文献类型：期刊文献

英文题名：Organocatalytic binary system enables high-performance alternating poly(propylene carbonate) from CO2 and propylene oxide

作者：Ul Haq, Ijaz[1];Jie, Wang[1];Miao, Shuqin[1];Shen, Weihua[1];Fang, Yunjin[1]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, State Key Lab Chem Engn & Low Carbon Technol, Shanghai, Peoples R China

年份：2026

卷号：334

外文期刊名：CHEMICAL ENGINEERING SCIENCE

收录：;EI(收录号：20262320828937);WOS:【SCI-EXPANDED(收录号:WOS:001785367600001)】；

基金：This work is supported by Zhejiang Zheneng Technology & Envi-ronment Group Co., Ltd.China under Grant [KH-KJ-24-004-W001] .

语种：英文

外文关键词：Poly(propylene carbonate); Sulfate anion; Copolymerization; Carbon dioxide; Sustainable polymer; Density functional theory

摘要：Poly(propylene carbonate) (PPC), a sustainable polymer derived from CO2, has emerged as an attractive alternative to petrochemical-based polyether polyols. Nevertheless, achieving high activity, a perfectly alternating microstructure, narrow dispersity (& Dstrok;), and excellent selectivity simultaneously in PPC synthesis has remained challenging. Herein, a binary catalyst system composed of tetrabutylammonium hydrogen sulfate or tetrabutylphosphonium hydrogen sulfate (TBAHS or TBPHS) in combination with triethylboron (Et3B) is reported. Density functional theory (DFT) calculations revealed that CO2 is initially activated by the hydrogen sulfate anion to generate a carbonate intermediate, which subsequently undergoes nucleophilic attack on propylene oxide (PO) activated by Et3B. Under optimized conditions, the TBPHS/Et3B system delivered a turnover frequency (TOF) of 1051 h-1, an average molecular weight (Mn) of 57.88 kg mol-1, & Dstrok; = 1.67, 99 % selectivity, and perfect alternating PPC. This binary system thus provides a scalable and environmentally benign route to CO2 utilization, establishing a compelling platform for commercial PPC production with high activity, excellent selectivity, and precise alternating microstructural control.