Copolymerization of carbon monoxide with phenylacetylene by palladium complex

✍ Scribed by Der-Jang Liaw; Biing-Ferng Lay

• Publisher: Elsevier Science
• Year: 1997
• Tongue: English
• Weight: 597 KB
• Volume: 115
• Category: Article
• ISSN: 1381-1169
• DOI: 10.1016/s1381-1169(96)00092-1

✦ Synopsis

Carbon monoxide was copolymerized with phenylacetylene (PA) using initiation by a palladium complex [Pd '(CH ,CN),] (BF,), under various conditions. Good yields were obtained at 90°C in methanol. Elementary analysis, infrared and NMR spectroscopy showed that the copolymers contained ketone and olefinic structures. 2,2'-bipyridine was a more effective stabilizing ligand than monodentate phosphorus, arsenic or nitrogen ligands. The copolymer yield, molar mass and trun.s configuration of the vinylene increased with increasing temperature. Methanol and the protonic acid served as coinitiator and chain-transfer agents. The copolymers have increasingly higher tran~ vinylene structure with the increase of pressure of carbon monoxide. X-ray diffraction analysis shows the copolymer to be partially crystalline. Thermogravimetric analysis showed that the copolymer started to lose mass at 213°C and that maximum decomposition occurred at 390°C. The PA/CO copolymer obtained under the influence of various ligands has a glass transition temperature (T,) in the range 7S-130°C. Hydrogenation of PA/CO copolymer with a reducing agent yielded a hydroxy-containing polymer.