Thermal decomposition characteristics of poly(ether imide) by TG/MS

Thermal degradation of poly(ether imide) (PEI) was studied by the combination of pyrolysis/gas chromatography/mass spectrometry (Py-GC/MS) and thermogravimetric analysis/mass spectrometry (TG/MS) techniques. The composition of evolved gases was determined by Py-GC/MS and the real-time formation curves were obtained through TG/MS. The thermal degradation mechanisms of PEI were resolved through TG/MS methods. The major pyrolysis mechanisms with the two-stage reaction regions were main chain random scission and carbonization. In the first stage pyrolysis, the decomposition of the hydrolyzed-imide, ether and isopropylene groups caused the evolution of CO₂ and phenol as major products accompanied by a chain transfer of carbonization to form partially carbonized solid residue. In the second stage pyrolysis, the decomposition of partially carbonized solid residue and the remaining imide group produced CO₂ as a major product along with benzene and small a amount of benzonitrile. Afterward, the chain transfer of carbonization dominated the decomposition of solid residue in higher temperatures to produce a high char yield. A kinetic model was proposed from the calculation of two flat regions in the activation energy curve. The theoretical pyrolysis curve from the proposed model was calculated and compared with the experimental curve, which were quite well matched.     

Comparison of thermal degradation characteristics of poly(arylene sulfone)s using thermogravimetric analysis/mass spectrometry

Thermal degradation of poly(arylene sulfone)s had been studied by the combination of thermogravimetric analysis/mass spectrometry (TG/MS) with pyrolysis/gas chromatography/mass spectrometry (Py‐GC/MS) techniques. Through these two methods, the pyrolysates from poly(ether sulfone) (PES) and polysulfone (PSF) were identified in 11 and 21 sets of evolution curves, respectively, from room temperature to 900 °C. Among these pyrolysates, 12 products from PES and 25 products from PSF were obtained. The major mechanism for both PES and PSF was one‐stage pyrolysis involving main chain random scission and carbonization with evolution of SO₂ and phenol as major products. Although the initial thermal stability of PES was lower than that of PSF, the formation of sulfide groups in the condensed phase from PES, through reduction of sulfone group by hydrogen radicals, increased the fire retardation behavior of PES. In PES, the ether and sulfone groups showed similar thermal stability. The thermal stability of functional groups in PSF were in the order of sulfone < ether < isopropylidene group. The scission of the ether group in PSF, with evolution of phenol as the major product, reached maximum evolution amount at the temperature of the maximum thermogravimetry loss of TG (T_max). The scission of isopropylidene groups at high temperature (>580 °C) evolved higher mass derivatives that lower the fire retardancy of PSF. By using a simplified kinetic model, PES showed maximum activation energy with a conversion ratio of 0.2–0.3, which implies a high fire retardant effect of sulfide formation in PES. A comparative study with the proposed model and experimental data showed the theoretical pyrolysis curves to be in agreement with the experimental curves for PES and PSF pyrolysis, respectively. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2387–2398, 2001     

Thermal degradation mechanisms of poly[diethyl 2-(methacryloyloxy)ethyl phosphate] by Py-GC/MS

Thermal decomposition properties of poly[diethyl 2-(methacryloyloxy)ethylphosphate] (PDMP) were studied using a stepwise pyrolysis-gas chromatography/mass spectrometry (stepwise Py-GC/MS) method. The individual mass chromatograms of the various pyrolysates were correlated with the pyrolysis temperature in order to elucidate the degradation mechanisms. The scission of PDMP in helium atmosphere showed the presence of two-stage pyrolysis regions. Triethylphosphate reached maximum evolution at the initial pyrolysis temperature, indicating that scisson of PDMP was initiated by the selective cleavage at the chain end and phosphate ester side chain as the dominant pyrolysis mechanism in the first stage. This local instability at chain end and phosphate ester side chain might explain the thermal instability of PDMP at lower pyrolysis temperatures. Acetaldehyde and water, as major products, were formed in significant amounts above 300 °C, indicating that random chain scission became the dominant pyrolysis mechanism in the second stage. Thus, the random chain scission reaction favored the occurrence of crosslinking and cyclization through chain transfer of carbonization catalyzed by phosphate ester along with the evolution of the arylene-containing and cyclic compounds. From mechanism analysis of PDMP pyrolysis, the introduction of a chemically bonded phosphorous-containing pendant group could promote its fire retardancy to form the high char yield of solid residue.     

