Terpolymer (2-ATPHMDAF-I) has been synthesized by the condensation of 2-aminothiophenol and hexamethylenediamine with formaldehyde in the presence of 2?M hydrochloric acid as a catalyst with 1?:?1?:?2 molar proportion of reacting monomers. The structure of newly synthesized terpolymer has been elucidated and confirmed on the basis of elemental analysis and various spectral techniques, that is, UV-visible, FT-IR, and 1H-NMR spectroscopy. Number average molecular weight ( ) has been determined by conductometric titration in nonaqueous medium. The viscosity measurements in dimethyl sulfoxide (DMSO) have been carried out to ascertain the characteristic functions and constants. The studies have been further extended to nonisothermal thermogravimetric analysis for determination of their mode of decomposition and relative thermal stability. Activation energy , order of reaction , and frequency factor were calculated by Friedman, Chang, Sharp-Wentworth and Freeman-Carroll methods. Activation energy calculated by Friedman and Chang methods are in close agreement with each other while the results obtained from Freeman-Carroll and Sharp-Wentworth’s methods are found to be in a similar order. 1. Introduction Study of thermal analysis comprises a group of techniques in which a physical property of substance is measured as a function of temperature when the substance is subjected to a controlled temperature program. Thermally stable terpolymers have recently become boon to polymer chemist due to their superior and high performance utility. Since the modern history of thermogravimetry, thermal degradation of polymers and the study of their kinetics have been at the center of thermal analysis. Many researchers tried to improve the thermal stability at elevated temperature by changing the monomer composition in polymer synthesis. The thermal degradation study of terpolymer has become a subject of recent interest, being an important property which primarily decides thermal stability and processability. A wide variety of thermally stable polymers have been synthesized and studied their thermogravimetric property and finds many applications such as ion-exchangers [1–5], semiconductors [6], high dielectric constant for energy storage capacitors [7], packaging, adhesives and coatings in electrical sensors, activators, catalysts and thermally stable materials [8–10]. Phenolic resins are known for their wide applications in various areas because of their thermal stability, easy availability, cost effectiveness, and some of their excellent properties [11]. The thermal stability
References
[1]
W. B. Gurnule, P. K. Rahangdale, L. J. Paliwal, and R. B. Kharat, “Chelation ion-exchange properties of copolymer resin derived from 4-hydroxyacetophenone, oxamide, and formaldehyde,” Journal of Applied Polymer Science, vol. 89, no. 3, pp. 787–790, 2003.
[2]
V. D. Mane, N. J. Wahane, and W. B. Gurnule, “Copolymer resin. VII. 8-hydroxyquinoline-5-sulfonic acid-thiourea- formaldehyde copolymer resins and their ion-exchange properties,” Journal of Applied Polymer Science, vol. 111, no. 6, pp. 3039–3049, 2009.
[3]
M. V. Tarase, A. B. Zade, and W. B. Gurnule, “Resin I: synthesis, characterization, and ion-exchange properties of terpolymer resins derived from 2,4-dihydroxypropiophenone, biuret, and formaldehyde,” Journal of Applied Polymer Science, vol. 108, no. 2, pp. 738–746, 2008.
[4]
A. D. Kushwaha, A. B. Kalambe, V. V. Hiwase, and D. N. Urade, “Structural and antibacterial study of resin-II derived from p-nitrophenol, resorcinol and formaldehyde,” Journal of Chemical and Pharmaceutical Research, vol. 4, no. 2, pp. 1111–1116, 2012.
[5]
W. Hackenberger, R. Alberta, W. Paul, D. Jeong, and Q. Zhang, “High dielectric constant terpolymers for energy storage capacitors,” in Proceedings of the 25th Symposium for Passive Components, pp. 239–243, Palm Springs, 2005.
[6]
S. K. Kapse, V. V. Hiwase, and A. B. Kalambe, “Synthesis and semi conducting behaviour of the ter-polyligand derived from p-hydroxyacetophenone, quinhydrone and melamine,” Journal of Chemical and Pharmaceutical Research, vol. 4, no. 3, pp. 1734–1739, 2012.
[7]
D. N. Urade, V. V. Hiwase, and A. B. Kalambe, “Structural and thermokinetic parameters of terpolymeric resin derived from p-hydroxyacetophenone, bis (2-amino- 1, 3, 4 -thiadiazole) and glycerol,” Journal of Chemical and Pharmaceutical Research, vol. 4, no. 1, pp. 732–740, 2012.
[8]
S. Pashaei, S. Siddaramaiah, M. M. Avval, and A. A. Syed, “Thermal degradation kinetics of nylon6/gf/crysnano nanoclay nanocomposites by TGA,” Chemical Industry and Chemical Engineering Quarterly, vol. 17, no. 2, pp. 141–151, 2011.
[9]
A. Gardziella, L. A. Pilato, and A. Knop, Phenolic Resins, Chemistry, Applications, Standardization, Safely and Ecology, Springer, 2000.
[10]
G. E. Zaikov, Degradation and Stabilization of Polymers, Theory and Practice, Nova Science Publishers, New Delhi, India, 1995.
[11]
N. G. Grassie, Scott Polymer Degradation and Stabilization, Cambridge Press, Cambridge, Mass, USA, 1985.
[12]
R. N. Singru, A. B. Zade, and W. B. Gurnule, “Thermoanalytical study and kinetics of new 8-hydroxyquinoline 5-sulphonic acid-oxamide-formaldehyde terpolymer resins,” E-Journal of Chemistry, vol. 6, no. 1, pp. S171–S182, 2009.
[13]
R. N. Singru, A. B. Zade, and W. B. Gurnule, “Synthesis, characterization, and thermal degradation studies of copolymer resin derived from p-cresol, melamine, and formaldehyde,” Journal of Applied Polymer Science, vol. 109, no. 2, pp. 859–868, 2008.
