负载型离子液体催化生物基多元酸酯的制备

doi:10.6023/A25110367

摘要/Abstract

本工作以弱酸性离子交换树脂为载体,以有机胺为修饰剂,通过简单的酸碱中和反应制备得到了一系列负载型离子液体催化剂,并将其应用到生物基多元酸酯的制备当中。以2,5-呋喃二甲醛(DFF)和丙二酸二甲酯(DMM)为底物,以活性最佳的Pyrrolidine-YLST-3为催化剂时,生物基多元酸酯的产率可以达到99.2%。这种制备方法极大的减少了传统氧化过程中氧气等强氧化剂的使用,安全性更高,对设备要求较低。此外,目标产物选择性较高,副产物主要为水,对环境更加友好,更加符合绿色化学原则。通过核磁共振(NMR)、红外光谱(FTIR)、X射线衍射(XRD)和X射线光电子能谱(XPS)等方法对催化剂进行了表征,发现吡咯烷与离子交换树脂之间发生了质子转移,形成了新的负载型离子液体。通过对多种底物的Knoevenagel缩合反应进行研究均取得了较高的收率,说明Pyrrolidine-YLST-3催化剂具有很强的普适性。

关键词: 生物基多元酸酯, 绿色化学, 负载型离子液体, 非均相催化, Knoevenagel缩合反应

Biomass resources, characterized by their wide distribution, carbon neutrality, and renewability, have emerged as ideal alternatives to fossil fuels. Derived from these resources, biobased platform compounds such as 5-hydroxymethylfurfural (HMF) and 2,5-diformylfuran (DFF) exhibit diverse application potential. These biobased platform compounds can be converted into high-value-added chemicals through organic chemical reactions. Bio-based polyacid esters show broad potential for applications in fields such as chemical engineering, polymer materials, and biomedicine, where they can serve as crosslinking agents, lubricants, emulsifiers, among other roles. Conventional methods for synthesizing polybasic acid esters typically involve strong oxidants, intricate processes, and demanding equipment requirements. In this study, we prepared a series of supported ionic liquid catalysts via in-situ acid-base neutralization reaction, employing weak acidic ion exchange resin as the solid support and organic amines as functional modifiers, and used them to the preparation of bio-based polyacid esters. When 2,5-diformylfuran (DFF) and Dimethyl malonate (DMM) were employed as substrates, the yield of bio-based polyacid esters can reach 99.2% in the presence of Pyrrolidine-YLST-3. The structural modifications of the resins were comprehensively characterized using multiple analytical techniques, including Elemental Analysis (EA), Nuclear Magnetic Resonance(NMR), Fourier Transform Infrared Spectroscopy (FTIR), X-ray Diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS). These comprehensive analyses provided conclusive evidence for the successful surface modification of YLST-3 resin with pyrrolidine, revealing distinct chemical interactions between the modifier and the resin. Comprehensive characterization of both fresh and deactivated catalysts was performed using EA, FTIR, and XRD to investigate catalyst deactivation mechanisms. Successful regeneration was accomplished through a two-step protocol involving hydrogen peroxide oxidation followed by pyrrolidine re-modification, which substantially improved cycling stability. Substrate scope evaluation demonstrated that the Pyrrolidine-YLST-3 catalyst exhibited excellent activity in Knoevenagel condensation reactions across diverse substrates, confirming its broad applicability.

Key words: bio-based polyacid ester, Green Chemistry, supported ionic liquids, heterogeneous catalysis, Knoevenagel condensation reaction

引用此文

赵馨雨, 韩燕楠, 徐吉磊, 安庆大, 肖作毅, 苏鑫, 黄家辉. 负载型离子液体催化生物基多元酸酯的制备[J]. 化学学报, doi: 10.6023/A25110367.

Zhao Xinyu, Han Yannan, Xu Jilei, An Qingda, Xiao Zuoyi, Su Xin, Huang Jiahui. Preparation of bio-based polyacid esters catalyzed by supported ionic liquids[J]. Acta Chimica Sinica, doi: 10.6023/A25110367.

