Benzoxazine Monomers and Polymers Based on 3,3′-Dichloro-4,4′-Diaminodiphenylmethane: Synthesis and Characterization
To reveal the effect of chlorine substituents in the ring of aromatic amine on the synthesis process of benzoxazine monomer and on its polymerization ability, as well as to develop a fire-resistant material, a previously unreported benzoxazine monomer based on 3,3′-dichloro-4,4′-diaminodiphenylmetha...
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| Format: | Article |
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MDPI AG
2021-04-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/13/9/1421 |
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| author | Viktoria V. Petrakova Vyacheslav V. Kireev Denis V. Onuchin Igor A. Sarychev Vyacheslav V. Shutov Anastasia A. Kuzmich Natalia V. Bornosuz Mikhail V. Gorlov Nikolay V. Pavlov Alexey V. Shapagin Ramil R. Khasbiullin Igor S. Sirotin |
| author_facet | Viktoria V. Petrakova Vyacheslav V. Kireev Denis V. Onuchin Igor A. Sarychev Vyacheslav V. Shutov Anastasia A. Kuzmich Natalia V. Bornosuz Mikhail V. Gorlov Nikolay V. Pavlov Alexey V. Shapagin Ramil R. Khasbiullin Igor S. Sirotin |
| author_sort | Viktoria V. Petrakova |
| collection | DOAJ |
| description | To reveal the effect of chlorine substituents in the ring of aromatic amine on the synthesis process of benzoxazine monomer and on its polymerization ability, as well as to develop a fire-resistant material, a previously unreported benzoxazine monomer based on 3,3′-dichloro-4,4′-diaminodiphenylmethane was obtained in toluene and mixture toluene/isopropanol. The resulting benzoxazine monomers were thermally cured for 2 h at 180 °C, 4 h at 200 °C, 2 h at 220 °C. A comparison between the rheological, thermal and fire-resistant properties of the benzoxazines based on 3,3′-dichloro-4,4′-diaminodiphenylmethane and, for reference, 4,4′-diaminodimethylmethane was made. The effect of the reaction medium on the structure of the oligomeric fraction and the overall yield of the main product were studied and the toluene/ethanol mixture was found to provide the best conditions; however, in contrast to most known diamine-based benzoxazines, synthesis in the pure toluene is also possible. The synthesized monomers can be used as thermo- and fire-resistant binders for polymer composite materials, as well as hardeners for epoxy resins. Chlorine-containing polybenzoxazines require more severe conditions for polymerization but have better fire resistance. |
| first_indexed | 2024-03-10T11:52:45Z |
| format | Article |
| id | doaj.art-184a16f4127346b2a42bc6873f24ba64 |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-10T11:52:45Z |
| publishDate | 2021-04-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Polymers |
| spelling | doaj.art-184a16f4127346b2a42bc6873f24ba642023-11-21T17:30:51ZengMDPI AGPolymers2073-43602021-04-01139142110.3390/polym13091421Benzoxazine Monomers and Polymers Based on 3,3′-Dichloro-4,4′-Diaminodiphenylmethane: Synthesis and CharacterizationViktoria V. Petrakova0Vyacheslav V. Kireev1Denis V. Onuchin2Igor A. Sarychev3Vyacheslav V. Shutov4Anastasia A. Kuzmich5Natalia V. Bornosuz6Mikhail V. Gorlov7Nikolay V. Pavlov8Alexey V. Shapagin9Ramil R. Khasbiullin10Igor S. Sirotin11Faculty of Petroleum Chemistry and Polymeric Materials, Mendeleev University of Chemical Technology of Russia, Miusskaya Sq. 9, 125047 Moscow, RussiaFaculty of Petroleum Chemistry and Polymeric Materials, Mendeleev University of Chemical Technology of Russia, Miusskaya Sq. 9, 125047 Moscow, RussiaFaculty of Petroleum Chemistry and Polymeric Materials, Mendeleev University of Chemical Technology of Russia, Miusskaya Sq. 9, 125047 Moscow, RussiaFaculty of Petroleum Chemistry and Polymeric Materials, Mendeleev University of Chemical Technology of Russia, Miusskaya Sq. 9, 125047 Moscow, RussiaFaculty of Petroleum Chemistry and Polymeric Materials, Mendeleev University of Chemical Technology of