The thermal decomposition of polyurethanes and polyisocyanurates

The thermal decomposition of a number of TDI- and MDI-based biscarbamates (model compounds for polyurethane foams) between 200°C and 1000°C showed that the urethane linkage undergoes an O-acyl fission at about 300°C to generate the free isocyanate and alcohol. In the case of the flexible foam analogues, the newly generated TDI reacts further to generate volatile polyureas, termed ‘yellow smoke’. The MDI residues generated in the decomposition of a rigid foams react to yield non-volatile polycarbodiimides. Both the yellow smokes and the polycarbodiimides decompose above 600°C to give a mixture of nitriles (including HCN) as well as a number of olefinic and aromatic compounds. The use of ¹³C labeling indicated that HCN and all the other nitriles generated during the high temperature decompositions originate in the thermal fission of the aromatic ring, the nitrile carbon being the 2-, 4- or 6- carbon of MDI.     

Toxic products from the combustion and pyrolysis of polyurethane foams

Products from the thermal decomposition of four polyurethane foams heated to temperatures in the range 220 to 400 °C, in atmospheres of nitrogen, of 6% oxygen in nitrogen and of air were examined for some of the anticipated toxic materials. When phosphorus-containing inhibitors were added to or chemically incorporated in the foams, phosphorus compounds were evolved under most of the conditions employed. Other materials detected were hydrogen cyanide, isocyanate, urea, halogenated compounds and alkenes. A brief discussion is given of the hazard presented by polyurethane foams decomposing under these conditions.     

The thermal decomposition of some polyurethane foams

Polyurethanes exposed to fire conditions might generate decomposition products which would be responsible for a significant part of the toxicity of the fire gases. Polyurethanes have been prepared from a commercial mixture of tolylene-2, 4- and 2,6-di-isocyanates, pure tolylene-2,4-di-isocyanate, pure tolylene-2,6-di-isocyanate and pure m-phenylene di-isocyanate. All polymers except that prepared from tolylene-2,6-di-isocyanate were obtained as flexible foams. When each polyurethane was heated at 300°C in a stream of nitrogen, a sublimate was obtained. The sublimates were all apparently polymers derived from the di-isocyanate rather than from the diol constituents of the polyurethanes. Pyrolysis of these materials at high temperatures (800–1000°C) led to similar mixtures of volatile products: at 1000°C the most abundant nitrogenous product, in each case, was hydrogen cyanide.     

The thermal decomposition of some tolylene bis-carbamates

In fires, flexible polyurethane foams can decompose to give smokes which are subsequently degraded with the generation of hydrogen cyanide. In order to understand the general nature of this hazard it is first necessary to obtain information about the decomposition mechanism of the polyurethane foams and the structures of the intermediate smokes. The complexity of this problem has required the use of suitable model compounds. The preparation is described of (i) the four bis-carbamates based on pure tolylene 2, 4-diisocyanate and pure tolylene 2,6-di-isocyanate, each in combination with 2-ethoxyethanol and with triethylene glycol monomethyl ether, and (ii) a urethane-carbodi-imide-urethane and a urethane-urea-urethane based on pure tolylene 2,6-di-isocyanate and 2-ethoxyethanol. All were decomposed by heating under nitrogen at temperatures near 300°C. The two di-2-ethoxyethyl bis-carbamates ( la and IIa ) gave volatile monoisocyanate-monourethanes and 2-ethoxyethanol. The two di-2-[2-(2-methoxyethoxy)ethoxy] ethyl bis-carbamates ( Ib and IIb ) gave corresponding products and residue which contained carbodi-imide functions. The urethane-carbodi-imide-urethane ( Va ) gave a volatile urethane-carbodi-imide-isocyanate ( Via ) and 2-ethoxyethanol. The urethane-urea-urethane ( VIIIa ) decomposed through isocyanate- and carbodi-imide-containing materials to a volatile polymeric urea, which was obtained as a smoke and appeared to be virtually identical with the smoke obtained in earlier work from a commercial polyurethane. These results suggest that poly-urethanes based on tolylene di-isocyanate and polyether polyols decompose, when heated under nitrogen at 300°C, by cleavage of urethane groups to regenerate isocyanate groups and liberate alcohols. The isocyanato groups may react either with other isocyanato groups to give carbodi-imides, which are then rapidly hydrated to ureas, or with water to give amines, which react with other isocyanato groups again to give ureas. Whether these processes occur separately or together, the ultimate product at 300°C, i.e. the smoke, will be a polymeric urea.     

