Influence of the pentaerythritol phosphate melamine salt content on the combustion and thermal decomposition process of intumescent flame‐retardant ethylene–vinyl acetate copolymer composites

Pentaerythritol phosphate melamine salt (PPMS) as a single‐molecule intumescent fire retardant was synthesized and characterized. The influence of the PPMS content on the combustion and thermal decomposition processes of intumescent‐flame‐retardant (IFR) ethylene–vinyl acetate copolymer (EVA) composites was studied by limiting oxygen index (LOI) measurement, UL 94 rating testing, cone calorimetry, thermogravimetric analysis, and scanning electron microscopy. The LOI and UL 94 rating results illustrate that PPMS used in EVA improved the flame retardancy of the EVA composites. The cone calorimetry test results show that the addition of PPMS significantly decreased the heat‐release rate, total heat release, and smoke‐production rate and enhanced the residual char fire performance of the EVA composites. The IFR–EVA3 composite showed the lowest heat‐release and smoke‐production rates and the highest char residue; this means that the IFR–EVA3 composite had the best flame retardancy. The thermogravimetry results show that the IFR–EVA composites had more residual char than pure EVA; the char residue yield increased with increasing PPMS content. The analysis results for the char residue structures also illustrated that the addition of PPMS into the EVA resin helped to enhance the fire properties of the char layer and improve the flame retardancy of the EVA composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42148.     

用锥形量热仪研究无卤阻燃HDPE体系的燃烧性

在35kW／m^2热辐照条件下,利用锥形量热仪研究了膨胀型阻燃剂／Mg(OH)2阻燃高密度聚乙烯(HDPE)体系的燃烧性。结果表明：膨胀型阻燃剂／Mg(OH)2能明显降低HDPE的热释放速率、总热释放量、最大生烟速率及总烟释放量。与膨胀型阻燃剂单独使用相比,Mg(OH)2与膨胀型阻燃剂复合使用的阻燃效果明显,总烟释放量减少了38％,总热释放量减少了10％,达到了低发炯、高效阻燃的目的。     

A novel phytic acid based flame retardant to improve flame retardancy,hydrophobicity and mechanical properties of linear low-density polyethylene

Exploiting high phosphorus content of phytic acid, it was grafted onto magnesium hydroxide (MH) by neutralization reaction to obtain MGPA, a flame retardant. A current study investigated the effect of MGPA on hydrophobicity, flame retardancy, and mechanical properties of MGPA-linear low-density polyethylene (LLDPE) composites. The LLDPE composite with 50 parts of MGPA has the better flame retardancy and thermal stability with a limiting oxygen index of 23.3%, which is higher than that of neat LLDPE (17%). In addition, MGPA could effectively promoted LLDPE to form a continuous and compact char residue during combustion, which reduce the peak of heat release rate and total smoke production value of LLDPE composite by 70% and 36%, respectively, and the char residue rate increase to 67.5%. Furthermore, the maximum of loss-rate showed by LLDPE composite with MGPA reduce to 1.25%/min while the value of LLDPE composite with MH is 1.8%/min. Meanwhile, the LLDPE composite with MGPA show remarkable elongation at break and hydrophobicity, which are 398% and 99°, respectively. In addition, this study presents a substantial flame retardancy and interfacial compatibility of MGPA for extending the applications of flame-retardant LLDPE composites.     

壳聚糖/聚磷酸铵膨胀阻燃PP的阻燃及抑烟性能

为了提高聚丙烯(PP)的阻燃和抑烟性能,将壳聚糖(CS)作为膨胀型阻燃剂的碳源、聚磷酸铵(APP)作为膨胀型阻燃剂的酸源和气源,在此基础上通过熔融共混的方法制备了PP/CS/APP复合材料。采用极限氧指数仪、锥形量热仪等仪器研究了PP/CS/APP复合材料的的抑烟性及阻燃性。研究结果表明:CS/APP添加量为30%时,复合材料的极限氧指数值最大可达28.1%;且复合材料在烟气释放总量、CO和CO_2排放上明显降低,抑烟性得到了提升;热释放速率峰值、平均热释放速率值、平均有效燃烧热值、总热释放量值降低,成炭率升高,PP/CS/APP复合材料更难点燃;火灾性能指数明显提高,阻燃性能得到了大幅度提升,火灾蔓延指数显著减小,同时火灾危险性也相应降低。     

