Journal of Thermal Analysis and Calorimetry

, Volume 108, Issue 3, pp 1111–1119 | Cite as

DSC study of polyhydroxyethylmethacrylate filled with modified silicas



Effects of the nature of functional groups (namely, hydroxyl, methyl, silicon hydride, amino, and vinyl) on the surface of pristine and modified silicas on polymerization of 2-hydroxyethylmethacrylate (HEMA) and on structural characteristics of the filled composites have been studied. DSC, FTIR spectroscopy and equilibrium water sorption (ESI) techniques were applied for the composites characterization. Results obtained testify that the chemical nature of the grafted groups has a strong influence on the monomer orientation in the surface layer of the filler. More uniform and cross-linked structures were detected in the composites with particularly methylated silica. Filler with chemically active silicon hydride groups promotes formation of ordered structure with rigid macromolecules. The presence of amino and vinyl groups on the silica surface results in formation of flexible polymer chains with a low cross-linking density or with a low polymerization degree, even at 2 wt% filling degree. Water uptake for composites with vinyl- and amine-containing silicas was low, indicating the close-packing of polymeric molecules in the filled polyHEMA.


2-Hydroxyethylmethacrylate (HEMA) Silica fillers Surface groups DSC Composite structure 


  1. 1.
    Tsarevsky NV, Min K, Jahed NM, Gao H, Matyjaszewski K. Functional degradable polymeric materials prepared by atom transfer radical polymerization. Degrad Polym Mater. ACS Symp Ser. 2006;939:184–200.CrossRefGoogle Scholar
  2. 2.
    Sun YM, Huang J–J, Lin F-C, Lai J-Y. Composite poly(2-hydroxyethyl methacrylate) membranes as rate-controlling barriers for transdermal applications. Biomaterials. 1997;18:527–33.CrossRefGoogle Scholar
  3. 3.
    Billaud C, Sarakha M, Bolte M. Polymerization of 2-hydroxyethyl methacrylate initiated by excitation of [Co(NH3)5N3]2+ at 365 and 546 nm. Eur Polym J. 2000;36:1401–8.CrossRefGoogle Scholar
  4. 4.
    Montheard JP, Chatzopoulos M, Chappard D. 2-Hydroxyethyl methacrylate (HEMA): chemical properties and applications in biomedical fields. J Macromol Sci C. 1992;32:1–34.CrossRefGoogle Scholar
  5. 5.
    Bajpai AK, Shrivastava MJ. Water sorption dynamics of a binary copolymeric hydrogel of 2-hydroxyethyl methacrylate (HEMA). Biomater Sci Polym Edn. 2002;13:237–56.CrossRefGoogle Scholar
  6. 6.
    Arica MY. Epoxy-derived pHEMA membrane for use bioactive macromolecules immobilization: covalently bound urease in a continuous model system. J Appl Polym Sci. 2000;77:2000–8.CrossRefGoogle Scholar
  7. 7.
    Sahoo SK, Prusty AK. Two important biodegradable polymers and their role in nanoparticle preparation by complex coacervation method—a review. Int J Pharm Appl Sci. 2010;1:1–8.Google Scholar
  8. 8.
    Samaržija-Jovanović S, Jovanović V, Konstantinović S, Marković G, Marinović-Cincović M. Thermal behavior of modified urea-formaldehyde resins, J. Therm Anal Calorim. 2011;104:1159–66.CrossRefGoogle Scholar
  9. 9.
    Alvarez VA, Pérez CJ. Effect of different inorganic filler over isothermal and non-isothermal crystallization of polypropylene homopolymer. (2011). J Therm Anal. doi:10.1007/s10973-011-1705-4.
  10. 10.
    Pracella M, Pancrazi C, Haque M, D’Alessio A. Thermal and microstructural characterization of compatibilized polystyrene/natural fillers composites. J Appl Polym Sci. 2011;103:95–101.Google Scholar
