Flame-retardant Epoxy Research Articles

High-performance epoxy resin with flame-retardant, transparent, and ultraviolet shielding properties based on a vanillin-based multifunctional macromolecule

Flame-retardant epoxy resins with tough, transparent, ultraviolet shielding, and low dielectric properties have fascinating prospects in electronic and electrical applications, but it is still challenging at present. In this work, a bio-based macromolecule was synthesized from vanillin (a lignin derivative), phenyl dichlorophosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO), and poly(propylene glycol) bis(2-aminopropyl ether). The bio-based macromolecule, namely, MFR, was designed and added to the epoxy resin (EP). The cured EP containing 15 wt% MFR (i.e., EP/MFR15) exhibits excellent flame retardancy with an Underwriter Laboratory 94 (UL-94) V-0 rating and a limiting oxygen index (LOI) of 29.2 %. Furthermore, the peak heat release rate (PHRR) and total heat release rate (THR) are drastically reduced by 59.5 % and 40.7 %, respectively. Meanwhile, EP/MFR15 shows 20.3 % and 43.8 % improvements in tensile strength and toughness, respectively. Moreover, MFR simultaneously endows EP with accessional ultraviolet shielding performance and low dielectric constant without sacrificing transparency. This work provides a promising strategy for fabricating a bio-based macromolecular flame retardant and preparing a high-performance EP composite with versatile properties.

Latent heat absorption of alkali metal hydrates enables delayed ignition and improved flame retardancy of epoxy resin

In this work, alkali metal hydrates, barium hydroxide octahydrate (BHO) and sodium acetate trihydrate (SAT) were added into epoxy resin (EP) to prepare a series of flame-retardant EP composites. It showed that EP samples can pass the V-0 rating of UL-94 when the amount of hydrated salt exceeds 45 wt%. When the additional amount of SAT is 50 wt%, the LOI of the EP sample increases to as high as 39% compared to 19% of pure EP. In addition, the time to ignition (TTI) of EP with 50 wt% SAT was prolonged to 157 s from 63 s of pure EP, which can provide valuable time for fire escape. The peak heat release rate (PHRR) was reduced by 63.9% compared with that of pure EP (from 1392.4 kW/m2 to 502.18 kW/m2), which indicated that phase change heat absorption plays a crucial role in reducing fire hazards of EP.

Investigating the changing dynamics of processing, temperature‐based mechanics, and flame retardancy in the transfer of ammonium polyphosphate/inorganic silicate flame retardants from epoxy resins to glass fiber composites

AbstractAlthough numerous investigations study the improvement of flame retardancy of epoxy resins using additives, maintaining the flame retardant (FRs) modes of action present in the resins upon transfer to composites is challenging. In this study, ammonium polyphosphate (APP) and inorganic silicate (InSi) are loaded at 10%, 30%, and 50% by weight, in a diglycidyl ether of bisphenol A (DGEBA) resin cured with dicyandiamide and transferred to bidirectional (BD) glass fiber (GF) composites. Although a 50% loading of the FRs impacts the curing kinetics of the resin system, the effect on the glass transition temperature of the resin system remains negligible compared to reactive FRs in the state of the art integrated into the resin's chemical structure. Increasing the FR content improved the heat release characteristics in both the resins and composites. However, the charring mode of action is completely suppressed in the formulation with 10% APP + InSi. A 30% concentration of the FRs restored the charring action in the composite and the GFs provide increased protective layer action upon transfer to the composites. This study highlights the importance of accounting for the changing dynamics related to processing and flame retardancy upon transferring FRs from resins to composites.

