论文部分内容阅读
合成了一系列α-二亚胺钴配合物[ArN=C(Me)-(Me)C=NAr]CoCl2(Ar = C6H5, 3a; 4-MeC6H4, 3b; 4-MeOC6H4, 3c; 4-FC6H4,3d; 4-ClC6H4, 3e; 2-MeC6H4, 3f; 2-EtC6H4, 3g; 2-iPrC6H4, 3h; 2,4,6-Me3C6H2, 3i; 2,6-Et2C6H3, 3j; 2,6-iPrC6H3, 3k)和作为对比的吡啶双亚胺二氯化钴配合物(4a), 并用X射线单晶衍射方法研究了配合物3i, 3k和4a的分子结构. α-二亚胺钴配合物在倍半乙基氯化铝的作用下对丁二烯聚合有较高的催化活性, 得到的顺式-1,4结构含量达98%, 且有较高分子量(Mn≈ 1×104-1×105)的聚丁二烯. 配体的电子效应影响催化剂的活性及顺式-1,4选择性, 而配体的空间位阻对丁二烯聚合几乎没有影响. 详细研究了聚合时间、聚合温度、烷基铝助催化剂及铝比等条件对丁二烯聚合行为的影响.
A series of α-diimine cobalt complexes [ArN = C (Me) - (Me) C = NAr] CoCl2 have been synthesized (Ar = C6H5, 3a; 4-MeC6H4, 3b; 4-MeOC6H4, 3c; , 3d; 4-ClC6H4, 3e; 2-MeC6H4, 3f; 2-EtC6H4, 3g; 2-iPrC6H4, 3h; 2,4,6-Me3C6H2, 3i; 2,6-Et2C6H3, 3j; 2,6-iPrC6H3 , 3k) and the corresponding pyridine bisimine cobalt dichloride complex (4a), and the molecular structures of complexes 3i, 3k and 4a were investigated by X-ray single crystal diffraction method.α-Diimide cobalt complex The polymerization of butadiene was catalyzed by sesquichloroaluminum chloride. The content of cis-1,4 was 98% and the molecular weight was higher (Mn≈1 × 104-1 × 105) .The electronic effect of the ligand affects the activity of the catalyst and the cis-1,4 selectivity, and the steric hindrance of the ligand has little effect on butadiene polymerization.The polymerization time, polymerization Effect of Temperature, Alkyl Aluminum Cocatalyst and Aluminum Ratio on Butadiene Polymerization.