纳米Cu2O催化二苯甲烷二氨基甲酸苯酯无溶剂热分解制备二苯甲烷二异氰酸酯

doi:10.1016/S1872-2067(11)60494-4

催化学报 ›› 2013, Vol. 34 ›› Issue (3): 548-558.DOI: 10.1016/S1872-2067(11)60494-4

纳米Cu₂O催化二苯甲烷二氨基甲酸苯酯无溶剂热分解制备二苯甲烷二异氰酸酯

王庆印^a,b, 康武魁^c, 张毅^a,b, 杨先贵^a, 姚洁^a, 陈彤^a, 王公应^a

a 中国科学院成都有机化学研究所, 四川成都 610041;
b 中国科学院大学, 北京 100049;
c 中青岛农业大学化学与药学院, 山东青岛 266109

收稿日期:2012-09-18 修回日期:2012-11-26 出版日期:2013-04-02 发布日期:2013-04-03
通讯作者: 王公应
基金资助:
国家科技支撑计划(2006BAC02A08);中国科学院知识创新工程重要方向项目(KGCX2-YW-215-2).

Solvent-free thermal decomposition of methylenediphenyl di(phenylcarbamate) catalyzed by nano-Cu₂O

WANG Qingyin^a,b, KANG Wukui^c, ZHANG Yi^a,b, YANG Xiangui^a, YAO Jie^a, CHEN Tong^a, WANG Gongying^a

a Chengdu Institute of Organic Chemistry, the Chinese Academy of Sciences, Chengdu 610041, Sichuan, China;
b University of Chinese Academy of Sciences, Beijing 100049, China;
c College of Chemistry and Pharmaceutical Sciences, Qingdao Agricultural University, Qingdao 266109, Shandong, China

Received:2012-09-18 Revised:2012-11-26 Online:2013-04-02 Published:2013-04-03
Supported by:
This work was supported by the National Key Technology R&D Program (2006BAC02A08); Knowledge Innovation Project of the Chinese Academy of Sciences (KGCX2-YW-215-2).

摘要/Abstract

摘要：

研究了无溶剂条件下纳米Cu₂O催化二苯甲烷二氨基甲酸苯酯(MDPC)热分解制备二苯甲烷二异氰酸酯(MDI),考察了纳米Cu₂O的制备条件与反应条件对MDPC热分解反应性能的影响.结果表明,水解法制备的纳米Cu₂O在Ar中于300℃焙烧2h,其催化性能最佳;最佳的反应条件为Cu₂O用量为原料总重的0.06%,反应温度220℃,反应压力0.6kPa,反应时间12min,此时MDPC转化率达到99.8%,MDI选择性86.2%.

关键词: 纳米氧化亚铜, 二苯甲烷二异氰酸酯, 催化热分解, 二苯甲烷二氨基甲酸苯酯, 异氰酸酯, 二苯甲烷二氨基甲酸甲酯

Abstract:

Methylene di(phenylisocyanate) (MDI) was prepared by thermal decomposition of methylenediphenyl di(phenylcarbamate) (MDPC) under solvent-free conditions with a nano-Cu₂O catalyst. The preparation of nano-Cu₂O was investigated in detail to obtain the optimal catalytic performance. The thermal decomposition reaction conditions, including reaction temperature, reaction pressure, and reaction time, were studied in the presence of nano-Cu₂O. The results show that Cu₂O prepared using a hydrolysis method and then calcined at 300℃ in Ar atmosphere for 2 h exhibited the optimal catalytic activity. The optimal reaction conditions were as follows: mass ratio of catalyst to MDPC 6.0 × 10^-4, reaction temperature 220℃, reaction time 12 min, and reaction pressure 0.6 kPa. Under these conditions, the conversion of MDPC reached 99.8% and 86.2% MDI selectivity was achieved.

Key words: Nano cuprous oxide, Methylene-di(phenylisocyanate), Catalytic thermal decomposition, Methylenediphenyldi(phenylcarbamate), Isocyanate, Methylene-di(phenylene carbamate)

王庆印, 康武魁, 张毅, 杨先贵, 姚洁, 陈彤, 王公应. 纳米Cu₂O催化二苯甲烷二氨基甲酸苯酯无溶剂热分解制备二苯甲烷二异氰酸酯[J]. 催化学报, 2013, 34(3): 548-558.

WANG Qingyin, KANG Wukui, ZHANG Yi, YANG Xiangui, YAO Jie, CHEN Tong, WANG Gongying. Solvent-free thermal decomposition of methylenediphenyl di(phenylcarbamate) catalyzed by nano-Cu₂O[J]. Chinese Journal of Catalysis, 2013, 34(3): 548-558.

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纳米Cu₂O催化二苯甲烷二氨基甲酸苯酯无溶剂热分解制备二苯甲烷二异氰酸酯

Solvent-free thermal decomposition of methylenediphenyl di(phenylcarbamate) catalyzed by nano-Cu₂O

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