Biomass phytic acid has potential flame retardant value as the main form of phosphorus in plant seeds.In this study,phytate-based flame retardants aluminum phytate(PA-Al)and iron phytate(PA-Fe)were synthesized and cha...Biomass phytic acid has potential flame retardant value as the main form of phosphorus in plant seeds.In this study,phytate-based flame retardants aluminum phytate(PA-Al)and iron phytate(PA-Fe)were synthesized and characterized.Subsequently,they were introduced into rigid polyurethane foam(RPUF)as flame retardants by one-step water-blown method.The results indicated that RPUF/PA-Fe30 exhibited the highest char residue of 22.1 wt%,significantly higher than 12.4 wt%of RPUF.Cone calorimetry analysis showed that the total heat release(THR)of RPUF/PA-Al30 decreased by 17.0%and total smoke release(TSR)decreased by 22.0%compared with pure RPUF,which were the lowest,demonstrating a low fire risk and good smoke suppression.Thermogravimetric analysis-Fourier transform infrared spectrometer(TG-FTIR)implied the release intensity of flammable gases(hydrocarbons,esters)and toxic gases(isocyanate,CO,aromatic compounds,HCN)of composites was significantly reduced after the addition of PA-Fe.The analysis of char residue indicated that the RPUF composites formed a dense char layer with a high degree of graphitization after the addition of PA-Al/PA-Fe,endowing RPUF composites with excellent mass&heat transmission inhibition effect and fire resistance in the combustion process.展开更多
Rigid polyurethane foams were fabricated with five kinds of liquefied sugarcane bagasse polyols （LBP）. The foams derived from sugarcane bagasse were investigated by thermogravimetric analysis （TGA）, and the therma...Rigid polyurethane foams were fabricated with five kinds of liquefied sugarcane bagasse polyols （LBP）. The foams derived from sugarcane bagasse were investigated by thermogravimetric analysis （TGA）, and the thermal degradation data were analyzed using the Coast-Redfern method and Ozawa method to obtain the reaction order and activation energy. The results indicate that the sugarcane bagasse-foams exhibit an excellent heat-resistant property, whereas their pyrolysis procedures are quite complicated. The reaction as first order only takes place from 250 to 400 ℃, and the pyrolysis activation energies vary from 20 to 140 kJ/mol during the whole pyrolysis process.展开更多
This article deals with the study of the viscoelastic and thermal properties of polyurethane (PU) rigid foamsfrom biobased and recycled components. Rapeseed oil (RO) and recycled poly(ethylene terephthalate)(PET) were...This article deals with the study of the viscoelastic and thermal properties of polyurethane (PU) rigid foamsfrom biobased and recycled components. Rapeseed oil (RO) and recycled poly(ethylene terephthalate)(PET) were used to synthesize PU polyols. Addition of adipic acid (ADA) to polyol resulted in improvedthermal and viscoelastic properties of foam materials. ADA content was varied from 1 to 6 wt%. Results ofthe dynamic mechanical spectra indicate an increase of the storage modulus E′ and the loss modulus E″ inthe whole temperature range for specimens with higher loading of ADA. In addition, damping factor shiftedto higher temperatures, but damping intensity remained almost unaffected by the compositions. Scanningelectron microscopy of the foams’ cross sections testified that the average cells’ size of 110 mm was unaffectedby the ADA content in polyol.展开更多
In this study,orthogonal experiments were conducted to investigate the influence of expandable graphite(EG),dimethyl methylphosphonate(DMMP),triethanolamine(TEA),and isocyanate content on the compressive and bonding s...In this study,orthogonal experiments were conducted to investigate the influence of expandable graphite(EG),dimethyl methylphosphonate(DMMP),triethanolamine(TEA),and isocyanate content on the compressive and bonding strengths,oxygen index,and fluidity of rigid polyurethane foam(RPUF).The results revealed that EG significantly increased the oxygen index of RPUF,enlarged the diameter of foam cells,and decreased the cell-closed content in foam;thus,leading to a pressure drop in RPUF.However,excessive EG was capable of reducing the fluidity of polyurethane slurry.TEA exhibited significant influence on the compressive strength of RPUF,which dropped initially,and then increased.DMMP had a remarkable effect on the flame retardant property and compressive strength of RPUF.Compressive strength of RPUF initially displayed an increase followed by a decrease with increasing dosage of DMMP,and achieved the maximum value at DMMP dosage of 4%.DMMP could effectively reduce the diameter of RPUF cells leading to an increase in the percentage of close area in foam.DMMP displayed the flame-retardation effects mainly in the gas phase leading to a significant enhancement in the oxygen index of RPUF.Moreover,the compressive strength and bonding strength of RPUF decrease significantly with the increase of isocyanate content due to the increased blowing efficiency by the CO_2.The oxygen index and flowing length of foam increased with the increase in isocyanate dosage.展开更多
