文献类型：期刊文献

英文题名：A combined computational and experimental study on the tetrabutylammonium bromide supported organometallic/triethylboron catalytic system for the copolymerization of carbon dioxide and propylene oxide

作者：Ul Haq, Ijaz[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：19

期号：8

外文期刊名：ARABIAN JOURNAL OF CHEMISTRY

收录：;WOS:【SCI-EXPANDED(收录号:WOS:001856123600001)】；

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

语种：英文

外文关键词：Alkali metals; Carbon dioxide; Polypropylene carbonate; Propylene oxide; Triethylboron

摘要：The ring opening copolymerization (ROCOP) of propylene oxide (PO) and carbon dioxide (CO2) provides a sustainable route to poly (propylene carbonate) (PPC); however, achieving high catalytic activity, selectivity, and fully alternating copolymer remains a significant challenge in ROCOP. Herein, a ternary catalytic system, [(MOtBu/TBAB) Et3B], is reported, in which metal tert-butoxide (MOtBu), tetrabutylammonium bromide (TBAB), and triethylboron (Et3B) act synergistically to enhance catalytic performance. Density functional theory (DFT) calculations reveal that CO2 is activated via dual interactions with metal cation (M+) and tert-butoxide anion (OtBu-), while Et3B promotes PO activation. These cooperative effects polarize the monomers and substantially lower the kinetic barriers for both PO ring opening and CO2 insertion. Furthermore, TBAB functions as a phase-transfer agent and enhances CO2 solubility in the reaction medium. Experimentally, this ternary system enables highly alternating copolymerization, delivering PPC with 99% selectivity, high average molecular weight (Mn = 47.72 kg mol-1), narrow dispersity (& Dstrok; = 1.03) and turnover frequency (TOF) = 90.6 h-1. Notably, the KOtBu-based catalyst exhibits superior performance compared to its NaOtBu analogue. Overall, this work advances mechanistic understanding while establishing an efficient and selective catalytic platform for the sustainable production of PPC.