Laser Mass Spectrometry Analysis of the Formation of Phosphazene-Containing Epoxy Oligomers

The main features of two methods for the synthesis of phosphazene-containing epoxy oligomers— namely, the methods based on oxidation of double bonds in organooxyphosphazenes and on the reaction of chlorocyclophosphazenes with diphenols and the subsequent interaction of the resulting hydroxy-aryloxy phosphazenes with epichlorohydrin—were examined. Using the example of hexa- and octa-eugenol derivatives of the corresponding cyclophosphazenes, optimal conditions were established for the oxidation of allyl groups of these compounds with peroxy acids and hexa- and octa-epoxide cyclophosphazenes were characterized. It was noted that the epoxidation of eugenol derivatives of a mixture of cyclophosphazenes with three to eight phosphazo groups is accompanied by side reactions leading to the formation of P–OH bonds and the partial opening of oxirane cycles. Bisphenol A phosphazene-containing oligoepoxides were synthesized both via the stage involving the formation of hydroxy-aryloxy cyclophosphazenes and their subsequent epoxidation with epichlorohydrin and via the direct interaction of chlorocyclophosphazenes with an excess of bisphenol A (BPA) in the presence of solid alkali. In the latter case, the resulting oligomers are mixtures of the conventional epoxide and phosphazene-containing epoxy oligomers. The content of the latter can be adjusted up to 50%. The synthesized oligomers contain 1–5% phosphorus. They can be cured by conventional hardeners to form flameproof or noncombustible compositions. © 2018, Pleiades Publishing, Ltd

Laser Mass Spectrometry Analysis of the Formation of Phosphazene-Containing Epoxy Oligomers

The main features of two methods for the synthesis of phosphazene-containing epoxy oligomers— namely, the methods based on oxidation of double bonds in organooxyphosphazenes and on the reaction of chlorocyclophosphazenes with diphenols and the subsequent interaction of the resulting hydroxy-aryloxy phosphazenes with epichlorohydrin—were examined. Using the example of hexa- and octa-eugenol derivatives of the corresponding cyclophosphazenes, optimal conditions were established for the oxidation of allyl groups of these compounds with peroxy acids and hexa- and octa-epoxide cyclophosphazenes were characterized. It was noted that the epoxidation of eugenol derivatives of a mixture of cyclophosphazenes with three to eight phosphazo groups is accompanied by side reactions leading to the formation of P–OH bonds and the partial opening of oxirane cycles. Bisphenol A phosphazene-containing oligoepoxides were synthesized both via the stage involving the formation of hydroxy-aryloxy cyclophosphazenes and their subsequent epoxidation with epichlorohydrin and via the direct interaction of chlorocyclophosphazenes with an excess of bisphenol A (BPA) in the presence of solid alkali. In the latter case, the resulting oligomers are mixtures of the conventional epoxide and phosphazene-containing epoxy oligomers. The content of the latter can be adjusted up to 50%. The synthesized oligomers contain 1–5% phosphorus. They can be cured by conventional hardeners to form flameproof or noncombustible compositions. © 2018, Pleiades Publishing, Ltd

Methacrylate-Containing Phosphazene Oligomers

Abstract: Methacrylate-containing phosphazene oligomers are synthesized by the reaction of phosphazene-containing epoxy compounds with methacrylic acid and characterized by 1Н and 31Р NMR spectroscopy, MALDI-TOF mass spectrometry, and functional analysis. Methacrylate-containing phosphazene oligomers with the addition of 0.5% hydroquinone are stable under storage at normal temperature for 2 to 3 weeks but are easily involved in benzoyl peroxide-initiated copolymerization with methyl acrylate to give rise to copolymers with the quantitative content of the gel fraction. © 2022, Pleiades Publishing, Ltd

Oligomeric Hydroxyaryloxycyclotriphosphazenes with Decreased Functionality Based on Resorcinol

Abstract: Oligomeric hydroxyaryloxycyclotriphosphazenes P3N3Cln(OC6H5)x(OC6H4OH)y are obtained by the polycondensation of phenoxychlorocyclotriphosphazenes with the general formula P3N3Cl(6 −x)(OC6H5)x (x = 3.1, 4.5) with an excess of resorcinol under homogeneous (pyridine) and heterogeneous (K2CO3) acceptance of HCl in a yield of 60–85%. Full substitution of the chlorine atoms in the specified oligomers (n = 0) under homogenous acceptance of HCl by pyridine is reached only at a molar ratio of phenoxychlorocyclophosphazene : resorcinol = 1 : 12; the formed oligomers contain up to 3% Cl at a ratio of 1 : 6. The structure of the compounds present in the composition of oligohydroxyaryloxycyclotriphosphazenes and their relative concentration are determined by 31P NMR spectroscopy and MALDI-TOF mass spectrometry. © 2020, Pleiades Publishing, Ltd