A DOPO modified cyclosiloxane reactive diluent as an effective flame retardant for a high-performance epoxy network

A novel phosphorus-siloxane containing liquid flame retardant epoxy resin was synthesized and incorporated into an epoxy amine network, maintaining low viscosity and rapid cure characteristics, good mechanical and thermal properties, and affording excellent flame retardancy at low concentration. The synthesized flame retardant incorporated a tetra-functional glycidyl ether cyclosiloxane substructure which was substituted with two DOPO segments to obtain a liquid bi-functional flame-retardant epoxy resin (BGTS-DOPO). At only 10 wt% BGTS-DOPO, the modified epoxy amine resin had a viscosity of less than 210 mPa s at 90 °C, gelled rapidly at 150 °C, (9.3 min at 150 °C), exhibited a Tg of 198.7 (extrapolated onset of E’) and 233.0 °C (tan δ max), and possessed improved flexural strength (4.5 %), modulus (4.1 %), strain (7.7 %) and fracture toughness (26.1 %). The self-extinguishing behaviour easily achieved a UL-94 V0 rating, exhibited a maximum limiting oxygen index of 36.7 %, while cone calorimetry produced a 24 % improvement in combustion behaviour of the carbon fibre composite. Presented here therefore is a new highly fire-retardant epoxy resin system that exhibited fast cure, low viscosity and excellent mechanical and thermal properties.

Synthesis of novel reactive flame retardant to improve fire resistance and mechanical properties in epoxy resin

A novel reactive flame-retardant (FR), phosphorus-modified tetraethylenepentamine (TEPA-m-MVP), was prepared via aza-Michael addition process, using dimethyl vinylphosphonate (MVP). TEPA-m-MVP was successfully covalently introduced into the structure of the epoxy system, into the epoxy resin matrix synthesised from tetraethylenepentamine (TEPA) and diglycidyl ether bisphenol A (DGEBA) reaction, leading to the development of a flame-retardant epoxy resin (FR-EP). The curing behaviour, mechanical properties, thermal stability and flame-retardant behaviour of FR-EP samples were investigated and compared to the behaviour of the neat epoxy resin (EP). FR-EPs showed an increase in glass transition temperature (Tg), from 120 to 147 °C upon integrating TEPA-m-MVP into the epoxy resin structure, while the value of the E modulus remained unaffected. Furthermore, FR-EP-2%P sample with the optimal P content, approximately 2 wt%, displayed excellent flame-retardant properties. In comparison to EP, total heat release (THR) and peak heat release rate (pHRR) for FR-EP-2%P decreased from 22.6 to 15.3 kJ.g−1 and from 1557 to 572 kW.m−2, respectively. In addition, an interesting impact of the crosslinking density of FR-EP samples on the fire behaviour was observed. This work presents a new strategy for the simultaneous modification of the flame retardancy and mechanical properties of epoxy systems.

A Curing Agent for Facile Fabrication of Intrinsically Flame-Retardant Epoxy Vitrimers with Catalyst-Free Mixed Carboxylate/Phosphonate Transesterification

A Curing Agent for Facile Fabrication of Intrinsically Flame-Retardant Epoxy Vitrimers with Catalyst-Free Mixed Carboxylate/Phosphonate Transesterification

Synthesis of a syringaldehyde derivative to enhance the fire resistance and structural strength of epoxy resin

AbstractIn light of growing environmental apprehensions, the threat of global warming, and the depletion of oil reserves, it is advisable to opt for bio‐epoxy resins sourced from sustainable materials. In response to these issues, syringaldehyde (SH) flame retardant epoxy resin derivatives have been formulated and synthesized. Initially, SH was reacted with 4, 4‐diaminodiphenylmethane (DDM) to yield an intermediate compound, DDM‐SH. Subsequently, the inherently flame‐retardant curing agent (DDM‐SH‐DOPO) and the bio‐based epoxy monomer (DDM‐SH‐EP) were produced by reacting with DOPO and epichlorohydrin, respectively. These resulting compounds were then integrated into bisphenol A epoxy resin, enhancing its flame retardant and mechanical characteristics. The flammability was assessed through limiting oxygen index (LOI), UL‐94, and cone calorimeter tests. The DDM‐SH‐EP‐20/5 sample exhibits notable improvements. It elevates the LOI to 25.3%, achieving a UL‐94 rating to V‐0 and effectively reducing smoke and heat release from the epoxy resin. The ternary cross‐linking network formed between DGEBA, DDM‐SH‐EP, and DDM‐SH‐DOPO primarily contributes to this mechanical enhancement, DDM‐SH‐EP‐20/5 has excellent overall performance, bending strength and bending modulus are 103% and 108% higher than DGEBA/DDM. This study offers a viable solution for producing flame‐retardant epoxy resin with superior mechanical properties.

