1 / 47

The Russian Academy of Sciences A.N.Nesmeyanov Institute of Organoelement Compounds

INEOS RAS. The Russian Academy of Sciences A.N.Nesmeyanov Institute of Organoelement Compounds. Russia, 119991, GSP-1, Moscow V-334, Vavilova str. 28, INEOS Phone : 7(095) 135-6166; Fax : 7(095)135-5085; E-mail : val @ineos.ac.ru. http://www . ineos . ac.ru. History of the institute.

kiral
Download Presentation

The Russian Academy of Sciences A.N.Nesmeyanov Institute of Organoelement Compounds

An Image/Link below is provided (as is) to download presentation Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author. Content is provided to you AS IS for your information and personal use only. Download presentation by click this link. While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server. During download, if you can't get a presentation, the file might be deleted by the publisher.

E N D

Presentation Transcript

  1. INEOS RAS The Russian Academy of Sciences A.N.Nesmeyanov Institute of Organoelement Compounds Russia, 119991, GSP-1, Moscow V-334, Vavilova str. 28, INEOS Phone: 7(095) 135-6166; Fax: 7(095)135-5085; E-mail: val@ineos.ac.ru http://www.ineos.ac.ru

  2. History of the institute • The Institute of Organoelement Compounds of the Russian Academy of Sciences (INEOS) was founded in 1954 • At present INEOS is a research center with 800 employees including 613 researchers, among them 83 Professors (D.Sc.) and 291 Ph.D. researchers • INEOS is a worldwide-recognized institute, where the chemistry of organoelement and macromolecular compounds is developed http://www.ineos.ac.ru

  3. Current Activities of the Institute • Division of organoelement compounds Basic research in the field of organoelement and organic chemistry including the study of novel structures, reactivity, and kinetics • Division of macromolecular compounds Investigation of fundamental problems of the synthesis, structure and properties of polymers and composites • Physical division Application of the modern physical methods to the study of structure and reactivity of organic, organoelement and polymer compounds http://www.ineos.ac.ru

  4. Industry Partners: -Du Pont de Nemours (USA) -Hitachi Chemical Co. (Japan) -Crompton Corporation (USA) -Nippon Mektron (Japan) -The Dow Chemical Co. (USA) -General Electric (USA) -Bayer AG (Germany) -ExxonMobil Chemical(USA) Scientific Partners: - Freiburg University (Germany) - Montpellier University (France) - Max-Planck Institute for Polymer Science (Germany) - Tokyo Institute of Technology (Japan) - Polytechnic University (USA) List of cooperation partners http://www.ineos.ac.ru

  5. Application of Technologies • Chemical Technology • Aerospace Industry • Microelectronics • Automotive Industry • Medicine • Agriculture http://www.ineos.ac.ru

  6. Offers special analytical service • The Department of Microanalysis is the leader in the elemental analysis in Russia • We are ready to determine more than 50 elements in organic, heteroelement and organometallic compounds within the wide range of element concentrations We can provide you with following information: • Qualitative analysis per element; • Content of C, H, N; • Content of heteroelements and metals (Hal, S, P, Si,B,Li, Na, K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, As, Rh, Pd, Ru, Os, Pt, Sn, Hg, Pb etc.) http://www.ineos.ac.ru

  7. Type of cooperation we are looking for • Commercialization of our scientific results • Financial support of our investigations which are in progress • Evaluation of the compounds and materials developed by INEOS including feedback http://www.ineos.ac.ru

  8. Polymer Nanostructures as Nanoreactors for Metal Nanoparticle Formation • S.N. Sidorov, D.M. Chernyshov, Yu.A. Kabachii, L.M. Bronstein, P.M. Valetsky • A.N. Nesmeyanov Institute of Organoelement Compounds Russian Academy of Sciences, 28 Vavilov Str., Moscow 119 991, Russia

  9. I. Block Copolymer Nanostructures Used: Outline a) Micelles in organic solvents b) Micelles in aqueous solutions c) Nanoporous networks II. Catalytic Properties of Nanoparticles

  10. Organic Solutions Polystyrene-poly(4-vinylpyridine) (PS-b-P4VP) synthesized via anionic polymerization (MPI on Colloid and Interface Science) metals: Pd, Pt, n and m - numbers of units Seregina, M.V.; Bronstein, L.M.; Platonova, O.A.; Chernyshov, D.M.; Valetsky, P.M.; Hartmann, J.; Wenz, E.; Antonietti, M. Chem. Mater. (1997), 9(4), 923-931.

  11. Scematic Image of Micellar Nanoreactor Depending on reducing agent different morphology of metal nanoparticles (III and IV). could be obtained

  12. TEM Images of Pd Nanoparticles PS-P4VP + Pd(CH3COO)2 reduced with N2H4 (IV) average particle size 3.3±0.2 nm PS-P4VP + Pd(CH3COO)2 reduced with NaBH4 (III) average particle size 1.8±0.2 nm

  13. Parameters of Arrhenius Equation and TOF for Mono- and Bimetallic Colloidal Catalystsin a selective hydrogenation of dehydrolinalool(in all cases selectivity of 99.8% is achieved) * Experimental conditions: th 90 C, toluene, volume of reaction mixture V = 30·10-3 L, C0= 0.44 mol/L, Cc = 2.3·10-5 mol Pd/L, 960 shakings per minute. L.M. Bronstein, D.M. Chernyshov, I.O. Volkov, M.G. Ezernitskaya, P.M. Valetsky, V.G. Matveeva, E.M. Sulman, J. of Catalysis, 2000, 196, (2), 302-314.

