A liquid phosphorous flame retardant combined with expandable graphite or melamine in flexible polyurethane foam

A systematic series of flexible polyurethane foams (FPUF) with different concentrations of flame retardants, bis([dimethoxyphosphoryl]methyl) phenyl phosphate (BDMPP), and melamine (MA) or expandable graphite (EG) was prepared. The mechanical properties of the FPUFs were evaluated by a universal testing machine. The pyrolysis behaviors and the evolved gas analysis were done by thermogravimetric analysis (TGA) and TGA coupled with Fourier-transform infrared (TG-FTIR), respectively. The fire behaviors were studied by limiting oxygen index (LOI), UL 94 test for horizontal burning of cellular materials (UL 94 HBF), and cone calorimeter measurement. Scanning electronic microscopy (SEM) was used to examine the cellular structure's morphology and the postfire char residue of the FPUFs. LOI and UL 94 HBF tests of all the flame retarded samples show improved flame retardancy. BDMPP plays an essential role in the gas phase because it significantly reduces the effective heat of combustion (EHC). This study highlights the synergistic effect caused by the combination of BDMPP and EG. The measured char yield from TGA is greater than the sum of individual effects. No dripping phenomenon occurs during burning for FPUF-BDMPP-EGs, as demonstrated by the result of the UL 94 HBF test. EG performs excellently on smoke suppression during burning, as evident in the result of the cone calorimeter test. MA reduces the peak heat release rate (pHRR) significantly. The synergistic effect of the combination of BDMPP and EG as well as MA offers an approach to enhance flame retardancy and smoke suppression.     

软质聚氨酯泡沫塑料用无卤阻燃剂的研究

本文以羟基苯氧膦丙烯酸(CEPP)和三聚氰胺(MA)为原料合成了一种含磷、氮无卤阻燃剂(CMA),采用FT-IR表征了阻燃剂的化学结构,并将该阻燃剂用于软质聚氨酯泡沫(FPUF)的阻燃。用扫描电镜(SEM)研究了阻燃剂的加入对FPUF的形态的影响,通过LO I和垂直燃烧(Cal.117A)测试研究了该阻燃剂对FPUF的阻燃效果。结果表明,CMA可以有效提高FPUF的阻燃性:当CMA的添加量为10%时,FPUF即可通过Cal.117A测试,其LO I值也从17.3提高到23.0;随阻燃剂添加量的增加,FPUF的阻燃性能也逐渐提高。TG测试结果表明CMA的加入对FPUF的热稳定性没有多大影响。     

Flame retardant effects of organic inorganic hybrid intumescent flame retardant based on expandable graphite in silicone rubber composites

In this work, an organic inorganic hybrid intumescent flame retardant (functionalized expandable graphite, FEG) was synthesized and characterized by Fourier transform infrared spectrometry (FTIR). The flame retardant effects of FEG in silicone rubber (SR) composites were investigated by cone calorimeter test (CCT), and the thermal stability of SR composites was studied using TGA. The CCT results showed that FEG can effectively reduce the flammable properties including peak heat release rate (PHRR), total heat release (THR), smoke production rate (SPR), total smoke release (TSR), and smoke factor (SF). An improvement of thermal stability of SR/FEG was also observed. Compared with EG, FEG can further reduce THR, SPR, and TSR of SR/FEG composites in combustion process. Moreover, there is a more obvious intumescent char layer formed from the sample with FEG than the sample with EG at the same loading in SR composites. Copyright © 2014 John Wiley & Sons, Ltd.     

Effects of flame‐retardant ramie fiber on enhancing performance of the rigid polyurethane foams

Ramie fiber (RF) with excellent tensile strength was treated by a flame retardant and obtained the modified RF (MRF) that is incombustible. Then, MRF was used to improve the performance of rigid polyurethane foams (RPUF). The mechanical properties of the composite were investigated by compressive strength test and shear stress test. The fire characteristics were studied using a cone calorimeter. And the thermal decomposition and flammable properties were further evaluated using thermogravimetric analysis and limiting oxygen index. The results showed that MRF improve the mechanical properties of RPUF and eliminate the harm of flammability of RF on the RPUF.     