Dual function of carboxymethyl cellulose scaffold: A one-stone-two-birds strategy to prepare double‐layer hollow ZIF-67 derivates for flame retardant epoxy composites

Aluminum hypophosphite (AHP) has been used as a flame retardant for a long time. Previous studies about AHP employed in flame retardant materials mostly focus on coating, modification, and complex system. It is valuable to explore simple experimental steps to prepare nano hybrids with AHP and metal–organic frameworks (MOFs). We found acidic substances could etch zeolitic imidazolate framework-67 (ZIF-67) to obtain MOF derivatives. Unfortunately, AHP and ZIF-67 could not directly form a hybrid. Therefore, carboxymethylcellulose (CMC) is introduced as a dual function layer (buffer and support). The CMC resists the complete conversion of ZIF-67 etched by phosphoric acid to amorphous cobalt phosphate hydrate (ACP). Meanwhile, CMC containing hydroxyl groups combines with AHP through electrostatic interaction and coordination bonds. A double-layer hollow MOF derivative is synthesized through this one-stone-two-birds strategy. Due to multiple flame retardant elements and unique nanostructure, this MOF derivative endows epoxy (EP) resin with excellent flame retardancy. With 2.0 wt% addition, the peak heat release rate (pHRR) and total heat release (THR) of EP/AHP/ACP@CMC are decreased by 47.8 and 21.0 %, respectively. This study proposes a novel scheme that converts AHP into MOF derivatives as high-performance FRs.

Impact of nanohybrid on the performance of non-reinforced biocomposites and glass-fiber reinforced biocomposites: Synthesis, mechanical properties, and fire behavior

Biobased polymers are gaining increasing popularity particularly within key industries such as construction and building materials. However, glass fiber-reinforced polymer composites (GFRCs) based on biobased epoxy thermoset are inherently vulnerable against fire, producing huge fire hazards and eventually loss of structural integrity. In this work, a cobalt-based nanohybrid filler (CNH) was designed and synthesized to act as a high-performance synergist for biobased epoxy resin when combined with phosphorous flame retardants (FRs). An optimized formulation was found, resulting in a flame-retarded epoxy resin with a limiting oxygen index (LOI) value of 39.7 % and a V 0 rating in the vertical burning test. The GFRCs were then fabricated with optimized formulation. Interestingly, results showed that the percentage of peak heat release (PHRR) rate reduction was retarded from 74 % for the mixed resin to 36 % for GFRCs, potentially due to the interference of glass fiber. The optimized laminate with CNH showed improved mechanical properties at ambient temperature. Additionally, delayed time-to-failure values were found when sample coupons with CNH were subjected to a constant axial force loading while being ignited and burning, indicating higher resistance against fire for mechanical integrity.

