吡唑亚胺镍配合物的合成、表征及催化1,3-丁二烯聚合  

Pyrazolylimine Ni( Ⅱ) Complexes: Synthesis,Characterization,and Catalytic Behaviors for 1,3-Butadiene Polymerization

作　　者：韩超[1] 刘恒[2] 杨凤[1] 胡雁鸣[2] 张学全[2] 

机构地区：[1]沈阳化工大学材料科学与工程学院,沈阳110142 [2]中国科学院长春应用化学研究所,中国科学院合成橡胶重点实验室,长春130022

出　　处：《应用化学》2015年第8期909-915,共7页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金青年科学基金项目(51203092)资助项目~~

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。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.

关 键 词：吡唑亚胺 镍配合物 液体聚丁二烯 配位聚合 

分 类 号：O632.1[理学—高分子化学]