应用化学 ›› 2010, Vol. 27 ›› Issue (03): 257-261.DOI: 10.3724/SP.J.1095.2010.90229

• 研究论文 • 上一篇    下一篇

以氯代酰氯为试剂的交联聚苯乙烯微球的Friedel-Crafts酰基化反应

王玲,高保娇   

  1. (中北大学化学工程系 太原 030051)
  • 收稿日期:2009-03-31 修回日期:2009-06-11 出版日期:2010-03-10 发布日期:2010-03-10
  • 通讯作者: 高保娇,女,教授; E-mail:gaobaojiao@126.com; 研究方向:功能高分子材料的化学与物理
  • 基金资助:
    山西省自然科学基金资助项目(2008021013)

Friedel-Crafts Acylation Reaction of Crosslinked Polystyrene Microspheres using Chloroacyl Chlorides as Reactants

WANG Ling, GAO Bao-Jiao*   

  1. (Department of Chemical Engineering,North University of China,Taiyuan 030051)
  • Received:2009-03-31 Revised:2009-06-11 Published:2010-03-10 Online:2010-03-10

摘要:

采用ω-氯代酰氯试剂氯乙酰氯和氯丁酰氯,在Lewis酸催化剂存在下,于室温下分别与交联聚苯乙烯(CPS)微球进行了Friedel-Crafts酰基化反应,制备了氯代酰基化(chloroacylation,CA)的交联聚苯乙烯微球(CACPS),用红外光谱与佛尔哈德分析法表征了产物的化学结构与组成,研究了各种因素对反应过程的影响。 结果表明,在Friedel-Crafts酰基化反应过程中,伴随的副反应─微球表面聚苯乙烯大分子之间的Friedel-Crafts烷基化附加交联反应,不但降低了在CPS微球表面引入氯代酰基的效率,还使微球变脆。 在室温(25  ℃)下,以CHCl3溶剂、催化剂SnCl4与白球中聚苯乙烯链节的摩尔比为1.2∶1、采用10 mL/g CPS微球的溶剂用量反应5 h,可以达到酰基化反应和烷基化交联副反应的最佳平衡点(此时的氯含量最高)。 结果还表明,采用氯丁酰氯对CPS微球进行氯代酰基化反应的效果明显好于氯乙酰氯。

关键词: 聚苯乙烯微球,氯乙酰氯,Friedel-Crafts酰基化反应,Friedel-Crafts烷基化反应,附加交联

Abstract:

Friedel-Crafts acylation reaction of crosslinked polystyrene(CPS) microspheres was conducted in the precence of a Lewis acid catalyst at room temperature using two kinds of ω-chloroacyl chloride, chloroacetyl chloride and chlorobutyryl chloride, and chloroacylation crosslinked polystyrene(CACPS) microspheres were prepared. The chemical structure and composition of the resultant microspheres were characterized and determined by means of infrerad spectroscopy and Volhard methods. The effects of various factors on the chloroacylation reaction were investigated. The experimental results show that the chloroacylation process is always accompanied by Friedel-Crafts alkylation reaction, which is a side reaction leading to additional crosslinking. This side reaction not only decreases the content of the chloroacyl groups on CACPS microspheres, but also makes the property of the microspheres poor. An optimal equilibrium point, at which the chlorine content of CACPS microspheres is the highest, between acylation reaction and alkylation crosslinking reaction can be reached under the following conditions: room temperature, CHCl3 as the solvent, SnCl4 as the catalyst, a 1.2∶1 molar ratio of catalyst to chain unit of polystyrene of CPS, 10 mL used solvent per 1 g CPS microspheres. The result still indicates that the chloroacylation via chlorobutyryl chloride is better than that via chloroacetyl chloride.

Key words: polystyrene microspheres,chloroacetyl chloride,Friedel-Crafts acetylation reaction,Friedel-Crafts alkylation reaction,additional crosslinking

中图分类号: