The school of thought of the Department of Organic Chemistry is focused on polyfunctional peroxide modifiers and polymer composites. The school was founded by the world-famed Prof. Tymofiy Yurzhenko and it has been developing for more than 50 years. Prof. T. Yurzhenko began original studies on the polymerization of vinyl and diene monomers in the presence of free radical initiators of various structures. The impact of the chemical structure and reactivity of the peroxide initiators on their distribution in different heterogeneous systems was revealed.
The intensive development of fundamental research favored the transformation of the research area. Based on these results, the basic research laboratory of the synthesis of novel polymeric materials, which was such a first laboratory at the Institute, was founded in 1958. Under the guidance of Prof. T. Yurzhenko, a novel class of chemical compounds, peroxide monomers, i.e. unsaturated peroxides capable of polymerizing and copolymerizing, were synthesized in this laboratory for the first time in the world. In the structure of the peroxide monomers, two reactive sites which are apparently incompatible with each other – a polymerizable double bond and a thermolabile peroxide group capable of initiating – were successfully combined in the same molecule. Different types of unique peroxide monomers and peroxide-containing polymers and rubbers, based on the peroxide monomers, were developed. More than 500 of such the monomers were synthesized and some of them are manufactured industrially.
In 1972, the further development of the research on peroxides was headed by Prof. Volodymyr Puchyn who was a disciple of Prof. T. Yurzhenko. Prof. V. Puchyn defended his dissertation, entitled ‘Research on the unsaturated polymerizable organic peroxides as surface modifiers’, in fulfillment for the degree of Doctor of Science in 1970. Pure and applied research has been conducted in the research area focused on the development of the theory of the synthesis and chemical modification of polymers and composites based on organic peroxides that reflected progress in the school of thought of the Department. Dr. Myrrha Vilenska, who elaborated synthetic approaches to the peroxide monomers, made a significant contribution to the development of the research area. A distinctive feature of the peroxide monomers developed by the school of thought of the Department of Organic Chemistry is the presence of conjugated multiple bonds in their molecules.
Based on the peroxide monomers, peroxide-containing oligomers and resins were synthesized under the guidance of Sc.D. Leonid Chuyko for the first time. The crosslinking of these oligomers and resins can be carried out due to the decomposition of the peroxide groups without adding sulfur (dissertation ‘Research on the synthesis, crosslinking, and application of peroxide-containing oligomers, resins, and latexes’ in fulfillment for the degree of Doctor of Science, 1980). This leads to the formation of rubbers with improved characteristics, e.g. enhanced ozone resistance, heat resistance, etc.
The systematic long-term study on aralkyl peroxides resulted in the synthesis of a range of original peroxides which are important practically. Some of them, such as Monoperoxin, are industrially manufactured. This part of the research was developed by Prof. Mykhaylo Dykyi (dissertation ‘Development of the methods of synthesis, properties, and application of functional aralkyl peroxides’ in fulfillment for the degree of Doctor of Science, 1988).
At the same time, the research on chemistry of functional peroxyesters based on aliphatic dicarboxylic acids and aromatic polycarboxylic acids was conducted under the guidance of Prof. Vladilena Fedorova (dissertation ‘Functional peroxyesters of polycarboxylic acids’ in fulfillment for the degree of Doctor of Science, 1991). The synthetic pathways to peroxide monomers and polymers – maleic acid derivatives – as well as surface active peroxyesters, based on pyromellitic dianhydride and poly(ethylene glycols), were elaborated.
The study on the synthesis of a new class of peroxides – organosilicon peroxides – carried out under the guidance of Dr. Oleksiy Litkovets was an important contribution into the development of the school of thought. The systematic study in this area resulted in the development of the novel original methods of the synthesis of unsaturated and polyreactive functional organosilicon peroxides. Peroxide polysiloxanes with a controlled number of peroxide groups were successfully synthesized. The peroxide polysiloxanes are able to crosslink by heating without additional crosslinkers.
Within the school of thought of the Department, a new research direction on the chemical modification of synthetic resins with organic peroxides and the synthesis of functional azodinitrile initiators was founded under the guidance of Prof. Michael Bratychak (dissertation ‘Synthesis, properties, and application of oligomers and aliphatic azodinitrile compounds with peroxy and epoxy groups’ in fulfillment for the degree of Doctor of Science, 1990).
