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     

Effects of liquid‐type silane additives and organoclay on the morphology and thermal conductivity of rigid polyisocyanurate‐polyurethane foams

This article investigates the effects of liquid‐type silane additives and organoclay as a solid‐type additive on the morphological, mechanical and thermal insulating properties of polyisocyanurate‐polyurethane (PIR‐PUR) foams. The organoclay likely acted as nucleating agents during the formation of PIR‐PUR foams. When the liquid silane additives and organoclay were added, the cell size and thermal conductivity of the PIR‐PUR foams appeared to be decreased. However, organoclay did not contribute to reduce the cell size distribution of the foam. PIR‐PUR foams synthesized with tetramethylsilane as a liquid‐type additive showed a smaller average cell size and lower thermal conductivity than that of PIR‐PUR foams synthesized with the other silane additives or with organoclay as a solid‐type additive. For the PIR‐PUR foam with organoclay/TEMS (1.5/1.5 php) mixture, cell size and thermal conductivity of the foam showed similar to the foam with TEMS. These results suggest that smaller cell size appears to be one of the major factors in the improvement of thermal insulation properties of the PIR‐PUR foams. Silane additives did not seem to have a strong effect on the flammability of the PIR‐PUR foams. However, heat resistance was more dominant for the foam with the organoclay at the higher temperature. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of a novel phosphorus‐containing compound on the flame retardancy and thermal degradation of intumescent flame retardant polypropylene

A novel flame retardant, tetra(5,5‐dimethyl‐1,3‐ dioxaphosphorinanyl‐2‐oxy) neopentane (DOPNP), was synthesized successfully, and its structure was characterized by FT‐IR, ¹H NMR, and ³¹P NMR. The thermogravimetric analysis (TGA) results demonstrate that DOPNP showed a good char‐forming ability. Its initial decomposition temperature was 236.4°C based on 1% mass loss, and its char residue was 41.2 wt % at 600°C, and 22.9 wt % at 800°C, respectively. The flame retardancy and thermal degradation behavior of novel intumescent flame‐retardant polypropylene (IFR‐PP) composites containing DOPNP were investigated using limiting oxygen index (LOI), UL‐94 test, TGA, cone calorimeter (CONE) test, and scanning electron microscopy (SEM). The results demonstrate that DOPNP effectively raised LOI value of IFR‐PP. When the loading of IFR was 30 wt %, LOI of IFR‐PP reached 31.3%, and it passed UL‐94 V‐0. TGA results show that DOPNP made the thermal decomposition of IFR‐PP take place in advance; reduced the thermal decomposition rate and raised the residual char amount. CONE results show that DOPNP could effectively decrease the heat release rate peak of IFR‐PP. A continuous and compact char layer observed from the SEM further proved the flame retardance. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Enhanced fire behavior of rigid polyurethane foam by intumescent flame retardants

Using expandable graphite (EG) and ammonium polyphosphate (APP) as flame retardants, we prepared two series of polyisocyanurate–polyurethane (PIR–PUR) foams (i.e., EG foams filled with different amounts of EG alone and APEG foams containing different amounts of expanded EG and APP) and evaluated the effect of the additives on the physical–mechanical property, fire behavior and thermal stability of the foams based on compressive strength test, limiting oxygen index (LOI), cone calorimeter test, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The addition of EG alone or both EG and APP into the foam greatly influences the physical–mechanical property. The compressive strength of APEG foams is closely related to the apparent density. The LOI value showed good improvement in both EG and APEG foams. The addition of APP in APEG foams gave better fire behavior than the EG foams with an obvious decrease in PHRR and increase in residue. In addition, the TGA curves illustrated that APP might be an effective charring agent to promote char formation. The SEM results showed that the incorporation of APP and EG allowed the formation of a cohesive and dense char layer, which inhibited the transfer of heat and combustible gas and increased the thermal stability of PIR‐PUR. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of aminophosphonate polyols and polyurethane foams with improved fire retardant properties

Aminophosphonated polyols with flame retardant properties are synthesized by ring opening polymerization using diethyl-N,N-bis(2-hydroxyethyl) aminomethyl phosphonate (Fyrol-6) as initiator. The influence of the catalyst type and its concentration on the polymerization rate are studied. The catalyst system formed by potassium methoxide (MeOK) in DMSO as a solvent presents the highest polymerization rate and allows reducing the polydispersity. The thermal resistance of the synthesized polyols is confirmed by the char residues formation. Finally, PU foams are synthesized containing up to a 50 pph of PFyCs[1:1], preserving good cellular structure up to a 25 pph content and improving the fire resistance by increasing the char residue from 7.79 to 22.13 wt % and decreasing the PHRR and the smoke production according to TGA and cone calorimeter tests, respectively. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47780.     

