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用各种钴化合物与烷基铝组成催化体系聚合丁二烯,研究其催化活性以及对高聚物链结构的影响,试验结果表明: 1.卤化钴呲啶络合物,有机酸钴盐呲啶络合物、乙酰基丙酮合钴等外轨型钴络合物均能与(i-C_4H_9)_2AlCl,(C_2H_5)_2AlCl,(C_2H_5)_2AlBr组成高活性催化体系,聚合所得到的高聚物的链结构,顺式-1,4含量大于92％,但都不能与(C_2H_5)_2AlI组成定向催化剂。 2.用内轨型的钴络合物与(i-C_4H_9)_2AlCl,(C_2H_5)_2AlCl,(C_2H_5)_2AlBr,组合为催化剂时,对高聚物的链结构没有影响,但其活性比外轨型钴络合物差得多。 3.当一卤代二烷基铝上卤素改变时,所得高聚物平均分子量的大小变化的顺序是Cl>Br>I。 4.在适当的水量存在下,(i-C_4H_9)_3Al或C_2H_5AlCl_2始能与CoCl_2·4C_5H_5N组成高活性的定向催化剂。
A variety of cobalt compounds and aluminum alkyl catalyst system polymerization of butadiene polymerization to study its catalytic activity and the impact of the polymer chain structure, the experimental results show that: 1. Halobaltite pyridine complexes, organic acid cobalt salt b In addition, the cobalt complexes such as acetylacetonato and acetylacetonato cobalt can form highly active catalytic system with (C 2 H 5) 2 AlCl, (C 2 H 5) 2 AlCl and (C 2 H 5) 2 AlBr. Chain structure, cis-1,4 content greater than 92%, but not with (C_2H_5) _2AlI directional catalyst composition. With the combination of the inner-rail type cobalt complex and (i-C_4H_9) _2AlCl, (C_2H_5) _2AlCl, (C_2H_5) _2AlBr, the chain structure of the polymer has no effect, but its activity is lower than that of the outer rail Cobalt complexes are much worse. 3. When the halogen on the monohalogenated dialkylaluminium is changed, the order of magnitude of the change in the average molecular weight of the resulting polymer is Cl> Br> I. 4. In the presence of appropriate amount of water, (i-C_4H_9) _3Al or C_2H_5AlCl_2 can initiate a highly active directional catalyst with CoCl_2 · 4C_5H_5N.