinyl ether in the presence of PADI as a Brønsted acid catalyst,which unveils that the Z group of RAFT agents could not only affect the polydispersity of the products,but also exert a profound effect on the stereoselectivity.After extensive screening of the RAFT agents,high stereoregularity(isotacticity,90%m)was obtained when using dithiocarbonate ester-type RAFT agents with a benzyloxy Z group.