吡唑亚胺镍配合物的合成、表征及催化1, 3-丁二烯聚合

doi:10.11944/j.issn.1000-0518.2015.08.140425

摘要/Abstract

摘要：

合成了一系列吡唑亚胺二齿Ni(Ⅱ)配合物(4a~4e), 并通过红外光谱、元素分析及单晶衍射等对配合物进行了表征。配合物4b属于单斜晶系, 以Ni原子为中心形成扭曲的三角双锥构型。该系列配合物在倍半乙基氯化铝(EASC)的活化下, 对1, 3-丁二烯聚合表现出较高的顺-1, 4选择性, 得到了相对分子质量为4500~9000、顺-1, 4含量在91%左右的液体聚丁二烯。随着取代基空间位阻的增大, 催化活性逐渐减低。进一步详细研究了Al/Ni摩尔比和温度对聚合的影响。在20~60 ℃范围内, 催化活性随着聚合温度的升高而提高, 聚合温度为80 ℃时, 聚合物收率仅略有降低, 表明该系列催化剂产生的活性中心具有良好的高温稳定性。

关键词: 吡唑亚胺, 镍配合物, 液体聚丁二烯, 配位聚合

Abstract:

A series of NN-bidentate nickel(Ⅱ) complexes bearing pyrazolylimine ligands(4a~4e) was synthesized and characterized by FTIR and elemental analysis. Determined by X-ray single crystal diffraction, complex 4b adopted distorted trigonal bipyramidal geometry around the central metal. Activated by ethylaluminum sesquichloride(EASC), all complexes exhibited high cis-1, 4 selectivity towards 1, 3-butadiene polymerization to afford liquid polybutadienes(PB) with relative molecular mass of 4500~9000 and 91% cis-1, 4 content. The catalytic activity of the complex decreased as the hindrance of the substituent on the ligand increased. The effects of Al/Ni molar ratio and polymerization temperature on the polymerization were further investigated in details. The catalytic activity increased with the increase of polymerization temperature from 20 ℃ to 60 ℃, and the polymer yield only slightly decreased even at a high temperature of 80 ℃, indicating high thermal stability of the active species generated by the present catalytic system.

Key words: pyrazolylimine, nickle complex, liquid polybutadiene, coordination polymerization

中图分类号:

韩超, 刘恒, 杨凤, 胡雁鸣, 张学全. 吡唑亚胺镍配合物的合成、表征及催化1, 3-丁二烯聚合[J]. 应用化学, 2015, 32(8): 909-915.

HAN Chao, LIU Heng, YANG Feng, HU Yanming, ZHANG Xuequan. Pyrazolylimine Ni(Ⅱ) Complexes: Synthesis, Characterization, and Catalytic Behaviors for 1, 3-Butadiene Polymerization[J]. Chinese Journal of Applied Chemistry, 2015, 32(8): 909-915.

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