Major fundamental and applied research results

New reaction: quadricyclane and vinyl silanes condensation

A new reaction in chemistry of organoelemental compounds was found: quadricyclane and vinyl silanes condensation. This reaction allowed to carry out synthesis of the new norbornene-type monomers containing bulky substituents – trimethylsilyl groups. An important feature of the produced monomers is their ability to active vinyl polymerization with formation of the new-class high-molecular polycarbosilanes with the side Me3Si groups responsible for the high gas-separating characteristics. Thus, the principle goal of synthesis of saturated, thermo- and chemo-stable polycarbosylanes - perspective materials for membranes – was achieved.

Professor E. Sh. Finkelstein
(495) 955-43-79

Nanostructured metal-carbon catalysts of hydrocarbon dehydrogenation

New nanostructured metal-carbon catalysts of hydrocarbon dehydrogenation were developed.  Introduction of metal into the carbon carrier structure is carried out in situ during the composition infrared pyrolysis based on polyacrylonitrile (PAN), detonating nanodiamonds (DND) and salts PtCl4 and RuCl3 at the ratio Pt:Ru=9:1, PAN:DND=1:100 – 1:10. It was found by the methods of X-ray diffraction and X-ray phase analysis that in the infrared pyrolysis conditions in situ Pt-Ru alloy nanoparticles are forming with the mean size 6-8 nm. Using produced catalysts 100% cyclohexane conversion to benzene at 100% selectivity was achieved.

Professor G.P. Karpacheva
(495) 955-43-55

Membrane switch module of the new generation for the energy carriers (methane, hydrogen) separation from low-caloric gas mixtures

Membrane switch module of the new generation for the energy carriers (methane, hydrogen) separation from low-caloric biogenous gas mixtures was developed. High gas-separating parameters of the module are achieved by using original high-permeable composite membranes based on trimethylsilypropyne, and also by new structural solutions of the gas-liquid membrane package. Biogas components separation selectivities achieve 103.
A draft design of the gas-separating unit of 50m3/h on input biogas was developed.

Professor V.V. Teplyakov
(495) 955-43-46

TIPS RAS developments prepared or assigned for the implementation

Catalyst production technology of direct DME synthesis from syngas

Catalyst production technology of direct DME synthesis from syngas was developed. A trial catalyst batch (10kg) was produced and pilot testing was carried out on the NIAP plant industrial equipment (Novomoskovsk town) which showed widespread compliance with the laboratory samples.

N.V. Kolesnichenko, Doctor of Chemistry
(495) 955-42-89
M.A. Kipnis, Candidate of Chemistry
(495) 955-41-44

Catalyst production technology of gasoline synthesis from dimethyl ether

Specifications for the zeolite catalyst production of gasoline synthesis from dimethyl ether were developed jointly with Angarsk plant of catalysts and organic synthesis. Recommendation for the trial catalyst batch (50kg) production was issued on the basis of testing of the trial catalyst samples prepared according to TIPS RAS recipes. The catalyst will be tested on the pilot unit constructed under the joint project of EON plc and TIPS RAS. Obtained data allowed to conclude that TIPS RAS-developed technology of gasoline production from syngas via DME without its intermediate separation includes conditions for stable catalyst operation for a long time (at least two years) without regeneration.

N.V. Kolesnichenko, Doctor of Chemistry
(495) 955-42-89

Fuel oil-to-ethylene processing technology

Regulations for the pilot unit design of thermochemical fuel oil processing with ethylene production were developed. The process technology based on thermochemical initiation principle consisting in production of heat carrier in which combustion reactions are not finished yet, with the subsequent fuel oil feed to the flow of such heat carrier. This principle combines high temperature and big amount of high-active ions, electrons and radicals allowing to decrease methane and hydrogen yield in comparison of traditional processes and to provide the maximum process effectiveness on ethylene yield.

S.N. Khadzhiev, academician
Kh.M. Kadiev, Candidate of Chemistry
(495) 955-42-38

High-octane petrol component production by isobutene alkylation with olefins

A high-effective clean technology of isobutene alkylation with C2-C4 olefins over heterogeneous zeolite nanostructured catalytic systems was developed. The catalyst production technology was tested on Angarsk, Novokuibyshevsk and Grozny catalyst plants. The developed alkylation technology was proved on the pilot and demonstration units of GrozNII pilot plant.
Olefins conversion is more than 92%, selectivity to isooctane alkylate fraction is 82%. The alkylation product, so-called alkylgasoline, has octane number 92 according to the motor method and 99 - according to the research method. It is highly competitive with alkylgasoline produced by the traditional energy-consuming sulfuric alkylation, which causes big ecological problems. The work is patented by Russian patents and is ready for implementation.

