Phosphazene-Containing Epoxy Resins Based on Bisphenol F with Enhanced Heat Resistance and Mechanical Properties: Synthesis and Properties
Organophosphazenes are of interest due to the combination of increased mechanical and thermal properties of polymer materials obtained with their use, however, they are characterized by a complex multi-stage synthesis. Moreover, the high viscosity of phosphazene-containing epoxy resins (PhER) makes...
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MDPI AG
2022-10-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/14/21/4547 |
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| author | Ilya V. Tarasov Anastasiya V. Oboishchikova Roman S. Borisov Vyacheslav V. Kireev Igor S. Sirotin |
| author_facet | Ilya V. Tarasov Anastasiya V. Oboishchikova Roman S. Borisov Vyacheslav V. Kireev Igor S. Sirotin |
| author_sort | Ilya V. Tarasov |
| collection | DOAJ |
| description | Organophosphazenes are of interest due to the combination of increased mechanical and thermal properties of polymer materials obtained with their use, however, they are characterized by a complex multi-stage synthesis. Moreover, the high viscosity of phosphazene-containing epoxy resins (PhER) makes their processing difficult. To simplify the synthesis of PhER, a one-step method was developed, and bisphenol F was chosen, which also provided a decrease in viscosity. In the current study, PhER were formed by a one-stage interaction of hexachlorocyclotriphosphazene (HCP) with bisphenol F isomers and epichlorohydrin in the presence of alkali, which was a mixture of epoxycyclophosphazenes (ECPh) with a functionality from 1 to 4 according to the results of MALDI-TOF analysis. Conventional epoxy resins based on bisphenol F, also formed during the process, showed high mechanical properties and glass transition temperature, and the reactivity of the obtained resins is similar to the base epoxy resins based on bisphenols A and F. Cured PhER had higher or the same mechanical properties compared to base epoxy resins based on bisphenol A and F, and a glass transition temperature comparable to base epoxy resins based on bisphenol F: glass transition temperature (Tg) up to 174.5 °C, tensile strength up to 74.5 MPa, tensile modulus up to 2050 MPa, tensile elongation at break up to 6.22%, flexural strength up to 146.6 MPa, flexural modulus up to 3630 MPa, flexural elongation at break up to 9.15%, and Izod impact strength up to 4.01 kJ/m<sup>2</sup>. Analysis of the composition of the obtained PhER was carried out by <sup>1</sup>H and <sup>31</sup>P NMR spectroscopy, MALDI-TOF mass spectrometry, X-ray fluorescence elemental analysis, and contained up to 3.9% phosphorus and from 1.3% to 4.2% chlorine. The temperature profile of the viscosity of the resulting epoxy resins was determined, and the viscosity at 25 °C ranged from 20,000 to 450,000 Pa·s, depending on the ratio of reagents. The resins studied in this work can be cured with conventional curing agents and, with a low content of the phosphazene fraction, can act as modifiers for traditional epoxy resins, being compatible with them, to increase impact strength and elasticity while maintaining the rest of the main mechanical and processing properties, and can be used as a resin component for composite materials, adhesives, and paints. |
| first_indexed | 2024-03-09T18:42:59Z |
| format | Article |
| id | doaj.art-63fd84cf7429402aa928201634df8a75 |
| institution | Directory Open Access Journal |
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| language | English |
| last_indexed | 2024-03-09T18:42:59Z |
| publishDate | 2022-10-01 |
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| spelling | doaj.art-63fd84cf7429402aa928201634df8a752023-11-24T06:28:02ZengMDPI AGPolymers2073-43602022-10-011421454710.3390/polym14214547Phosphazene-Containing Epoxy Resins Based on Bisphenol F with Enhanced Heat Resistance and Mechanical Properties: Synthesis and PropertiesIlya V. Tarasov0Anastasiya V. Oboishchikova1Roman S. Borisov2Vyacheslav V. Kireev3Igor S. Sirotin4Department of Plastics, Mendeleev University of Chemical Technology of Russia, Miusskaya sq. 9, 125047 Moscow, RussiaDepartment of Plastics, Mendeleev University of Chemical Technology of Russia, Miusskaya sq. 9, 125047 Moscow, RussiaDepartment of Plastics, Mendeleev University of Chemical