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以膨胀计法研究了在乙醚溶剂中以正丁基锂引发的丁二烯聚合增长反应动力学。结果发现,增长反应速度对单体浓度的反应级数为1;对活性种浓度的反应级数在0.8—0.9之间,并随着温度的升高,反应级数增大,这说明在乙醚溶剂中,存在少量的缔合体。求得表观活化能56kJ/mol和真实潘化能41.8kJ/mol。根据金关泰等提出的反应机理,求出了生成1,2-和1,4-结构的分速度常数,分别为k_(1,2)=1.38×10~8e~(-9640/RT)和 k_(1,4)=1.28×10~9e~(-11300/RT).
The kinetics of polymerization of butadiene initiated by n-butyllithium in ether solvent was investigated by dilatometry. The results showed that the reaction rate of the growth rate to the monomer concentration was 1, the reaction order to the concentration of the active species was between 0.8 and 0.9, and the reaction order increased with the increase of the temperature, In the solvent, there is a small amount of association. Obtained apparent activation energy of 56kJ / mol and real panning energy of 41.8kJ / mol. According to the reaction mechanism proposed by Jin Guantai et al., The partial velocity constants of 1,2 and 1,4-structures were obtained, which are k1,2 = 1.38 × 10 ~ 8e ~ -9640 / RT and k_ (1,4) = 1.28 × 10 ~ 9e ~ (-11300 / RT).