Flame‐retardant rigid polyurethane foam with a phosphorus‐nitrogen single intumescent flame retardant

A phosphorous‐nitrogen intumescent flame‐retardant, 2,2‐diethyl‐1,3‐propanediol phosphoryl melamine (DPPM), was synthesized and characterized by Fourier transform infrared spectroscopy and nuclear magnetic resonance. Flame‐retardant rigid polyurethane foams (RPUFs) with DPPM (DPPM‐RPUF) as fire‐retardant additive were prepared. Scanning electron microscope (SEM) and mechanical performance testing showed that DPPM exhibited a favorable compatibility with RPUF and negligibly negative influence on the mechanical properties of RPUF. The flame retardancy of DPPM on RPUF was investigated by the limiting oxygen index (LOI), vertical burning test and cone calorimeter. The LOI of DPPM‐RPUF could reach 29.5%, and a UL‐94 V‐0 rating was achieved, when the content of DPPM was 25 php. Furthermore, the DPPM‐RPUF exhibited an outstanding water resistance that it could still obtain a V‐0 rating after water soaking. Thermogravimetric analysis showed that the residual weight of RPUF was relatively low, while the charring ability of DPPM‐RPUF was improved greatly. Real‐time Fourier transform infrared spectroscopy was employed to study the thermo‐oxidative degradation reactions of DPPM‐RPUF. The results revealed that the flame‐retardancy mechanism of DPPM in RPUF was based on the surface charred layer acting as a physical barrier, which slowed down the decomposition of RPUF and prevented the heat and mass transfer between the gas and the condensed phases.     

Synthesis of a carbon nanotubes/ZnAl‐layered double hydroxide composite as a novel flame retardant for flexible polyurethane foams

A composite consisting of carbon nanotubes and zinc aluminum‐layered double hydroxide (CNT/ZnAl‐LDH) with good solubility in liquid media was synthesized by a co‐precipitation method. The structural characterization and morphological observation demonstrated that the composite displayed a heterostructure with CNTs embedded in ZnAl‐LDH nanosheets. The influence of CNT/ZnAl‐LDH on the thermal stability and flammability performance of flexible polyurethane (PU) foams was characterized. It was established that CNT/ZnAl‐LDH could improve the thermal stability while reduce the peak heat release rate as well as the total smoke release of PU foams. The formation of a protective char with increased mechanical properties and high graphitization degree was mostly postulated for the improved flame retardancy. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and characterization of expandable graphite-poly(methyl methacrylate) composite particles and their application to flame retardation of rigid polyurethane foams

The expandable graphite (EG) is well proved to be a good intumescent flame retardant for rigid polyurethane foam (RPUF), however, as it is pulverized into fine particles (pEG) for the purpose of improving the mechanical properties of the foam composite, the flame-retardant properties of pEG-filled RPUF (pEG/RPUF) are deteriorated. To improve both the mechanical properties and flame-retardant performance of pEG/RPUF composite, the pEG particles were encapsulated with a layer of polymer, poly(methyl methacrylate) (PMMA). The Fourier transform infrared spectroscopy (FTIR) examination, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) observation well demonstrated that the pEG-PMMA particles were successfully synthesized via emulsion polymerization, with 22.09 wt% PMMA. In contrast to the pEG, the addition of 10 wt% of pEG-PMMA particles into RPUF led to a considerable increase of the compressive strength and modulus and flame retardancy (limiting oxygen index, horizontal and vertical burning rates). The improvement of mechanical properties and flame-retardant behavior of pEG-PMMA particles filled RPUF was attributed to the desirable dispersion of pEG in PU matrix without destroying the integrality of the RPUF cell system, the good interfacial adhesion between PMMA and RPUF, and sealing the fine EG particles without losing oxidant, hence, to increase their expanded volume as exposed to fire.     