A novel boron-coated expandable graphite（BEG） material was prepared by first wrapping polyvinyl alco- hoI（PVA） onto expandable graphite（EG） and then condensing with boric acid. The obtained BEG was characterized...A novel boron-coated expandable graphite（BEG） material was prepared by first wrapping polyvinyl alco- hoI（PVA） onto expandable graphite（EG） and then condensing with boric acid. The obtained BEG was characterized by scanning electron microscopy（SEM）, Fourier transform infrared（FT1R） spectroscopy, X-ray photoelectron spec- troscopy（XPS）, and tbermogravimetric analysis（TGA）. The fire performance and mechanical properties of the rigid polyurethane foam（RPUF） filled with BEG were investigated by limiting oxygen index（LOl）, horizontal and vertical burning, cone calorimetry（CONE）, and electronic tensile tests. BEG shows an improved compactness of the char layers upon thermal expansion, which is effective for the flame retardancy of RPUF. With a loading of 10%, RPUF/BEG exhibited a higher LOI, 〉10% reduction in heat release rate and carbon monoxide release, as well as a decrease in smoke release during the beginning of combustion compared to RPUF/EG. Moreover, the compressive strength and modulus of RPUF/BEG were increased. The improved flame retardancy of BEG on RPUF can be attributed to the suppression of the ＂popcorn effect＂ of EG by PVA-boric acid, and the improved mechanical property can be attributed to the presence of PVA.展开更多
Rigid polyurethane foams blown by varying water level were prepared in this study. The structures and physical properties of rigid polyurethane foams blown by water were measured with FT-IR, universal testing machine ...Rigid polyurethane foams blown by varying water level were prepared in this study. The structures and physical properties of rigid polyurethane foams blown by water were measured with FT-IR, universal testing machine (Instron3365), scanning electron microscope (SEM) and differential scanning calorimeter (DSC). The results show that polyurea and polybiuret were the typical charac- teristics, and the cream time and gel time were shorter for the fully water blown rigid foams than that for the fully cyclopentane blown foams. The density of foam samples decreased from 45.0 kg/m3 to 27.4 kg/m3 with the increase of water level from 3 pph to 7 pph. Compressive strength exhibited the similar behavior with density. The average cell size of foam samples ranged from 241 μm to 356 μm with the increase of water level from 3 pph to 7 pph, respectively. At the same time, poorer dimen- sional stability was encountered with the increase of average cell size due to fast diffusion rate of CO2 out of the foam. The results of thermal analysis show that the glass transition temperature (Tg) shifted to a higher temperature with the increase of isocyanate level when more water was used as chemical blowing agent.展开更多
Driven by global environmental concerns,many efforts have been made to develop halogen-free flame retardants for rigid polyurethane foam(RPUF).These environmentally benign flame retardants are mainly divided into(i)re...Driven by global environmental concerns,many efforts have been made to develop halogen-free flame retardants for rigid polyurethane foam(RPUF).These environmentally benign flame retardants are mainly divided into(i)reactive,(ii)additive,and(iii)coating types.The last decade has witnessed great progress of these three strategies,which enhance the fire safety of RPUF and maintain even improve the thermal insulation properties.This comprehensive review focuses on the up-to-date design of the reactive,additive,and coating flame retardants,and their effects on flame retardancy and thermal conductivity of RPUF.Moreover,the practical applications of the as-prepared flame-retardant RPUFs are highlighted.Finally,key challenges associated with these three kinds of flame retardants are discussed and future research opportunities are also proposed.展开更多
