Synthesis and gas permeation properties of various Si-containing poly(diarylacetylene)s and their desilylated membranes

Diarylacetylene monomers having trimethylsilyl groups and other substituents (substituted biphenyl, 1a and 1b; trimethylsilylmethylphenyl, 1c–e) were synthesized and polymerized with TaCl5-n-Bu4Sn catalyst to produce the corresponding poly(diarylacetylene)s (2a–d). Polymers 2a–c had high molecular weights and were soluble in common organic solvents. Free-standing membranes of 2a–c as well as previously reported 2f–h were prepared by the solution-casting method. Desilylation of these Si-containing polymer membranes was carried out with trifluoroacetic acid to afford 3a, 3b, and 3f–h. Upon desilylation, biphenyl-containing membranes became less permeable (3a, b), whereas fluorene-containing membranes became more permeable (3f–h). In particular, 3h exhibited extremely high gas permeability (PO2 = 9800 barrers), which is about the same as that of poly(1-trimethylsilyl-1-propyne). Desilylated membranes 3a and 3f–h showed different gas permeability from that of polymers 2i–k which have the identical chemical structures and obtained directly by the polymerization of the corresponding monomers.