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Microporous Titanosilicates as Heterogeneous Catalysts for Basic Organic Synthesis

Received: 25 November 2021    Accepted: 11 January 2022    Published: 21 January 2022
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Abstract

The products of the reactions of ethylene oxide with fatty alcohols, acids and amines are of great industrial importance. They include surfactants, plasticizers and insecticides. The reactions can be generally represented as oligomerization. Interaction between ethylene oxide and alcohols can proceed in the presence of acidic as well as basic catalysts; the main distinction being in the quantitative distribution of reaction products. In the presence of basic catalysts the rate of reaction increases with the molecular weight of the products and polyaddition reaction products have a wide distribution of molecular weights. Most of the information available comes from the well investigated uses of homogeneous bases as catalysts. Research on the use of solid catalysts in this area is comparatively recent. Heterogeneous catalysts, such as the synthetic zeolites, are better known as acid catalysts. Heterogeneous catalysts with well-defined sites able to display basic properties over a wide pH range, whilst retaining insolubilty and thermal stability, are little known. This work described herein studies the basic properties of two microporous titanosilicates, known as ETS-4 and ETS-10. Determinations of surface basicity were also carried out by following the titration method. The titanosilicates were examined as catalysts for the ethoxylation of ethylene glycol. One-parameter experiments showed that the processes observed had a first-order dependence on the concentrations of ethylene oxide and catalyst. The excess of alcohol present was assumed to lead to a first-order dependence on alcohol concentration as confirmed by studies on basic. The interaction of the proton donor agent with ethylene oxide proceeds through a tri-molecular transition state. The activated C-O bond is opened by a nucleophilic attack; a similar mechanism to an SN2 nucleophilic replacement. Titanosilicates are very effective catalysts with basic sites for organic synthesis processes.

Published in Modern Chemistry (Volume 10, Issue 1)
DOI 10.11648/j.mc.20221001.11
Page(s) 1-4
Creative Commons

This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited.

Copyright

Copyright © The Author(s), 2022. Published by Science Publishing Group

Keywords

Titanosilicates, Alcohol Ethoxylation, Basic Catalyst

References
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[2] A. E. Kapustin, N. N. Grekova and O. V. Lebedeva. (1997) J. Ukr. Chem., 63, 25.
[3] N. N. Lebedev and V. F. Shvets. (1980) Trans. Mendeleev Univ., 115, 87.
[4] M. N. Timofeeva, A. E. Kapustin and E. O. Butenko. Synthetic and natural materials with the brucite-like layers as high active catalyst for synthesis of 1-methoxy-2-propanol from methanol and propylene oxide (2016) J. Mol. Cat. A: Chem., 423, 22. doi: 10.1016/j.molcata.2016.06.006.
[5] E. O. Butenko, A. E. Kapustin (2020) Mercarbide catalyst for alcohol ethoxylatiom. Journal. of Siberian Federal University. Chemistry, 13, 3. doi: 10.17516/1998-2836-0186.
[6] Tapio Salmi (2012) Ethylene oxide – kinetics and mechanism. Current Opinion in Chemical Engineering, V. 1-3. doi: 10.1016/j.coche.2012.06.002.
[7] Georges, A. M.; Arturo, G.; Marc, E. L. (2001) Kinetics of the reactions of ethylene oxide with water and ethylene glycols. Process Safety Progress, V. 20. doi: 10.1002/prs.680200405.
[8] Butenko E., Kapustin A., Dan, O. (2018) Propylene oxide polymerization in the presence of layered double hydroxides. Chemistry-Didactics-Ecology-Metrology, V. 23, N. 1-2. doi: 10.1515/cdem-2018-0009.
[9] Butenko, E.; Kapustin, A. (2019) Catalysis by Pillared Layered Double Hydroxides. Biomedical Journal of Scientific & Technical Research (BJSTR), V. 22, N1. doi: 10.26717/BJSTR.2019.22.003681.
[10] David P. Penaloza. (2019) Modified clay for the synthesis of clay-based nanocomposites. Epitoanyag, V. 71, N 1. doi: 10.14382/epitoanyag-jsbcm.2019.2.
[11] Butenko, E.; Kapustin, A. (2019) Sorption reseaches on the removal of the bond ammonia from the wastewater. Epitoanyag, V. 71, N 3, doi: 10.14382/epitoanyag-jsbcm.2019.15.
[12] Jinchang, Z.; Tiechun, L. (2019) Facile synthesis of a highly effective layered double hydroxide catalyst and its application in the one-step ethoxylation of butyl acetate to oligo-ethylene glycol butyl ether acetates. Ind. Eng. Chem. Res. doi: 10.1021/acs.iecr.9b01892.
[13] Rupp M., Klemm E., Ruback W. (2013) Alcohol ethoxylation kinetics: Proton transfer influence on product distribution in microchannels. Chemical Engineering and Processing, V. 74 doi: 10.1016/j.cep.2013.09.006.
[14] Kozlovskiy R., Makarov M. G., Shvets V. F. (2011) Oxyethylation kinetics of acetic acid and acetic anhydride during catalysis by polymer anion exchangers. Chemical industry today. № 6.
[15] Wadhmode S., Thakur V. (2001) Efficient liquid phase acylation of alcohols over basic ETS-10 molecular sieves. Tetrahedron Letters. 2001. V. 42. N. 17. doi: 10.1016/S0040-4039(01)00389-6.
[16] Bialowas E., Scymanowski (2004) J. Catalysts for Oxyethylation of Alcohols and Fatty Acid Methyl Esters. Ind. Eng. Chem. Res. V. 43. doi: 10.3389/fceng.2021.617701.
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    Eleonora Butenko, Alexey Kapustin. (2022). Microporous Titanosilicates as Heterogeneous Catalysts for Basic Organic Synthesis. Modern Chemistry, 10(1), 1-4. https://doi.org/10.11648/j.mc.20221001.11