The synthesis of a new class of polyreactive polymers also known as heterofunctional polyperoxides, which contain both peroxide and other active functional groups in their structure, was a great stride in the development of the school of thought done under the guidance of Prof. Stanislav Voronov (dissertation ‘Synthesis, properties, and application of heterofunctional polyperoxides’ in fulfillment for the degree of Doctor of Science, 1984). The presence of peroxide groups capable of homolytic reactions and polar functional groups capable of chemical or adsorption interactions opened the way to the modification and design of polymer composites using the heterofunctional polyperoxides. They have turned out multifunctional compounds which allow localizing a certain number of peroxide groups at the interface in various colloidal systems, e.g. emulsion, latexes, and filled polymers. The polyperoxides are capable of chemical transformation by the condensation mechanism to form water-soluble multicenter macroinitiators, polymeric peroxide emulsifiers, as well as various peroxide-modified fillers for polymer matrixes. The heterofunctional polyperoxides can interact with organic and mineral substrates through either simultaneous or consecutive consumption of both types of the functional groups to afford a controlled number of chemical bonds at the interface. Conducting these works resulted in the transformation of the research direction and the formation of a new research area which has been evolving under the guidance of Prof. Stanislav Voronov and is focused on the development of reactive and initiating systems for the functionalization (including peroxidation) of the interface, formation of special polymer nanolayers at the interface, and design of filled composites and biocompatible, biodegradable polymer materials.
The synthesis of the heterofunctional compounds and the development of the new research area gave a new powerful incentive to scientific research on novel possibilities to use chemical reactions for the formation and modification of polymeric materials. This led to the development of the theoretical foundations of the synthesis of polymeric materials and their modification with the heterofunctional polyperoxides and favored the further development of the school of thought of the Department (Prof. Volodymyr Shybanov, Prof. Sergiy Minko, Prof. Victor Tokarev, Sc.D. Orest Hevus, Prof. Olga Budishevska, Sc.D. Volodymyr Samaryk, Sc.D. Sergiy Varvarenko, Sc.D. Ananiy Kohut – adviser Prof. Stanislav Voronov).
- in 1993, Sergiy Minko defended his Sc.D. thesis entitled ‘Radical polymerization at the liquid – solid interface’.The main quantitative characteristics of the radical polymerization at the liquid – solid interface were determined. The kinetic models were developed to solve the parameters of a polymer adsorption layer, the features of mass transfer in the system, and the reactivity of the solid surface and the adsorbed macromolecule;
- in 1993, Volodymyr Shybanov defended his Sc.D. thesis entitled ‘Synthesis of photoinitiators and solid photopolymerizable materials’;
- in 2004, Victor Tokarev defended his Sc.D. thesis entitled ‘Interfacial reactions of functional oligomers, as a method for creation of nanolayers and composite materials’. A new approach to the formation of polymer layers with a prescribed structure and desirable properties on diverse substrates (either mineral or organic) has been developed and realized. The approach is based on the use of interfacial reactions of the functional oligomers. The oligomers’ functional groups facilitate the immobilization of the macromolecules at the substrate surface and participate in the formation of polymer compatibilizing layers grafted to the surface;
- in 2009, Volodymyr Samaryk defended his Sc.D. thesis entitled ‘Modification of polymer surfaces using polyperoxides’. The concept of peroxidizing the interface in various heterogeneous systems (i.e., polymer (surface) – gas (air), polymer – liquid, polymer – polymer) via the localization of the macromolecules of surface active heterofunctional polyperoxides and their controlled grafting to the polymer surface has been substantiated and developed. The mathematical model, describing the interface peroxidation processes during the formation of polyperoxide nanolayer grafted to the surface, has been developed;
