Study of calcium-containing compounds as catalysts for the esterification of glycerol with higher carboxylic acids

Objectives. To investigate the catalytic activity of calcium-containing basic catalysts for the esterification of glycerol with higher carboxylic acids in order to develop a low-waste technology for the production of multifunctional additives, as well as to assess the possibility of using the reacti...

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Main Authors: Yu. L. Zotov, D. M. Zapravdina, E. V. Shishkin, Yu. V. Popov
Format: Article
Language:Russian
Published: MIREA - Russian Technological University 2023-08-01
Series:Тонкие химические технологии
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Online Access:https://www.finechem-mirea.ru/jour/article/view/1969
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author Yu. L. Zotov
D. M. Zapravdina
E. V. Shishkin
Yu. V. Popov
author_facet Yu. L. Zotov
D. M. Zapravdina
E. V. Shishkin
Yu. V. Popov
author_sort Yu. L. Zotov
collection DOAJ
description Objectives. To investigate the catalytic activity of calcium-containing basic catalysts for the esterification of glycerol with higher carboxylic acids in order to develop a low-waste technology for the production of multifunctional additives, as well as to assess the possibility of using the reaction products for the processing of polyvinyl chloride.Methods. The consumption of oleic acid during synthesis was monitored using a titrimetric method of analysis with visual indication. The structure of the synthesized calcium-containing catalysts was confirmed by infrared spectroscopy; elemental analysis was additionally performed for calcium glyceroxide. Quantitative and qualitative analyses of the resulting mixtures of oleic acid glycerides were carried out using chromato-mass spectrometry. A sample of a multifunctional additive was tested in a model formulation of a medical plastic compound based on polyvinyl chloride.Results. It is shown that the catalytic activity of calcium derivatives in the reaction of esterification of glycerol with higher carboxylic acids increases in the series СаО < Са(ОН)2 < Ca(C17H33COO)2 < Ca(C2H5O)2 < Ca(C4H9O)2 < Ca(C3H7O3)2, while the use of calcium glyceroxide as a catalyst in an amount from 1 to 6 mol % increases the conversion of carboxylic acid from 58 to 86% in 10 h of synthesis. However, varying the amount of calcium glyceroxide from 1.5 to 6 mol % results in no observed changes in the conversion of carboxylic acid. The multifunctional additive obtained by selecting calcium glyceroxide as a catalyst has a thermally stabilizing and plasticizing effect on the polymer composition. The introduction of the developed additive into the formulation of a polyvinyl chloride composition for medical purposes reduces the processing torque and time to reach the dry point. By combining these factors, energy costs during production were reduced by more than 11% compared to the control composition.Conclusions. It is established that calcium alcoholates catalyze the reaction of esterification of glycerol with oleic (or higher) acid to increase the conversion of the initial substances and selectivity for the formation of monoglycerides as compared with calcium oxide, hydroxide, and oleate. By optimizing the ratio of glycerol : oleic acid : calcium glyceroxide at 1 : 1 : 0.015, the maximum conversion of oleic acid of up to 86% in 10 h was obtained via synthesis. The proposed method for esterification of glycerol with higher carboxylic acids in the presence of a calcium-containing catalyst avoids the stage of purification from the catalyst to obtain a composition with multifunctional additive properties for the processing of polyvinyl chloride.