Flame retardancy and smoke suppression of silicone foams with microcapsulated aluminum hypophosphite and zinc borate

The flame‐retardant microcapsules were successfully fabricated with an aluminum hypophosphite (AHP) core. Fourier transform infrared (FTIR) and X‐ray photoelectron spectroscopy (XPS) were used to verify that AHP was encapsulated in the microcapsules, and thermogravimetry analysis showed that microencapsulated AHP (MAHP) possessed higher thermal stability than that of AHP. Then, a flame‐retardant and smoke suppression system for silicone foams (SiFs) was obtained through a synergistic effect of MAHP and zinc borate (2ZnO·3B₂O₃·3.5H₂O). The mechanical properties, flame retardance, and smoke suppression of SiFs with MAHP and zinc borate were tested using the tensile test, limiting oxygen index (LOI) test, UL‐94 test, and cone calorimeter test. The mechanical properties indicated that the tensile strength and elongation at break of SiFs could evidently improve with the incorporation of MAHP. Compared with pure SiF, SiF8 with 4.5‐wt% MAHP and 1.5‐wt% zinc borate could achieve an LOI value of 30.7 vol% and an UL‐94 V‐0 rating, the time to ignition amplified almost six times, the peak heat release rate and total heat release were 51.10% and 46.00% less than that of pure SiF, respectively, the fire performance index increased nearly 13 times, and the fire growth index value was only 13.18% of pure SiF. Moreover, the partial substitution of zinc borate imparted a substantial improvement in both flame retardancy and smoke suppression. Especially, the peak smoke production rate and total smoke production of SiF8 were merely 38.46% and 38.84% of pure SiF.     

Synergistic effect between phosphorus tailings and aluminum hypophosphite in flame‐retardant thermoplastic polyurethane composites

The massive accumulation of phosphorus tailings (PT) not only occupies land resources and also causes great threat to ecological environment and human security. It is of great significance to explore the resource utilization of PT in some fields. Herein, aluminum hypophosphite (AHP) and PT are blended together to enhance the flame retardancy of thermoplastic polyurethane (TPU) composites, and the synergistic effects between AHP and PT are investigated systematically. Cone calorimeter test (CCT) results indicate that the peak heat release rate (PHRR) and total heat release (THR) of the samples containing 25 wt% AHP are decreased by 89% and 68%, respectively, and the total smoke release (TSR) show a reduction of 58.8%, in comparison with those of neat TPU. For the sample TPU/22.5AHP/2.5PT, the PHRR, THR, and TSR are decreased by 91.2%, 70%, and 63%, respectively. Scanning electron microscopy (SEM) analysis results demonstrate that the addition of PT can facilitate the generation of dense and compact char layers, preventing the release of heat and smoke effectively. All the abovementioned results indicate that the synergistic effects are existed between AHP and PT for enhancing the fire safety of TPU composites, which can provide a new way for the utilization of PT.     

Effect of blowing agent content on the structure and flame-retardant properties of rigid polyurethane foam/expanded graphite composites

Driven by global environmental issues, the development of green building materials has become an immediate focus. In this work, n-pentane was used as an environmentally friendly blowing agent to prepare flame-retardant rigid polyurethane foam (RPUF) with the addition of expandable graphite (EG) successfully, and the effect of n-pentane content on flame retardancy and compressive properties of RPUF/EG composites was investigated through limit oxygen index (LOI), vertical burning test (UL-94), scanning electron microscope (SEM), thermogravimetric analysis (TGA), and compressive properties test. SEM results show that the content of EG and n-pentane causes a change in the cell structure of RPUF. The change of the n-pentane content has also an obvious effect on the thermal stability, flame retardancy, and specific compressive strength of RPUF/EG composites. In addition, the cell structure of RPUF matrix has an obvious influence on the distribution of EG in the composites, which indirectly affects the flame-retardant efficiency of EG. This research explores the conditions for the application of environmentally friendly RPUF and expands its application prospects.     

