Nonisothermal Decomposition Kinetics of Abietic Acid in Argon

Nov 10, 2011 - Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, Guangxi University,. Nanning 530004...
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Nonisothermal Decomposition Kinetics of Abietic Acid in Argon Atmosphere Weijian Nong,† Xiaopeng Chen,†,‡ Linlin Wang,†,‡ Jiezhen Liang,†,‡ Lingping Zhong,† and Zhangfa Tong*,†,‡ † ‡

School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, PR China Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, Guangxi University, Nanning 530004, PR China

bS Supporting Information ABSTRACT: Abietic acid was isolated from rosin by means of reaction-crystallization coupled with exposure to ultrasonic waves, and it was then characterized by its specific rotation, infrared spectra, and 13C nuclear magnetic resonance spectra. The thermal decomposition of abietic acid in argon atmosphere was studied under nonisothermal conditions using TG-DTG techniques with heating rates of 5, 10, 20, and 25 K/min. For the kinetic study, the nonisothermal kinetic parameters were obtained via the analysis of the TG-DTG curves by using the Flynn-Wall-Ozawa (FWO) method, the Kissinger method, and the integral method. The results showed that the nonisothermal decomposition mechanism of abietic acid in argon atmosphere followed Mampel Power law with n = 3/2, whose differential and integral forms were f(α) = 2/3α1/2 and G(α) = α3/2. The apparent activation energy Ea and the preexponential factor A were 123.44 kJ/mol and 1.78  1011 s1, respectively. The kinetic equation can be expressed as dα/dt = 1.19  1011 α1/2 exp(1.48  104/T). The thermodynamic parameters (ΔHq, ΔGq, and ΔSq) were calculated as well.

1. INTRODUCTION Rosin is an abundantly natural product which is obtained directly by the distillation of the exudates of pines trees. It is a mixture of acidic (ca. 90%) and neutral (ca. 10%) compounds. The acidic components, generally named as rosin (or resin) acids, are also a mixture containing mainly isomeric abietic-type acids (4060%) and pimaric-type (927%) acids on the basis of total rosin weight.1 They are usually seven to eight diterpene monocarboxylic acids (abietic, neoabietic, dehydroabietic, palustric, pimaric, isopimaric, levopimaric, and sandaracopimaric acid).24 The exact composition of the rosin acids depending on the tree species and the geographic origin of the trees. The chemical structure of abietic acid, a primary component of rosin (4050%),5 is shown in Figure 1. As is shown, abietic acid is a tricyclic diterpene carboxylic acid with conjugated double bonds. Due to its special structure, abietic acid is by far the most actively studied rosin acid. Abietic acid and its derivatives have a wide range of potential applications as a precursor for the synthesis of compounds furnishing an ambergris-type fragrance,69 a good chiral pool for many biologically active compounds10,11 and pharmaceuticals including antitumor,12,13 anti-inflammatory,14,15 antiviral,16 antimycotic,17,18 and antiarteriosclerotic.19 Thermal analysis is a technique widely used to study the thermal decomposition of substances. Different methods such as thermogravimetric analysis (TGA), differential thermal analysis (DTA), and differential scanning calorimeter (DSC) have been employed to study the kinetics of such a process either by isothermal or nonisothermal conditions. Some of these methods have been applied to a thermal degradation of epoxy resins20,21 and evaluate the thermal stability of polymers2224 and energetic materials.2529 However, no work has been reported thus far on the thermal decomposition kinetics of abietic acid. Therefore, in r 2011 American Chemical Society

this work, the thermal behavior and the related decomposition kinetics of abietic acid were investigated by means of TG-DTG techniques under nonisothermal conditions.

