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

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

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

收稿日期:2008-12-25 修回日期:2009-08-17 出版日期:2009-10-28 发布日期:2009-10-28
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)

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)

摘要/Abstract

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

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

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.

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.

参考文献

1 Fukuoka, S., Chono, M., Watanabe, T., Kohno, M., “Method for manufacture of diphenylmethane diisocyanates”, U.S. Pat., 4547322 (1985).
2 Li, F., Miao, J., Wang, Y.J., Zhao, X.Q., “Synthesis of methyl N-phenyl carbamate from aniline and dimethyl carbonate over supported zirconia catalyst”, Ind. Eng. Chem. Res., 45 (14), 4892-4897 (2006).
3 Tsutomu, Y., Masaaki, S., Fumiaki, H., Yukio, K., Koji, I., Akio, I., Kazuhito, M., Tsuneo, E., Toshihide, B., “Highly selective methoxycarbonylation of aliphatic diamines with methyl phenyl carbonate to the corresponding methyl N-alkyl dicarbamates”, Appl. Catal. A Gen., 289 (2), 174-178 (2005).
4 Zhao, X., Wang, Y.J., Wang, S.F., Yang, H.J., Zhang, J.Y., “Synthesis of MDI from dimethyl carbonate over solid catalysts”, Ind. Eng. Chem. Res., 41 (21), 5139-5144 (2002).
5 Grzegorz, L., Eugeniusz, M., “Thermal decomposition of methylene4,4'-di(ethylphenylcarbamate) to methylene-4,4'-di(phenylisocyanate)”, J. Hazard. Mater., A119, 19-24 (2005).
6 Kim, S.D., Lee, K.H., “Control of regioselectivity by cation-exchanged sulfonie acid resin catalysts”, J. Mol. Catal. A Chem., 78 (2), 237-248 (1993).
7 Wang, F.Q., Chen, T., Ma, F., Yao, J., Wang, G.Y., “Synthesis of methylene diphenyl dicarbamate over silicotungstic acid catalyst”, Petrochemical Technology, 35 (3), 260-263 (2006). (in Chinese)
8 Clerici, M.G., Bellussi, G., Romano, U., “Process for the preparation of 4, 4'-diaminodiphenyl-methane and its derivatives”, U.S. Pat., 5241119 (1993).
9 Zhao, X.Q., Wang, Y.J., Li, F., Zhang, W.H., Hao, D.Z., “Study of cleansynthesis process for methylene diphenyl diisocynate II Catalytic synthesis and cleavage of methylene diphenyl dicarbamate”, Acta Petrol. Sinica (Petroleum Processing Section), 17, 53-58 (2001). (in Chinese)
10 Wang, N., Zhao, X.Q., Wu, X.L., Wang, Y.J., “MDC synthesis reaction catalyzed by [HSO₃-bpy ]CF₃SO₃ ionic liquid”, J. Chem. Ind. Eng. (China), 59 (4), 887-891 (2008). (in Chinese)
11 Hu, L.Y., Geng, Y.L., Zhao, X.Q., Wang, Y.J., “Synthesis of 4,4'-MDC in the presence of [emim]BF₄ ionic liquid modified with H⁺”, J. Chem. Eng. Chin. Univ., 21 (3), 467-470 (2007). (in Chinese)
12 Gu, Y.L., Shi, F., Deng, Y.Q., “Esterification of aliphatic acids with olefin promoted by Br nsted acidic ionic liquids”, J. Mol. Catal. A:Chem., 212 (1/2), 71-75 (2004).
13 Gui, J.Z., Ban, H.Y., Cong, X.H., Zang, X.T., Hu, Z.D., Sun, Z.L., “Selective alkylation of phenol with tert-butyl alcohol catalyzed by Br nsted acidic imidazolium salts”, J. Mol. Catal. A Chem., 225 (1), 27-30 (2005).
14 Amanda, C.C., Jessica, L.J., Loanna, N., Kim, L.T., Kristin, J.W., David, C.F., James, H.D., “Novel Br sted acidic ionic liquids and their use as dual solvent-catalysts”, J. Am. Chem. Soc., 124 (21), 5962-5963 (2002).
15 Duan, Z.Y., Gu, Y.L., Zhang, J., Zhu, L.Y., Deng, Y.Q., “Protic pyridinium ionic liquids:Synthesis, acidity determination and their performances for acid catalysis”, J. Mol. Catal. A Chem., 250 (1/2), 163-168 (2006).
16 Hocker, J., Born, L., “The structure of two modifications of the MDI-bismethylurethane as a model substance for hard segments in polyurethane elastomers”, J. Polym. Sci. Polym. Lett. Ed., 17 (11), 723-730 (1979).
17 Xing, H.B., Wang, T., Zhou, Z.H., Dai, Y.Y., “The sulfonic acid-functionalized ionic liquids with pyridinium cations:Acidities and their acidity-catalytic activity relationships”, J. Mol. Catal. A Chem., 264 (1/2), 53-59 (2007).
18 Fukuoka, S., Watanabe, T., “Process for producing diphenylmethane dicarbamates”, U.S. Pat., 4552974 (1985).

