Measurement and Modeling of Semi-Batch Solution Radical Copolymerization of <i>N-tert</i>-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...
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| Format: | Article |
| Language: | English |
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MDPI AG
2022-12-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/15/1/215 |
| _version_ | 1797431283937181696 |
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| author | Gagandeep Kaur Maryam Agboluaje Robin A. Hutchinson |
| author_facet | Gagandeep Kaur Maryam Agboluaje Robin A. Hutchinson |
| author_sort | Gagandeep Kaur |
| collection | DOAJ |
| 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 <i>N</i>-<i>tert</i>-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. |
| first_indexed | 2024-03-09T09:42:40Z |
| format | Article |
| id | doaj.art-6d98e7b22bf048bb8dbe93068e384535 |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-09T09:42:40Z |
| publishDate | 2022-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Polymers |
| spelling | doaj.art-6d98e7b22bf048bb8dbe93068e3845352023-12-02T00:50:03ZengMDPI AGPolymers2073-43602022-12-0115121510.3390/polym15010215Measurement and Modeling of Semi-Batch Solution Radical Copolymerization of <i>N-tert</i>-Butyl Acrylamide with Methyl Acrylate in Ethanol/WaterGagandeep Kaur0Maryam Agboluaje1Robin A. Hutchinson2Department of Chemical Engineering, Queen’s University, 19 Division St., Kingston ON K7L 3N6, CanadaDepartment of Chemical Engineering, Queen’s University, 19 Division St., Kingston ON K7L 3N6, CanadaDepartment of Chemical Engineering, Queen’s University, 19 Division St., Kingston ON K7L 3N6, CanadaThe 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 <i>N</i>-<i>tert</i>-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.https://www.mdpi.com/2073-4360/15/1/215radical polymerizationpolymerization kineticscopolymerizationreactivity ratiossemi-batch reactionmethyl acrylate |
| spellingShingle | Gagandeep Kaur Maryam Agboluaje Robin A. Hutchinson Measurement and Modeling of Semi-Batch Solution Radical Copolymerization of <i>N-tert</i>-Butyl Acrylamide with Methyl Acrylate in Ethanol/Water Polymers radical polymerization polymerization kinetics copolymerization reactivity ratios semi-batch reaction methyl acrylate |
| title | Measurement and Modeling of Semi-Batch Solution Radical Copolymerization of <i>N-tert</i>-Butyl Acrylamide with Methyl Acrylate in Ethanol/Water |
| title_full | Measurement and Modeling of Semi-Batch Solution Radical Copolymerization of <i>N-tert</i>-Butyl Acrylamide with Methyl Acrylate in Ethanol/Water |
| title_fullStr | Measurement and Modeling of Semi-Batch Solution Radical Copolymerization of <i>N-tert</i>-Butyl Acrylamide with Methyl Acrylate in Ethanol/Water |
| title_full_unstemmed | Measurement and Modeling of Semi-Batch Solution Radical Copolymerization of <i>N-tert</i>-Butyl Acrylamide with Methyl Acrylate in Ethanol/Water |
| title_short | Measurement and Modeling of Semi-Batch Solution Radical Copolymerization of <i>N-tert</i>-Butyl Acrylamide with Methyl Acrylate in Ethanol/Water |
| title_sort | measurement and modeling of semi batch solution radical copolymerization of i n tert i butyl acrylamide with methyl acrylate in ethanol water |
| topic | radical polymerization polymerization kinetics copolymerization reactivity ratios semi-batch reaction methyl acrylate |
| url | https://www.mdpi.com/2073-4360/15/1/215 |
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