Grafting modification bamboo kraft lignin and its performance in rigid polyurethane foams

In order to improve the efficiency of intumescent flame retardant (IFR), bamboo kraft lignin (BKL) was chemically functionalized by grafting melamine (MEL) and diethyl phosphite (DEP) and used for rigid polyurethane (RPU) foam. The BKL, MEL, and DEP in IFR system were used as char forming agent, gas, and acid source, respectively. The FTIR and XPS results indicated that the nitrogen (N) and phosphorus (P) containing BKL was successfully synthesized. The limiting oxygen index (LOI) value of N-BKL and N/P-BKL RPU foams were higher than BKL RPU foam, suggesting that N-BKL and N/P-BKL improved flame retardancy of the foams. The total heat release (THR), heat release rate (HRR), effective heat of combustion (EHC), and fire growth rate (FIGRA) values of N-BKL and N/P-BKL RPU foams were much lower than that of BKL RPU foam. The flame retardancy index value of N/P-BKL RPU foams was higher comparing to N-BKL RPU foam. These results indicated that the synergistic interaction between N containing compound of MEL and P containing compound of DEP led to the improvement flame retardant properties. Comparing to BKL RPU foam, the N/P-BKL RPU foam increased 74°C of maximum weight loss temperature and decreased 18.1 wt% of mass loss, indicating enhanced thermal stability. The morphology of char after cone calorimeter testing showed the N/P-BKL RPU foam presented more continuous and compact char residues, which could reduce heat and mass transfer, protecting underlying materials from further combustion in a fire, thus resulting in good flame retardancy and thermal stability properties. This work suggests a promising route to enhancing the flame-retardant performance of RPU foam using nontoxic and more environmentally friendly grafted bamboo lignin.     

典型添加型磷酸酯/可膨胀石墨阻燃聚氨酯泡沫行为研究

对比了3种典型的添加型磷酸酯,亚磷酸二甲酯（DP）、甲基膦酸(5乙基2甲基2氧代1,3,2二氧磷杂环己5基)甲基甲基酯（EMD）和甲基膦酸二甲酯（DMMP）分别与可膨胀石墨（EG）复合阻燃硬质聚氨酯泡沫（RPUF）,研究了3种不同结构的磷酸酯对材料阻燃性能的影响。结果表明,在3种磷酸酯添加相同质量的情况下,添加DMMP和DP样品的极限氧指数明显高于添加EMD的,且添加DMMP样品的热释放速率峰值和热释放总量最低,在3种磷酸酯中具有最好的阻燃行为表现;DP由于在燃烧过程中发生氧化反应而加剧了体系放热从而降低了阻燃效果;EMD通过分解首先释放DMMP,但由于其磷含量偏低,因此阻燃效率低于DMMP;DMMP由于具有磷含量高、气相和凝聚相阻燃效率高等优点与EG配合产生了最佳的阻燃效果。     

Synthesis and characterization of bio-based intumescent flame retardant and its application in polyurethane

A novel bio-based P-N containing intumescent flame retardant melamine starch phytate (PSTM) was prepared via the reaction of phytic acid starch ester with melamine and characterized by Fourier transform infrared, scanning electron microscopy and thermogravimetric analysis (TGA). The effects of PSTM on thermal properties and flammability of rigid polyurethane (PU) foams were analyzed by TGA, limit oxygen index (LOI), vertical burning tests (UL-94) and cone calorimeter measurement. The TGA results demonstrated that the thermal stabilities of PU/PSTM foam at high temperature was enhanced with the increasing additive amount of PSTM. The results showed that PU foam with 30 php PSTM (PU/PSTM-30%) observed an LOI value of 25.9 and a UL-94 rating of V-0. Cone calorimetry data showed that peak heat release rate, total heat release and smoke production rate of PU/PSTM-30% were distinctly lower than that of pure PU. Further experimental results demonstrated that PSTM promotes well charring of PU which could protect the foam from combustion. This work developed a novel bio-based intumescent flame retardant by suing phytic acid and starch as the acid source and carbon source, respectively, which is of great significance to the preparation of environmental-friendly flame retardants.     

