Processing Properties and Thermal Stability of Poly(vinyl chloride-co-vinyl acetate) by Experiments and Molecular Dynamics Simulations

The effects of copolymerized monomer vinyl acetate (VAc) on processing properties and thermal stability of poly(vinyl chloride-co-vinyl acetate) (PVCA) are investigated via experiment and molecular dynamics simulation. Experimental results showed that PVCA with higher VAc content has larger loss tangent (tanδ), lower complex viscosity (η*), and glass transition temperature (Tg), which improved the processing properties of PVCA. A series of PVCA models are constructed to study the microstructure on the processing properties of PVCA, and the results showed the PVCA with higher VAc content exhibits larger molecular chain mobility and free volume fraction (FFV), smaller intermolecular interactions, and the mean square end-to-end distance (<Ree²>). Furthermore, the IR spectra of gas products indicated that thermal degradation of PVCA mainly generated hydrogen chloride (HCl), carboxylic acid, and aliphatic hydrocarbons between 200 and 500 °C, and the removal of HCl and carboxylic acid is almost simultaneous. The degradation models of PVCA chains demonstrated the CCl bond in vinyl chloride (VC) and CO bond in VAc have similar thermal stability, which corresponded to the experimental results. In a word, the work provides a promising technique to study the structure and property of PVCA at molecular dynamic level.