Synthesis and performance of a novel nitrogen‐containing cyclic phosphate for intumescent flame retardant and its application in epoxy resin

A novel nitrogen‐containing cyclic phosphate (NDP) was synthesized and well characterized by ¹H, ¹³C, ³¹P NMR, mass spectra and elemental analysis. NDP was used as an additive intumescent flame retardant (AIFR) to impart flame retardancy and dripping resistance for diglycidyl ether of bisphenol‐A epoxy resin (DGEBA) curied by 4,4′‐diaminodiphenylsulfone (DDS) with different phosphorus content. The flammability, thermal stability, and mechanical properties of NDP modified DGEBA/DDS thermosets were investigated by UL‐94 vertical burning test, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and Izod impact strength and flexural property tests. The results showed that NDP modified DGEBA/DDS thermosets exhibited excellent flame retardancy, moderate changes in glass transition temperature and thermal stability. When the phosphorus content reached only 1.5 wt %, the NDP modified DGEBA/DDS thermoset could result in satisfied flame retardancy (UL‐94, V‐0). The TGA curves under nitrogen and air atmosphere suggested that NDP had good ability of char formation, and there existed a distinct synergistic effect between phosphorus and nitrogen. The flame retardant mechanism was further realized by studying the structure and morphology of char residues using FT‐IR and scanning electron microscopy (SEM). It indicated that NDP as phosphorus‐nitrogen containing flame retardant worked by both of the condensed phase action and the vapor phase action. Additionally, the addition of NDP decreased slightly the flexural strength of the flame retarded DGEBA epoxy resins, and increased the Izod impact strength of these thermosets. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41859.     

Intrinsic flame-retardant epoxy resin composites with benzoxazine: Effect of a catalyst and a low curing temperature

Three kinds of inherent flame-retardant epoxy resin (EP) composites with 20 wt % benzoxazine (BOZ) were prepared with different curing processes with 2-methyl-1H-imidazole (MI) as a catalyst or/and changes in the curing temperature. The effects of the curing process on the flame retardancy, thermal stability, mechanical properties, and curing behaviors were investigated. The composite with added MI cured at low temperature (EBM–LT) had the best properties. It possessed a 35.3% limiting oxygen index and achieved a UL 94 V-0 rating. Thermogravimetric analysis indicated that EBM–LT had the best thermal stability among the three kinds of EP composites with BOZ. The EP composites with BOZ mainly displayed a condensed-phase flame-retardant mechanism. The mechanical properties improvement was attributed to the formation of a heterogeneous network. Differential scanning calorimetry indicated that MI reacted with EP and catalyzed the homopolymerization of BOZ, and EP reacted with BOZ. Fourier transform infrared spectroscopy analysis indicated that curing at lower temperature caused the formation of more homopolymers of BOZ. The relationship of the curing process, network structure, and properties of EP composites with BOZ was established; this could help with the design of high-performance EP composites with BOZ. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47847.     

Effect of functionalized graphene oxide with phosphaphenanthrene and isocyanurate on flammability,mechanical properties,and thermal stability of epoxy composites

Maleic anhydride, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 1, 3, 5-triglycidyl isocyanurate functionalized graphene oxide (GO) was prepared in this paper. The resultant phosphorus-nitrogen functionalized GO called GOMT was homogeneously dispersed and incorporated into diglycidyl ether of bisphenol A to prepare composites. The char residue of GOMT/EP composites increased and its LOI value increased to 28.1% with UL-94 V-1 rating. T _g of composite containing 1 phr GOMT increases to 165.6 °C, and the storage modulus of the sample with 3 phr GOMT was increased by 19% compared with pure EP. Furthermore, the elastic modulus and flexural strength of epoxy composite with 5 phr GOMT were increased by 17.9 and 26.7% at room temperature, respectively. Besides, the incorporation of GOMT into EP significantly reduces the PHRR and THR of the matrix. Therefore, the as-designed GOMT not just obviously enhances the flame retardancy with low loading but raises the mechanical behavior and thermal stability of epoxy resins. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48761.     

