Macrocyclic Allylic Sulfone as a Universal Comonomer in Organocatalyzed Photocontrolled Radical Copolymerization with Vinyl Monomers
Macrocyclic Allylic Sulfone as a Universal Comonomer in Organocatalyzed Photocontrolled Radical Copolymerization with Vinyl Monomers
复制标题
DOI：
10.1021/acs.macromol.2c02025
复制
发表时间：
2023-01
期刊：
影响因子：
5.5
通讯作者：
Wenqi Wang;B. Rondon;Zeyu Wang;Junpeng Wang;Jia Niu
中科院分区：
文献类型：
--
作者：
Wenqi Wang;B. Rondon;Zeyu Wang;Junpeng Wang;Jia Niu
乙烯基单体和环状单体的自由基共聚是制备可降解乙烯基塑料的通用方法。尽管最近取得了进展，但一类与各种类型的乙烯基单体具有广泛反应性的“通用”环状单体仍然难以捉摸。本文报道了大环烯丙基砜与丙烯酸酯、丙烯酰胺、苯乙烯和甲基丙烯酸酯等乙烯基单体进行有机催化光控自由基开环级联共聚的一般方法。曙红Y催化下可见光照射下，大环烯丙基砜和丙烯酸类单体的共聚反应显示出接近统一的共聚单体的竞聚率通过拟合的共聚物组成的Beckingham-Sanoya-Lynd集成模型。大环烯丙基砜还成功地与苯乙烯（r1= 3.02和rSt = 0.35）或甲基丙烯酸甲酯（r1= 0.18和rMMA = 5.81）共聚生成可降解的聚苯乙烯和聚甲基丙烯酸甲酯。这些可降解的乙烯基共聚物表现出可调的热性能与可降解的主链二酯基序的掺入。大环烯丙基砜在有机催化的光控rROCCP中表现出的前所未有的反应性为具有各种结构和功能的广泛的可降解乙烯基塑料提供了一种通用方法。
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 andrSt= 0.35) or methyl methacrylate (r1= 0.18 andrMMA= 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.