This study investigated the influence of various organically modified montmorillonites （organoclays） on the structure and properties of rigid polyurethane foam （RPUF） nanocomposites. The organoclays were modified ...This study investigated the influence of various organically modified montmorillonites （organoclays） on the structure and properties of rigid polyurethane foam （RPUF） nanocomposites. The organoclays were modified with cetyltrimethyl ammonium bromide （CTAB）, methyl tallow bis（2-hydroxyethyl） quaternary ammonium chloride （MT2ETOH） and tris（hydroxymethyl）aminomethane （THMA） and denoted as CMMT, Cloisite 30B and OMMT, respectively. MT2ETOH and THMA contain hydroxyl groups, while THMA does not have long aliphatic tail in its molecule. X-ray diffraction and transmission electron microscopy show that OMMT and Cloisite 30B can be partially exfoliated in the RPUF nanocomposites because their intercalating agents MT2ETOH and THMA can react with isocyanate. However, CMMT modified with nonreactive CTAB is mainly intercalated in the RPUF matrices. At a relatively low filler content, the RPUF/CMMT composite foam has a higher specific compressive strength （the ratio of compressive strength against the apparent density of the foams）, while at relatively high filler contents, RPUF/Cloisite 30B and RPUF/OMMT composites have higher specific compressive strengths, higher modulus and more uniform pore size than the RPUF/CMMT composite.展开更多
A new kind of rigid polyurethane(PU)foam was synthesized from the oil phase of bio-oils from microwave-assisted pyrolysis of corn stover.The recipes for the PU foams consisted of polyol-rich bio-oils,water as blowing ...A new kind of rigid polyurethane(PU)foam was synthesized from the oil phase of bio-oils from microwave-assisted pyrolysis of corn stover.The recipes for the PU foams consisted of polyol-rich bio-oils,water as blowing agent,polyethylene glycol(PEG)as both polyol donor and plasticizer,diphenylmethane-4,4’-diisocyanate(polymeric MDI)as cross-linking agent,silicon-based surfactant,and tin-based catalyst.The mechanical properties of rigid foams were measured with universal testing machine(Instron4206).The effects of individual ingredients on the physical and mechanical properties of the foams were studied.It was found that water content,bio-oil content,and isocyanate dosage were important variables in making PU foams in terms of mechanical strength,density,and cellular structure Under optimal conditions,the compression strength of the prepared PU foams reached 1130 kPa with a density of 152.9 g/L.The results show that bio-oils are potential renewable polyol sources for making rigid PU foams.展开更多
基金This research was supported by National Key Research and Development Project(No.2017YFE0113200)National Natural Science Fund of China(Nos.51403004,U1833113).
文摘Biomass phytic acid has potential flame retardant value as the main form of phosphorus in plant seeds.In this study,phytate-based flame retardants aluminum phytate(PA-Al)and iron phytate(PA-Fe)were synthesized and characterized.Subsequently,they were introduced into rigid polyurethane foam(RPUF)as flame retardants by one-step water-blown method.The results indicated that RPUF/PA-Fe30 exhibited the highest char residue of 22.1 wt%,significantly higher than 12.4 wt%of RPUF.Cone calorimetry analysis showed that the total heat release(THR)of RPUF/PA-Al30 decreased by 17.0%and total smoke release(TSR)decreased by 22.0%compared with pure RPUF,which were the lowest,demonstrating a low fire risk and good smoke suppression.Thermogravimetric analysis-Fourier transform infrared spectrometer(TG-FTIR)implied the release intensity of flammable gases(hydrocarbons,esters)and toxic gases(isocyanate,CO,aromatic compounds,HCN)of composites was significantly reduced after the addition of PA-Fe.The analysis of char residue indicated that the RPUF composites formed a dense char layer with a high degree of graphitization after the addition of PA-Al/PA-Fe,endowing RPUF composites with excellent mass&heat transmission inhibition effect and fire resistance in the combustion process.
基金Funded by Guangdong Provincial Natural Science Foundation (No.E06200692)Guangdong Provincial Scientific and Technological Project(No. 2006A20401001)
文摘Rigid polyurethane foams were fabricated with five kinds of liquefied sugarcane bagasse polyols （LBP）. The foams derived from sugarcane bagasse were investigated by thermogravimetric analysis （TGA）, and the thermal degradation data were analyzed using the Coast-Redfern method and Ozawa method to obtain the reaction order and activation energy. The results indicate that the sugarcane bagasse-foams exhibit an excellent heat-resistant property, whereas their pyrolysis procedures are quite complicated. The reaction as first order only takes place from 250 to 400 ℃, and the pyrolysis activation energies vary from 20 to 140 kJ/mol during the whole pyrolysis process.