利用硬质PU泡沫醇解回收料制备PU防水涂料的研究

研究了以醋酸钾为催化剂、三甘醇(TEG)为醇解剂对硬质聚氨酯(PU)泡沫的醇解规律,并以醇解产物(PUP)作为原料制备预聚体;探讨了预聚体中醇解产物用量对制备PU防水涂料物理、机械性能的影响。研究结果表明:当催化剂醋酸钾(KAc)/PU质量比为0.02,醇解产物掺量w(PUP)/w(N220)=0.2时,制备的预聚体可以得到满足性能要求的聚氨酯防水涂料。     

腰果酚对聚异氰脲酸酯性能的改性研究

聚异氰脲酸酯(PIR)泡沫是一种新型的热固性保温材料,它具有密度低、耐热性能及耐寒性能优越、阻燃性能好、尺寸稳定性高等优点,但纯PIR泡沫质脆,无法直接使用。为了改善PIR泡沫的韧性,以异氰酸酯和聚醚多元醇为原料,通过腰果酚对其增韧改性,研究了腰果酚用量对PIR泡沫性能的影响。结果表明:引入腰果酚会显著提高PIR的韧性,PIR发泡塑料的密度、压缩强度、韧性均会随着腰果酚用量的增加而变大;而随着腰果酚用量的增加,PIR泡沫吸水率逐渐下降,粉化度下降,导热系数也会降低。加入适量的腰果酚可以改善泡沫的韧性,提高泡沫的保温防水性能。     

Phosphorus‐containing silica gel‐coated ammonium polyphosphate: Preparation,characterization, and its effect on the flame retardancy of rigid polyurethane foam

A phosphorus‐containing silica gel was synthesized via a reaction between phenyl dichlorophosphate, poly(ether polyol), and γ‐aminopropyltriethoxysilane. Ammonium polyphosphate (APP) was modified by the synthesized phosphorus‐containing silica gel (MAPP) and then incorporated into the rigid polyurethane foam (PU). Results showed that APP had a smaller particle size, lower initial decomposition temperature, better heat resistance at high temperature, and better compatibility with PU matrix after the modification. The cone calorimeter test results showed that the incorporation of MAPP obviously reduced the values including peak of heat release rate, total heat release, average effective heat of combustion, and total smoke release, and increased the char yield of PU composite comparing with APP. The improved flame retardancy of PU/MAPP composite was attributed to the quenching effect of PO· and PO₂· free radicals released by MAPP in the early stage and the improved thermal stability of phosphorus‐ and silicon‐containing char layer formed in the later stage. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46334.     

A novel halogen‐free intumescent flame retardant containing phosphorus and nitrogen and its application in polypropylene systems

A novel halogen‐free intumescent flame retardant, pentaerythritol spirobisphosphoryl‐dicyandiamide (SPDC), was synthesized and characterized by FTIR, ¹H NMR, and ³¹P NMR spectra. The new flame retardant was used in polypropylene (PP) to prepare flame‐retardant materials whose flammability and thermal behavior were studied by the limiting oxygen index (LOI) method, thermogravimetric analysis (TGA), and cone calorimetry (CONE). The mechanical properties were also investigated. The results indicated that when the addition of SPDC reached 30 wt%, the material showed both excellent flame retardancy and anti‐dripping abilities for PP. Moreover, the LOI value of the PP‐IFR(30%) was 32.5, and it passed the UL‐94 V‐0 rating test. The CONE results revealed that in PP, SPDC(30%) significantly decreased the peak heat release, total heat release, and smoke relative to their values for pure PP. The morphological structures observed by SEM demonstrated that SPDC could promote the formation of a homogeneous and compact intumescent char layer. The TGA data showed that SPDC could enhance the thermal stability of PP and effectively increase the char residue formation. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

次磷酸铝添加量对碱木质素基聚氨酯 泡沫阻燃性能的影响

利用精制后的碱木质素部分代替聚醚多元醇制备碱木质素基聚氨酯泡沫材料(PUF/木质素)。将次磷酸铝(AHP)作为阻燃剂添加到材料中制备PUF/木质素/AHP材料。通过极限氧指数(LOI)测试PUF/木质素/AHP材料的阻燃性能,通过热重分析(TG)研究了材料的热降解行为和成炭性能,通过锥形量热(CONE)测试和扫描电子显微镜(SEM)分别研究了PUF/木质素/AHP材料的燃烧行为和残炭的表面形貌。结果表明：当碱木质素添加量为聚醚多元醇的5%、AHP的添加量为30%时,PUF/5%木质素/30%AHP材料的LOI值达到了25.6%,同时降低了材料的热分解速率和热释放量,促进了材料的成炭。当AHP受热分解时,产生的PO自由基会捕捉材料燃烧时产生的氢氧自由基,从而抑制燃烧反应,同时产生磷酸铝和焦磷酸铝,形成致密的炭层阻隔物质和能量的传递,阻止材料进一步燃烧,从而提高材料的阻燃性能。     

