Abstract The iminopyridylcobalt complexes Co1-Co5 bearing bulky phenethyl or benzhydryl substituents were synthesized. Determined by single crystal X-ray crystallographic analysis, complexes Co3 and Co4 displayed tetrahedron geometries. The present complexes displayed high cis-1,4 selectivity for 1,3-butadiene polymerization upon activation with ethylaluminum sesquichloride (EASC). While upon activation with either methylaluminoxane (MAO) or trialkylaluminum-free MAO (dMAO) cocatalyst, these complexes exhibited moderate activities, addition of PPh3 into the catalyst system resulted in the increase in catalytic activities and the change of the selectivity from cis-1,4 to 1,2 manner. Moreover, the livingness of Co4/dMAO system enabled synthesis of cis-1,4-b-syn-1,2 stereodiblock polybutadiene with PPh3 as a selectivity regulating agent in one-pot polymerization process. Crystallization of syn-1,2 block and attendant expulsion of cis-1,4 block from the crystalline structure led to micro-phase separation in this stereoblock polymer.

中文翻译：

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亚氨基-吡啶钴配合物催化剂一锅法合成具有顺式1,4和间同立构1,2链段的立体嵌段聚丁二烯

摘要 合成了带有庞大苯乙基或二苯甲基取代基的亚氨基吡啶钴配合物Co1-Co5。通过单晶 X 射线晶体学分析确定，配合物 Co3 和 Co4 显示出四面体几何形状。本复合物在用乙基铝倍半氯化物 (EASC) 活化后对 1,3-丁二烯聚合显示出高顺式 1,4 选择性。虽然在用甲基铝氧烷 (MAO) 或不含三烷基铝的 MAO (dMAO) 助催化剂活化后，这些配合物表现出中等活性，将 PPh3 添加到催化剂体系中导致催化活性增加和选择性从 cis-1 改变， 4 到 1,2 的方式。此外，Co4/dMAO 系统的活性能够合成 cis-1,4-b-syn-1，2 立体二嵌段聚丁二烯与 PPh3 作为一锅聚合工艺中的选择性调节剂。Syn-1,2 嵌段的结晶和随之而来的 cis-1,4 嵌段从晶体结构中的排出导致该立体嵌段聚合物发生微相分离。