COPOLYMERIZATION OF CARBON-MONOXIDE AND NORBORNADIENE WITH A PALLADIUM CATALYST

Carbon monoxide (CO) and norbornadiene (NBD) with Pd(CH3CN)(4)(BF4)(2) were copolymerized under various conditions at 50 degrees C. Elementa l analysis, infrared spectra, UV, Raman, and NMR spectra showed that t he copolymers contained both ketone and unsaturated ring structures. B identate nitrogen Ligands and phosphorus Ligands proved to be more eff ective at stabilizing catalytic activity than monodentate arsenic Liga nds or phosphorus ligands. Methanol, protic acid, and an oxidant serve d as the coinitiator and chain transfer agent, respectively. X-ray dif fraction analysis showed the copolymer to be partially crystalline. Th ermogravimetric analysis showed that the TG curve for the NBD/CO copol ymer has two stages with two maxima peaks at 251 and 470 degrees C. Th is phenomenon was probably due to increased instability of the copolym ers as CO content is increased. Hydrogenation of norbornadiene/CO copo lymer with LiAlH4 and Pd/C in THF yields a hydroxyl-containing polymer and norbornene/CO copolymer, respectively. (C) 1997 John Wiley & Sons , Inc.