Synthesis and properties of a novel phosphorous‐containing flame‐retardant hardener for epoxy resin

An aryl phosphinate dianhydride 1,4‐bis(phthalic anhydride‐4‐carbonyl)‐2‐(6‐oxido‐6H‐dibenz[c,e][1,2]‐oxaphosphorin‐6‐yl)‐phenylene ester (BPAODOPE) was synthesized and its structure was identified by FTIR and ¹H‐NMR. BPAODOPE was used as hardener and flame retardant for preparing halogen‐free flame‐retarded epoxy resins when coupled with another curing agent. Thermal stability, morphologies of char layer, flame resistance and mechanical properties of flame‐retarded epoxy resins were investigated by thermogravimetric analysis, SEM, limiting oxygen index (LOI), UL‐94 test, tensile, and charpy impact test. The results showed that the novel BPAODOPE had a better flame resistance, the flame resistance and char yield of flame‐retarded epoxy resins increased with an increase of phosphorus content, tensile strength and impact strength of samples gradually decreased with the addition of BPAODOPE. The flame‐retarded sample with phosphorus contents of 1.75% showed best combination properties, LOI value was 29.3, and the vertical burning test reached UL‐94 V‐0 level, tensile strength and impact strength were 30.78 MPa and 3.53 kJ/m², respectively. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and flammability testing of epoxy functionalized phosphorous‐based flame retardants

Several potential new phosphorus‐containing flame retardant molecules were evaluated for heat release reduction potential by incorporation of the molecules into a polyurethane, generated from methylene diphenyl diisocyanate and 1,3‐propane diol. The heat release reduction potential of these substances was evaluated using the pyrolysis combustion flow calorimeter (PCFC). The polyurethanes were prepared in the presence of the potential flame retardants via solvent mixing and copolymerization methods to qualitatively evaluate their potential reactivity into the polyurethane prior to heat release testing. The functionality of the flame retardants was epoxide based that would potentially react with the diol during polyurethane synthesis. Flammability testing via PCFC showed that the heat release reduction potential of each of the flame retardants was structure dependent, with phosphates tending to show more effectiveness than phosphonates in this study, and alkyl functionalized phosphorus groups (phosphate or phosphonate) being more effective at heat release reduction than cyclic functionalized groups. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42296.     

Novel multi-element DOPO derivative toward low-flammability epoxy resin

In order to obtain cured epoxy resin (EP) with satisfactory thermal stability and flame retardancy, a multi-element P/N/Si-containing flame retardant (DPAK) was synthesized by a facile way and was used as a reactive flame retardant to prepare flame-retardant EP. The flame-retardant efficiency of DPAK was subsequently evaluated by limiting oxygen index (LOI), UL-94, and cone calorimeter (CC) test. With a low incorporation amount of DPAK (4 wt%), the resultant EP achieve to UL-94 V-0 rating, and the corresponding LOI value reached to 30%, which was higher than that of EP containing DOPO (2.9 wt%). More importantly, the thermogravimetric analysis (TGA) revealed their higher thermal stability than those of EP containing DOPO. Furthermore, dynamic mechanical analysis (DMA) shown the maintained glass transition temperature of DPAK-EP. The increase of CO/CO₂ ratio in the CC test for the DPAK-EP samples proved the gas-phase activity of DPAK. Additionally, DPAK showed evidence of condensed phase activity by increasing char residue in TGA and CC test. The scanning electronic microscope together with the energy dispersive X-ray spectrometer (SEM–EDX) and X-ray photoelectron spectroscopy (XPS) exhibited that DPAK promoted the formation of compacted phosphorus-silicon char layer. Subsequently, TG-FTIR results indicated that DPAK-EP produced lesser combustible gases than neat sample did, improving flame-retardant properties of epoxy resin.     

Preparation and curing behavior of latent 2-PhIm-PS microcapsule curing agent for epoxy resin

A core–shell microcapsule latent epoxy curing agent (2-PhIm-PS) is obtained by solvent evaporation method with 2-phenyl imidazole (2-PhIm) as the core material and polystyrene (PS) as the wall material. The microcapsule parameters, morphology, structure, curing behavior, and the mechanic properties of cured epoxy resin with this microcapsule latent curing agent were characterized through comparing with 2-PhIm. The particle size distribution of the microcapsule is narrow, the average particle size is about 10.56 μm, and the core material content is 23%. The prepared 2-PhIm-PS microcapsule curing agent has excellent latent curing properties. It can completely cure epoxy resin E-51 within 10 min at 130°C, and its latent period can be more than 40 days at room temperature. In addition, the curing kinetics of one-component epoxy resin curing system (E-51/2-PhIm-PS) composed of 2-PhIm-PS microcapsules and epoxy resin E-51 is also studied by using Kissinger equation, Flynn–Wall–Ozawa and Crane formula. The results provide an outline for the evaluation on the applicability of the microcapsule curing agent of 2-PhIm-PS for epoxy resin.     

