Thermal decomposition behavior of oligo(4‐hydroxyquinoline)

In this study, the kinetic parameters and reaction mechanism of decomposition process of oligo(4‐hydroxyquinoline) synthesized by oxidative polymerization were investigated by thermogravimetric analysis (TGA) at different heating rates. TGA‐derivative thermogravimetric analysis curves showed that the thermal decomposition occurred in two stages. The methods based on multiple heating rates such as Kissinger, Kim–Park, Tang, Flynn–Wall–Ozawa method (FWO), Friedman, and Kissinger–Akahira–Sunose (KAS) were used to calculate the kinetic parameters related to each decomposition stage of oligo(4‐hydroxyquinoline). The activation energies obtained by Kissinger, Kim–Park, Tang, KAS, FWO, and Friedman methods were found to be 153.80, 153.89, 153.06, 152.62, 151.25, and 157.14 kJ mol^?1 for the dehydration stage, 124.7, 124.71, 126.14, 123.75, 126.19, and 124.05 kJ mol^?1 for the thermal decomposition stage, respectively, in the conversion range studied. The decomposition mechanism and pre‐exponential factor of each decomposition stage were also determined using Coats–Redfern, van Krevelen, Horowitz–Metzger methods, and master plots. The analysis of the master plots and methods based on single heating rate showed that the mechanisms of dehydration and decomposition stage of oligo(4‐hydroxyquinoline) were best described by kinetic equations of A_n mechanism (nucleation and growth, n = 1) and D_n mechanism (dimensional diffusion, n = 6), respectively. POLYM. ENG. SCI., 54:992–1002, 2014. © 2013 Society of Plastics Engineers     

Synthesis,characterization, and thermal degradation kinetics of poly(decamethylene 2‐oxoglutarate)

Poly(decamethylene 2‐oxoglutarate) [poly (DMOG)] was synthesized by a melt polycondensation reaction. The structure of poly(DMOG) was confirmed by means of Fourier transform infrared, ¹H‐NMR, and ¹³C NMR spectroscopies. The molecular weight distribution values of poly(DMOG) were determined with size exclusion chromatography. The number‐average molecular weight, weight‐average molecular weight, and polydispersity index values of poly(DMOG) were found to be 13,200, 19,000, and 1.439, respectively. Also, characterization was made by thermogravimetry (TG)–dynamic thermal analysis. The kinetics of the thermal degradation of poly (DMOG) was investigated by thermogravimetric analysis at different heating rates. TG curves showed that the thermal decomposition of poly(DMOG) occurred in one stage. The apparent activation energies of thermal decomposition for poly(DMOG), as determined by the Tang method, the Flynn–Wall–Ozawa method, the Kissinger–Akahira–Sunose method, and the Coats–Redfern method were 122.5, 126.8, 121.4, and 122.9 kJ/mol, respectively. The mechanism function and pre‐exponential factor were also determined by the master plots method. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Schiff base‐substituted polyphenol: synthesis,characterisation and non‐isothermal degradation kinetics

BACKGROUND: Polymers of phenols and aromatic amines have emerged as new materials in fields such as superconductors, coatings, laminates, photoresists and high‐temperature environments. The stability, kinetics and associated pollution of the thermal decomposition of oligophenols are of interest for the aforementioned fields. RESULTS: A new Schiff base polymer, derived from N,N′‐bis(2‐hydroxy‐3‐methoxyphenylmethylidene)‐2,6‐pyridinediamine, was prepared by oxidative polycondensation. Characterisations using Fourier transform infrared, UV‐visible, ¹H NMR and ¹³C NMR spectroscopy, thermogravimetric/differential thermal analysis, gel permeation chromatography, cyclic voltammetry and conductivity measurements were performed. The number‐average (M_n) and weight‐average molecular weight (M_w) and dispersity (D = M_w/M_n) of the polymer were found to be 61 000 and 94 200 g mol^?1 and 1.54, respectively. Apparent activation energies of the thermal decomposition of the polymer were determined using the Tang, Flynn–Wall–Ozawa, Kissinger–Akahira–Sunose and Coats–Redfern methods. The most likely decomposition process was a D_n deceleration type in terms of the Coats–Redfern and master plot results. CONCLUSION: The mechanism of the degradation process can be understood through the use of kinetic parameters obtained from various non‐isothermal methods. Copyright © 2009 Society of Chemical Industry     

