Polymerization of 1,3-butadiene catalyzed by Co(ii) and Ni(ii) complexes of 6,6'-dihydroxy-2,2'-bipyridine ligands: 1,4-cis-polymerization versus isospecific 1,2-polymerization

6,6'-二羟基-2,2'-联吡啶配体的Co(II)和Ni(II)配合物催化1,3-丁二烯的聚合:1,4-顺式聚合与等规1,2-聚合

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Abstract

Co and Ni complexes having the 6,6'-dihydroxy-2,2'-bipyridine (DHBP) ligand [CoCl(2)(dhbp), NiBr(2)(dhbp)] in the presence of organoaluminum cocatalysts showed much higher catalytic activity in 1,3-butadiene polymerization than the complexes having the 2,2'-bipyridine or 6,6'-dimethoxy-2,2'-bipyridine ligand without hydroxy groups. The polybutadienes obtained had 1,4-cis structure (up to 94.6%). In contrast, addition of 5-norbornene-2-methyl amine in 1,3-butadiene polymerization catalyzed by NiBr(2)(dhbp)/methylaluminoxane (MAO) caused a marked change in the microstructure of the polybutadiene to the iso-1,2-structure with high chemo- and stereoselectivities (mm > 99%).

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