Molecular Simulation and Experimental Study of Substituted Polyacetylenes: Fractional Free Volume, Cavity Size Distributions and Diffusion Coefficients

摘要: Glassy, disubstituted acetylene-based polymers exhibit extremely high gas permeabilities and vapor/gas selectivities, which is quite unusual for conventional glassy such as polysulfone. Diffusion coefficients of poly[1-phenyl-2-[p-(trimethylsilyl)phenyl]acetylene] (PTMSDPA) poly[diphenylacetylene] (PDPA) were obtained using both molecular simulation experimental techniques. PTMSDPA, a polymer, exhibits higher diffusivity than its desilylated analogue, PDPA. Simulation results are in good agreement with data. Cavity size (free volume) distributions also an energetic-based algorithm (in't Veld et al., J. Phys. Chem. B 2000, 104, 12028) developed recently. Larger cavities PTMSDPA contribute to diffusivity, permeability.