文献类型：期刊文献

英文题名：Kinetic modeling of cationic ring-opening polymerization for the synthesis of biodegradable poly(ε-caprolactone)

作者：Fu, Wei-Dong[1];Jiang, Jie[1];Zhang, Yinxu[3];Li, Jin-Jin[1,2];Zhao, Ling[1,2];Xi, Zhenhao[1,2]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Shanghai Key Lab Multiphase Mat Chem Engn, Shanghai 200237, Peoples R China;[3]Hoshine Silicon Ind Co Ltd, Jiaxing 314001, Peoples R China

年份：2024

卷号：290

外文期刊名：CHEMICAL ENGINEERING SCIENCE

收录：;EI(收录号：20240915647583);WOS:【SCI-EXPANDED(收录号:WOS:001197819500001)】；

基金：This work was supported by the National Natural Science Foundation of China (Grant No. 22378116, 21978089) , the Program of Shanghai Rising-Star (Grant No. 22QA1402800) , the Program of Shanghai Aca- demic/Technology Researcher Leader (Grant No. 21XD1433000) , and the Key Research and Development Program of Xinjiang Uygur Auton- omous Region (Grant No. 2022B01030-2) . We also appreciated Prof. Yin-Ning Zhou at Shanghai Jiao Tong University for his constructive guidance in model validation and manuscript revision.

语种：英文

外文关键词：Kinetic modeling; Ring-opening polymerization (ROP); Simulation; Method of moments (MoM); Poly(e-caprolactone); Transesterification reaction

摘要：Ring-opening polymerization (ROP) of e-caprolactone (e-CL) is an efficient way to produce a widely used biodegradable polymer, i.e., poly(e-caprolactone) (PCL). Compared to coordination ROP, ionic ROP receives great attentions in recent years due to mild reaction conditions and well-defined polymer microstructure. To fully exploit the potential of ionic ROP, in this work, a mathematical kinetic model for activated monomer mechanism (AMM) based cationic ROP of e-CL was developed based on method of moments (MoM). Using the developed model, we estimated the values of the kinetic coefficients of monomer activation and monomeric units' protonation reactions. The simulated results are found to be in good agreement with experimental data, as well as the benchmark by kinetic equation. Moreover, the simulations reveal the crucial role of transesterification reaction in molar mass distribution broadening and how the concentrations of acid and alcohol affect the monomer conversion and average molar masses of the polymer. Finally, the model was successfully extended to a newly reported system using trityl tetrafluoroborate (TrBF4) as catalyst, proving the universality of our model. This study provides deeper understanding of the cationic ROP and allows to optimize process conditions to increase the industrial sustainability of PCL-based materials.