The effect of steam on pyrolysis and char reactions behavior during rice straw gasification

Steam gasification of biomass can generate hydrogen-rich, medium heating value gas. We investigated pyrolysis and char reaction behavior during biomass gasification in detail to clarify the effect of steam presence. Rice straw was gasified in a laboratory scale, batch-type gasification reactor. Time-series data for the yields and compositions of gas, tar and char were examined under inert and steam atmosphere at the temperature range of 873-1173 K. Obtained experimental results were categorized into those of pyrolysis stage and char reaction stage. At the pyrolysis stage, low H₂, CO and aromatic tar yields were observed under steam atmosphere while total tar yield increased by steam. This result can be interpreted as the dominant, but incomplete steam reforming reactions of primary tar under steam atmosphere. During the char reaction stage, only H₂ and CO₂ were detected, which were originated from carbonization of char and char gasification with steam (C + H₂O→CO + H₂). It implies the catalytic effect of char on the water-gas shift reaction. Acceleration of char carbonization by steam was implied by faster hydrogen loss from solid residue.     

Study on pyrolysis of oil sludge with microalgae residue additive

The pyrolysis of oil sludge (OS) with microalgae residue (MR) additive was conducted with a TGA and a tube furnace. The pyrolysis process of OS with the MR additive can be divided into three stages: 1) water evaporation, 2) the release of light groups of hydrocarbon compounds, the cracking of heavy groups, and carbon decomposition, and 3) minerals decomposition. With the MR addition ratio increasing, the yield of oil and gas increased, and oil to gas ratio increased during OS pyrolysis. The MR addition improved the quality of pyrolysis oil and gas from OS pyrolysis. The proportion of light oil increased from 38 % with a 5 % MR addition ratio to 45 % with a 30 % addition ratio. Major components of pyrolysis gas included H₂, CO, CO₂, and C_xH_y. With the increase of the MR blending ratio, CO and CO₂ contents increased, while H₂ and C_xH_y contents decreased. Adding MR favoured the transformation of heavy hydrocarbons (C₆₊), resulting in a high content of light hydrocarbons. This work can help promote massive synergistic treatment of OS and microalgae biomass.

     

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.     

The pyrolysis behaviors of polyimide foam derived from 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride/4,4′‐oxydianiline

The thermal stability and pyrolysis behaviors of polyimide (PI) foam derived from 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA)/4,4′‐oxydianiline (4,4′‐ODA) in air and in nitrogen were studied. The decomposition products of PI foam were analyzed by thermogravimetry‐Fourier transform infrared spectroscopy (TG‐FTIR). Several integral and differential methods reported in the literatures were used in decomposition kinetics analysis of PI foam. The results indicated that the PI foam was easier to decompose in air than in nitrogen, with ～ 55% residue remaining in nitrogen versus zero in air at 800^oC. The main pyrolysis products were CO₂, CO, and H₂O in air and CO₂, CO, H₂O, and small organic molecules in nitrogen. The different dynamic methods gave similar results that the apparent activation energies, pre‐exponential factors, and reaction orders were higher in nitrogen than those in air. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Ultrapyrolysis of automobile shredder residue