Melamine amino trimethylene phosphate as a novel flame retardant for rigid polyurethane foams with improved flame retardant,mechanical and thermal properties

Melamine amino trimethylene phosphate (MATMP) as a novel nitrogen‐phosphorus flame retardant, was synthesized by the reaction of melamine with amino trimethylene phosphonic acid (ATMP) in aqueous solution. The structure of MATMP was characterized by Fourier transform infrared spectroscopy, solid state 31 P nuclear magnetic resonance, and thermogravimetric analysis. Rigid polyurethane (RPU) foams were prepared by one‐shot and free‐rise method, using MATMP as a flame retardant. The flame retardant, mechanical and thermal properties of MATMP in RPU foams were studied. It is found that the RPU foam containing 15 wt % MATMP (sample RPUMA‐15) can pass the UL‐94 V0 test with a limiting oxygen index of 25.5%. The cone calorimeter test results show that the peak heat release rate of RPUMA‐15 is reduced about 34% compared with that of untreated RPU foam. SEM results indicate that the RPU foams with MATMP can form the good and compact char during burning which provides better flame retardancy. The compressive strength of the RPU foams filled with MATMP first increases and then slightly decreases with an increase in the MATMP content comparing with that of untreated RPU foam. Moreover, thermal conductivities of the MATMP filled RPU foams are about 0.03 W/m K. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45234.     

Investigation on flammability of rigid polyurethane foam‐mineral fillers composite

This study investigates the incorporation of castor oil–based rigid polyurethane foam with mineral fillers feldspar or kaolinite clay in order to enhance the mechanical, thermal, and flame retardant properties. Influence of mineral fillers on the mechanical strength was characterized by compressive strength and flexural strength measurement. Thermogravimetric analysis (TGA) was performed to diagnose the changes in thermal properties, while cone calorimeter test was performed to ascertain the flame retardancy of the mineral filler–incorporated rigid polyurethane foam composites. Results showed that the foams incorporated with mineral filler demonstrated up to 182% increase in compressive strength and 351% increase in flexural strength. Thermal stability of these composite foams was also found to be enhanced on the incorporation of kaolinite clay filler with an increase in 5% weight loss temperature (T_5%) from 192°C to 260°C. Furthermore, peak heat release rate (PHRR), total heat release (THR), smoke production rate (SPR), and total smoke release (TSR) were also found to decreased on the incorporation of mineral filler in the rigid polyurethane foam. So mineral fillers are ascertained as a potential filler to enhance the mechanical, thermal, and flame retardant behaviors of bio‐based rigid polyurethane foam composites.     

Flame‐retardant mechanism of expandable polystyrene foam with a macromolecular nitrogen–phosphorus intumescent flame retardant

Expandable polystyrene (EPS) foam is largely used as the thermally insulating external wall in buildings and constructions, but it is extremely flammable because of the presence of almost 98% air into its porous structure, its high surface‐area‐to‐mass ratio, and its elemental composition. Lots of serious fire disasters caused by EPS foam have posed great threats to people's properties and lives in recent years. Thus, a halogen‐free, flame‐retardant EPS is urgently needed, and its preparation is still a global challenge. To solve the problem that it is easy for EPS foam to form melt dripping and difficult for it to generate a char layer during the combustion process, a macromolecular nitrogen–phosphorus intumescent flame retardant (MNP) was selected to prepare flame‐retardant EPS foam and good mechanical and flame‐retardant properties were obtained. The scanning electron microscopy characterization revealed that MNP could penetrate into the gap between the beads, and a thin physical coating layer formed on the surface of the bead. The data from the thermogravimetry–Fourier transform infrared test indicated that a nitrogenous noncombustible gas was generated by the pyrolysis of MNP. When the MNP content increased to 30%, the limiting oxygen index and the smoking density rate of the EPS–MNP foam were 28.8 and 23.6, respectively, and a UL94 V‐0 classification was achieved. In addition, the heat‐release rate, total heat‐release, smoke produce rate, and carbon dioxide production of the EPS–MNP foams all decreased obviously; this was attributed to the flame‐retardant effects of MNP in both the condensed and gas phases. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44356.     

