文献类型：期刊文献

英文题名：Mechanism Study on Synthesis of Biobased Polycarbonate from Diphenyl Carbonate and Isosorbide with Metal-Free Catalysts by Identifying Reactivity of endo-OH and exo-OH

作者：Shen, Junyao[1];Gao, Xinyi[1];Guo, Wenze[1];Jiang, Jie[1];Li, Jin-Jin[1];Zhao, Ling[1];Xi, Zhenhao[1];Yuan, Weikang[1]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China

年份：2024

卷号：12

期号：12

起止页码：5036

外文期刊名：ACS SUSTAINABLE CHEMISTRY & ENGINEERING

收录：;EI(收录号：20241215757270);WOS:【SCI-EXPANDED(收录号:WOS:001185395400001)】；

基金：This work was financially supported by the National Natural Science Foundation of China (Grant No. 21978089), the National Natural Science Foundation of China (Grant No. 22278129), the Program of Shanghai Academic/Technology Research Leader (Grant No. 21XD1433000), and Key Research and Development Program of Xinjiang Uygur Autonomous Region (Grant No. 2022B01032-1).

语种：英文

外文关键词：density functionaltheory; poly(isosorbide carbonate); quaternary ammonium; mechanism; metal-freecatalyst

摘要：Isosorbide (ISB), a promising biobased monomer with two asymmetric hydroxyl groups, however, exhibits an unsatisfying reactivity in the poly(isosorbide carbonate) (PIC) synthesis with metal-free catalysts. In this work, we employed density functional theory (DFT) calculations to address the existing disputes surrounding the catalytic mechanisms, focusing on two potential reaction pathways catalyzed by tetraethylammonium hydroxide ([TEA][OH]). Energy profiles reveal that the synergistic catalytic mechanism represents the energetically favorable route for the PIC synthesis. Meanwhile, calculations disclose the quaternary ammonium base as the catalyst precursor with tetraethylammonium phenol ([TEA][Ph]) acting as the effective catalyst in the catalytic cycle. Seeking enhanced catalytic efficiency, cation modification of the quaternary ammonium base was conducted, and hexadecyl trimethylammonium hydroxide ([HTMA][OH]) exhibits exceptional performance with low energy barriers of 29.1 and 30.0 kcal/mol for exo-OH and endo-OH, respectively. This aligns with kinetic experiments, emphasizing the superior catalytic efficiency of [HTMA][OH]. The proposed mechanism model enables accurate predictions of the terminal hydroxyl group distribution. A thorough examination of steric hindrance and electronic effect impact on reaction pathway and catalytic efficiency during transesterification for PIC offers significant insights for efficient catalyst design not only for biobased polyester synthesis but also for the chemical recycling strategy of wasted ones.