Brønsted-acidic ionic liquids as efficient catalysts for the synthesis of polyoxymethylene dialkyl ethers

doi:10.1016/S1872-2067(17)62816-X

Abstract

Abstract:

Acetalation of formaldehyde (HCHO) with dialkyl formal or aliphatic alcohol to prepare polyoxymethylene dialkyl ethers (RO(CH₂O)_nR, n ≥ 1) catalyzed by Brønsted-acidic ionic liquids has been developed. The correlation between the structure and acidity activity of various ionic liquids was studied. Among the ionic liquids investigated, 1-(4-sulfonic acid)butyl-3-methylimidazolium hydrogen sulfate ([MIMBs]HSO₄) exhibited the best catalytic performance in the reaction of diethoxymethane (DEM₁) with trioxane. The influences of ionic liquid loading, molar ratio of DEM₁ to HCHO, reaction temperature, pressure, time, and reactant source on the catalytic reaction were explored using [MIMBs]HSO₄ as the catalyst. Under the optimal conditions of n([MIMBs]HSO₄):n(DEM₁):n(HCHO) = 1:80:80, 140℃, and 4 h, the conversion of HCHO and selectivity for DEM_2-8 were 92.6% and 95.1%, respectively. The [MIMBs]HSO₄ catalyst could be easily separated and reused. A feasible mechanism for the catalytic performance of [MIMBs]HSO₄ was proposed.

Key words: Acetalation reaction, Polyoxymethylene dialkyl ether, Diethoxymethane, Formaldehyde, Brø, nsted-acidic ionic liquid

Heyuan Song, Meirong Kang, Fuxiang Jin, Guoqin Wang, Zhen Li, Jing Chen. Brønsted-acidic ionic liquids as efficient catalysts for the synthesis of polyoxymethylene dialkyl ethers[J]. Chinese Journal of Catalysis, 2017, 38(5): 853-861.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(17)62816-X

https://www.cjcatal.com/EN/Y2017/V38/I5/853

References

[1] Y. H. Lei, Q. Sun, Z. X. Chen, J. Y. Shen, Acta Chim. Sin., 2009, 67, 767–772.
[2] T. H. Fleisch, R. A. Sills, Stud. Surf. Sci. Catal., 2004, 147, 31–36.
[3] W. Mashiro, U. Hiroyuki, B. Steve, D. Jean-Lue, EP Patent 1 993 159, 2008.
[4] H. Staudinger, M. Lüthy, Helv. Chim. Acta, 1925, 8, 41–64.
[5] W. F. Gresham, R. E. Brooks, US Patent 2 449 469, 1948.
[6] P. Renata, M. Marchionna, EP Patent 1 505 049 A1, 2005.
[7] R. Patrial, M. Marchionna, US Patent 6 534 685 B1, 2003.
[8] H. Schelling, E. Stroefer, R. Pinkos, A. Haunert, G. D. Tebben, H. Hasse, S. Blagov, US Patent 20 070 260 094 A1, 2007.
[9] E. Stroefer, H. Hasse, S. Blagov, US Patent 20 080 207 954 A1, 2008.
[10] J. Burger, M. Siegert, E. Ströfer, H. Hasse, Fuel, 2010, 89, 3315–3319.
[11] Y. Y. Zheng, Q. Tang, T. F. Wang, Y. H. Liao, J. F Wang, Chem. Eng. Technol., 2013, 36, 1951–1956.
[12] Q. Zhao, H. Wang, Z. F. Qin, Z. W. Wu, J. B. Wu, W. B. Fan, J. G. Wang, J. Fuel Chem. Technol., 2011, 39, 918–923.
[13] J. Cao, H. Q. Zhu, H. Wang, L. Z. Huang, Z. F. Qin, W. B. Fan, J. G. Wang, J. Fuel Chem. Technol., 2014, 42, 986–993.
[14] J. Q. Zhang, D. Y. Fang, D. H. Liu, Ind. Eng. Chem. Res., 2014, 53, 13589–13597.
[15] X. Zhang, M. B. Tu, M. G. Paice, Bioenergy Res., 2011, 4, 246–257.
[16] A. S. Amarasekara, Chem. Rev., 2016, 116, 6133–6183.
[17] A. Pinkert, K. N. Marsh, S. S. Pang, M. P. Staiger, Chem. Rev., 2009, 109, 6712–6728.
[18] M. E. Zakrzewska, E. Bogel-Lukasik, R. Bogel-Lukasik, Chem. Rev., 2011, 111, 397–417.
[19] V. I. Parvulescu, C. Hardacre, Chem. Rev., 2007, 107, 2615–2665.
[20] J. P. Hallett, T. Welton, Chem. Rev., 2011, 111, 3508–3576.
[21] D. Yang, D. L. Wang, H. Liu, X. L. Zhao, Y. Lu, S. J. Lai, Y. Liu, Chin. J. Catal., 2016, 37, 405–411.
[22] A. H. Tamboli, A. A. Chaugule, F. A. Sheikh, W. J. Chung, H. Kim, Chin. J. Catal., 2015, 36, 1365–1371.
[23] J. Chen, H. Y. Song, C. G. Xia, Z. H. Tang, US Patent 8 344 183 B2, 2013.
[24] J. Chen, H. Y. Song, C. G. Xia, Z. Li, US Patent 8 816 131 B2, 2014.
[25] C. G. Xia, H. Y. Song, J. Chen, Z. Li, US Patent 8 987 521 B2, 2015.
[26] J. Chen, H. Y. Song, C. G. Xia, M. R. Kang, R. H. Jin, US Patent 9 067 188 B2, 2015.
[27] C. G. Xia, H. Y. Song, J. Chen, F. X. Jin, M. R. Kang, US Patent 9 169 186 B2, 2015.
[28] J. Chen, H. Y. Song, C. G. Xia, M. R. Kang, US Patent 9 168 503 B2, 2015.
[29] Q. Wu, M. Wang, Y. Hao, H. S. Li, Y. Zhao, Q. Z. Jiao, Ind. Eng. Chem. Res., 2014, 53, 16254–16260.
[30] A. C. Cole, J. L. Jensen, I. Ntai, K. L. T. Tran, K. J. Weaver, D. C. Forbes, J. H. Davis Jr, J. Am. Chem. Soc., 2002, 124, 5962–5963.
[31] D. Fang, Q. R. Shi, J. Cheng, K. Gong, Z. L. Liu, Appl. Catal. A, 2008, 345, 158–163.
[32] Y. P. Zhao, Z. Xu, H. Chen, Y. C. Fu, J. Y. Shen, J. Energy Chem., 2013, 22, 833–836.
[33] F. Wang, G. L. Zhu, Z. Li, F. Zhao, C. G. Xia, J. Chen, J. Mol. Catal. A, 2015, 408, 228–236.
[34] M. A. Paul, J. Am. Chem. Soc., 1950, 72, 3813–3814.