2. EXPERIMENTAL PROCEDURE 2.1. Materials. Rosin was purchased from Wuzhou Sun Shine Forestry and Chemicals Co., Ltd. of Guangxi, PR China. Its softening point was 348 K and its acid number was 165 mg KOH/g. Ethanolamine (purity g99.0%), glacial acetic acid (purity g99.5%), and ethanol (95%, v/v) were all purchased from Guangdong Guanghua Chemical Co., Ltd., PR China. 2.2. Isolation of Abietic Acid. The sample of abietic acid used in the study was obtained according to the following steps. First, rosin was isomerized in concentrated hydrochloric acid at 55 °C for 40 min exposed to ultrasonic waves. Then the isomerized rosin was reacted with ethanolamine at 30 °C for 40 min by means of reaction-crystallization coupled with ultrasonic waves to obtain ethanolamine salt. Pure ethanolamine salt was obtained by recrystallization from 95% ethanol. Finally, pure abietic acid with a purity of 99.11% was obtained via acidification with glacial acetic acid. 2.3. Methods and Apparatus. The specific rotation was obtained using a Perkin-Elmer Model 341LC polarimeter. Infrared spectra were recorded using a Nexus-470 spectrometer (Nicolet Co., USA) with KBr disks at room temperature in the range of 4000400 cm1. 13C nuclear magnetic resonance Received: August 19, 2011 Accepted: November 10, 2011 Revised: November 8, 2011 Published: November 10, 2011 13727

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Table 1. 13C NMR-DEPT Data of Abietic Acid (CDCl3, 125 MHz) C-atom

δ/ppm

C-atom

δ/ppm

1

38.28

11

22.49

2 3

18.06 37.18

12 13

27.46 145.24

4

46.35

14

122.41

5

44.93

15

34.88

6

25.51

16

20.87

7

120.50

17

21.41

8

135.58

18

184.96

9

50.95

19

16.71

10

34.48

20

14.03

Figure 1. The chemical structure of abietic acid.

(NMR) spectra were obtained by an AVANCE-500 MHz (Bruker Co., Switzerland) NMR apparatus with CDCl3 as the solvent and tetramethylsilane as the internal standard material. The TG-DTG experiments of abietic acid were achieved using a Perkin-Elmer TGA7 thermogravimetric analyzer. Abietic acid (5.0 ( 0.2 mg) was placed in alumina crucible. An empty alumina crucible was used as reference. The abietic acid was heated from ambient temperature to 600 °C in a constant 30 cm3/min flow of argon at heating rates of 5, 10, 20, and 25 K/min. Continuous recordings of sample temperature, sample weight, and heating flow were taken.

3. THEORETICAL BACKGROUND The reaction rate (s1) of heterogeneous solid-state reaction can empirically be described by a single-step kinetic equation3032 dα ¼ kf ðαÞ dt

ð1Þ

Figure 2. DTG curves of abietic acid at different heating rates. 1: β = 5 K/min, 2: β = 10 K/min, 3: β = 20 K/min, 4: β = 25 K/min.

where t is the time (s), T is the temperature (K), k is the reaction rate constant, α is the conversion degree, and f(α) is the differential form of mechanism function. The rate constant k can be expressed by the Arrhenius equation k ¼ A expðEa =RTÞ

ð2Þ

where A (s1) is pre-exponential factor, Ea is the apparent activation energy (kJ/mol), and R is the universal gas constant. Replacing k in eq 1 with the Arrhenius equation gives dα ¼ A expðEa =RTÞf ðαÞ dt

ð3Þ

Under a nonisothermal condition, at constant heating rate β = dT/dt, eq 3 may be written as   dα dα 1 A ¼ ð4Þ ¼ expðEa =RTÞf ðαÞ dT dt β β

4. RESULTS AND DISCUSSION 4.1. Characterization. The specific rotation of abietic acid was 105.4° when using 95% ethanol as solvent (c = 2% ethanol) and determining at a wavelength of 589 nm. Data were collected at room temperature (25 °C). The value was in close agreement with that of Harris.33

Figure 3. TG-DTG curves of abietic acid at a heating rate of 10 K/min.