Thermal decomposition kinetics of poly(nButMA‐b‐St) diblock copolymer synthesized by ATRP

The reaction mechanism of decomposition process and the kinetic parameters of the poly(n‐butyl methacrylate‐b‐styrene), poly(nButMA‐b‐St), diblock copolymer synthesized by atom transfer radical polymerization (ATRP) were investigated by thermogravimetric analysis (TGA) at different heating rates. TGA curves showed that the thermal decomposition occurred in one stage. The apparent activation energies of thermal decomposition for copolymer, as determined by the Kissinger's, Flynn–Wall–Ozawa and Tang methods, which does not require knowledge of the reaction mechanism (RM), were 112.52, 116.54, and 113.41 kJ/mol, respectively. The experimental results were compared with master plots, in the range of the Doyle approximation. Analysis of experimental results suggests that in the conversion range studied, 3–18%, the actual RM is an A₂ sigmoidal type. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Non-isothermal degradation kinetics of poly (2,2′-dihydroxybiphenyl)

Catalytic oxidative polymerization of 2,2′-dihydroxybiphenyl (DHBP) was performed by using Schiff base polymer-Cu (II) complex and hydrogen peroxide as catalyst and oxidant, respectively. According to size exclusion chromatography (SEC) analysis, the number-average molecular weight (M _n), weight-average molecular weight (M _w) and polydispersity index (PDI) values of poly (2,2′-dihydroxybiphenyl) (PDHBP) were found to be 37,500, 90,000 g mol⁻¹ and 2.4, respectively. The thermal degradation kinetics was investigated by thermogravimetric analysis in dynamic nitrogen atmosphere at four different heating rates: 5, 10, 15 and 20 °C min⁻¹. The derivative thermogravimetry curves of PDHBP showed that its thermal degradation process had one weight-loss step. The apparent activation energies of thermal decomposition for PDHBP as determined by Tang, Flynn–Wall–Ozawa (FWO), Kissenger–Akahira–Sunose (KAS), Coats–Redfern (CR) and Invariant kinetic parameter (IKP) methods were 109.1, 109.0, 110.0, 108.4 and 109.8 kJ mol⁻¹, respectively. The mechanism function and pre-exponential factor were determined by master plots and Criado–Malek–Ortega method. The most likely decomposition process was a D _n Deceleration type in terms of the CR, master plots and Criado–Malek–Ortega results.     

Thermal Behavior and Thermolysis Kinetics of the Explosive Trans‐1,4,5,8‐Tetranitro‐1,4,5,8‐Tetraazadecalin (TNAD)

Trans‐1,4,5,8‐Tetranitro‐1,4,5,8‐Tetraazadecalin (TNAD), a cyclic nitroamine, has been studied with regard to the kinetics and mechanism of thermal decomposition, using thermogravimetry (TG), IR spectroscopy, and pressure differential scanning calorimetry (PDSC). The IR spectra of TNAD have also been recorded, and the kinetics of thermolysis has been followed by non‐isothermal TG. The activation energy of the solid‐state process was determined by using the Flynn‐Wall‐Ozawa method. Compared with the activation energy obtained from the Ozawa method, the reaction mechanism of the exothermic process of TNAD was classified by the Coats‐Redfern method as a nucleation and nuclear growth (Avrami equation 1) chemical reaction (α=0.30–0.60) and a 2D diffusion (Valensi equation) chemical reaction (α=0.60–0.90). E_a and ln A were established to be 330.14 kJ mol⁻¹ and 29.93 (α=0.30–0.60) or 250.30 kJ mol⁻¹ and 21.62 (α=0.60–0.90).     

