A novel intumescent flame retardant imparts high flame retardancy to epoxy resin

Intumescent flame retardant (IFR) has received the considerable attention ascribed to the inherent advantages including non‐halogen, low toxicity, low smoke release and environmentally friendly. In this work, a novel charring agent poly (piperazine phenylaminophosphamide) named as PPTA was successfully synthesized and characterized by Fourier transform infrared spectra (FTIR) and X‐ray photoelectron spectroscopy (XPS). Then, a series of flame‐retardant EP samples were prepared by blending with ammonium polyphosphate (APP) and PPTA. Combustion tests include oxygen Index (LOI), vertical Burning Test (UL‐94) and cone calorimeter testing,these test results showed that PPTA greatly enhances the flame retardancy of EP/APP. According to detailed results, EP containing 10 wt% APP had a LOI value of 30.2%,but had no enhancement on UL‐94 rating. However, after both 7.5 wt% APP and 2.5 wt% PPTA were added, EP‐7 passed UL‐94 V‐0 rating with a LOI value of 33.0%. Moreover, the peak heat release rate (PHRR) and peak of smoke product rate (PSPR) of EP‐7 were greatly decreased. Meanwhile, the flame‐retardant mechanism of EP‐7 was investigated by scanning electron microscopy (SEM), thermogravimetric analysis/infrared spectrometry (TG‐IR) and X‐ray photoelectron spectroscopy (XPS). The corresponding results presented PPTA significantly increased the density of char layer, resulting in the good flame retardancy.     

A vanillin-derived flame retardant based on 2-aminopyrimidine for enhanced flame retardancy and mechanical properties of epoxy resin

In order to give epoxy resin good flame retardance, a novel bio-based flame retardant based on 2-aminopyrimidine (referred to as VAD) was synthesized from renewable vanillin as one of the starting materials. Its structure was confirmed by NMR and mass spectra. The epoxy resins containing VAD were prepared by utilizing 4,4-diaminodiphenylmethane (DDM) as a co-curing agent, and their flame-retardant, mechanical and thermal properties and corresponding mechanisms were studied. VAD accelerated the cross-linking reaction of DDM and E51 (diglycidyl ether of bisphenol A). 12.5 wt% VAD made the epoxy resin achieve UL-94 V-0 rating and its limited oxygen index (LOI) value increase from 22.4% to 32.3%. The cone calorimetric testing results revealed the decline in the values of total heat release (THR) and peak of heat release rate (pk-HRR) and the obvious enhancement of residue yield. A certain amount of VAD enhanced the flame inhibition, charring and barrier effects, resulting in good flame retardance of the epoxy resin. Furthermore, the tensile strength, flexural strength and flexural modulus of the epoxy resin with 12.5 wt% loading of VAD were 6.5%, 14.9%, 15.2% higher than those of EP, indicating the strengthening effect of VAD. This work guarantees VAD to be a promising flame retardant for enhancing the fire retardancy of epoxy resin without compromising its mechanical properties.     

Synthesis and properties of phosphorus-containing bio-based epoxy resin from itaconic acid

A phosphorus-containing bio-based epoxy resin (EADI) was synthesized from itaconic acid (IA) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO). As a matrix, its cured epoxy network with methyl hexahydrophthalic anhydride (MHHPA) as the curing agent showed comparable glass-transition temperature and mechanical properties to diglycidyl ether in a bisphenol A (DGEBA) system as well as good flame retardancy with UL94 V-0 grade during a vertical burning test. As a reactive flame retardant, its flame-resistant effect on DGEBA/MHHPA system as well as its influence on the curing behavior and the thermal and mechanical properties of the modified epoxy resin were investigated. Results showed that after the introduction of EADI, not only were the flame retardancy determined by vertical burning test, LOI measurement, and thermogravimetric analysis significantly improved, but also the curing reactivity, glass transition temperature (T _g), initial degradation temperature for 5% weight loss (T _d(5%)), and flexural modulus of the cured system improved as well. EADI has great potential to be used as a green flame retardant in epoxy resin systems.     

