Dynamic Ring-chain Equilibrium of Nucleophilic Thiol-yne "Click" Polyaddition for Recyclable Poly(dithioacetal)s

作     者：Jin-Xia Lei Qi-Yuan Wang Fu-Sheng Du Zi-Chen Li Jin-Xia Lei;Qi-Yuan Wang;Fu-Sheng Du;Zi-Chen Li

作者机构：Beijing National Laboratory for Molecular Sciences(BNLMS)Key Laboratory of Polym.Chem.&Physics of Ministry of EducationDepartment of Polymer Science&EngineeringCollege of Chemistry and Molecular EngineeringCenter for Soft Matter Science and EngineeringPeking UniversityBeijing 100871China 

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

年 卷 期：2021年第39卷第9期

页      面：1146-1154页

核心收录：

学科分类：08[工学] 0805[工学-材料科学与工程（可授工学、理学学位）] 080502[工学-材料学] 

基　　金：This work was financially supported by the National Key Research and Development Program of China(No.2016YFA0201400) the National Natural Science Foundation of China(Nos.21971005 and 21534001) 

主　　题：Poly(dithioacetal)s Nucleophilic thiol-yne"click"polyaddition Chemical recycling Ring-chain equilibrium 

摘      要：We report a dynamic polymerization system based on the reversible nucleophilic Michael polyaddition of activated alkynes and *** poly(dithioacetal)s(P1-P4)were prepared via the base-catalyzed thiol-yneclickpolyaddition of two dithiols(1,4-butanedithiol(4S)and 1,5-pentanedithiol(5S))and two alkynones(3-butyn-2-one(Y1)and 1-phenyl-2-propyn-1-one(Y2))at high *** systematically investigated the base-catalyzed polymerization of 4S and Y1(for polymer PI)under different conditions,and found that this polymerization was a highly concentration-dependent dynamic system:polymer PI was formed at high concentration,while seven-membered dithioacetal,1-(1,3-dithiepan-2-yl)propan-2-one(C1),was obtained at low *** polymerization of 4S and Y2(for polymer P4)displayed similar polymerization behavior,generating 2-(1,3-dithiepan-2-yl)-1-phenylethanone(C4)at low *** the contrary,polymer P2(from Y1 and 5S)was exclusively obtained with no formation of eight-membered *** polymerizations of Y1 with 1,2-ethanedithiol(2S)and 1,3-dimercaptopropane(3S)only afforded corresponding five-and six-membered dithioacetals,1-(1,3-dithiolan-2-yl)propan-2-one(C2)and 1-(1,3-dithian-2-yl)propan-2-one(C3).This dynamic behavior of PI and P4 was attributed to the concentration-dependent retro-Michael addition reaction between a thiol and a β-sulfido-α,β-unsaturated carbonyl compound catalyzed by ***,polymers P1 and P4 could be depolymerized into Cl and C4 in yields of 58% and 95%,*** ring-opening polymerization of Cl at high concentration could successfully regenerate polymer ***,a new type of closed-loop recyclable poly(dithioacetal)s was developed.