The main infrared (IR) bands for the purified compound are summarized as follows: all bands confirmed that the purified acid was abietic acid. IR (KBr) ν, cm1: 3422.16 (w, νOH), 2959.23, 2933.54 (vs, νCH3), 1691.91 (vs, νCdO), 1462.43, 1386.34 (m, δCH), 1282.08 (s, νCO), 891.82 (w, γOH). The 13C NMR chemical shifts of abietic acid (δ in ppm from TMS for CDCl3 solutions, 125 MHz) are shown in Table 1. The results were in good agreement with those of Feliciano.34 All evidence indicated that the purification product was abietic acid. 4.2. Nonisothermal Kinetics. 4.2.1. Thermal Decomposition Behaviors of Abietic Acid. Typical DTG curves at different heating rates and TG-DTG curves at a heating rate of 10 K/min are 13728

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Table 2. Kinetic Analysis Methods method

equation

Coats-Redfern

ln½GðαÞ=T 2  ¼ lnðAR=βEÞ  E=RT

ð5Þ

Satava-Sestak

lgGðαÞ ¼ lgðAS ES =RβÞ  2:315  0:4567ES =RT

ð6Þ

MacCallum-Tanner

lgGðαÞ ¼ lgðAE=RβÞ  0:4828E0:4357  ð0:449 þ 0:217EÞ=0:001TðEðkcal 3 mol  1 ÞÞ

ð7Þ

1:921503

 ¼ ln½ðAR=βEÞ þ 3:772050  1:921503ln E  0:120394E=T

ð8Þ

Madhusudanan-Krishnan -Ninan

ln½GðαÞ=T

Ordinary Integral

ln½GðαÞ=T 2  ¼ ln½ðAR=βEÞð1  2RT=EÞ  E=RT

Agrawal

ln½GðαÞ=T 2  ¼ lnfðAR=βEÞ½1  2ðRT=EÞ=½1  5ðRT=EÞ2 g  E=RT

ð10Þ

Flynn-Wall-Ozawa

lgβ ¼ lgfAE=½RGðαÞg  2:315  0:4567E=RT

ð11Þ

Kissinger

lnðβi =T 2pi Þ ¼ lnðAk R=Ek Þ  Ek =RTpi i ¼ 1, 2:::, 4

ð12Þ

Figure 4. The Eaα curve obtained by the FWO method.

shown as Figures 2 and 3. From Figure 2, one can find that with the increase in heating rate, the DTG peak temperature (Tp/K) rises because of the heat lag of the process.35 It can be seen from Figure 3 that there is only one main mass loss stage in TG curves, corresponding one peak in DTG curves. Mass loss begins at 470.36 K and stops at 578.46 K, accompanying with nearly 100% mass loss. As is shown by the DTG curve, the decomposition rate of abietic acid increases rapidly with temperature and reached the maximum at 570.33 K. 4.2.2. Calculation of Ea and A. In order to obtain the kinetic parameters [apparent activation energy (Ea/kJ mol1), pre-exponential constant (A/s1)] and the most probable mechanism function of the decomposition reaction for abietic acid, the TG-DTG curves at heating rates of 5, 10, 20, and 25 K/min were dealt by mathematic means, seven integral methods (eqs 511) and one differential method (eq 12) listed in Table 2 are employed.3639 In these equations, Tp is the peak temperature in the DTG curves, G(α) is the integral form of mechanism function, T, α, R, β, f(α), Ea, and A are mentioned above. The data needed for the equations of the integral and differential methods, i, αi, β, Ti, and Tp are obtained from the TG-DTG curves and summarized in Table S1 (see the Supporting Information). The values of Ea obtained by the FWO method (eq 11) with α changing from 0.07 to 1.00 and the Eaα curve is shown in Figure 4. From Figure 4 we can find that activation energy making great changes with the increase of conversion degree.