Investigation of the Thermal Decomposition Kinetics of Chalcopyrite Ore Concentrate usıng Thermogravimetric Data

The kinetics of the thermal decomposition of chalcopyrite concentrate was investigated by means of thermal analysis techniques, Thermogravimetry/Derivative thermogravimetry (TG/DTG) under ambient air conditions in the temperature range of 0–900°C with heating rates of 2, 5, 10, 15, and 20°C min^?1. TG and DTG measurements showed that the thermal behavior of chalcopyrite concentrate shows a two-step decomposition. The decomposition mechanism was confirmed using X-ray diffraction (XRD), Scanning Electron Microscope (SEM)/energy-dispersive X-ray spectroscopy (EDS), and Fourier transform infrared spectroscopy (FTIR) analyses. Kinetic parameters were determined from the TG and DTG curves for steps I and II by using two model-free (isoconversional) methods—Flyn–Wall–Ozowa (FWO) and Kissinger–Akahira–Sunose (KAS). The kinetic parameters consisting of E_a, A, and g(α) models of the materials were determined. The average activation energies (E_a) obtained from both models for the decomposition of chalcopyrite concentrate were 72.55 and 300.77 kJ mol^?1 and the pre-exponential factors (A) were 15.07 and 29.39 for steps I and II, respectively. The most probable kinetic model for the decomposition of chalcopyrite concentrate is an first-order mechanism, i.e., chemical reaction [g(α) = (?ln(1?α))], and an Avrami–Eroeyev equation mechanism, i.e., nucleation and growth for n = 2 [g(α) = (?ln(1?α)^1/2)], for steps I and II, respectively.     

Synthesis,characterization, and thermal degradation kinetics of the copolymer poly(4‐methoxybenzyl methacrylate‐co‐isobornyl methacrylate)

A copolymer of 4‐methoxybenzyl methacrylate and isobornyl methacrylate was synthesized by atom transfer radical polymerization. The structure of poly(4‐methoxybenzyl methacrylate‐co‐isobornyl methacrylate) was confirmed by means of Fourier transform infrared, ¹H‐NMR, and ¹³C‐NMR techniques. The molecular weight distribution values of the copolymer were determined with gel permeation chromatography. The number‐average molecular weight and polydispersity index values of poly(4‐methoxybenzyl methacrylate‐co‐isobornyl methacrylate) were found to be 12,500 and 1.5, respectively. The kinetics of the thermal degradation of the copolymer was investigated with thermogravimetric analysis at different heating rates. The activation energy values obtained with the Kissinger, Flynn–Wall–Ozawa, and Tang methods were determined to be 166.38, 167.54, and 167.47 kJ/mol, respectively. Different integral and differential methods were used, and the results were compared with these values. Doyle approximation was also used for comparing the experimental results to master plots. An analysis of the experimental results suggested that the reaction mechanism was an R₁ deceleration type in the conversion range studied. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Non‐Isothermal Kinetic Study of the Thermal Decomposition of Melamine 3‐Nitro‐1,2,4‐triazol‐5‐one Salt

Study on thermal behavior of 3‐nitro‐1,2,4‐triazol‐5‐one (NTO) salts was required to obtain important data for application purposes. These compounds have been shown to be useful intermediates for gun propellant ingredients, high energetic ballistic modifiers for solid propellants and other potential applications. In this paper, thermal decomposition and non‐isothermal kinetics of melamine 3‐nitro‐1,2,4‐triazol‐5‐one salt (MNTO) were studied under non‐isothermal conditions by DSC and TG methods. The kinetic parameters were obtained from analysis of the DSC and TG curves by Kissinger and Ozawa methods. The critical temperature of thermal explosion (T_b) was 574 K. The results show that MNTO is thermally more stable than NTO when compared in terms of the critical temperature of thermal explosion. Finally, the values of ΔS^#, ΔH^#, and ΔG^# of its decomposition reaction were calculated.     

