Abstract
Glycidyl polyhedral oligomeric silsesquioxane (POSS) was used as a cross-linking agent to prepare a new organic–inorganic hybrid material from carboxyl-terminated poly(acrylonitrile-co-butadiene) (CTBN). The structure of the reacted material was characterized by Fourier transform infrared spectroscopy. Differential scanning calorimetry (DSC) at different heating rates in the presence and absence of catalyst, triphenyl phosphine (TPP), was conducted to investigate the curing kinetics. The reaction is catalyzed by the addition of TPP, and rate is maximum at higher catalyst concentrations. Different kinetic models were used to analyze the kinetic parameters. The effect of catalyst on curing process was determined by calculating the activation energy (E a) using Kissinger method. Dependency of E a with extent of conversion was monitored by different isoconversional methods. The curing mechanism of POSS–CTBN system followed autocatalytic model. Moreover, the predicted curves from the kinetic models fit well with the non-isothermal DSC curve. The E a of gelation obtained from rheological studies matched with that from DSC study, in league with the Flory’s theory of cross-linking.
Similar content being viewed by others
References
Markovic E, Constantopolous K, Matisons J. Polyhedral oligomeric silsesquioxanes: from early and strategic development through to materials application. In: Hartmann-Thompson C, editor. Applications of polyhedral oligomeric silsesquioxanes. Advances in silicon science. Netherlands: Springer; 2011. p. 1–46.
Schwab JJ, Lichtenhan JD. Polyhedral oligomeric silsesquioxane(POSS)-based polymers. Appl Organomet Chem. 1998;12(10–11):707–13. doi:10.1002/(sici)1099-0739(199810/11)12:10/11<707:aid-aoc776>3.0.co;2-1.
Laine RM, Roll MF. Polyhedral phenylsilsesquioxanes. Macromolecules. 2011;44(5):1073–109.
Liu Q, Ren W, Zhang Y, Zhang Y-X. Hydrogenated carboxylated nitrile rubber/modified zinc carbonate basic composites with photoluminescence properties. Eur Polym J. 2011;47(5):1135–41.
Varghese T, Muthiah R, David J, Kurian A, Athithan S, Krishnamurthy V, et al. Studies on composite extrudable propellant with varied burning rate pressure Index’n’. Defence Sci J. 2013;39(1):1–12.
Wang Y, Wang C, Yin H, Wang L, Xie H, Cheng R. Carboxyl-terminated butadiene-acrylonitrile-toughened epoxy/carboxyl-modified carbon nanotube nanocomposites: thermal and mechanical properties. Express Polym Lett. 2012;6(9):719–728.
Kuo S-W, Chang F-C. POSS related polymer nanocomposites. Prog Polym Sci. 2011;36(12):1649–96.
Lee Y-J, Kuo S-W, Huang C-F, Chang F-C. Synthesis and characterization of polybenzoxazine networks nanocomposites containing multifunctional polyhedral oligomeric silsesquioxane (POSS). Polymer. 2006;47(12):4378–86.
Liu Q, Ren W, Zhang Y, Zhang Y. Curing reactions and properties of organic–inorganic composites from hydrogenated carboxylated nitrile rubber and epoxycyclohexyl polyhedral oligomeric silsesquioxanes. Polym Int. 2011;60(3):422–9.
Liu Q, Ren W, Zhang Y, Zhang Y. A study on the curing kinetics of epoxycyclohexyl polyhedral oligomeric silsesquioxanes and hydrogenated carboxylated nitrile rubber by dynamic differential scanning calorimetry. J Appl Polym Sci. 2012;123(5):3128–36.
Brown ME, Dollimore D, Galwey AK. Reactions in the solid state. Amsterdam: Elsevier; 1980.
Murias P, Byczyński Ł, Maciejewski H, Galina H. A quantitative approach to dynamic and isothermal curing of an epoxy resin modified with oligomeric siloxanes. J Therm Anal Calorim. 2015. doi:10.1007/s10973-015-4703-0.
Tripathi M, Kumar D, Rajagopal C, Roy PK. Curing kinetics of self-healing epoxy thermosets. J Therm Anal Calorim. 2015;119(1):547–55.
Vyazovkin S, Wight C. Kinetics in solids. Annu Rev Phys Chem. 1997;48(1):125–49.
Janković B. Kinetic analysis of the nonisothermal decomposition of potassium metabisulfite using the model-fitting and isoconversional (model-free) methods. Chem Eng J. 2008;139(1):128–35.