Synthesis of novel triazine charring agent and its effect in intumescent flame‐retardant polypropylene

A novel charring agent (CNCA‐DA) containing triazine and benzene ring, using cyanuric chloride, aniline, and ethylenediamine as raw materials, was synthesized and characterized. The effects of CNCA‐DA on flame retardancy, thermal degradation, and flammability properties of polypropylene (PP) were investigated by limited oxygen index (LOI), vertical burning test (UL‐94), thermogravimetric analysis (TGA), and cone calorimeter test (CCT). The TGA results showed that CNCA‐DA had a good char forming ability, and a high initial temperature of thermal degradation; the char residue of CNCA‐DA reached 18.5% at 800°C; Ammonium polyphosphate (APP) could improve the char residue of APP/CNCA‐DA system, the char residue reached 31.6% at 800°C. The results from LOI and UL‐94 showed that the intumescent flame retardant (IFR) containing CNCA‐DA and APP was very effective in flame retardancy of PP. When the mass ratio of APP and CNCA‐DA was 2 : 1, and the IFR loading was 30%, the IFR showed the best effect; the LOI value reached 35.6%. It was also found that when the IFR loading was only 20%, the flame retardancy of PP/IFR can still pass V‐0 rating in UL‐94 tests, and its LOI value reached 27.1%. The CCT results demonstrated that IFR could clearly change the decomposition behavior of PP and form a char layer on the surface of the composites, consequently resulting in efficient reduction of the flammability parameters, such as heat release rate (HRR), total heat release (THR), smoke production rate (SPR), total smoke production (TSP), and mass loss (ML). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

An efficient approach to improving fire retardancy and smoke suppression for intumescent flame‐retardant polypropylene composites via incorporating organo‐modified sepiolite

In this work, an efficient approach to improving the fire retardancy and smoke suppression for intumescent flame‐retardant polypropylene (PP) composites is developed via incorporating functionalized sepiolite (organo‐modified sepiolite [ONSep]). The PP composites with different amounts of intumescent flame retardants and ONSep were prepared by melt compounding. The morphology, thermal behavior, fire retardancy, smoke suppression, and mechanical property of flame‐retardant PP composites were studied. The results indicate an appropriate amount of ONSep in the flame‐retardant PP composites can increase thermal degradation temperature and char formation as well as a reduction of the peak heat release rate and total heat release; moreover, the addition of ONSep significantly decreases the CO production, total smoke production, smoke production rate, and smoke temperature. Simultaneously, the impact strength of intumescent flame‐retardant PP composite is also maintained by introducing an appropriate amount of ONSep as compared with that without ONSep.     

Enhanced flame-retardant performance of rigid polyurethane foam by using APTES-MMT and ATH mixed intumescent coatings

The design of environment-friendly fireproof rigid polyurethane foams (RPUFs) that completely prevent ignition or the spread of fires is important for energy conservation and emission reductions. In this paper, an intumescent flame-retardant coating was prepared and coated onto the surface of a RPUF to improve its flame retardancy. Vertical combustion experiments (UL-94) showed that, compared with the pure RPUF, a RPUF coated with the expansion coating successfully self-extinguished without a droplet formed after ignitor removal. Thermogravimetric analyses showed that the expanded coating effectively increased the rate of carbon residue formation. Cone calorimetry showed that when the pigment-to-binder ratio was 3.5:1, with 5% modified montmorillonite, 6% aluminum hydroxide, and 4% titanium dioxide, the intumescent coating effectively reduced the heat release rate and total heat release of the RPUF. Remarkably, the smoke release rate and total exhaust gas volume showed that the expanded coating provided obviously enhanced smoke suppression. Therefore, the flame retardancy and toxic smoke suppression provided by the RPUF thermal insulation material is essential and very useful for healthy development of human society and the environment.     