Synthesis of Carbon‐Rich Hybrid Foam from GAP‐Modified Polyurethane

4,4′‐Diisocyanato diphenylmethane (MDI)‐based polyurethanes melt and start to burn at 150–200 °C. Mainly H₂O, CO₂, CO, HCN, and N₂ are formed. The new modified polyurethane shows a different pyrolysis behavior. GAP‐diol (glycidyl azide polymer), which was used as a modifying agent, is a well‐known energetic binder with a high burning velocity and a very low adiabatic flame temperature. The modified polyurethane starts to burn at approximately 190 °C because of the emitted burnable gases, but it does not melt. The PU foam shrinks slightly and a black, solid, carbon‐rich hybrid foam remains. TGA and EGA‐FTIR revealed a three‐step decomposition mechanism of pure GAP‐diol, the isocyanate‐GAP‐diol, and PU‐GAP‐diol formulations. The first decomposition step is caused by an exothermic reaction of the azido group of the GAP‐diol. This decomposition reaction is independent of the oxygen content in the atmosphere. In the range of 190–240 °C the azido group spontaneously decomposes to nitrogen and ammonia. This decomposition is assumed to take place partly via the intermediate hydrogen azide that decomposes spontaneously to nitrogen and ammonia in the range of 190–240 °C. The second decomposition step was attributed to the depolymerization of the urethane and bisubstituted urea groups. The third decomposition step in the range of 500–750 °C was attributed to the carbonization process of the polymer backbone, which yielded solid, carbon‐rich hybrid foams at 900 °C. In air, the second and the third decomposition step shifted to lower temperatures while no solid carbon hybrid foam was left. Samples of PU‐GAP‐diol, which were not heated by a temperature program but ignited by a bunsen burner, formed a similar carbon‐rich hybrid foam. It was therefore concluded that the decomposition products of the hydrogen azide, ammonia and mainly nitrogen act as an inert atmosphere. FTIR, solid‐state ¹³C‐NMR, XRD, and heat conductivity measurements revealed a high content of sp²‐hybridized, aromatic structures in the hybrid foam. The carbon‐rich foam shows a considerable hardness coupled with high temperature resistance and large specific surface area of 2.1 m²⋅g⁻¹.     

Reactions of fuel-nitrogen compounds under conditions of inert pyrolysis

As part of a study of the chemical mechanisms involved in the conversion of fuel-nitrogen compounds to nitric oxide during combustion, fossil fuels and model nitrogen compounds were pyrolysed in helium in a small quartz flow reactor. Hydrogen cyanide was the major nitrogen-containing product obtained in all cases indicating that hydrogen cyanide is formed during the initial pre-flame stages of combustion and is the principal intermediate in the formation of fuel nitric oxide. At a nominal residence time of one second, 50% decomposition of pyrrole, quinoline, benzonitrile and pyridine occurs at 905, 910, 922 and 954 °C, respectively. The fraction of the nitrogen in pyridine that is converted to hydrogen cyanide increases from 40% at 960 °C to 100% at 1100 °C. Benzonitrile produces similar amounts of hydrogen cyanide (49 and 82%). The hydrogen cyanide yields from coals and residual fuel oils increase from the range of 15–25% at 950 °C to 23–42% at 1100 °C. It is not possible to determine from these single-stage experiments if most of the hydrogen cyanide forms in the primary pyrolysis process or in secondary reactions.     

The incapacitative effects of exposure to the thermal decomposition products of polyurethane foams

The mechanisms of incapacitation resulting from exposures to the thermal decomposition products of flexible and rigid polyurethane foams (PUF) were studied over a range of different temperatures under pyrolytic or non-flaming oxidative decomposition conditions. Individual cynomolgus monkeys were exposed to atmospheres increasing in separate experiments from very low concentrations until early physiological signs of incapacitation were detected. When flexible PUF was pyrolysed at 900°C and rigid PUF was oxidized at 600°C, clear atmospheres containing CO and HCN were produced and the signs of toxicity were very similar to those produced by HCN gas alone, consisting of an episode of hyperventilation followed by a semi-conscious state. Pyrolysis of flexible PUF at 600°C and 300°C produced a dense yellow smoke but no HCN. The signs, consisting of hyperventilation throughout exposure and dyspnoea afterwards, were consistent with pulmonary irritation, Since TDI monmer is not present at 600⁰ C it is concluded that some as-yet unidentified but highly irritant chemical species is present in smoke from flexible PUF.     

