Pyrolysis and combustion of cellulose. III. Mechanistic basis for the synergism involving organic phosphates and nitrogenous bases

The flame retardation mechanisms for cellulose treated with systems based on aromatic phosphates and phosphoramides have been investigated through pyrolysis studies on cellulose and related model compounds. Pyrolysis of cellulose treated with phosphates or phosphoramides proceeds through formation of cellulose phosphate or phosphoramide esters, followed by subsequent ester pyrolysis to yield a dehydrated cellulose char. Formation of phosphoramides during pyrolysis of flame retardants containing phosphorus and nitrogen constitutes a possible basis for reported phosphorus-nitrogen synergistic effects observed in commercial flame retardants. Efficiency of ester formation is higher, and subsequent pyrolysis is lower for phosphoramides than for phosphate esters. The build-up of a thermally stable crosslinked matrix in the residue occurs on pyrolysis of cellulose treated with phosphoramides. Such crosslinking seems to be effective in enhancing flame retardation.     

Investigation of the action of flame retardants in cellulose. I. Investigation of the flame retardant action of 2,2′-oxybis(5,5-dimethyl-1,3,2-dioxaphosphorinane-2,2′-disulfide) in cellulose

Pyrolysis experiments were performed in high vacuum and under reduced air pressure (100 Pa). The volatile products of pure cellulose and cellulose containing various amounts of flame retardant 2,2′-oxybis (5,5-dimethyl-1,3,2-dioxaphosphorinane-2,2′-disulfide), i.e., Sandoflam 5060 of Sandoz AG, were studied by means of gas chromatography in combination with mass spectroscopy. The volatile products were characterized with infrared spectroscopy. The studied revealed that the incorporation of the flame retardant enhanced the water release and shifted the onset of this reaction to lower temperature. On the basis of these findings an explanation for the mechanism of flame retardancy in generated cellulose fibers modified with this particular flame retardant is attempted. From experiments with different residual air pressure the influence of oxygen on the primary processes of the pyrolytic degradation of cellulose is being discussed.     

The pyrolysis of cellulose and the action of flame-retardants

In further work on the vacuum pyrolysis of cotton cellulose, alone or with flame-retardants, at temperatures usually near 420°, products have been identified and determined. In the tar, laevoglucosan has been determined by an infra-red absorption method, and by gas-liquid chromatography of its trimethylsilyl ether; 5-(hydroxymethyl)furfural and 1,6-anhydro-β-D -glucofuranose have been identified and determined similarly by gas-liquid chromatography. By thin-layer chromatography of the 2,4-dinitrophenylhydrazones, 19 carbonyl compounds have been identified in the products from pure cotton; fewer were found from cotton treated with flame-retardants. The distribution of boron, nitrogen, phosphorus and chlorine from appropriate flame-retardants has been determined among the products of pyrolysis of cotton. It is concluded that borax/boric acid, and APO-THPC, act predominantly in the solid phase; Proban appears to act partly in the vapour phase. Mechanisms of pyrolysis are proposed. In a pure cotton cellulose, 1,2-anhydroglucoses are regarded as important intermediates.     

Pyrolysis and combustion of cellulose. II. Thermal analysis of mixtures of methyl α-D-glucopyranoside and levoglucosan with model phosphate flame retardants

The thermal degradation of methyl α-D -glucopyranoside, a cellulose model of intermediate complexity, was investigated in an attempt to gain insight into the pyrolytic reactions of analogous cellulose systems. The pure glucoside pyrolysis proceeds through formation of an intermediate of higher thermal stability. Nitrogenous bases bring about decomposition of the glucoside at lower temperatures and without formation of a detectable intermediate. Phenyl phosphates and phosphoramides induce thermal degradation of methyl α-D -glucopyranoside at lower temperatures than observed for the pure glucoside. The postulated degradation mechanism involves esterification of the glucoside followed by dehydration and skeletal rearrangements. Nitrogenous bases assist the dehydration process but reduce the yield of residue and bound phosphorus. Levoglucosan, the cellulose degradation product responsible for flaming combustion, was pyrolyzed in the presence of model flame retardants. Nitrogenous bases were found to inhibit thermal polymerization of levoglucosan and to induce its decomposition at lower temperatures. Zinc chloride exerted its effects in two stages: acid-catalyzed polymerization at lower temperatures and dehydration at higher temperatures. Phenyl phosphates and phosphoramides alter levoglucosan pyrolysis by action as Lewis acids in a manner similar to zinc chloride.     