A fast pyrolysis (Ultrapyrolysis) process was employed to convert automobile shredder residue (ASR) into chemical products. Experiments were conducted at atmospheric pressure and temperatures between 700 and 850°C with residence times between 0.3 and 1.4 seconds. Pyrolysis products included 59 to 68 mass% solid residue, 13 to 23 mass% pyrolysis gas (dry) and 4 to 12 mass% pyrolytic water from a feed containing 39 mass% organic matter and 2 mass% moisture. No measurable amounts of liquid pyrolysis oil were produced. The five most abundant pyrolysis gases, in vol%, were CO (18–29), CO₂ (20–23), CH₄ (17–22), C₂H₄ (20–22) and C₃H₆ (1–11), accounting for more than 90% of the total volume. The use of a higher organic content ASR feed (58 mass%) resulted in less solid residue and more pyrolysis gas. However, no significant changes were noted in the composition of the pyrolysis gas.     

Characteristics of the degradation and improvement of the thermal stability of poly(siloxane urethane) copolymers

This work investigates the characteristics of the thermal degradation of poly(ether urethane) (E‐PU) and poly(siloxane urethane) (S‐PU) copolymers by thermogravimetric analysis (TGA) and thermogravimetric analysis/Fourier transform infrared spectroscopy (TG–FTIR). The stage of initial degradation for E‐PU was demonstrated as a urethane‐B segment consisting of 4,4′‐diphenylmethane diisocyanate (MDI) and 1,4‐butanediol. Moreover, the urethane‐B segment in the copolymers had the lowest temperature of degradation (ca. 200°C). The degradation of E‐PU was determined by TGA and TG–FTIR analyses and had three stages including seven steps. Although the soft segment of S‐PU possessed the thermal stability of polydimethylsiloxane (PDMS), the unstable urethane‐B segment existed in S‐PU. Therefore, the initial degradation of S‐PU appeared around 210°C. The four stages of degradation of S‐PU involved eight steps, as revealed by TG–FTIR, which identified the main decomposition products: CO₂, tetrahydrofuran, and siloxane decomposition products. The imide group with high thermal stability was to replace the urethane‐B segment of S‐PU, which had the lowest thermal stability herein. The poly(siloxane urethane imide) (I‐PU) copolymer around 285°C exhibited a high initial temperature of degradation, and the initial degradation occurred at the urethane‐S segment consisting of MDI and PDMS. The degradation of I‐PU was similar to that of S‐PU and had four stages including six steps. Moreover, the degradation region of the imide group between 468 and 625°C was merged into the degradation stage of the siloxane decomposed products. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Thermal decomposition of poly(oxytetramethylene) glycol

Studies of thermal decomposition on poly(oxytetramethylene) glycol have been conducted by pyrolysis gas chromatography–mass spectrometry, infrared spectroscopy, and thermogravimetric anaylysis (TGA). The major volatile decomposition products are suggested to be a series of molecules made up by the repetition of oxytetramethylene with formyl and/or methyl ends. Absorption peaks, associated with formyl appear in infrared spectrum of a sample preheated at 523°K lower than the onset temperature obtained from the TGA curve. The isothermal TGA curves fit well to the Shimha rate equation for the random decomposition of polymers. The proper activation energies obtained from the thermally controlled and the isothermal TGA data are approximately 60–70 kJ mol⁻¹ and lower than those for other polymers in ordinary thermal decomposition. These data suggest that the major reaction in the thermal decomposition of poly(oxytetramethylene) glycol is an ether cleavage. Two pathways, a radical scission accompanied by β‐hydrogen transfer and a nonradical reaction through a four‐membered ring transition state, are proposed and discussed for the ether cleavage. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1538–1544, 2000     

Synthesis,optical, and thermal properties of polyimides containing flexible ether linkage