Thermal degradation kinetics of rigid polyurethane foams blown with water

The thermal decomposition behavior of rigid polyurethane foams blown with water was studied by dynamic thermogravimetric analysis (TGA) in both nitrogen and air atmosphere at several heating rates ranging from room temperature to 800°C. The kinetic parameters, such as activation energy (E), degradation order (n), and pre‐exponential factor (A) were calculated by three single heating rate techniques of Friedman, Chang, and Coats–Redfern, respectively. Compared with the decomposition process in nitrogen, the decomposition of foams in air exhibits two distinct weight loss stages. The decomposition in nitrogen has the same mechanism as the first stage weight loss in air, but the second decomposition stage in air appears to be dominated by the thermo‐oxidative degradation. The heating rates have insignificant effect on the kinetic parameters except that the kinetic parameters at 5°C/min have higher values in nitrogen and lower values in air, indicating different degradation kinetics in nitrogen and air. The kinetic parameters of foam samples blown with different water level in formulation decline firstly and then increase when water level increases from 3.0 to 7.0 pph. According to the prediction for lifetime and half‐life time of foams, water‐blown rigid foams have excellent thermostability, when used as insulation materials below 100°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4149–4156, 2006     

A shock tube study of the high temperature reactions of nitrogen with hydrocarbons

A single pulse shock tube has been used to study the reactions of nitrogen with methane, ethane and acetylene at 1400°-6000°K. Reactants heated by the reflected shock for about 1–1.5 milliseconds are cooled by rarefaction waves, and samples obtained through a quick-opening check valve are analyzed by gas chromatography. The effect of nitrogen on hydrocarbon pyrolysis appears to be negligible below about 2000°K. At higher temperatures, vibrationally excited nitrogen molecules react with free radicals and produce hydrogen cyanide. Activation energies in the range 23 to 54 Kcal/mole are calculated for the formation of hydrogen cyanide.     

Effect of processing variables on the thermophysical properties of polybenzimidazole foams

Polybenzimidazole foams in the density range of 24 to 80 kg/m³ have excellent thermophysical properties, fire resistance, and low smoke evolution when exposed to heat or flame; they also retain their mechanical properties up to 200°C without any significant degradation. In addition to superior thermal properties, the foams maintain a high degree of flexibility and a good modulus-to-weight ratio, as well as high strength-to-weight relationship at high temperatures. These properties make this foam an attractive candidate as a low-weight, high-temperature insulation for aerospace applications. This paper describes the relationship between prepolymer purity, processing parameters, and additives to the thermophysical and chemical properties of these foams. Foam properties are shown to be affected by differences in prepolymer purity, curing schedule, and the presence of additives in the foam. High-temperature compressive properties were imporved by postcuring at 527°C. Surfactant additives were found to improve uniformity of cell size. Foams were characterized according to high-temperature mechanical properties, density, porosity, thermal diffusivity, thermal conductivity, and specific heat.     

Thermally initiated oxidation and ignition of flexible polyurethane foams

Oxidation and ignition of flexible polyurethane foams have been investigated by observing the effects of internal and external heating. External temperatures of some 190°C are required to induce combustion. Internal temperatures of 250 ?350°C initiate a self-propagating internal reaction which results in foam ignition when the reaction reaches the foam surface. The stability of a polyurethane foam to such heating increases with the age of the foam.     

Polyurethane‐infiltrated carbon foams: A coupling of thermal and mechanical properties

The thermal and mechanical properties of polyurethane‐infiltrated carbon foam of various densities were investigated. By combining the high thermal conductivity of the carbon foam with the mechanical toughness of the pure polyurethane, a mechanically tough composite (relative to the unfilled foam) that could be used at higher temperatures than the polyurethane's degradation was formed. Both the tensile strength and the modulus increased by an order of magnitude for the composites compared to unfilled foam, while the compressive and shear strengths and moduli of the composites approached values exhibited by pure polyurethane. At both 300 and 400°C, the rectangular blocks of pure polyurethane lost their mechanical integrity due to decomposition in air. Thermogravimetric analysis confirms substantial initial weight loss above 290°C. Filled carbon foam blocks, however, maintain their mechanical integrity at both 300 and 400°C indefinitely, although the bulk of the rectangular block mass is polyurethane. Three different carbon foam densities are examined. As expected, the higher density foams show greater heat transfer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2348–2355, 2003     

