Group of high-performance materials (GHPM)

Head of group- Dr. Sci. - Evgenij Malykhin

Phone: 8(383)330-67-48
internal phone: 2-64
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The group was founded on May, 19, 2008, as a result of the integration of researchers of Technology Department and Group of plant material exploration.

The main tasks – development of the scientific basis for the formation of synthetic and native covalent, coordination, and hydrogen-bonded polymers and their compositions; study of specific physical, chemical and bioactive properties of these materials allowing to position them as functional materials for Hi-Tech Applications.

The group collaborates with scientific and technological departments of NIOC, Institutes of SB RAS. Research results are presented in the joint publications and reports on the Russian and international conferences.

The major scientific trends

• The development of the scientific basis for functionalization of perfluoroarenes to prepare the components for polymers, molecular associates and compositions.

• The synthesis of aromatic polymers of condensation type, investigating the relationships between structure and properties of macromolecules to create advanced high-performance materials. Developing approaches to modifying and doping polymer matrices with light-sensitive materials, pigments, nanoparticles to impart reguired properties for Hi-Tech applications.

• The design of crystal hydrogen-bonded supramolecular assemblies based on proton donor polyfluoroarenes and macrocyclic receptors; investigating the influence of the components nature on the parameters and properties of co-cryctals to develop mechanisms controlling the molecular recognition and creation of supramolecular assemblies with predictable architecture and properties.

• The isolation of native plant secondary metabolites and obtaining synthetic compositions, especially by affecting chemical materials with non-traditional physicochemical methods (supercritical conditions, ultrasonic-microwave assistance); elucidation of the regularities, which control the occurring processes; finding and detecting of new physicochemical and bioactive properties of the compositions for their use in Human-Friendly applications.

Scientific achievements

• The convenient method of selective aminodefluorination of polyfluoro(het)arenes having various substituents, based on the use of anhydrous ammonia as a reagent and a solvent simultaneously, was elaborated. The original effective technique for isolation of the individual polyfluoroaromatic diamines from non-selective reaction product mixtures, based on the molecular recognition phenomena under the action of crown ether, was elaborated. The technique is used for the preparation of highly pure diamine monomers.

• The methods of synthesis of highly fluorinated polyimides based on the novel perfluoroaromatic diamines were developed. The polyimides possess a valuable complex of the key properties (optical and dielectric) and good processability (solubility and thermal stability), thus being promising materials for high technologies. The first hydrogen-free aromatic polyimide of the AB-type was synthesized; the near-IR spectrum of the polyimide exhibit “the transparency window” needed for optical communication systems.

• The new group of objects for the crystals engineering was offered – the supramolecular 1D assemblies of polyfluoro(het)arylenediamines with 18-crown-6, which provide wide opportunities for the design of crystalline phases having desired structure and properties. The series of zigzag-like 1D assemblies of meta-arylenediamines with varied framework and substituents was designed. The dependences of the molar melting heat of co-crystals on the architecture of 1D assemblies and the supramolecular structural unit were revealed, which control the selective formation of a crystalline phase having the certain composition and structure.

• n cooperation with IC SB RAS. The high-temperature reactions of some monoterpenic hydrocarbons (pinenes, limonene, pyronenes, ocimenes, etc.) were studied under supercritical conditions (SCF). Aliphatic lower alcohols (methanol, ethanol, propanol, isopropanol, n-butanol), water, and its mixtures were used as SCF media. The influence of the reaction parameters (reaction temperature and pressure, duration, initial molar ratios of chemical components and so on) on products distributions was examined. The main pathways of monoterpenes conversion were identified, macrokinetics of reactions was studied in detail, the kinetic, thermodynamic, and thermochemical parameters of principal reactions were estimated and evaluated. The kinetic models of monoterpene thermal reactions, most of which are multidirectional and reversible, were developed based on all experimental and kinetic data obtained. New processing of sulfate turpentine and turpentine oil with using SCF media was developed.

• In cooperation with Technological department. The universal and low-waste technology of processing fir wood green was developed. The technology made it possible to triple productivity and obtain new prospective bioactive composition for agriculture and veterinary.

• In cooperation with NOICH departments, NSU, NSAU, Institutes of SB RAS, SB RAMS, SB RAAS, AS RUz, KIST (Korea). The screening of herbs trees and mushrooms extracts was carried out; some bioactive constituents including polyprenols and triterpenoids were discovered for the first time.

• In cooperation with ICKC SB RAS. The mechanism of reducing the flammability of ultrahigh-molecular-weight polyethylene with triphenyl phosphate additives was investigated.

A list of current projects

• Integration project SB RAS #97 “Investigation of physicochemical mechanisms of controlling mechanical, heat-conducting, and electrical insulating properties of composite polymeric materials with nanoadditives”. Coordinator – E.V. Malykhin (NIOCH SB RAS).
• RFBR 2011-2012, 11-03-12049-ofr-m, “Structural and dynamic properties of SCF: from the molecules-probes to the mechanisms of heterogeneous catalytic processes”. Leader – O.N. Martianov (IC SB RAS).

