ポリ（１‐トリメチルシリル‐１‐プロピン）の紫外線照射下および未照射状態での臭素化反応とそれらの膜の気体透過特性

Abstract

Bromination of poly (1-trimethylsilyl-1-propyne) [PMSP] films were performed with and without ultraviolet (UV) irradiation. Bromine atoms were added to carbon-carbon double bonds on the chain backbone of PMSP without UV irradiation. In the case of bromination with UV irradiation, removal of trimethylsilyl groups and oxidation occurred on the UV-irradiated side of the polymer film, while the non-irradiated side had the same structure as that of films brominated without UV irradiation. As bromine content in the polymer increases, the gas permeability decreases. The reduction in gas permeability is dependent on a decrease in gas diffusivity. Unlike conventional glassy polymers, PMSP and brominated PMSP films do not exhibit decreasing gas permeabilities with increasing penetrant size. For example, permeability coefficients of hydrocarbons in these films increase as hydrocarbon penetrant size increases. No difference between the gas permeabilities of irradiated and non-irradiated films is observed. As bromine content increases, the activation energies of permeation (E p) increase because of higher activation energies of diffusion (E D). However, the activation energies of permeation decrease with increasing critical temperature (T c) of the penetrants as a result of a decrease in the heat of solution (ΔH s). No difference between the activation energies of permeation for irradiated and non-irradiated films is observed.