双烯类聚合物的热分析——Ⅲ.铁与其它催化体系聚1,2-丁二烯及其衍生物的热分析

<正> 由不同催化体系制得的聚1,2-丁二烯,由于其立体规整性(如等规、间规和无规)不同,其形态、热学性质也会有所不同。关于它们的热学性质文献报道不多。我们曾报道,由三乙酰基丙酮钴-三异丁基铝-二硫化碳催化体系制备的间规聚1,2-丁二烯是晶态的;而由正丁基锂和MoCl_4OR-(i-Bu),AlOR′制得的是无规聚1,2-丁二烯;是非晶态

THERMAL ANALYSIS OF POLYDIENES——Ⅲ. Thermal Analysis of Poly-1,2-Butadiene and Its Derivative Polymerized by FeCl_3-(i-C_4H_9)_3Al-Phen and Other Catalyst System

The poly-1,2-butadiene prepared with FeCl3-(i-C4H2)3Al-phen catalyst system (Fe-), as with MoCl4OR-(i-Bu)2AlOR' system (Mo-), is also amorphous. For different 1,2-unit content poly-l,2-butadienes, both thermo-oxidative exothermic peak-temperatures on dynamic DSC curves and induction times determined from constant temperature experiments increase with increasing 1,2-unit contents.The exothermic peak disappears for the sample hydrogenated high cis-l,4-polybutadiene, but an endothermic peak at -120℃ appears, corresponding to the melting point of PE.The thermo-cross-linking exothermic peak temperatures of poly-1,2-butadienes decreased with increasing vinyl group content in macromolecule.The peak areas on DSC curves of samples poly-1,2-butadiene after hydrosilylation with (CH3)3SiH in nitrogen atmosphere were decreased.The apparent thermo-oxidative activation energies for polymers prepared by Fe- and Mo-catalyst system are 88-93, 99-105kJ mol-1 respectively, and their thermo-cross-linking activation energies are 164-185 kJ mol-1. These results show that thermo- and thermo-oxidative stabilities of these polymers prepared with different catalyst system are similar.