Macrochain configuration, stucture of free volume and transport properties of poly(1-trimethylsilyl-1-propyne) and poly(1-trimethylgermyl-1-propyne)

Abstract

The relationship between poly(1-trimethylsilyl-1-propyne) (PTMSP) and poly(1-trimethylger- myl-1-propyne) (PTMGP) microstructure, gas permeability and structure of free volume is reported. n-Butane/methane mixed-gas permeation properties of PTMSP and PTMGP membranes with different cis-/trans-composition have been investigated. The n-butane/methane selectivities for mixed gas are by an order higher than the selectivities calculated from pure gas measurements (the mixed-gas n-butane/methane selectivities are 20-40 for PTMSP and 22-35 for PTMGP). Gas permeability and n-butane/methane selec- tivity essentially differ in polymers with different cis-/trans-composition. Positron annihilation lifetime spec- troscopy investigation of PTMSP and PTMGP with different microstructure has determined distinctions in total amount and structure of free volume, i.e. distribution of free volume elements. The correlation between total amount of free volume and gas transport parameters is established: PTMSP and PTMGP with bigger free volume exhibit higher n-butane permeability and mixed-gas n-butane/methane selectivity. Such behav- ior is discussed in relation to the submolecular structure of polymers with different microstructure and sorp- tion of n-butane in polymers with different free volume. © Pleiades Publishing, Ltd., 2012.