The ring-opening polymerization of cyclic ester and carbonate catalyzed by trimethyl glycine and catalyst design: A DFT study

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis Pub Date : 2025-03-22 DOI:10.1016/j.mcat.2025.115050

Shuang Li , Xiaowei Xu , Ziqiang Li , Lijuan Ding , Ying Peng , Xiaohui Kang , Yi Luo

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引用次数: 0

Abstract

Organic catalytic ring-opening polymerization (ROP) of cyclic esters and carbonates is an effective strategy for obtaining biodegradable and biocompatible aliphatic polyesters and polycarbonates. The challenge is to develop highly active and green organocatalysts in this domain. Herein, the zwitterionic carboxybetaine catalyzed the ROP mechanism of trimethylene carbonate (TMC) cyclic ester and lactide (LA) was investigated by density functional theory (DFT). By comparing the ROP of TMC catalyzed by natural trimethyl glycine (TMG) and unnatural tetramethylammonium acetate (TMAA), we found the proton-accepting ability of the anion part in zwitterionic carboxybetaine is the main influencing factor of polymerization activity. Based on this finding, it is proposed to enhance the proton-accepting ability of the anion part in TMG by extending carbon spacer lengths between CH₃COO^‒ and N(CH₃)₄⁺ of TMG. Among them zwitterionic carboxybetaine molecules ((CH₃)₃N⁺(CH₂)_nCOO^‒ (n = 1–5)), the (CH₃)₃N⁺(CH₂)₄COO^‒ shows the highest catalytic activity in the ROP of TMC. Moreover, the ROP of LA catalyzed by (CH₃)₃N⁺(CH₂)₄COO^‒ showed very high catalytic activity compared to the TMG in both theoretical calculation and experiment. This work will inspire the future development of natural organocatalysts with high catalytic performance.

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来源期刊

Molecular Catalysis Chemical Engineering-Process Chemistry and Technology

CiteScore

6.90

自引率

10.90%

发文量

700

审稿时长

40 days

期刊介绍： Molecular Catalysis publishes full papers that are original, rigorous, and scholarly contributions examining the molecular and atomic aspects of catalytic activation and reaction mechanisms. The fields covered are: Heterogeneous catalysis including immobilized molecular catalysts Homogeneous catalysis including organocatalysis, organometallic catalysis and biocatalysis Photo- and electrochemistry Theoretical aspects of catalysis analyzed by computational methods