Ozawa T. Estimation of activation energy by isoconversion methods. Thermochim Acta. 1992;203:159–65.
Friedman HL. New methods for evaluating kinetic parameters from thermal analysis data. J Polym Sci B. 1969;7(1):41–6. doi:10.1002/pol.1969.110070109.
Kissinger HE. Reaction kinetics in differential thermal analysis. Anal Chem. 1957;29(11):1702–6.
Flynn JH, Wall LA. General treatment of the thermogravimetry of polymers. J Res Nat Bur Stand. 1966;70(6):487–523.
Vyazovkin S. Modification of the integral isoconversional method to account for variation in the activation energy. J Comput Chem. 2001;22(2):178–83.
Liu YL, Chang GP, Hsu KY, Chang FC. Epoxy/polyhedral oligomeric silsesquioxane nanocomposites from octakis (glycidyldimethylsiloxy) octasilsesquioxane and small-molecule curing agents. J Polym Sci, Part A: Polym Chem. 2006;44(12):3825–35.
Ramírez C, Rico M, Torres A, Barral L, López J, Montero B. Epoxy/POSS organic–inorganic hybrids: ATR-FTIR and DSC studies. Eur Polym J. 2008;44(10):3035–45.
Konnola R, Parameswaranpillai J, Joseph K. Mechanical, thermal, and viscoelastic response of novel in situ CTBN/POSS/epoxy hybrid composite system. Polym Compos. 2015;. doi:10.1002/pc.23390.
Deng Y, Martin GC. Diffusion and diffusion-controlled kinetics during epoxy-amine cure. Macromolecules. 1994;27(18):5147–53.
Vyazovkin S, Wight CA. Model-free and model-fitting approaches to kinetic analysis of isothermal and nonisothermal data. Thermochim Acta. 1999;340:53–68.
Zhang C, Liu X, Cheng J, Zhang J. Study on curing kinetics of diglycidyl 1, 2-cyclohexane dicarboxylate epoxy/episulfide resin system with hexahydro-4-methylphthalic anhydride as a curing agent. J Therm Anal Calorim. 2015;120(3):1893–903.
Bai Y, Yang P, Zhang S, Li Y, Gu Y. Curing kinetics of phenolphthalein–aniline-based benzoxazine investigated by non-isothermal differential scanning calorimetry. J Therm Anal Calorim. 2015;120(3):1755–64.
Kasemsiri P, Neramittagapong A, Chindaprasirt P. Curing kinetic, thermal and adhesive properties of epoxy resin cured with cashew nut shell liquid. Thermochim Acta. 2015;600:20–7.
Xiong X, Ren R, Liu S, Lu S, Chen P. The curing kinetics and thermal properties of epoxy resins cured by aromatic diamine with hetero-cyclic side chain structure. Thermochim Acta. 2014;595:22–7.
Zabihi O, Aghaie M, Zare K. Study on a novel thermoset nanocomposite form DGEBA–cycloaliphatic diamine and metal nanoparticles. J Therm Anal Calorim. 2013;111(1):703–10.
Fernandez B, Corcuera M, Marieta C, Mondragon I. Rheokinetic variations during curing of a tetrafunctional epoxy resin modified with two thermoplastics. Eur Polym J. 2001;37(9):1863–9.
Núñez L, Taboada J, Fraga F, Núñez M. Kinetic study and time-temperature-transformation cure diagram for an epoxy-diamine system. J Appl Polym Sci. 1997;66(7):1377–88.
Auad ML, Nutt SR, Stefani PM, Aranguren MI. Rheological study of the curing kinetics of epoxy–phenol novolac resin. J Appl Polym Sci. 2006;102(5):4430–9.
Zlatanic A, Dunjic B. Rheological study of the copolymerization reaction of acrylate-terminated unsaturated copolyesters with styrene. Macromol Chem Phys. 1999;200(9):2048–58.
Santhosh Kumar K, Nair CR, Ninan K. Rheokinetic investigations on the thermal polymerization of benzoxazine monomer. Thermochim Acta. 2006;441(2):150–5.
Flory PJ. Principles of polymer chemistry. Ithaca: Cornell University Press; 1953.
Acknowledgements
One of the authors (Raneesh Konnola) thanks IIST for providing research fellowship.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Konnola, R., Nair, C.P.R. & Joseph, K. Cross-linking of carboxyl-terminated nitrile rubber with polyhedral oligomeric silsesquioxane. J Therm Anal Calorim 123, 1479–1489 (2016). https://doi.org/10.1007/s10973-015-5019-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10973-015-5019-9