Novel nanocomposites based on epoxy resin and modified magnesium hydroxide: Focus on flame retardancy and mechanical properties

In this work, a novel multifunctional organic‐inorganic hybrid flame agent (AM‐MEL) was prepared from magnesium hydroxide nanosheets decorated by nitrilotrimethylene triphosphonic acid and melamine. Then, an intrinsic flame‐retardant epoxy resin (EP) was prepared by covalently incorporating AM‐MEL nanoparticles. Meanwhile, ammonium polyphosphate (APP) was added into EP to form an intumescent flame retardant system with AM‐MEL. The chemical structure of AM‐MEL was characterized by Fourier transform infrared spectra, X‐ray photoelectron spectroscopy, and scanning electron microscopy. With the incorporation of 5 wt% AM‐MEL and 15 wt% APP, EP/AM‐MEL/APP could reach a limiting oxygen index value of 32.0% and achieve UL‐94 V‐0 rating, along with 88.0%, 70.0%, 81.5%, and 87.3% decrease in the peak heat release rate, total heat release, total smoke production, and the peak CO production rate, respectively, with respect to that of pure EP. The mechanisms of its flame retardant and smoke suppression were investigated.     

Achieving flame retardancy and mechanical integrity via phosphites in bio-based resins

Bio-based flame retardant (FR) resins typically exhibit diminished mechanical properties compared with their petroleum-based counterparts. Recent experiments identified a promising FR phosphorus-bearing vanillin-based epoxy resin, EP2, that exhibited superior thermomechanical properties compared to that of petroleum-based diglycidyl ether of bisphenol A. However, the structure/property relationships of such phosphorus-containing bio-based resins are relatively under-explored and cannot be resolved via experiments alone. Here, molecular simulations are used to explore these relationships for a resin comprising EP2 cured with 4,4-diaminodiphenylmethane. The predicted thermomechanical properties are consistent with experimental observations, and critically, the structural analysis reveals the importance of the pendant phosphite group in the monomer as central to maintaining extensive hydrogen-bonding networks, giving rise to the excellent Young's modulus. This work provides the foundation for knowledge-based strategies to systematically improve the structure/property relationships in FR bio-based epoxy resins.     

Simultaneously improving flame retardancy and dynamic mechanical properties of epoxy resin nanocomposites through synergistic effect of zirconium phenylphosphate and POSS

Journal of Thermal Analysis and Calorimetry - To simultaneously improve flame retardancy and dynamic mechanical properties of epoxy resin (EP) nanocomposites, layered zirconium phenylphosphate...     

Improving flame retardancy and mechanical properties of halogen-free unsaturated polyester resin with diethylene glycol as comonomer

Unsaturated polyester resin (UPR) is a widely applied engineering material with drawbacks of high fire risks and brittleness. In this paper, low-cost diethylene glycol (DEG) was used as one of diols to react with saturated and unsaturated anhydrides for unsaturated polyester pre-polymers. Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, gel permeation chromatograph were used for studying their structures and differential scanning calorimetry, thermogravimetric analysis (TG) for studying their thermal properties. Incorporated DEG comonomer improves limited oxygen index values of cross-linked UPR from 20 to 26% as the mole proportion of DEG increases from 0 to 50 mol% in diols. Combustion test indicates that the UPR sample with 70 mol% DEG in diols is self-extinguishing with none drop, referring to nonflammable burning grade. What is more, mechanical properties are also increased greatly by comparing with typical UPR base. Pyrolysis behaviors of UPR in nitrogen atmosphere suggest that the polyesters incorporated with DEG will produce more char and residues during the degradation process. By comparing the pyrolysis behaviors of UPR having DEG with those of UPR adding ammonium polyphosphate in TG curves, the flame-retarding mechanism of DEG incorporation is probably due to residual char forming in temperature range of 500–800 °C, which is close to the burning temperature. This study suggests that DEG element increases effectively and environmental friendly the fire safety of UPR materials.

     

A novel multi-claw reactive flame retardant derived from DOPO for endowing lyocell fabric with high effective flame retardancy

Cellulose - A novel DOPO derived multi-claw reactive flame retardant (DMCFR) was designed to improve the flame retardancy of lyocell fabric. The chemical structure of DMCFR was identified by proton...     

