Thermal and Fire Behavior of a Bio-Based Epoxy/Silica Hybrid Cured with Methyl Nadic Anhydride
Thermosetting polymers have been widely used in many industrial applications as adhesives, coatings and laminated materials, among others. Recently, bisphenol A (BPA) has been banned as raw material for polymeric products, due to its harmful impact on human health. On the other hand, the use of arom...
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| Format: | Article |
| Language: | English |
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MDPI AG
2020-07-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/12/8/1661 |
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| author | Aurelio Bifulco Angela Marotta Jessica Passaro Aniello Costantini Pierfrancesco Cerruti Gennaro Gentile Veronica Ambrogi Giulio Malucelli Francesco Branda |
| author_facet | Aurelio Bifulco Angela Marotta Jessica Passaro Aniello Costantini Pierfrancesco Cerruti Gennaro Gentile Veronica Ambrogi Giulio Malucelli Francesco Branda |
| author_sort | Aurelio Bifulco |
| collection | DOAJ |
| description | Thermosetting polymers have been widely used in many industrial applications as adhesives, coatings and laminated materials, among others. Recently, bisphenol A (BPA) has been banned as raw material for polymeric products, due to its harmful impact on human health. On the other hand, the use of aromatic amines as curing agents confers excellent thermal, mechanical and flame retardant properties to the final product, although they are toxic and subject to governmental restrictions. In this context, sugar-derived diepoxy monomers and anhydrides represent a sustainable greener alternative to BPA and aromatic amines. Herein, we report an “in-situ” sol–gel synthesis, using as precursors tetraethylorthosilicate (TEOS) and aminopropyl triethoxysilane (APTS) to obtain bio-based epoxy/silica composites; in a first step, the APTS was left to react with 2,5-bis[(oxyran-2-ylmethoxy)methyl]furan (BOMF) or diglycidyl ether of bisphenol A (DGEBA)monomers, and silica particles were generated in the epoxy in a second step; both systems were cured with methyl nadic anhydride (MNA). Morphological investigation of the composites through transmission electron microscopy (TEM) demonstrated that the hybrid strategy allows a very fine distribution of silica nanoparticles (at nanometric level) to be achieved within a hybrid network structure for both the diepoxy monomers. Concerning the fire behavior, as assessed in vertical flame spread tests, the use of anhydride curing agent prevented melt dripping phenomena and provided high char-forming character to the bio-based epoxy systems and their phenyl analog. In addition, forced combustion tests showed that the use of anhydride hardener instead of aliphatic polyamine results in a remarkable decrease of heat release rate. An overall decrease of the smoke parameters, which is highly desirable in a context of greater fire safety was observed in the case of BOMF/MNA system. The experimental results suggest that the effect of silica nanoparticles on fire behavior appears to be related to their dispersion degree. |
| first_indexed | 2024-03-10T18:11:52Z |
| format | Article |
| id | doaj.art-3d6d1f1404b546e29f46be174cd6888c |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-10T18:11:52Z |
| publishDate | 2020-07-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Polymers |
| spelling | doaj.art-3d6d1f1404b546e29f46be174cd6888c2023-11-20T08:00:14ZengMDPI AGPolymers2073-43602020-07-01128166110.3390/polym12081661Thermal and Fire Behavior of a Bio-Based Epoxy/Silica Hybrid Cured with Methyl Nadic AnhydrideAurelio Bifulco0Angela Marotta1Jessica Passaro2Aniello Costantini3Pierfrancesco Cerruti4Gennaro Gentile5Veronica Ambrogi6Giulio Malucelli7Francesco Branda8Department of Chemical, Materials and Production Engineering (DICMaPI), University of Naples Federico II, P. le Tecchio 80, 80125 Napoli, ItalyDepartment of Chemical, Materials and Production Engineering (DICMaPI), University of Naples Federico II, P. le Tecchio 80, 80125 Napoli, ItalyDepartment of Chemical, Materials and Production Engineering (DICMaPI), University of Naples Federico II, P. le Tecchio 80, 80125 