Russia, Miusskaya Sq. 9, 125047 Moscow, RussiaFaculty of Petroleum Chemistry and Polymeric Materials, Mendeleev University of Chemical Technology of Russia, Miusskaya Sq. 9, 125047 Moscow, RussiaFaculty of Petroleum Chemistry and Polymeric Materials, Mendeleev University of Chemical Technology of Russia, Miusskaya Sq. 9, 125047 Moscow, RussiaFaculty of Petroleum Chemistry and Polymeric Materials, Mendeleev University of Chemical Technology of Russia, Miusskaya Sq. 9, 125047 Moscow, RussiaFaculty of Petroleum Chemistry and Polymeric Materials, Mendeleev University of Chemical Technology of Russia, Miusskaya Sq. 9, 125047 Moscow, RussiaFrumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences (IPCE RAS), 119071 Moscow, RussiaFrumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences (IPCE RAS), 119071 Moscow, RussiaFaculty of Petroleum Chemistry and Polymeric Materials, Mendeleev University of Chemical Technology of Russia, Miusskaya Sq. 9, 125047 Moscow, RussiaTo reveal the effect of chlorine substituents in the ring of aromatic amine on the synthesis process of benzoxazine monomer and on its polymerization ability, as well as to develop a fire-resistant material, a previously unreported benzoxazine monomer based on 3,3′-dichloro-4,4′-diaminodiphenylmethane was obtained in toluene and mixture toluene/isopropanol. The resulting benzoxazine monomers were thermally cured for 2 h at 180 °C, 4 h at 200 °C, 2 h at 220 °C. A comparison between the rheological, thermal and fire-resistant properties of the benzoxazines based on 3,3′-dichloro-4,4′-diaminodiphenylmethane and, for reference, 4,4′-diaminodimethylmethane was made. The effect of the reaction medium on the structure of the oligomeric fraction and the overall yield of the main product were studied and the toluene/ethanol mixture was found to provide the best conditions; however, in contrast to most known diamine-based benzoxazines, synthesis in the pure toluene is also possible. The synthesized monomers can be used as thermo- and fire-resistant binders for polymer composite materials, as well as hardeners for epoxy resins. Chlorine-containing polybenzoxazines require more severe conditions for polymerization but have better fire resistance.https://www.mdpi.com/2073-4360/13/9/1421benzoxazinespolybenzoxazinesdiaminodiphenylmethane3,3′-dichloro-4,4′-diaminodiphenylmethaneheterocyclesthermosetting binders |
| spellingShingle | Viktoria V. Petrakova Vyacheslav V. Kireev Denis V. Onuchin Igor A. Sarychev Vyacheslav V. Shutov Anastasia A. Kuzmich Natalia V. Bornosuz Mikhail V. Gorlov Nikolay V. Pavlov Alexey V. Shapagin Ramil R. Khasbiullin Igor S. Sirotin Benzoxazine Monomers and Polymers Based on 3,3′-Dichloro-4,4′-Diaminodiphenylmethane: Synthesis and Characterization Polymers benzoxazines polybenzoxazines diaminodiphenylmethane 3,3′-dichloro-4,4′-diaminodiphenylmethane heterocycles thermosetting binders |
| title | Benzoxazine Monomers and Polymers Based on 3,3′-Dichloro-4,4′-Diaminodiphenylmethane: Synthesis and Characterization |
| title_full | Benzoxazine Monomers and Polymers Based on 3,3′-Dichloro-4,4′-Diaminodiphenylmethane: Synthesis and Characterization |
| title_fullStr | Benzoxazine Monomers and Polymers Based on 3,3′-Dichloro-4,4′-Diaminodiphenylmethane: Synthesis and Characterization |
| title_full_unstemmed | Benzoxazine Monomers and Polymers Based on 3,3′-Dichloro-4,4′-Diaminodiphenylmethane: Synthesis and Characterization |
| title_short | Benzoxazine Monomers and Polymers Based on 3,3′-Dichloro-4,4′-Diaminodiphenylmethane: Synthesis and Characterization |
| title_sort | benzoxazine monomers and polymers based on 3 3 dichloro 4 4 diaminodiphenylmethane synthesis and characterization |
| topic | benzoxazines polybenzoxazines diaminodiphenylmethane 3,3′-dichloro-4,4′-diaminodiphenylmethane heterocycles thermosetting binders |
| url | https://www.mdpi.com/2073-4360/13/9/1421 |
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