The Composition and Some Properties of Epoxy Oligomers Based on Hexachlorocyclotriphosphazene and Diphenylolpropane

Phosphazene-containing epoxy oligomers (PEOs) were synthesized by the one-pot method by means of the interaction of hexachlorocyclotriphosphazene, diphenylolpropane, and epichlorohydrin at 80°C in the presence of solid KOH. In contrast to similar PEOs previously obtained at a lower temperature, according to MALDI–TOF spectrometry, the phosphazenes synthesized in this work contain about 10% of compounds with two or three phosphazene rings linked by one or two oxyaryleneoxy radicals, while the total number of epoxide groups in the molecules of these compounds is from four to eight. PEOs are cured with polyamine hardeners to form compositions with increased fire resistance, while retaining the basic properties of conventional epoxy materials

Oligomeric Hydroxyaryloxyphosphase Based on Resorcinol

Abstract: By the reaction of hexachlorocyclosphosphazene with resorcinol in the immiscible pyridine–cyclohexane system, hexa-(m-hydroxyphenoxy)cyclotriphosphazene is synthesized, the optimum yield of which of 84% is achieved in a uniform mixture of the indicated solvents and the molar ratio HCP : resorcinol = 1 : 12. When used for the synthesis of oligomers mixtures of chlorocyclophosphazenes (PNCl2)n, where n = 3, 4, and 6, also complete replacement of chlorine atoms occurs, and with a yield of up to 80%, the formation of mixed oligohydroxyphenoxycyclophosphazenes takes place. The synthesized oligomers are characterized using 31P NMR spectroscopy and MALDI-TOF mass spectrometry. © 2019, Pleiades Publishing, Ltd

Synthesis of resorcinol-based phosphazene-containing epoxy oligomers

Phosphazene-containing epoxy-resorcinol oligomers (PERO) are synthesized in one stage with the direct interaction of hexachlorocyclotriphosphazene (HCP), resorcinol, and epichlorohydrin in the presence of solid NaOH. Depending on the initial ratio of HCP:resorcinol, PERO contains from 20 to 50 wt.% phosphazene component (2.0-4.8% of phosphorus) and have an epoxy group content up to 30 %. Products are characterized using 1 H and 31 P NMR spectroscopy, MALDI-TOF mass spectrometry, and elemental analysis. According to mass spectrometry, the phosphazene fractions of PERO include up to 30 individual compounds with a predominance of cyclotriphosphazenes with one unsubstituted chlorine atom and four or five glycidyl groups. PERO has a lower viscosity in comparison with similar resins based on bisphenol A, which can simplify their use as a binder for polymer composites, adhesives, and paints. © 2019 by the authors

Synthesis of Bisphenol A Based Phosphazene-Containing Epoxy Resin with Reduced Viscosity

Phosphazene-containing epoxy oligomers (PEO) were synthesized by the interaction of hexachlorocyclotriphosphazene (HCP), phenol, and bisphenol A in a medium of excess of epichlorohydrin using potassium carbonate and hydroxide as HCl acceptors with the aim of obtaining a product with lower viscosity and higher phosphazene content. PEOs are mixtures of epoxycyclophosphazene (ECP) and a conventional organic epoxy resin based on bisphenol A in an amount controlled by the ratio of the initial mono- and diphenol. According to P-31 NMR spectroscopy, pentasubstituted aryloxycyclotrophosphazene compounds predominate in the ECP composition. The relative content in the ECP radicals of mono- and diphenol was determined by the MALDI-TOF mass spectrometry method. The organic epoxy fraction, according to gas chromatograpy-mass spectrometry (GC-MS), contains 50-70 wt % diglycidyl ether of bisphenol A. PEO resins obtained in the present work have reduced viscosity when compared to other known phosphazene-containging epoxy resins while phosphazene content is still about 50 wt %. Resins with an epoxy number within 12-17 wt %, are cured by conventional curing agents to form compositions with flame-retardant properties, while other characteristics of these compositions are at the level of conventional epoxy materials