Phosphorylation of cellulose with phosphorous acid and thermal degradation of the product

The reaction of cellulose with phosphorous acid in molten urea afforded a white, water-soluble product. The product was a monoester of phosphorous acid, and all the phosphorus residues were in phosphonic form, i.e., cellulose phosphonate. Quantitative addition of acrylonitrile to the P? H bonds in cellulose phosphonate occurred in the presence of sodium ethoxide. By alkali hydrolysis of the adduct, a polyelectrolyte having two different ionization groups, P? OH and COOH, could be prepared. Thermal degradation of three cellulose phosphonates, ammonium cellulose phosphonate (I), ammonium cellulose 2-cyanoethlyphosphonate (II), and ammonium cellulose 2-carboxyethylphosphonate (III), was examined. All three samples decomposed at a temperature around 270°C, but their thermal behaviors were different. Replacement of hydrogen in the phosphonic residue by 2-cyanoethyl and 2-carboxyethyl groups retarded dehydration of cellulose. Sample I had a satisfactory flame retardance; samples II and III were not flame resistant. Reduction of flame retardance may be due to the electron-withdrawing effect of the cyano and carboxyl groups.     

Dielectric loss microwave degradation of polymers: Cellulose

The pyrolysis of organic waste polymers to produce fuels and chemicals is of interest to augment petroleum-based processes. The wide variety of pyrolysis products of low yield and the uncertain role that heat transfer rate plays in determining these have been deterrents to utilization in the past. A possible approach to increased selectivity for products is to heat them rapidly and homogeneously with the aim of narrowing the product distribution. A very rapid means of homogeneous heat transfer throughout the substrate is microwave heating. A laboratory study has been done to determine what effect high-intensity microwave energy has on the thermal degradative pathways of cellulose. The product distribution found when cellulose is pyrolyzed in the absence of a microwave discharge is similar to that found in conventional furnace pyrolysis. The major products are levoglucosan (27%), carbon dioxide (2–5%), water, and charred residue. However, the total heat-up and reaction times for even large pellets are reduced to less than 2–3 min when high-intensity microwave irradiation is employed. Effects of pressure and microwave power are reported. Low external gas temperature also prevents secondary reactions.     

Thermal properties of tritylated and tosylated cellulose

Triphenylchloromethane and p-toluenesulfonyl chloride were reacted with chopped or powdered cellulose, with and without premercerization, to form trityl–cellulose ethers or tosyl–cellulose esters. Powdered and premercerized cellulose samples were more readily derivatized. Differential scanning calorimetric (DSC) and thermogravimetric (TG) analyses were performed in nitrogen on these derivatives. DSC and TG thermograms were affected by the particular derivative and the degree of substitution. The decomposition temperatures for both derivatives were lower than for the unmodified cellulose. Trityl cleavage may have been detected by DSC as a broad endothermic area showing no weight loss that preceded the major endothermic decomposition peak. Decomposition temperatures were lowered, but not sufficiently to prevent decomposition products from being combustible. No increase in residue was effected. Thermal decomposition of tosyl–cellulose was substantially different from that of the trityl derivative. As the degree of tosyl substitution increased, decomposition occurred at lower temperatures as an increasing exotherm. Tosyl derivatives all produced high residues. These changes in thermal characteristics were indicative of increased flame resistance. Oxygen index (OI) values relate to flame resistance and show that tritylation was detrimental to the cellulose and that tosylation imparted some degree of flame resistance.     

Improvement of the fire behavior of poly(1,4‐butanediol succinate)/flax biocomposites by fiber surface modification with phosphorus compounds: molecular versus macromolecular strategy