一种耐热型聚氨酯弹性体的合成

在三聚催化剂的作用下,合成出了异佛尔酮二异氰酸酯的三聚体异氰脲酸酯,然后使它与聚酯多元醇反应,采用两步法手工浇注合成含异氰脲酸酯环的聚氨酯弹性体。采用红外光谱对该三聚产物进行了表征,并证实了异氰脲酸酯的存在。采用六氢吡啶法测出了异氰脲酸酯的质量分数。分别采用热重法和机械性能测试分析了弹性体的热稳定性和机械性能。结果显示,与普通聚氨酯弹性体相比,用异氰酸酯改性后的聚氨酯弹性体的热稳定性明显得到了提高。     

Preparation and characterization of highly thermostable polyisocyanurate foams modified with epoxy resin

A series of epoxy resin–modified polyisocyanurate (EP‐PIR) foams with oxazolidone (OX) rings and isocyanurate (IS) rings have been successfully prepared by the reaction of polymethylene polyphenyl isocyanate (PAPI) and diglycidyl ether of bisphenol‐A (DGEBA). Fourier transform infrared spectroscopy and differential scanning calorimetry are performed to investigate the influence of curing temperature on the chemical structure of EP‐PIR foams. The results indicate that low temperature is beneficial to the formation of the IS ring, and high temperature is in favor of the OX ring. The influence of the mole ratio of [PAPI]/[DGEBA] on the mechanical properties and thermal stability has also been studied. With the increase of [PAPI]/[DGEBA], the specific compressive strength shows a maximum of 0.0135 ± 0.0003 MPa m³/kg. The optimized mole ratio of [PAPI]/[DGEBA] is around 2.5 to reach the better mechanical and thermal properties, and the glass‐transition temperature is as high as 323.5°C. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43085.     

催化剂对废旧PU硬泡回收再利用的影响

用含有小分子醇的交联剂和催化剂使废旧聚氨酯（PU）硬泡进行降解能够获得多元醇,将降解料与聚醚多元醇、催化剂和发泡剂共混以制备白料,然后与黑料异氰酸酯混合均匀,得到再生PU硬泡。通过对降解产物的黏度、羟值以及获得的再生PU硬泡材料的密度、强度、吸水率、热稳定性、扫描电子显微镜、红外光谱和热失重等进行测试分析,得出了催化剂添加量对废旧PU材料回收再利用的影响因素。结果表明,催化剂（KOH）用量为0.9 g时废旧PU的降解效果最好,获得的再生PU硬泡的密度为37.6 kg/cm³,压缩强度为164.2 kPa,热导率为0.015 24 W/（m·K）,吸水率为0.429 5 %。     

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.     

Role of additives in fabrication of soy-based rigid polyurethane foam for structural and thermal insulation applications

Environmental concerns continue to pose the challenge to replace petroleum-based products with renewable ones completely or at least partially while maintaining comparable properties. Herein, rigid polyurethane (PU) foams were prepared using soy-based polyol for structural and thermal insulation applications. Cell size, density, thermal resistivity, and compression force deflection (CFD) values were evaluated and compared with that of petroleum-based PU foam Baydur 683. The roles of different additives, that is, catalyst, blowing agent, surfactants, and different functionalities of polyol on the properties of fabricated foam were also investigated. For this study, dibutyltin dilaurate was employed as catalyst and water as environment friendly blowing agent. Their competitive effect on density and cell size of the PU foams were evaluated. Five different silicone-based surfactants were employed to study the effect of surface tension on cell size of foam. It was also found that 5 g of surfactant per 100 g of polyol produced a foam with minimum surface tension and highest thermal resistivity (R value: 26.11 m²·K/W). However, CFD values were compromised for higher surfactant loading. Additionally, blending of 5 g of higher functionality soy-based polyol improved the CFD values to 328.19 kPa, which was comparable to that of petroleum-based foam Baydur 683.     