ð9Þ

However, the average value of Ea in the α range of 0.20 to 0.95 in Figure 4 is in good agreement with the calculated values obtained by Kissinger method, which means that it is feasible to study the decomposition mechanism and kinetics in this section. Forty types of kinetic model functions in ref 40 and the original data tabulated in Table S1 (see the Supporting Information) were put into eqs 510 for calculation, respectively. The values of Ea (kJ/mol), lgA (s1), linear correlation coefficient (r), and standard mean square deviations (Q) calculated on computer with the linear least-squares method at various heating rates of 5, 10, 20, and 25 K/min were listed in Table S2 (see the Supporting Information). The most probable mechanism function was selected by the better values of r and Q based on the following four conditions: (1) the values of Ea (kJ/mol) and lgA (s1) selected are in the ordinary range of the thermal decomposition kinetic parameters for solid materials (Ea (kJ/mol)) = 80250 and (lgA (s1)) = 730); (2) linear correlation coefficient (r) is greater than 0.98; (3) the values of Ea (kJ/mol) and lgA (s1) obtained with the differential and integral methods are approximately the same; (4) the mechanism function selected must be in agreement with the tested sample state. The results of satisfying the above-mentioned conditions at the same time are the final results as listed in Table S2 (see the Supporting Information). From Table S2 (see the Supporting Information), it would be found that the values of Ea and lgA for each method present some deviations at different heating rates. However, their values of Ea and lgA for different methods present similar results at the same heating rate. The mean values of Ea (kJ/mol) and lgA (s1) for Coats-Redfern, Satava-Sestak, MacCallum-Tanner, Madhusudanan-Krishnan-Ninan, Ordinary Integral, and Agrawal methods are 122.70 and 10.85, 125.47 and 11.18, 124.12 and 12.81, 122.95 and 10.90, 122.70 and 10.89, and 122.70 and 10.88, respectively. They are in good agreement with the calculated values obtained by Kissinger and FWO methods, which indicate that these six integral methods can be employed to investigate the nonisothermal decomposition kinetic mechanism of abietic acid in argon atmosphere. Therefore, we conclude that the nonisothermal decomposition kinetic mechanism of the title compound is classified as Mampel power law f(α) = 2/3α1/2. Substituting f(α) with 2/3α1/2, Ea with 123.44 kJ/mol, and A with 1.78  1011 s1 in eq 3, the kinetic equation of the nonisothermal 13729

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decomposition process of abietic acid may be described as

University (X081020), and the Scientific Research Innovative Foundation of Doctoral Candidates (105930901008).

dα ¼ 1:19  1011 α1=2 expð  1:48  104 =TÞ dt 4.2.3. Calculation of Thermodynamic Parameters. The value of peak temperature (Tp) corresponding to β f 0 obtained by eq 13 taken from ref 39 is 544.86 K Tp ¼ Tpo þ aβi þ bβ2i ði ¼ 1  4Þ

ð13Þ

where a and b are coefficients. The entropy of activation (ΔSq), enthalpy of activation (ΔHq), and free energy of activation (ΔGq) corresponding to T = Tpo, Ea = Ek, and A = Ak obtained by eqs 141636,37 are 42.98 J mol1 K1, 117.48 and 140.90 kJ/mol, respectively. A¼

kB T ΔSq =R e h

ð14Þ

ΔH q ¼ Ea  RT

ð15Þ

ΔGq ¼ ΔH q  TΔSq where kB is the Boltzmann constant (1.3807  10 h is Plank's constant (6.626  1034 J/s).

ð16Þ 23

J/K), and

5. CONCLUSIONS The thermal behavior of the title compound under the nonisothermal conditions by TG-DTG techniques was studied. The most probable thermal decomposition mechanism of abietic acid follows Mampel Power law with n = 3/2. The activation energy and pre-exponential factor are 123.44 kJ/mol and 1.78  1011 s1, respectively. The differential form and the integral form of the mechanism function are f(α) = 2/3α1/2 and G(α) = α3/2. Therefore, the kinetic equation can be expressed as dα/dt = 1.19  1011 α1/2 exp(1.48  104/T). The ΔSq, ΔHq, and ΔGq of the thermal decomposition reaction at the temperature (T = Tpo) are 42.98 J mol1 K1, 117.48 and 140.90 kJ/mol, respectively. ’ ASSOCIATED CONTENT

bS

Supporting Information. (Table S1) Data for the decomposition process of abietic acid determined by TG at different heating rates. (Table S2) Kinetic parameters obtained from different methods for the decomposition process of abietic acid. This material is available free of charge via the Internet at http://pubs.acs.org.

’ AUTHOR INFORMATION Corresponding Author

*Phone: + 86 771 3239697. Fax: + 86 771 3236634. E-mail: [email protected].

