Inorganic/organic phosphorus-based flame retardants synergistic flame retardant rigid polyurethane foam

The flame-retardant rigid polyurethane foam (RPUF) composites are fabricated by ammonium polyphosphate (APP) with pentaerythritol phosphate (PEPA), phenoxycycloposphazene (PCP), and aluminum diethylphosphinate (ADP), respectively, which are labeled as RPUF-1, RPUF-2, and RPUF-3. The influence of flame retardants on the apparent density and compressive strength of RPUF is studied. The results reveal that flame retardants not only improve the apparent density, but also improve the compressive strength of RPUF composites. The limiting oxygen index (LOI) results reveal that these inorganic/organic phosphorus-based flame retardants improve the LOI significantly, especially for RPUF-2 and RPUF-3 systems. The cone calorimeter test results suggest that the peak of heat release of RPUF-1, RPUF-2, and RPUF-3 systems decrease by 38%, 41%, and 52% likened to that of pure RPUF. And APP and ADP system performs best in declining the heat release. And APP and PEPA systems perform best in decreasing the smoke release. The flame retardancy mechanism of RPUF composites is analyzed in details.     

关于硬泡聚氨酯在外保温中的应用探讨

综述了硬泡聚氨酯的燃烧方式和阻燃原理。介绍了阻燃技术的研究现状和最新进展。硬质泡沫塑料是第五大塑料的总称。是氨基甲酸酯段多元醇与多异氰酸酯反应生成的聚合物。聚氨酯泡沫塑料是聚氨酯产品的一大分支,它占聚氨酯材料总量的20%左右。是近十年来发展最快的合成材料。它具有优异的物理机械性能和保温性能。硬质聚氨酯泡沫塑料具有重量轻、强度高、导热系数低、隔音效果好等特点,在建筑工程中得到了广泛的应用,也应用于工业、运输、石油化工管道、航海、军事等领域。     

新型含磷阻燃型桐油基聚氨酯硬泡的制备及性能表征

桐油与甘油在甲醇钠为催化剂的条件下发生醇解反应得到桐油醇解产物（GTO）,GTO经环氧化得到环氧化桐油醇解产物（EGTO）,EGTO与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）发生开环反应生成新型含磷阻燃型桐油基多元醇（PTOP）。PTOP部分取代聚醚多元醇（PPG4110）与异氰酸酯及助剂反应,通过一步法制备聚氨酯硬泡（RPUF）。采用万能试验机、热导率测定仪、热重分析仪和锥形量热仪分别考察RPUF的力学性能、热稳定性和燃烧行为。结果表明：随着PTOP替代石油基多元醇的比率增大,RPUF的压缩强度、密度、热导率先增大后减小,热稳定性提高,极限氧指数（LOI）由18.1%提高至26.0%,而总放热量先减小后增大,这主要是由于PTOP结构中的DOPO基团具有阻燃作用而PTOP结构中含有的桐油基脂肪链易于燃烧且热释放量较大。以上结果表明PTOP部分取代PPG4110制备的RPUF具有良好的阻燃性能和热稳定性。     

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.     

Properties of a novel inherently flame-retardant rigid polyurethane foam composite bearing imide and oxazolidinone

A novel inherently flame-retardant rigid polyurethane (PU) foam with imide and oxazolidinone was prepared by using 3,3′,4,4′-biphenyltetracarboxylic dianhydride (PTDA) and 9,10-dihydro-9-oxa-(10-glycidoxypropylene)-10-phosphap-henanthrene-10-oxide (e-DOPO) as reactive flame retardants. The physical and mechanical properties of the prepared PU foams were investigated. The compressive strength was improved to 0.22 MPa, the thermal conductivity decreased, and the density hardly changed. Thermogravimetric (TG) analysis and TG analysis coupled with Fourier transform infrared spectroscopy indicated that the PTDA and e-DOPO showed a small improvement in thermal properties. The fire behaviors were evaluated based on the limited oxygen index (LOI), cone-calorimetry experiment, and smoke-density test. The LOI of the PU foam with PTDA and e-DOPO reached 22.4%. The peak of heat release rate and total heat release decreased to 227.50 kW m⁻² and 11.27 MJ m⁻² from 281.28 kW m⁻² and 14.05 MJ m⁻², respectively. The morphologies of the PU foam and residues after the cone-calorimetry test were characterized by scanning electron microscopy. X-ray photoelectron spectroscopy analysis indicated that PTDA and e-DOPO lead to an increase in graphite in the residue and the formation of a better barrier to prevent burning by the condensed-phase mechanism. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47943.     