A reactive flame retardant based on thiadiazole and phosphaphenanthrene for improving the flame retardant and smoke inhibition properties of epoxy resins

AbstractIt is difficult to effectively manage the emission of harmful smoke from flame‐retardant modified epoxy resins (EP). In order to solve this difficulty, a highly efficient flame‐resistant PAD containing phosphorus, nitrogen, and sulfur was synthesized using a simply one‐pot method employing 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO), 2‐amino‐5‐mercapto‐1,3,4‐thiadiazole (AMT), and terephthalaldehyde for not only enhancing its flame retardant properties but also effectively suppressing the emission of fumes. Results have confirmed that the incorporation of 5 wt% flame retardant into the EP successfully passed the UL‐94 V‐0 rating, besides 24.2% reduction in the peak of smoke produce rate (PSPR), with outstanding fire‐resistant properties and effectively reduce smoke emissions. In addition, incorporating 7.5% of PAD into EP increased its flexural strength and modulus, from 78.4 and 2917.5 to 86.6 and 3162.9 MPa, respectively. Due to the abundance of reactive groups including sulfhydryl and secondary amine in PAD, as well as the nitrogen atoms presented in the thiadiazole and benzene rings of the phosphaphenanthrene structure, which could create hydrogen bonds with the matrix and participated in π‐π interactions, therefore, the mechanical properties of flame retardant epoxy resin (FREP) were greatly enhanced.

Intrinsic flame-retardant epoxy resin based on phosphorus-containing liquid imidazole compound: Simultaneously improving fire safety, mechanical property and heat resistance

In this work, two phosphorus-containing liquid imidazole compounds with different phosphorus oxidation states (1,1′-(phenylphosphanediyl)bis(1H-imidazole) (DCPPI) with + 1 valence phosphorus, and imidazole-phenylphosphate (PPOAI) with + 3 valence phosphorus) were designed and synthesized. Both of DCPPI and PPOAI were used as curing agents to obtain intrinsic flame-retardant epoxy resin (EP-DCPPI and EP-PPOAI), in which the imidazole group was used as the curing group of EP, and the phosphorus-containing group was directly connected to the EP crosslinking network. On the one hand, the efficient flame-retardant groups containing + 1 or + 3 valence phosphorus were incorporated into the EP system to obtain excellent flame-retardant properties; on the other hand, the introduction of phenylphosphine or phenoxyphosphine groups in the molecular chain of EP greatly enhanced the interaction between molecular chains, adjusted crosslinking density and endowed EP with excellent tensile strength and toughness. Compared with imidazole cured EP (EP-MZ), the peak heat release rate (PHRR) of EP-15DCPPI and EP-15PPOAI decreased by 70 % and 68 %, and the total heat release rate (THR) decreased by 37 % and 36 %, respectively. Meanwhile, EP-15DCPPI passed UL-94 V-0 rating, and the limiting oxygen index (LOI) reached 36.1 %. EP-15PPOAI passed UL-94 V-1 rating and the LOI reached 29.1 %. The flame-retardant mechanism was analyzed and discussed. Compared with EP-MZ, the dynamic and static mechanical properties of EP-15DCPPI and EP-15PPOAI were enhanced simultaneously, and the glass transition temperature (Tg) was obviously increased.

Phase change material microcapsules doped with phosphorus-based flame retardant filled titanium dioxide nanotubes for enhancing the energy storage and temperature regulation performance of buildings

Solar energy is not only a green alternative to fossil energy but also a candidate for future mainstream energy sources. To improve the efficiency and application range of solar energy, we investigated tris (1-chloro-2-propyl) phosphate (TCPP) modified titanium dioxide nanotubes (TNTs) doped phase change material microcapsules (p-t-MPCMs) to enhance the temperature regulation and flame retardancy of epoxy resin (EP) coatings. Transmission electron microscopy (TEM) and Fourier transform infrared (FTIR) spectroscopy determined the successful preparation of p-TNTs and p-t-MPCMs. Moreover, it was confirmed that the p-t-MPCMs had great thermal stability and reliability by the thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The p-t-MPCMs increased residual mass by 12.2 % at 600 ℃ while correcting the initial melting temperature of MPCMs by 1.0 ℃. Based on the principle of oxygen consumption, the heat release rate (HRR) of EP coatings containing the p-t-MPCMs (p-t-MPCM/EP) was reduced from 665.92 kW/m2 to 443.78 kW/m2, resulting in a total heat release reduction (THR) of 17.73 % tested by a conical calorimeter. Then the results of the miniature chamber model demonstrated that p-t-MPCM/EP had outstanding temperature control ability. In summary, the p-t-MPCMs expressed great potential in regulating building temperature timely and improving the fire safety of EP coatings.