Napoli, ItalyDepartment of Chemical, Materials and Production Engineering (DICMaPI), University of Naples Federico II, P. le Tecchio 80, 80125 Napoli, ItalyInstitute for Polymers, Composites and Biomaterials (IPCB)-CNR, Via Campi Flegrei 34, 80078 Pozzuoli (NA), ItalyInstitute for Polymers, Composites and Biomaterials (IPCB)-CNR, Via Campi Flegrei 34, 80078 Pozzuoli (NA), ItalyDepartment of Chemical, Materials and Production Engineering (DICMaPI), University of Naples Federico II, P. le Tecchio 80, 80125 Napoli, ItalyDepartment of Applied Science and Technology, Politecnico di Torino, Viale Teresa Michel 5, 15121 Alessandria, ItalyDepartment of Chemical, Materials and Production Engineering (DICMaPI), University of Naples Federico II, P. le Tecchio 80, 80125 Napoli, ItalyThermosetting polymers have been widely used in many industrial applications as adhesives, coatings and laminated materials, among others. Recently, bisphenol A (BPA) has been banned as raw material for polymeric products, due to its harmful impact on human health. On the other hand, the use of aromatic amines as curing agents confers excellent thermal, mechanical and flame retardant properties to the final product, although they are toxic and subject to governmental restrictions. In this context, sugar-derived diepoxy monomers and anhydrides represent a sustainable greener alternative to BPA and aromatic amines. Herein, we report an “in-situ” sol–gel synthesis, using as precursors tetraethylorthosilicate (TEOS) and aminopropyl triethoxysilane (APTS) to obtain bio-based epoxy/silica composites; in a first step, the APTS was left to react with 2,5-bis[(oxyran-2-ylmethoxy)methyl]furan (BOMF) or diglycidyl ether of bisphenol A (DGEBA)monomers, and silica particles were generated in the epoxy in a second step; both systems were cured with methyl nadic anhydride (MNA). Morphological investigation of the composites through transmission electron microscopy (TEM) demonstrated that the hybrid strategy allows a very fine distribution of silica nanoparticles (at nanometric level) to be achieved within a hybrid network structure for both the diepoxy monomers. Concerning the fire behavior, as assessed in vertical flame spread tests, the use of anhydride curing agent prevented melt dripping phenomena and provided high char-forming character to the bio-based epoxy systems and their phenyl analog. In addition, forced combustion tests showed that the use of anhydride hardener instead of aliphatic polyamine results in a remarkable decrease of heat release rate. An overall decrease of the smoke parameters, which is highly desirable in a context of greater fire safety was observed in the case of BOMF/MNA system. The experimental results suggest that the effect of silica nanoparticles on fire behavior appears to be related to their dispersion degree.https://www.mdpi.com/2073-4360/12/8/1661bio-based epoxy resinsilica nanoparticlesin-situsol-gelmethyl nadic anhydrideflame retardance |
| spellingShingle | Aurelio Bifulco Angela Marotta Jessica Passaro Aniello Costantini Pierfrancesco Cerruti Gennaro Gentile Veronica Ambrogi Giulio Malucelli Francesco Branda Thermal and Fire Behavior of a Bio-Based Epoxy/Silica Hybrid Cured with Methyl Nadic Anhydride Polymers bio-based epoxy resin silica nanoparticles in-situ sol-gel methyl nadic anhydride flame retardance |
| title | Thermal and Fire Behavior of a Bio-Based Epoxy/Silica Hybrid Cured with Methyl Nadic Anhydride |
| title_full | Thermal and Fire Behavior of a Bio-Based Epoxy/Silica Hybrid Cured with Methyl Nadic Anhydride |
| title_fullStr | Thermal and Fire Behavior of a Bio-Based Epoxy/Silica Hybrid Cured with Methyl Nadic Anhydride |
| title_full_unstemmed | Thermal and Fire Behavior of a Bio-Based Epoxy/Silica Hybrid Cured with Methyl Nadic Anhydride |
| title_short | Thermal and Fire Behavior of a Bio-Based Epoxy/Silica Hybrid Cured with Methyl Nadic Anhydride |
| title_sort | thermal and fire behavior of a bio based epoxy silica hybrid cured with methyl nadic anhydride |
| topic | bio-based epoxy resin silica nanoparticles in-situ sol-gel methyl nadic anhydride flame retardance |
| url | https://www.mdpi.com/2073-4360/12/8/1661 |
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