A list of the most important publications

• 1. O.P. Korobeinichev , A.A. Paletsky , L.V. Kuibida, M.B. Gonchikzhapov, I.K. Shundrina. Reduction of flammability of ultrahigh-molecular-weight polyethylene by using triphenyl phosphate additives. Proc. Combust. Inst. 2013, 34 (2), 2699–2706.
• T.A. Vaganova, S.Z. Kusov, I.K. Shundrina, Yu. V. Gatilov, E.V. Malykhin. Design and structural regularities of zigzag-like supramolecular 1D assemblies of polyhalogenated 2,6-, 2,4-diaminopyridines and 18-crown-6. J. Mol. Struct., 2013, 1033, 27-37.
• Khidyrova, N. K.; Rakhmatova, M. Zh.; Kukina, T. P.; Shakhidoyatov, R. Kh.; Shakhidoyatov, Kh. M. Polyprenols and triterpenoids from leaves of Alcea nudiflora. Chemistry of Natural Compounds, 2012, 48, 180-184.
• I. V. Shilova, T. P. Kukina, O. I. Salnikova, N. I. Suslov GC-MS analysis of meadowsweet overgraund part Filipendula ulmaria (Rosaceae) ethanolic extract. Plant resources (Russia), 2012, 48 (2), 244-253.
• I.V. Kozhevnikov, A.L. Nuzhdin, G.A. Bukhtiyarova, O.N. Martyanov, A.M. Chibiryaev. Tetramethyl orthosilicate as a sharp-selective catalyst of C3-methylation of indole by supercritical methanol. Journal of Supercritical Fluids, 2012, 69, 82–90.
• Method of obtaining of biologically active lipid fraction of Siberian fir (Abies Sibirica) wood green extract. RU 2336889; Method of processing fir tree greenery extraction wastes. RU 2348168; Method of obtaining biologically active sum of acids in complex extradiction processing of wood greens of Siberian fir (Abies Sibirica). RU 2372930; Agent for increasing yield of grain, leguminous and vegetable crops. RU 2437286.
• T.A. Vaganova, I.K. Shundrina, S.Z. Kusov, E.V. Karpova, I.Yu. Bagryanskaya, E.V. Malykhin. Synthesis and characterization of the first perfluoroaromatic polyimide of the AB-type. J. Fluorine Chem., 2012, 135, 129-136.
• Eun Ha Lee, S. A. Popov, Joo Young Lee, A. V. Shpatov, T. P. Kukina, Suk Woo Kang, Cheol-Ho Pan, Byung Hun Um, Sang Hoon Jung. Inhibitory Effect of Ursolic Acid Derivatives on Recombinant Human Aldose Reductasе. Bioorg Khim., 2011, 37 (5), P. 637-644.
• T. P. Kukina, E.N. Shmidt. Triterpenoids in the Conferous Plants of Pinaceae Family. Chemistry for Sustainable Development, 2011, (6), 655-59.
• A.M. Chibiryaev, A. Yermakova, I.V. Kozhevnikov, Activation parameters of supercritical and gas-phase β-pinene thermal isomerization. Russian Journal of Physical Chemistry A, 2011, 85 (9), 1505–1515.
• I.K. Shundrina, T.A. Vaganova, S.Z. Kusov, V.I. Rodionov, E.V. Karpova, E.V. Malykhin. Synthesis and properties of organosoluble polyimides based on novel perfluorinated monomer hexafluoro-2,4-toluenediamine. J. Fluorine Chem., 2011, 132 (3), 207-215.
• T.A. Vaganova, S.Z. Kusov, I.K. Shundrina, Yu. V. Gatilov, E.V. Malykhin. Design of zigzag-like supramolecular 1D assemblies of polyfluorinated meta-arylenediamines and 18-crown-6. J. Mol. Struct., 2011, 995, 109-115.
• A.M. Chibiryaev, A. Yermakova, I.V. Kozhevnikov. Chemical and phase equilibria calculation of α-pinene hydration in CO₂-expanded liquid. Journal of Supercritical Fluids, 2010, 51 (3), 295–305.
• S.Z. Kusov, V.I. Rodionov, T.A. Vaganova, I.K. Shundrina, E.V. Malykhin. Direct di- and triamination of polyfluoropyridines in anhydrous ammonia. J. Fluorine Chem., 2009, 130 (5), 461-465.
• I.K. Shundrina, T.A. Vaganova, S.Z. Kusov, V.I. Rodionov, E.V. Karpova, V.V. Koval, Yu.V. Gerasimova, E.V. Malykhin. Synthesis and characterization of polyimides based on novel isomeric perfluorinated naphthylenediamines. J. Fluorine Chem., 2009, 130 (8), 733-741.
• A.M. Chibiryaev, A. Yermakova, I.V. Kozhevnikov, Comparative reactivity of b-pinene thermolysis at gas-phase and supercritical conditions. Supercritical Fluids: Theory and Practice, 2008, 3 (4), 66–82 (in Russian).
• Thermal isomerization of α-pinene in supercritical fluids. RU 2300514; Thermal isomerization of α-/β-pinenes or turpentine. RU 2320630; The production of monoterpenic monomers and oligomers by isomerization of sulfate turpentine. RU 2369593.
• S.N. Kim, B.H. Um, C.Y. Kim, W. Lee, Y.S. Park, A.M. Chibiryaev, T.P. Kukina, E.V. Malykhin, T.A. Vaganova, S.A. Popov. Novel Types of Bioactivities for Extracts from Abies sibirica. Chemistry for Sustainable Development, 2008, N 1, 53-57.
• T.A. Vaganova, S.Z. Kusov, V.I. Rodionov, I.K. Shundrina, G.E. Sal’nikov, V.I. Mamatyuk, E.V. Malykhin. Amination of octafluoronaphthalene in liquid ammonia. 2,6- and 2,7-Diaminohexafluoronaphthalenes selective preparation. J. Fluorine Chem., 2008, 129 (4), 253-260.