Bio-based flame-retardant rigid polyurethane foam with high content of soybean oil polyols containing phosphorus

Rigid polyurethane foam (RPUF) is prepared from petroleum-based polyols and isocyanate, which consumes a large amount of petroleum. To alleviate the consumption of petroleum, it is necessary to synthesize green and sustainable polyols. However, the greatest disadvantage of RPUF is its flammability. To reduce the risk of fire caused by RPUF, phosphorylated soybean oil polyol (Polyol-P) and phenyl phospho-soybean oil polyol (Polyol-PPOA) were synthesized by ring-opening reactions of epoxy soybean oil with phosphoric acid and phenylphosphonic acid, respectively. A flame-retardant RPUF was prepared via polymeric 4,4-diphenylmethane diisocyanate (p-MDI), which reacted after mixing Polyol-P and Polyol-PPOA with polyether polyol-330N in different proportions. Scanning electron microscopy (SEM) showed that the cell sizes of the RPUF-P and RPUF-PPOA increased first and then decreased and the cell number decreased first and then increased with the increase in the contents of Polyol-P and Polyol-PPOA. Mechanical property tests showed that the compressive strength of the RPUF-P4 reached 0.1 MPa, and the compressive strength of the RPUF-PPOA4 reached 0.07 MPa. The limiting oxygen index values of the RPUF-P4 and RPUF-PPOA4 were 20.9% and 24.3%, respectively. The UL 94 of the RPUFs indicated that the rating of the RPUF-PPOA3 was improved to V-1. The results showed that the flame-retardancy mechanism of the Polyol-P and Polyol-PPOA in the RPUF was based on the charred surface as a physical barrier, which slowed down the decomposition of RPUF and prevented heat and mass transfer between the gas and the condensed phase.     

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。     

高密度聚氨酯硬泡塑料／玻纤粉复合材料的研究

以聚醚多元醇、PAPI、催化剂、发泡剂和玻璃纤维等为原料,制备高密度聚氨酯硬泡及它与磨碎玻纤粉的复合材料。研究了不同密度硬泡的强度及磨碎玻纤粉粒径、预处理及其含量对复合材料强度的影响,不同复合材料的热稳定性。结果表明,随着密度的增加,硬泡的各种强度值总体上均呈逐渐增加趋势,其中500kg/m^3的聚氨酯的拉伸强度比200kg/m^3的提高了104．74％,冲击强度提高了194．84％;400目粒径的玻纤粉可使复合材料具有更高的拉伸强度、弯曲强度及压缩强度;玻纤的加入将降低材料的强度值,但偶联剂预处理可使它们有所改善;加入磨碎玻纤粉后,材料的热稳定性增加,且采用偶联剂KH550对玻纤粉进行预处理可进一步改善复合材料的耐热性能。     

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

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

高回弹聚氨酯软泡的无卤阻燃研究

随着人们环保意识的不断提高,卤系阻燃剂的毒性问题受到越来越多的关注,阻燃剂无卤化已经成为必然趋势。间苯二酚双(二苯基磷酸酯)齐聚物(RDP)阻燃剂是一种无卤添加型阻燃剂,因具有优异的热稳定性和低挥发性而得到广泛应用。实验中分别用它与膨胀石墨来阻燃高回弹聚氨酯软泡并进行了二者协同阻燃聚氨酯软泡的研究。用氧指数仪和民航飞机用垂直燃烧方法测试表征了制备的泡沫样品,并对其阻燃性能进行了研究。     

Effects of ammonium polyphosphate microencapsulated on flame retardant and mechanical properties of the rigid polyurethane foam

In this article, a flame retardant microcapsule ammonium polyphosphate microencapsulated by polyurea (POAPP) was successfully synthesized by interfacial polymerization method using ammonium polyphosphate (APP) as core and polyurea as shell. The microencapsulation is observed by scanning electron microscopy and characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis and hydroscopicity test, which prove the success in synthesizing microencapsulation. When the POAPP is added into rigid polyurethane foam (RPUF), the flame retardant and mechanical properties are investigated using cone calorimeter, limited oxygen index test, and compressive strength test. The PHRR of RPUF-POAPP20 decreased from 336.52 kW/m² (Ref. RPUF) to 203.84 kW/m² and the THR of RPUF-POAPP20 was only 7.6 MJ/m², which is 33.9% lower than that of Ref. RPUF. Furthermore, the limiting oxygen index of RPUF-POAPP20 reaches 24.8%, which increased by 36.3% compared to Ref. RPUF. Whereas the maximum compressive strength of RPUF-POAPP5 was 7.46 MPa, which is higher than that of RPUF-APP5.     

