Sorption,diffusion, and partial molar volumes of C4 hydrocarbons in rubbery polymers

Sorption and dilation isotherms and diffusion coefficients for seven hydrocarbons (n-butane, isobutane, 1-butene, cis-2-butene, trans-2-butene, isobutylene, and 1,3-butadiene) in two rubbery polymers, 1,2-polybutadiene (PB) and poly(ethylene-co-vinyl acetate) (EVAc), were measured at 25°C. Dissolution parameters (Henry's law coefficient and Flory-Huggins interaction parameter), partial molar volumes, and diffusion coefficients were determined. PB exhibited greater affinity and lower diffusivity than EVAc to the C₄ gases, although the gases showed nearly the same partial molar volumes in the two polymers. The diffusivity of such elongated molecules as trans-2-butene in both polymers was higher than that of bulky molecules with similar partial molar volume, such as cis-2-butene and isobutylene. Pressure-dependent permeabilities of PB and EVAc films to the hydrocarbons were predicted and discussed based on the dissolution parameters and the diffusivities. © 1995 John Wiley & Sons, Inc.