S.N. Khadzhiev, academician
I.M. Gerzeliev
(495) 955-42-27

Benzene alkylation with ethylene over heterogeneous nanostructured catalysts

TIPS RAS jointly with GrozNII and Salavatnefteorgsintez plc developed and implemented the first Russian technology of benzene alkylation with ethylene over heterogeneous zeolite catalysts. The technology is characterized by low energy consumption, high productivity and selectivity to ethylbenzene, ecological cleanness compared to the traditional technology using aluminum chloride as a catalyst. The developed catalytic system operates 4,000 hours without loss of activity and allows to use ethylene with 10-90% pureness. Catalyst regeneration is carried out in situ without discharge by oxygen feed. Ethylbenzene yield at the quantitative ethylene conversion is 99%. The technology is implemented in Salavatnefteorgsintez plc and allows to produce 230,000 tons of high-quality ethylbenzene – the feed for styrene production – monomer for polystyrene, one of the bulkiest polymers.

S.N. Khadzhiev, academician
I.M. Gerzeliev
(495) 955-42-27

Polymeric nanocomposites for medicine and cosmetology

Nanocomposites with high adhesion to skin and wet biological tissues were produced for the first time on the basis of the method of tailor-made polymeric hydrogels and hydrocolloids design developed by TIPS RAS. Injection of clay nanoparticles, which act as structure reinforcers and humid sorbents, into composites allowed to use interplanar spaces of crystalline structure for medicine immobilization. The work was performed with financial support from CRDF and within the contract with Corium Int. (USA). The work is patented with a number of USA and European Union patents (jointly with Corium Int.). on the base of these polymeric nanocomposites TIPS RAS developed hydrogel- and film-based preparations and Corium Int. established its production in USA. At present enamel-recovering preparations, sticky feet supinators are realized on American and Canada pharmaceutical markets.

V.G. Kulichikhin, RAS corresponding member
M.M. Feldstein, Candidate of Chemistry
(495) 955-43-72

Membrane technology of pure hydrogen separation (99,9999%) from industrial gas mixtures

TIPS RAS developed the technology of pure hydrogen separation from industrial hydrogen-containing gas mixtures using flat metal membranes based on alloys of palladium and I, III, IV, VI-VIII Groups metals. Jointly with Institute of Metallurgy RAS physical, chemical and membrane properties of the alloys were studied, foil 20-50 μm in thickness, membrane elements and apparatus were produced. Pilot testing of membrane modules and modular-type units with the pure hydrogen capacity from several tens of liters to 1,000 m3/g on different gas mixtures showed high specific permeability (up to 300 m3/m2·h·MPa 0,5) with absolute selectivity to hydrogen of 99,9999% pureness. Continuous lifetime of the membrane modules is more than 15,000 hours without loss of performance. The work is patented with Russian patents.
Recently investors are interested in the process of hydrogen concentration regulation to use it in polysilicon production processes for solar batteries and microelectronics and also for organosilicon compounds production. TIPS RAS has an arrangement with Fraunhofer Institute for Solar Energy Systems (Germany) and a number of Russian enterprises about pilot testing in 2009-2010 to prove the technology of pure hydrogen production under polysilicon production, and also an arrangement with GNIIKhTEOS – to prove the technology in organosilicon compounds production.

Professor D.I. Slovetsky
(495) 955-42-41

Scientific-organizational and publishing activities

In 2008 the Institute organized a number of scientific conferences:

• V International Symposium on theoretical and applied plasma chemistry, September 3-8, Ivanovo.
• Russian-French Seminar “Membranes and molecular selective separation processes”, October 7-10, Zvenigorod.
• 24th Symposium on Rheology, June 3-7, Karacharovo.
• IX Conference of young scientists on petroleum chemistry for the Kh.M. Minachev 100th anniversary, October 7-10, Zvenigorod.

In November 2008 Russian-Dutch International Laboratory “Membrane separation technologies for petroleum and gas industry” was established by TIPS RAS and Netherlands Organization for Applied Scientific Research (TNO).

