| 吡啶双亚胺酰氯Ni(Ⅱ)配合物的合成、 表征及催化合成液体聚丁二烯 |
| |
| 引用本文： | 刘恒,刘李,王凤,贾翔宇,白晨曦,张春雨,张学全.吡啶双亚胺酰氯Ni(Ⅱ)配合物的合成、 表征及催化合成液体聚丁二烯[J].高等学校化学学报,2014,35(6):1336. |
| |
| 作者姓名： | 刘恒 刘李 王凤 贾翔宇 白晨曦 张春雨 张学全 |
| |
| 作者单位： | 1. 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, 长春 1300222. 中国科学院大学, 北京 1000493. 吉林大学材料科学与工程学院, 长春 130022 |
| |
| 基金项目： | 中国科学院“百人计划”项目(批准号: Y220011001)、 国家自然科学基金(批准号: 51203147)和吉林省基础研究计划基金(批准号: 20130102007JC)资助 |
| |
| 摘 要： | 合成了一系列吡啶双亚胺酰氯三齿Ni(Ⅱ) 配合物(1a~1c, 2a~2c), 通过傅里叶变换红外光谱和元素分析对配合物进行表征, 测定了配合物1a~1c的晶体结构. 3个化合物同属于单斜晶系, 且都具有以Ni原子为中心的近似于Cs对称的扭曲三角双锥构型. 该系列配合物通过倍半乙基氯化铝(EASC)活化, 在20 ℃下对丁二烯聚合表现出良好的催化活性, 得到分子量为4700~5200、 cis-1,4含量为74.8%~77.2%(摩尔分数)的液体聚丁二烯. 通过改变配体的结构和聚合条件, 可在一定范围内调控聚丁二烯的结构和分子量.
|
| 关 键 词： | 吡啶双亚胺酰氯 镍配合物 1 3-丁二烯聚合 |
| 收稿时间： | 2013-12-18 |
Synthesis,Characterization of Bis(arylcarboximidoylchloride)pyridine Ni(Ⅱ) Complexes and Their Catalytic Behavior for the Synthesis of Liquid Polybutadiene† |
| |
| LIU Heng,LIU Li,WANG Feng,JIA Xiangyu,BAI Chenxi,ZHANG Chunyu,ZHANG Xuequan.Synthesis,Characterization of Bis(arylcarboximidoylchloride)pyridine Ni(Ⅱ) Complexes and Their Catalytic Behavior for the Synthesis of Liquid Polybutadiene†[J].Chemical Research In Chinese Universities,2014,35(6):1336. |
| |
| Authors: | LIU Heng LIU Li WANG Feng JIA Xiangyu BAI Chenxi ZHANG Chunyu ZHANG Xuequan |
| |
| Institution: | 1. R & D Centre of High-performance Synthetic Rubber, Changchun Institute of Applied Chemistry,Chinese Academy of Sciences, Changchun 130022, China2. University of Chinese Academy of Sciences, Beijing 100049, China3. College of Material Science and Engineering, Jilin University, Changchun 130022, China |
| |
| Abstract: | A series of bis(arylcarboximidoylchloride)pyridine Ni(Ⅱ) complexes with the general formula 2,6-(ArN═CCl)2C5H3N]NiX2Ar=2,6-Me2C6H3, X=Br(1a) or Cl(2a); Ar=2,4,6-Me3C6H2, X=Br(1b) or Cl(2b); Ar=4-Cl-2,6-Me2C6H2, X=Br(1c) or Cl(2c)] were synthesized and characterized by FTIR and elemental analysis. The molecular structures of 1a—1c were further characterized by X-ray single crystal diffraction, and the geometry at the metal centre for all the three complexes can be best described as distorted trigonal bipyramidal. At the presence of ethylaluminum sesquichloride(EASC), all the Ni(Ⅱ)-based complexes performed high activities towards butadiene polymerization at 20 ℃, liquid polybutadienes(PB) with molecular weight of 4700—5200 and medium cis-1,4-PB content(74.8%—77.2%) was obtained. Catalytic activities of the catalysts and the microstructures of the resulting polymers were little depen-dent on the ligand environment and highly dependent on polymerization conditions. |
| |
| Keywords: | Bis(arylcarboximidoylchloride)pyridine Ni(Ⅱ) complex 1 3-Butadiene polymerization |
|
| 点击此处可从《高等学校化学学报》浏览原始摘要信息 |
| 点击此处可从《高等学校化学学报》下载免费的PDF全文 |
|