Flame-retardant epoxy resin with good smoke-suppression endowed by chitosan–cobalt/phosphorus complex

Chitosan-based flame-retardant CS–Co–DOPA (CCD) was synthesized by the neutralization reaction of 10-hydroxy-9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide (DOPA) with chitosan-cobalt complex and fully characterized by scanning electron microscopy (SEM), energy-dispersive spectrometer, x-ray diffraction, X-ray photoelectron spectroscopy (XPS), optical emission spectrometer, and Fourier transform infrared (FTIR) characterizations. The epoxy resin (EP) modified with CCD exhibited good flame retardancy. With the addition of 5 wt% CCD, the EP/CCD achieved UL-94 V-1 rating and possessed limiting oxygen index (LOI) value of 30%. Cone calorimetry (CC) test demonstrated that EP/CCD resulted in a remarkable reduction of peak smoke production rate (pSPR) and total smoke production (TSP) by 63% and 40%, respectively, showing an outstanding smoke suppression. The char residue obtained from the CC test was further characterized using SEM, FTIR, Raman, and XPS techniques. The results revealed that CCD facilitated the formation of a dense and compact char layer on EP during combustion, thereby impeding gas and heat transfer. In addition, TG-IR was employed to investigate the gas-phase flame-retardant effect of EP/CCD composites, which revealed that CCD promotes the release of water, CO_2, and other incombustible gases, altering the decomposition path of EP.     

Enhancement of fire safety in epoxy resin composites through incorporation of microencapsulated diatomite

Diatomite (DIA) particles are commonly employed as flame-retardant additives for polymers, yet their intrinsic inefficiency requires substantial quantities for optimal efficacy. To address this issue, we proposed a novel approach involving the microencapsulation of DIA with polyethylene glycol phosphate (PEGP) to enhance the flame retardancy of epoxy resin (EP). Characterization of the prepared DIA@PEGP utilized scanning electron microscopy with energy-dispersive x-ray spectrometry and Fourier transform infrared spectroscopy. The resulting EP composite, DIA@PEGP-4/EP, achieved a limiting oxygen index of 33.2% and achieved a V-0 level in vertical combustion tests. Compared to EP, DIA@PEGP-4/EP demonstrated significantly improved fire performance, with 38.6%, 47.8%, 25.0%, 41.3%, and 60.4% reduction in peak heat release rate, total heat release, peak smoke production rate, total smoke production, and CO yield. Furthermore, the highest FPI value of 0.080 m²·s/kW for DIA@PEGP-1/EP and the lowest FGI value of 8.734 kW/m²·s for DIA@PEGP-4/EP, indicate that the incorporation of DIA@PEGP into EP enhances its fire safety. The flame retardancy mechanism of DIA@PEGP-4 involves the formation of a phosphorus-containing aromatic carbon layer during EP char formation, capturing radicals in the gas phase during combustion.     

Zirconium-Embedded Polyhedral Oligomeric Silsesquioxane Containing Phosphaphenanthrene-Substituent Group Used as Flame Retardants for Epoxy Resin Composites

A zirconium hybrid polyhedral oligomeric silsesquioxane derivative (Zr–POSS–bisDOPO) is synthesized by the corner-capping and Kabachnik–Fields reactions. It is characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR), and then used as a flame retardant in diglycidyl ether of bisphenol A (DGEBA) to endow epoxy resin (EP) with flame retardancy. The flame retardancy, thermal stability, and mechanical properties of the cured EP/Zr–POSS–bisDOPO composites are investigated. The results show that when Zr–POSS–bisDOPO is added by 5–7 wt%, the EP/Zr–POSS–bisDOPO composites pass the UL-94 V-0 rating test. In addition, they have a better flame-retardant effect than pure EP. The combination of Zr atom embedded in the Si O cubic cage and the two phosphaphenanthrene substituent groups in one corner of cubic cage is expected to realize the Zr/Si/P ternary intramolecular hybrid synergistic effect and achieve the possibility of dispersing metal–POSS cages at a sub-micrometer-scale level into polymer matrix. It also proves that Zr–POSS–bisDOPO produces phosphorus-containing free radicals and terminates the chain reactions in gas phase. Meanwhile the Si O Si and Zr O units are retained in the solid phase, which promote the char formation and enhance the flame retardancy. This kind of Zr-doped POSS will be helpful for developing the new metal–POSS hybrid flame-retardant and polymer composites.     