Thermal Behavior and Specific Heat Capacity of 1‐t‐Butyl‐3,3‐dinitroazetidinium Perchlorate

1‐t‐Butyl‐3,3‐dinitroazetidinium perchlorate (TDNAZ ⋅ HClO₄) was synthesized, DSC and TG/DTG methods were used to study the thermal behavior of TDNAZ⋅HClO₄ under a non–isothermal condition. The intense exothermic decomposition process of DSC curves were analyzed to obtain its kinetic parameters. Continuous specific heat capacity (C _p) mode of micro–calorimeter was used to determine its C _p, its specific molar heat capacity (C _{p ,m}) was 365.70 J mol⁻¹ K⁻¹ at 298.15 K. The self‐accelerating decomposition temperature (T _SADT), thermal ignition temperature (T _TIT), and critical temperature of thermal explosion (T _b) were obtained to evaluate its thermal stability and safety. The above results of TDNAZ ⋅ HClO₄ were compared with those of 3,3‐dinitroazetidinium perchlorate (DNAZ ⋅ HClO₄), and the effect of tert‐butyl group on them was discussed.     

ZnS as fire retardant in plasticised PVC

The flame retardant effect of zinc sulphide (ZnS) in plasticised poly(vinyl chloride) (PVC‐P) materials was investigated. PVC‐P containing different combinations of additives such as 5% ZnS, 5% of antimony oxide (Sb₂O₃) and 5% of mixtures based on Sb₂O₃ and ZnS were compared. The thermal degradation and the combustion behaviour were studied using thermogravimetry (TG), coupled with FTIR (TG–FTIR) or with mass spectroscopy (TG–MS), and a cone calorimeter, respectively. A detailed and unambiguous understanding of the decomposition and release of the pyrolysis products was obtained using both TG–MS and TG–FTIR. The influence of ZnS, Sb₂O₃ and the corresponding mixtures on the thermal decomposition of PVC‐P was demonstrated. Synergism was observed for the combination of the two additives. The combustion behaviour (time to ignition, heat release, smoke production, mass loss, CO production) was monitored versus external heat fluxes between 30 and 75 kW m^?2 with the cone calorimeter. Adding 5% of ZnS has no significant influence on the fire behaviour of PVC‐P materials beyond a dilution effect, whereas Sb₂O₃ works as an effective fire retardant. Synergism of ZnS and Sb₂O₃ allows the possibility of replacing half of Sb₂O₃ by ZnS to reach equivalent fire retardancy. © 2002 Society of Chemical Industry     

Thermal decomposition of cellulose ethers

The thermostability and thermal decomposition kinetics of methyl cellulose (MC), ethyl cellulose (EC), carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), and hydroxypropyl–methyl cellulose (HPMC) were characterized in nitrogen and air by thermogravimetry (TG). Various methods of kinetic analysis were compared in case of thermal degradation of the five cellulose ethers. The initial decomposition temperature (T_d), temperature at the maximum decomposition rate (T_dm), activation energy (E), decomposition reaction order (n), and pre-exponential factor (Z) of the five cellulose ethers were evaluated from common TG curves and high-resolution TG curves obtained experimentally. The decomposition reactions in nitrogen were found to be of first order for MC, EC, and HPMC with the average E and ln Z values of 135 kJ/mol and 25 min⁻¹, although there were slight differences depending on the analytical methods used. The thermostability of cellulose ethers in air is substantially lower than in nitrogen, and the decomposition mechanism is more complex. The respective average E, n, ln Z values for HEC in nitrogen/air were found to be 105/50 kJ/mol, 2.7/0.5, and 22/8.3 min⁻¹, from constant heating rate TG method. The respective average E, n, and ln Z values for three cellulose ethers (EC/MC/HPMC) in air are 123/144/147 kJ/mol, 2.0/1.8/2.2, 24/28/28 min⁻¹ by using high-resolution TG technique. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2927–2936, 1999     

