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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

THERMAL ANALYSIS OF POLYDIENES——Ⅲ. Thermal Analysis of Poly-1,2-Butadiene and Its Derivative Polymerized by FeCl3-(i-C4H93Al-Phen and Other Catalyst System

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【作者】 刘振海刘冬梅王凤江金海珠

【Author】 LIU Zhenhai, LIU Dongmei, WANG Fengjiang and JIN Haizhu(Changchun Institute of Applied Chemistry, Academia Sinica, Changchun)

【机构】 中国科学院长春应用化学研究所吉林工学院中国科学院长春应用化学研究所 长春长春长春

【摘要】 <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MoCl4OR-(i-Bu),AlOR′制得的是无规聚1,2-丁二烯;是非晶态

【Abstract】 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.

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