Search Results (5)

Epoxy resins (EP) are widely used in aerospace, electronics, and coatings due to their excellent mechanical and thermal properties. However, their inherent flammability and brittleness limit high-end applications. In this work, a novel reactive flame retardant epoxy monomer (EP-DVGA) containing DOPO and triazole units was designed and synthesized via a molecular engineering strategy. The chemical structure was confirmed by FTIR and NMR. A series of modified epoxy thermosets were prepared by co-curing EP-DVGA with bisphenol A epoxy resin (E51) using DDM as curing agent. The results showed that EP-DVGA significantly enhanced flame retardancy: At 16.31 wt% loading, the limiting oxygen index increased from 25.9% to 34.3% with UL-94 V-0 rating, and cone calorimetry revealed 73.2% and 69.2% reductions in peak heat release rate and total heat release, respectively. Mechanistic studies demonstrated a dual flame retardant effect involving phosphorus radical quenching in the gas phase and formation of a dense graphitized char layer in the condensed phase. Remarkably, EP-DVGA also improved mechanical properties—impact strength increased by 47% and tensile strength by 33.1% at optimal loadings—attributed to energy dissipation through reversible hydrogen bonding and π–π interactions. This molecular design successfully overcomes the traditional trade-off between flame retardancy and mechanical performance, offering a promising strategy for developing high-performance intrinsically flame retardant epoxy materials. Full article

A set of polyphenylene oxides incorporating DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) functionality, denoted as DOPO−R−PPO, was synthesized by copolymerization of 2,6-dimethylphenol (2,6-DMP) with various DOPO-substituted tetramethyl bisphenol monomers. In the initial step, a Friedel–Crafts acylation reaction was employed to react 2,6-DMP with different acyl chlorides, leading to the formation of ketone derivatives substituted with 2,6-dimethylphenyl groups. Subsequently, the ketones, along with DOPO and 2,6-DMP, underwent a condensation reaction to yield a series of DOPO-substituted bisphenol derivatives. Finally, polymerizations of 2,6-dimethylphenol with these DOPO-substituted bisphenols were carried out in organic solvents using copper(I) bromide/N-butyldimethylamine catalysts (CuBr/DMBA) under a continuous flow of oxygen, yielding telechelic PPO oligomers with DOPO moieties incorporated into the polymer backbone. The chemical structures of the synthesized compounds were characterized using various analytical techniques, including Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (¹H NMR), phosphorus nuclear magnetic resonance (³¹P NMR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). When compared to conventional poly(2,6-dimethyl-1,4-phenylene oxide)s with a similar molecular weight range, all DOPO−PPOs exhibited higher glass transition temperatures, enhanced thermal degradability, and increased char yield formation at 800 °C without compromising solubility in organic solvents. Full article

Despite a recent sustained preoccupation for developing biobased epoxies with enhanced applicability, such products have not been widely accepted for industry because of their inferior characteristics compared to classic petroleum-based epoxy thermosets. Therefore, significant effort is being made to improve the flame retardance of the most commonly used epoxies, such as diglycidyl ether-based bisphenol A (DGEBA), bisphenol F (DGEBF), novalac epoxy, and others, while continuously avoiding the use of hazardous halogen-containing flame retardants. Herein, a phosphorus-containing bisphenol, bis(4-(((4-hydroxyphenyl)amino)(6-oxido-6H-dibenzo[c,e][1,2]oxaphosphinin-6-yl)methyl)phenyl) phenylphosphonate (BPH), was synthesized by reacting bis(4-formylphenyl)phenylphosphonate with 4-hydroxybenzaldehyde followed by the addition of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) to the resulting azomethine groups. Environmentally friendly epoxy-based polymer thermosets were prepared by using epoxy resin as polymer matrix and a mixture of BPH and 4,4′-diaminodiphenylsulfone (DDS) as hardeners. A hyperbranched phthalocyanine polymer (HPc) and BaTiO₃ nanoparticles were incorporated into epoxy resin to improve the characteristics of the final products. The structure and morphology of epoxy thermosets were evaluated by infrared spectroscopy and scanning electron microscopy (SEM), while the flammability characteristics were evaluated by microscale combustion calorimetry. Thermal properties were determined by thermogravimetric analysis and differential scanning calorimetry. The surface morphology of the char residues obtained by pyrolysis was studied by SEM analysis. Full article

A novel liquid phosphorous-containing flame retardant anhydride (LPFA) with low viscosity was synthesized from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and methyl tetrahydrophthalic anhydride (MeTHPA) and further cured with bisphenol-A epoxy resin E-51 for the preparation of the flame retardant epoxy resins. Both Fourier transform infrared spectroscopy (FT-IR), mass spectrometry (MS) and nuclear magnetic resonance (NMR) measurements revealed the successful incorporation of DOPO on the molecular chains of MeTHPA through chemical reaction. The oxygen index analysis showed that the LPFA-cured epoxy resin exhibited excellent flame retardant performance, and the corresponding limiting oxygen index (LOI) value could reach 31.2%. The UL-94V-0 rating was achieved for the flame retardant epoxy resin with the phosphorus content of 2.7%. With the addition of LPFA, the impact strength of the cured epoxy resins remained almost unchanged, but the flexural strength gradually increased. Meanwhile, all the epoxy resins showed good thermal stability. The glass transition temperature (T_g) and thermal decomposition temperature (T_d) of epoxy resin cured by LPFA decreased slightly compared with that of MeTHPA-cured epoxy resin. Based on such excellent flame retardancy, low viscosity at room temperature and ease of use, LPFA showed potential as an appropriate curing agent in the field of electrical insulation materials. Full article

A series of biobased phosphorus flame retardants has been prepared by converting starch-derived bis-2,5-(hydroxymethyl)furan to the corresponding diacrylate followed by Michael addition of phosphite to generate derivatives with phosphorus moieties attached via P–C bonds. All compounds behave as effective flame retardants in DGEBA epoxy resin. The most effective is the DOPO derivative, 2,5-di[(3-dopyl-propanoyl)methyl]furan. When incorporated into a DGEBA blend at a level to provide 2% phosphorus, a material displaying a LOI of 30, an UL 94 rating of V0 and a 40% reduction in combustion peak heat release rate compared to that for resin containing no additive is obtained. The analogous compounds generated from bisphenol A and tetrabromobisphenol A exhibit similar flame-retarding properties. Full article