’ ACKNOWLEDGMENT The authors gratefully acknowledge financial support for this research from the National Natural Science Foundation of China (20976031, 31060102), the Natural Science Foundation of Guangxi Autonomous Region (0991030, 2010GXNSFA013042), the Science and Technology Program Foundation of Wuzhou city (200901011), the Scientific Research Foundation of Guangxi

’ NOMENCLATURE A pre-exponential factor (s1) pre-exponential factor obtained by Kissinger method AK (s1) pre-exponential factor obtained by Satava-Sestak methAS od (s1) apparent activation energy (kJ/mol) Ea apparent activation energy obtained by Kissinger methEK od (kJ/mol) apparent activation energy obtained by Satava-Sestak ES method (kJ/mol) f(α) differentia form of mechanism function G(α) integral form of mechanism function free energy of activation (kJ/mol) ΔGq enthalpy of activation (kJ/mol) ΔHq k thermal decomposition rate constant (s1) n reaction order r correlation coefficient R gas constant = 8.314 (J mol1 K1) Q standard mean square deviation entropy of activation (J mol1 K1) ΔSq t thermal decomposition time (s) T thermal decomposition temperature (K) peak temperature of DTG curve (K) TP Greek letters

α β

conversion degree heating rate (K/min)

’ REFERENCES (1) Wang, H.-H.; Liu, B.; Liu, X.-Q.; Zhang, J.-W.; Xian, M. Synthesis of biobased epoxy and curing agents using rosin and the study of cure reactions. Green Chem. 2008, 10, 1190–1196. (2) Yamada, A.; Ezaki, Y.; Matsuo, K.; Yarita, T.; Nomura, A. Supercritical fluid chromatography of free resin acids on an ODS-silica gel column. J. Chromatogr., A 1995, 709, 345–349. (3) Findeisen, A.; Kolivoska, V.; Kaml, I.; Baatz, W.; Kenndler, E. Analysis of diterpenoic compounds in natural resins applied as binders in museum objects by capillary electrophoresis. J. Chromatogr., A 2007, 1157, 454–461. (4) Sadhra, S.; Gray, C. N.; Foulds, I. S. High-performance liquid chromatography of unmodifed rosin and its applications in contact dermatology. J. Chromatogr., B 1997, 700, 101–110. (5) Karlberg, A. T.; Bergstedt, E.; Boman, A.; Bohlinder, K.; Liden, C.; Lars, J.; Nilsson, G.; Wahlberg, J. E. Is abietic acid the allergenic component of colophony? Contact Dermitis 1985, 13, 209–215. (6) Cambie, R. C.; Franich, R. A.; Larsen, D.; Rutledge, P. S.; Ryan, G. R.; Woodgate, P. D. Potential ambergris odorants from abietic acid. Aust. J. Chem. 1990, 43, 21–46. (7) Cambie, R. C.; Rutledge, P. S.; Ryan, G. R.; Strange, G. A.; Woodgate, P. D. Conversion of abietic acid into analogs of ambergris odorants. Aust. J. Chem. 1990, 43, 867–881. (8) Costa, M. C.; Alves, S. P.; Correia, M. E.; Marcelo-Curto, M. J. Synthesis of an ambergris-type ketal from abietic acid. Synthesis 2006, 2006, 1171–1175. (9) Yadav, J. S.; Baishya, G.; Dash, U. Synthesis of (+) -amberketal and its analog from L-abietic acid. Tetrahedron 2007, 63, 9896–9902. (10) Presser, A.; Haslinger, E.; Weis, R.; H€ufner, A. Synthetic transformations of abietic acid IV [1]. B- and C-Ring oxidation. Monatsh. Chem. 1998, 129, 921–930. 13730