Well-designed flame retardants for epoxy resin composites that simultaneously improve heat resistance, mechanical properties and fire safety

Epoxy resin (EP) flammability severely limits its application in some industrial fields, while flame retardant epoxy resin (FREP) often suffers from the problem of not being able to balance flame retardant properties with mechanical properties. To solve the problem, in this work, HDP, a reactive flame retardant was succeeded in synthesizing by the one-pot method using protocatechuic aldehyde (PH), 2,4-diamino-6-phenyl-1,3,5-triazine (DPT), and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) as reactive monomers, was used to improve the flame retardancy of EP. And evaluated the effect of HDP on the curing reaction, heat resistance and mechanical property of EP. The introduced of four phenolic hydroxyl groups and two secondary amine groups enhanced the compatibility of the flame retardant HDP in EP and improved process performance. The apparent activation energy (Ec) was reduced by 8.1 %, facilitating the curing of EP/DDM. When 5 wt% of HDP (with only 0.36 wt% phosphorus content) was added to EP, the flexural strength and modulus of FREP increased by 21.0 % and 14.9 %, respectively, and the Tg increased by 9.0 % compared to EP. Cone calorimeter test (CCT) data showed that compared to EP, samples of EP/HDP-5 showed a 14.5 % and 21.6 % reduction in total heat release (THR) and total smoke production (TSP), respectively, and a 13.7 % increase in coke yield (CY). EP/HDP-5 has a high limited oxygen index (32.5 %) and passes the UL-94 V-0 classification. The excellent char formation and flame retardancy was owed to the dual role of the condensed and gas phases of FREP in the combustion process.

A Simple and Efficient Magnesium Hydroxide Modification Strategy for Flame-Retardancy Epoxy Resin.

Magnesium hydroxide, as a green inorganic flame-retardancy additive, has been widely used in polymer flame retardancy. However, magnesium hydroxide is difficult to disperse with epoxy resin (EP), and its flame-retardancy performance is poor, so it is difficult to use in flame-retardant epoxy resin. In this study, an efficient magnesium hydroxide-based flame retardant (MH@PPAC) was prepared by surface modification of 2-(diphenyl phosphine) benzoic acid (PPAC) using a simple method. The effect of MH@PPAC on the flame-retardancy properties for epoxy resins was investigated, and the flame-retardancy mechanism was studied. The results show that 5 wt% MH@PPAC can increase the limiting oxygen index for EP from 24.1% to 38.9%, achieving a V-0 rating. At the same time, compared to EP, the peak heat release rate, peak smoke production rate, total smoke production rate, and peak CO generation rate for EP/5 wt% MH@PPAC composite material decreased by 53%, 45%, 51.85%, and 53.13% respectively. The cooperative effect for PPAC and MH promotes the formation of a continuous and dense char layer during the combustion process for the EP-blend material, significantly reducing the exchange for heat and combustible gases, and effectively hindering the combustion process. Additionally, the surface modification of PPAC enhances the dispersion of MH in the EP matrix, endowing EP with superior mechanical properties that meet practical application requirements, thereby expanding the application scope for flame-retardant EP-blend materials.

