Preview

Fine Chemical Technologies

Advanced search

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

Full Text:

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

1. Gromova V.V., Mamarasulova Z.V. Thermak esterification of penthaerytrite by aliphatic monocarbonic acids. Izvestiya Sankt-Peterburgskogo gosudarstvennogo tekhnologicheskogo instituta = Bulletin of Saint Petersburg State Institute of Technology. 2013;20(46):64–67 (in Russ.).

2. Faizullina S.R., Builova E.A., Nedopekin D.V., Aminova G.K. Synthesis and properties of some pentaerythritol esters. Bashkirskii khimicheskii zhurnal = Bashkir Chemical Journal. 2016;23(3):41–44 (in Russ.).

3. Kopyshev M.V., Khasin A.V., Minyukova T.P., Khassin A.A., Yurieva T.M. Esterification of pentaerythritol by carboxylic acids. Reac. Kinet. Mech. Cat. 2016;117(2):417–427. https://doi.org/10.1007/s11144-015-0964-7

4. Golysheva E.A., Zhdaneev O.V., Korenev V.V., Lyadov A.S., Rubtsov A.S. Petrochemical industry of Russia: state of the art and prospects for development. Russ. J. Appl. Chem. 2020;93(10):1596–1603. https://doi.org/10.1134/S107042722010158

5. Emel’yanov V.V., Krasnykh E.L., Fetisov D.A., Levanova S.V., Shakun V.A. Synthesis, identification and isolation of esters of pentaerythritol and linear С4–С7 carboxylic acids. Pet. Chem.2021;61(5):1027–1032. https://doi.org/10.1134/S0965544121090048

6. Rabinovich V.A., Khavin Z.Ya. Kratkii khimicheskii spravochnik (Short chemical reference book). 2nd ed., rev. and add. Moscow: Khimiya; 1978.392 p. (in Russ.).

7. Marochkin D.V., Noskov Yu.G., Kron T.E., Karchevskaya O.G., Korneeva G.A. Products of oxo-process in the production of ester lubricating oils. Nauchno-tekhnicheskii vestnik OAO “NK Rosneft’”. 2016;4(45):74–81 (in Russ.).

8. Mancini G., Imparato L., Berti F. Organic ester for use in lubricant compositions: Pat. 4317780 USА. Publ. 02.03.1982.

9. Shabarov Yu.S. Organicheskaya khimiya: ucheb. dlya VUZov (Organic chemistry: textbook for universities). Moscow: Khimiya; 2000. 846 p. (in Russ.). ISBN 5-7245-1180-0

10. Nosovsky Yu.E., Kutsenko A.I., Kochergina G.K., Belkina F.R., Vorobyov V.A., Zhitkov V.I. Method of ester purification: Pat. SU592815A1 USSR. Publ. 15.02.1978.

11. Abdrakhmanova L.K., Rysaev D.U., Aminova G.K., Mazitova A.K. Clarification of di-(2-ethylhexyl)phthalate plasticizer with an aqueous solution of sodium hypochlorite. Bashkirskii khimicheskii zhurnal = Bashkir Chemical Journal. 2008;15(4):38–40 (in Russ.).

12. Kolah A.K., Astana N.S., Vu D.T., Lira C.T., Miller D.J. Reaction kinetics for the heterogeneously catalyzed esterification of succinic acid with ethanol. Ind. Eng. Chem. Res. 2008;47(15):5313–5317. https://doi.org/10.1021/ie0706616

13. Amirkhanov I.R., Kaleeva E.S., Yazmukhamedova I.M., Dzhabarov G.V., Men’shchikova A.A., Balaeva A.V., Zhila M.Yu., Shpakova P.I. Development of a method for the production of synthetic lube oils. Uspekhi v khimii i khimicheskoi tekhnologii = Advances in Chemistry and Chemical Technology. 2017;31(12):36–38 (in Russ.)

14. Ladero M., de Gracia M., Trujillo F., Garcia-Ochoa F. Phenomenological kinetic modelling of the esterification of rosin and polyols. Chem. Eng. J. 2012;197:387–397. https://doi.org/10.1016/j.cej.2012.05.053

15. Emel’yanov V.V., Krasnykh E.L., Portnova S.V. Retention Indices and Sorption Enthalpies of Pentaerythritol and С2 –С8 Acid Esters on Nonpolar Stationary Phases. Russ. J. Phys. Chem. A. 2020;94(10):2168–2176. https://doi.org/10.1134/S003602442010009X


Supplementary files

1. GC–MS spectrum of the obtained pentaerythritol tetrapivalate.
Subject
Type Исследовательские инструменты
View (635KB)    
Indexing metadata
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.
Subject CERTIFICATE OF EDITING
Type Other
View (420KB)    
Indexing metadata
  • 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

Views: 261


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