A high-efficiency DOPO-based reactive flame retardant with bi-hydroxyl for low-flammability epoxy resin

A high-efficiency DOPO-based reactive flame retardant (DPE) with bi-hydroxyl was successfully synthesized via reacting DOPO with imine obtained from the condensation of ethanolamine and 1,4-phthalaldehyde, and used as co-curing agent to improve the fire safety of epoxy resin (EP). Its chemical structure was characterized by Fourier transform infrared (FTIR) spectra, ¹H, ³¹P nuclear magnetic resonance (NMR) spectra and elemental analysis. The curing behavior, thermal properties, flame-retardant properties of EP/DPE systems were investigated. The results revealed that DPE slightly decreased the glass transition temperature (T_g), but accelerated the curing cross-linking reaction of EP. Furthermore, DPE decreased thermal degradation rate of epoxy matrix and promoted the formation of residual char at high temperature. After adding DPE, the flame retardant of epoxy thermosets was greatly improved. Especially, the thermoset modified with 5 wt% DPE achieved limiting oxygen index (LOI) value of 33.6% and V-0 rating in UL-94 test, demonstrating the highly efficient flame retardancy. While its peak heat release rate (PHRR), total heat release (THR) and total smoke production (TSP) were respectively decreased by 32.6%, 17.8%, and 13.9% compared with neat EP. Moreover, the research on flame retardant mechanism disclosed that DPE played dual flame-retardant effect in the gaseous and condensed phases.     

锥形量热法研究木质素基膨胀型阻燃剂对环氧树脂阻燃抑烟效果

以来自自然界储量第二的木质素作为膨胀型阻燃剂的基体,通过接枝氮、磷元素成功合成碳源、酸源、气源三位一体的木质素基膨胀型阻燃剂（Lig-T）,实现了良好的阻燃性能。将Lig?T按照不同含量添加到环氧树脂（EP）中制备EP/Lig-T复合材料,以锥形量热测试考察复合材料的热稳定性能和阻燃性能,并重点考察复合材料在接近真实火灾事故时的热释放和烟释放规律。结果表明,当Lig-T含量为20 %（质量分数,下同）时,复合材料的热释放速率峰值为1 374 kW/m²、热释放总量为41.63 MJ/m²、烟释放总量为1 634 m²/m²,与EP参比试样的数值相比,均呈现下降的趋势,燃烧结束的残炭率从4.26 %增至10.01 %。基于气相和凝聚相的协效阻燃机理,木质素作为膨胀型阻燃剂的碳源使得复合材料在高温条件下具备更好的成炭效果,在燃烧过程中形成稳定且致密的炭层结构,在实现高效阻燃的同时减少有毒烟气的释放,降低火灾的危害。     

Effect of different zeolitic imidazolate frameworks nanoparticle-modified β-FeOOH rods on flame retardancy and smoke suppression of epoxy resin

A simple method was used to load zeolitic imidazolate frameworks (ZIFs) onto β-FeOOH nanorods to ameliorate the flame retardancy and smoke suppression of epoxy resin (EP). The morphology and structure of ZIF-8-β-FeOOH (Z8Fe) and ZIF-67-β-FeOOH (Z67Fe) nano hybrids were systematically characterized by field emission scanning electron microscope, Fourier transform infrared and X-ray diffraction (XRD) spectra, which proved the successful preparation of the hybrids. 3 wt% of Z8Fe and Z67Fe were added to the EP matrix, and their combustion properties were studied, respectively. The results showed that the composites' limiting oxygen index values were ameliorated to 27.3% and 28.1%, respectively. Their UL94 flame retardant rating was improved, their peak heat release rate and total heat release were reduced, their flame retardant performance was considerably improved, and their generation of toxic smoke was significantly suppressed. Further, through X-ray photoelectron spectroscopy, XRD and laser Raman spectroscopy analysis of the char residue, their potential mechanism of flame retardancy and smoke suppression were studied.     