dx.doi.org/10.1021/ie201863n |Ind. Eng. Chem. Res. 2011, 50, 13727–13731

Industrial & Engineering Chemistry Research (11) Presser, A.; P€otschger, I.; Haslinger, E.; H€ufner, A. Synthetic transformations of abietic acid Va: structure modification and ozonization. Monatsh. Chem. 2002, 133, 231–239. (12) Bang, S. D.; Johnson, S. K.; Park, J. C. S. Composition and method for treating tumors. U.S. Patent Application US5248696, 1993. (13) Lin, C.-H.; Chuang, H. S. Use of abietic acid or derivative thereof for modulation permeability of plasma membrane. U.S. Patent Application US2004063788, 2004. (14) Fernandez, M. A.; Tornos, M. P.; García, M. D.; Heras, B. D. L.; Villar, A. M.; Saenz, M. T. Anti-inflammatory activity of abietic acid, a diterpene isolated from pimenta racemosa var.grissea. J. Pharm. Pharmacol. 2001, 53, 867–872. (15) Takahashi, N.; Kawada, T.; Goto, T.; Kim, C. S.; Taimatsu, A.; Egawa, K.; Yamamotoa, T.; Jisaka, M.; Nishimura, K.; Yokota, K.; Yu, R.; Fushiki, T. Abietic acid activates peroxisome proliferator-activated receptor-γ(PPARγ) in RAW264.7 macrophages and 3T3-L1 adipocytes to regulate gene expression involved in inflammation and lipid metabolism. FEBS Lett. 2003, 550, 190–194. (16) Gigante, B.; Santos, C.; Silva, A. M.; Curto, M. J. M.; Nascimento, M. S. J.; Pinto, E.; Pedro, M.; Cerqueira, F.; Pinto, M. M.; Duarte, M. P.; Laires, A.; Rueff, J.; Gonc, J.; Pegado, M. I.; Valdeira, M. L. Catechols from abietic acid: synthesis and evaluation as bioactive compounds. Bioorg. Med. Chem. 2003, 11, 1631–1638. (17) Alvarez-manzaneda, E.; Chahboun, R.; Bentaleb, F.; Alvarez, E.; Escobar, M. A.; Sad-Diki, S.; Cano, M. J.; Messouri, I. Regioselective routes towards 14-hydroxyabietane diterpenes. A formal synthesis of immunosuppressant ()-triptolide from (+)-abietic acid. Tetrahedron 2007, 63, 11204–11212. (18) Gonzalez, M. A.; Correa-Royero, J.; Agudelo, L.; Mesa, A.; Betancur-Galvis, L. Synthesis and biological evaluation of abietic acid derivatives. Eur. J. Med. Chem. 2009, 44, 2468–2472. (19) Murai, H.; Ohata, K.; Enomoto, H.; Sempuku, K.; Kitaguchi, K.; Fujita, Y.; Yoshikuni, Y.; Kuri, K.; Saito, K.; Mori, T. Abietamide derivatives, their production and use. U.S. Patent Application US4210671, 1980. (20) Montserrat, S.; Malek, J.; Colomer, P. Thermal degradation kinetics of epoxy-anhydride resins: I.: influence of a silica filler. Thermochim. Acta 1998, 313, 83–95. (21) Wang, Q.-F.; Shi, W.-F. Kinetics study of thermal decomposition of epoxy resins containing flame retardant components. Polym. Degrad. Stab. 2006, 91, 1747–1754. (22) Ramirez, M. L.; Walters, R.; Lyon, R. E.; Savitski, E. P. Thermal decomposition of cyanate ester resins. Polym. Degrad. Stab. 2002, 78, 73–82. (23) Chrissafis, K.; Paraskevopoulos, K. M.; Bikiaris, D. N. Thermal degradation mechanism of poly(ethylene succinate) and poly(butylene succinate): comparative study. Thermochim. Acta 2005, 435, 142–150. (24) Zorba, T.; Chrissafis, K.; Paraskevopoulos, K. M.; Bikiaris, D. N. Synthesis, characterization and thermal degradation mechanism of three poly(alkylene adipate)s: Comparative study. Polym. Degrad. Stab. 2007, 92, 222–230. (25) Keshavarz, M. H. Simple method for prediction of activation energies of the thermal decomposition of nitramines. J. Hazard. Mater. 2009, 162, 1557–1562. (26) Roduit, B.; Xia, L.; Folly, P.; Berger, B.; Mathieu, J.; Sarbach, A.; Andres, H.; Ramin, M.; Vogelsanger, B.; Spitzer, D.; Moulard, H.; Dilhan, D. The simulation of the thermal behavior of energetic materials based on DSC and HFC signals. J. Therm. Anal. Calorim. 2008, 93, 143–152. (27) Pourmortazavi, S. M.; Hosseini, S. G.; Rahimi-Nasrabadi, M.; Hajimirsadeghi, S. S.; Momenian, H. Effect of nitrate content on thermal decomposition of nitrocellulose. J. Hazard. Mater. 2009, 162, 1141–1144. (28) Sovizi, M. R.; Hajimirsadeghi, S. S.; Naderizadeh, B. Effect of particle size on thermal decomposition of nitrocellulose. J. Hazard. Mater. 2009, 168, 1134–1139. (29) Pisharath, S.; Ang, H. G. Synthesis and thermal decomposition of GAP-Poly(BAMO) copolymer. Polym. Degrad. Stab. 2007, 92, 1365–1377.

