title: Evaluation of CO2-philicity of poly(vinyl acetate) and poly(vinyl acetate-alt-maleate) copolymers through molecular modeling and dissolution behavior measurement.
abstract: 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, Flory-Huggins 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.
authors.affiliation: State Key Laboratory of Chemical Engineering, East China University of Science and Technology , Shanghai 200237, People's Republic of China.
authors.forename: Dongdong
authors.initials: D
authors.lastname: Hu
authors.forename: Shaojun
authors.initials: S
authors.lastname: Sun
authors.forename: Peiqing
authors.initials: P
authors.lastname: Yuan
authors.forename: Ling
authors.initials: L
authors.lastname: Zhao
authors.forename: Tao
authors.initials: T
authors.lastname: Liu