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利用多核Nd-Al双金属配合物可单独引发双烯烃聚合的特点,考察了烷基铝种类对丁二烯加聚过程的影响,并与一般混合稀土催化体系进行了比较.烷基铝对活性体催化活性的影响与其用量有关,低n(Al)/n(Nd)值时,活性次序为:AlMe3,AlEt3,HAlBui2>Al(C8H17)3>AlBui3;高n(Al)/n(Nd)值时,活性次序相反:AlMe3,AlEt3,HAlBui2<Al(C8H17)3<AlBui3.烷基铝链转移作用强弱次序为:HAlBui2≥AlEt3>AlBui3>AlMe3>Al(C8H17)3.根据聚丁二烯微观结构与其分子量的关系,可将烷基铝对聚丁二烯顺式含量的影响分为3类:(1)AlEt3和Al(C8H17)3;(2)HAl-Bui2和AlBui3;(3)AlMe3.所得结果有助于对稀土催化定向聚合过程的深入了解.
The multi-core Nd-Al bimetallic complexes can be used to initiate the polymerization of diolefin separately. The effects of Al-Al-species on the polyaddition of butadiene were investigated and compared with the general mixed rare-earth catalysts. Al (Al) 3, AlEt3, HAlBui2> Al (C8H17) 3> AlBui3; high n (Al) / N (Nd) values, the order of activity is opposite: AlMe3, AlEt3, HAlBui2 AlBui3> AlMe3> Al (C8H17) 3. According to the relationship between the microstructure of polybutadiene and its molecular weight, the influence of aluminum alkyl on the cis content of polybutadiene can be divided into three categories: (1) AlEt3 and Al (C8H17) 3; (2) HA1-Bui2 and AlBui3; (3) AlMe3. The results obtained help to understand the rare earth catalytic polymerization process.