Chemoselective Polymerization of Fully Biorenewableα-Methylene-γ-Butyrolactone Using Organophosphazene/Urea Binary Catalysts Toward Sustainable Polyesters  

作　　者：Yong Shen Wei Xiong Yongzheng Li Zhichao Zhao Hua Lu Zhibo 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 [2]Key Laboratory of Biobased Polymer Materials,Shandong Provincial Education Department,College of Polymer Science and Engineering,Qingdao University of Science and Technology,Qingdao 266042 [3]Beijing National Laboratory for Molecular Sciences,Center for Soft Matter Science and Engineering,Key Laboratory of Polymer Chemistry and Physics of Ministry of Education,College of Chemistry and Molecular Engineering,Peking University,Beijing 100871

出　　处：《CCS Chemistry》2021年第1期620-630,共11页中国化学会会刊（英文）

基　　金：This research was made possible as a result of generous grants from National Natural Science Foundation of China(no.21801151);Shandong Provincial Natural Science Foundation,China(ZR2018BEM029);the 111 Project(no.D17004);the Taishan Scholars Constructive Engineering Foundation(no.tsqn20161031).

摘　　要：Despite the great potential of biorenewableα-methylene-γ-butyrolactone(MBL)to produce functional,recyclable polyester,the ring-opening polymerization(ROP)of MBL remains a challenge due to the competing polymerization of the highly reactive exocyclic double bond and low-strained five-membered ring.In this contribution,we present the first organocatalytic chemoselective ROP of MBL to exclusively produce functional unsaturated polyester by utilizing a phosphazene base/urea binary catalyst.We show that delicate chemoselectivity can be realized by controlling the temperature and using selected urea catalysts.The obtained polyester can be completely recycled back to its monomer by chemolysis under mild conditions.Experimental and theoretical calculations provide mechanistic insights and indicate that the ROP pathway is kinetically favored by using urea with stronger acidity at low temperatures.

关 键 词：ORGANOCATALYST ring-opening polymerization polyester sustainable polymer RECYCLABILITY 

分 类 号：O62[理学—有机化学]