应用化学 ›› 2019, Vol. 36 ›› Issue (10): 1128-1134.DOI: 10.11944/j.issn.1000-0518.2019.10.190171

• 研究论文 • 上一篇    下一篇

自负载吡啶双亚胺酸酯钒(Ⅲ)催化剂的合成及催化乙烯聚合

梁姗姗a,刘恒b*(),胡雁鸣b*(),张学全b   

  1. a沈阳化工大学材料科学与工程学院 沈阳 110142
    b中国科学院长春应用化学研究所,中国科学院高性能合成橡胶及其复材重点实验室 长春 130022
  • 收稿日期:2019-06-20 接受日期:2019-08-25 出版日期:2019-10-01 发布日期:2019-09-29
  • 通讯作者: 刘恒,胡雁鸣
  • 基金资助:
    吉林省科技厅优秀青年基金项目(20190103122JH)项目资助

Self-immobilization of Alkenyl-Functionalized Bis(imidate)pyridine Vanadium(Ⅲ) Complexes for Ethylene Homo(co)polymerization

LIANG Shanshana,LIU Hengb*(),HU Yanmingb*(),ZHANG Xuequanb   

  1. aCollege of Material Science and Engineering,Shenyang University of Chemical Technology,Shenyang 110142,China
    bChangchun Institute of Applied Chemistry,Chinese Academy of Sciences,CAS Key Laboratory of High-Performance Synthetic Rubber and Its Composite Materials,Changchun 130022,China
  • Received:2019-06-20 Accepted:2019-08-25 Published:2019-10-01 Online:2019-09-29
  • Contact: LIU Heng,HU Yanming
  • Supported by:
    Supported by Jilin Provincial Science and Technology Development Program(No.20190103122JH)

摘要:

合成了一系列自负载吡啶双亚胺酸酯钒(Ⅲ)催化剂(V(Ⅲ)),并通过傅里叶变换红外光谱仪(FTIR)、元素分析及核磁共振波谱仪(NMR)等技术手段对配合物进行了表征。 在倍半乙基氯化铝(EASC)活化下,V(Ⅲ)催化剂对乙烯聚合表现出很高的催化活性(7.2~12.1 g/(mol·h·Pa)),且自负载基团的链长对催化剂的活性及所得聚合物的性质影响较小。 同时,该类V催化剂催化乙烯与1-己烯共聚合性能良好,得到高相对分子质量(高达68.1×103)的聚合物。 所得聚合物经扫描电子显微镜(SEM)表征,其微观结构为片层叠加结构。

关键词: 自负载, 钒催化剂, 聚烯烃

Abstract:

A series of alkenyl-functionalized bis(imidate)pyridine vanadium V(Ⅲ) complexes was synthesized and used for olefin polymerization in a self-immobilization mode. All the complexes were well-characterized by Fourier transform infrared spectrometer(FTIR), elemental analysis and nuclear magnetic resonance spectroscopy(NMR). Being activated by ethylaluminum sesquichloride(EASC), the V(Ⅲ) complexes displayeded high activity in ethylene polymerization(7.2~12.1 g/(mol·h·Pa)). Additionally, the length of self-immobilized alkenyl chains showed a little influence on the catalytic activity of the precatalysts. These V(Ⅲ) complexes also exhibited high activity in initiating ethylene/1-hexene copolymerization, affordiong copolymer products with high molecular weight(up to 68.1×103). Scanning electron microscope(SEM) studies showed that the polymer products formed platelet clusters.

Key words: self-immobilization, vanadium precatalyst, polyolefin