Abstract
AbstractNovel phenylacetylene (PA) monomers, which have o‐silylmethyl groups of different bulkinesses, i.e., o‐Me3SiCH2PA, o‐Et3SiCH2PA, and o‐t‐BuMe2Si‐CH2PA, polymerized with W and Mo catalysts in high yields. The MoCl5‐Ph4Sn catalyst achieved the highest weight‐average molecular weights (Mw 7 × 105 − 12 × 105), and the Mw increased as the ortho‐substitutent became bulkier (e.g., Mw of o‐t‐BuMe2SiCH2PA: 12 × 105). These monomers polymerized in a living fashion by the MoOCl4‐n‐Bu4Sn‐EtOH catalyst. The resulting polymers were soluble in common solvents such as toluene and chloroform. In the UV‐visible spectra, a tendency was observed that absorption maxima shifted to longer wavelengths as the substituents became bulkier. Membranes of the polymers were fairly permeable to gases (e.g., oxygen permeability coefficients 30‐80 barrers). Though o‐(Me3Si)2CHPA also polymerized with W and Mo catalysts, the product polymer was partly insoluble in any solvent. © 1995 John Wiley & Sons, Inc.
Published Version
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