Synthesis, characterization, thermal properties and flame retardancy of a novel nonflammable phosphazene-based epoxy resin

Hexakis(4-hydroxyphenoxy)-cyclotriphosphazene (PN-OH) was synthesized through nucleophilic substitution of the chloride atoms of hexachlorocyclotriphosphazene and reduction of the aldehyde groups, and its chemical structure was characterized by elemental analysis, ¹H and ³¹P NMR, and Fourier transform infrared (FTIR) spectroscopy. A new phosphazene-based epoxy resin (PN-EP) was successfully synthesized through the reaction between diglycidyl ether of bisphenol-A (DGEBA) and PN-OH, and its chemical structure was confirmed by FTIR and gel permeation chromatography. Four PN-EP thermosets were obtained by curing with 4,4′-diaminodiphenylmethane (DDM), dicyandiamide (DICY), novolak and pyromellitic dianhydride (PMDA). The reactivity of PN-EP with the four curing agents presents an increase in the order of DDM, PMDA, novolak and DICY. An investigation on their thermal properties shows that the PN-EP thermosets achieve higher glass-transition and decomposition temperatures in comparison with the corresponding DGEBA ones while their char yields increase significantly. The PN-EP thermosets also exhibit excellent flame retardancy. The thermosets with novolak, DICY and PMDA achieve the LOI values above 30 and flammability rating of UL94 V-0, whereas the one with DDM reaches the V-1 rating. The nonflammable halogen-free epoxy resin synthesized in this study has potential applications in electric and electronic fields in consideration of the environment and human health.     

Effect of ethyl‐bridged diphenylphosphine oxide on flame retardancy and thermal properties of epoxy resin

Three commercialized flame retardants, 1,2‐bis(diphenylphosphinoyl)ethane (EDPO), 6,6‐(1,2‐phenethyl)bis‐6H‐dibenz[c,e][1,2]oxaphosphorin‐6,6‐dioxide (HTP‐6123), and hexa‐phenoxy‐cyclotriphosphazene (HPCTP), were used to prepare the flame retardant diglycidyl ether of bisphenol A (DGEBA) epoxy resin (EP) under the same experimental conditions. The effects of T_g, thermal stability, and water absorption properties of EP caused by the three flame retardants were investigated and compared, together with their flame retardant efficiency. Results showed that the introduction of the three flame retardants improved the flame retardant performance of EP but led to decreases in T_g and decomposition temperature. EDPO showed higher flame retardant efficiency than the other two flame retardants. EP/EDPO showed higher thermal stability, better flame retardant performance, higher T_g value, and lower water absorption than EP/HTP‐6123 and EP/HPCTP. The study discovered that EDPO and HTP‐6123 primarily act through the gas phase flame retardant mechanism, while HPCTP is primarily driven by the condensed phase mechanism.     

Synergistic effect of chitosan derivative and DOPO for simultaneous improvement of flame retardancy and mechanical property of epoxy resin

In this work, the effects of a chitosan-based derivative (CSA), DOPO (9, 10-dihydro-9-oxa-10- phosphaphenanthreene-10-oxide) and CSA-DOPO additives on the flammable properties of EP (epoxy resin) composites were systematically studied, where CSA was synthesized by a facile condensation between chitosan (CS) and 9-anthralaldehyde. The mass ratio of CS and 9-anthralaldehyde in CSA was determined by elemental analysis and theoretical calculation. Under the 8% addition in EP, EP/2.66%/5.34%DOPO sample was the only one passing the UL-94 V-0 rating and exhibiting the highest LOI value of 36.4%. The cone calorimeter test (CC) showed that the total smoke emission value and the peak heat release rate of the EP/2.66%/5.34%DOPO decreased by 36.0% and 61.9%, and the residual char amount increased by 151%, respectively, when compared with EP. Moreover, the incorporation of CSA/DOPO effectively improved the flexural strength by 52.3%. According to the results obtained from Py-GC/MS analyses for EP and EP/2.66%CSA/5.34%DOPO samples, together with Raman spectra, XPS (X-ray photoelectron spectra) for their char residues, and the real time FTIR (Fourier-transform infrared) spectra at different pyrolysis temperatures and cone calorimeters, it was proposed that CSA/DOPO played roles in both gaseous and condensed phases, and the synergistic effect of CSA and DOPO significantly improved the flame retardancy and mechanical strength of EP.

Graphical abstract

     

Preparation, thermal properties and flame retardancy of phosphorus- and silicon-containing epoxy resins

Phosphorus- and silicon-containing epoxy resins were prepared from (2,5-dihydroxyphenyl)diphenyl phosphine oxide (Gly-HPO), diglycidyloxy methylphenyl silane (DGMPS) and 1,4-bis(glycidyloxydimethyl silyl)-benzene (BGDMSB) as epoxy monomers and diaminodiphenylmethane (DDM), bis(3-aminophenyl)methyl phosphine oxide (BAMPO) and bis(4-aminophenoxy)dimethyl silane (APDS) as curing agents. Epoxy resins with different phosphorus and silicon content were obtained. Their thermal, dynamic mechanical and flame retardant properties were evaluated. The high LOI values confirmed that epoxy resins containing hetero-atoms are effective flame retardants, but a synergistic efficiency of phosphorus and silicon on flame retardation was not observed.     