A novel flame retardant epoxy thermoset based on renewable honokiol and furfuryl alcohol

In this study, honokiol epoxy resin was directly functionalized by bio-based material honokiol, which was combined with furfuryl alcohol-derived flame retardant by Diels-Alder reaction to prepare bio-based epoxy cross-linking system. After curing with 4,4′-diaminodiphenyl methane, HE1/FP0.5/DDM (121.37 °C) offered higher glass transition temperature than EP/DDM (91.75 °C). Meanwhile, the HE1/FP0.5/DDM exhibited excellent thermal stability and flame retardancy compared to EP/DDM. The char residue of HE1/FP0.5/DDM was obviously increased from 12.8% (EP/DDM) to 35.6% at 700 °C. Notably, the HE1/FP0.5/DDM achieved a limiting oxygen index value of 37.4% and UL-94 V-0 rating. Cone calorimeter demonstrated that the peak heat release rate, total heat release and fire growth rate of HE1/FP0.5/DDM were 400.29 kW/m2, 33.45 MJ/m2 and 4.40 kW/m2·s, reduced by 57.47%, 63.39% and 41.1% compared with EP/DDM, respectively. The satisfactory flame retardancy and smoke suppression were attributed to the flame-retardant function of FP in the condensed and gas phases. Thus, this work not only provided a simple but also eco-friendly approach to achieve flame retardant thermosets from honokiol to replace bisphenol A epoxy.

Preparation and properties of eugenol based flame-retarding epoxy resin

In this work, eugenol, a phenolic monomer derived from lignin, was reacted with phenylphosphinyl dichloride to produce the intermediate compound bis(4-allyl-2-methoxyphenyl) phenylphosphinate (BEP), which was then epoxydized to yield the bio-based epoxy monomer bis(2-methoxy-4-(oxirane-2-methyl) phenyl) phenylphosphinate (BEEP). Subsequently, it was reacted with commercial bisphenol A-type epoxy resin (DER) in varying proportions and cured using 4,4′-diaminodiphenyl disulfide (APDS) to obtain the flame-retarding epoxy resin. The flame-retardant performance of the bio-based epoxy resin was analyzed, and it was observed that a significant enhancement in flame resistance was achieved when the mixture ratio of DER to BEEP stands at 7:3, the limiting oxygen index (LOI) reaching 27.4% and UL-94 reaching V-0 grade. The improvement of flame retardancy primarily arises from the introduction of phosphorus, which produces free radicals capable of inhibiting the combustion chain reaction and can improve the surface structure of the epoxy resin. Furthermore, the epoxy resin possesses recyclability, maintaining a bending strength of 73% after being reprocessed. This study may provide an insight for the study of bio-based flame-retarding epoxy resin.

Interface construction of phosphorus-based hybrid with micro/nano hierarchical structure toward intumescent flame-retardant epoxy resins with robust mechanical properties

The facile strategy for constructing phosphorus-based hybrid (APP@Zn-PT) is proposed to the simultaneous optimization of flame-retardant properties and mechanical properties of epoxy resins (EP), which is a long-term concern for the intumescent flame-retardant systems. Herein, APP@Zn-PT was fabricated via the assembly of nano-sheet phosphorus-containing triazole-zinc complex (Zn-PT) on the surface of ammonium polyphosphate micro-particles (APP). Notably, EP modified with APP@Zn-PT synchronously displayed highly fire-safe performance and excellent mechanical properties, which is seldom found in the traditionally intumescent flame-retardant EP systems. In the presence of 7 wt% APP@Zn-PT, EP acquired a high limiting oxygen index (LOI) of 31.1 %, and succeeded to meet the requirement for a UL-94 V-0 rating. Meanwhile, the results of cone calorimeter test (CCT) showed that the crucial parameters involving smoke production and heat release of EP/APP@Zn-PT presented significant decrease, that total smoke production (TSP) was dropped from 55.7 m2 of EP to 36.2 m2, and the peak of heat release rate (PHRR) was decreased from 1156 to 384 kW/m2. In addition, the interfacial interaction of APP@Zn-PT in epoxy matrix was improved as compared to APP due to the embedment of nano-sheet Zn-PT, which possessed reinforcing effect as well, and thereby the mechanical performances of EP/APP@Zn-PT were superior to neat EP and EP/APP. Generally, this work lays a foundation for the construction of phosphorus-based micro-nano hybrids, showing a great potential in high-performance polymers for practical application.