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spelling doaj-art-2c1bf2cfa0724d12934dd765f0a49ca92025-08-20T03:23:07ZrusMIREA - Russian Technological UniversityТонкие химические технологии2410-65932686-75752023-08-0118317518610.32362/2410-6593-2023-18-3-175-1861715Study of calcium-containing compounds as catalysts for the esterification of glycerol with higher carboxylic acidsYu. L. Zotov0D. M. Zapravdina1E. V. Shishkin2Yu. V. Popov3Volgograd State Technical UniversityVolgograd State Technical UniversityVolgograd State Technical UniversityVolgograd State Technical UniversityObjectives. To investigate the catalytic activity of calcium-containing basic catalysts for the esterification of glycerol with higher carboxylic acids in order to develop a low-waste technology for the production of multifunctional additives, as well as to assess the possibility of using the reaction products for the processing of polyvinyl chloride.Methods. The consumption of oleic acid during synthesis was monitored using a titrimetric method of analysis with visual indication. The structure of the synthesized calcium-containing catalysts was confirmed by infrared spectroscopy; elemental analysis was additionally performed for calcium glyceroxide. Quantitative and qualitative analyses of the resulting mixtures of oleic acid glycerides were carried out using chromato-mass spectrometry. A sample of a multifunctional additive was tested in a model formulation of a medical plastic compound based on polyvinyl chloride.Results. It is shown that the catalytic activity of calcium derivatives in the reaction of esterification of glycerol with higher carboxylic acids increases in the series СаО < Са(ОН)2 < Ca(C17H33COO)2 < Ca(C2H5O)2 < Ca(C4H9O)2 < Ca(C3H7O3)2, while the use of calcium glyceroxide as a catalyst in an amount from 1 to 6 mol % increases the conversion of carboxylic acid from 58 to 86% in 10 h of synthesis. However, varying the amount of calcium glyceroxide from 1.5 to 6 mol % results in no observed changes in the conversion of carboxylic acid. The multifunctional additive obtained by selecting calcium glyceroxide as a catalyst has a thermally stabilizing and plasticizing effect on the polymer composition. The introduction of the developed additive into the formulation of a polyvinyl chloride composition for medical purposes reduces the processing torque and time to reach the dry point. By combining these factors, energy costs during production were reduced by more than 11% compared to the control composition.Conclusions. It is established that calcium alcoholates catalyze the reaction of esterification of glycerol with oleic (or higher) acid to increase the conversion of the initial substances and selectivity for the formation of monoglycerides as compared with calcium oxide, hydroxide, and oleate. By optimizing the ratio of glycerol : oleic acid : calcium glyceroxide at 1 : 1 : 0.015, the maximum conversion of oleic acid of up to 86% in 10 h was obtained via synthesis. The proposed method for esterification of glycerol with higher carboxylic acids in the presence of a calcium-containing catalyst avoids the stage of purification from the catalyst to obtain a composition with multifunctional additive properties for the processing of polyvinyl chloride.https://www.finechem-mirea.ru/jour/article/view/1969esterificationglycerololeic acidcalcium alcoholatescalcium glyceroxide
spellingShingle Yu. L. Zotov
D. M. Zapravdina
E. V. Shishkin
Yu. V. Popov
Study of calcium-containing compounds as catalysts for the esterification of glycerol with higher carboxylic acids
Тонкие химические технологии
esterification
glycerol
oleic acid
calcium alcoholates
calcium glyceroxide
title Study of calcium-containing compounds as catalysts for the esterification of glycerol with higher carboxylic acids
title_full Study of calcium-containing compounds as catalysts for the esterification of glycerol with higher carboxylic acids
title_fullStr Study of calcium-containing compounds as catalysts for the esterification of glycerol with higher carboxylic acids
title_full_unstemmed Study of calcium-containing compounds as catalysts for the esterification of glycerol with higher carboxylic acids
title_short Study of calcium-containing compounds as catalysts for the esterification of glycerol with higher carboxylic acids
title_sort study of calcium containing compounds as catalysts for the esterification of glycerol with higher carboxylic acids
topic esterification
glycerol
oleic acid
calcium alcoholates
calcium glyceroxide
url https://www.finechem-mirea.ru/jour/article/view/1969
work_keys_str_mv AT yulzotov studyofcalciumcontainingcompoundsascatalystsfortheesterificationofglycerolwithhighercarboxylicacids
AT dmzapravdina studyofcalciumcontainingcompoundsascatalystsfortheesterificationofglycerolwithhighercarboxylicacids
AT evshishkin studyofcalciumcontainingcompoundsascatalystsfortheesterificationofglycerolwithhighercarboxylicacids
AT yuvpopov studyofcalciumcontainingcompoundsascatalystsfortheesterificationofglycerolwithhighercarboxylicacids