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Measurement and Modeling of Semi-Batch Solution Radical Copolymerization of N-tert-Butyl Acrylamide with Methyl Acrylate in Ethanol/Water
The synthetic polymer industry is transitioning from the use of organic solvents to aqueous media in order to reduce environmental impact. However, with radical polymerization kinetics affected by hydrogen-bonding solvents, there is limited information regarding the use of water as a solvent for spa...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9824515/ https://www.ncbi.nlm.nih.gov/pubmed/36616564 http://dx.doi.org/10.3390/polym15010215 |
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author | Kaur, Gagandeep Agboluaje, Maryam Hutchinson, Robin A. |
author_facet | Kaur, Gagandeep Agboluaje, Maryam Hutchinson, Robin A. |
author_sort | Kaur, Gagandeep |
collection | PubMed |
description | The synthetic polymer industry is transitioning from the use of organic solvents to aqueous media in order to reduce environmental impact. However, with radical polymerization kinetics affected by hydrogen-bonding solvents, there is limited information regarding the use of water as a solvent for sparingly soluble monomers. Thus, in this paper, the radical polymerization of methyl acrylate (MA) and N-tert-butylacrylamide (t-BuAAm) is studied in water and ethanol (EtOH), as the copolymer product is of commercial interest. A series of semi-batch reactions are conducted under a range of operating conditions (i.e., reaction temperature, solvent-to-monomer ratio, and comonomer composition) to demonstrate that the copolymer can be successfully synthesized without significant drifts in product molar masses or composition. The experiments provide additional data to probe the influence of the solvent on the polymerization rate and copolymer properties, as the low monomer concentration maintained under starved-feed operation leads to a solvent-to-monomer ratio different from that in a batch system. A model that captures the influence of backbiting and solvent effects on rate, previously developed and tested against batch polymerizations, also provides an excellent description of semi-batch operation, validating the set of mechanisms and kinetic coefficients developed to represent the system. |
format | Online Article Text |
id | pubmed-9824515 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-98245152023-01-08 Measurement and Modeling of Semi-Batch Solution Radical Copolymerization of N-tert-Butyl Acrylamide with Methyl Acrylate in Ethanol/Water Kaur, Gagandeep Agboluaje, Maryam Hutchinson, Robin A. Polymers (Basel) Article The synthetic polymer industry is transitioning from the use of organic solvents to aqueous media in order to reduce environmental impact. However, with radical polymerization kinetics affected by hydrogen-bonding solvents, there is limited information regarding the use of water as a solvent for sparingly soluble monomers. Thus, in this paper, the radical polymerization of methyl acrylate (MA) and N-tert-butylacrylamide (t-BuAAm) is studied in water and ethanol (EtOH), as the copolymer product is of commercial interest. A series of semi-batch reactions are conducted under a range of operating conditions (i.e., reaction temperature, solvent-to-monomer ratio, and comonomer composition) to demonstrate that the copolymer can be successfully synthesized without significant drifts in product molar masses or composition. The experiments provide additional data to probe the influence of the solvent on the polymerization rate and copolymer properties, as the low monomer concentration maintained under starved-feed operation leads to a solvent-to-monomer ratio different from that in a batch system. A model that captures the influence of backbiting and solvent effects on rate, previously developed and tested against batch polymerizations, also provides an excellent description of semi-batch operation, validating the set of mechanisms and kinetic coefficients developed to represent the system. MDPI 2022-12-31 /pmc/articles/PMC9824515/ /pubmed/36616564 http://dx.doi.org/10.3390/polym15010215 Text en © 2022 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Kaur, Gagandeep Agboluaje, Maryam Hutchinson, Robin A. Measurement and Modeling of Semi-Batch Solution Radical Copolymerization of N-tert-Butyl Acrylamide with Methyl Acrylate in Ethanol/Water |
title | Measurement and Modeling of Semi-Batch Solution Radical Copolymerization of N-tert-Butyl Acrylamide with Methyl Acrylate in Ethanol/Water |
title_full | Measurement and Modeling of Semi-Batch Solution Radical Copolymerization of N-tert-Butyl Acrylamide with Methyl Acrylate in Ethanol/Water |
title_fullStr | Measurement and Modeling of Semi-Batch Solution Radical Copolymerization of N-tert-Butyl Acrylamide with Methyl Acrylate in Ethanol/Water |
title_full_unstemmed | Measurement and Modeling of Semi-Batch Solution Radical Copolymerization of N-tert-Butyl Acrylamide with Methyl Acrylate in Ethanol/Water |
title_short | Measurement and Modeling of Semi-Batch Solution Radical Copolymerization of N-tert-Butyl Acrylamide with Methyl Acrylate in Ethanol/Water |
title_sort | measurement and modeling of semi-batch solution radical copolymerization of n-tert-butyl acrylamide with methyl acrylate in ethanol/water |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9824515/ https://www.ncbi.nlm.nih.gov/pubmed/36616564 http://dx.doi.org/10.3390/polym15010215 |
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