Hugely enhanced flame retardancy and smoke suppression properties of UHMWPE composites with silicone‐coated expandable graphite

In this paper, silicone‐coated intumescent flame retardants was prepared by an efficient and simple approach, aiming at enhancing the flame‐retardant efficiency and smoke suppression properties. The surface of expandable graphite (EG) was treated prior to the coverage of nonflammable silicone. The resultant silicone‐modified EG hybrid (SEG) was combined with ammonium polyphosphate (APP) and applied as a flame‐retardant and smoke‐suppressant for ultrahigh molecular weight polyethylene (UHMWPE). Compared with UHMWPE/APP/EG (with 15 wt% APP/EG), UHMWPE/APP/SEG (with 15 wt% APP/SEG) gives decrement by 18.5% in the peaks of the heat release rate, 6.33% in total heat release and 13.6% in total smoke release, whereas increment by 23% in tensile strength and 12.1% in elongation at break, respectively. It is suggested that the introduction of silicone on the surface of EG can improve the interfacial compatibility between EG and UHMWPE. Moreover, it can lead to forming more char residue and reducing the release of smoke particulates during combustion process of the composites.     

Synthesis and morphology of rigid polyurethane foams with POSS as pendant groups or chemical crosslinks

This work reports on the preparation of polyurethane foams (PUFs) chemically modified by functionalized 1,2‐propanediolisobutyl polyhedral oligosilsesquioxane (PHI‐POSS) as pendant groups and octa(3‐hydroxy‐3‐methylbutyldimethylsiloxy) POSS (OCTA‐POSS) as chemical crosslinks. The resulting foams, which contain 0 to 15 wt% POSS (versus polyol), were characterized in terms of their structure, morphology, density, thermal conductivity, compressive strength, and water absorption. Fourier transform infrared‐attenuated total reflectance revealed good reaction rate between POSS and PUF. PHI‐POSS suppresses the formation of the hydrogen bonds in the soft phase. The composite foams with OCTA‐POSS showed a reduced number of cells and increased average area of foam cells in comparison with the PUF, while the addition of PHI‐POSS causes an increase in the number of cells of the foam as compared with the reference, and thus a reduction in the average area of cells. Scanning electron microscopy–energy‐dispersive X‐ray spectroscopy analysis revealed that POSS moieties form lamellae‐shaped crystals of different sizes, distributed homogeneously in the bulk (PHI‐POSS) or close to the self surfaces (OCTA‐POSS). The compressive strength of PUF/POSS hybrids in the direction parallel and perpendicular to the direction of foam rise is greater than the strength of the reference foam. PHI‐POSS improves monotonically the compressive strength in the studied loading range. About 5 wt% OCTA‐POSS also provides reinforcement, but further loading reverses the phenomenon. PUF/POSS hybrids absorb less water than the pristine foam because of an increase of foam density. Copyright © 2015 John Wiley & Sons, Ltd.     

Melamine,silica, and ionic liquid as a novel flame retardant for rigid polyurethane foams with enhanced flame retardancy and mechanical properties

Rigid polyurethane (PU) foams were successfully filled with different weight ratios of melamine (1 wt%, 5 wt%, 10 wt%), silica (0.1 wt%) and ionic liquid, 1-Ethyl-3-methylimidazolium chloride, [EMIM]Cl (0.3 wt%). The aim of this study was to improve the flame retardancy of PU foams and to develop the synergistic effect between melamine, silica and ionic liquid on the flame-retardant PU foams. The influence of different loadings of the fillers was examined. The results showed that in comparison with unfilled foam, all modified compositions are characterized by higher density (41–46 kg m⁻³), greater compression strength (134–148 kPa), and comparable thermal conductivity (0.023–0.026 W m⁻¹ K⁻¹). Moreover, the reaction to fire of the PU composites has been investigated by the cone calorimeter test. The results showed that the fire resistance of PU foams containing as little as 1 wt% of melamine is significantly improved. For example, the results from the cone calorimeter test showed that the incorporation of the melamine, silica and ionic liquid significantly reduced the peak of heat release rate (pHRR) by ca. 84% compared with that of unmodified PU foam. SEM results showed that incorporated fillers can form an intumescent char layer during combustion which improves the reaction to fire of the composite foams.     

