Department of Synthesis and Characterization of Polymers

The aim of the department is to cover completely the expertise in synthesis of polymers using various polymerization techniques including free radical, reversible-deactivation radical and anionic polymerizations. The second object of synthesis represents preparation, spectral characterization and mainly utilization of different fluorescence probes for characterization of polymer microstructure and for polymerization study mechanism. Modification of polymers by grafting, crosslinking and functionalizations and preparation of polymeric and inorganic nanoparticles and hybrids represents another part of synthetic direction. Prepared as well as comercial polymers are characterised by spectral methods (UV-VIS, FTIR, Fluorescence and Raman spectroscopy), thermal analysis (DSC, TGA, chemiluminescence, thermal and photo stability, flammability) and their molar characteristics by advanced HPLC techniques. Electron spin resonance (ESR) and positron annihilation lifetime spectroscopy (PALS) techniques are used for the microscopic structural-dynamic characterization of various pure and composed organic materials.

Research Topics:

1. Study and development of reversible-deactivation radical polymerizations and synthesis of functional polymers
2. Inorganic and carbon (nano)particles and hybrids
3. Polymeric (nano)particles, (hydro)gels and (nano)fibres
4. Synthesis and properties of photoactive compounds
5. Synthesis of polymers and polymeric materials from renewable monomers
6. Degradation, stabilization and flammability of polymers
7. Liquid chromatography research for effective separation of macromolecules
8. Structure and physico - chemical properties of polymers

4. Synthesis, spectral properties and application of photoactive compounds

Fluorescent probes for study of polymers structures, microenvironment, processes in polymer fims and behaviour of polymers in solutions

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Main interest in this field is focused to the synthesis and spectral characterization of novel multifunctional fluorescence probes suitable for the characterization of microenvironment of complex polymer systems dynamic processes in this systems and their behavior in radical processes. The attention is also focused on general study of influence of paramagnetic center of stabile radical to the quenching of fluorescence of different fluorophores.

Related recent publications:

  • M. Danko, P. Kasák, P. Hrdlovič, „The interactions of probes based on substituted pyrene derivatives in polymer matrices; spectral study“, J. Photochem Photobiol. A: Chem., Vol. 307, p. 79-87 (2015). doi: 10.1016/j.jphotochem.2015.04.008M
  • J. Kollár, S. Chmela, P. Hrdlovič, „Spectral properties of bichromophoric probes based on pyrene and benzothioxanthene in solution and in polymer matrices“, J. Photochem. Photobiol A Chem., Vol. 270, p. 28 – 36 (2013).
  • C. Kósa, M. Danko, P. Hrdlovič, „Preparation and Spectral Characterization of Fluorescence Probes Based on 4-N,N-Dimethylamino Benzoic Acid and Sterically Hindered Amines“, J. Fluorescence, Vol. 22 (5), p. 1371-1381 (2012), DOI:10.1007/s10895-012-1076-7
  • M. Danko, E. Szabo, P. Hrdlovic, „Synthesis and Spectral Characteristics of Fluorescent Dyes Based on Coumarin Fluorophore and Hindered Amine Stabilizer in Solution and Polymer Matrices“, Dyes Pigm., Vol. 90 (2), p. 129-138 (2011), DOI: 10.1016/j.dyepig.2010.12.006
  • M. Danko, P. Hrdlovič, Š. Chmela, „The photolysis in polymer matrices of dyes containing a benzothioxanthene chromophore linked with a hindered amine“, Polym. Degrad. Stab., Vol. 96, p. 1955-1960, (2011). doi:10.1016/j.polymdegradstab.2011.08.006

New electro- and photo-active derivatives for electronic devices and other applications

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Synthesis and complex spectral characterization of novel electro- and photo-active derivatives and fluorescent labels with targeted spectral properties and their application in photonic and sensoric chemistry represents one of the major topic of the group with partners form SAS or abroad co-operations. In modern material research of novel organic molecules suitable for the application in electronics is connected with the tuning of the optical and electrochemical properties, e.g. using the suitable combination of chromophoric moieties. The defined combination of fluorene, perylene, phthalimide, tetrahydroquinoline, naphthyl phenothiazine and oxadiazole units represent nowadays an innovative basis for this material research. As a part of this research, synthesis of reactive fluorescent labels for preparation of different inorganic/organic hybrid materials as layered silicates or graphite-based nanoparticles is focused as well.