Excellent role of Cu2O on fire safety of epoxy resin with ammonium polyphosphate based on the construction of self-intumescent flame retardant system

This work reports an effective self-intumescent flame retardant system for epoxy resin (EP) based on the remarkable synergistic effect between Cu₂O and ammonium polyphosphate (APP). The effect of Cu₂O/APP on improving EP's fire performance was evaluated by limited oxygen index (LOI), UL-94, and cone calorimeter test. The optimal mass ratio of Cu₂O: APP was shown to be 2:8. With 15 wt% total flame retardant loading, the EP with optimum Cu₂O/APP formulation reached V-0 classification and high LOI (33.5%), while the EP with APP only got NR and low LOI (26.5%). Additionally, the pHRR, total heat release, total smoke production, CO production of the EP with optimum Cu₂O/APP formulation were primarily decreased. All the improvements were ascribed to the formation of the self-intumescent char layer of EP resulted from the catalyzing effect of Cu₂O for char formation and CO to CO₂ conversion. These findings will consolidate approaches for conferring flame retardancy to flammable polymers or their blends.     

The degradation and charring of flame retarded epoxy resin during the combustion

To study flame retardant mechanism of epoxy resin (EP) by octaphenyl silsesquioxane and 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide, an experimental method is set up to investigate the residue of the EPs, which is extinguished during the cone calorimeter testing at different times. The chemical structures of the residues are investigated by the FTIR and XPS. The breakdown of EPs network and formation of new crosslinking structure are supported by the FTIR analysis. The changes of C and O concentrations in the condensed phase during the combustion are investigated by XPS in detail. Moreover, formation of organic carbon is uncovered by the plasmon loss curves based on XPS that could track the carbon crosslinking. These results exhibited a whole degradation and charring process of EP during the combustion: degradation of EP chain, more crosslinking charring, and thermal oxidation of the char. Furthermore, a program of combustion and degradation process of EPs is described in this research. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4119–4128, 2013     

含磷羧酸类环氧树脂固化剂的合成及固化性能研究

以邻苯基苯酚和三氯氧磷为原料,无水三氯化铝为催化剂,首先合成9,10-二氢-9-氧杂菲-10-膦酰氯(ODC)。再以乙酸为溶剂,通过ODC与酒石酸(TA)的反应,合成了新型含磷羧酸类环氧树脂固化剂2,3-二9,110-二氢-9-氧杂菲-10-膦氧基)丁二酸(ODC-TA)。通过红外光谱、H核磁共振谱对ODC和ODC-TA的结构进行了表征,并通过DSC和TGA对ODC-TA/CYD-128型环氧树脂固化体系的固化性能及阻燃性能进行了研究。     

新型环氧树脂固化剂的合成及其环氧胶粘剂

以4,4’-二氨基二苯甲烷为原料,经乙酰化、硝化、酸解、还原、中和5步反应合成得到了一种新型环氧树脂固化剂,即3,3’,4,4’-四氨基二苯甲烷,并通过FT—IR分析及熔点测定对其进行了表征。此外,对改性环氧树脂／3,3’,4,4’-四氨基二苯甲烷体系也作了性能研究。     

A simple imide compound as a curing agent for epoxy resin. I. Synthesis and properties

A simple imide compound, 4‐amino‐phthalimide (APH), was synthesized as a curing agent for epoxy resin. APH was prepared from the hydration of 4‐nitro‐phthalimide, which was prepared from the nitration of phthalimide. The chemical structure of APH was verified by IR and ¹H‐NMR spectra. The thermal properties and dielectric constant (ε) of a phosphorus‐containing novolac epoxy resin cured by APH were determined and compared with those of epoxy resins cured by either 4,4′‐diamino diphenyl methane (DDM) or 4,4′‐diamino diphenyl sulfone (DDS). The results indicate that the epoxy resin cured by APH showed better thermal stability and a lower ε than the polymer cured by either DDM or DDS. This was due to the introduction of the imide group of APH into the polymer structure. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of a novel,multifunctional inorganic curing agent and its effect on the flame‐retardant and mechanical properties of intrinsically flame retardant epoxy resin