文摘This article deals with the study of the viscoelastic and thermal properties of polyurethane (PU) rigid foamsfrom biobased and recycled components. Rapeseed oil (RO) and recycled poly(ethylene terephthalate)(PET) were used to synthesize PU polyols. Addition of adipic acid (ADA) to polyol resulted in improvedthermal and viscoelastic properties of foam materials. ADA content was varied from 1 to 6 wt%. Results ofthe dynamic mechanical spectra indicate an increase of the storage modulus E′ and the loss modulus E″ inthe whole temperature range for specimens with higher loading of ADA. In addition, damping factor shiftedto higher temperatures, but damping intensity remained almost unaffected by the compositions. Scanningelectron microscopy of the foams’ cross sections testified that the average cells’ size of 110 mm was unaffectedby the ADA content in polyol.
基金supported by the National Natural Science Foundation of China(No.51304027)China Postdoctoral Science Foundation(2014M560567 and 2015T80730)+4 种基金Shandong Province Science and Technology Development Plan(2014GSF120012)the State Key Program of Coal Joint Funds of National Natural Science Foundation of China(Nos.51134020 and U1261205)Shandong Province Natural Science Foundation(No.ZR2011EL036)the Doctoral Scientific Research Foundation of Binzhou University(No.2013Y06)the Key Technology Projects for Preventing Major Accident of National Security State Administration of Work Safety
文摘In this study,orthogonal experiments were conducted to investigate the influence of expandable graphite(EG),dimethyl methylphosphonate(DMMP),triethanolamine(TEA),and isocyanate content on the compressive and bonding strengths,oxygen index,and fluidity of rigid polyurethane foam(RPUF).The results revealed that EG significantly increased the oxygen index of RPUF,enlarged the diameter of foam cells,and decreased the cell-closed content in foam;thus,leading to a pressure drop in RPUF.However,excessive EG was capable of reducing the fluidity of polyurethane slurry.TEA exhibited significant influence on the compressive strength of RPUF,which dropped initially,and then increased.DMMP had a remarkable effect on the flame retardant property and compressive strength of RPUF.Compressive strength of RPUF initially displayed an increase followed by a decrease with increasing dosage of DMMP,and achieved the maximum value at DMMP dosage of 4%.DMMP could effectively reduce the diameter of RPUF cells leading to an increase in the percentage of close area in foam.DMMP displayed the flame-retardation effects mainly in the gas phase leading to a significant enhancement in the oxygen index of RPUF.Moreover,the compressive strength and bonding strength of RPUF decrease significantly with the increase of isocyanate content due to the increased blowing efficiency by the CO_2.The oxygen index and flowing length of foam increased with the increase in isocyanate dosage.
基金Supported by the National Natural Science Foundation of China（No.21474008）.
文摘A novel boron-coated expandable graphite（BEG） material was prepared by first wrapping polyvinyl alco- hoI（PVA） onto expandable graphite（EG） and then condensing with boric acid. The obtained BEG was characterized by scanning electron microscopy（SEM）, Fourier transform infrared（FT1R） spectroscopy, X-ray photoelectron spec- troscopy（XPS）, and tbermogravimetric analysis（TGA）. The fire performance and mechanical properties of the rigid polyurethane foam（RPUF） filled with BEG were investigated by limiting oxygen index（LOl）, horizontal and vertical burning, cone calorimetry（CONE）, and electronic tensile tests. BEG shows an improved compactness of the char layers upon thermal expansion, which is effective for the flame retardancy of RPUF. With a loading of 10%, RPUF/BEG exhibited a higher LOI, 〉10% reduction in heat release rate and carbon monoxide release, as well as a decrease in smoke release during the beginning of combustion compared to RPUF/EG. Moreover, the compressive strength and modulus of RPUF/BEG were increased. The improved flame retardancy of BEG on RPUF can be attributed to the suppression of the ＂popcorn effect＂ of EG by PVA-boric acid, and the improved mechanical property can be attributed to the presence of PVA.