[1]	Eileen Katherine Coronado-Aldana, Cindy Lizeth Ferreira-Salazar, Nubia Yineth Piñeros-Castro, Rubén Vázquez-Medina, Felipe A. Perdomo. Thermodynamic analysis, synthesis, characterization, and evaluation of 1-ethyl-3-methylimidazolium chloride: Study of its effect on pretreated rice husk[J]. 中国化学工程学报, 2023, 60(8): 143-154.
[2]	Zhonghao Li, Yuanyuan Yang, Huanong Cheng, Yun Teng, Chao Li, Kangkang Li, Zhou Feng, Hongwei Jin, Xinshun Tan, Shiqing Zheng. Measurement and model of density, viscosity, and hydrogen sulfide solubility in ferric chloride/trioctylmethylammonium chloride ionic liquid[J]. 中国化学工程学报, 2023, 59(7): 210-221.
[3]	Chen Chen, Qiong Tang, Hong Xu, Mingxing Tang, Xuekuan Li, Lei Liu, Jinxiang Dong. Alkyl-tetralin base oils synthesized from coal-based chemicals and evaluation of their lubricating properties[J]. 中国化学工程学报, 2023, 58(6): 20-28.
[4]	Yutong Jiang, Yifeng Chen, Fuliu Yang, Jixue Fan, Jun Li, Zhuhong Yang, Xiaoyan Ji. Efficient SO₂ removal using aqueous ionic liquid at low partial pressure[J]. 中国化学工程学报, 2023, 58(6): 355-363.
[5]	Zhihao Zhu, Ying Sun, Haijun Yu, Meng Li, Xingming Jie, Guodong Kang, Yiming Cao. Effect of polytetrafluoroethylene hollow fiber microstructure on formaldehyde carbonylation performance in membrane contactor[J]. 中国化学工程学报, 2023, 55(3): 148-155.
[6]	Jialei Sha, Chenyi Liu, Zhihong Ma, Weizhong Zheng, Weizhen Sun, Ling Zhao. Understanding the interfacial behaviors of benzene alkylation with butene using chloroaluminate ionic liquid catalyst: A molecular dynamics simulation[J]. 中国化学工程学报, 2023, 54(2): 44-52.
[7]	Yifeng Chen, Hang Yu, Jingjing Chen, Xiaohua Lu, Xiaoyan Ji. Viscous behavior of 1-hexyl-methylimidazolium bis(trifluoromethylsulfonyl)imide/titanium dioxide/polyethylene glycol[J]. 中国化学工程学报, 2023, 54(2): 280-287.
[8]	Mi Feng, Bin He, Xinyan Chen, Junli Xu, Xingmei Lu, Cai Jia, Jian Sun. Separation of chitin from shrimp shells enabled by transition metal salt aqueous solution and ionic liquid[J]. 中国化学工程学报, 2023, 53(1): 133-141.
[9]	Xinqiang You, Kai Zhao, Ling Li, Ting Qiu. Ionic liquids as entrainer in extractive distillation for effectively separating 1-propanol–water azeotropic mixture[J]. 中国化学工程学报, 2022, 49(9): 224-233.
[10]	Minjie Shi, Hangtian Zhu, Cheng Yang, Jing Xu, Chao Yan. Chemical reduction-induced fabrication of graphene hybrid fibers for energy-dense wire-shaped supercapacitors[J]. 中国化学工程学报, 2022, 47(7): 1-10.
[11]	Xiangjun Li, Shujun Li, Xiaoping Wang, Muhammad Asif Nawaz, Dianhua Liu. Polyoxymethylene dimethyl ethers synthesis from methanol and formaldehyde solution over one-pot synthesized spherical mesoporous sulfated zirconia[J]. 中国化学工程学报, 2022, 46(6): 161-172.
[12]	Song Hu, Jinlong Li, Qihua Wang, Weisheng Yang. Design and optimization of an integrated process for the purification of propylene oxide and the separation of propylene glycol by-product[J]. 中国化学工程学报, 2022, 45(5): 111-120.
[13]	Alireza Afsharpour. A new approach for correlating of H₂S solubility in [emim][Lac], [bmim][ac] and [emim][pro] ionic liquids using two-parts combined models[J]. 中国化学工程学报, 2022, 44(4): 521-527.
[14]	Haiyan Jiang, Lu Bai, Bingbing Yang, Shaojuan Zeng, Haifeng Dong, Xiangping Zhang. The effect of protic ionic liquids incorporation on CO₂ separation performance of Pebax-based membranes[J]. 中国化学工程学报, 2022, 43(3): 169-176.
[15]	Kaili Zhang, Ligang Wei, Qingqin Sun, Jian Sun, Kunlan Li, Shangru Zhai, Qingda An, Junwang Zhang. Effects of formaldehyde on fermentable sugars production in the low-cost pretreatment of corn stalk based on ionic liquids[J]. 中国化学工程学报, 2022, 42(2): 406-414.

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

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价