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Features of the synthesis of pentaerythritol esters and carboxylic acids of aliphatic isomeric structure

https://doi.org/10.32362/2410-6593-2022-17-1-7-17

Abstract

Objectives. Due to their structures, pentaerythritol esters have a number of appealing properties such as high viscosity index when used as oils and excellent compatibility with polyvinyl chloride when used as plasticizers. For the production of pentaerythritol and carboxylic acids, natural gas can be used as a feedstock, which implies a strategic development of the petrochemical industry, a decrease in the amount of gas used for combustion, and its applications for the production of chemical products.

Methods. The synthesis process was conducted in a self-catalysis mode with excess acids in a molar ratio of 8:1 and in the presence of a solvent (toluene) of ~30% per reaction mass. This ensures a uniform distillation of the reaction water at a constant temperature of 100–110 °C, a decrease in the side reaction products, and an increase in process selectivity. The products from the reaction mass were isolated by vacuum distillation, and identification of all the synthesized tetraesters was performed by chromatography–mass spectrometry analysis.

Results. This work proposes options for optimizing the conditions of the thermal esterification of pentaerythritol with isomeric monocarboxylic acids (isobutyric, isovaleric, pivalic, and 2-ethylhexanoic acids) that have different reactivities due to their structures. Methods for isolating tetraesters of pentaerythritol and corresponding acids have been developed. The characteristics of the main series of ions of tetraesters of pentaerythritol and aliphatic isomeric acids C4–C8 in the mass spectra were obtained.

Conclusions. The yields of tetraesters were at 95%–96% of the theoretical value, and product purity was >99.6%. The resulting target products (tetraesters) were characterized by relative color stability, where the maximum degree of color after cleaning was less than 20 units according to Hazen (180 units for tetra-2-ethylhexnoate), which corresponds to the standards in GOST 29131-91 (ISO 2211-73). The esterification rates were compared, and it was shown that the quantitative yields of isomeric tetraesters at 100–110 °C were achieved in 12–15 h for isobutyric and isovaleric acids, 25–27 h for 2-ethyl-hexanoic acid, and ~40 h for pivalic acid.  

About the Authors

V. V. Emelyanov
Samara State Technical University
Russian Federation

Vladimir V. Emelyanov, Postgraduate Student, Technology of Organic and Petrochemical Synthesis Department

244, Molodogvardeyskaya ul., Samara, 443100


Competing Interests:

The authors declare no conflicts of interest



E. L. Krasnykh
Samara State Technical University
Russian Federation

Eugen L. Krasnykh, Dr. Sci. (Chem.), Associate Professor, Head of the Technology of Organic and Petrochemical Synthesis Department

244, Molodogvardeyskaya ul., Samara, 443100


Competing Interests:

The authors declare no conflicts of interest



D. A. Fetisov
Samara State Technical University
Russian Federation

Dmitriy A. Fetisov, Master Student, Technology of Organic and Petrochemical Synthesis Department

244, Molodogvardeyskaya ul., Samara, 443100


Competing Interests:

The authors declare no conflicts of interest



S. V. Levanova
Samara State Technical University
Russian Federation

Svetlana V. Levanova, Dr. Sci. (Chem.), Professor, Technology of Organic and Petrochemical Synthesis Department

244, Molodogvardeyskaya ul., Samara, 443100


Competing Interests:

The authors declare no conflicts of interest



V. A. Shakun
Samara State Technical University
Russian Federation

Vladimir A. Shakun, Cand. Sci. (Chem.), Associate Professor, Technology of Organic and Petrochemical Synthesis Department

244, Molodogvardeyskaya ul., Samara, 443100


Competing Interests:

The authors declare no conflicts of interest



References

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Supplementary files

1. GC–MS spectrum of the obtained pentaerythritol tetrapivalate.
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2. This is to certify that the paper titled Features of the synthesis of pentaerythritol esters and carboxylic acids of aliphatic isomeric structure commissioned to us by Vladimir V. Emelyanov, Eugen L. Krasnykh, Dmitriy A. Fetisov, Svetlana V. Levanova, Vladimir A. Shakun has been edited for English language and spelling by Enago, an editing brand of Crimson Interactive Inc.
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  • Options for optimizing the conditions of thermal esterification of pentaerythritol with isomeric monocarboxylic acids (isobutyric, isovaleric, pivalic, and 2-ethylhexanoic acids) were proposed.
  • Methods for isolating tetraesters of pentaerythritol and corresponding acids were developed.
  • The characteristics of the main series of ions of tetraesters of pentaerythritol and aliphatic isomeric acids C4–C8 in mass spectra were obtained.
  • The resulting target products (tetraesters) are relative color stable.

Review

For citations:


Emelyanov V.V., Krasnykh E.L., Fetisov D.A., Levanova S.V., Shakun V.A. Features of the synthesis of pentaerythritol esters and carboxylic acids of aliphatic isomeric structure. Fine Chemical Technologies. 2022;17(1):7-17. https://doi.org/10.32362/2410-6593-2022-17-1-7-17

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ISSN 2410-6593 (Print)
ISSN 2686-7575 (Online)