1,3-Butadiene Polymerizations Catalyzed by Cobalt and Iron Dichloride Complexes Bearing Pyrazolylimine Ligands  

作　　者：Liang Fang Wen-Peng Zhao Chao Han Chun-Yu Zhang Heng Liu Yan-Ming Hu Xue-Quan Zhang 

机构地区：[1]CAS Key Laboratory of High-Performance Synthetic Rubber and its Composite Materials,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences [2]University of Chinese Academy of Sciences [3]School of Materials Science and Engineering,Shenyang University of Chemical Technology

出　　处：《Chinese Journal of Polymer Science》2019年第5期462-470,共9页高分子科学（英文版）

基　　金：financially supported by the National Basic Research Program of China(No.2015CB654700(2015CB654702));the National Natural Science Foundation of China(No.21801236)

摘　　要：A series of pyrazolylimine ligated Co(II) and Fe(II) complexes with general formula of(PhC=N(C_6H_3(R_1)2-2,6)(C_3 HN_2(R_2)2-3,5)MtCl_2(R_1 = Me, R_2 = H, Mt = Co(1 a), Fe(2 a); R_1 = Me, R_2 = Me, Mt = Co(1b), Fe(2b); R_1 = iPr, R_2 = H, Mt = Co(1 c), Fe(2 c); R_1 = i Pr, R_2 = Me, Mt = Co(1 d), Fe(2 d); R_1 = i Pr, R_2 = Ph, Mt = Co(1 e), Fe(2 e)) were synthesized and thoroughly characterized.Determined by single crystal X-ray diffraction, complexes 1 b and 2 b revealed dimeric structures, in which distorted trigonal bipyramid geometries were adopted for each metal centers. In the presence of ethylaluminum sesquichloride(EASC), all the cobalt complexes displayed high activities in 1,3-butadiene polymerization, affording polybutadienes with predominant cis-1,4 contents(up to 97.0%).Influences of ligand structure and polymerization parameters on catalytic performance were investigated systematically. For pyrazolylimine iron(II) dichloride complexes, the catalytic activities and microstructures of the resultant polybutadienes were highly dependent on ligand structures and polymerization conditions. For complex 2 a, changing cocatalyst from trialkyl aluminums to methyl aluminoxane(MAO) led to an shift of selectivity from high cis-1,4-to trans-1,4-/1,2-manner. Being activated by MAO, complexes 2 a and 2 b gave trans-1,4-/1,2-binary polybutadienes, while complexes 2 c, 2 d, and 2 e afforded cis-1,4-enriched polymers.A series of pyrazolylimine ligated Co(II) and Fe(II) complexes with general formula of(PhC=N(C_6H_3(R_1)2-2,6)(C_3 HN_2(R_2)2-3,5)MtCl_2(R_1 = Me, R_2 = H, Mt = Co(1 a), Fe(2 a); R_1 = Me, R_2 = Me, Mt = Co(1b), Fe(2b); R_1 = iPr, R_2 = H, Mt = Co(1 c), Fe(2 c); R_1 = i Pr, R_2 = Me, Mt = Co(1 d), Fe(2 d); R_1 = i Pr, R_2 = Ph, Mt = Co(1 e), Fe(2 e)) were synthesized and thoroughly characterized.Determined by single crystal X-ray diffraction, complexes 1 b and 2 b revealed dimeric structures, in which distorted trigonal bipyramid geometries were adopted for each metal centers. In the presence of ethylaluminum sesquichloride(EASC), all the cobalt complexes displayed high activities in 1,3-butadiene polymerization, affording polybutadienes with predominant cis-1,4 contents(up to 97.0%).Influences of ligand structure and polymerization parameters on catalytic performance were investigated systematically. For pyrazolylimine iron(II) dichloride complexes, the catalytic activities and microstructures of the resultant polybutadienes were highly dependent on ligand structures and polymerization conditions. For complex 2 a, changing cocatalyst from trialkyl aluminums to methyl aluminoxane(MAO) led to an shift of selectivity from high cis-1,4-to trans-1,4-/1,2-manner. Being activated by MAO, complexes 2 a and 2 b gave trans-1,4-/1,2-binary polybutadienes, while complexes 2 c, 2 d, and 2 e afforded cis-1,4-enriched polymers.

关 键 词：Late transition metal Cobalt(Ⅱ) COMPLEXES Iron(Ⅱ)complexes Stereoselective polymerization Polybutadiene 

分 类 号：O6[理学—化学]