Dynamic mechanical properties of glass-filled epoxy resin

Composite specimens were prepared using soda glass beads and a purified epoxy resin cured with 1,3-propylene diamine. Some beads were treated with a silane coupling agent. The dynamic mechanical properties of these specimens were measured in the temperature range ?190 to +180°C using a free-oscillation torsion pendulum. The dynamic mechanical relaxation spectrum showed no feature that could be attributed to the formation of a new interfacial phase and the torsional moduli were unaffected by the use of the coupling agent. Increasing the glass content of the specimens decreased the damping and increased the modulus. An attempt was made to predict the composite modulus using the Kerner equation. When the specimens were immersed in boiling water, two effects were noted. First, water was absorbed in the epoxy resin matrix and changes in the dynamic spectrum were observed. Second, in samples filled with untreated glass debonding occurred and the presence of free water at the interface was indicated by the appearance of a new peak near 0°C.     

Synthesis, characterization and properties of novel crystalline epoxy resin with good melt flowability and flame retardancy based on an asymmetrical biphenyl unit

A novel crystalline epoxy resin—4-(p-glycidyloxyphenoxy)-4′-glycidyloxybiphenyl (DGEBP) was synthesized via a four-step procedure on base 4,4′-biphenol as the starting material. The obtained epoxy exhibited good crystallinity with a melting point of 165.7°C. A monoclinic crystal phase was elucidated by a single crystal X-ray diffraction measurement. The curing behavior of DGEBP with a commercial phenol-4,4′-dimethylbiphenylene novolac resin (trade name GPH65) as the hardener was investigated. For comparison, another two epoxy systems based on the same hardener and two commercially-available biphenyl-containing epoxy resins, including a crystalline epoxy compound, 3,3′,5,5′-tetramethyl-4,4′-dihydroxybiphenyl diglycidyl ether (trade name: YX4000H) and an amorphous 4,4′-dimethylbiphenylene type epoxy resin (trade name NC3000H) were also prepared. It was found that the DGEBP/GPH65 formulation exhibited a superior melt flow behavior to those of YX4000H/GPH65 and NC3000/GPH65 systems. DGEBP/GPH65 epoxy formulation exhibited a minimum melt viscosity of 0.12 Pa s at 150°C. This value is obviously lower than those of YX4000H/GPH65 (0.27 Pa s) and NC3000H/GPH65 (0.59 Pa s) systems. The cured DGEBP/GPH65 thermoset exhibited good thermal stability with a glass transition temperature of 123°C and a 5% weight loss temperature of 415°C. In addition, the DGEBP/GPH65 thermoset possessed good tensile and flexural properties, low water uptake, good dielectric properties and flame retardancy.     

Synergistic effect of methyl phenyl silicone resin and DOPO on the flame retardancy of epoxy resins

Polymers based on styrene (STY) and divinylbenzene (DVB) are widely used for water treatment. The chemical modification of these materials, with the introduction of chemical groups, increases their selectivity for certain types of contaminants. The incorporation of magnetic particles makes these systems useful for removing contaminants from aquifers, due to their magnetic attraction of certain residues. In this work, STY–DVB resins (unmodified, sulfonated, and impregnated with nickel and cobalt particles) were analyzed by thermogravimetry. The thermal stabilities of all the samples were compared, showing that sulfonation reduces the thermal stability of the resin, but the incorporation of metal particles restores that stability, with the extent of this recovery depending on the type of metal. This result shows that even when the incorporation of metal particles does not involve removal of contaminants by magnetic attraction, this inclusion is still justified because it increases the material’s thermal stability and also makes it more efficient for removing certain types of non-metallic contaminants, as observed in a previous study. Besides this, the thermogravimetric analysis was highly useful to ascertain the changes caused to the materials, including allowing inferences on the semi-quantitative results of the degree of sulfonation and confirming that metal compounds are not only physical mixtures.     