Preparation,Crystal Structure,Thermal Decomposition,and Explosive Properties of [Cd(en)(N3)2]n

A new multi‐ligand coordination polymer of cadmium(II) ethylenediamine azide, [Cd(en)(N₃)₂]_n (en=ethylenediamine), was synthesized and characterized by using elemental analysis and FT‐IR spectrum. Its crystal structure was determined by means of X‐ray single crystal diffraction. The obtained results show that this crystal belongs to monoclinic, P2₁/n space group, a=0.6548(1) nm, b=1.0170(2) nm, c=1.2246(2) nm, β=90.23(1)°, V=0.8156(2) nm³, D_c=2.090 g⋅cm⁻³, Z=4, R₁=0.024, wR₂ (I>2σ(I))=0.0416 and S=0.998. The Cd(II) ion is six‐coordinated with four azido ligands by μ‐1, 1 azido bridges, and two ethylenediamine molecules which serve as bidentate ligands through the nitrogen atoms. The thermal decomposition mechanism of the title complex was studied by using differential scanning calorimetry (DSC) and thermogravimetry‐differential thermogravimetry (TG–DTG) techniques. Under nitrogen atmosphere with a heating rate of 10 K⋅min⁻¹, the thermal decomposition of the complex contains two main successive exothermic processes between 519 and 701 K in the DSC curve, and the final decomposed residue at 725 K is Cd. The non‐isothermal kinetics parameters were calculated by using the Kissinger's method, Ozawa–Doyle's method, pervasive integration method, and differential method, respectively. The sensitivity properties of [Cd(en)(N₃)₂]_n were also determined with standard methods.     

Synthesis,Thermal Decomposition,and Properties of [Mn(CHZ)3][C(NO2)3]2

A new coordination compound, [Mn(CHZ)₃][C(NO₂)₃]₂, was synthesized and characterized by elemental analysis, IR and UV spectra, and its crystal structure was determined by X‐ray single crystal diffraction. The crystal belongs to the triclinic system and space group with a=0.88737(18) nm, b=1.1804(2) nm, c=1.1936(2) nm, β=83.73(3)°, V=1.1121(4) nm³, Z=2, D_c=1.867 g cm⁻³. Every Mn(II) ion is six‐coordinated to three CHZ molecules through three carbonyl oxygen atoms and three terminal nitrogen atoms to form a distorted octahedral structure. Mn(II) ions, carbohydrazide ligand molecules, and trinitromethanide anions are jointed to a complicated three‐dimensional netted structure through coordination bonds, electrostatic forces, and extensive hydrogen bonds. The thermal decomposition character and mechanism was studied by DSC, TG‐DTG, and FTIR techniques. The non‐isothermal kinetics has also been studied on the exothermic decomposition by using Kissinger's method and Ozawa–Doyle's method. In addition, the impact, friction, and flame sensitivity data were determined. All properties data observed show that the title complex has high energy, good thermal stability, and moderately friction sensitivity.     

Thermal Decomposition,Kinetics and Compatibility Studies of Poly(3‐difluoroaminomethyl‐3‐methyloxetane) (PDFAMO)