- in 2010, Orest Hevus defended his Sc.D. thesis entitled ‘Functional surface active peroxides and monomers as reagents for obtaining reactive modifiers of surface’. The concept of the targeted synthesis of surface active peroxide monomers and other functional monomers has been offered for the first time. The concept consists in the application of functional compounds (i.e., peroxides, monomers, and substances forming the required surfmer type) as synthetic operators for the design of a surfmer molecule. Varying the nature of a peroxide fragment (hydroperoxides, peroxyesters, peroxides) with a desired temperature of a free radical process initiation, selecting a monomer constituent with a known activity of a C=C bond in copolymerization reactions (styrene, acrylate, methacrylate, maleate, maleimide), and a necessary nature and length of moieties forming lipophilic and hydrophilic constituents of a surfactant (alkyls, peroxyalkyls, fluoroalkyls, polydimethylsiloxanes, polyethylene glycols, saccharides, propane sultone, functional tetraalkylammonium salts) allows for synthesizing surfmers with a wide range of activity in copolymerization reactions, controlled surface activity and initiating properties;
- In 2011, Olga Budishevska defended her Sc.D. thesis entitled ‘Polymeranalogic conversion of polyanhydride and chitosan for creating selforganization of polymeric systems’. Theoretical and practical foundations of the synthesis of new heterofunctional alternating comb-like amphiphilic polyperoxides have been developed. The new copolymers contain a controlled ratio of lipophilic and hydrophilic moieties and a controlled number of peroxide groups in their structure that causes their surface activity and ability to initiate free radical reactions. New alternating amphiphilic comb-like copolymers poly(-olefin (or octyl methacrylate)-co-maleic anhydride—co-methylpolyoxyethyl maleate) with a controlled ratio of lipophilic and hydrophilic side chains have been synthesized via the polymeranalogic reactions of the acylation of polyethylene glycol monomethyl ethers with comb-like polyanhydrides which are able to change their conformation and microphase separate depending on a solvent nature. Optimal reaction conditions for the synthesis of the new copolymers have been determined. For the first time, the method for the synthesis of peroxychitosans with primary-tertiary peroxide groups has been developed using the polymeranalogic conversion of chitosan through its reaction with butenedioic acid tert-butylperoxymethyl ester. The peroxychitosan contains a controlled number of peroxide groups in the macromolecules that enables its ability to take part in free radical reactions;
- in 2013, Sergiy Varvarenko defended his Sc.D. thesis entitled ‘Aminofunctional polyesters of natural dibasic amino acids and polyether diols’.Scientific and practical foundations of the synthesis of aminofunctional polyesters based on dibasic -amino acids and different polyether diols have been developed. The chemistry and mechanism of the formation of their macromolecules have been studied and determined. The methods of the synthesis of amphiphilic polymers – aminofunctional copolyesters based on dibasic -amino acids and polyether diols – have been elaborated via a systematic study of the features of polyesterification utilizing a Steglich reaction. The mechanism of polyester-ether macromolecule formation has been studied using a kinetic method. For the first time, the assessment of variations of copolyester formation by the Steglich reaction has been carried out and optimization of the copolyester synthesis with a yield of over 90% has been conducted;
- in 2014, Alexander Zaichenko defended his Sc.D. thesis entitled ‘The synthesis of surface-active oligoperoxides, oligoperoxide metal complexes for obtaining functional nano- and microcomposites’. The basic foundations and the methods of the synthesis of novel in essence surface-active oligoperoxides, oligoperoxide metal complexes and derived functional polymer-polymeric and polymer-inorganic nano- and microcomposites for using in biology, medicine, and physics were developed. Main parameters of the control of their structure, colloidal, and chemical properties were determined.;
- in 2015, Ananiy Kohut defended his Sc.D. thesis entitled ‘Synthesis of invertible and reactive amphiphilic polymers and development of micellar structures based on them’. Theoretical and practical foundations of the synthesis of amphiphilic invertible polymers based on polyether diols of different nature and either diisocyanates or dicarboxylic acid anhydrides have been developed.Synthetic routes to segmented amphiphilic invertible polyurethanes based on polyether diols (i.e., polyethylene glycol and polytetrahydrofuran) and 2,4-tolylene diisocyanate have been elaborated via a systematic study of step-growth polymerization. Synthetic pathways towards amphiphilic invertible copolyesters based on succinic anhydride and the polyether diols have been developed. The effect of reaction conditions on the course of the reaction and the macromolecular configuration of the amphiphilic invertible polymers has been revealed. The chemistry of the formation of amphiphilic invertible polymer macromolecules has been studied and determined.
