Abstract
In this research, an effort was undertaken to investigate radical polymerization kinetics using experimental data from DSC measurements and mechanistic or isoconversional models. Polymerization of a polar monomer, namely 2-hydroxyethyl methacrylate in the presence of benzoyl peroxide initiator was studied. The variation of the effective activation energy with conversion was directly interpreted in terms of the physical phenomena taking place during the reaction in a microscale. Both isothermal and non-isothermal DSC data were employed and the effect of diffusion-controlled phenomena on the reaction kinetics at different conversion regimes was assessed. Finally, the effect of the presence of nanofiller on polymerization kinetics and the activation energy values were estimated and correlated to physical phenomena taking place during polymerization.
Similar content being viewed by others
References
Achilias DS, Nikolaidis AK, Karayannidis GP. PMMA/organomodified montmorillonite nanocomposites prepared by in situ bulk polymerization. Study of the reaction kinetics. J Therm Anal Calorim. 2010;102(2):451–60.
Achilias DS, Sideridou I. Kinetics of the benzoyl peroxide/amine initiated free-radical polymerization of dental dimethacrylate monomers: experimental studies and mathematical modelling for TEGDMA and bis-EMA. Macromolecules. 2004;37:4254–65.
Viciosa MT, Quiles Hoyo J, Dionisio M, Gomez Ribelles JL. Temperature modulated DSC study of the kinetics of free radical isothermal network polymerization. J Therm Anal Calorim. 2007;90:407–14.
Ye G, Cui Y, Liu X, Zhou H. Kinetic investigation of photopolymerization initiated by oligomeric photolatent base. J Therm Anal Calorim. 2013;112:1499–506.
Achilias DS. A review of modelling of diffusion-controlled polymerization reactions. Macromol Theory Simul. 2007;16:319–47.
Holmes RL, Campbell JA, Linser R, Hook JM, Burford RP. In-situ preparation of poly(2-hydroxyethyl methacrylate)-titania hybrids using γ-radiation. Polymer. 2011;52:4471–9.
Oral A, Shahwan T, Güler C. Synthesis of poly(2-hydroxyethyl methacrylate)–montmorillonite nanocomposites via in situ atom transfer radical polymerization. J Mater Res. 2008;23:3316–22.
Bolbukh Yu, Tertykh V, Klonos P, Pissis P. DSC study of polyhydroxyethylmethacrylate filled with modified silicas. J Therm Anal Calorim. 2012;108:1111–9.
Ajzenberg N, Ricard A. Kinetic study by DSC of the bulk copolymerization of 2-hydroxyethyl methacrylate with ethyleneglycol dimethacrylate. J Appl Polym Sci. 2001;80:1220–8.
Sbirrazzuoli N, Vyazovkin S. Learning about epoxy cure mechanisms from isoconversional analysis of DSC data. Thermochim Acta. 2002;388:289–98.
Zeng X, Yu S, Sun R. Effect of functionalized multiwall carbon nanotubes on the curing kinetics and reaction mechanism of bismaleimide-triazine. J Therm Anal Calorim. 2013;114:387–95.
Zabihi O, Omrani A, Rostami A. Thermo-oxidative degradation kinetics and mechanism of the system epoxy nanocomposite reinforced with nano-Al2O3. J Therm Anal Calorim. 2012;108:1251–60.
Liang K, Hutchinson RA. Solvent effects on free radical copolymerization propagation kinetics of styrene and methacrylates. Macromolecules. 2010;43:6311–20.
Zavaglia R, Guigo N, Sbirrazzuoli N, Mija A, Vincent L. Complex kinetic pathway of furfuryl alcohol polymerization catalyzed by green montmorillonite clays. J Phys Chem B. 2012;116:8259–68.
Acknowledgements
I would like to thank ELKE, A.P.Th for financial supporting of this research (Project No 89569).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Achilias, D.S. Investigation of the radical polymerization kinetics using DSC and mechanistic or isoconversional methods. J Therm Anal Calorim 116, 1379–1386 (2014). https://doi.org/10.1007/s10973-013-3633-y
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10973-013-3633-y