DFT Modeling of the Alternating Radical Copolymerization and Alder-Ene Reaction between Maleic Anhydride and Olefins
The free radical copolymerization of electron-acceptor and electron-donor vinyl monomers represents a particular case of sequence-controlled polymerization. The reactions of maleic anhydride (MA) or related compounds (acceptor comonomers) with α-olefins (donor comonomers) result in the formation of...
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MDPI AG
2020-03-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/12/4/744 |
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| author | Ilya Nifant’ev Alexander Vinogradov Alexey Vinogradov Pavel Ivchenko |
| author_facet | Ilya Nifant’ev Alexander Vinogradov Alexey Vinogradov Pavel Ivchenko |
| author_sort | Ilya Nifant’ev |
| collection | DOAJ |
| description | The free radical copolymerization of electron-acceptor and electron-donor vinyl monomers represents a particular case of sequence-controlled polymerization. The reactions of maleic anhydride (MA) or related compounds (acceptor comonomers) with α-olefins (donor comonomers) result in the formation of the alternating copolymers that have clear prospects for petrochemical and biomedical applications. However, in contrast to the well-established polymerization of acrylate monomers, these processes have not been studied theoretically using the density functional theory (DFT) calculations. In our research, we performed a comprehensive theoretical analysis of the free radical copolymerization of MA and closely related maleimide with different structural types of olefins at mpw1pw91/6-311g(d) level of the DFT. The results of our calculations clearly indicated the preference of the alternating reaction mode for the copolymerization of MA with α-olefins, isobutylene and prospective unsaturated monomers, as well as methylenealkanes. The DFT modeling of the thermally induced Alder-ene reaction between MA and olefins allowed to exclude this reaction from the scope of possible side processes at moderately high temperatures. Comparative analysis of MA and N-methylmaleimide (MMI) reactivity shown that the use of MMI instead of MA makes no sense in terms of the reaction rate and selectivity. |
| first_indexed | 2024-03-11T10:11:31Z |
| format | Article |
| id | doaj.art-218673d59e564b2fa00b12fb0135e9fc |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-11T10:11:31Z |
| publishDate | 2020-03-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Polymers |
| spelling | doaj.art-218673d59e564b2fa00b12fb0135e9fc2023-11-16T14:29:04ZengMDPI AGPolymers2073-43602020-03-0112474410.3390/polym12040744DFT Modeling of the Alternating Radical Copolymerization and Alder-Ene Reaction between Maleic Anhydride and OlefinsIlya Nifant’ev0Alexander Vinogradov1Alexey Vinogradov2Pavel Ivchenko3A.V. Topchiev Institute of Petrochemical Synthesis RAS, 29 Leninsky Pr., Moscow 119991, RussiaA.V. Topchiev Institute of Petrochemical Synthesis RAS, 29 Leninsky Pr., Moscow 119991, RussiaA.V. Topchiev Institute of Petrochemical Synthesis RAS, 29 Leninsky Pr., Moscow 119991, RussiaA.V. Topchiev Institute of Petrochemical Synthesis RAS, 29 Leninsky Pr., Moscow 119991, RussiaThe free radical copolymerization of electron-acceptor and electron-donor vinyl monomers represents a particular case of sequence-controlled polymerization. The reactions of maleic anhydride (MA) or related compounds (acceptor comonomers) with α-olefins (donor comonomers) result in the formation of the alternating copolymers that have clear prospects for petrochemical and biomedical applications. However, in contrast to the well-established polymerization of acrylate monomers, these processes have not been studied theoretically using the density functional theory (DFT) calculations. In our research, we performed a comprehensive theoretical analysis of the free radical copolymerization of MA and closely related maleimide with different structural types of olefins at mpw1pw91/6-311g(d) level of the DFT. The results of our calculations clearly indicated the preference of the alternating reaction mode for the copolymerization of MA with α-olefins, isobutylene and prospective unsaturated monomers, as well as methylenealkanes. The DFT modeling of the thermally induced Alder-ene reaction between MA and olefins allowed to exclude this reaction from the scope of possible side processes at moderately high temperatures. Comparative analysis of MA and N-methylmaleimide (MMI) reactivity shown that the use of MMI instead of MA makes no sense in terms of the reaction rate and selectivity.https://www.mdpi.com/2073-4360/12/4/744Alder-ene reactionalkenesalternating copolymerizationdensity functional theoryfree radical polymerizationmaleic anhydride |
| spellingShingle | Ilya Nifant’ev Alexander Vinogradov Alexey Vinogradov Pavel Ivchenko DFT Modeling of the Alternating Radical Copolymerization and Alder-Ene Reaction between Maleic Anhydride and Olefins Polymers Alder-ene reaction alkenes alternating copolymerization density functional theory free radical polymerization maleic anhydride |
| title | DFT Modeling of the Alternating Radical Copolymerization and Alder-Ene Reaction between Maleic Anhydride and Olefins |
| title_full | DFT Modeling of the Alternating Radical Copolymerization and Alder-Ene Reaction between Maleic Anhydride and Olefins |
| title_fullStr | DFT Modeling of the Alternating Radical Copolymerization and Alder-Ene Reaction between Maleic Anhydride and Olefins |
| title_full_unstemmed | DFT Modeling of the Alternating Radical Copolymerization and Alder-Ene Reaction between Maleic Anhydride and Olefins |
| title_short | DFT Modeling of the Alternating Radical Copolymerization and Alder-Ene Reaction between Maleic Anhydride and Olefins |
| title_sort | dft modeling of the alternating radical copolymerization and alder ene reaction between maleic anhydride and olefins |
| topic | Alder-ene reaction alkenes alternating copolymerization density functional theory free radical polymerization maleic anhydride |
| url | https://www.mdpi.com/2073-4360/12/4/744 |
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