Effect of auxiliary blowing agents on properties of rigid polyurethane foams based on liquefied products from peanut shell

The bio‐based rigid polyurethane (PU) foams were successfully prepared based on liquefied products from peanut shell with water as the blowing agent. The influence of reaction parameters on properties of rigid PU foams was investigated. Rigid PU foams showed excellent compressive strength and low shrinkage ratio, whereas their open‐cell ratio and water absorption were higher. Therefore, rigid PU foams were synthesized with petroleum ether, diethyl ether, and acetone as auxiliary blowing agents and their inner temperature, shrinkage performance, density, compressive strength, water absorption, and open‐cell ratio were determined. The results indicated that above rigid PU foams showed lower compressive strength than the original foam but their water absorption and close‐cell ratio were improved. Compared with the original foam, the highest inner temperature of rigid PU foams with petroleum ether, diethyl ether, and acetone as auxiliary blowing agents was reduced by 11, 19, and 23 °C, respectively. Typically, foams with petroleum ether as auxiliary blowing agent displayed better water absorption and swelling ratio in water and exhibited obvious improvement in close‐cell ratio. These foams were preferable for application in thermal insulation materials because of low thermal conductivity and better corrosion resistance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45582.     

A novel intumescent flame‐retardant system for flame‐retarded LLDPE/EVA composites

A new intumescent flame retardant (IFR) system consisting of ammonium polyphosphate (APP) and charing‐foaming agent (CFA) and a little organic montmorillonite (OMMT) was used in low‐density polyethylene (LLDPE)/ethylene‐vinyl acetate (EVA) composite. According to limiting oxygen index (LOI) value and UL‐94 rating obtained from this work, the reasonable mass ratio of APP to CFA was 3 : 1, and OMMT could obviously enhance the flame retardancy of the composites. Cone calorimeter (CONE) and thermogravimetric analysis (TGA) were applied to evaluate the burning behavior and thermal stability of IFR‐LLDPE/EVA (LLDPE/EVA) composites. The results of cone calorimeter showed that heat release rate peak (HRR‐peak) and smoke production rate peak (SPR‐peak) and time to ignition (TTI) of IFR‐LLDPE/EVA composites decreased clearly compared with the pure blend. TGA data showed that IFR could enhance the thermal stability of the composites at high temperature and effectively increase the char residue. The morphological structures of the composites observed by scanning electron microscopy (SEM) and X‐ray diffraction (XRD) demonstrated that OMMT could well disperse in the composites without exfoliation, and obviously improve the compatibility of components of IFR in LLDPE/EVA blend. The morphological structures of char layer obtained from Cone indicated that OMMT make the char layer structure be more homogenous and more stable. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

固体酸催化合成三(三溴苯氧基)异氰脲酸酯及其阻燃聚氨酯脲的研究

以异氰脲酸(CA)和三溴苯酚(TBP)为原料,用SO42-/MxOy型固体酸作催化剂合成三(三溴苯氧基)异氰脲酸酯(TTBPC)。利用红外光谱(FT-IR)、差示扫描量热法(DSC)和热重(TG)对其结构及热稳定性、热分解行为进行了表征,并研究了添加该阻燃剂的聚氨酯脲(PUU)的力学性能与阻燃性能,结果表明此阻燃剂能够增加PUU的力学性能,且能阻止其燃烧。     

硼酸锌在膨胀型阻燃聚丙烯中的协同阻燃机理研究

通过氧指数，热重分析（TGA）和扫描电子显微镜（SEM）研究了硼酸锌在膨胀型阻燃丙烯中的协同阻燃作用，硼酸锌的加入在用量低时可显著增加膨胀型阻燃聚丙烯（PP）的氧指数,而当用量超过一定值后，氧指数则急剧降低，TGA显示硼酸锌用量为2．5份时，500℃的剩焦量出现最大值。这与氧指数的数值非常吻合。扫描电子显微镜观察到硼酸锌用量为2．5份时，燃烧剩炭出现大泡孔结构，这种大泡孔具有非常薄的壁，为此，我们认为该体系的阻燃机理是聚磷酸铵分解后形成的玻璃状物与硼酸锌分解物形成一种乳液体系覆盖在燃烧物表面，该体系使聚磷酸铵分解产生的气泡稳定，形成有效的隔离层使阻燃性能得到提高。     

Apparatus for investigating the burning and dripping of vertically oriented polyurethane foams

The burning and dripping behaviour of polyurethane (PU) foam is crucial for upholstered furniture fires due to the melting and dripping behaviour of the foam that results in a pool fire under the furniture, which enhances the combustion. The sample feeding vertical cone is developed to investigate the two-dimensional small-scale burning and dripping behaviour of vertically oriented PU foams where a constant irradiance is maintained at the exposed surface by means of automatic sample compensation. Seven different PU foams were investigated and classified as conventional foam or char-forming foam according to the observed surface phenomena during exposure to heat fluxes. The burning and dripping behaviour is found to depend on the foam density as well as the solid-phase char formation by the presence of fire retardant additives. The total mass loss rate and the dripping rate increase with higher foam density and with the presence of char formation. In contrary, the vaporisation rate is favoured at lower foam density and with the absence of char formation. Flexible foams of low density without the ability to form char tend to achieve low dripping rate where majority of the mass loss is via vaporisation, contributing directly to the gas-phase combustion.