The goal of this article was to synthesize a series of flexible polyimides containing ether linkage in main chain and clarified the effect of this ether linkage on some physical properties such as optical and thermal decomposition. Also, different functional group effects such as carbonyl (? C?O), hexa‐fluoro‐isopropylidene [? C(CF₃)₂? ] and phenyl (? C₆H₅) on these physical properties were evaluated. The structural characterization of poly(ether imide)s was performed using Fourier transform infrared, ¹H‐nuclear magnetic resonance (NMR), and ¹³C‐NMR techniques. Optical band gap of polyimides was calculated in the range from 2.57 to 2.81 eV. Thermal characterization of poly(ether imide)s was carried out using thermogravimetry–differential thermal analysis and differential scanning calorimetry. Thermal stability of poly(ether imide)s was evaluated by initial decomposition temperature (T_on) and char. T_on value of polymers was determined in the range from 100 to 195 °C. In addition, glass transition temperatures of poly(ether imide)s were found between 144 and 148 °C. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46573.     

Time‐resolved measurements of pyrolysis and combustion products of PMMA

We studied transient chemical speciation during high‐temperature solid material pyrolysis and combustion in air. Our objective was to develop a database of chemical burn signatures. The material tested was the thermoplastic PMMA. Material samples were heated in an infrared furnace until they pyrolyzed, ignited, and combusted in air. Time‐resolved quantitative measurements of the exhaust species CO₂, O₂, hydrocarbons, and CO along with exhaust gas temperature were obtained. Two categories of experiments were conducted: (1) pyrolysis tests in which there was no combustion; (2) combustion tests with chemical reaction and heat release. During heating, the sample underwent numerous processes that appear as diagnostic sequences. In the pyrolysis tests, as the furnace temperature was raised, the CO and hydrocarbon (HC) signals underwent transition from one peak to two peaks. In the combustion tests, spontaneous ignition occurred at higher test temperatures as evidenced by an exothermic reaction reported by the thermocouples, leading to three‐peak CO and HC profiles. The measured O₂/CO₂ ratio of 1.3 ± 0.1 agreed with stoichiometric methyl‐methacrylate monomer decomposition. Calculations of the power output using two independent methods supported (1) that combustion was experimentally observed in the furnace, and (2) the accuracy of the combustion gas analysis. Copyright © 2012 John Wiley & Sons, Ltd.     

Thermal decomposition mechanisms of bis(2-fluoro-2,2-dinitroethyl) formal (FEFO) and bis(2-fluoro-2,2-dinitroethyl) difluoroformal (DFF) from simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS) measurements

The simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS) technique has been applied to measure the vapor pressures and evaluate the thermal decomposition chemistry of two energetic liquids, bis(2-fluoro-2,2-dinitroethyl)formal (FEFO) and bis(2-fluoro-2,2-dinitroethyl)difluoroformal (DFF). The resulting heat of vaporization (ΔH_vap) and vapor pressure at 25°C are 20.3 ± 0.2 kcal/mol and 0.4 ± 0.1 millitorr for FEFO, and 17.3 ± 0.2 kcal/mol and 5.1 ± 1.1 millitorr for DFF. The thermal decomposition of FEFO indicates there are six major pyrolysis pathways. The results suggest that FEFO initially decomposes at 150°C by rearrangement of the nitro group ( NO₂) to the nitrite group ( O NO), followed by loss of NO. Some NO₂ is also formed at 170°C. Between 200°C–300°C, further pyrolysis occurs. In one pathway, the FEFO backbone remains intact and a high molecular-weight product is formed. The other three pathways involve scission of the FEFO backbone; one yielding CO₂ (possibly N₂O), one yielding CH₂O and CO, and one yielding C₃H₂NOF. Differences in the thermal decomposition behaviors in the liquid and gas phases are observed. In the thermal decomposition of DFF, the formal fluorine atoms stabilize the backbone structure. Numerous minor thermal decomposition products are also reported.     