Traditional curing agents have only a single property, while traditional synthetic organic flame‐retardant hardeners often show poor tolerance to oxidants, strongly acidic or alkaline reagents, and organic solvents and have toxicity problems. Here, a novel and multifunctional flame‐retardant curing agent of the inorganic substrate multifunctional curing agent of the inorganic substrate (FCIN) was proposed first and successfully prepared, and then an intrinsically flame‐retardant epoxy resin (EP) was prepared by covalently incorporating FCIN nanoparticles (FCINs) into the EP. The curing behavior of the FCINs was investigated, showing that FCIN/EP expresses a higher global activation energy than tetraethylenepentamine (TEPA)/EP and that the FCINs had strong interfacial adhesion to the EP matrix. Additionally, the FCINs were well dispersed and provided a remarkable improvement in mechanical and flame‐retardant properties of the intrinsically flame‐retardant EP. With the incorporation of 9 wt % FCINs into the EP, dramatic enhancements in the strength, modulus under bending, and toughness (～36%, ～109%, and ～586%, respectively) were observed, along with 85.2%, 46.4%, 98.3%, and 77.26% decreases in the peak heat release rate, total heat release, smoke production rate peak, and total smoke production, respectively, with respect to that of TEPA/EP. The mechanisms of its flame‐retardant, smoke‐suppression, and failure behaviors were investigated. The development of this unconventional, multifunctional flame‐retardant curing agent based on an inorganic substrate showed promise for enabling the preparation of a variety of new high‐performance materials (such as intrinsically flame‐retardant EP and functional modified polyesters). © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46410.     

Synthesis and properties of phosphorus and nitrogen containing intumescent flame-retardant curing agent for epoxy resin

A kind of intumescent ?ame-retardant curing agent (PCDSPB) was synthesised by using pentaerythritol, phosphorus oxycholoride, cyclohexane-1,3-diyldimethanamine (1,3- BAC) as raw materials and the structure was characterised by FTIR and MS. The composite materials were investigated by using TG, TG-FTIR, LOI, UL-94, SEM, and CCT. The results show that the ?lling of PCDSPB can improve the ?ame resistance of EP composites. When the phosphorus content of the composite system was 1.74 wt-%, the initial weight loss temperature was 299°C and the char yield was 26.3% at 600°C. Tensile strength was 35.4 MPa, impact strength was4.3 kJ m?2, LOI was 27.9, and the UL94 passed V-0 level. In the CCT, the peak heat release rate reduced to 276.0 kW m?2(EP-2) from 622.8 kW m?2 (EP-0), the total heat release decreased from 121.8 MJ m?2 (EP-0) to 89.5 MJ m?2 (EP-2). Therefore, the PCDSPB is a good intumescent ?ame-retardant curing agent for EP.     

Synthesis and properties of flame‐retardant epoxy resins based on DOPO and one of its analog DPPO

Two phosphorus‐containing heterocyclic flame retardants ‐9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) and 2,8‐dimethyl‐phenoxaphosphin‐10‐oxide (DPPO) ‐ and their derivatives were characterized and incorporated in the backbone of epoxy novolac to obtain flame‐retardant epoxy resins. The structures and spectroscopic data including high‐resolution mass spectroscopy of these flame retardants were determined. Flame‐retardant epoxy resins with a phosphorus content of up to 2% based on heterocyclic DOPO and DPPO were cured with 4,4′‐diaminodiphenylmethane (DDM), and their features were examined by UL 94, LOI, and DSC. In this manner, high‐performance polymers with glass transition temperatures around 190°C and the UL 94 rating V0 were obtained. These polymers were compared with epoxy resins incorporating diphenyl phosphite and diphenyl phosphate, which are nonheterocyclic and do not pass the UL 94 test up to 2% phosphorus. DPPO has a similar flame retardancy like the commercially available DOPO. Furthermore, to explain the difference in the efficiency of the tested flame retardants, key experiments for the determination of the active species during the flame‐retarding process were performed and the PO radical was identified. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007.     

Synthesis and characterization of dicyclic silicon-/phosphorus-grafted alumina and its application in improving flame retardancy of epoxy resin

A new phosphorous/silicon/aluminum hybrid flame retardant (SAlu) was prepared by a surface grafting modification of alumina with a polymer (SDPS). The polymer was prepared by a condensation reaction between 3,9-dichloro-2,4,8,10-tetrahydroxy-3,9-diphosphate heterocyclic-3,9-dioxide [5.5] undecane (SPDPC) and diphenyldisiloxol. The structure of the SAlu was further characterized by Fourier transform infrared spectroscopy, X-ray diffraction, UV–Vis absorption, and particle size analysis. Thermogravimetric analysis showed that SPDS was grafted over 40% of the alumina surface. When introduced into epoxy resin, SAlu effectively improved the thermal stability and carbonization rate of the epoxy composites at high temperature. Carbonization studies showed that SAlu promoted formation of a ceramic-carbon coking structure with a porous morphology of aggregates, which isolate combustible materials, heat, and oxygen. These features improved the flame retardant performance of the composite. The solidified materials were evenly dispersed in the network structure to improve the elastic deformation ability and glass transition temperature of the solidified resin.     

