Synthesis of 4,4'-MDC in the Presence of Sulfonic Acid-functionalized Ionic Liquids

›› 2009, Vol. 17 ›› Issue (5): 756-760.

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Synthesis of 4,4'-MDC in the Presence of Sulfonic Acid-functionalized Ionic Liquids

GENG Yanlou, HU Liyan, ZHAO Xinqiang, AN Hualiang, WANG Yanji

Hebei Provincial Key Lab of Green Chemical Technology and High Efficient Energy Saving, Hebei University of Technology, Tianjin 300130, China

Received:2008-12-25 Revised:2009-08-17 Online:2009-10-28 Published:2009-10-28
Supported by:
Supported by the National Natural Science Foundation of China (20576025);the National Key Basic Project of China (2005CCA06100);the Science and Technological Research and Development Project of Hebei Province (07215602D);the Natural Science Foundation of Hebei Province (B2007000010)

Synthesis of 4,4'-MDC in the Presence of Sulfonic Acid-functionalized Ionic Liquids

耿艳楼, 胡利彦, 赵新强, 安华良, 王延吉

Hebei Provincial Key Lab of Green Chemical Technology and High Efficient Energy Saving, Hebei University of Technology, Tianjin 300130, China

通讯作者: ZHAO Xinqiang,E-mail:zhaoxq@hebut.edu.cn
基金资助:
Supported by the National Natural Science Foundation of China (20576025);the National Key Basic Project of China (2005CCA06100);the Science and Technological Research and Development Project of Hebei Province (07215602D);the Natural Science Foundation of Hebei Province (B2007000010)

Abstract

Abstract: The synthesis of methylene diphenyl dimethylcarbamate(4,4'-MDC) from methyl N-phenyl carbonate (MPC) and formaldehyde (HCHO) was conducted in the presence of sulfonic acid-functionalized ionic liquids (ILs) as dual solvent-catalyst.The influences of the kind of anion in the ionic liquids,reaction conditions and the recycle of the ionic liquid on 4,4'-MDC synthesis reaction were investigated.In addition,the acid strength of ILs was determined by the Hammett method with UV-visible spectroscopy,and the acid strength-catalytic activity relationship was correlated.The activity estimation results showed that HSO₃-bmimCF₃SO₃ was the optimal dual solvent-catalyst.Under the suitable reaction conditions of 70℃,40 min,molar ratio of n_MPC/n_HCHO=10/1 and mass ratio of W_ILs/W_MPC=4.5/1,the yield of 4,4'-MDC based on HCHO was 89.9% and the selectivity of 4,4'-MDC with respect to MPC was 74.9%.Besides,[HSO₃-bmim]CF₃SO₃ was reused four times after being purified and no significant loss in the catalytic activity was observed.

Key words: ionic liquids, methyl N-phenyl carbonate, formaldehyde, methylene diphenyl dimethylcarbamate, Brnsted acidity, catalyst recycling

摘要： The synthesis of methylene diphenyl dimethylcarbamate(4,4'-MDC) from methyl N-phenyl carbonate (MPC) and formaldehyde (HCHO) was conducted in the presence of sulfonic acid-functionalized ionic liquids (ILs) as dual solvent-catalyst.The influences of the kind of anion in the ionic liquids,reaction conditions and the recycle of the ionic liquid on 4,4'-MDC synthesis reaction were investigated.In addition,the acid strength of ILs was determined by the Hammett method with UV-visible spectroscopy,and the acid strength-catalytic activity relationship was correlated.The activity estimation results showed that HSO₃-bmimCF₃SO₃ was the optimal dual solvent-catalyst.Under the suitable reaction conditions of 70℃,40 min,molar ratio of n_MPC/n_HCHO=10/1 and mass ratio of W_ILs/W_MPC=4.5/1,the yield of 4,4'-MDC based on HCHO was 89.9% and the selectivity of 4,4'-MDC with respect to MPC was 74.9%.Besides,[HSO₃-bmim]CF₃SO₃ was reused four times after being purified and no significant loss in the catalytic activity was observed.

关键词: ionic liquids, methyl N-phenyl carbonate, formaldehyde, methylene diphenyl dimethylcarbamate, Brnsted acidity, catalyst recycling

GENG Yanlou, HU Liyan, ZHAO Xinqiang, AN Hualiang, WANG Yanji . Synthesis of 4,4'-MDC in the Presence of Sulfonic Acid-functionalized Ionic Liquids[J]. , 2009, 17(5): 756-760.

耿艳楼, 胡利彦, 赵新强, 安华良, 王延吉. Synthesis of 4,4'-MDC in the Presence of Sulfonic Acid-functionalized Ionic Liquids[J]. , 2009, 17(5): 756-760.

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Synthesis of 4,4'-MDC in the Presence of Sulfonic Acid-functionalized Ionic Liquids

Synthesis of 4,4'-MDC in the Presence of Sulfonic Acid-functionalized Ionic Liquids

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