Study on characterization of pyrolysis and hydrolysis products of poly(vinyl chloride) waste

Poly(vinyl chloride) PVC pyrolysis and hydrolysis are conducted in a fixed bed reactor and in an autoclave, respectively, under different operating conditions such as the temperature and time. The product distribution is studied. For the PVC pyrolysis process, the main gas product is HCl (55% at 340°C), there is 9% hydrocarbon gas (C₁–C₅), the liquid product fraction is about 5% (at 340°C), and the solid residue fraction is about 31% (at 340°C). For the hydrolysis process, the main gas product is HCl (55.8% at 240°C) and the solid residue is about 49.6% (at 240°C). The pyrolysis liquid product is analyzed by using gas chromatography with magic‐angle spinning. Aromatic hydrocarbons are the main class (90%), of which the major part is benzene (33%). The residue produced through pyrolysis and hydrolysis is investigated by high‐resolution solid‐state ¹³C‐NMR. These details revealed by the high‐field NMR spectra provide importmant information about the chemical changes in the PVC pyrolysis and hydrolysis process. The mechanism of PVC hydrolysis dechlorination is also discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3252–3259, 2003     

Modification of the pyrolysis/carbonization of PPTA polymer by intermediate isothermal treatments

Pyrolysis/carbonization of poly (p-phenylene terephtalamide) (PPTA) was investigated, studying the possibility of modifying the pyrolysis/carbonization behavior and hence the carbon yield by introducing intermediate isothermal treatments. Thermogravimetric analysis (TG) was used to establish the main degradation steps of the material. It showed that the yield of solid residue at 950 °C increases by more than 15 wt.% by introducing an isothermal step at 500 °C for at least 50 min. Intermediate decomposition products at different temperatures/times of PPTA decomposition were characterized by X-ray diffraction (XRD), elemental microanalysis and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). XRD results showed that carbonization progresses during the isothermal step, so that the material is degraded loosing its crystallinity in a continuous way. DRIFTS spectra showed that PPTA undergoes a rupture of polymeric chains during the isothermal stage enhancing aryl nitrile formation. This favors crosslinking reactions that take place with increasing temperature, yielding a solid residue with a higher nitrogen content and higher char yield.     

Synthesis and characterization of new cardo poly(ether imide)s derived from 9,9‐bis [4‐(4‐aminophenoxy)phenyl]xanthene

A series of new cardo poly(ether imide)s bearing flexible ether and bulky xanthene pendant groups was prepared from 9,9‐bis[4‐(4‐aminophenoxy)phenyl]xanthene with six commercially available aromatic tetracarboxylic dianhydrides in N,N‐dimethylacetamide (DMAc) via the poly(amic acid) precursors and subsequent thermal or chemical imidization. The intermediate poly(amic acid)s had inherent viscosities between 0.83 and 1.28 dL/g, could be cast from DMAc solutions and thermally converted into transparent, flexible, and tough poly(ether imide) films which were further characterized by X‐ray and mechanical analysis. All of the poly(ether imide)s were amorphous and their films exhibited tensile strengths of 89–108 MPa, elongations at break of 7–9%, and initial moduli of 2.12–2.65 GPa. Three poly(ether imide)s derived from 4,4′‐oxydiphthalic anhydride, 4,4′‐sulfonyldiphthalic anhydride, and 2,2‐bis(3,4‐dicarboxyphenyl))hexafluoropropane anhydride, respectively, exhibited excellent solubility in various solvents such as DMAc, N,N‐dimethylformamide, N‐methyl‐2‐pyrrolidinone, pyridine, and even in tetrahydrofuran at room temperature. The resulting poly(ether imide)s with glass transition temperatures between 286 and 335°C had initial decomposition temperatures above 500°C, 10% weight loss temperatures ranging from 551 to 575°C in nitrogen and 547 to 570°C in air, and char yields of 53–64% at 800°C in nitrogen. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Microstructures and electrothermal characterization of aromatic poly(azomethine ether)-derived carbon films

