| Abstract: | Thermal cis-trans isomerization and decomposition of polyacetylene film prepared with a Ti(OC4H9)4–Al(C2H5)3 (Al/Ti = 4) system were investigated under inert gas or in vacuum by means of thermal analysis and infrared spectroscopy. Thermograms of differential thermal analysis of cis-polyacetylene revealed the existence of two exothermic peaks at 145 and 325°C and one endothermic peak at 420°C which were assigned to cis-trans isomerization, hydrogen migration accompanied with crosslinking reaction, and thermal decomposition, respectively. The isomerization was followed by infrared spectroscopy over the temperature range 75–115°C. The reaction did not obey simple kinetics. The apparent activation energy for the cis-trans isomerization was 17.0 kcal/mole for the polymer containing 88% cis configuration and increased with increasing trans content up to 38.8 kcal/mole for 80% trans content. |