The grafting of phosphorus compounds onto natural fibers has been investigated as a strategy for improving poly(1,4‐butanediol succinate)/flax biocomposite fire behavior. Three phosphorus compounds ? dihydrogen ammonium phosphate, poly(methacryloyloxy)methyl phosphonic acid homopolymer and poly(methacryloyloxy)methyl phosphonic acid methylmethacrylate copolymer ? were selected. The aim of this work was to compare the fire performance conferred by the grafted compounds depending on whether phosphorus is brought by a molecule or a macromolecule. TGA, pyrolysis combustion flow calorimetry and cone calorimetry were used to characterize the thermal stability and fire behavior of the samples. The pyrolysis combustion flow calorimetry results showed that in all cases the presence of phosphorus changes the degradation pathway and thus the flammability properties of flax. The ability of the grafted flame retardant to promote char formation and residue formation was found to be dependent on the nature and quantity of phosphorus covalently bonded to flax. Conversely, cone calorimeter tests revealed similar fire behavior whatever the grafting agent. A significant increase of the char amount and a global enhancement of fire parameters were observed with increasing grafting rate. Moreover, phosphonated polymers promoted a charred sheath around the fibers which acts in addition to their charring, conferring a fire performance close to that of dihydrogen ammonium phosphate for the biocomposite.     

Combustion inhibition of cellulose by powders: Preliminary data and hypotheses

Small-scale qualitative tests were used to screen 185 inorganic powders for flame and inhibiting effects upon cellulose. Nearly half of the compounds inhibited smoldering. These were limited to inorganic salts whose anions include boron, phosphorus, sulfur or halogen. Over half the compounds inhibited flaming, and about one-third inhibited both flaming and smoldering. Differences were found between the actions of the powders and of similar retardants used in other forms and conditions. An appendix is included reporting the effects of alkali metal halides on the pyrolysis of cellulose. Implications of the results to the inhibitors are discussed.     

Red phosphorus–controlled decomposition for fire retardant PA 66

The thermal degradation and the combustion behavior of glass fiber–reinforced PA 66 materials containing red phosphorus were investigated. Thermogravimetry (TG), TG coupled with FTIR, and TG coupled with mass spectroscopy were used to investigate the thermal decomposition. The flame retardant red phosphorus was investigated with respect to the decomposition kinetics and the release of volatile products. The combustion behavior was characterized using a cone calorimeter. Fire risks and fire hazards were monitored versus external heat fluxes between 30 and 75 kW/m². Red phosphorus acts in the solid phase and its efficiency depends on the external heat flux. The use of red phosphorus results in an increased amount of residue and in a corresponding decrease in total heat release. The decrease of the mass loss rate peak results in a corresponding decrease of the peak heat release. With increasing external heat flux applied the first effect on the total heat release decreases linearly, whereas the second effect on the peak heat release expands linearly. The investigation provides insight into the mechanisms of how the fire retardant PA 66 is achieved by red phosphorus controlling the degradation kinetics. Taking into account that a decrease of the volatile products also leads to a decrease of heat production in the flame zone and that the char acts as heat transfer barrier, a reduced pyrolysis temperature is suggested as a further feedback effect. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2060–2071, 2002     

Heat propagation in thermally conductive polymers of PA6 and hexagonal boron nitride

Thermally conductive polymers offer new possibilities for the heat dissipation in electric and electronic components, for example, by a three‐dimensional shaping of the heat sinks. To face safety regulations, improved fire performance of those components is required. In contrast to unfilled polymers, those materials exhibit an entirely different thermal behavior. To investigate the flammability, a phosphorus flame retardant was incorporated into thermally conductive composites of polyamide 6 and hexagonal boron nitride. The flame retardant decreased the thermal conductivity only slightly. However, the burning behavior changed significantly, due to a different heat propagation, which was investigated using a thermographic camera. An optimum content of hexagonal boron nitride for a sufficient thermal conductivity and fire performance was found between 20 and 30 vol%. The improvement of the fire performance was due to a faster heat release out of the pyrolysis zone and an earlier decomposition of the flame retardant. For higher contents of hexagonal boron nitride, the heat was spread faster within the part, promoting an earlier ignition and increasing the decomposition rate of the flame retardant.     