We report the microstructural evolution and electrothermal properties of aromatic poly(azomethine ether) (PAME)-derived carbon films, which were fabricated by a facile spin-coating and following carbonization at different temperatures of 300–1,000°C. For the purpose, poly[3-(4-nitrilophenoxy)phenylenenitrilomethine-1,3-phenylenemethine] (mPAME) with a high residue of ~56.4 wt% after carbonization at 1,000°C was synthesized for a polymeric precursor for carbon films. The X-ray photoelectron spectroscopy, Raman spectroscopy, and X-ray diffraction analyses revealed that the molecular structures of mPAME films changed into an intrinsically nitrogen-doped graphitic structure, dominantly at the carbonization temperatures of 800–100°C. The electrical conductivity increased considerably from ~10⁻⁷ S/cm for mPAME-derived films fabricated at 300–700°C to ~10⁰ S/cm for the film carbonized at 800°C to ~10¹ S/cm for the films carbonized at 900–1,000°C. Accordingly, mPAME-derived carbon films, which were carbonized at 900–1,000°C, exhibited excellent electrothermal performance, such as rapid temperature responsiveness, high maximum temperatures, and high electric power efficiency to relatively low applied voltages of 5–13 V.     

Microporous carbon membranes from sulfonated poly(phthalazinone ether sulfone ketone): Preparation,characterization, and gas permeation

Microporous carbon membranes (MCM) were prepared from sulfonated poly(phthalazinone ether sulfone ketone) (SPPESK) through stabilization and pyrolysis processes. The effects of sulfonation degree (SD) of SPPESK and the stabilization temperature on the structure and gas permeation of MCM were investigated. The thermal decomposition behavior of SPPESK was studied by thermogravimetric analysis‐mass spectrometry. The evolution of functional groups on membrane surface was detected by Fourier transform infrared spectroscopy during heat treatment. The resultant MCM was characterized by X‐ray diffraction, Raman spectroscopy, nitrogen adsorption technique and pure gas permeation test (including the gases of H₂, CO₂, O₂, and N₂), respectively. The results have shown that the removal of sulfonic acid groups in SPPESK leads to a weight loss stage in the temperature range of 250–450°C. The surface area, maximum pore volume, and gas permeability of MCM increase with the SD increasing from 59 to 75%, together with the reduction of selectivity. Similarly, the gas permeability of MCM also increases with elevating the stabilization temperature from 350 to 400°C at the loss of selectivity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The pyrolysis behaviors of ternary copolyimide derived from aromatic dianhydride and aromatic diisocyanates

A polyimide (PI) based on benzophenone‐3,3′,4,4′‐tetracarboxylic acid dianhydride, toluene diisocyanate (TDI), and 4,4′‐methylenebis (phenyl isocyanate) (MDI) has been synthesized via a one‐step polycondensation procedure. The resulting PI possessed excellent thermal stability with the glass transition temperature (T_g) 316°C, the 5% weight loss temperature (T_5%) in air and nitrogen 440.4°C and 448.0°C, respectively. The pyrolysis behaviors were investigated with dynamic thermogravimetric analysis (TGA), TGA coupled with Fourier transform infrared spectrometry (TGA–FTIR) and TGA coupled with mass spectrometry (TGA–MS) under air atmosphere. The results of TGA–FTIR and TGA–MS indicated that the main decomposition products were carbon dioxide (CO₂), carbonic oxide (CO), water (H₂O), ammonia (NH₃), nitric oxide (NO), hydrogen cyanide (HCN), benzene (C₆H₆), and compounds containing NH₂, C?N, N?C?O or phenyl groups. The activation energy (E_a) of the solid‐state process was estimated using Ozawa–Flynn–Wall (OFW) method which resulted to be 143.8 and 87.8 kJ/mol for the first and second stage. The pre‐exponential factor (A) and empirical order of decomposition (n) were determined by Friedman method. The activation energies of different mechanism models were calculated from Coats–Redfern method. Compared with the activation energy values obtained from the OFW method, the actual reaction followed a random nucleation mechanism with the integral form g(α) = ?ln(1 ? α). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40163.