Facile Synthesis of Polycarbonate Diol via Copolymerization of CO_(2) and Cyclohexene Oxide Catalysed by a Combination of One-Component Phosphonium Borane Lewis Pair and Water  

作　　者：Xiao-Wu Wang Ji-Wen Hui Yu-Tao Li Yan-Ru Gu Zhi-Bo Li 

机构地区：[1]State Key Laboratory Base of Eco-Chemical Engineering/College of Chemical Engineering,Qingdao University of Science and Technology,Qingdao 266042,China [2]Key Laboratory of Biobased Polymer Materials,Shandong Provincial Education Department/School of Polymer Science and Engineering,Qingdao University of Science and Technology,Qingdao 266042,China

出　　处：《Chinese Journal of Polymer Science》2023年第5期735-744,I0009,共11页高分子科学（英文版）

基　　金：financially supported by the National Key R&D Program of China(No.2021YFA1501600);the National Natural Science Foundation of China(Nos.22175105 and 22031005)。

摘　　要：Well-defined polycarbonate diol was successfully synthesized through a strategy using a combination of organocatalyst and water.Such strategy was less developed in organocatalyzed polymerization and frequently regarded as side reactions.Herein,one-component phosphonium borane Lewis pairs PB1-PB8 were successfully applied in the copolymerization of CO_(2) and cyclohexene oxide(CHO)to generate poly(CHO-alt-CO_(2))carbonate(PCHC).Parameters of linker length and counter anion effects on the catalyst activity were investigated.It was found that Lewis pair PB3 served as a dual initiator and catalyst in the copolymerization of CHO and CO_(2) with or without the presence of water.In contrast,Lewis pair PB8 can serve as a true catalyst for the preparation of well-definedα,ω-hydroxyl PCHC diols.This was achieved by introducing a labile CF3COO group as counter anion through anion exchange reaction while water molecules acted as chain transfer agents.The function of trifluoroacetate group in the polymerization process was investigated in detail and possible mechanism was proposed.Upon changing the amount of water and catalyst loading,PCHC diols with varied molecular weight(1.5 kg/mol to 7.5 kg/mol),low dispersities(D<1.2)and carbonate content(>99%)could be easily obtained.The low molecular weight PCHC diol was used as a bifunctional macroinitiator for the ring-opening polymerization of L-lactide(LLA)to afford ABA triblock copolymer in one-pot synthesis.

关 键 词：Polycarbonate Phosphonium borane Lewis pair CO_(2)utilization Organocatalysis Ring-opening polymerization 

分 类 号：O631.5[理学—高分子化学]