Synthesis, geometric structure, and properties of poly(phenylacetylenes) with bulky para-substituents

✍ Scribed by Yoji Fujita; Yoshihiko Misumi; Masayoshi Tabata; Toshio Masuda

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: English
• Weight: 173 KB
• Volume: 36
• Category: Article
• ISSN: 0887-624X
• DOI: 10.1002/(sici)1099-0518(199812)36:17<3157::aid-pola18>3.0.co;2-u

✦ Synopsis

Phenylacetylenes (PAs) with bulky substituents (adamantyl, tert-butyl, and n-butyl groups) at the para-position polymerized in good yields with Fe, Rh, Mo, and W catalysts. The formed polymers were soluble, and their number-average molecular weights were in the range of thousands to hundred thousands. Whereas it is known that the poly(PA) obtained with the Fe catalyst is an insoluble cis-cisoidal polymer, the present polymers formed with the same catalyst were totally soluble in many solvents such as benzene and CHCl 3 . The 1 H-and 13 C-NMR and DSC data revealed that both of the polymers formed with the Fe and Rh catalysts had virtually all-cis structures, while those with the Mo and W catalysts had cis-rich and trans-rich structures, respectively. Cis-cisoidal and cis-transoidal structures of para-substituted poly(PAs) could not be distinguished because of their good solubility. The bulky substituents raised the temperature of cis-trans isomerization and improved the thermal stability of the polymers. Poly( p-t-BuPA) showed gas permeability higher than that of poly(PA).