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    ACS Style

    Eleonora Butenko; Alexey Kapustin. Microporous Titanosilicates as Heterogeneous Catalysts for Basic Organic Synthesis. Mod. Chem. 2022, 10(1), 1-4. doi: 10.11648/j.mc.20221001.11

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    AMA Style

    Eleonora Butenko, Alexey Kapustin. Microporous Titanosilicates as Heterogeneous Catalysts for Basic Organic Synthesis. Mod Chem. 2022;10(1):1-4. doi: 10.11648/j.mc.20221001.11

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  • @article{10.11648/j.mc.20221001.11,
      author = {Eleonora Butenko and Alexey Kapustin},
      title = {Microporous Titanosilicates as Heterogeneous Catalysts for Basic Organic Synthesis},
      journal = {Modern Chemistry},
      volume = {10},
      number = {1},
      pages = {1-4},
      doi = {10.11648/j.mc.20221001.11},
      url = {https://doi.org/10.11648/j.mc.20221001.11},
      eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.mc.20221001.11},
      abstract = {The products of the reactions of ethylene oxide with fatty alcohols, acids and amines are of great industrial importance. They include surfactants, plasticizers and insecticides. The reactions can be generally represented as oligomerization. Interaction between ethylene oxide and alcohols can proceed in the presence of acidic as well as basic catalysts; the main distinction being in the quantitative distribution of reaction products. In the presence of basic catalysts the rate of reaction increases with the molecular weight of the products and polyaddition reaction products have a wide distribution of molecular weights. Most of the information available comes from the well investigated uses of homogeneous bases as catalysts. Research on the use of solid catalysts in this area is comparatively recent. Heterogeneous catalysts, such as the synthetic zeolites, are better known as acid catalysts. Heterogeneous catalysts with well-defined sites able to display basic properties over a wide pH range, whilst retaining insolubilty and thermal stability, are little known. This work described herein studies the basic properties of two microporous titanosilicates, known as ETS-4 and ETS-10. Determinations of surface basicity were also carried out by following the titration method. The titanosilicates were examined as catalysts for the ethoxylation of ethylene glycol. One-parameter experiments showed that the processes observed had a first-order dependence on the concentrations of ethylene oxide and catalyst. The excess of alcohol present was assumed to lead to a first-order dependence on alcohol concentration as confirmed by studies on basic. The interaction of the proton donor agent with ethylene oxide proceeds through a tri-molecular transition state. The activated C-O bond is opened by a nucleophilic attack; a similar mechanism to an SN2 nucleophilic replacement. Titanosilicates are very effective catalysts with basic sites for organic synthesis processes.},
     year = {2022}
    }
    

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  • TY  - JOUR
    T1  - Microporous Titanosilicates as Heterogeneous Catalysts for Basic Organic Synthesis
    AU  - Eleonora Butenko
    AU  - Alexey Kapustin
    Y1  - 2022/01/21
    PY  - 2022
    N1  - https://doi.org/10.11648/j.mc.20221001.11
    DO  - 10.11648/j.mc.20221001.11
    T2  - Modern Chemistry
    JF  - Modern Chemistry
    JO  - Modern Chemistry
    SP  - 1
    EP  - 4
    PB  - Science Publishing Group
    SN  - 2329-180X
    UR  - https://doi.org/10.11648/j.mc.20221001.11
    AB  - The products of the reactions of ethylene oxide with fatty alcohols, acids and amines are of great industrial importance. They include surfactants, plasticizers and insecticides. The reactions can be generally represented as oligomerization. Interaction between ethylene oxide and alcohols can proceed in the presence of acidic as well as basic catalysts; the main distinction being in the quantitative distribution of reaction products. In the presence of basic catalysts the rate of reaction increases with the molecular weight of the products and polyaddition reaction products have a wide distribution of molecular weights. Most of the information available comes from the well investigated uses of homogeneous bases as catalysts. Research on the use of solid catalysts in this area is comparatively recent. Heterogeneous catalysts, such as the synthetic zeolites, are better known as acid catalysts. Heterogeneous catalysts with well-defined sites able to display basic properties over a wide pH range, whilst retaining insolubilty and thermal stability, are little known. This work described herein studies the basic properties of two microporous titanosilicates, known as ETS-4 and ETS-10. Determinations of surface basicity were also carried out by following the titration method. The titanosilicates were examined as catalysts for the ethoxylation of ethylene glycol. One-parameter experiments showed that the processes observed had a first-order dependence on the concentrations of ethylene oxide and catalyst. The excess of alcohol present was assumed to lead to a first-order dependence on alcohol concentration as confirmed by studies on basic. The interaction of the proton donor agent with ethylene oxide proceeds through a tri-molecular transition state. The activated C-O bond is opened by a nucleophilic attack; a similar mechanism to an SN2 nucleophilic replacement. Titanosilicates are very effective catalysts with basic sites for organic synthesis processes.
    VL  - 10
    IS  - 1
    ER  - 

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Author Information
  • Department of Chemical Technology and Engineering, Priazovskiy State Technical University, Mariupol, Ukraine

  • Department of Chemical Technology and Engineering, Priazovskiy State Technical University, Mariupol, Ukraine

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