Dependence of flame‐retardant properties on density of expandable graphite filled rigid polyurethane foam

Different density rigid polyurethane foams (RPUF) filled with various expandable graphite loadings were fabricated by cast molding. The flame retardant properties of these composites were assessed by limiting oxygen index and horizontal and vertical burning tests. The results showed that the flame retardant efficiency got better with increase in the foam density at the fixed EG weight percent or with increase in the EG weight percent at the fixed foam density. After burning, the low density (0.065 g/cm³) pure burned RPUF produced the highly collapsed and carbonized material, while the high density (0.510 g/cm³) pure RPUF had little change in size and had reduced destruction of the material. Moreover, the scanning electronic microscope (SEM) observation showed that the higher density EG/RPUF composites had a more compact outer layer (burned layer) after burned, in which more wormlike materials composed of expanded graphite particles appeared. In addition, higher foam density led to less plastic deformation in the interface layer between the burned and the inside layers. These results indicated that a weight percent of a flame retardant additive that achieves satisfactory flame retardancy for a certain density foam cannot effectively be applied for another density foam. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

环境友好型阻燃高回弹聚氨酯软泡性能

开发环境友好型聚氨酯是目前聚氨酯（polyurethane,PU）泡沫塑料领域的热点课题。在PU中引入大豆分离蛋白质（soy protein isolate,SPI）,采用阻燃聚醚制备了环境友好型阻燃高回弹聚氨酯软泡。研究了SPI的不同添加方式及用量对聚氨酯软泡物理、力学、阻燃和生物降解性能的影响。结果表明,SPI以添加的方式而不是替代聚醚的方式加入软泡性能更好;少量添加SPI可以提高PU软泡的开孔率、密度、压陷硬度、舒适因子、回弹率和断裂伸长率,对压缩永久变形率、拉伸强度和极限氧指数影响不大。SPI改变了PU的硬段结构,可以有效促进聚氨酯泡沫的生物降解。     

Experimental study of horizontal flame spread over rigid polyurethane foam on a plateau: effects of sample width and ambient pressure

The effects of sample width and ambient pressure on horizontal flame spread over horizontal rigid polyurethane foams are experimentally studied. A series of comparative experiments are conducted at two places with different altitudes in China. The sample surface temperature, spread rate, and height of flame are measured over a range of sample widths from 4 to 16 cm. Experimental results show that the horizontal flame spread rate decreases as the sample width increases in a negative power law at both two altitudes and the flame spread rate in the Hefei plain (at an altitude of 30 m) is larger than that on the Tibetan plateau (at an altitude of 3658 m) of the same width. The horizontal flame spread mechanism on the rigid polyurethane foam is analyzed qualitatively in comparison with the results of the flame spread rate of expanded polystyrene foams. The relationship between the dimensionless flame height (H_f/W) and the sample width (W) is obtained by using Froude number similarity. It is found based on the experimental data under two different ambient pressures that the average value of the exponent of the ambient pressure in the power law for the horizontal flame spread rate is about 1.9, which is in good agreement with the theoretical value 2.0. Copyright © 2014 John Wiley & Sons, Ltd.     

Influence of thermal behavior of phosphorus compounds on their flame retardant effect in PU rigid foam

Phosphorus‐containing compounds have been widely used as flame retardants for polyurethane rigid foam (PURF). In this work, a number of phosphorus compounds were utilized and studied as flame retardants for PURF, including ammonium polyphosphate, pentaerythritol phosphate, triethyl phosphate, and dimethyl methyl phosphonate. The thermal behavior of flame retardants was thoroughly investigated, such as degradation, vaporization, and the properties of degraded products. The influence of thermal behavior of phosphorus flame retardants on PURF was examined and analyzed. The results indicated that the effect of flame retardant was highly related to their thermal behavior. Phosphorus compounds for gas phase flame retardants were very effective in decreasing the heat release rate and increase limited oxygen index of PURF, while condensed phase flame retardants showed better comprehensive flame retardant effect, such as reducing the toxicity of combustion product. Copyright © 2015 John Wiley & Sons, Ltd.     

