Flame Retardancy Behaviors of Flexible Polyurethane Foam Based on Reactive Dihydroxy P-N-containing Flame Retardants.
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ABSTRACT:
SUBMITTER: Ding Y
PROVIDER: S-EPMC8246474 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:The role of various additives (emulsifier, anti-dripping agent) and formulation procedures (pre-dispersion of solid additives in polyol via milling) which influence the flame retardancy of 6,6'-[ethan-1,2-diylbis(azandiyl)]bis(6H-dibenzo[c,e][1,2]oxaphosphin-6-oxid) (EDA-DOPO) containing flexible polyurethane foams has been investigated in this work. For comparison, the flame retardancy of two additional structurally-analogous bridged 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)-based compounds, i.e., ethanolamine-DOPO (ETA-DOPO) and ethylene glycol-DOPO (EG-DOPO) were also evaluated together with EDA-DOPO in flexible PU foams of various formulations. The flame retardancy of these three bridged-DOPO compounds depends on the type of PU formulation. For certain PU formulations containing EDA-DOPO, lower fire performance was observed. Addition of emulsifier and polytetrafluoroethylene (PTFE) to these PU formulations influenced positively the flame retardancy of EDA-DOPO/PU foams. In addition, dispersion of EDA-DOPO and PTFE via milling in polyol improved the flame retardancy of the PU foams. Mechanistic studies performed using a microscale combustion calorimeter (MCC) and its coupling to FTIR showed no difference in the combustion efficiency of the bridged-DOPO compounds in PU foams. From MCC experiments it can be concluded that these bridged-DOPO compounds and their decomposition products may work primarily in the gas phase as flame inhibitors. The physiochemical behavior of additives in PU formulation responsible for the improvement in the flame retardancy of PU foams was further investigated by studying the dripping behavior of the PU foams in the UL 94 HB test. A high-speed camera was used to study the dripping behavior in the UL 94 HB test and results indicate a considerable reduction of the total number of melt drips and flaming drips for the flame retardant formulations. This reduction in melt drips and flaming drips during the UL 94 HB tests help PU foams achieve higher fire classification.
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Project description:With the phase-out of PentaBDE in 2004, alternative flame retardants are being used in polyurethane foam to meet flammability standards. However, insufficient information is available on the identity of the flame retardants currently in use. Baby products containing polyurethane foam must meet California state furniture flammability standards, which likely affects the use of flame retardants in baby products throughout the U.S. However, it is unclear which products contain flame retardants and at what concentrations. In this study we surveyed baby products containing polyurethane foam to investigate how often flame retardants were used in these products. Information on when the products were purchased and whether they contained a label indicating that the product meets requirements for a California flammability standard were recorded. When possible, we identified the flame retardants being used and their concentrations in the foam. Foam samples collected from 101 commonly used baby products were analyzed. Eighty samples contained an identifiable flame retardant additive, and all but one of these was either chlorinated or brominated. The most common flame retardant detected was tris(1,3-dichloroisopropyl) phosphate (TDCPP; detection frequency 36%), followed by components typically found in the Firemaster550 commercial mixture (detection frequency 17%). Five samples contained PBDE congeners commonly associated with PentaBDE, suggesting products with PentaBDE are still in-use. Two chlorinated organophosphate flame retardants (OPFRs) not previously documented in the environment were also identified, one of which is commercially sold as V6 (detection frequency 15%) and contains tris(2-chloroethyl) phosphate (TCEP) as an impurity. As an addition to this study, we used a portable X-ray fluorescence (XRF) analyzer to estimate the bromine and chlorine content of the foam and investigate whether XRF is a useful method for predicting the presence of halogenated flame retardant additives in these products. A significant correlation was observed for bromine; however, there was no significant relationship observed for chlorine. To the authors knowledge, this is the first study to report on flame retardants in baby products. In addition, we have identified two chlorinated OPFRs not previously documented in the environment or in consumer products. Based on exposure estimates conducted by the Consumer Product Safety Commission (CPSC), we predict that infants may receive greater exposure to TDCPP from these products compared to the average child or adult from upholstered furniture, all of which are higher than acceptable daily intake levels of TDCPP set by the CPSC. Future studies are therefore warranted to specifically measure infants exposure to these flame retardants from intimate contact with these products and to determine if there are any associated health concerns.
