文献类型：期刊文献

英文题名：Evaluation of CO2-Philicity of Poly(vinyl acetate) and Poly(vinyl acetate-alt-maleate) Copolymers through Molecular Modeling and Dissolution Behavior Measurement

作者：Hu, Dongdong[1];Sun, Shaojun[1];Yuan, Peiqing[1];Zhao, Ling[1];Liu, Tao[1]

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

年份：2015

卷号：119

期号：7

起止页码：3194

外文期刊名：JOURNAL OF PHYSICAL CHEMISTRY B

收录：;EI(收录号：20150900573593);WOS:【SCI-EXPANDED(收录号:WOS:000349942300041)】；

基金：The authors are grateful to the National Science Foundation of China (21376087), the 111 Project (B08021), and the Fundamental Research Funds for the Central Universities. Prof. Liu H. L. and Prof. Sun W. Z., East China University of Science and Technology, are thanked for having a useful discussion with us on the manuscript.

语种：英文

外文关键词：Dissolution - Free radicals - Molecular dynamics - Distribution functions - Free radical polymerization - Molecular modeling - Dimers - Polyvinyl acetates

摘要：Multiscale molecular modeling and dissolution behavior measurement were both used to evaluate the factors conclusive on the CO2-philicity of poly(vinyl acetate) (PVAc) homopolymer and poly(vinyl acetate-alt-maleate) copolymers. The ab initio calculated interaction energies of the candidate CO2-philic molecule models with CO2, including vinyl acetate dimer (VAc), dimethyl maleate (DMM), diethyl maleate (DEM), and dibutyl maleate (DBM), showed that VAc was the most CO2-philc segment. However, the cohesive energy density, solubility parameter, FloryHuggins parameter, and radial distribution functions calculated by using the molecular dynamics simulations for the four polymer and polymer-CO2 systems indicated that poly(VAc-alt-DBM) had the most CO2-philicity. The corresponding polymers were synthesized by using free radical polymerization. The measurement of cloud point pressures of the four polymers in CO2 also demonstrated that poly(VAc-alt-DBM) had the most CO2-philicity. Although copolymerization of maleate, such as DEM or DBM, with PVAc reduced the polymer-CO2 interactions, the weakened polymer-polymer interaction increased the CO2-philicity of the copolymers. The polymer-polymer interaction had a significant influence on the CO2-philicity of the polymer. Reduction of the polymer-polymer interaction might be a promising strategy to prepare the high CO2-philic polymers on the premise that the strong polymer-CO2 interaction could be maintained.