α-二亚胺钴配合物催化1,3-丁二烯高活性与高顺式-1,4选择性聚合

doi:10.1016/S1872-2067(12)60625-1

催化学报 ›› 2013, Vol. 34 ›› Issue (8): 1560-1569.DOI: 10.1016/S1872-2067(12)60625-1

α-二亚胺钴配合物催化1,3-丁二烯高活性与高顺式-1,4选择性聚合

贾翔宇^a,b, 刘恒^a,b, 胡雁鸣^c, 代全权^a, 毕吉福^a, 白晨曦^a, 张学全^a

a 中国科学院长春应用化学研究所高性能合成橡胶工程技术中心, 吉林长春130012;
b 中国科学院大学, 北京100049;
c 大连理工大学化工学院高分子科学与工程系, 辽宁大连116012

收稿日期:2012-03-11 修回日期:2013-05-10 出版日期:2013-08-16 发布日期:2013-07-30
通讯作者: 胡雁鸣,张学全
基金资助:
国家科技支撑计划(2007BAE14B01-06); 国家自然科学基金委员会创新研究群体科学基金(50621302).

Highly active and cis-1,4 selective polymerization of 1,3-butadiene catalyzed by cobalt(II) complexes bearing α-diimine ligands

Xiangyu Jia^a,b, Heng Liu^a,b, Yanming Hu^c, Quanquan Dai^a, Jifu Bi^a, Chenxi Bai^a, Xuequan Zhang^a

a Research Center of High Performance Synthetic Rubber, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, Jilin, China;
b University of Chinese Academy of Sciences, Beijing 100049, China;
c Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116012, Liaoning, China

Received:2012-03-11 Revised:2013-05-10 Online:2013-08-16 Published:2013-07-30
Supported by:
This work was supported by the National Key Technology R&D Program of China (2007BAE14B01-06) and the Fund for Creative Research Groups of the National Natural Science Foundation of China (50621302).

摘要/Abstract

摘要： 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(M_n≈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.

关键词: 钴, α-二亚胺, 1,3-丁二烯, 聚丁二烯, 聚合

Abstract: A series of cobalt(II) complexes bearing α-diimine ligands were synthesized and characterized by elemental and spectroscopic analysis. These complexes had the general formulas [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). 2,6-Bis[(2,6-diisopropylphenylimino)ethyl]pyridine CoCl₂ (4a) was also synthesized for comparison. The structures of complexes 3i, 3k, and 4a were further analyzed by X-ray crystallography. When the Co(II) complexes were activated with ethylaluminum sesquichloride, they exhibited high catalytic activity for 1,3-butadiene polymerization. The polymers produced have high cis-1,4 stereoregularity (up to 98.0%) and high molecular weights (M_n=1×10⁴-1×10⁵). The substituent ligand affected both catalytic activity and stereoselectivity through an electronic effect while steric hindrance by the substituent was not important. The effects of the polymerization conditions, such as polymerization time, temperature, different alkylaluminum compounds used as cocatalyst, and [Al]/[Co] molar ratio, on polymerization behavior were investigated.

Key words: Cobalt, α-Diimine, 1,3-Butadiene, Polybutadiene, Polymerization

贾翔宇, 刘恒, 胡雁鸣, 代全权, 毕吉福, 白晨曦, 张学全. α-二亚胺钴配合物催化1,3-丁二烯高活性与高顺式-1,4选择性聚合[J]. 催化学报, 2013, 34(8): 1560-1569.

Xiangyu Jia, Heng Liu, Yanming Hu, Quanquan Dai, Jifu Bi, Chenxi Bai, Xuequan Zhang. Highly active and cis-1,4 selective polymerization of 1,3-butadiene catalyzed by cobalt(II) complexes bearing α-diimine ligands[J]. Chinese Journal of Catalysis, 2013, 34(8): 1560-1569.

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α-二亚胺钴配合物催化1,3-丁二烯高活性与高顺式-1,4选择性聚合

Highly active and cis-1,4 selective polymerization of 1,3-butadiene catalyzed by cobalt(II) complexes bearing α-diimine ligands

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