催化学报

催化学报 ›› 2006, Vol. 27 ›› Issue (4): 355-360.

• 研究论文 • 上一篇    下一篇

Zn-Co双金属氰化络合物催化氧化环己烯/二氧化碳共聚反应

陈上1,2,张兴宏2, 戚国荣2   

  1. 1 吉首大学化学化工学院, 湖南吉首, 416000; 2 浙江大学高分子科学与工程系, 浙江杭州, 310027
  • 收稿日期:2006-04-25 出版日期:2006-04-25 发布日期:1984-12-26

Copolymerization of Cyclohexene Oxide with Carbon Dioxide Catalyzed by Zn-Co Double Metal Cyanide Complex

CHEN Shang1,2*, ZHANG Xinghong2, QI Guorong2   

  1. 1 College of Chemistry and Chemical Engineering, Jishou University, Jishou 416000, Hunan, China; 2 Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China
  • Received:2006-04-25 Online:2006-04-25 Published:1984-12-26

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被引次数

29

摘要： 制备了基于Zn3［Co(CN)6］2的双金属氰化络合物催化剂,考察了其催化氧化环己烯/CO2共聚反应的特点,以及制备过程中有机配体和卤化锌种类对催化剂催化性能和共聚产物组成的影响. 结果表明,该催化剂能高效催化共聚反应,在催化剂含量为1.8×10-4时其催化效率可达6?000 g/g以上, FT-IR和 1H NMR表征证实聚合产物为接近交替的共聚物. 催化剂催化效率受有机配体和卤化锌种类影响,但共聚物组成只受卤化锌种类影响,而不受有机配体种类影响,其中叔丁醇和ZnCl2分别是较好的有机配体和锌盐. 动力学研究表明,该共聚反应对催化剂浓度是一级反应,反应的平均活化能为41.6 kJ/mol.

关键词: 双金属氰化络合物, 锌, 钴, 氧化环己烯, 二氧化碳, 共聚合

Abstract: Double metal cyanide complexes based on Zn3［Co(CN)6］2 were prepared and used for copolymerization of cyclohexene oxide with carbon dioxide. The catalytic characteristics and the effect of preparation conditions on catalytic performance and product composition were investigated. The results showed that these catalysts could catalyze copolymerization effectively. The catalytic efficiency could reach over 6?000 g/g when the catalyst content was 1.8×10-4, and the products were confirmed to be nearly alternative copolymers by FT-IR and1H NMR. The effects of complexing agents and zinc halides (ZnX2, X=F, Cl, Br, I) on catalytic performance were studied. The catalytic efficiency was influenced by the kind of complexing agents and zinc halides employed in preparation of catalysts. However, the composition of copolymers was only influenced by the kind of zinc halides. Among those complexing agents and zinc halides investigated, tert-butanol and zinc chloride were preferable, respectively. The kinetic study indicated that the initial reaction rate of copolymerization exhibited first order dependence on the catalyst content, and average activation energy of copolymerization was 41.6 kJ/mol.

Key words: double metal cyanide complex, zinc, cobalt, cyclohexene oxide, carbon dioixde, copolymerization