This Article Abstract Free Full Text (Free PDF) Free Alert me when this article is cited Alert me if a correction is posted Services Email this article to a friend Similar articles in this journal Similar articles in Web of Science Alert me to new issues of the journal Add to Saved Citations Download to citation manager Request Permissions Request Reprints Add to My Marked Citations Citing Articles Citing Articles via Google Scholar Citing Articles via Scopus Google Scholar Articles by Hurduc, N. Articles by Hurduc, N. Search for Related Content Social Bookmarking                         What's this?

The Non-isothermal Degradation Process of some Polyethers and Azo-polyethers

Gh. Asachi' Technical University Iasi, Faculty of Chemical Engineering, B-dul D. Mangeron 71, Iasi-700050, Romania

Gabriela Lisa

Gh. Asachi' Technical University Iasi, Faculty of Chemical Engineering, B-dul D. Mangeron 71, Iasi-700050, Romania, gapreot{at}ch.tuiasi.ro or gapreot{at}yahoo.com

Cristina Damian

Al. I. Cuza' University Iasi, Faculty of Chemistry, B-dul Carol I, No. 11, 700506 Iasi, Romania

Violeta Toader

Department of Pharmacology & Toxicology, Queen's University, Kingston K7L 3N6, Canada

Natalia Hurduc

Al. I. Cuza' University Iasi, Faculty of Chemistry, B-dul Carol I, No. 11, 700506 Iasi, Romania

The paper presents a non-isothermal kinetic study of the degradation process of some aromatic copolyethers containing a tetra-methylenic spacer. The polymers were synthesized using the phase transfer catalysis technique, starting from 1,4-dichlorobutane and various bisphenols (4,4^'-dihidroxyazobenzene, 4,4^'-dihydroxydiphenyl, bisphenol A and 2,7-dihydroxynaphthlene). Dynamic thermal analysis methods such as ATG, DTG and ATD were used. In order to work out the basic kinetic parameters and the reliance between activation energy and conversion degree, differential methods based on the `order reaction model' were applied and standard kinetic models were also used. The thermostability of the good samples up to 320^°C was demonstrated. The degradation mechanism took place by successive reactions, controlled by a nucleation process influenced by the polymer molecular structure.

Key Words: Thermal behavior • thermal stability • aromatic copolyethers • kinetic parameters

