钛系Ziegler催化剂合成1,2-聚丁二烯的聚合动力学

研究了Ti(n-C_4H_9O)_(4-x)Cl_x-Al(i-C_4H_9)_3体系当x不同时,在已烷中催化丁二烯聚合的动力学特征和规律.测得聚合速率和表观活化能均随体系中氯含量增大而降低.在Al/Ti=15-90(摩尔比)范围,聚合速率对单体和钛化合物浓度均为一级反应,而受烷基铝浓度影响较小.催化剂的利用率仅为0.5-1.5％左右,随体系氯含量增大略有提高,但相应的增长速率常数却大为减小,因此聚合速率仍随氯含量增大而降低.

A KINETIC STUDY OF 1,2-POLYMERIZATION OF BUTADIENE BASED ON TITANIUM ZIEGLER CATALYSTS

The kinetic behaviour of polymerization of butadiene with Ti(n-C4H9O)4-xClx-Al(i-C4H9)3 systems in hexane with variable X values has been studied. The results showed that both the catalyst activity and the apparent activation energy decrease as the chlorine content of the system increases. In the range of AI/Ti value from 15 to 90 (mole ratio), the polymerication rate is first order with respect to the concentration of both monomer and Ti catalyst, but is not much effected by the concentration of Al cocatalyst. The efficiency of the catalysts is only 0.5-1.5%, increasing slightly with increase of the X value, while the relevant propagation rate constants decrease greatly. Therefore the polymerization rate reduces as the chlorine contents of the systems increase.