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探讨了以NdCl_3的磷酸三丁酯(TBP)溶液为主催化剂、烷基铝为助催化剂、MgCl_2为载体组成的Ziegler-Natta型催化体系引发丁二烯(Bd)聚合的某些规律。用AlEt_3作助催化剂,聚合物的顺1,4-结构含量仅为57％,反1,4-结构含量为42％;而以Al(i-Bu)_3作助催化剂,聚合物的顺1,4-结构含量为88％,反1,4-结构含量为11％。各种陈化体系中,以NdCl_3·nTBP/MgCl_2-Al(i-Bu)_3-Ip三元体系的催化活性最高,当Nd/Bd(摩尔比)为7×10~(-5)时,单体转化率达80％。低温聚合可获得高顺式、高分子量聚合物。
In this paper, the polymerization of butadiene (Bd) initiated by Ziegler-Natta catalytic system consisting of NdCl_3 solution of TBP as the main catalyst, aluminum alkyl as the promoter and MgCl_2 as carrier was investigated. With AlEt_3 as cocatalyst, the cis-1,4-content of the polymer was only 57% and the content of trans 1,4-structure was 42%. With Al (i-Bu) _3 as cocatalyst, , 4- structure content of 88%, anti-1,4-structure content of 11%. The catalytic activity of NdCl_3 · nTBP / MgCl_2-Al (i-Bu) _3-Ip ternary system was the highest in all kinds of aging systems. When Nd / Bd molar ratio was 7 × 10 ~ (-5) Monomer conversion rate of 80%. Low temperature polymerization gives high cis, high molecular weight polymers.