活性炭催化热解纤维素协同制备酚类和合成气

苯酚和合成气均为工业生产中重要的基础化工原料。以自制的活性炭为催化剂,以纤维素为原料实现了催化热解液相产物中苯酚和气相产物中CO的同时富集。实验发现,生物质灰分中的钾、热解过程中催化剂/纤维素质量比和热解温度均对气液相产物的品质有着不同程度的影响。研究表明：钾的存在不利于热解产物品质的提高。钾虽然提高了生物油中苯酚的富集度,但降低了实际产率。而热解气中CO的浓度和产率均下降。对催化热解条件的研究表明热解温度450℃,催化剂比例为1∶1时可获得最佳的热解产物。此时,生物油中酚类物质占可检测有机物相对含量的62.31%,其中苯酚为45.37%,产率为1.78%（质量）。热解气中CO的浓度和产率分别为69.21%（体积）和 169.95 ml/g,热值为12.93 MJ/m³。     

基于离子液体再生的纤维素热解特性

利用离子液体1-丁基-3-甲基咪唑氯([Bmim]Cl)溶解PH-101微晶纤维素,通过不同的再生方法获得两种再生的纤维素,并利用XRD确定其结晶度,场发射扫描电镜(SEM)获得其形貌特征,热重(TG)分析表征其热稳定性.采用Py-GC/MS 对不同结晶度纤维素进行快速热解,并对热解挥发分进行在线分析,观察结晶度对纤维素热解特性的影响.研究表明左旋葡聚糖产率随结晶度降低而减少,而小分子产物随结晶度降低而增多.     

Synergistic effects of fumed silica on intumescent flame‐retardant polypropylene

The synergistic effects of fumed silica on the thermal and flame‐retardant properties of intumescent flame retardant (IFR) polypropylene based on the NP phosphorus‐nitrogen compound have been studied by Fourier transfer infrared (FTIR) spectroscopy, cone calorimeter test (CCT), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), limiting oxygen index (LOI), and UL‐94 tests. The LOI and UL‐94 data show that when ≤1 wt % fumed silica substituted for the IFR additive NP can increase 2 to 4% LOI values of the PP blends and keep the V‐0 rating. The data obtained from the CCT tests indicate the heat release rates (HRR) reduce by about 23% for the PP/NP sample with 0.5 wt % fumed silica, whereas the mass loss rates (MLR) and total heat release (THR) values are much lower than those of the PP/NP samples without fume silica. The TGA data demonstrate that a suitable amount of fumed silica can increase the thermal stability and charred residue of the PP/IFR/SiO₂ blends after 500°C. The morphological structures of charred residues observed by SEM give positive evidence that a suitable amount of fumed silica can promote the formation of compact intumescent charred layers and prevent the charred layers from cracking, which effectively protects the underlying polymer from burning. The dynamic FTIR spectra reveal that the synergistic flame‐retardant mechanism of a suitable amount of fumed silica with IFR additive is due to its physical process in the condensed phases. However, a high loading of fumed silica restricts the formation of charred layers with P? O? P and P? O? C complexes formed from burning of polymer materials and destroys the swelling behavior of intumescent charred layers, which deteriorates the flame retardant and thermal properties of the PP/IFR blends. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Thermal degradation and flammability of cellulosics

The course of pyrolysis, thermooxidation, flame combustion and glowing combustion has been observed with differently treated cellulose samples by means of thermoanalytical methods. The impregnation of cellulose materials by inorganic salts produces a less combustible material, less stable at relatively low temperatures, yet giving more of the solid residue resistant to pyrolysis and combustion processes. The more thermally stable cellulose derivatives, but with insufficient resistance to flame and particularly glowing combustion, have been obtained by cyanoethylation and grafting of acrylonitrile on to cellulose.     

The influence of temperature on the yields of compounds existing in bio-oils obtained from biomass samples via pyrolysis

The influence of temperature on the compounds existing in liquid products obtained from biomass samples via pyrolysis were examined in relation to the yield and composition of the product bio-oils. The product liquids were analysed by a gas chromatography mass spectrometry combined system. The bio-oils were composed of a range of cyclopentanone, methoxyphenol, acetic acid, methanol, acetone, furfural, phenol, formic acid, levoglucosan, guaiacol and their alkylated phenol derivatives. Thermal depolymerization and decomposition of biomass structural components, such as cellulose, hemicelluloses, lignin form liquids and gas products as well as a solid residue of charcoal. The structural components of the biomass samples mainly affect the pyrolytic degradation products. A reaction mechanism is proposed which describes a possible reaction route for the formation of the characteristic compounds found in the oils. The supercritical water extraction and liquefaction partial reactions also occur during the pyrolysis. Acetic acid is formed in the thermal decomposition of all three main components of biomass. In the pyrolysis reactions of biomass: water is formed by dehydration; acetic acid comes from the elimination of acetyl groups originally linked to the xylose unit; furfural is formed by dehydration of the xylose unit; formic acid proceeds from carboxylic groups of uronic acid; and methanol arises from methoxyl groups of uronic acid     