Synthesis and characterization of epoxy film cured with phosphorous‐containing phenolic resin

Through the electrophilic addition reaction of ? P(O)? H and C?C, a series of novel phosphorus‐containing phenolic resins bearing maleimide (P‐PMFs) were synthesized and used as curing agent for preparing high performance and flame retardancy epoxy resins. The structure of the resin was confirmed with FTIR and elemental analysis. Thermal properties and thermal degradation behaviors of the thermosetted resin was investigated by using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The epoxy resins exhibited high glass transition temperature (143–156°C), goof thermal stability (>330°C) and retardation on thermal degradation rates. High char yields (700°C, 52.9%) and high limited oxygen indices (30.6–34.8) were observed, indicating the resins' good flame retardance for the P‐PMFs/CNE cured resins. The developed resin may be used potentially as environmentally preferable products in electronic fields. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3813–3817, 2007     

Cross-linked Salen-based polyphosphazenes (Salen-PZNs) enhancing the fire resistance of epoxy resin composites

In this work, two cross-linked Salen-based polyphosphazenes (Salen-PZNs: Salen-PZN-1 microspheres and layered Salen-PZN-2), which contains Salen-Schiff base and phosphazene components, were synthesized. The results showed that the peak heat release rate and total smoke production of 3% Salen-PZN-1/epoxy resin (EP) (3 wt% addition) were reduced by 23.8% and 87.3%, respectively. Meanwhile, after introducing the layered Salen-PZN-2 into EP, efficient flame resistance was obtained. The results of thermogravimetric analysis/infrared spectrometry proved that the harmful gasses of 5% Salen-PZN-1/EP composites were reduced during the combustion. The possible flame retardancy mechanism was considered to be the synergy of phosphate group catalysis, release of nitrogen-containing noncombustible gasses and gas phase quenching. Therefore, this work provides a method for preparing polymers with highly efficient flame-retardant properties.     

Novel strategy for molybdenum disulfide nanosheets grown on titanate nanotubes for enhancing the flame retardancy and smoke suppression of epoxy resin

A novel hybrid consisting of a molybdenum disulfide (MoS₂) coating on a titanium dioxide nanotube (TNT) surface (MoS₂–TNT) was synthesized by a hydrothermal method. The MoS₂, TNTs, and MoS₂–TNT hybrid were incorporated into epoxy resin (EP) to study their effects on its thermal performance and flame retardancy. Thermogravimetric analysis results show that the char yield at 700 °C of EP–MoS₂–TNTs was obviously increased compared with that of the EP–MoS₂ or EP–TNTs; this indicated that MoS₂–TNTs had a good carbonization effect. The limiting oxygen index, cone calorimetry, and smoke density tests showed that MoS₂–TNTs effectively improved the flame retardancy and smoke suppression of EP. This was attributed to the physical barrier effect of MoS₂ and the adsorption of TNTs. Moreover, the flame retardancy and smoke suppression of the EP–MoS₂–TNTs were better than those of the EP–MoS₂ or EP–TNTs alone with the same amount of addition; this indicated that there was a synergistic effect between MoS₂ and TNTs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46064.     

DOPO-based curing flame retardant of epoxy composite material for char formation and intumescent flame retardance

Phosphorus-containing flame retardant (HBAEA-DOPO) for epoxy resin was synthesized by addition reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) with bis[2-(4-hydroxybenzylideneamino)ethyl]amine (HBAEA) that was synthesized via 4-hydroxybenzaldehyde with diethylenetriamine. HBAEA-DOPO was mixed with 4,4′-diaminodiphenyl sulfone to co-cure the epoxy resin of diglycidyl ether bisphenol A. The silane modified nano-silica (nano-SiO₂) was used to reinforce the epoxy resin. Thermal stability and dynamic mechanical properties of the cured epoxy materials were studied with the use of thermogravimetric analysis and dynamic mechanical thermal analysis. Flame retardance and burning behavior were evaluated by the limiting oxygen index (LOI), vertical burning test, and the cone calorimetry. The cured epoxy materials have excellent thermal stability, and the temperatures at the maximum weight loss rate are over 384.0°C. The characteristic temperature corresponding to 5.00 wt% of thermal decomposition reaches 341.5°C as 1.00 wt% of phosphorus content is loaded. Flame retardant grade meets the V-0 level. The fire residue mass gradually increases with HBAEA-DOPO and nano-SiO₂. The characteristics of high flame retardance and smoke suppression of HBAEA-DOPO and nano-SiO₂ on the cured epoxy composites have been demonstrated to be related to char formation and intumescent flame retardance in the condensed phase.