Novel high Tg flame retardancy approach for epoxy resins

A novel halogen-free phosphorus- and nitrogen-containing heterocyclic flame retardant - 5,10-dihydro-phenophosphazine-10-oxide (DPPA) - was synthesised and characterised by NMR, MS, and XRD analyses. DPPA and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) were successfully incorporated in the backbone of diglycidyl ether of bisphenol A (DGEBA). The resultant prepolymers were cured with 4,4′-diaminodiphenylmethane (DDM) and diethyldiamino toluene (DETDA 80). The burning behaviours of the thermosets obtained were studied by UL 94 and LOI and compared to each other. Also their glass transition temperatures (Tgs) were determined by differential scanning calorimetry (DSC). Due to the bridging incorporation of DPPA in DGEBA by fusion process, high T_gs for these samples were achieved.     

Thermal degradation and flame retardancy of epoxy resins containing intumescent flame retardant

Pentaerythritol diphosphonate melamine-urea-formaldehyde resin salt, a novel cheap macromolecular intumescent flame retardants (IFR), was synthesized, and its structure was a caged bicyclic macromolecule containing phosphorus characterized by IR. Epoxy resins (EP) were modified with IFR to get the flame retardant EP, whose flammability and burning behavior were characterized by UL 94 and limiting oxygen index (LOI). 25 mass% of IFR were doped into EP to get 27.2 of LOI and UL 94 V-0. The thermal properties of epoxy resins containing IFR were investigated with thermogravimetry (TG) and differential thermogravimetry (DTG). Activation energy for the decomposition of samples was obtained using Kissinger equation. The resultant data show that for EP containing IFR, compared with EP, IFR decreased mass loss, thermal stability and R _max, increased the char yield. The activation energy for the decomposition of EP is 230.4 kJ mol⁻¹ while it becomes 193.8 kJ mol⁻¹ for EP containing IFR, decreased by 36.6 kJ mol⁻¹, which shows that IFR can catalyze decomposition and carbonization of EP.     

Facile synthesis of bio-based phosphorus-containing epoxy resins with excellent flame resistance

The development of high-performance biomass-derived epoxy thermosets with excellent flame resistance is vital to various applications (i.e., composites, coatings and adhesives). Herein, a difunctional epoxy monomer bis(2-methoxy-4-(oxiran-2-ylmethyl)phenyl) phenyl phosphate (BEU-EP) was synthesized from abundant and biobased eugenol. In addition, BEU-EP was cured by 4,4′-diaminodiphenyl methane (DDM) and the cured resin diglycidyl ether of bisphenol A (DGEBA)/DDM was used as a reference. Results indicated that BEU-EP/DDM not only showed a 58.1%, 28.8% and 35.1% increase in residual char (at 700 °C), flexural and storage modulus (at 30 °C) compared with DGEBA/DDM, but also exhibited excellent flame resistance and smoke suppression. BEU-EP/DDM passed V-0 rating (in UL-94 testing) with limiting oxygen index (LOI) of 38.4% and greatly decreased the peak heat release rate (pHRR) and total smoke production (TSP) by 84.9% and 80.5%, respectively. The mechanism analysis confirmed that the phosphorus-containing group and aromatic structure from BEU-EP contributed both the gas and condensed-phase flame retardation of BEU-EP/DDM network. This work provides an efficient and scalable route for synthesizing biobased epoxy thermosets with high integrated performance and superior flame resistance.     

Effect of different ionic layered compounds decorated with zinc hydroxystannate on flame retardancy and smoke performance of epoxy resin

ZHS@ Mg‐Al‐LDH and ZHS@α‐ZrP hybrid materials were prepared by electrostatically loading zinc hydroxystannate (ZHS) on the layered compounds (Mg‐Al‐LDH and α‐ZrP) in this work. With the addition of 2 wt% of the two hybrid materials to epoxy resin (EP), respectively, the fire hazard of EP and its composites were investigated. The limiting oxygen index (LOI) of ZHS@ Mg‐Al‐LDH/EP composite increased by 19.0% compared with pure EP, while its peak heat release rate (PHRR), total heat release rate (THR), and peak smoke release rate (SPR) decreased by 48.2%, 20.8%, and 21.6%, respectively, evidenced by the results of the LOI test and cone calorimetry test (CCT). The LOI of ZHS@α‐ZrP/EP composite increased by 20.4%, and its PHRR, THR, and SPR decreased by 47.7%, 21.4%, and 27.1%, respectively. Both hybrid materials showed prominent flame retardant and smoke suppressing properties. In addition, through the analysis of the TG‐IR and Raman spectrum of residual char, the specific mechanism of flame retardance and smoke suppression was explored.