  14. Aqueous Solutions Polyethylenoxide-block-Polyethyleneimine(PEO-b-PEI)synthesized from commercial (Aldrich) blocks • Sidorov, S.N.; Bronstein, L.M.; Valetsky, P.M.; Hartmann, J.; Coelfen, H.; Schnablegger, H.; Antonietti, M.. J. Colloid Interface Sci. (1999), 212(2), 197-211. Polyethyleneoxide-block-Polyvinylpyridine (PEO-b-P2VP) synthesized via anionic polymerization (Polymer Source, Canada) Bronstein, L.M.; Sidorov, S.N.; Valetsky, P.M.; Hartmann, J.; Coelfen, H.; Antonietti, M.. Langmuir (1999), 15(19), 6256-6262.

  15. Scheme of PEO-PEI Synthesis PEO-b-PEI was synthesized by coupling of a semi-methylated PEO (M= 2,000; Aldrich) and PEI (M= 700, Aldrich) with the sequence of reactions shown below: The reaction (4) was performed with the two ratios of PEO to PEI: 1:1 and 5:1 to provide diblock and multiblock copolymers.

  16. PEO-b-PEImicellization due to coordination with metal ions

  17. TEM Micrographs of Pt Nanoparticlesprepared in aqueous solution of diblock PEO-b-PEI N2H4 reduction H2 reduction

  18. Micellization of PEO-b-P2VP Introduction of metal ions leads to micelle formation at pH<5

  19. TEM Micrographs of Pt Nanoparticlesprepared in PEO-b-P2VP with NaBH4 reduction 50 nm 50 nm reduction at pH = 2 reduction at pH = 10

  20. Aqueous Solutions(Hybrid Systems) Polyethyleneoxide-block-Polystyrene (PEO-b-PS)synthesized via polymerization with active center transfer (Goldschmidt AG) PEO-b-PS forms micelles with PS core and PEO corona in water but unable to interact with metal compounds Bronstein, L. M.; Chernyshov, D. M.; Timofeeva, G. I.; Dubrovina, L. V.; Valetsky, P. M.; Khokhlov, A. R. Langmuir (1999), 15(19), 6195-6200.

  21. PEO-b-PS Hybrid Micelle in Water with Embedded Surfactant Molecules Surfactant - cetylpyridinium chloride (CPC)

  22. TEM Micrographs of Pt Nanoparticlesprepared in PEO-b-PS-CPC hybrid micelles Pt nanoparticles with av. diameter 2-3 nm cover micelle surface

  23. Nanostructured Network:Hypercrosslinked Polystyrene* (HPS) • -formal degree of crosslinking 200% • -apparent inner surface area of 833 m2/g • -narrow pore size distribution with maximum at 2 nm METAL CONTAINING PRECURSOR: H2PtCl6 solution in THF * Davankov, V. A.; Tsyurupa, M. P. Reactive Polym. 1990,13, 27.

  24. Industrial Oxidation of L-sorbose to 2-keto-L-gulonic acid L-sorbose First stage is acetone treatment: 12-folds volume excess of acetone to L-sorbose and 5% of conc. H2SO4. Yield 80%. Second stage is oxidation with KMnO4, NaClO, electrochemically (yield 90%) or catalytically on Pt/carbon (yield 98%). Product is isolated with filtration and hydrolysis yield 90%. L-ascorbic acid

  25. TEM Micrograph of Pt-containing HPS after Sorbose Treatment Pt nanoparticles are formed in situ after interaction with substrate (L-sorbose) Pt nanoparticle average sizes is 1-2 nm.

  26. Direct Catalytic Oxidation of L-sorbose to 2-keto-L-gulonic acidimportant stage of industrial Vitamin C synthesis REGULATED REACTION CONDITIONS: 1)concentration of catalyst (СC = 20-75 g/L), L-sorbose (С0 = 0.22-0.44 mol/L), base (NaHCO3) (СNaHCO3 = 0.22-0.44 mol/L); 2)temperature of process (T = 60-80С); 3)oxygen flow velocity (VO = 6-14 cm3/s); 4)stirring intensity (I = 900-1000 rpm).