The thermal decomposition of poly(3‐difluoroaminomethyl‐3‐methyloxetane) (PDFAMO) with an average molecular weight of about 6000 was investigated using thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). The kinetics of thermolysis were studied by a model‐free method. The thermal decomposition of PDFAMO occurred in a two‐stage process. The first stage was mainly due to elimination of HF and had an activation energy of 110–120 kJ mol⁻¹. The second stage was due to degradation of the polymer chain. The Fourier transform infrared (FTIR) spectra of the degradation residues showed that the difluoroamino groups decomposed in a two‐step HF loss at different temperatures. The remaining monofluoroimino groups produced by the incomplete elimination of HF were responsible for the two‐stage thermolysis process. The compatibility of PDFAMO with some energetic components and inert materials used in polymer‐bonded explosives (PBXs) and solid propellants was studied by DSC. It was concluded that the binary systems of PDFAMO with cyclotrimethylenetrinitramine (RDX), 2,4,6‐trinitrotoluene (TNT), 2,4‐dinitroanisole (DNAN), pentaerythritol tetranitrate (PETN), ammonium perchlorate (AP), aluminum powder (Al), aluminum oxide (Al₂O₃) and 1,3‐diethyl‐1,3‐diphenyl urea (C₁) were compatible, whereas the systems of PDFAMO with lead carbonate (PbCO₃) and 2‐nitrodiphenylamine (NDPA) were slightly sensitized. The systems with cyclotetramethylenetetranitroamine (HMX), hexanitrohexaazaisowurtzitane (CL‐20), 3‐nitro‐1,2,4‐triazol‐5‐one (NTO), ammonium nitrate (AN), magnesium powder (Mg), boron powder (B), carbon black (C. B.), diphenylamine (DPA), and p‐nitro‐N‐methylamine (PNMA) were incompatible. The results of compatibility studies fully supported the suggested thermal decomposition mechanism of PDFAMO.     

Synthesis and characterization of a random terpolymer of L‐lactide, ϵ‐caprolactone and glycolide

A random terpolymer of L ‐lactide (LL), ?‐caprolactone (CL) and glycolide (G) has been synthesized in bulk at 130 °C using stannous octoate as the coordination–insertion initiator. The terpolymer, poly(LL‐ran‐CL‐ran‐G), has been characterized by a combination of analytical techniques: GPC, ¹H NMR, ¹³C NMR, DSC and TG. Molecular weight characterization by GPC shows a unimodal molecular weight distribution with values of M _n = 1.01 × 10⁵ g mol^?1 and M _w / M _n = 2.17. Compositional and microstructural analysis by ¹H NMR and ¹³C NMR, respectively, reveal a terpolymer composition of LL:CL:G = 74:15:11 (mol%) with a chain microstructure consistent with random monomer sequencing. This latter view is supported by the terpolymer temperature transitions (T_g and T_m) from DSC and the thermal decomposition profile from TG. The results and, in particular, the conclusion that it is a random rather than a statistical terpolymer are discussed in the light of current theories regarding the mechanism of this type of polymerization. © 2001 Society of Chemical Industry     

Synthesis,characterization, and kinetic of thermal degradation of oligo‐2‐[(4‐bromophenylimino)methyl]phenol and oligomer‐metal complexes

Oligo‐2‐[(4‐bromophenylimino)methyl]phenol (OBPIMP) was synthesized from the oxidative polycondensation reaction of 2‐[(4‐bromophenylimino)methyl]phenol (BPIMP) with air and NaOCl oxidants in an aqueous alkaline medium between 50 and 90°C. The yield of OBPIMP was found to be 67 and 88% for air and NaOCl oxidants, respectively. Their structures were confirmed by elemental and spectral such as IR, ultraviolet–visible spectrophotometer (UV–vis), ¹H‐NMR, and ¹³C‐NMR analyses. The characterization was made by TG‐DTA, size exclusion chromatography, and solubility tests. The resulting complexes were characterized by electronic and IR spectral measurements, elemental analysis, AAS, and thermal studies. According to TG analyses, the weight losses of OBPIMP, and oligomer‐metal complexes with Co⁺², Ni⁺², and Cu⁺² ions were found to be 93.04%, 59.80%, 74.23%, and 59.30%, respectively, at 1000°C. Kinetic and thermodynamic parameters of these compounds investigated by Coats‐Redfern, MacCallum‐Tanner, and van Krevelen methods. The values of the apparent activation energies of thermal decomposition (E_a), the reaction order (n), preexponential factor (A), the entropy change (ΔS*), enthalpy change (ΔH*), and free energy change (ΔG*) obtained by earlier‐mentioned methods were all good in agreement with each other. It was found that the thermal stabilities of the complexes follow the order Cu(II) > Co(II) > Ni(II). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Kinetics of thermal degradation studies of some new terpolymers derived from 2,4‐dihydroxypropiophenone,oxamide, and formaldehyde