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Project description:Tris(1-chloro-2-propyl) phosphate (TCPP, also referenced as TCIPP), a flame retardant used in spray polyurethane foam insulation, increases cell toxicity and affects fetal development. Spray polyurethane foam workers have the potential to be exposed to TCPP during application. In this study, we determined exposure to TCPP and concentrations of the urinary biomarker bis(1-chloro-2-propyl) phosphate (BCPP) among 29 spray polyurethane foam workers over 2 work days. Work was conducted at residential or commercial facilities using both open-cell (low density) and closed-cell (high density) foam. Study participants provided two personal air samples (Day 1 and Day 2), two hand wipe samples (Pre-shift Day 2 and Post-shift Day 2), and two spot urine samples (Pre-shift Day 1 and Post-shift Day 2). Bulk samples of cured spray foam were also analyzed. Sprayers were found to have significantly higher TCPP geometric mean (GM) concentration in personal air samples (87.1 μg/m3), compared to helpers (30.2 μg/m3; p = 0.025). A statistically significant difference was observed between TCPP pre- and post-shift hand wipe GM concentrations (p = 0.004). Specifically, TCPP GM concentration in post-shift hand wipe samples of helpers (106,000 ng/sample) was significantly greater than pre-shift (27,300 ng/sample; p < 0.001). The GM concentration of the urinary biomarker BCPP (23.8 μg/g creatinine) was notably higher than the adult male general population (0.159 μg/g creatinine, p < 0.001). Urinary BCPP GM concentration increased significantly from Pre-shift Day 1 to Post-shift Day 2 for sprayers (p = 0.013) and helpers (p = 0.009). Among bulk samples, cured open-cell foam had a TCPP GM concentration of 9.23% by weight while closed-cell foam was 1.68%. Overall, post-shift BCPP urine concentrations were observed to be associated with TCPP air and hand wipe concentrations, as well as job position (sprayer vs. helper). Spray polyurethane foam workers should wear personal protective equipment including air-supplied respirators, coveralls, and gloves during application.
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Project description:Flexibility, stretchability, and flame retardancy are of ever increasing importance in constructing grouting materials. Herein, a simple and effective strategy to make organic-inorganic composite grouting material in a "flexible, stretchable, and flame retardant" way was based on the excellent synergistic interactions among polyurethane prepolymer, red mud, polyethylene glycol, and trimethylolpropane. The resultant polyurethane/red mud composite grouting material with three-dimensional network structure presented a favorable flexibility, desirable compressive strength of 29.2 MPa at 50% compression state, and a good elongation at 15.1%. The grouting material was mainly composed of amorphous polyurethane and crystalline red mud, and its probable formation mechanism was reaction of prepolymer with H₂O, polyethylene glycol and trimethylolpropane under vigorous stirring in the presence of catalyst. Furthermore, the grouting material possessed favorable thermal stability, flame retardancy and repairment performance for roadway cracks. This work may open a simple and convenient avenue for the massive engineering application of red mud and preparation of flexible organic-inorganic hybrid grouting material.
| S-EPMC6403916 | biostudies-literature
Project description:Nitrogen-containing flame retardants have been extensively applied due to their low toxicity and smoke-suppression properties; however, their poor charring ability restricts their applications. Herein, a representative nitrogen-containing flame retardant, polyheptanazine, was investigated. Two novel, cost-effective phosphorus-doped polyheptazine (PCN) and cobalt-anchored PCN (Co@PCN) flame retardants were synthesized via a thermal condensation method. The X-ray photoelectron spectroscopy (XPS) results indicated effective doping of P into triazine. Then, flame-retardant particles were introduced into thermoplastic polyurethane (TPU) using a melt-blending approach. The introduction of 3 wt% PCN and Co@PCN could remarkably suppress peak heat release rate (pHRR) (48.5% and 40.0%), peak smoke production rate (pSPR) (25.5% and 21.8%), and increasing residues (10.18 wt%→17.04 wt% and 14.08 wt%). Improvements in charring stability and flame retardancy were ascribed to the formation of P-N bonds and P=N bonds in triazine rings, which promoted the retention of P in the condensed phase, which produced additional high-quality residues.