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参考文献

[1] Kaygusuz K.Energy Sources, Part B. 2007, 2, 73.
[2] Qiao X. L.; Murshed M.; Alam M. M.; Das N.; Khudoykulov K.; Tariq S.Gondwana Res. 2024, 126, 355.
[3] Deng Y.; Xing C. Y.; Xie X. D.; Cai L.Sustain. Comput.: Inform. Syst. 2022, 36, 100782.
[4] Ayed C.; Huang W.; Kizilsavas G.; Landfester K.; Zhang K. A.I.ChemPhotoChem. 2020, 4, 571.
[5] Eseyin A. E.; Steele P. H.Int. J. Adv. Chem. 2015, 3, 42.
[6] Edumujeze D.;Fournier-Salaün, M.-C.; Leveneur, S.Fuel. 2025, 381, 133423.
[7] Ju J. H.; Xu J. L.; Wang K. J.; Huang J. H.Acta Chim. Sin. 2024, 82, 1216(in Chinese).
(鞠嘉浩,徐吉磊,王康军,黄家辉,化学学报,2024,82,1216.)
[8] Sun W. Q.; Xu J. L.; Li L.; Liu Z.; Xiao Z. Y.; An Q. D.; Huang J. H.Mol. Catal. 2025, 573, 114842.
[9] Han Y. N.; Xu J. L.; Li B. Z.; An Q. D.; Xiao Z. Y.; Huang J. H.ChemCatChem. 2025, 17, e02127.
[10] Kwiatkowska M.; Kowalczyk I.; Szymczyk A.Mater. Today Commun. 2019, 20, 100577.
[11] Bouyahya C.; Patrício R.; Paço A.; Lima M. S.; Fonseca A. C.; Rocha-Santos, T.; Majdoub, M.; Silvestre, A. J. D.; Sousa, A. F.Polymers. 2022, 14, 3868.
[12] Xin C.; Jiang J.; Deng Z. W.; Ou L. J.; He W. M.Acta Chim. Sin. 2024, 82, 1109(in Chinese).
(辛翠,蒋俊,邓紫微,欧丽娟,何卫民,化学学报, 2024, 82, 1109.)
[13] Guo J. R.; Zhang S. Y.; He J. H.; Ren S. X.Acta Chim. Sinica. 2024, 82, 242(in Chinese).
(郭建荣,张书玉,贺军辉,任世学,化学学报,2024, 82, 242.)
[14] Iroegbu A. O.; Sadiku E. R.; Ray S. S.; Hamam Y.Chem. Afr. 2020, 3, 481.
[15] Demirbas M. F.; Balat M.; Balat H.Energy Convers. Manage. 2009, 50, 1746.
[16] Obermeier F.; Hense D.; Stockmann P. N.; Strube O. I.Green Chem. 2024, 26, 4387.
[17] Damle S.; Madankar C.Tenside Surfact. Deterg. 2023, 60, 611.
[18] Tang L. S.; He X. Y.; Huang R.Int. J. Mol. Sci. 2025, 26, 727.
[19] Zhu X. Y.; Jiang P. P.; Leng Y.; Lu M. J.; Lv Z. H.; Li Y. C.; Li Z. H.J. Vinyl Addit. Technol. 2024, 30, 1066.
[20] Fiume M. M.; Bergfeld W. F.; Belsito D. V.; Hill R. A.; Klaassen C. D.; Liebler D. C.; Marks J. G.; Shank R. C.; Slaga T. J.; Snyder P. W.; Gill L. J.; Heldreth B.Int. J. Toxicol. 2023, 42, 5S.
[21] Illa O.; Serra A.; Ardiaca A.; Herrero X.; Closa G.; Ortuño R. M.Int. J. Mol. Sci. 2019, 20, 4333.
[22] Perez F. M.; Gatti M. N.; Fermanelli C. S.; Saux C.; Renzini M. S.; Pompeo F.Next Mater. 2024, 2, 100125.
[23] Yanagawa F.; Sugiura S.; Takagi T.; Sumaru K.; Camci‐Unal, G.; Patel, A.; Khademhosseini, A.; Kanamori, T.Adv. Healthcare Mater. 2014, 4, 246.
[24] Nagendramma P.Lubr. Sci. 2011, 23, 355.
[25] Wei J. J.; Zhu L. L.; Lu Q. Y.; Li G. C.; Zhou Y. L.; Yang Y. M.; Zhang L. Z.J. Controlled Release. 2023, 354, 337.
[26] Picataggio S.; Rohrer T.; Deanda K.; Lanning D.; Reynolds R.; Mielenz J.; Eirich L. D.Bio-Technol. 1992, 10, 894.
[27] Han L.; Peng Y. F.; Zhang Y. Y.; Chen W. J.; Lin Y. P.; Wang Q. H.Front. Microbiol. 2017, 8, 2184.