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     

The synthesis of biphenyl ether/vanillin-based flame retardants for enhancing both the flame retardant properties and mechanical performance of epoxy resin

Imparting good flame retardancy and mechanical properties to epoxy resin (EP), while pursuing the sustainable and safe application of EP, we synthesized a novel reactive phosphorus/nitrogen flame retardant for biomass through nucleophilic addition reaction, which contains flexible ether bonds and rigid aromatic ring structure (DVD). Owing to the cooperative effect of aryl ether diamine, phosphorus phenanthrene, and biomass vanillin, the DVD exhibited excellent flame retardancy. EP/DVD-1 (0.4 wt% phosphorus content) achieved UL-94 V-0 rating, with an improvement in limiting oxygen index value from 26.5% (pure EP) to 32.5%. In the CCT, the modified DVD EP showed a 44.5% reduction in peak peak of heat release rate (PHRR) and a 38.0% reduction in total heat release compared to pure EPs. And flame retardant epoxy resin (FREP) still had good transparency after the addition of DVD, which indicated the nice compatibility between DVD andEP. What was noteworthiness was that at high levels of addition, the mechanical properties of modified EP for DVD was still improved compared to pure EP. These results demonstrate that DVD is an excellent and multifunctional bio-based flame retardant with broad application prospects in the field of EP material modification.     

扩链剂在阻燃高回弹聚氨酯泡沫中的应用

分别采用三乙醇胺(TEOA)、二乙醇胺(DEOA)和甘油(GLY)三种扩链剂制备阻燃高回弹聚氨酯(FRHRPU)泡沫塑料.探讨了TEOA,DEOA,GLY对FRHRPU泡沫塑料反应活性、泡孔结构及制品力学性能的影响.结果表明:以DEOA为扩链剂制备的FRHRPU泡孔孔径为200.00 μm、氧指数为28.7％,工艺稳定性及力学性能优于其他两种扩链剂制备的FRHRPU.DEOA可广泛应用于FRHRPU泡沫塑料.     

Enhanced mechanical and thermal properties of rigid polyurethane foam composites containing graphene nanosheets and carbon nanotubes

The comparative study of rigid polyurethane foam (RPUF) nanocomposites based on graphene nanosheets (GNSs) and carbon nanotubes (CNTs) has been reported. A GNS content of 0.3 wt% in polyol turns to be optimal for its foamability with the isocyanate component, as verified by rheology measurements. Scanning electron microscopy and transmission electron microscopy observations reveal a homogeneous dispersion of GNSs and CNTs in the RPUF nanocomposites. Only 0.3 wt% loading of GNSs and CNTs led to 36% and 25% improvement respectively in the compressive modulus of the RPUF nanocomposites. Meanwhile, 16 °C and 14 °C improvements in the glass transition temperature confirm the important role of both the nanofillers in the heat resistance of RPUF nanocomposites. These results additionally indicate that GNSs work more effectively than CNTs in mechanical property and heat resistance enhancement of the RPUF nanocomposites. The superiority of GNSs over CNTs can be attributed to their wrinkled surface structure, unique two‐dimensional geometrical morphology and higher specific surface area, which results in stronger interaction and restriction of segmental motion at the interface between the GNSs and the RPUF matrix. In addition, changes in the thermal conductivity of the nanocomposites are negligible, indicating that incorporation of GNSs and CNTs will not hinder the application of RPUF nanocomposites as thermal insulators. On the contrary, the enhancement in mechanical properties and heat resistance will undoubtedly expand the application range of polyurethane foam materials. Copyright © 2012 Society of Chemical Industry     

磷化合物对氢氧化镁阻燃聚氨酯密封胶性能的影响

研究了磷化合物对氢氧化镁阻燃聚氨酯(PU)密封胶性能的影响。研究结果表明,聚磷酸铵(APP)与间苯二酚双-(二苯基磷酸酯)(RDP)复合磷系阻燃剂对氢氧化镁阻燃PU密封胶具有良好的协效作用;当m(APP)∶m(RDP)=6∶4时,阻燃PU密封胶的综合性能较好,此时该密封胶的氧指数由28.9提高到31.7、垂直燃烧级别也由FV-1级提升到FV-0级(3.2mm)、拉伸强度为2.7MPa、断裂伸长率为376%且邵A硬度为56。