ALTERNATING OLEFIN CARBON-MONOXIDE COPOLYMERS AND THEIR DERIVATIVES -PREPARATION AND CHARACTERIZATION BY PYROLYSIS-GAS CHROMATOGRAPHY MASS-SPECTROMETRY (PY-GC MS)/

Alternating copolymers of carbon monooxide and olefins (ethylene, styr enes and norbornadienes) and their modified polymers with primary amin es, P2S5 and P2O5 were prepared. These were then pyrolyzed at 550 degr ees C for 10 s in a Py-GC/MS system. In each pyrolysis, hydrocarbons a rising from the corresponding olefin comonomer were detected as the Vo latile products. Py-GC/MS confirmed that these 1,4-arrangements of the ketonic groups in the alternating copolymers were converted into pyrr ole-, thiophene-, or furan-containing chains with primary amines, P2S5 or P2O5, respectively. The oxygen-containing groups, which remained i ntact during the modification with P2S5, were detected in small amount s in the pyrolysates. While the pyrolysis of poly(dimethyl 7-oxabicycl o[2,2,1]hepta-2,5-diene-2, 3-dicarboxylate) yielded benzene (derived f rom an acetylene triad formed by the retro-Diels Alder reaction), its alternating copolymer with carbon monoxide did not yield benzene upon pyrolysis. (C) 1997 Elsevier Science B.V.