[28] Kulsrestha G. N.; Shankar U.; Sharma J. S.; Singh J.J. Chem. Technol. Biotechnol. 2007, 50, 57.
[29] Tian H.; Zhang Y. J.; Yu D.; Yang X.; Wang H.; Matindi C.; Yin Z.; Hui H. S.; Mamba B. B.; Li J. X.Electrochim. Acta. 2022, 426, 140796.
[30] Matsumura Y.; Yamamoto Y.; Moriyama N.; Furukubo S.; Iwasaki F.; Onomura O.Tetrahedron Lett. 2004, 45, 8221.
[31] Gauthard F.; Horvath B.; Gallezot P.; Besson M.Appl. Catal., A. 2005, 279, 187.
[32] Lisicki D.; Orlinska B.Pol. J. Chem. Technol. 2018, 20, 102.
[33] Ribeiro A. P.C.; Spada, E.; Bertani, R.; Martins, L. M. D. R. S.Catalysts. 2020, 10, 1443.
[34] Li J.; Liu Y.; Gan F. F.; Yang Y. X.Chin. J. Anal. Lab. 2017, 36, 726.
[35] Hu Y. C.; Yuan L.; Zhang X. L.; Zhou H.; Wang P.; Li G.; Wang A. Q.; Cong Y.; Zhang T.; Liang X. M.; Li W.; Li N.ACS Sustainable Chem. Eng. 2019, 7, 2980.
[36] Yuan L.; Hu Y. C.; Li G. Y.; Han F. G.; Wang A. Q.; Cong Y.; Zhang T.; Wang F.; Li N.Green Energy Environ. 2024, 9, 1267.
[37] Liu S. S.; Dong W. W.; Li Z. Z.; Zhang Y. Y.; Li C.; Jiao L. Y.Acta Chim. Sinica. 2025, 83, 479(in Chinese).
(刘珊珊, 董微微,李珍珍,张瑶瑶,李超,焦林郁,化学学报,2025,83, 479.)
[38] Sood K.; Saini Y.; Thakur K. K.Mater. Today: Proc. 2023, 81, 739.
[39] Aggarwal A.; Singh A.; Chopra H. K.Curr. Org. Chem. 2023, 27, 130.
[40] Ma M.; Li H. S.; Yang W.; Wu Q.; Shi D. X.; Zhao Y.; Feng C. H.; Jiao Q. Z.Catal. Lett. 2017, 148, 134.
[41] Yao N.; Tan J.; Liu X.; Liu Y.; Hu Y. L.J. Saudi Chem. Soc. 2019, 23, 740.
[42] Rui Li, J.; Chen, C.; Hu, Y. L.ChemistrySelect. 2020, 5, 14578.
[43] Korhonen H.; Helminen A. O.; Seppälä J. V.Macromol. Chem. Phys. 2004, 205, 937.
[44] Wójcika M. J.; Tatara W.; Boczar M.; Apola A.; Ikeda S.J. Mol. Struct. 2001, 596, 207.
[45] Galkina Y. A.; Kryuchkova N. A.; Vershinin M. A.; Kolesov B. A.J. Struct. Chem. 2017, 58, 911.
[46] Herbert J. M.;Head-Gordon, M.J. Am. Chem. Soc. 2006, 128, 13932.
[47] Lees R. M.; Sun Z. D.; Billinghurst B. E.J. Chem. Phys. 2011, 135, 104306
[48] Hasnat A.; Juvekar V. A.AIChE J. 2004, 42, 161.
[49] Kwan Y. C.G.; Ng, G. M.; Huan, C. H. A.Thin Solid Films. 2015, 590, 40.
[50] Rushdi A. I.; Simoneit B. R.T.Astrobiology. 2004, 4, 211.
[51] Su M. D.; Liu Y. F.; Nie Z. W.; Yang T. L.; Cao Z. Z.; Li H.; Luo W. P.; Liu Q.; Guo C. C.J. Org. Chem. 2022, 87, 7022.
[52] Masoudi-Khoram, M.; Zargarian, M.; Nematollahi, D.; Zolfigol, M. A.; Sepehrmansourie, H.; Khazalpour, S.Electrochim. Acta. 2023, 437, 141512.
[53] Wang L.; Xu G.; Xiao J.; Tao M. L.; Zhang W. Q.Ind. Eng. Chem. Res. 2019, 58, 12401.
[54] Zhao S. X.J. Mol. Struct. 2018, 1167, 11.
[55] Anbu N.; Maheswari R.; Elamathi V.; Varalakshmi P.; Dhakshinamoorthy A.Catal. Commun. 2020, 138, 105954.
[56] Sobrinho R. C.M. A.; Oliveira, P. M. d.; D'Oca, C. R. M.; Russowsky, D.; D'Oca, M. G. M.RSC Adv. 2017, 7, 3214.
[57] Hu X. M.; Ngwa C.; Zheng Q. G.Curr. Org. Synth. 2016, 13, 101.