Stride Strategy to Enable a Quasi-ergodic Search of Reaction Pathways Demonstrated by Ring-opening Polymerization of Cyclic Esters

作     者：Wei-Han Rao Lin Yu Jian-Dong Ding Wei-Han Rao;Lin Yu;Jian-Dong Ding

作者机构：State Key Laboratory of Molecular Engineering of PolymersDepartment of Macromolecular ScienceFudan UniversityShanghai 200438China 

出 版 物：《Chinese Journal of Polymer Science》 (高分子科学（英文版）)

年 卷 期：2023年第41卷第5期

页      面：745-759,I0009页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070305[理学-高分子化学与物理] 080501[工学-材料物理与化学] 0805[工学-材料科学与工程（可授工学、理学学位）] 0703[理学-化学] 

基　　金：financially supported by the National Natural Science Foundation of China(No.52130302) 

主　　题：Coordination-insertion mechanism Ring-opening polymerization Density functional theory Biodegradable polymer Lactide Lactone Cyclic ester 

摘      要：Coordination-insertion ring-opening polymerization(ROP)of cyclic esters is an industrial way to synthesize polyesters,which are widely applied in biomedical and environment-benign ***,the rate-determining transition state(TS)identified by the conventional reaction pathways(pathway A and pathway B)presented in the literature did not well describe the structure-reactivity *** misidentification of the rate-determining TS might arise from the less ergodicity in the search of reaction ***,we suggested a stride strategy based on the insight that even a partial double bond is rotatable at the catalysis *** a result,we revealed a new reaction pathway,pathway C with a torsion transition state TSC2,by density functional theory(DFT).We also carried out kinetic experiments of ROP of D-lactide(D-LA),L-lactide(L-LA),ε-caprolactone(CL),andδ-valerolactone(VL),using poly(ethylene glycol)as the initiator and stannous octoate as the *** excellent linearity between the calculated free energy barriers and logarithms of the experimental kinetic constants of the two kinds of lactide and lactone monomers,was established,validating the quasi-ergodic search of reaction pathways and the scaling predicted by transition state *** linearity was highly predictive for the other lactide and lactone monomers,demonstrated by glycolide(GA)and trimethylene urethane(TU).