Viscoelastic behavior of flexible slabstock polyurethane foam as a function of temperature and relative humidity. II. Compressive creep behavior

The compression creep behavior was monitored at constant temperature and/or relative humidity for two slabstock foams with different hard-segment content. The tests were performed by applying a constant load (free falling weight) and then monitoring the strain as a function of time over a 3-h time period. A near linear relationship is obtained for linear strain versus log time after a short induction period for both foams and at most conditions studied (except at temperatures near and above 125°C). The slope of this relationship or the initial creep rate is dependent on the initial strain level, espcially in the range of 10–60% deformation. This dependence is believed to be related to the cellular structs buckling within this range of strain. At deformations greater than 60% and less than 10%, the solid portion of the foam is thought to control the compressive creep behavior in contrast to the cellular texture. Increasing relative humidity does cause a greater amount of creep to occur and is believed to be a result of water acting as a plasticizer. For low humidities increasing the temperature from 30 to 85°C, a decrease in the rate of creep is observed at a 65% initial deformation. At 125°C, an increase in the creep rate is seen and is believed to be related to chemical as well as additional structural changes taking place in the solid portion of the foams. The creep rate is higher for the higher hard-segment foam (34 wt %) than that of the lower (21 wt %) at all of the conditions studied and for the same initial deformation level. This difference is principally attributed to the greater amount of hydrogen bonds available for disruption in the higher hard-segment foam. © 1994 John Wiley & Sons, Inc.     

Thermal decomposition products of polyacrylonitrile

The decomposition products of a polyacrylonitrile yarn thermally decomposed at temperatures of 400°, 600°, and 800°C, under a flow of either air or nitrogen, have been analyzed by GC and GCMS. Hydrogen cyanide and 16 other nitriles were identified and quantified. Decomposition products contained a series of aliphatic nitriles of various chain lengths, and HCN was the predominant toxic product.     

Physical properties of ethylene vinyl acetate copolymer (EVA)/natural rubber (NR) blend based foam

In this study an attempt was made to improve the rebound resilience and to decrease the density of ethylene‐vinyl acetate copolymer (EVA) foam. For this purpose, EVA was blended with natural rubber (NR), and EVA/NR blends were foamed at 155°C, 160°C, and 165°C. To investigate the correlation between crosslinking behavior and physical properties of foams, crosslinking behavior of EVA/NR blends was monitored. The physical properties of the foams were then measured as a function of foaming temperatures and blend compositions: 165°C was found to be the optimal temperature for a crosslinking of EVA/NR foam. As a result, the density of EVA/NR blend foamed at 165°C was found to be the lowest. EVA/NR (90/10) blend, foamed at 165°C, showed lower density, better rebound resilience, and greater tear strength than EVA foam. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2212–2216, 2004     

Effects of 3,4′-oxydianiline on the structures and properties of a novel aromatic polyimide foam

Aiming at the low volumetric shrinkage, a novel aromatic polyimide foam is successfully prepared from polymethane polyphenyl isocyanate (PAPI) and a poly(amic-acid) precursor which has been synthesized from 3,4′-oxydianiline (3,4′-ODA) and pyromellitic dianhydride (PMDA). In this research, five polyimide foams, with different contents of 3,4′-ODA, are comparatively studied including structural, thermal, mechanical, shrink, and degradation properties. The results indicate that the content of 3,4′-ODA has minor influence on chemical structures, but significant influence on cell structures of the foams. With the increase of 3,4′-ODA, the volumetric shrinkages, apparent densities and the compressive and flatwise tensile strengths of the materials decrease. The glass transition temperatures (T_g) decrease from 301°C to 279°C, and the 5% weight loss temperatures (T_5%) increase from 323°C to 340°C. Through TG-FTIR analysis, we can observe that the addition of 3,4′-ODA has no influence on the pyrolysis mechanism of polyimide foams. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Ultrahigh compressive strength and heat resistance of polystyrene/polyphenylene oxide foams of supercritical carbon dioxide foaming

