DOI: https://doi.org/10.15587/1729-4061.2017.114324

Research into esterification of mixture of lower dicarboxylic acids by 2-ethylhexan-1-ol in the presence of p-toluensulfonic acid

Stepan Melnyk, Yuriy Melnyk, Irena Nykulyshyn, Liliya Shevchuk

Abstract


Regularities of esterification of the mixture of lower dicarboxylic acids (succinic, glutaric, adipic) by 2-ethylhexan-1-ol in the presence of catalysts – p-toluensulfonic and sulfuric acids under non-stationary conditions were studied. It was found that in the presence of mineral acid, the reaction flows at a lower rate. Application of benzene as a substance that facilitates separation of water, formed in the esterification reaction, makes it possible, due to a lower reaction temperature, to decrease energy consumption of the process at an increase in conversion of dicarboxylic acids from 95.8 to 99.5 %. It was shown that the use of activated carbon of different brands simultaneously with catalysis by p-toluensulfonic acid with virtually the same effectiveness can decrease chromaticity intensity of esterification products by more than three times. The use of finely dispersed activated carbon 208CP and DCL 200 compared with coarse-grained activated carbon BAU-A additionally provides higher intensity of esterification reaction due to improvement of removal of water from the reaction mixture. It was found that an increase in the content of activated carbon DLC 200 by more than 0.3 % by weight in the reaction mixture contributes to a sharp decrease in the process intensity. This influence is explained by neutralization of a part of the catalysts by alkaline components of activated carbon, which decreases its active concentration and inhibits the reaction. Optimum conditions of the esterification process were proposed. The authors determined dependences of density and kinematic viscosity of the mixture of diesters of succinic, glutaric and adipic acids, and 2-ethylhexan-1-ol, separated from the esterification reaction products, on temperature and described them with regression equations


Keywords


esterification; lower dicarboxylic acids; 2-ethylhexan-1-ol; p-toluensulfonic acid; diesters.

References


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GOST Style Citations


FlexiSolv® solvent solutions – The Balanced Alternative [Electronic resource]. – Available at: http://flexisolv.com/en/index.html

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Nafikova, R. F. Poluchenie ftalatnogo plastifikatora s ispol'zovaniem kubovyh ostatkov butilovyh spirtov [Text] / R. F. Nafikova, Zh. F. Rahmatullina, A. A. Rahimkulova et. al. // Bashk. him. zhurnal. – 2006. – Vol. 13, Issue 3. – P. 60–62.

Enyutina, M. V. Nekotorye aspekty reaktsii eterifikatsii spirtovyh othodov pishchevyh i neftekhimicheskih proizvodstv [Text] / M. V. Enyutina, Yu. M. Petyhin // Materialy 41 otchetnoy nauchnoy konferentsii za 2002 god. – Voronezh: Izd-vo VGTA, 2003. – P. 207–208.

DOA – dioktiladipinat [Electronic resource]. – Available at: http://rpch.ru/katalog/plastifikatory/doa-dioktiladipinat/

Altnau, G. G. Alternative Lösemittel: Mehr Mut zum Wechseln [Text] / G. G. Altnau // Git Sicherheit+Management. – 2000. – Issue 2. – P. 178–179.

Otera, J. Esterification: Methods, Reactions, and Applications [Text] / J. Otera, J. Nishikido. – WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, Second, Completely Revised, and Enlarged Edition, 2010. – 374 р. doi: 10.1002/9783527627622 

Baghernejad, B. Application of p-toluenesulfonic Acid (PTSA) in Organic Synthesis [Text] / B. Baghernejad // Current Organic Chemistry. – 2011. – Vol. 15, Issue 17. – P. 3091–3097. doi: 10.2174/138527211798357074 

Sakakura, A. Open-air and solvent-free ester condensation catalyzed by sulfonic acids [Text] / A. Sakakura, Y. Koshikari, K. Ishihara // Tetrahedron Letters. – 2008. – Vol. 49, Issue 34. – P. 5017–5020. doi: 10.1016/j.tetlet.2008.06.058 

Kriska, C. E. The efficacy of some catalysts used in synthesis of phthalates [Text] / C. E. Kriska, D. Modra // Annals of West University of Timisoara. Series of Chemistry. – 2012. – Vol. 21, Issue 2. – Р. 47–56.

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Pacheco, B. S. Eco-friendly synthesis of esters under ultrasound withp-toluenesulfonic acid as catalyst [Text] / B. S. Pacheco, C. F. P. Nunes, C. T. Rockembach, P. Bertelli, M. F. Mesko, M. Roesch-Ely et. al. // Green Chemistry Letters and Reviews. – 2014. – Vol. 7, Issue 3. – P. 265–270. doi: 10.1080/17518253.2014.941950 

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Melnyk, S. R. Syntez diesteriv na osnovi spyrtiv S4–S5 [Text] / S. R. Melnyk, Yu. R. Melnyk, N. Ya. Kachmar, V. V. Reutskyi // Visnyk Natsionalnoho universytetu „Lvivska politekhnika”. – 2005. – Issue 529. – P. 128–130.

Ekofil'tr-Sorbosgrup. Aktivirovannyy ugol' Chemviron Carbon [Electronic resource]. – Available at: http://activcarbon.com.ua/category/21.html

Methodology for Lipids. Estimation of free fatty acids [Electronic resource]. – Available at: http://www.biocyclopedia.com/index/plant_protocols/lipids/Estimation_of_free_fatty_acids.php

Technical Data Sheet Eastman™ 2-Ethylhexanol [Electronic resource]. – Available at: http://ws.eastman.com/ProductCatalogApps/PageControllers/ProdDatasheet_PC.aspx?product=71000124

Ekofil'tr-Sorbosgrup. Aktivirovannyy ugol' 208CP [Electronic resource]. – Available at: http://activcarbon.com.ua/product/32.html

SORBIS GROUP. Sorbenty tol'ko vysshego kachestva. Ugol' aktivirovannyy (BAU-A) [Electronic resource]. – Available at: http://sorbis-group.com/products/ugol-aktivirovan/ugol-aktivirovan-bau-a.php

Melnyk, S. Selectivity of Formation and Yield of Dicarboxylic Acid Mono- and Diesters under Stationary Conditions [Text] / S. Melnyk, B. Dzinyak // Chemistry & Chemical Technology. – 2015. – Vol. 9, Issue 3. – P. 325–332. doi: 10.23939/chcht09.03.325 







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ISSN (print) 1729-3774, ISSN (on-line) 1729-4061