双核钒配合物催化烯烃聚合的研究

文章从含有酰亚胺配体的五价钒三氯化物出发，以不同结构的双酚类试剂为连接单元，成功合成了一系列双核钒的二氯化物（B1～B3），并进行了核磁共振和元素分析表征。在烷基铝助催化剂的作用下，双核钒配合物在降冰片烯的均聚中表现出良好的催化活性，得到具有开环易位结构的聚合物；在乙烯均聚中则表现出极高的催化活性，得到超高分子量聚乙烯，其数均分子量达到了 $ 1.84\times10^{6} $；在乙烯与极性单体（如十一烯醇或十一烯酸甲酯）的共聚中表现出很高的催化活性（活性可达 $ 654\ \mathrm{kg/(mol\cdot h)} $），成功制备出相应的烯烃共聚物。

This paper synthesized a series of binuclear vanadium complexes(B1~B3) from imido vanadium complex using various biphenol as linker. The vanadium complexes were characterized by nuclear magnetic resonance(NMR) spectra and elemental analysis. Under the activation of aluminum reagents as cocatalyst, the complex exhibited good activity in norbornene polymerization and formed the ROMP product. The complex showed high activity in ethylene polymerization and obtained the ultrahigh molecular weight polyethylene( $ M_{n} $ was up to $ 1.84 \times 10^{6} $). Especially the complex still showed good activity(up to 654 kg/(mol·h)) in the copolymerization with polar monomers such as 10-undecen-1-ol(UOH) and methyl 10-undecenoate(UA).