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Project description:The effect of expandable graphite (EG) and modified halloysite nanotubes (HNTs) on the flame retardant properties of silicone rubber foam (SiF) was studied in this paper. Modified HNTs were obtained by surface modification of the silane-coupling agent A-171. The flame retardancy of SiF was studied by limiting oxygen index (LOI), vertical combustion and cone calorimeter tests. The mechanical properties of SiF were analyzed by a universal mechanical testing machine. The LOI results showed that EG/HNTS@A-171 could enhance the LOI of SiF. The cone calorimeter test results showed that EG/HNTS@A-171 effectively reduced the peak heat release rate, the total heat release rate, the smoke production rate, the total smoke production rate, the CO production rate and the CO2 production rate and increased the carbon residue rate. TGA shows that main chain pyrolysis temperature of the SiF is delayed by 123 °C. The mechanical properties test results showed that EG/HNTS@A-171 improved the tensile strength of SiF. These results indicated that EG/HNTS@A-171 can significantly improve the flame retardant performance of SiF.
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Project description:Restrictions on the use of polybrominated diphenyl ethers (PBDEs) have resulted in the increased use of alternate flame retardant chemicals to meet flammability standards. However, it has been difficult to determine which chemical formulations are currently being used in high volumes to meet flammability standards since the use of flame retardant formulations in consumer products is not transparent (i.e., not provided to customers). To investigate chemicals being used as replacements for PentaBDE in polyurethane foam, we analyzed foam samples from 26 different pieces of furniture purchased in the United States primarily between 2003 and 2009. Samples included foam from couches, chairs, mattress pads, pillows, and, in one case, foam from a sound-proofing system of a laboratory-grade dust sieve, and were analyzed using gas chromatography mass spectrometry. Fifteen of the foam samples contained the flame retardanttris(1,3-dichloro-2-propyl) phosphate (TDCPP; 1-5% by weight), four samples contained tris(1-chloro-2-propyl) phosphate (TCPP; 0.5 -22% by weight), one sample contained brominated chemicals found in a new flame retardant mixture called Firemaster 550 (4.2% by weight), and one foam sample collected from a futon likely purchased prior to 2004 contained PentaBDE (0.5% by weight). Due to the high frequency of detection of the chlorinated phosphate compounds in furniture foam,we analyzed extracts from 50 house dust samples collected between 2002 and 2007 in the Boston, MA area for TDCPP, TCPP, and another high volume use organophosphate-based flame retardant used in foam, triphenylphosphate (TPP). Detection frequencies for TDCPP and TPP in the dust samples were > 96% and were log normally distributed, similar to observations for PBDEs. TCPP was positively detected in dust in only 24% of the samples, but detection was significantly limited by a coelution problem. The geometric mean concentrations for TCPP, TDCPP, and TPP in house dust were 570, 1890, and 7360 ng/g, respectively, and maximum values detected in dust were 5490, 56,080 and 1,798,000 ng/g, respectively. These data suggest that levels of these organophosphate flame retardants are comparable, or in some cases greater than, levels of PBDEs in house dust. The high prevalence of these chemicals in foam and the high concentrations measured in dust (as high as 1.8 mg/g) warrant further studies to evaluate potential health effects from dust exposure, particularly for children.
