催化学报

催化学报 ›› 2007, Vol. 28 ›› Issue (8): 737-742.

• 研究论文 • 上一篇    下一篇

含空间位阻侧链取代炔烃的合成及其催化聚合

查代军1,陈义旺1,2,谌烈2,秦志勇1,周丹1   

  1. 1 南昌大学理学院化学系, 江西南昌 330031; 2 南昌大学材料科学与工程学院高分子研究所, 江西南昌 330031
  • 收稿日期:2007-08-25 出版日期:2007-08-25 发布日期:2011-08-19

Synthesis and Catalytic Polymerization of Acetylene with Steric Substitute

ZHA Daijun1, CHEN Yiwang1,2*, CHEN Lie2, QIN Zhiyong1, ZHOU Dan1   

  1. 1 Department of Chemistry, School of Science, Nanchang University, Nanchang 330031, Jiangxi, China; 2 Institute of Polymer Materials, School of Materials Science and Engineering, Nanchang University, Nanchang 330031, Jiangxi, China
  • Received:2007-08-25 Online:2007-08-25 Published:2011-08-19

PDF

1064

被引次数

13

摘要： 设计并合成了具有较大空间位阻侧链的取代炔烃2-炔丙氧基-1,4-对苯二甲酸二甲酯单体,分别采用WCl6, WCl6-SnPh4和[Rh(nbd)Cl]2催化体系使其聚合,考察了不同催化剂对聚合的影响. 采用红外光谱和核磁共振等技术对单体及聚合物结构进行了表征,并用紫外光谱和荧光光谱研究了所得聚合物的光学性能. 结果表明,使用[Rh(nbd)Cl]2催化剂时得到的聚合物是高反式结构,荧光光谱中除了侧基的350 nm发射峰外,还在429 nm处存在较弱的共轭主链发射. 使用WCl6-SnPh4催化体系得到的聚合物由于较高的顺式含量,主要是侧基的发射,而较大侧基位阻使主链共轭降低. 尽管存在较短的间隔基,引入较大空间位阻侧基仍然迫使聚合物主链扭曲,顺式结构中侧基空间位阻的影响更大.

关键词: 聚乙炔, 催化聚合, 铑, 过渡金属催化剂, 荧光光谱

Abstract: A novel acetylene derivative, 2-propargyloxy-1,4-dimethyl terephthalate, was synthesized. The monomer acetylene with steric substitute was polymerized using WCl6, WCl6-SnPh4, and [Rh(nbd)Cl]2 as catalyst. The structure and optical properties of polyacetylene were studied by means of nuclear magnetic resonance, infrared spectroscopy, ultraviolet-visible absorption spectroscopy, and photoluminescence spectroscopy. The polymerization using WCl6-SnPh4 as catalyst afforded polyacetylene with only 60% of cis-content due to the steric substitute. The polymerization yield was strongly dependent on reaction temperature and solvent. High yield and high trans-content of polyacetylene were obtained by polymerization using [Rh(nbd)Cl]2 catalyst. The steric effect of bulky substitute led to a narrow conjugation of polyacetylene.

Key words: polyacetylene, catalytic polymerization, rhodium, transition metal catalyst, photoluminescence