文摘Rigid polyurethane foams blown by varying water level were prepared in this study. The structures and physical properties of rigid polyurethane foams blown by water were measured with FT-IR, universal testing machine (Instron3365), scanning electron microscope (SEM) and differential scanning calorimeter (DSC). The results show that polyurea and polybiuret were the typical charac- teristics, and the cream time and gel time were shorter for the fully water blown rigid foams than that for the fully cyclopentane blown foams. The density of foam samples decreased from 45.0 kg/m3 to 27.4 kg/m3 with the increase of water level from 3 pph to 7 pph. Compressive strength exhibited the similar behavior with density. The average cell size of foam samples ranged from 241 μm to 356 μm with the increase of water level from 3 pph to 7 pph, respectively. At the same time, poorer dimen- sional stability was encountered with the increase of average cell size due to fast diffusion rate of CO2 out of the foam. The results of thermal analysis show that the glass transition temperature (Tg) shifted to a higher temperature with the increase of isocyanate level when more water was used as chemical blowing agent.
基金financially supported by the Australian Research Council(Nos.DP190102992,FT190100188)the National Natural Science Foundation of China(No.51873196)the Key Research and Development Projects of Zhejiang Province(No.2019C01098)。
文摘Driven by global environmental concerns,many efforts have been made to develop halogen-free flame retardants for rigid polyurethane foam(RPUF).These environmentally benign flame retardants are mainly divided into(i)reactive,(ii)additive,and(iii)coating types.The last decade has witnessed great progress of these three strategies,which enhance the fire safety of RPUF and maintain even improve the thermal insulation properties.This comprehensive review focuses on the up-to-date design of the reactive,additive,and coating flame retardants,and their effects on flame retardancy and thermal conductivity of RPUF.Moreover,the practical applications of the as-prepared flame-retardant RPUFs are highlighted.Finally,key challenges associated with these three kinds of flame retardants are discussed and future research opportunities are also proposed.
基金supported by the National Natural Science Foundation of China(Nos.20574060 and 50773066)
文摘This study investigated the influence of various organically modified montmorillonites （organoclays） on the structure and properties of rigid polyurethane foam （RPUF） nanocomposites. The organoclays were modified with cetyltrimethyl ammonium bromide （CTAB）, methyl tallow bis（2-hydroxyethyl） quaternary ammonium chloride （MT2ETOH） and tris（hydroxymethyl）aminomethane （THMA） and denoted as CMMT, Cloisite 30B and OMMT, respectively. MT2ETOH and THMA contain hydroxyl groups, while THMA does not have long aliphatic tail in its molecule. X-ray diffraction and transmission electron microscopy show that OMMT and Cloisite 30B can be partially exfoliated in the RPUF nanocomposites because their intercalating agents MT2ETOH and THMA can react with isocyanate. However, CMMT modified with nonreactive CTAB is mainly intercalated in the RPUF matrices. At a relatively low filler content, the RPUF/CMMT composite foam has a higher specific compressive strength （the ratio of compressive strength against the apparent density of the foams）, while at relatively high filler contents, RPUF/Cloisite 30B and RPUF/OMMT composites have higher specific compressive strengths, higher modulus and more uniform pore size than the RPUF/CMMT composite.
基金the Initiative for Renewable Energy and the Environment and Center for Biorefining at the University of Minnesota,Minnesota Environment and Natural Resources Trust Fund,US DOT/Sun Grant Initiative,and China Ministry of Education PCSIRT Program(IRT0540)。
文摘A new kind of rigid polyurethane(PU)foam was synthesized from the oil phase of bio-oils from microwave-assisted pyrolysis of corn stover.The recipes for the PU foams consisted of polyol-rich bio-oils,water as blowing agent,polyethylene glycol(PEG)as both polyol donor and plasticizer,diphenylmethane-4,4’-diisocyanate(polymeric MDI)as cross-linking agent,silicon-based surfactant,and tin-based catalyst.The mechanical properties of rigid foams were measured with universal testing machine(Instron4206).The effects of individual ingredients on the physical and mechanical properties of the foams were studied.It was found that water content,bio-oil content,and isocyanate dosage were important variables in making PU foams in terms of mechanical strength,density,and cellular structure Under optimal conditions,the compression strength of the prepared PU foams reached 1130 kPa with a density of 152.9 g/L.The results show that bio-oils are potential renewable polyol sources for making rigid PU foams.