ARTICLE

(30) Al-Othman, A. A.; Al-Farhan, K. A.; Mahfouz, R. M. Kinetic analysis of nonisothermal decomposition of (Mg5(CO3)4(OH)2 3 4H2O/ 5Cr2O3) crystalline mixture. J. King Saud Univ., Sci. 2009, 21, 133–143. (31) Erceg, M.; Kovacic, T.; Perinovic, S. Kinetic analysis of the nonisothermal degradation of poly(3-hydroxybutyrate) nanocomposites. Thermochim. Acta 2008, 476, 44–50. (32) Rodante, F.; Vecchio, S.; Tomassetti, M. Kinetic analysis of thermal decomposition for penicillin sodium salts: model-fitting and model-free methods. J. Pharm. Biomed. Anal. 2002, 29, 1031–1043. (33) Harris, G. C.; Sanderson, T. F. Resin Acids.I. an improved method of isolation of resin acids; the isolation of a new abietic-type acid, neoabietic acid. J. Am. Chem. Soc. 1948, 70, 334–339. (34) Feliciano, A. S.; Miguel del Corral, J. M.; Gordaliza, M.; Salinero, M. A. 13C NMR data for abieta-7,13-diene diterpenoids. Magn. Reson. Chem. 1993, 31, 841–844. (35) Ren, Y.-L.; Cheng, B.-W.; Jiang, A.-B.; Lu, Y.-C.; Xu, L. Thermal degradation kinetics of poly(O,O-diethyl-O-allylthiophosphate-co-acrylonitrile) in nitrogen. J. Appl. Polym. Sci. 2010, 115, 3705–3709. (36) Yi, J.-H.; Zhao, F.-Q.; Xu, S.-Y.; Zhang, L.-Y.; Gao, H.-X.; Hu, R.-Z. Effects of pressure and TEGDN content on decomposition reaction mechanism and kinetics of DB gun propellant containing the mixed ester of TEGDN and NG. J. Hazard. Mater. 2009, 165, 853–859. (37) Yi, J.-H.; Zhao, F.-Q.; Gao, H.-X.; Xu, S.-Y.; Wang, M.-C.; Hu, R.-Z. Preparation, characterization, non-isothermal reaction kinetics, thermodynamic properties, and safety performances of high nitrogen compound: Hydrazine 3-nitro-1,2,4-triazol-5-one complex. J. Hazard. Mater. 2008, 153, 261–268. (38) Ma, H.-X; Yan, B.; Li, Z.-N.; Song, J.-R.; Hu, R.-Z. Synthesis, molecular structure, non-isothermal decomposition kinetics and adiabatic time to explosion of 3, 3-dinitroazetidinium 3, 5-dinitrosalicylate. J. Therm. Anal. Calorim. 2009, 95, 437–444. (39) Ma, H.-X.; Yan, B.; Li, J.-F.; Ren, Y.-H.; Chen, Y.-S.; Zhao, F.-Q.; Song, J.-R.; Hu, R.-Z. Molecular structure, thermal behavior and adiabatic time-to-explosion of 3,3-dinitroazetidinium picrate. J. Mol. Struct. 2010, 981, 103–110. (40) Hu, R.-Z.; Gao, S.-L.; Zhao, F.-Q.; Shi, Q.-Z.; Zhang, T.-L.; Zhang, J.-J. Thermal Analysis Kinetics; Science Press: Beijing, 2008 (in Chinese).

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