Polystyrene (PS) foam materials are lightweight, but suffer from poor compressive strength and heat resistance, among other problems, which limit their application. Herein, a method for preparing PS foam with high compressive strength and high heat resistance using supercritical CO₂ is proposed. PS/polyphenylene oxide (PPO) blends were prepared using a corotating intermeshing twin-screw extruder. The results showed that PPO exhibited excellent molecular-level compatibility with PS, which substantially improved mechanical properties and heat resistance of PS. Foam samples of PS/PPO blends with the same expansion ratio were prepared via batch foaming experiments, and the compressive strength of different foams was determined at different temperatures. At room temperature, the compressive strength of the PS/PPO-30% foam increased by 173% compared with pure PS foam. As the testing temperature increased from 30 to 120°C, the compressive strength of pure PS foams decreased rapidly. Nevertheless, PS/PPO foams maintained high compressive strength at high temperatures.     

Mechanical properties and antibacterial activity of peroxide‐cured silicone rubber foams

Silicone rubber (SR) foams were prepared by the peroxide curing of a silicone compound with 2,4‐dichlorobenzoyl peroxide (DCBP), di‐t‐butyl peroxide (DTBP), or 2,5‐dimethyl‐2,5‐di(t‐butylperoxy) hexane (DBPH) in the presence of 2,2′‐azobisisobutyronitrile (AIBN) as a blowing agent. The cells were formed in the foam as a result of nitrogen produced by the decomposition of AIBN during the foaming process. The cell size, hardness, and tensile properties of the SR foams were examined as a function of the peroxide concentration. When the peroxide concentration increased, the hardness and tensile strength of the SR foams increased, whereas the cell size and elongation at break decreased. The antibacterial activity of the prepared foams was also evaluated via their effects on Staphylococcus aureus and Escherichia coli. The peroxide‐cured SR foams had antibacterial activity because a toxic residue was generated by the peroxide decomposition. The foam prepared by the AIBN/DCBP system showed more antibacterial activity than the AIBN/DBPH and AIBN/DTBP ones. However, after postcuring at 250°C for 2 h, the antibacterial activity of the SR foams significantly decreased. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Ignition,combustion, toxicity,and fire retardancy of polyurethane foams: A comprehensive review

This review provides insight into the ignition, combustion, smoke, toxicity, and fire‐retardant performance of flexible and rigid polyurethane foams. This review also covers various additive and reactive fire‐retardant approaches adopted to render polyurethane foams fire‐retardant. Literature sources are mostly technical publications, patents, and books published since 1961. It has been found by different workers that polyurethane foams are easily ignitable and highly flammable, support combustion, and burn quite rapidly. They are therefore required to be fire‐retardant for different applications. Polyurethane foams during combustion produce a large quantity of vision‐obscuring smoke. The toxicity of the combustion products is much higher than that of many other manmade polymers because of the high concentrations of hydrogen cyanide and carbon monoxide. Polyurethane foams have been rendered fire‐retardant by the incorporation of phosphorus‐containing compounds, halogen‐containing compounds, nitrogen‐containing additives, silicone‐containing products, and miscellaneous organic and inorganic additives. Some heat‐resistant groups such as carbodiimide‐, isocyanurate‐, and nitrogen‐containing heterocycles formed with polyurethane foams also render urethane foams fire‐retardant. Fire‐retardant additives reduce the flammability, smoke level, and toxicity of polyurethane foams with some degradation in other characteristics. It can be concluded that despite many significant attempts, no commercial solution to the fire retardancy of polyurethane foams without some loss of physical and mechanical properties is available. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Temperature‐dependent pyrolytic product evolution profile for polypropylene

The composition of the pyrolysis products of plastics depends on disintegration of the macromolecule into variety of hydrocarbon fractions. In this work, a detailed gas chromatographic study of pyrolysis products of polypropylene (PP) between 200 and 600°C was carried out. The pyrograms have been analyzed in terms of amount of different products evolved at various pyrolysis temperatures. At low pyrolysis temperatures (200–300°C), the yield of lighter hydrocarbons (C5‐C10) is low; it gradually increases until maximum decomposition temperature (446°C) and decreases thereafter. The following reaction types were considered to explain the decomposition mechanism of PP: (a) main chain cleavage to form chain‐ terminus radicals; (b) intramolecular hydrogen transfer to generate internal radicals; (c) intermolecular hydrogen transfer to form both volatile products and radicals; and (d) β‐scission to form both volatiles and terminally unsaturated polymer chains. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011