Characteristics of hemicellulose,cellulose and lignin pyrolysis

The pyrolysis characteristics of three main components (hemicellulose, cellulose and lignin) of biomass were investigated using, respectively, a thermogravimetric analyzer (TGA) with differential scanning calorimetry (DSC) detector and a pack bed. The releasing of main gas products from biomass pyrolysis in TGA was on-line measured using Fourier transform infrared (FTIR) spectroscopy. In thermal analysis, the pyrolysis of hemicellulose and cellulose occurred quickly, with the weight loss of hemicellulose mainly happened at 220–315 °C and that of cellulose at 315–400 °C. However, lignin was more difficult to decompose, as its weight loss happened in a wide temperature range (from 160 to 900 °C) and the generated solid residue was very high (∼40 wt.%). From the viewpoint of energy consumption in the course of pyrolysis, cellulose behaved differently from hemicellulose and lignin; the pyrolysis of the former was endothermic while that of the latter was exothermic. The main gas products from pyrolyzing the three components were similar, including CO₂, CO, CH₄ and some organics. The releasing behaviors of H₂ and the total gas yield were measured using Micro-GC when pyrolyzing the three components in a packed bed. It was observed that hemicellulose had higher CO₂ yield, cellulose generated higher CO yield, and lignin owned higher H₂ and CH₄ yield. A better understanding to the gas products releasing from biomass pyrolysis could be achieved based on this in-depth investigation on three main biomass components.     

硼-铝在膨胀型阻燃聚丙烯中的协同作用

通过热分析和锥形量热研究了硼-铝在膨胀型阻燃聚丙烯（PP）中的协同作用。热分析显示膨胀型阻燃剂KDIFR中,引入铝元素,由于催化脱水促进降解的作用,使剩碳率降低至14.6 %;引入硼元素,由于促进可燃小分子的生成,催化降解,也使剩碳率降低至5.9 %;硼铝共存时二者之间的协同作用可以降低在高温区的降解速率,提高剩碳率至19.7 %。PP/KDIFR的锥形量热表明,铝元素增大了热释放速率、释热总量、CO、CO₂和烟释放量;硼元素燃烧前期能减少热释放速率、释热总量、CO和CO₂释放量,有明显的抑烟作用,使阻燃效果略有提高。硼铝共存显著降低热释放速率、释热总量、CO、CO₂和烟释放量,大大提高了阻燃效果。     

Cellulose propionylpropionate as a side product in the reaction of cotton cellulose with propionyl chloride

In the reaction of cotton cellulose fiber with propionyl chloride in pyridine–DMF medium, the degree of substitution based on weight gain was much higher than that based on saponification. Gas–liquid chromatograms of the pyrolysis products of the samples showed an extra peak. This was identified as 3-pentanone, which arises from the pyrolysis of α-propionylpropionic acid, a substance which was proposed by Malm and co-workers as a possible side product. This conclusion was further confirmed by the infrared and NMR spectra of the liquid, collected fractionally on pyrolysis of the sample. Quantitative GLC showed that one òut of every four hydroxyl groups is substituted with an α-propionylpropionyl moiety, the rest with propionyl groups. A possible mechanism for the side reaction has been proposed.     

Thermal degradation studies of cellulose phosphates and cellulose thiophosphates

The thermal degradation of cellulose, cellulose phosphates, and cellulose thiophosphates was studied by differential thermal analysis, dynamic thermogravimetry, and derivative thermogravimetry from ambient temperature up to 750°C. Various thermodynamic parameters for different stages of thermal degradation of cellulose and its derivatives have been obtained following the methods of Broido, and Freeman and Carroll. Infrared spectra of thermally degraded samples were obtained. The data were analyzed in an effort to obtain more information concerning the flame-retardant mechanisms of cellulose phosphates and cellulose thiophosphates. Lower values of decomposition temperatures and activation energies of decomposition and higher char yields of cellulose phosphates as compared to cellulose lead to the conclusion that cellulose phosphorus esters are good flame retardants, and this property is retained even when these esters were subjected to ion exchange by Na⁺ and K⁺ ions. However, with the introduction of sulphur atoms, there was some decrease in this property.