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以二氧六环为溶剂,以正丁基锂为引发剂,在充氮条件下,利用膨胀计进行了丁二烯聚合增长反应动力学研究。结果表明,增长反应对单体浓度和活性种浓度的反应级数皆为一级关系;活化能为34.54kJ/mol,频率因子为2.44×10~7L·mol~(-1)·min~(-1);并求出生成1,4-和1,2-结构含量的分速度常数分别为k_3=7.70×10~7 e~(-9900/RT)L·mol~(-1)·min~(-1),k_4=9.44×10~6 e~(-7800/RT)L·mol~(-1)·min~(-1);同时求出在二氧六环溶剂中 1,2-结构含量与温度关系的经验公式为 a=85.39-0.178 t,指数关系式为a=0.387 e~(450/RT)。
Using dioxane as solvent and n-butyllithium as initiator, the reaction kinetics of butadiene polymerization was investigated by using a dilatometer under nitrogen atmosphere. The results showed that the reaction order of growth response to both monomer concentration and active species concentration was first order. The activation energy was 34.54 kJ / mol and the frequency factor was 2.44 × 10 -7 L · mol -1 (-1) min ~ ( -1). The partial velocity constants for the formation of 1,4-and 1,2-structure were obtained as follows: k_3 = 7.70 × 10-7 e ~ (-9900 / RT) L · mol ~ (-1) · min ~ (-1), k_4 = 9.44 × 10 ~ 6 e ~ (-7800 / RT) L · mol ~ (-1) · min ~ The empirical formula for the relationship between structure content and temperature is a = 85.39-0.178 t, and the exponential relationship is a = 0.387 e ~ (450 / RT).