Related recent publications:

  • E. Kozma, G. Grisci, W. Mróz, M. Catellani, A. Eckstein-Andicsová, K. Pagano, F. Galeotti, “Water-soluble aminoacid functionalized perylene diimides: The effect of aggregation on the optical properties in organic and aqueous media“, Dyes and Pigments, Vol. 125, p. 201-209 (2016).
  • E. Kozma, W. Mróz, F. Villafiorita-Monteleone, F. Galeottia, A. Andicsová-Eckstein, M. Catellani, C. Botta, „Perylene Diimide Derivatives as Red and Deep Red-Emitters for Fully Solution Processable OLEDs“, RSC Adv., Vol. 6, p. 61175-61179 (2016).
  • M. Ilčíková, M. Danko, M. Doroshenko, A. Best, M. Mrlík, K. Csomorová, M. Šlouf, D. Chorvát Jr., K. Koynov, J. Mosnáček, Visualization of carbon nanotubes dispersion in composite by using confocal laser scanning microscopy. Eur. Polym. J., Vol. 79, p. 187-197 (2016). doi:10.1016/j.eurpolymj.2016.02.015
  • P. Kasák, J. Mosnáček, M. Danko, I. Krupa, G. Hloušková, D. Chorvát, M. Koukaki, S. Karamanou, A. Economou, I. Lacík, A polysulfobetaine hydrogel for immobilization of a glucose-binding protein. RSC Advances, Vol. 6, p. 83890-83900 (2016). doi: 10.1039/c6ra14423c;
  • S. Sas, M. Danko, K. Lang, J. Bujdák, „Photoactive hybrid material based on kaolinite intercalated with a reactive fluorescent silane“, Appl. Clay Sci., Vol. 108, p. 208-214 (2015), http://dx.doi.org/10.1016/j.clay.2015.02.031
  • M. Danko, A. Andicsová, P. Hrdlovič, D. Račko, D. Végh, „Spectral Characteristics of Carbonyl Substituted 2,2’-Bithiophenes in Polymer Matrices and Low Polar Solvents“, Photochem. Photobiol. Sci., Vol. 12 (7), p. 1210 – 1219 (2013), doi: 10.1039/c3pp50049g
  • M. Danko, A. Andics, C. Kosa, P. Hrdlovič, D. Vegh, Spectral Properties of Chalcone Containing Triphenylamino Structural Unit in Solution and in Polymer Matrices, Dyes Pigm., Vol. 92(3), p. 1257-1265, (2012). doi:10.1016/j.dyepig.2011.07.011

Photochemically active compounds for cross-linking and/or tailoring of degradability of polymers

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Special attention is devoted to the synthesis and evaluation of reactivity of photoactive compounds (phenyl ketones, 1,2-diketones) in synthetic (polystyrene, poly(methyl methacrylate), etc.) and biocompatible (poly(L-lactide), poly(-caprolactone), etc.) polymer matrices, photochemical in situ synthesis of free or pendant diacyl peroxides in polymer films, exploitation of diacyl peroxides for grafting and cross-linking and characterization of the final functional polymer materials. Crosslinking of polystyrene film with bis(dibenzoyl peroxides) formed from dibenzils by photoperoxidation with oxygen and visible light was studied too.

Related recent publications:

  • I. Lukáč, B. Husár, C. Kósa, J. Faryová „Method for cross-linking of polymer films”. International application No. PCT/SK2014/050008 (WO2014209241)
  • Cs. Kosa, M. Sedlacik, A. Fiedlerova, Š. Chmela, K. Borska, J. Mosnacek „Photochemically cross-linked poly(e-caprolactone) with accelerated hydrolytic degradation”, Eur. Polym. J., Vol. 68, p. 601–608 (2015).
  • I. Lukáč, Cs. Kósa, B. Husár, „1,4-Bisbenzil: Visible-light- and heat-assisted crosslinking of polystyrene films”, Macromol. Chem. Phys., Vol. 215, p. 171 – 176 (2014).
  • J. Mosnáček, K. Borská, M. Danko, I. Janigová, „Photochemically promoted degradation of poly(ɛ-caprolactone) film“, Mater. Chem. Phys., Vol. 140, p. 191-199 (2013), doi: 10.1016/j.matchemphys.2013.03.021
  • J. Mosnacek, I. Lukac, M. Bertoldo, F. Ciardelli „Applicability of photochemically generated pendant benzoyl peroxides in both “grafting from” and “grafting to” techniques”, Chem. Papers, Vol. 67 (1), p. 9-17 (2013).
  • B. Husár, N. Moszner, I. Lukáč, „Synthesis and photooxidation of styrene copolymer bearing camphorquinone pendant groups”, Beilst. J. Org. Chem., Vol. 8, p. 337 – 343 (2012).
  • B. Husár, I. Lukáč, „Photooxidation of camphorquinone in polystyrene matrix”, J. Photochem. Photobiol. A Chem., Vol. 233, p. 189–193 (2011).
  • Š. Chmela, A. Fiedlerová, I. Janigová, I. Novák, E. Borsig „Grafting of iPP powder with methacrylate monomers in water medium”, J. Appl. Polym. Sci., Vol. 119, p. 2750–2758 (2011).