Intrinsic flame-retardant epoxy resin composite containing schiff base structure with satisfied flame retardancy and mechanical properties

To solve the non-renewable and flammability of traditional epoxy composites, a new type of intrinsic flame-retardant epoxy (VH/GF) composite was fabricated from vanillin-based epoxy resin (VH) and glass fibre (GF). The T5% of VH/GF was higher than that of DGEBA/GF, and CY800 of VH/GF reached above 84 wt%. VH/GF obtained a limiting oxygen index as high as above 90 % and passed UL-94 V-0 rating. Compared with DGEBA/GF, the total heat release, total smoke production, maximal smoke density of VH/GF reduced by more than 72 %, 91 % and 81 %, respectively. The physical barrier of glass fibre and excellent char formation ability of VH endowed VH/GF composite with good condensed phase flame-retardant effect. When the mass ratio of matrix and glass fibre was 5:5, the storage modulus and glass transition temperature of VH/GF were 6.34 GPa and 205 °C, and its tensile strength and elongation at break were 348.36 MPa and 4.01 %. This work provides new research insights for bio-based epoxy resin in high-performance fire safety composites.

A functional phosphorus/nitrogen‐containing compound for endowing epoxy resin simultaneously with better fire safety, comparable transparency and improved toughness

AbstractCurrently, the flame retardancy of epoxy resin (EP) was achieved at the expenses of the transparency and/or toughness. In the present work, a phosphorus/nitrogen‐containing compound (FDNP) was synthesized by one‐pot method using 9,10‐dihydro‐9‐oxa‐10‐phospha‐phenanthrene‐10‐oxide, furfural and N‐phenyl‐p‐phenylenediamine as raw materials, and further adopted as a functional agent for epoxy resin. The results demonstrated that the FDNP remarkably improved the fire safety of EP. The incorporation of 4 wt% FDNP enabled EP to pass UL‐94 V‐0 rating test and achieve a limiting oxygen index value of 35.5%; meanwhile, the peak heat release rate, total heat release rate and total smoke release were significantly reduced by 41.3%, 41.6% and 72.5% as compared with the pure EP, respectively. What is more, the EP/4 wt% FDNP composite kept almost the same transparency of the pure EP, simultaneously its impact strength was more than doubled as that of the pure EP. Herein, the improved flame retardancy is contributed to a synergistic biphasic flame retardant effect including the formation of a compact protective carbon layer and the release of both non‐combustible gases and phosphorus‐containing radicals.

A P/N/S containing flame retardant for epoxy resins with excellent optical, mechanical and flame retardant properties

A highly efficient flame retardant TFD was synthesized based on 2-thenaldehyde, furfurylamine and DOPO. When 4 % of TFD is incorporated into EP, EP/TFD-4 exhibits 38.9 % of LOI value and UL-94 V-0 rating. In cone calorimeter test, the peak of heat release rate, total heat release, total smoke production are dropped by 20 %, 9 % and 65 % respectively, and the char residue is increased by 67 % as compared with the pure EP. The P/N/S elements in TFD play important roles both in gas phase and condensed phase. The decomposition of 2-thenaldehyde and furfurylamine moieties produces NH3, H2S, H2O, etc., which partly leak and dilute flammable gases, but majorly participate into structural reorganization in the char layer. The degradation of DOPO group releases phosphorus-containing free radicals and phosphate-like compounds. The former quenches the chain combustion reaction, and the later promotes the formation of a stable carbon layer as a barrier effect. Benefited from the good compatability between TFD and EP, and the fine balance between the increased rigidity and the declined cross-linking density, the EP/TFDs exhibit the strikingly similar transmittance to pure EP in the range of 200–800 nm, and the improved mechanical performance in tensile, flexural, and impact tests.