文献类型：期刊文献

英文题名：A green catalytic pathway to sustainable poly(propylene carbonate) production: potassium phenyl thiolate/triethylboron mediated copolymerization of CO2 and propylene oxide

作者：Haq, Ijaz Ul[1];Liu, Shiyu[1];Jie, Wang[1];Ali, Nawab[2];Shen, Weihua[1];Fang, Yunjin[1]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, State Key Lab Chem Engn, Shanghai, Peoples R China;[2]East China Univ Sci & Technol, Shanghai Key Lab Funct Mat Chem, Shanghai, Peoples R China

年份：2026

卷号：50

期号：4

起止页码：2023

外文期刊名：NEW JOURNAL OF CHEMISTRY

收录：;EI(收录号：20260319914639);WOS:【SCI-EXPANDED(收录号:WOS:001662198800001)】；

基金：This work was supported by Zhejiang Zheneng Technology & Environment Group Co., Ltd. under grant KH-KJ-24-004-W001. We are particularly indebted to our industrial collaborators, Xiaojiong Wu, Delong Ding, Chunliang Ge, and Yi Yang, for their step-by-step guidance, for generously sharing their practical expertise, and for their steadfast encouragement, which were instrumental in scaling up the production of PPC to an industrial level.

语种：英文

外文关键词：Carbon dioxide - Carbonation - Catalyst selectivity - Copolymerization - Density functional theory - Potassium

摘要：The ring-opening copolymerization (ROCOP) of propylene oxide (PO) and CO2 offers a practical and sustainable approach for producing poly(propylene carbonate) (PPC). However, when this copolymerization is mediated by heavy-metal catalysts, the process often suffers from limited CO2 incorporation, undesirable formation of polyether linkages, and poor selectivity toward PPC. To overcome these limitations, we introduce a potassium phenyl thiolate/triethylborane (PhSK/Et3B) catalytic system that enables highly selective production of strictly alternating PPC while completely suppressing polyether formation. Mechanistic studies supported by density functional theory (DFT) reveal that the catalyst operates through a cooperative pathway: PhSK initially captures CO2 to generate a phenyl carbonate nucleophile, which subsequently attacks Et3B-activated PO. This synergistic polarization significantly lowers the kinetic barriers for both PO ring-opening and CO2 insertion, thereby facilitating efficient alternating copolymerization. A systematic investigation further highlights the strong interplay among CO2 pressure, temperature, and catalyst loading in governing polymer growth. Under optimized conditions, this approach yields high average molecular weight PPC (Mn = 40.33 kg mol-1) with narrow dispersity (& Dstrok; = 1.04), excellent selectivity (99%), and complete suppression of polyether linkages. Overall, the PhSK/Et3B system provides a scalable and environmentally benign platform for CO2 utilization, advancing the development of high-performance polycarbonate materials.