Modified polysulfones 5: synthesis and characterization of tetramethyl polysulfones containing trimethylsilyl groups and their gas transport properties

Polysulfones with rigid backbone structures and silyl-containing substituents were prepared as membrane materials with potentially enhanced gas transport properties. Tetramethylbisphenol-A polysulfone (TMPSf) and tetramethylbiphenol polysulfone (TMPPSf) were made by polycondensation then post-modified to introduce trimethylsilyl (TMS) groups by bromination and lithiation methodology. Substitution of high levels of TMS groups at the ortho-sulfone sites was achieved using direct lithiation followed by addition of a trimethylsilane electrophile. In an approach to increase the overall TMS substitution level as well as introduce these groups on the bisphenol segment, both TMPSf and TMPPSf were cleanly brominated to a degree of substitution (DS) of 2.0 for bromine. While the subsequent lithium–halogen exchange and reaction with TMS electrophile did not give high regioselectivity because of steric hindrance, the overall DS of TMS in the polymers was increased when excess n-butyllithium was used to activate both brominated and ortho-sulfone sites. The polymer structures were characterized by NMR spectroscopy. Their thermal properties as well as O2, N2, CO2 and CH4 gas transport properties were measured. Polymers with a high DS of TMS had very high CO2 and O2 permeabilities and good permselectivities from N2. The permselectivities of CO2/N2 were at or close to the Robeson upper-bound performance line [J. Membr. Sci. 62 (1991) 165].