Preparation of bio-based soybean oil polyol modified 3630 polyol-based rigid polyurethane foam and its improved thermal stability,flame retardant,and smoke suppression performances

Rigid polyurethane foam (RPUF) with 3630 polyol-based components was modified using bio-based soybean oil (SO) polyol. The effects of soybean oil polyol on the thermal stability, flame retardant and smoke suppression performances of the modified RPUFs were investigated by thermogravimetric analysis, integral programmed decomposition temperature (IPDT), pyrolysis kinetic analysis, limiting oxygen index, conical calorimetry and smoke toxicity analysis. The results indicated that the RPUF-SO2 (10 wt% soybean oil polyol) had the highest thermal decomposition rate temperature, initial thermogravimetric temperature, termination temperature, residual rate, IPDT and activation energy. Under various circumstances, the total heat release (THR) of RPUF-SO2 was 1.41, 1.61, and 2.51 MJ/m², respectively, and the peak heat release rate (PHRR) was lowered by 22.40%, 45.68%, and 19.86% in comparison to the original RPUF-0. In the meantime, RPUF-SO2 had the best light transmittance (57.20 and 60.60%), the lowest toxic gas emissions (0.31, 0.44, and 0.38 kg/s), and the lowest Ds (32.46 and 29.07). It also had an excellent smoke suppression effect. According to the current study, RPUF-SO2 performed better in terms of heat stability, flame retardancy and smoke suppression. This made it a good benchmark for further bio-based soybean oil polyol modified RPUFs.     

Synthesis and characterization of a novel organophosphorus flame retardant and its application in polypropylene

A novel organophosphorus containing spiro and caged bicyclic phosphate, 3,9‐Bis‐(1‐oxo‐2,6,7‐trioxa‐1‐phospha‐bicyclo[2.2.2]oct‐4‐ylmethoxy)‐2,4,8,10‐tetraoxa‐3,9‐diphospha‐spiro[5.5]undecane 3, 9‐dioxide (SBCPO), was synthesized and characterized by Fourier transform infrared (FTIR), hydrogen‐1 nuclear magnetic resonance (NMR) and phosphorus‐31 NMR. The flame retardancy of polypropylene (PP) containing the novel intumescent flame retardant (IFR) based on the combination between SBCPO and melamine (MA) was studied by limiting oxygen index (LOI), UL‐94 test and cone calorimeter test. Results indicated that this combination showed the excellent flame retardancy for PP at appropriate proportions (with the total loading of 30 wt. % and SBCPO: MA = 4:1). The value of LOI was as high as 31.6, and the rating in UL94 reached to V‐0. Moreover, the HRR and THR of IFR/PP decreased significantly in comparison with that of neat PP. The scanning electron microscopy results indicated that the incorporation of SBCPO could induce the formation of intumescent char layer, which retarded the degradation and combustion process of PP. The thermal oxidative degradation of the PP samples at different temperature was analyzed by FTIR. The thermal stabilities of the composites were further investigated by thermogravimetric analysis. It was found that the amount of residues was increased greatly with the addition of SBCPO that remained in the form of polyaromatic stacks and phosphoric or polyphosphoric acid at the residual chars. Copyright © 2013 John Wiley & Sons, Ltd.     

Structures and physical properties of rigid polyurethane foams with water as the sole blowing agent

Polyurethane rigid foams have been used for many applications such as pipelines insulation materials, automotive parts, solar water heater and construction materials[1,2], due to their desirable physical properties. Traditional rigid foam is made by the reaction of a polyol and 4,4′-diphenylmethane diisocyanate (MDI) with chlorofluorocarbons (CFCs), in particular tri- chlorofluoromethane (CFC-11) and/or HCFC-141b as blowing agents. However, the CFCs blowing agents contain halogens, whic…     

Flame‐retardant performance and mechanism of epoxy thermosets modified with a novel reactive flame retardant containing phosphorus,nitrogen, and sulfur

