共单体
共聚物
高分子化学
单体
烯丙基重排
砜
甲基丙烯酸甲酯
苯乙烯
聚苯乙烯
甲基丙烯酸酯
化学
材料科学
有机化学
聚合物
催化作用
作者
Wenqi Wang,Brayan Rondon,Zeyu Wang,Junpeng Wang,Jia Niu
标识
DOI:10.1021/acs.macromol.2c02025
摘要
Radical copolymerization of vinyl monomers and cyclic monomers is a versatile approach to degradable vinyl plastics. Despite recent advances, a class of “universal” cyclic monomers that possess broad reactivities with various types of vinyl monomers remains elusive. Herein, we report a general method for the organocatalyzed photocontrolled radical ring-opening cascade copolymerization (rROCCP) of macrocyclic allylic sulfone and various types of vinyl monomers, including acrylates, acrylamides, styrene, and methacrylate. Catalyzed by Eosin Y under visible light irradiation, the copolymerization of macrocyclic allylic sulfone and acrylic monomers displayed near unity comonomer reactivity ratios by fitting the copolymer composition to the Beckingham–Sanoya–Lynd integrated model. Macrocyclic allylic sulfone was also successfully copolymerized with styrene (r1 = 3.02 and rSt = 0.35) or methyl methacrylate (r1 = 0.18 and rMMA = 5.81) to generate degradable polystyrene and poly(methyl methacrylate). These degradable vinyl copolymers exhibited tunable thermal properties correlated with the incorporation of the degradable main-chain diester motif. The unprecedented reactivities that macrocyclic allylic sulfone demonstrated in the organocatalyzed photocontrolled rROCCP provide a general approach to the wide range of degradable vinyl plastics with various structures and functions.
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