  11. 11.
    Guar MS, Rathore BS, Singh PK, Indolia A, Awasthi AM, Bhardwaj S. Thermally stimulated current and differential scanning calorimetry spectroscopy for the study of polymer nanocomposites. J Appl Polym Sci. 2010;101:315–21.Google Scholar
  12. 12.
    Rybiński P, Janowska G, Kucharska-Jastrząbek A. Influence of surface modification on thermal stability and flammability of cross-linked rubbers. J Appl Polym Sci. 2010;100:1037–44.Google Scholar
  13. 13.
    Bolbukh Yu, Kuzema P, Tertykh V, Laguta I. Thermal degradation of polyethylene containing antioxidant and hydrophilic/hydrophobic silica. J Therm Anal Calorim. 2008;94:727–36.CrossRefGoogle Scholar
  14. 14.
    Bolbukh YN, Tertykh VA, Gawdzik B. TGA and DSC studies of filled porous copolymers. J Therm Anal Calorim. 2006;86:125–32.CrossRefGoogle Scholar
  15. 15.
    Imai Y, Suzuki A. Effects of water and carboxylic acid monomer on polymerization of HEMA in the presence of N-phenylglycine. Dent Mater. 1994;10:275–7.CrossRefGoogle Scholar
  16. 16.
    Lipatov YuS, Kosyanchuk LV, Nesterov AE, Antonenk OI. Filler effect on polymerization kinetics and phase separation in polymer blends formed in situ. Polym Int. 2003;52:664–9.CrossRefGoogle Scholar
  17. 17.
    Worzakowska M. The kinetic study of the curing reaction of mono- and di-epoxides obtained during the reaction of divinylbenzene and hydrogenperoxide with acid anhydrides. Polymer. 2007;48:1147–54.CrossRefGoogle Scholar
  18. 18.
    Yanchevsky LK, Levandovsky VV. Determination of the parameters of the relaxation spectrum of polymers from the result of calorimetric measurement. Acta Polym. 1993;44:20–30.CrossRefGoogle Scholar
  19. 19.
    Samuneva B, Djambaski P, Kashchieva E, Chernev G, Kabaivanova L, Emanuilova E, Salvado IMM, Fernandes MHV, Wu A. Sol-gel synthesis and structure of silica hybrid biomaterials. J Non-Cryst Solids. 2008;354:733–40.CrossRefGoogle Scholar
  20. 20.
    Bulychev NA. Conformational changes in polymers adsorbed on titanium and iron oxides. Inorg Mater. 2010;46:393–8.CrossRefGoogle Scholar
  21. 21.
    Lingenfelser D, Prunici P, Hess P. Characterization of silicon-oxide interfaces and organic monolayers by IR-UV ellipsometry and FTIR spectroscopy. In: Proceedings of SPIE 6325, August 31, 2006.Google Scholar
  22. 22.
    Nguyen TT, Raupach IM, Janik LJ. Fourier-transform infrared study of ethylene glycol monoethyl ether adsorbed on montmorillonite: implications for surface area measurements of clays. Clays Clay Min. 1987;35:60–7.CrossRefGoogle Scholar
  23. 23.
    Ferreira L, Vidal MM, Gil MH. Evaluation of poly(2-hydroxyethyl methacrylate) gels as drug delivery systems at different pH values. Int J Pharm. 2000;194:169–80.CrossRefGoogle Scholar
  24. 24.
    Tranoudis I, Efron N. Water properties of soft contact lens materials. Cont Lens Anterior Eye. 2004;27:193–208.CrossRefGoogle Scholar
  25. 25.
    Kiremitçi M, Çukurova H, Özkar S. Spectral characterization and thermal behaviour of crosslinked poly(hydroxyethylmethacrylate) beads prepared by suspension polymerization. Polym Int. 1993;30:357–61.CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2011

Authors and Affiliations

  1. 1.Chuiko Institute of Surface Chemistry of NAS UkraineKyivUkraine
  2. 2.National Technical University of AthensAthensGreece

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