Since 1950th, 14 Doctors of Science and about 100 Doctors of Philosophy have been trained within the school of thought of the Department. Over 600 research papers and several monographs were published for the past 10 years. The function of Specialized Scientific Council D 35.052.01 that has been working for over 50 years with the participation of leading scientist from the Department (Prof. Stanislav Voronov, the Council Chair, Prof. Olga Budishevska, the Council Scientific Secretary, Prof. Victor Tokarev, D.Sc. Volodymyr Samaryk, D.Sc. Orest Hevus, D.Sc. Sergiy Varvarenko). The collective of the school of thought maintains contacts with 14 academic and scientific institutions in Ukraine, cooperates and has common papers with many foreign scientific institutions, e.g.
North Dakota State University (USA), University of Georgia (USA), PPG INDUSTRIES, INC (USA), University of North Техаs, Denton (USA), Queen's University, Department of Chemical Engineering and Department of Chemistry (Canada), Friedrich-Alexander-Universität Erlangen-Nürnberg (Germany), Chemical Institute of the Max Planck Society, Mainz (Germany), Technische Universität Dresden (Germany), DIC Berlin GmbH R & D Laboratory, Berlin (Germany), Institut für Experimentell Onkologie und Therapieforschung, München (Germany), DESY Deutsche Elektronen-Synchrotron Hamburg (Germany), Helmholtz Centre for Environmental, Department of isotope Biogeichemistry, Leipzig, (Germany), Università degli Studi di Milano (Іtaly), Taiwanian Textile Research Institute Тaipei (Тaiwan), Université Henri Poincaré Nancy I (France), University of Liverpool (Great Britain), Uniwersytet Jagielloński, Krakow (Polska), Istanbul University (Turkey), Yeditepe University (Turkey) and others.
The research of the school of thought is recognized worldwide. The Department of Organic Chemistry takes an active part in carrying out international research projects, e.g. Ukrainian-German project M/422-2011 ‘Development of new polymeric biocompatible materials based on pH-sensitive hydrogels as drug delivery systems’ (Ukraine, Ministry of Education and Science of Ukraine – Department of Physical Chemistry of Polymers of the Max Planck Institute for Polymer Research, Germany, 01-08-2012 – 31-12-2012), Ukrainian-German project M/143-2012 ‘Development of new polymeric biocompatible materials based on pH-sensitive hydrogels as drug delivery systems’ (Ukraine, Ministry of Education and Science of Ukraine – Department of Physical Chemistry of Polymers of the Max Planck Institute for Polymer Research, Germany, 2012 –2013).
Within the school of thought, new functional compounds and polymers based on them have been developed. The bases of new technologies have been suggested:
- Functional initiators of free radical processes of new types, the methods of their synthesis and application as crosslinkers for rubbers and polyolefins. Synthesis of new functional monomers for the development of peroxide-containing polymers and surfactants.
- Heterofunctional oligomeric peroxides for the application as emulsifiers-initiators of dispersion polymerization of vinyl and acrylic monomers as well as modifiers of the surface of mineral and organic fillers of polymers.
- Methods of the development and application of peroxide-containing adhesives such as dressings for fibrous fillers (e.g., carbon fiber, glass fiber, cord, etc.)
- Methods of the development of synthetic latexes and aqueous polymer dispersions with a controlled particle size such as emulsifier-free latexes, core-shell latexes, etc. Magnetic and fluorescent polymer carriers for immunodiagnostics.
- Scientific principles and methods of peroxide activation (modification) of the interface in colloid polymer systems which are the basis for the development of new technologies for the formation of highly filled and reinforced polymer composites for special applications.
- Design of drug delivery systems, e.g. for cancer treatment, through grafting biocompatible, biodegradable hydrogels to the polymer surface followed by the loading with a drug (polypeptides and so forth). Formation of crosslinked hydrogel nanoparticles for their application as drug carriers.
- Synthesis of metal (Ag, Au, Pt, etc.) and metal oxide (Fe2O3, Fe3O4, etc.) nanoparticles. Formation of self-assembled metal-filled 2D- and 3D-polymer structures.
- Peroxide activation of dispersed particles of the natural biopolymers (chitosan, dextran, cellulose) and formation of filled degradable biocompatible polymer composites with enhanced physico-mechanical properties.
Associate Professor of the Department of Organic Chemistry Yuri Panchenko