A void surface flame retardant strategy for polymeric polyHIPEs

Effective flame retardant strategy for open-cell foam (e.g., polyHIPE) remains of a great challenge. Herein, a void surface flame retardant strategy for polyHIPE was presented. An open-cell polystyrene (PS) polyHIPE was fabricated through an emulsion-templating technique. Polyphosphazene (PSZ), a highly efficient flame retardant polymer, was then in situ fabricated and covalently attached to the void surface of the foam to be a uniform flame retardant protective layer, while the open-cell structure of the foam was perfectly preserved. Compared with the pristine PS polyHIPE, the PSZ modified one had significantly improved thermal stability (char residues yield at 800°C increased from 3.36 to 16.53 wt%) and mechanical properties (Young's modulus increased by 2.6 times); the values of average heat release rate and total heat release of combustion were reduced by 62.36% and 41.57%, respectively. While, the value of limiting oxygen index was increased from 17.39% to 19.75%, owing to the combined action of condensed phase flame retardant and gas phase flame retardant. These results indicate that the in situ surface modification strategy is effective for improving the flame retardancy of highly interconnected polymer foams.     

基于环三磷腈磷氮阻燃剂的合成及其在聚氨酯泡沫的应用

以六氯环三磷腈、对羟基苯甲醛、苯胺及亚磷酸二乙酯等原料，成功合成阻燃剂六（4-苯胺基次甲基苯氧基-亚磷酸二乙酯基）环三磷腈（HADPPCP），用于阻燃基于苹果酸多元醇的聚氨酯硬泡。HADPPCP具有良好的热稳定性和成炭性，氮气气氛下的初始分解温度为191.9℃，700℃时的残炭量高到46.8%（质量）。HADPPCP的加入可以改善聚氨酯硬泡的热稳定性、阻燃性能和燃烧行为。添加25%(质量)的HADPPCP可以将聚氨酯泡沫的氧指数从18%提高到25%，最大热释放速率和总热释放量分别从230 kW/m²和20.1 MJ/m²降低至213 kW/m²和16.6 MJ/m²，总产烟量从10.5 m²下降到5.3 m²。     

Flame resistance and foaming properties of NBR compounds with halogen‐free flame retardants

Acrylonitrile butadiene rubber (NBR) foams compounded with various halogen‐free flame retardants were prepared. The influence of nonhalogen flame retardants on the flame resistance and foaming properties of the NBR compounds were investigated. The foaming properties (expandability 980%–1050%, closed‐cell structure) of NBR compounds with expandable graphite (EG) and ammonium polyphosphate (APP) flame retardants were similar to the NBR base compounds which contained primarily aluminum hydroxide (ATH). The heat release capacity (HRC) ranged from 10 to 74 J/g‐K, the average heat release rate (A‐HRR) ranged from 8 to 60 kW/m², and the total heat release (THR) ranged from 2.6 to 7.3 MJ/m² for the nonhalogenated NBR foams with closed‐cell structure and were significantly decreased upon increasing the amounts of flame retardants. This reduction is attributed to the hard char formation and production of water from the interaction with ATH. The limiting oxygen index (LOI) and time to ignition (TTI) show opposite results. The smoke density (0.050–0.037) of the NBR foams with EG flame retardant was decreased when compared to the NBR foam (0.107). The EG flame retardant was more effective than the phosphorus/nitrogen flame retardants in reducing the HRR and smoke density. The use of both ATH and EG is very effective in improving flame resistance. POLYM. COMPOS., 2009. © 2009 Society of Plastics Engineers     