References

• Hurduc, N., Damian, C., Tarus, A., Toader, V. and Hurduc, N. (2005). Thermal Behavior of some Aromatic Copolyethers containing a Propylenic Spacer, CEJC, 3(1): 53—59.
• Hurduc, N., Prajinaru, M., Creanga, A., Alazaroaie S. and Hurduc, N. (2004). The Non-isothermal Kinetic Study of the Thermal Degradation Processes of some Aso-polymeric Liquid Crystals, Rev. Mat. Plast., 41(1): 41—44.
• Sfichi-Damian, C., Hurduc, N., Hurduc, N., Shanks, R., Yarovski, I. and Pavel D. (2003). Thermal behavior and molecular simulation of liquid crystalline polymers containing a pentamethylenic spacer, Comput. Mat. Sci., 2(4): 393—402.
• Hurduc, N., Creanga A., Pokol, G., Novák, C., Alazaroaie, S. and Hurduc, N. (2002). The Degradation Mechanism using TG-MS Technique of some Aromatic Polyethers containing Flexible Spacers, J. Therm. Anal. Cal., 70: 877—887.[CrossRef]
• Creanga, A., Pokol, G., Hurduc, N., Novák, C., Alazaroaie, S. and Hurduc, N. (2001). Thermal Behavior and Primary Degradation Mechanism of some Aromatic Polyethers with semi-flexible Chain, J. Therm. Anal. Cal., 66(3): 859—968.[CrossRef]
• Tarus, A., Hurduc, N., Catanescu, O., Cobzaru C. and Hurduc, N. (2000). Phase Transfer Catalysis in Polycondensation Processes XXIV. On the Thermal Stability of some Aromatic Polyethers containing a Propylenic Spacer, Polym. Degrad. Stab., 68: 87—91.[CrossRef]
• Hurduc, N., Prajinaru, M., Donose, B., Pavel, D. and Hurduc, N. (2001). Thermal Behaviour and Molecular Modelling of some Aromatic Polyethers containing a Hexamethylenic Spacer, Polym. Degrad. Stab., 72: 441—445.[CrossRef]
• Hurduc, N., Prajinaru, M., Hurduc, N. and Alazaroaie S. (2002). Influence of the Heating Rate on the Thermal Behavior of some Aromatic Co-polymers with Octamethylenic Spacer, Rev. Mat. Plast., 39(1): 231—234.
• Damian, C., Hurduc, N., Alazaroaie, S. and Hurduc, N. (2002). Kinetic Non-isothermal Studies on Thermal Degradation of some Aromatic Copolyethers with Flexible Spacer of Pentamethylenic Type, Anal. St. Univ. "Al.I.Cuza", s. Chimie, X(1): 49—56.
• Alazaroaie, S., Catanescu O., Toader, V., Taran, E., Pavel, D., Hurduc N. and Scutaru D. (2005). Liquid Crystalline Polymers. 15. Synthesis and Thermal Behavior of some Aromatic Polyethers containing Different Spacers, High Perform. Polym., 17: 149—160.[CrossRef]
• Alazaroaie, S., Hurduc, N., Scutaru, D., Dumitrascu, A., Petraru, L. and Simionescu, C.I. (2003). Phase Transfer Catalysis in the Polycondensation Processes. XXV. The Relationship between Structure and Supramolecular Ordering of some Polyethers containing Flexible Spacers, J. Macromolec. Sci.- Pure and Appl. Chemistry, A 40 (11): 1241—1251.
• Freeman, E. and Carroll, B. (1958). The Application of Thermoanalytical Techniques to Reaction Kinetics. The Thermogravimetric Evaluation of the Kinetics of the Decomposition of Calcium Oxalate Monohydrate, J. Phys. Chem., 62: 394—397.[CrossRef][Web of Science]
• Coats, A.N. and Redfern, R. (1964). Kinetic Parameters from Thermogravimetric Data, Nature, 201: 68— 73.[CrossRef]
• Flynn, J.N. and Wall, L.A. (1966). A Quick, Direct Method for the Determination of Activation Energy from Thermogravimetric Data, Polym. Lett., 4: 323—328.[CrossRef]
• Reich, L. and Lewi, D.W. (1963). Thermal stability indices for polymeric materials based on energy considerations. Macromol. Chem., 66: 102—110.[CrossRef]
• Garn, P.D. (1965). Thermoanalytical Methods of Investigation, Academic Press, New York.
• Gorbacev, V.M., Nicolaev, A.V. and Logvinenko, V.A., (1974). J. Therm. Anal., 6: 473—479 ref. in Gorbachev, V.M. (1975). A Solution to the Exponential Integral in the Non-isothermal Kinetics for Linear Heating, J. Therm. Anal., 6: 349—350.
• Vyazovkin, S. (2000). Kinetic Concepts of Thermally Stimulated Reactions in Solids: a View from a Historical Perspective, Int. Rev. Phys. Chem., 19: 45—60.[CrossRef]
• Vyazovkin, S. and Lesnikovich, A.L. (1992). Practical Application of Isoconversional Methods, Thermochim. Acta, 203: 177—185.[CrossRef]
• Vyazovkin, S., Dranca, I., Fan, X. and Advincula R. (2004). Degradation and Relaxation Kinetics of Polystyrene-Clay Nanocomposite Prepared by Surface Initiated Polymerization, J Phys Chem B, 108: 11672—11679.[Web of Science]
• Hurduc, N. and Ionescu, D. (1992). The Compensation Effect in the Field of Thermal Degradation of Grafted Celluloses under Non-isothermal Conditions, Cell. Chem. Techn., 26: 167—177.
• Galvey, A.K. and Brown, M.E. (1999). Thermal Decomposition of Ionic Solids. Amsterdam, Elsevier.
• Luo, Y., Chen, P., Zhao, F-Q., Hu, R-Z., Li, S-W. and Gao Y. (2004). Kinetics and Mechanism of the Thermal Decomposition Reaction of 3,3-bis(azidomethyl)oxetane/tetrahydrofuran Copolymer, Chin. J. Chem., 22: 1219—1224.

This version was published on August 1, 2007

High Performance Polymers, Vol. 19, No. 4, 477-496 (2007)
DOI: 10.1177/0954008307078520


CiteULike    Complore    Connotea    Del.icio.us    Digg    Reddit    Technorati    Twitter    What's this?

This Article Abstract Free Full Text (Free PDF) Free Alert me when this article is cited Alert me if a correction is posted Services Email this article to a friend Similar articles in this journal Similar articles in Web of Science Alert me to new issues of the journal Add to Saved Citations Download to citation manager Request Permissions Request Reprints Add to My Marked Citations Citing Articles Citing Articles via Google Scholar Citing Articles via Scopus Google Scholar Articles by Hurduc, N. Articles by Hurduc, N. Search for Related Content Social Bookmarking                         What's this?