Abstract
This review article surveys the synthesis and properties of substituted polyacetylenes, especially those which exhibit high gas permeability, such as poly [1- (trimethylsilyl) -1-propyne] [poly (TMSP)] and poly (diphenylacetylene) [poly (DPA)] derivatives. Poly (TMSP) having high molecular weight up to around 1 × 106 can be obtained by the metathesis polymerization of TMSP catalyzed by TaCl5 and NbCl5. This polymer is characterized by good solubility in many common solvents, formation of tough films by solution casting, a high glass transition temperature (> 250 °C), and fairthermal stability. Its oxygen permeability (Po2) at 25 °C reaches ca. 6, 000 barrers, which is the highest value of all existing polymers. The gas permeation properties of poly (TMSP) are reviewed. The TaCl5/n-Bu4Sn system is effective for the polymerization of DPAs. Most of the produced polymers are soluble in organic solvents, thermally highly stable, and film-forming by solution casting. Interestingly, large Po2 values (1, 100 barrers) are observed with poly (DPAs) bearing bulky spherical para-substituents. Desilylation of p-Me3Si-containing poly (DPA) membrane yields poly (DPA) membrane, which shows high Po2 of-6, 000 barrers.
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