Percolation and catalysis effect of bamboo‐based active carbon on the thermal and flame retardancy properties of ethylene vinyl‐acetate rubber

The effect of percolation and catalysis of bamboo‐based active carbon (BAC) on the thermal degradation and flame retardancy of ethylene vinyl‐acetate rubber (EVM) composites with intumescent flame retardants (IFR) consisting of ammonium polyphosphate (APP) and dipentaerythritol (DPER) has been investigated. The vulcanization characteristics were analyzed by a moving die rheometer. Thermogravimetric analysis (TGA) and fire behavior tests such as limiting oxygen index (LOI), vertical burning (UL 94), and cone calorimetry were used to evaluate the thermal properties and flame retardancy of EVM composites. Scanning electron microscopy (SEM) was used to study the morphology of residues of EVM composites. The addition of BAC significantly increased the maximum torque (M_H) of EVM composites and EVM matrices. The combination of IFR with BAC can improve the thermal stability of EVM composites. Moreover, BAC can enhance char residue and promote the formation of a network for IFR. The current EVM/37IFR/3BAC composite achieved an LOI of 33.6% and a UL 94 V‐0 rating. The PHRR, total heat release (THR), and total smoke release (TSR) for EVM/IFR/BAC were greatly reduced as compared to EVM/40IFR. Also, the mechanical properties of the EVMIFR/BAC composites increased with increasing BAC contents. The physical percolation effect between BAC and EVM before and after thermal degradation, and the chemical catalysis effect between BAC and IFR during thermal degradation are responsible for the improved flame retardancy of EVM composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42414.     

Preparation of organic–inorganic intumescent flame retardant with phosphorus,nitrogen and silicon and its flame retardant effect for epoxy resin

According to the requirement of fire life cycle assessment (LCA), chitosan ethoxyl urea phosphate (CEUP), an organic–inorganic intumescent flame retardant (IFR) containing phosphorus, nitrogen, and silicon, was synthesized by the reaction of chitosan, phosphorus pentoxide, and urea. FTIR, ¹H NMR, SEM, and XRD were employed to characterize the compounds. As a result, CEUP was successfully prepared with higher thermal stability, favorable to enhance fire resistance. Combined with OMMT, the organic/inorganic IFR was applied as EP flame-retardant agents. The combustion behavior of EP composite was investigated by LOI, UL-94, CCT, SEM, TGA, and TG-IR. It was observed that using 15% CEUP and 3% OMMT (EP3), LOI value reached 34.8% and passed the UL-94 V-0 rating, while THR and TSP of EP composite reduced 65 and 72% compared with pure EP. The char residue of EP composite was up to 22.4%. The thermal decomposition mechanism was traced from 100 to 600°C by TG-IR. It was suggestive that CEUP decomposition commenced at 100°C to create phosphoric acid and sublimation of urea occurred at 300°C. EP3 exhibited a strong thermal stability, namely even at 600°C, the volatile substances were detectable. Dense and expanded carbon layer was confirmed in SEM images.     

氨基树脂膨胀型阻燃剂处理环氧树脂的阻燃机理

合成了一种氨基树脂膨胀型阻燃剂(AIFR),将其用于环氧树脂(EP)中。采用热重、红外光谱和扫描电镜研究了阻燃EP的热解性能和阻燃机理。结果表明:AIFR用量为25%时,EP阻燃性能达到UL94V—0级,氧指数28.4%;AIFR使EP热解提前,热解活化能降低,剩炭增加,红外光谱中吸收峰强度减弱;AIFR对EP的热解具有催化成炭作用;AIFR阻燃EP具有很好的膨胀发泡效果,剩炭的连续性、韧性和强度得到了明显改善。     

Synthesis of a novel char-forming agent (PEIC): Improvement in flame retardancy,thermal stability,and smoke suppression for intumescent flame-retardant polypropylene composites

