有机化学 ›› 2014, Vol. 34 ›› Issue (10): 1986-1991.DOI: 10.6023/cjoc201405004 上一篇    下一篇

综述与进展

丙烯腈催化二聚反应的研究进展

俞磊a,b,c, 王俊a, 曹洪恩a, 丁克鸿a,b,c, 徐清a,b,c   

  1. a. 江苏省环境材料与环境工程重点实验室 扬州大学化学化工学院 扬州 225002;
    b. 温州大学化学与材料工程学院 温州 325035;
    c. 江苏扬农化工集团有限公司 扬州 225009
  • 收稿日期:2014-05-04 修回日期:2014-05-21 出版日期:2014-10-25 发布日期:2014-06-11
  • 通讯作者: 俞磊 E-mail:yulei@yzu.edu.cn;yzuyulei@163.com
  • 基金资助:

    国家自然科学基金(No. 21202141)、江苏省高校优势学科、江苏省环境材料与工程重点实验室开放基金(Nos. K100027,K090030)及贵州大学教育部绿色农药与农业生物工程重点实验室开放基金(No. 2010GDGP0106)资助项目.

A Review on Catalyzed Dimerization of Acrylonitrile

Yu Leia,b,c, Wang Juna, Cao Hongena, Ding Kehonga,b,c, Xu Qinga,b,c   

  1. a. Jiangsu Key Laboratory of Environmental Material and Environmental Engineering, School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002;
    b. College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035;
    c. Jiangsu Yangnong Chemical Engineering Co. Ltd., Yangzhou 225009
  • Received:2014-05-04 Revised:2014-05-21 Online:2014-10-25 Published:2014-06-11
  • Supported by:

    Project supported by the National Natural Science Fundation of China (No. 21202141), the Priority Academic Program Development of Jiangsu Higher Education Institutions, the Opening Foundation of the Key Laboratory of Environmental Materials and Engineering of Jiangsu Province (Nos. K100027, K090030) and the Opening Foundation of the Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Guizhou University (No. 2010GDGP0106).

丙烯腈是廉价易得的化工原料. 丙烯腈的线性二聚可以构建己(烯)二腈分子骨架,经过进一步的加氢还原可制备己二胺. 己二胺是重要的工业中间体,有着广泛的用途和广阔的市场,主要用于合成尼龙66. 因此,丙烯腈的线性二聚是非常重要的有机化学反应. 与已经实现工业化的电解法相比,催化二聚有着能耗低、装置要求低等优点. 除此之外,丙烯腈催化二聚还可能生成非线性聚合产物2-亚甲基戊二腈. 它是生产广谱抗菌剂溴菌腈的重要中间体. 溴菌腈的市场需求量虽然不如尼龙66巨大,但也是重要的化工产品之一. 然而,在丙烯腈的催化二聚领域,至今未有系统性的综述报导. 对丙烯腈催化二聚反应的研究进展进行整理与系统性地阐述,按照催化剂种类,主要分为钌催化、其它金属催化以及膦催化二聚等三部分,供国内相关领域技术人员参考.

关键词: 丙烯腈, 二聚, 催化, 己二腈, 己二胺, 高聚物, 尼龙66, 溴菌腈

Acrylonitrile (AN) is a cheap and accessible industrial material. Linear dimerization of acrylonitrile affords the skeleton of adiponitrile, which leads to hexamethylene diamine through further hydrogenation. Hexamethylene diamine is an important industrial intermediate with comprehensive applications and wide market requirement and is mainly applied in the synthesis of nylon 66. Therefore, linear dimerization of acrylonitrile is a very important organic reaction. Compared with the electrolytic process which has already been applied in industrial production, the catalyzed dimerization needs low energy consumption and low equipment requirements. Besides, the catalyzed dimerization of acrylonitrile may also afford the branched dimer 2-methyleneglutaronitrile, which is the important intermediate in the synthesis of bromothalonil. Although the market requirement of bromothalonil is not as huge as nylon 66, it is also one of the important chemical industrial products. However, currently, there was no systematic review on AN dimerization. Therefore, this review aims to reorganize and systematically describe the advances of catalyzed dimerization of acrylonitrile for reference of the related technicians in China, including the Ru-catalyzed dimerization, other metal-catalyzed dimerization and phosphorus-catalyzed dimerization.

Key words: acrylonitrile, dimerization, catalysis, adiponitrile, hexamethylene diamine, polymer, nylon 66, bromothalonil