The terpolymers (2,4‐DHPOF) have been synthesized by the condensation of 2,4‐dihydroxypropiophenone with oxamide and formaldehyde in the presence of 2M HCl as catalyst with varying proportions of reactants. Terpolymer composition has been determined on the basis of their elemental analysis. The terpolymer has been characterized by UV‐visible, IR, and ¹H NMR spectra. The thermal decomposition behavior of some new terpolymers was studied using thermogravimetric analysis in air atmosphere at heating rate of 10°C/min. Thermal decomposition curves are discussed with careful attention to minute details. The Freeman–Carroll and Sharp–Wentworth methods have been used to calculate activation energy and thermal stability. Thermal activation energy (E_a) calculated with the help of these methods are in agreement with each other. Thermodynamic parameters such as free energy change (ΔF), entropy change (ΔS), apparent entropy change (S*), and frequency factor (z) are also determined on the basis of the TG curves and by using data of the Freeman–Carroll method. The Freidman method evaluated the variation in the apparent activation energy changes by isoconversional (model‐free) kinetic methods. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The kinetics of the thermal decomposition of poly(3‐hydroxybutyrate) and maleated poly(3‐hydroxybutyrate)

The thermal decomposition mechanism of maleated poly(3‐hydroxybutyrate) (PHB) was investigated by FTIR and ¹H NMR. The results of experiments showed that the random chain scission of maleated PHB obeyed the six‐membered ring ester decomposition process. The thermal decomposition behavior of PHB and maleated PHB with different graft degree were studied by thermogravimetry (TGA) using various heating‐up rates. The thermal stability of maleated PHB was evidently better than that of PHB. With increase in graft degree, the thermal decomposition temperature of maleated PHB gradually increased and then declined. Activation energy E_a as a kinetic parameter of thermal decomposition was estimated by the Flynn‐Wall‐Ozawa and Kissinger methods, respectively. It could be seen that approximately equal values of activation energy were obtained by both methods. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1789–1796, 2002; DOI 10.1002/app.10463     

Synthesis,characterization, and thermal degradation kinetic of polystyrene‐g‐polycaprolactone

In the present study, it has been demonstrated that polystyrene‐g‐polycaprolactone (PS‐g‐PCL) was successfully prepared by “click chemistry.” For this purpose, first, poly(styrene‐co‐4‐chloromethylstyrene) (P(S‐co‐CMS)) with 4‐chloromethylstyrene content (10%) was synthesized. Second, alkyne‐functionalized polycaprolactone (PCL) was obtained using propargyl alcohol and caprolactone. P(S‐co‐CMS) and PCL were reacted in N,N‐dimethylformamide for 24 h at 25°C to give PS‐g‐PCL. The synthesized polymer was characterized by nuclear magnetic resonance (¹H‐NMR), gel permeation chromatography, Fourier transform infrared spectroscopy and thermogravimetric analysis. The apparent activation energies for thermal degradation of PS‐g‐PCL were obtained by differential (Kissenger) and integral methods (Flynn–Wall–Ozawa, Kissinger–Akahira–Sunose, Tang, Coats–Redfern, Van Krevelen et al.). The decomposition mechanism and pre‐exponential factor were calculated in terms of Coats–Redfern method. The most likely decomposition processes of first and second degradation stages were A_n type and F₃ type, respectively. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012