Structure and Properties of Poly(1-trimethylsilyl-1-propyne) Synthesized Using NbF 5 - and TaF 5 -Containing Catalytic Systems

The polymerization of 1-trimethylsilyl-1-propyne mediated by catalytic systems based on Nb and Ta pentafluorides is carried out. Using solid-state 13С NMR spectroscopy, it is shown that the catalysts based on group V metal fluorides possess a well-defined trans-stereoregulating ability and produce trans-enriched polymers compared with analogous samples synthesized using Nb and Ta chlorides and bromides since they have a smaller ligand at the active center of the growing chain. A high trans-stereoregularity of poly(1-trimethylsilyl-1-propyne) is responsible for its insolubility in organic solvents. As evidenced by low-temperature argon sorption, all the synthesized polymers have high BET specific surface area (above 600 m2/g) and micropore volume (above 0.30–0.45 cm3/g). In combination with resistance against organic compounds, this makes them attractive materials for use as fillers of composite membranes and sorbents for the sorption of gases and vapors of organic compounds from streams of commercial mixtures of various composition.