[14]
M. Karunakaran, C. T. Vijayakumar, C. Magesh, and T. Amudha, “Terpolymer resin-ii -thermal and metal ion binding properties of resorcinolthiourea- formaldehyde terpolymer resin,” International Journal of Engineering Science and Technology, vol. 3, no. 1, pp. 162–176, 2011.
[15]
M. V. Tarase, A. B. Zade, and W. B. Gurnule, “Kinetics of thermal degradation studies of some new terpolymers derived from 2, 4-dihydroxypropiophenone, oxamide, and formaldehyde,” Journal of Applied Polymer Science, vol. 116, no. 2, pp. 619–627, 2010.
[16]
S. S. Butoliya, W. B. Gurnule, and A. B. Zade, “Study of non-isothermal decomposition and kinetic analysis of 2,4-dihydroxybenzoic acid-melamine-formaldehyde copolymer,” E-Journal of Chemistry, vol. 7, no. 3, pp. 1101–1107, 2010.
[17]
P. E. P. Michael, P. S. Lingala, H. D. Juneja, and L. J. Paliwal, “Synthetic, structural, and thermal degradation of a tercopolymer derived from salicylic acid, guanidine, and formaldehyde,” Journal of Applied Polymer Science, vol. 92, no. 4, pp. 2278–2283, 2004.
[18]
P. E. P. Michael, J. M. Barbe, H. D. Juneja, and L. J. Paliwal, “Synthesis, characterization and thermal degradation of 8-hydroxyquinoline-guanidine-formaldehyde terpolymer,” European Polymer Journal, vol. 43, no. 12, pp. 4995–5000, 2007.
[19]
S. S. Rahangdale, A. B. Zade, and W. B. Gurnule, “Thermal degradation studies of terpolymer derived from 2, 4-dihydroxyacetophenone, dithiooxamide and formaldehyde,” Ultra Scienceno, vol. 19, pp. 213–218, 2007.
[20]
S. S. Katkamwar, A. B. Zade, and W. B. Gurnule, Ultra Science, vol. 73, no. 2, pp. 103–108, 2007.
[21]
S. K. Mandavgade, J. R. Dontulwar, and W. B. Gurnule, “Thermal degradation study of new polymer derived fr om 8-hydroxyquinoline 5-sulphonic acid and catechol,” Der Pharma Chemicano, vol. 4, no. 4, pp. 1695–1703, 2012.
[22]
M. V. Tarase, A. B. Zade, and W. B. Gurnule, “Kinetics of thermal degradation studies of some new terpolymers derived from 2, 4-dihydroxypropiophenone, oxamide, and formaldehyde,” Journal of Applied Polymer Science, vol. 116, no. 2, pp. 619–627, 2010.
[23]
R. N. Singru, W. B. Gurnule, V. A. Khati, A. B. Zade, and J. R. Dontulwar, “Eco-friendly application of p-cresol-melamine-formaldehyde polymer resin as an ion-exchanger and its electrical and thermal study,” Desalination, vol. 263, no. 1-3, pp. 200–210, 2010.
[24]
R. H. Gupta, A. B. Zade, and W. B. Gurnule, “Resin-IV: synthesis and characterization of terpolymers derived from 2-hydroxyacetophenone, melamine, and formaldehyde,” Journal of Applied Polymer Science, vol. 109, no. 5, pp. 3315–3320, 2008.
[25]
G. E. Dunn and R. C. Donald, “Infrared spectra of aqueous sodium benzoates and salicylates in the carboxyl-stretching region: chelation in aqueous sodium salicylates,” Canadian Journal of Chemistry, vol. 47, no. 24, pp. 4577–4588, 1969.
[26]
R. J. Young and P. A. Lovell, Introduction To Polymers, Nelson Thornes, 2nd edition, 1991.
[27]
N. P. S. Chauhan, “Terpolymerization of p-acetylpyridine oxime, p-methylacetophenone and formaldehyde, and its thermal studies,” Journal of Thermal Analysis and Calorimetry, vol. 110, no. 3, pp. 1377–1388, 2012.
[28]
M. L. Huggins, “The viscosity of dilute solutions of long-chain molecules. IV. Dependence on concentration,” Journal of the American Chemical Society, vol. 64, no. 11, pp. 2716–2718, 1942.
[29]
E. O. Kraemer, “Molecular weights of celluloses and cellulose derivates,” Industrial & Engineering Chemistry Research, vol. 30, no. 10, pp. 1200–1203, 1938.
[30]
H. L. Freidman, “Kinetics of thermal degradation of char-forming plastics from thermogravimetry. Application to a phenolic plastic,” Journal of Polymer Science C: Polymer Symposia, vol. 6, no. 1, pp. 183–195, 1964.
[31]
W. L. Chang, “Decomposition behavior of polyurethanes via mathematical simulation,” Journal of Applied Polymer Science, vol. 53, no. 13, pp. 1759–1769, 1994.
[32]
J. H. Sharp and S. A. Wentworth, “Kinetic analysis of thermogravimetric data,” Analytical Chemistry, vol. 41, no. 14, pp. 2060–2062, 1969.
[33]
E. S. Freeman and B. Carroll, “The application of thermoanalytical techniques to reaction kinetics. The thermogravimetric evaluation of the kinetics of the decomposition of calcium oxalate monohydrate,” The Journal of Physical Chemistry, vol. 62, no. 4, pp. 394–397, 1958.
[34]
J. J. Zsago, “Kinetic analysis of thermogravimetric data,” The Journal of Physical Chemistry, vol. 72, no. 7, pp. 2406–2411, 1968.