论文摘要
A series of pyrazolylimine ligated Co（II） and Fe（II） complexes with general formula of(PhC=N（C6H3（R1）2-2,6）（C3HN2（R2）2-3,5）MtCl2（R1 = Me, R2 = H, Mt = Co（1 a）, Fe（2 a）; R1 = Me, R2 = Me, Mt = Co（1b）, Fe（2b）; R1 = iPr, R2 = H, Mt = Co（1 c）, Fe（2 c）; R1 = i Pr, R2 = Me, Mt = Co（1 d）, Fe（2 d）; R1 = i Pr, R2 = 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.
论文目录
文章来源
类型: 期刊论文
作者: Liang Fang,Wen-Peng Zhao,Chao Han,Chun-Yu Zhang,Heng Liu,Yan-Ming Hu,Xue-Quan Zhang
来源: Chinese Journal of Polymer Science 2019年05期
年度: 2019
分类: 工程科技Ⅰ辑
专业: 化学
单位: CAS Key Laboratory of High-Performance Synthetic Rubber and its Composite Materials,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,University of Chinese Academy of Sciences,School of Materials Science and Engineering,Shenyang University of Chemical Technology
基金: financially supported by the National Basic Research Program of China(No.2015CB654700(2015CB654702)),the National Natural Science Foundation of China(No.21801236)
分类号: O631.5
页码: 462-470
总页数: 9
文件大小: 860K
下载量: 3
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