Flame retardation and thermal stability of novel phosphoramide/expandable graphite in rigid polyurethane foam

A novel flame retardant named diethylene N,N',N''‐tri (diethoxy)phosphoramide (DTP) was synthesized using diethyl phosphate and diethylenetriamine via Atherton–Todd reaction. Then, series of flame‐retardant water‐blown rigid polyurethane foams (RPUFs) with expandable graphite (EG) and DTP were prepared through box‐foaming. The results of thermogravimetric analysis showed that DTP/EG changed thermal degradation process of RPUF and promoted enhancing char residues. The complex flame‐retardant system (EG/DTP) endowed RPUF higher limiting oxygen index (LOI) values (29.1%–30.2%) and lower heat release rate peak (PHRR) values according to LOI and microscale combustion calorimeter tests. More importantly, the synergistic flame‐retardant effect between EG and DTP in RPUF was proved by the analysis of synergistic effectivity values. Based on the analysis of cone calorimetric tests, EG/DTP revealed remarkable effects to inhibit the fire intensity and smoke release of RPUF with decreased PHRR and total smoke production due to good char‐forming action. To further investigate the char‐residues of the foams after combustion, scanning electron microscope and energy dispersive X‐ray spectroscopy analyses were conducted. The results suggested that EG/DTP flame‐retardant system promoted RPUF forming a compact, continuous and phosphorus‐rich char layer as a good fire barrier in combustion. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46434.     

Preparation and investigation of flame‐retardant epoxy resin modified with a novel halogen‐free flame retardant containing phosphaphenanthrene,triazine‐trione,and organoboron units

In this article, a novel flame retardant (coded as BNP) was successfully synthesized through the addition reaction between triglycidyl isocyanurate, 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide and phenylboronic acid. BNP was blended with diglycidyl ether of bisphenol‐A to prepare flame‐retardant epoxy resin (EP). Thermal properties, flame retardancy, and combustion behavior of the cured EP were studied by thermogravimetric analysis, limited oxygen index (LOI) measurement, UL94 vertical burning test, and cone calorimeter test. The results indicated that the flame retardancy and smoke suppressing properties of EP/BNP thermosets were significantly enhanced. The LOI value of EP/BNP‐3 thermoset was increased to 32.5% and the sample achieved UL94 V‐0 rating. Compared with the neat EP sample, the peak of heat release rate, average of heat release rate, total heat release, and total smoke production of EP/BNP thermosets were decreased by 58.2%–66.9%, 27.1%–37.9%, 25.8%–41.8%, and 21.3%–41.7%, respectively. The char yields of EP/BNP thermosets were increased by 46.8%–88.4%. The BNP decomposed to produce free radicals with quenching effect and enhanced the charring ability of EP matrix. The multifunctional groups of BNP with flame retardant effects in both gaseous and condensed phases were responsible for the excellent flame retardancy of the EP/BNP thermosets. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45291.     

Effect of zinc oxide on properties of phenolic foams/halogen‐free flame retardant system

A halogen‐free flame retardant system consisting of ammonium polyphosphate (APP) as an acid source, blowing agent, pentaerythritol (PER) as a carbonific agent and zinc oxide (ZnO) as a synergistic agent, was used in this work to enhance flame retardancy of phenolic foams. ZnO was incorporated into flame retardant formulation at different concentrations to investigate the flammability of flame retardant composite phenolic foams (FRCPFs). The synergistic effects of ZnO on FRCPFs were evaluated by limited oxygen index (LOI), thermogravimetric analysis (TGA), cone calorimeter tests, and images of residues. Results showed that the flame retardant significantly increased the LOI of FRCPFs. Compared with PF, heat release rate (HRR), total heat release (THR), effective heat of combustion (EHC), production or yield of carbon monoxide (COP or COY) and Oxygen consumption (O₂C) of FRCPFs all remarkably decreased. However specific extinction area (SEA) and total smoke release (TSR) significantly increased, which agreed with the gas‐phase flame retardancy mechanism of the flame retardant system. The results indicated that FRCPFs have excellent fire‐retardant performance and less smoke release. And the bending and compression strength were decreased gradually with the increase of ZnO. The comprehensive properties of FRCPFs were better when the amount of ZnO was 1～1.5%. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42730.     

