Effects of Solvent and Monomer on the Kinetics of Radical Generation in Atom Transfer Radical Polymerization
Abstract Unlike classical radical polymerization, the kinetics of atom transfer radical polymerization show significant solvent dependence, possibly arising from solvent effects on the activation step. A kinetic study on the activation of the initiator ethyl α‐bromoisobutyrate by [CuITPMA]+ (TPMA=tr...
| Main Authors: | , , , , , , , |
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| Format: | Article |
| Language: | English |
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Wiley-VCH
2024-03-01
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| Series: | ChemElectroChem |
| Subjects: | |
| Online Access: | https://doi.org/10.1002/celc.202300662 |
| _version_ | 1797261427287785472 |
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| author | Dr. Marco Fantin Enrico Tognella Andrea Antonello Dr. Francesca Lorandi Elia Calore Angelika Macior Prof. Christian Durante Prof. Abdirisak A. Isse |
| author_facet | Dr. Marco Fantin Enrico Tognella Andrea Antonello Dr. Francesca Lorandi Elia Calore Angelika Macior Prof. Christian Durante Prof. Abdirisak A. Isse |
| author_sort | Dr. Marco Fantin |
| collection | DOAJ |
| description | Abstract Unlike classical radical polymerization, the kinetics of atom transfer radical polymerization show significant solvent dependence, possibly arising from solvent effects on the activation step. A kinetic study on the activation of the initiator ethyl α‐bromoisobutyrate by [CuITPMA]+ (TPMA=tris(2‐pyridylmethyl)amine), an initiator/catalyst combination frequently used in ATRP, was carried out in DMSO, DMF, MeCN, anisole, ethyl acetate, and their 50 vol % mixtures with styrene (STY) and methyl methacrylate (MMA). kact values varying about 3 orders of magnitude from 3.14×105 mol−1 dm3 s−1 in DMSO to 9.41×102 mol−1 dm3 s−1 in ethyl acetate were found. These values showed excellent correlation with the solvent polarity/polarizability parameter π*. The effect of MMA or STY depended on polarity compatibility between the monomer and the solvent: After monomer addition, kact decreased considerably in polar solvents, whereas it was almost unaffected in nonpolar solvents. |
| first_indexed | 2024-04-24T23:41:03Z |
| format | Article |
| id | doaj.art-3a025649f73f415089d67b8ed6b6cd47 |
| institution | Directory Open Access Journal |
| issn | 2196-0216 |
| language | English |
| last_indexed | 2024-04-24T23:41:03Z |
| publishDate | 2024-03-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | ChemElectroChem |
| spelling | doaj.art-3a025649f73f415089d67b8ed6b6cd472024-03-15T12:02:38ZengWiley-VCHChemElectroChem2196-02162024-03-01116n/an/a10.1002/celc.202300662Effects of Solvent and Monomer on the Kinetics of Radical Generation in Atom Transfer Radical PolymerizationDr. Marco Fantin0Enrico Tognella1Andrea Antonello2Dr. Francesca Lorandi3Elia Calore4Angelika Macior5Prof. Christian Durante6Prof. Abdirisak A. Isse7Department of Chemical Sciences University of Padova Via Marzolo 1 35131 Padova ItalyDepartment of Chemical Sciences University of Padova Via Marzolo 1 35131 Padova ItalyDepartment of Chemical Sciences University of Padova Via Marzolo 1 35131 Padova ItalyDepartment of Chemical Sciences University of Padova Via Marzolo 1 35131 Padova ItalyDepartment of Chemical Sciences University of Padova Via Marzolo 1 35131 Padova ItalyDepartment of Chemical Sciences University of Padova Via Marzolo 1 35131 Padova ItalyDepartment of Chemical Sciences University of Padova Via Marzolo 1 35131 Padova ItalyDepartment of Chemical Sciences University of Padova Via Marzolo 1 35131 Padova ItalyAbstract Unlike classical radical polymerization, the kinetics of atom transfer radical polymerization show significant solvent dependence, possibly arising from solvent effects on the activation step. A kinetic study on the activation of the initiator ethyl α‐bromoisobutyrate by [CuITPMA]+ (TPMA=tris(2‐pyridylmethyl)amine), an initiator/catalyst combination frequently used in ATRP, was carried out in DMSO, DMF, MeCN, anisole, ethyl acetate, and their 50 vol % mixtures with styrene (STY) and methyl methacrylate (MMA). kact values varying about 3 orders of magnitude from 3.14×105 mol−1 dm3 s−1 in DMSO to 9.41×102 mol−1 dm3 s−1 in ethyl acetate were found. These values showed excellent correlation with the solvent polarity/polarizability parameter π*. The effect of MMA or STY depended on polarity compatibility between the monomer and the solvent: After monomer addition, kact decreased considerably in polar solvents, whereas it was almost unaffected in nonpolar solvents.https://doi.org/10.1002/celc.202300662Activation kineticsATRPmedium effectcopper catalystLSER |
| spellingShingle | Dr. Marco Fantin Enrico Tognella Andrea Antonello Dr. Francesca Lorandi Elia Calore Angelika Macior Prof. Christian Durante Prof. Abdirisak A. Isse Effects of Solvent and Monomer on the Kinetics of Radical Generation in Atom Transfer Radical Polymerization ChemElectroChem Activation kinetics ATRP medium effect copper catalyst LSER |
| title | Effects of Solvent and Monomer on the Kinetics of Radical Generation in Atom Transfer Radical Polymerization |
| title_full | Effects of Solvent and Monomer on the Kinetics of Radical Generation in Atom Transfer Radical Polymerization |
| title_fullStr | Effects of Solvent and Monomer on the Kinetics of Radical Generation in Atom Transfer Radical Polymerization |
| title_full_unstemmed | Effects of Solvent and Monomer on the Kinetics of Radical Generation in Atom Transfer Radical Polymerization |
| title_short | Effects of Solvent and Monomer on the Kinetics of Radical Generation in Atom Transfer Radical Polymerization |
| title_sort | effects of solvent and monomer on the kinetics of radical generation in atom transfer radical polymerization |
| topic | Activation kinetics ATRP medium effect copper catalyst LSER |
| url | https://doi.org/10.1002/celc.202300662 |
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