• G. V. Kozlov, A. Kh. Malamatov, E. M. Antipov, A. K. Mikitaev.  The interrelations of elasticity modulus and amorphous chains lightness for nanocomposites based on the polypropylene. 2008 Chapter № 8 In Polymers, Polymer Blends, Polymer Composites and Filled Polymers: Synthesis, Properties, Applications. Eds. A. K. Mikitaev, M. Kh. Ligidov, G. E. Zaikov, N.-Y. Nova Science Publishers, Inc. P. 77.
• I. Benedek, M.M. Feldstein (Editors), Handbook of Pressure-Sensitive Adhesives and Products, vol. 1: Fundamentals of Pressure-Sensitivity; vol. 2: Technology of Pressure-Sensitive Adhesives and Products; vol. 3: Applications of Pressure-Sensitive Products; CRC - Taylor & Francis, Boca Raton, London, New York, 2008, 1100 pp.
• I. Benedek, M.M. Feldstein (Editors), Fundamentals of Pressure Sensitivity (Handbook of Pressure-Sensitive Adhesives and Products), CRC - Taylor & Francis, Boca Raton, London, New York, 2008, 368 pp.
• I. Benedek, M.M. Feldstein (Editors), Technology of Pressure-Sensitive Adhesives and Products (Handbook of Pressure-Sensitive Adhesives and Products), CRC - Taylor & Francis, Boca Raton, London, New York, 2008, 576 pp.
• I. Benedek, M.M. Feldstein (Editors), Applications of Pressure-Sensitive Products (Handbook of Pressure-Sensitive Adhesives and Products), CRC - Taylor & Francis, Boca Raton, London, New York, 2008, 384 pp.
• M.M. Feldstein, G.W. Cleary, P. Singh, Hydrophilic Adhesives, in: I. Benedek, M.M. Feldstein (Editors), Technology of Pressure-Sensitive Adhesives and Products (Handbook of Pressure-Sensitive Adhesives and Products), CRC - Taylor & Francis, Boca Raton, London, New York, 2008, Chapter 7, pp. 7-1 - 7-80
• M.M. Feldstein, M.B. Novikov, C. Creton, Significance of Relaxation for Adhesion of Pressure-Sensitive Adhesives, in: I. Benedek, M.M. Feldstein (Editors), Fundamentals of Pressure Sensitivity (Handbook of Pressure-Sensitive Adhesives and Products), CRC - Taylor & Francis, Boca Raton, London, New York, 2008, Chapter 11, pp. 11-1 - 11-62
• M.M. Feldstein, Molecular Nature of Pressure-Sensitive Adhesion, in: I. Benedek, M.M. Feldstein (Editors), Fundamentals of Pressure Sensitivity (Handbook of Pressure-Sensitive Adhesives and Products), CRC - Taylor & Francis, Boca Raton, London, New York, 2008, Chapter 10, pp. 10-1 - 10-43
• O.A. Soboleva, A.V. Semakov, S.V. Antonov, V.G. Kulichikhin. 2008. Surface Phenomena on a Solid-Liquid Interface and Rheology of Pressure Sensitivity. In Fundamentals of Pressure Sensitivity, I. Benedek and M. Feldstein, Ed., CRC Press, Boca Raton - London - New York, Chapter 1, pp. 1-1 - 1-24.
• S.V. Antonov, V.G. Kulichikhin. 2008. Shear Resistance. In Fundamentals of Pressure Sensitivity, I. Benedek and M. Feldstein, Ed., CRC Press, Boca Raton - London - New York, Chapter 8, pp. 8-1 - 8-18.
• V.G. Kulichikhin, S.V. Antonov, N.N. Zadymova. 2008. Skin Contact Pressure-Sensitive Adhesives. In Applications of Pressure-Sensitive Products, I. Benedek and M. Feldstein, Ed., CRC Press, Boca Raton - London - New York, Chapter 5, pp. 5-1 - 5-32.
• S.V. Kotomin. 2008. Durability of Viscoelastic Adhesive Joints. In Fundamentals of Pressure Sensitivity, I. Benedek and M. Feldstein, Ed., CRC Press, Boca Raton - London - New York, Chapter 8, pp. 8-1 - 8-18.
• В V. Zaikin, J. Halket, A Handbook of Derivatives for Mass Spectrometry, IMPublications, Chichester, 2008, 550 p.
• N.A. Sivov, A.I. Martynenko et al. “Conformational behavior of propagating chains of polyacrylate- and polymethacrylate guanidines in water solutions”. In “Modern Tendencies in Organic and Bioorganic Chemistry”. Nova Science Publishers Inc., New York, 2008.
• N.A. Sivov et al. “Biocide and toxicological properties of synthesized guanidine containing polymer and their structure”. In “Modern Tendencies in Organic and Bioorganic Chemistry”. Nova Science Publishers Inc., New York, 2008.
• N.A. Sivov et al. “Co-polymerization of diallyldimethylammonium chloride and diallylguanidine acetates on high conversion for creation of new biocide materials”. In “Modern Tendencies in Organic and Bioorganic Chemistry”. Nova Science Publishers Inc., New York, 2008.
• N.A. Sivov, A.N. Sivov et al. “The approach to calculation of different co-polymers composition by NMR1H spectroscopy method”. In “Modern Tendencies in Organic and Bioorganic Chemistry”. Nova Science Publishers Inc., New York, 2008.
• N.A. Sivov, M.P. Filatova, A.N. Sivov, A.I. Rebrov, E.B. Pomakhina et al. “Structure peculiarities of guanidine containing monomers on NMR spectroscopy data”. In “Modern Tendencies in Organic and Bioorganic Chemistry”. Nova Science Publishers Inc., New York, 2008.