酚醛泡沫的燃烧行为及阻燃研究进展

酚醛泡沫因兼具优异的保温性能和阻燃性能在工程领域得到广泛应用,但其经高温燃烧后质量残留率很低,炭层疏松、强度低,离开火焰后还易出现阴燃现象。目前有关酚醛泡沫燃烧行为的研究大多集中在如何进一步提高酚醛泡沫塑料的阻燃等级或在改善其脆性的同时不降低固有的阻燃性能,还未见关于酚醛泡沫燃烧全过程行为的综述报道。文章介绍了酚醛泡沫在明火燃烧和阴燃状态的燃烧行为,分析了影响酚醛泡沫燃烧行为的因素,并总结了现有酚醛泡沫阻燃研究的进展。目前酚醛泡沫的燃烧行为及阻燃研究主要集中在泡沫的明火燃烧,对酚醛泡沫阴燃问题的研究重视不足,缺乏针对酚醛泡沫燃烧全过程的行为和机理探究。因此,提出应加大对酚醛泡沫阴燃行为的研究投入,注重对酚醛泡沫燃烧全过程的机理探索与阻燃方案研究,设计并研发出解决酚醛泡沫燃烧全过程问题的有效途径。     

酚醛泡沫的燃烧行为及阻燃研究进展

酚醛泡沫因兼具优异的保温性能和阻燃性能在工程领域得到广泛应用,但其经高温燃烧后质量残留率很低,炭层疏松、强度低,离开火焰后还易出现阴燃现象。目前有关酚醛泡沫燃烧行为的研究大多集中在如何进一步提高酚醛泡沫塑料的阻燃等级或在改善其脆性的同时不降低固有的阻燃性能,还未见关于酚醛泡沫燃烧全过程行为的综述报道。文章介绍了酚醛泡沫在明火燃烧和阴燃状态的燃烧行为,分析了影响酚醛泡沫燃烧行为的因素,并总结了现有酚醛泡沫阻燃研究的进展。目前酚醛泡沫的燃烧行为及阻燃研究主要集中在泡沫的明火燃烧,对酚醛泡沫阴燃问题的研究重视不足,缺乏针对酚醛泡沫燃烧全过程的行为和机理探究。因此,提出应加大对酚醛泡沫阴燃行为的研究投入,注重对酚醛泡沫燃烧全过程的机理探索与阻燃方案研究,设计并研发出解决酚醛泡沫燃烧全过程问题的有效途径。     

A phosphorus‐containing phenolic derivative and its application in benzoxazine resins: Curing behavior,thermal, and flammability properties

In this work, flame‐retardant benzoxazine resins were prepared by copolymerization of bisphenol A based benzoxazine (BA‐a) and a phosphorous‐containing phenolic derivative (DOPO‐HPM). The curing behavior, thermal stability, and flame resistance of BA‐a/DOPO‐HPM composites were studied by differential scanning calorimeter (DSC), thermogravimetric analysis (TGA), limited oxygen index (LOI) measurement, UL94 test, and cone calorimeter. The DSC results indicated that DOPO‐HPM catalyzed the curing reaction because of its acidity. The TGA results revealed that the BA‐a/DOPO‐HPM thermosets possessed higher decomposition temperatures (T_5%) and char yields than that of BA‐a. The combustion tests indicated that the flame retardant properties of BA‐a/DOPO‐HPM thermosets were enhanced. The BA‐a/DOPO‐HPM‐20 sample acquired the highest LOI value of 32.6% and UL94 V‐0 rating. Moreover, the average of heat release rate (av‐HRR), peak of heat release rate (pk‐HRR), average of effective heat of combustion (av‐EHC) and total heat release (THR) of BA‐a/DOPO‐HPM‐20 were decreased by 24.6%, 53.1%, 14.9%, and 22.1%, respectively, compared with BA‐a. The attractive performance of BA‐a/DOPO‐HPM blends was attributed to the molecular structure of DOPO‐HPM composed of DOPO group with excellent flame‐retardant effect and phenolic hydroxyl group with catalysis. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43403.     