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Project description:Rigid polyurethane foams (RPUFs) are widely used in many fields, but they are easy to burn and produce a lot of smoke, which seriously endangers the safety of people's lives and property. In this study, tetraethyl(1,5-bis(bis(2-hydroxypropyl)amino)pentane-1,5-diyl)bis(phosphonate) (TBPBP), as a phosphorus-nitrogen-containing reactive-type flame retardant, was successfully synthesized and employed to enhance the flame retardancy of RPUFs, and silica aerogel (SA) powder was utilized to reduce harmful fumes. Castor oil-based rigid polyurethane foam containing SA powder and TBPBP was named RPUF-T45@SA20. Compared with neat RPUF, the obtained RPUF-T45@SA20 greatly improved with the compressive strength properties and the LOI value increased by 93.64% and 44.27%, respectively, and reached the V-0 rank of UL-94 testing. The total heat release (THR) and total smoke production (TSP) of RPUF-T45@SA20 were, respectively, reduced by 44.66% and 51.89% compared to those of the neat RPUF. A possible flame-retardant mechanism of RPUF-T45@SA20 was also proposed. This study suggested that RPUF incorporated with TBPBP and SA powder is a prosperous potential composite for fire and smoke safety as a building insulation material.
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Project description:A liquid-phosphorus-containing polyester diol, PPE, was prepared via condensation polymerization using commercial reactive flame retardant 9,10-dihydro-10-[2,3-di(hydroxycarbonyl)propyl]-10-phospha-phenanthrene-10-oxide, adipic acid, ethylene glycol, and 1,4-butanediol. PPE and/or expandable graphite (EG) were then incorporated into phosphorus-containing flame-retardant polyester-based flexible polyurethane foams (P-FPUFs). The structure and properties of the resultant P-FPUFs were characterized using scanning electron microscopy tensile measurements, limiting oxygen index (LOI), vertical burning tests, cone calorimeter tests, thermogravimetric analysis coupled with Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. Unlike the FPUF prepared using regular polyester polyol (R-FPUF), PPE increased the flexibility and elongation at break of the resultant forms. More importantly, the peak heat release rate (PHRR) and total heat release (THR) of P-FPUF were reduced by 18.6% and 16.3%, respectively, via gas-phase-dominated flame-retardant mechanisms, compared with those of R-FPUF. The addition of EG further reduced the peak smoke production release (PSR) and total smoke production (TSP) of the resultant FPUFs while increasing the LOI and char formation. Interestingly, it was observed that EG noticeably improved the residual quantity of phosphorus in the char residue. When the EG loading was 15 phr, the resulting FPUF (P-FPUF/15EG) attained a high LOI value (29.2%) and exhibited good anti-dripping performance. Meanwhile, the PHRR, THR, and TSP of P-FPUF/15EG were significantly decreased by 82.7%, 40.3%, and 83.4%, respectively, compared with those of P-FPUF. This superior flame-retardant performance can be attributed to the combination of the bi-phase flame-retardant behavior of PPE and condensed-phase flame-retardant characteristics of EG.
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Project description:This study was focused on evaluating the suitability of a wide range of lignins, a natural polymer isolated from different plant sources and chemical extractions, in replacing 20 wt.% of petroleum-based polyol in the formulation of PU flexible foams. The main goal was to investigate the effect of unmodified lignin incorporation on the foam's structural, mechanical, and thermal properties. The hydroxyl contents of the commercial lignins were measured using phosphorus nuclear magnetic resonance (31P NMR) spectroscopy, molar mass distributions with gel permeation chromatography (GPC), and thermal properties with differential scanning calorimetry (DSC) techniques. The results showed that incorporating 20 wt.% lignin increased tensile, compression, tear propagation strengths, thermal stability, and the support factor of the developed PU flexible foams. Additionally, statistical analysis of the results showed that foam properties such as density and compression force deflection were positively correlated with lignin's total hydroxyl content. Studying correlations between lignin properties and the performance of the developed lignin-based PU foams showed that lignins with low hydroxyl content, high flexibility (low Tg), and high solubility in the co-polyol are better candidates for partially substituting petroleum-based polyols in the formulation of flexible PU foams intended for the automotive applications.
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