Alternating olefin-carbon monoxide copolymers and their derivatives Preparation and characterization by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS)

摘要

Alternating copolymers of carbon monooxide and olefins (ethylene, styrenes and norbor-nadienes) and their modified polymers with primary amines, P_2S_5 and P_2O_5 were prepared. These were then pyrolyzed at 550℃ for 10 s in a Py-GC/MS system. In each pyrolysis, hydrocarbons arising from the corresponding olefin comonomer were detected as the volatile products. Py-GC/MS confirmed that these 1,4-arrangements of the ketonic groups in the alternating copolymers were converted into pyrrole-, thiophene-, or furan-containing chains with primary amines, P_2S_5 or P_2O_5, respectively. The oxygen-containing groups, which remained intact during the modification with P_2S_5, were detected in small amounts in the pyrolysates. While the pyrolysis of poly(dimethyl 7-oxabicyclo[2,2,1]hepta-2,5-diene-2,3-di-carboxylate) yielded benzene (derived from an acetylene triad formed by the retro-Diels Alder reaction), its alternating copolymer with carbon monoxide did not yield benzene upon pyrolysis.