Addition flame‐retardant effect of nonreactive phosphonate and expandable graphite in rigid polyurethane foams

A series of flame‐retardant rigid polyurethane foams (RPUFs) containing nonreactive phosphonate (5‐ethyl‐2‐methyl‐1,3,2‐dioxaphosphorinan‐5‐yl) methyl dimethyl phosphonate P‐oxide (EMD) and expandable graphite (EG) were prepared by water blown. The flame‐retardant properties and mechanism of EMD/EG on RPUFs were systematically investigated. The EMD/EG system effectively increased the limiting oxygen index (LOI) value and decreased the values of total heat release (THR), av‐effective heat of combustion (EHC), pk‐heat release rate (HRR), total smoke release (TSR) of RPUFs. The impact values of LOI, THR, and av‐EHC resulted by EMD/EG system are nearly equal to the sum of the impact values by EMD and EG individually in RPUFs, which implies the addition flame‐retardant effect from EMD and EG. EMD alone exerted excellent gas‐phase flame‐retardant effect by releasing PO fragments with quenching effect. The firm residue produced by EMD combined well with the loose and worm‐like expanded graphite from EG further to form compact and expanded char layer, which brought excellent barrier effect and filtration effect to matrix. That's why pk‐HRR and TSR values of RPUF reduced. Depending on the simultaneous actions of EMD/EG system in gas phase and condensed phase during combustion, the flame‐retardant effects from nonreactive phosphonate and EG on RPUFs were added together. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45960.     

A flame‐retardant composite foam: foaming polyurethane in melamine formaldehyde foam skeleton

A composite foam, polyurethane–melamine formaldehyde (PU/MF) foam, was prepared through foaming PU resins in the three‐dimensional netlike skeleton of MF foam. The chemical structure, morphology, cell size and distribution, flame retardancy, thermal properties and mechanical properties of such composite foam were systematically investigated. It was found that the PU/MF foam possessed better fire retardancy than pristine PU foam and achieved self‐extinguishment. Moreover, no melt dripping occurred due to the contribution of the carbonized MF skeleton network. In order to further improve the flame retardancy of the composite foam, a small amount of a phosphorus flame retardant (ammonium polyphosphate) and a char‐forming agent (pentaerythritol) were incorporated into the foam, together with the nitrogen‐rich MF, thus constituting an intumescent flame‐retardant (IFR) system. Owing to the IFR system, the flame‐retardant PU/MF foam can generate a large bulk of expanded char acting as an efficient shielding layer to hold back the diffusion of heat and oxygen. As a result, the flame‐retardant PU/MF foam achieved a higher limiting oxygen index of 31.2% and exhibited immediate self‐extinguishment. It exhibited significantly reduced peak heat release rate and total heat release, as well as higher char residual ratio compared to PU foam. Furthermore, the composite foam also showed obviously improved mechanical performance in comparison with PU foam. Overall, the present investigation provided a new approach for fabricating a polymer composite foam with satisfactory flame retardancy and good comprehensive properties. © 2018 Society of Chemical Industry     