A novel char-forming agent named PEIC was designed and synthesized combining pentaerythritol octahydrogen tetraphosphate (PEPA) and tris(2-hydroxyethyl) isocyanurate. PEIC was combined with the silica-gel-microencapsulated ammonium polyphosphate (OS-MCAPP), preparing intumescent flame-retardant polypropylene (PP) composites. The results of the limiting oxygen index (LOI) show that the composite containing 30 wt % IFR with OS-MCAPP:PEIC = 2:1 presents the optimal LOI of 32.7%. Meanwhile, the cone calorimeter tests show that its peak heat release rate is 432 kW m⁻², which decreases by 62.1% compared with that of pure PP, showing a high-efficient flame retardancy. The exhibited UL-94 V-0 rating for all the composites indicates that the IFR composed of PEIC and OS-MCAPP has high-efficient flame retardancy in PP. The analysis of residue char reveals that PEIC could improve the quality of char in compactness, intumescentia, and the degree of graphitization. Further, the effect of IFR on the mechanical properties of PP composites was also evaluated and discussed. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48296.     

Flame retardant synergy between interfacial and bulk carbonation in glass fiber reinforced polypropylene

Glass fiber reinforced polypropylene (GF-PP) composites have high flammability on account of wick effect which leads to accelerated flow of the polymer melt along the glass fibers (GF) surface to the flame zone. In this study, dipentaerythritol (DPER), a charring agent, was adsorbed on the GF surface through the hydrogen bond between silane coupling agent and DPER. DPER has a synergistic effect with the intumescent flame retardants (IFR) added in the composites, which can induce interfacial carbonization on the surface of GF, thus transforming the intrinsic smooth GF surface into roughness one. In this way, the negative effect of the wick effect in flame retardancy is weakened. Moreover, the char residues remained on the surface of GF can bring an improved adhesion between GF and char residues formed in the resin so that a more stable barrier char layer is formed. The PP composites with 20 wt% modified glass fiber (M-GF) and 30 wt% IFR can achieve the UL-94V-0, and its limiting oxygen index (LOI) value increased from 16.5% to 29.5%. Simultaneously, the heat release rate (HRR), total heat release (THR) and total smoke release (TSR) decreased significantly, and the peak of heat release rate (PHRR) reduced 60.6% compared with GF-PP.     

Boosting flame retardancy of epoxy resin composites through incorporating ultrathin nickel phenylphosphate nanosheets

Ultrathin nickel phenylphosphate (NiPP) nanosheets with layered structure are successfully synthesized through a mixed solvothermal method. The results indicate that NiPP is Ni(O₃PC₆H₅)·H₂O and has good thermal stability. To ameliorate the thermal stability and flame ratardancy of epoxy resin (EP), EP/NiPP nanocomposites are prepared by incorporating NiPP into EP matrix. The results show that adding NiPP can availably enhance thermal stability at high temperature due to the remarkable catalytic char performance of NiPP, and the residues yield of EP/NiPP nanocomposites with 6 wt% NiPP is 24.1% while the pure EP had only 14.2% at 700°C. In contrast with pure EP, the peak heat release rate, total heat release, smoke production rate, CO production, and CO₂ production of EP/6wt%NiPP nanocomposites reduced by 35.2%, 20.2%, 27.1%, 45.8%, and 35.5%. The synergistic effect of catalytic char performance and fire retardancy of NiPP make the EP/NiPP nanocomposites possess prominent flame retardancy, smoke suppression, and thermal stability.     

不同膨胀型阻燃剂改性聚丙烯/聚乳酸复合材料

用两种不同的膨胀型氮磷阻燃剂(IFR1和IFR2)阻燃改性聚丙烯(PP)/聚乳酸(PLA)复合材料。结果表明:两种阻燃剂在PP/PLA基体中都具有良好的分散性和界面粘合性。阻燃剂的加入降低了材料的力学性能,而含有25%阻燃剂的PP/PLA复合材料就能到达垂直燃烧试验(UL-94)的V0等级。燃烧过程中阻燃剂通过在材料表面形成致密的炭层来提高材料的阻燃性,其中IFR1对PP/PLA体系的阻燃改性效果更好。从力学性能和阻燃效果的双重考虑,质量含量25%的阻燃剂适合于PP/PLA材料的阻燃改性。