  27. Selectivity of Different Polymeric Systems in L-sorbose oxidation *- 2-keto-L-gulonic acid yield

  28. Conclusions and Outlook • Polymer nanostructures can be successfully applied for the controllable metal nanoparticle synthesis • Micelles of block copolymers can be regarded as a perspective candidates for the preparation of inorganic particles in solutions • Crosslinked polymer network provides a regulation of particle nucleation and growth in solid state • Corresponding polymer-inorganic composites demonstrate high catalytic activity and selectivity in variety of commercially important processes

  29. Yakov S.Vygodskii, A.A.Sakharova, A.M.Matieva, D.A.Sapozhnikov, T.V.Volkova MODIFIEDPOLYACRYLATES WITH IMPROVED THERMAL, MECHANICAL AND OTHER PROPERTIES • Outline •      Background •      Objectives •      Experimental •      Results •      Conclusions • Acknowledgements e-mail: yasvyg@ineos.ac.ru http://www.ineos.ac.ru

  30. Background • Poly(hetero)arylenes represent aromatic polymers containing benzene rings, heterocycles and/or other bridging groups in polymer backbones. Such polymers are differed by excellent thermal, mechanical, dielectric and other properties, used in the broad temperature range involving cryogenic temperatures and such high ones as 300-350 oC. e-mail: yasvyg@ineos.ac.ru http://www.ineos.ac.ru

  31. Background • Poly(hetero)arylenes having improved thermal properties (Tg), soluble in organic solvents contain cardo groups and (or) some fluorinated moieties, mainly C(CF3)2 groups. Phthalide (I), phthalimidine (II), fluorene (III), , anthrone (IV) cyclohexylidene (V) are typical examples of cardo groups: The combination of such fragments leads to polyheteroarylenes soluble in acetone, methyl ethyl ketone, ethyl acetate and even in some unsaturated monomers including methyl methacrylate. http://www.ineos.ac.ru e-mail: yasvyg@ineos.ac.ru

  32. Objectives • To formulate novel addition-condensation polymers having better thermal properties than poly(meth)acrylates, improved solubility and optical properties in comparison with polyheteroarylenes . e-mail: yasvyg@ineos.ac.ru http://www.ineos.ac.ru

  33. Monomers • Methyl methacrylate (MMA) • Ethyl acrylate (EA) • n-Butyl acrylate (BA) • Glycidyl methacrylate (GMA) • Methyl--fluoroacrylate (MFA) • Ethyl--fluoroacrylate (EFA) • Hexafluoro-iso-propyl methacrylate (HFMA) e-mail: yasvyg@ineos.ac.ru http://www.ineos.ac.ru

  34. Condensation Aromatic Polymers Polyimide (PI) e-mail: yasvyg@ineos.ac.ru http://www.ineos.ac.ru

  35. Condensation Aromatic Polymers Aromatic polyester (polyarylate) (PAr) e-mail: yasvyg@ineos.ac.ru http://www.ineos.ac.ru

  36. Condensation Aromatic Polymers Aromatic polyamide (PA) http://www.ineos.ac.ru e-mail: yasvyg@ineos.ac.ru

  37. Condensation Aromatic Polymers Poly(etherether)ketone (PEEK) e-mail: yasvyg@ineos.ac.ru http://www.ineos.ac.ru

  38. Condensation Aromatic Polymers Poly(arylene phthalide) (PAPh) e-mail: yasvyg@ineos.ac.ru http://www.ineos.ac.ru

  39. Experimentals • Free radical initiated polymerization of additional monomers containing dissolved condensation polymer. Initiator: dicyclohexyl peroxydicarbonate : azobis-iso-butyronitrile (1:1) mixture (0.1 wt.%) Condensation polymers portion: 4-25 wt % of monomer. (Cyclohexanone as a diluent.) e-mail: yasvyg@ineos.ac.ru http://www.ineos.ac.ru

  40. Results • Appearance Transparent (PMMA), cloudy [PEA, PBA, all poly- (fluoroacrylate)s, solid, hard (PMMA, PGMA) and rubber-like (PEA, PBA) bulk and film specimen are obtained. • Solubility  Polymers are soluble in different organic solvents including common ones, such as acetone, methyl ethyl ketone, ethyl acetate, cyclohexanone and in toluene and carbon tetrachloride in contrast of relevant condensation aromatic polymers. e-mail: yasvyg@ineos.ac.ru http://www.ineos.ac.ru

  41. Calorimetric measurements e-mail: yasvyg@ineos.ac.ru http://www.ineos.ac.ru

  42. Molecular weight characteristics e-mail: yasvyg@ineos.ac.ru http://www.ineos.ac.ru

  43. Heat resistance e-mail: yasvyg@ineos.ac.ru http://www.ineos.ac.ru

  44. Thermally stability e-mail: yasvyg@ineos.ac.ru http://www.ineos.ac.ru

  45. Film tough properties e-mail: yasvyg@ineos.ac.ru http://www.ineos.ac.ru

  46. Conclusions • By radical polymerization of different (meth)acrylates in the presence of various dissolved aromatic polymers new copolymers having improved solubility in thermal properties are obtained. The films and bulks made from such polymers are characterized by high optical transparency and satisfactory mechanical properties e-mail: yasvyg@ineos.ac.ru http://www.ineos.ac.ru

  47. Acknowledgements • Russian Foundation for Basic Studies (financial support) • Professor S.N.Salazkin (supply of PEEK and PAPh) • Mr.G.Gervits (Nikana Co.) (supply of fluoroacrylates) • Professors A.Askadskii and V.Papkov (physical tests) e-mail: yasvyg@ineos.ac.ru http://www.ineos.ac.ru

More Related