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

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

INEOS RAS

• Russia, 119991, GSP-1, Moscow
• V-334, Vavilova str. 28, INEOS
• Phone [phone]
• Fax [phone]
• E-mail val_at_ineos.ac.ru

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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

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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

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List of cooperation partners

• 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)

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Application of Technologies

• Chemical Technology
• Aerospace Industry
• Microelectronics
• Automotive Industry
• Medicine
• Agriculture

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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.)

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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

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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

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I. Block Copolymer Nanostructures Used
Outline

• a) Micelles in organic solvents
• b) Micelles in aqueous solutions
• c) Nanoporous networks
• II. Catalytic Properties of Nanoparticles

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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.
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Scematic Image of Micellar Nanoreactor

• Depending on
• reducing agent
• different
• morphology of
• metal nanoparticles
• (III and IV).
• could be obtained

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TEM Images of Pd Nanoparticles
PS-P4VP Pd(CH3COO)2 reduced with N2H4
(IV) average particle size 3.30.2 nm
PS-P4VP Pd(CH3COO)2 reduced with NaBH4
(III) average particle size 1.80.2 nm
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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 3010-3 L, C0
0.44 mol/L, Cc 2.310-5 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.
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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.
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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 11 and 51 to provide
diblock and multiblock copolymers.
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PEO-b-PEImicellization due to coordination with
metal ions
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TEM Micrographs of Pt Nanoparticles prepared in
aqueous solution of diblock PEO-b-PEI
N2H4 reduction
H2 reduction
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Micellization of PEO-b-P2VP
Introduction of metal ions leads to micelle
formation at pHlt5
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TEM Micrographs of Pt Nanoparticles prepared in
PEO-b-P2VP with NaBH4 reduction
50 nm
50 nm
reduction at pH 2
reduction at pH 10
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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.
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PEO-b-PS Hybrid Micelle in Water with Embedded
Surfactant Molecules
Surfactant - cetylpyridinium chloride (CPC)
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TEM Micrographs of Pt Nanoparticles prepared in
PEO-b-PS-CPC hybrid micelles
Pt nanoparticles with av. diameter 2-3 nm cover
micelle surface
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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.
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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
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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.
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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 (?C 20-75 g/L), L-sorbose (?0
0.22-0.44 mol/L), base (NaHCO3) (?NaHCO3
0.22-0.44 mol/L) 2) temperature of process (T
60-80??) 3) oxygen flow velocity (VO 6-14
cm3/s) 4) stirring intensity (I 900-1000 rpm).
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Selectivity of Different Polymeric Systems in
L-sorbose oxidation
- 2-keto-L-gulonic acid yield
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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

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MODIFIED POLYACRYLATES WITH IMPROVED THERMAL,
MECHANICAL AND OTHER PROPERTIES
Yakov S.Vygodskii, A.A.Sakharova, A.M.Matieva,
D.A.Sapozhnikov, T.V.Volkova

• Outline
•      Background
•      Objectives
•      Experimental
•      Results
•      Conclusions
• Acknowledgements

• e-mail yasvyg_at_ineos.ac.ru

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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.

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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.
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Objectives

• To formulate novel addition-condensation polymers
  having better thermal properties than
  poly(meth)acrylates, improved solubility and
  optical properties in comparison with
  polyheteroarylenes .

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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)

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Condensation Aromatic Polymers

• Polyimide (PI)

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Condensation Aromatic Polymers
Aromatic polyester (polyarylate) (PAr)
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Condensation Aromatic Polymers
Aromatic polyamide (PA)
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Condensation Aromatic Polymers
Poly(etherether)ketone (PEEK)
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Condensation Aromatic Polymers
Poly(arylene phthalide) (PAPh)
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Experimentals

• Free radical initiated polymerization of
  additional monomers containing dissolved
  condensation polymer.
• Initiator dicyclohexyl peroxydicarbonate
  azobis-iso-butyronitrile (11) mixture (0.1 wt.)
• Condensation polymers portion 4-25 wt of
  monomer.
• (Cyclohexanone as a diluent.)

Reaction conditions time 50-60 h.
Reaction conditions temperature gradual increase from 20 to 100 oC
Reaction conditions medium vacuum
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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.

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Calorimetric measurements
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Molecular weight characteristics
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Heat resistance
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Thermally stability
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Film tough properties
Copolymer obtained ?, MPa ?, E x 103, MPa
PEFA - PI (4 wt ) 51 2,16
PEFA 34 1,62
PMMA PAr (4 wt ) 60 4 2,20
PMMA 40 20 1,08
PMMA PA (4 wt ) 58 4 2,40
PMMA - PA (10 wt ) 14 3 0,53
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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

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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)

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