Physico‐mechanical properties of NBR/CPVC blend vulcanizates and foams

Foams were prepared from acrylonitrile‐butadiene rubber (NBR)/chlorinated polyvinyl chloride (CPVC) blend compounds using a chemical blowing agent during compression molding. The effect of varying NBR/CPVC blend ratio and the time on the foams were investigated. The curing parameters showed that both the maximum torque and the difference between the maximum and minimum torque decreased with increase of CPVC content. The limiting oxygen index (LOI) of the blend vulcanizate increased with increase of CPVC content, reached up to 30% for the NBR/CPVC blend with blend ratio 50/50. The SEM micrographs of the NBR/CPVC blend indicate semi‐compatibility between the blend phases. The NBR/CPVC foams prepared using a chemical blowing agent, showed closed cell structures, which were uniformly distributed across the blend phases. The average cell sizes increased and foam density decreased with increase of CPVC content. Tensile strength and tear strength of both vulcanizates and foams increased with increase CPVC content. Hardness of the foams increased but resilience of the foams decreased with increase of CPVC content. Density, tensile strength, tear strength, and hardness of the foams increased but resilience decreased when the compression molding time of the foam was increased. J. VINYL ADDIT. TECHNOL., 25:182–188, 2019. © 2018 Society of Plastics Engineers     

Relationship between the thermal degradation chemistry and flammability of commercial flexible polyurethane foams

In this article, we report the use of a variety of analytical methods, in particular, solid‐state ¹H‐NMR and ¹³C‐NMR to characterize the relationship between the condensed‐phase chemistry and burning behavior as determined by a series of combustion tests for two commercially derived flexible polyurethane foams, one combustion‐modified. The combustion tests showed that the foams met several regulatory requirements in terms of their fire performance, whether or not they were combustion‐modified. Both foams passed the MV SS 302 and CAL 117 small‐flame tests. The nonmodified foam failed the Crib 5 test, but this test had a much larger ignition source. The particular problem with the nonmodified foam was melt drip into the flame zone. This led to a steady maintenance of the fuel feed and a rapid escalation of the fire. In contrast, the combustion‐modified foam showed little melt drip and self‐extinguished. Thermal analysis data for the two foams showed that melamine acted in part as an endothermic heat sink. This alone did not account for the much reduced melt flow and drip of the combustion‐modified foam, but the solid‐state ¹H‐NMR data clearly showed that the molecular mobility of the combustion char from combustion‐modified foam was lower than the unmodified foam char, which indicated that the flame‐retardant formulation in the combustion‐modified foam acted by a condensed‐phase mechanism. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3024–3033, 2006     

The flame retardant behaviors and synergistic effect of expandable graphite and dimethyl methylphosphonate in rigid polyurethane foams

A series of flame‐retardant rigid polyurethane foams (RPUFs) containing dimethyl methylphosphonate (DMMP) and expandable graphite (EG) were prepared by box‐foaming. The RPUFs were characterized by thermogravimetric analysis (TGA), the limiting oxygen index (LOI), cone calorimeter, and scanning electron microscope (SEM). The decomposition process of DMMP was investigated by Pyrolysis‐Gas Chromatography/Mass Spectroscopy (Py‐GC/MS). Accordingly, their flame retardant behaviors and mechanism were also discussed. The results show that the DMMP/EG system can linearly enhance the LOI value from 19.2% of the pure RPUF to 33.0% of RPUFs containing 16 wt% flame retardant. In addition, the DMMP/EG system also remarkably increases yields of the residual char and drastically decreases the peak value of heat release rate (PHRR), heat release rate (HRR), total heat release (THR), total smoke release (TSR), and the yields of CO (COY). In the flame retardant RPUFs, when the matrix is ignited, the flame retardant DMMP should be decomposed to gaseous PO₂ fragments, which can inhibit free radical chain reaction of flammable alkyl free radical from the decomposed matrix; whereas the flame retardant EG can rapidly expand and form loose and worm‐like expanding graphite char layer accordingly, which can hinder the heat transmission to the inner matrix and reduce decomposing velocity of matrix. After the combination of the two flame retardant effects, the DMMP/EG flame retardant system provides the matrix with better flame retardant effects than one of them does. Namely, it shows excellent gas‐condensed bi‐phase synergistic effect. POLYM. COMPOS., 35:301–309, 2014. © 2013 Society of Plastics Engineers