Technology of Russia, Miusskaya sq. 9, 125047 Moscow, RussiaDepartment of Plastics, Mendeleev University of Chemical Technology of Russia, Miusskaya sq. 9, 125047 Moscow, RussiaDepartment of Plastics, Mendeleev University of Chemical Technology of Russia, Miusskaya sq. 9, 125047 Moscow, RussiaOrganophosphazenes are of interest due to the combination of increased mechanical and thermal properties of polymer materials obtained with their use, however, they are characterized by a complex multi-stage synthesis. Moreover, the high viscosity of phosphazene-containing epoxy resins (PhER) makes their processing difficult. To simplify the synthesis of PhER, a one-step method was developed, and bisphenol F was chosen, which also provided a decrease in viscosity. In the current study, PhER were formed by a one-stage interaction of hexachlorocyclotriphosphazene (HCP) with bisphenol F isomers and epichlorohydrin in the presence of alkali, which was a mixture of epoxycyclophosphazenes (ECPh) with a functionality from 1 to 4 according to the results of MALDI-TOF analysis. Conventional epoxy resins based on bisphenol F, also formed during the process, showed high mechanical properties and glass transition temperature, and the reactivity of the obtained resins is similar to the base epoxy resins based on bisphenols A and F. Cured PhER had higher or the same mechanical properties compared to base epoxy resins based on bisphenol A and F, and a glass transition temperature comparable to base epoxy resins based on bisphenol F: glass transition temperature (Tg) up to 174.5 °C, tensile strength up to 74.5 MPa, tensile modulus up to 2050 MPa, tensile elongation at break up to 6.22%, flexural strength up to 146.6 MPa, flexural modulus up to 3630 MPa, flexural elongation at break up to 9.15%, and Izod impact strength up to 4.01 kJ/m<sup>2</sup>. Analysis of the composition of the obtained PhER was carried out by <sup>1</sup>H and <sup>31</sup>P NMR spectroscopy, MALDI-TOF mass spectrometry, X-ray fluorescence elemental analysis, and contained up to 3.9% phosphorus and from 1.3% to 4.2% chlorine. The temperature profile of the viscosity of the resulting epoxy resins was determined, and the viscosity at 25 °C ranged from 20,000 to 450,000 Pa·s, depending on the ratio of reagents. The resins studied in this work can be cured with conventional curing agents and, with a low content of the phosphazene fraction, can act as modifiers for traditional epoxy resins, being compatible with them, to increase impact strength and elasticity while maintaining the rest of the main mechanical and processing properties, and can be used as a resin component for composite materials, adhesives, and paints.https://www.mdpi.com/2073-4360/14/21/4547epoxy resinepoxy oligomerphosphazenebisphenol Fmechanical propertiesglass transition temperature |
| spellingShingle | Ilya V. Tarasov Anastasiya V. Oboishchikova Roman S. Borisov Vyacheslav V. Kireev Igor S. Sirotin Phosphazene-Containing Epoxy Resins Based on Bisphenol F with Enhanced Heat Resistance and Mechanical Properties: Synthesis and Properties Polymers epoxy resin epoxy oligomer phosphazene bisphenol F mechanical properties glass transition temperature |
| title | Phosphazene-Containing Epoxy Resins Based on Bisphenol F with Enhanced Heat Resistance and Mechanical Properties: Synthesis and Properties |
| title_full | Phosphazene-Containing Epoxy Resins Based on Bisphenol F with Enhanced Heat Resistance and Mechanical Properties: Synthesis and Properties |
| title_fullStr | Phosphazene-Containing Epoxy Resins Based on Bisphenol F with Enhanced Heat Resistance and Mechanical Properties: Synthesis and Properties |
| title_full_unstemmed | Phosphazene-Containing Epoxy Resins Based on Bisphenol F with Enhanced Heat Resistance and Mechanical Properties: Synthesis and Properties |
| title_short | Phosphazene-Containing Epoxy Resins Based on Bisphenol F with Enhanced Heat Resistance and Mechanical Properties: Synthesis and Properties |
| title_sort | phosphazene containing epoxy resins based on bisphenol f with enhanced heat resistance and mechanical properties synthesis and properties |
| topic | epoxy resin epoxy oligomer phosphazene bisphenol F mechanical properties glass transition temperature |
| url | https://www.mdpi.com/2073-4360/14/21/4547 |
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