A novel phosphorus‐containing, nitrogen‐containing, and sulfur‐containing reactive flame retardant (BPD) was successfully synthesized by 1‐pot reaction. The intrinsic flame‐retardant epoxy resins were prepared by blending different content of BPD with diglycidyl ether of bisphenol‐A (DGEBA). Thermal stability, flame‐retardant properties, and combustion behaviors of EP/BPD thermosets were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), limited oxygen index (LOI) measurement, UL94 vertical burning test, and cone calorimeter test. The flame‐retardant mechanism of BPD was studied by TGA/infrared spectrometry (TGA‐FTIR), pyrolysis‐gas chromatography/mass spectrometry (Py‐GC/MS), morphology, and chemical component analysis of the char residues. The results demonstrated that EP/BPD thermosets not only exhibited outstanding flame retardancy but also kept high glass transition temperature. EP/BPD‐1.0 thermoset achieved LOI value of 39.1% and UL94 V‐0 rating. In comparison to pure epoxy thermoset, the average of heat release rate (av‐HRR), total heat release (THR), and total smoke release (TSR) of EP/BPD‐1.0 thermoset were decreased by 35.8%, 36.5% and 16.5%, respectively. Although the phosphorus content of EP/BPD‐0.75 thermoset was lower than that of EP/DOPO thermoset, EP/BPD‐0.75 thermoset exhibited better flame retardancy than EP/DOPO thermoset. The significant improvement of flame retardancy of EP/BPD thermosets was ascribed to the blocking effect of phosphorus‐rich intumescent char in condensed phase, and the quenching and diluting effects of abundant phosphorus‐containing free radicals and nitrogen/sulfur‐containing inert gases in gaseous phase. There was flame‐retardant synergism between phosphorus, nitrogen, and sulfur of BPD.     

Thermal characteristics of novel NaH2PO4/NaHSO4 flame retardant system for polyurethane foams

The thermal decomposition of iminodiacetic, oxydiacetic, and thiodiacetic acids in helium atmosphere has been studied by means of thermogravimetry (TG), differential thermal analysis (DTA) and temperature-programmed pyrolysis directly coupled with mass spectrometry (TPPy-MS). Evolved gas analysis (EGA) profiles of iminodiacetic and oxydiacetic acids were obtained and compared with TG and DTA profiles. The decomposition of iminodiacetic acid forms water, CO, CO₂, CH₃CN, HCN and some hydrocarbons. After water evolution a cyclic anhydride is formed, as well as for oxydiacetic acid. Thiodiacetic acid vaporizes without decomposition.     

Synthesis of a novel phosphate‐containing highly transparent PMMA copolymer with enhanced thermal and flame retardant properties

A novel poly(methyl methacrylate) (PMMA)‐based copolymer (PMMA‐co‐BDPA) rich in aromatic rings was synthesized via radical copolymerization between a phosphorus‐containing acrylic monomer (BDPA) and methyl methacrylate (MMA). UV‐vis spectroscopy demonstrated that the copolymer had high transparency. Thermogravimetric analysis (TGA) and a differential scanning calorimeter (DSC) were used to test the thermal properties of the composites. Additionally, the PMMA‐co‐BDPA‐15 copolymer exhibited a 23% increase in the limited oxygen index (LOI) value. A cone calorimeter test indicated that the peak heat release rate (pk‐HRR) of PMMA‐co‐BDPA was reduced by 29.2% compared with that of pure PMMA, and the carbon yield of burning was obviously increased. The combined test results demonstrated that the prepared copolymer material had good transparency, thermal stability, and flame retardancy.     

Zeolitic imidazolate frameworks‐8 modified graphene as a green flame retardant for reducing the fire risk of epoxy resin

A novel hybrid material of ZIF‐8/RGO (zeolitic imidazolate frameworks‐8 loaded the surface of graphene) was synthesised by a simple method and characterized. Then, ZIF‐8/RGO was added into epoxy resin (EP), and the flame retardancy and smoke suppression of the EP composites were studied. Compared with pure EP, the peak heat release rate and the total heat release of the EP composites were reduced remarkably, and their LOI and UL94 vertical burning rating were also improved. In addition, their smoke production rate and total smoke production were decreased drastically. The improved flame retardancy and smoke suppression were mainly attributed to the physical barrier effect of graphene. Meanwhile, the metal oxide decomposed from ZIF‐8 could contribute to the production of char residue and enhance the compactness of the char layer.