EP0876214A1 - Procede de preparation par hydrogenation de catalyseurs a base de metal de transition et de phosphine - Google Patents

Procede de preparation par hydrogenation de catalyseurs a base de metal de transition et de phosphine

Info

Publication number
EP0876214A1
EP0876214A1 EP96942425A EP96942425A EP0876214A1 EP 0876214 A1 EP0876214 A1 EP 0876214A1 EP 96942425 A EP96942425 A EP 96942425A EP 96942425 A EP96942425 A EP 96942425A EP 0876214 A1 EP0876214 A1 EP 0876214A1
Authority
EP
European Patent Office
Prior art keywords
phosphine
nickel
phenyl
radical
sulfo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96942425A
Other languages
German (de)
English (en)
French (fr)
Inventor
Marc Huser
Robert Perron
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Polyamide Intermediates SAS
Original Assignee
Rhone Poulenc Fibres SA
Rhodia Fiber and Resin Intermediates SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhone Poulenc Fibres SA, Rhodia Fiber and Resin Intermediates SAS filed Critical Rhone Poulenc Fibres SA
Publication of EP0876214A1 publication Critical patent/EP0876214A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • C07F15/045—Nickel compounds without a metal-carbon linkage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
    • B01J2531/96—Water

Definitions

  • the present invention relates to a process for the preparation, by reduction using hydrogen, of compounds which can be used as catalysts.
  • the compounds targeted by the process of the invention comprise at least one transition metal with an oxidation state of 0 or 1 associated with at least one water-soluble phosphine monodentate or bidentate.
  • Such compounds can be used, for example, as catalysts in place of the catalysts used in the hydrocyanation reaction of ethylenic compounds, as described in patent FR-A-2338253. In the present text, they will be called catalysts without this limiting their field of use.
  • the present invention allows their regeneration.
  • the transition metal which they contain, thus leading in the more or less long term to at least partial deactivation of said catalysts .
  • the process for the preparation of catalysts comprising at least one transition metal with an oxidation state of 0 or 1 associated with at least one water-soluble phosphine monodentate or bidentate, consists in treating with hydrogen, in the absence of carbon monoxide, an aqueous solution containing at least one transition metal compound and at least one water-soluble monodentate or bidentate phosphine.
  • the water-soluble phosphine used in the process of the invention is a monodentate phosphine corresponding to the general formula (I):
  • Ar1, Ar2 and Ar3, identical or different, represent aryl or aryl groups comprising one or more substituents such as:
  • -COOM, -SO3M, -PO3M, M representing an inorganic or organic cationic residue chosen from the proton, the cations derived from alkali or alkaline earth metals, the ammonium cations -N (R) 4 in the formula of which the symbols R, identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, the other cations derived from metals in which the salts of arylcarboxylic acids, arylsulfonic acids or arylphosphonic acids are soluble in water,
  • R > 3 in the formula of which the symbols R, which are identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms,
  • - D1, D2, D3, identical or different represent an alkyl group, a cycloalkyl group, an alkyl or cycloalkyl group comprising one or more substituents such as: - alkoxy radical having 1 to 4 carbon atoms,
  • - hydrophilic group such as: -COOM, -SO3M, -PO3M, M representing a mineral or organic cationic residue chosen from the proton, the cations derived from alkali or alkaline earth metals, the ammonium cations -N (R) 4 in the formula of which the symbols R, which are identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, the other cations derived from metals of which the salts of carboxylic acids, sulfonic acids or phosphonic acids are soluble in water,
  • R which are identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, -OH
  • - L represents a simple 14,iel link or a divalent hydrocarbon radical such as an alkylene radical, a cycloalkylene radical, an arylene radical, a radical derived from a heterocycle comprising one or two oxygen, nitrogen or sulfur atoms in the ring, these different cyclic radicals being directly linked to one of the phosphorus atoms or to the two phosphorus atoms or being linked to one of the atoms phosphorus .or both via a linear or branched alkylene radical having from 1 to 4 carbon atoms, the ring or rings which may be part of the divalent radical L may contain one or more substituents such as those defined for AM, Ar2, Ar3, D1, D2 and D3.
  • the salts of carboxylic acids, sulfonic acids or phosphonic acids are soluble in water, lead, zinc and tin.
  • water soluble is meant in the present text a compound soluble at least 0.01 g per liter of water.
  • the preferred water-soluble phosphines are the phosphines of formula (I) or of formula (II) in which Ar1, Ar2 and Ar3 are phenyl groups or phenyl groups comprising one or two substituents as defined above, D1, D2 and D3 represent a alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkyl group having 1 to 6 carbon atoms or cycloalkyl group having 5 to 8 carbon atoms having one or more substituents as defined previously, L is a simple supply link, an alkylene radical having from 1 to 6 carbon atoms, a monocyclic or bicyclic cycloalkylene radical having from 4 to 12 carbon atoms, a phenylene radical, a diphenylene radical, a naphthylene radical, a radical dinap
  • a radical derived from a heterocycle comprising one or two oxygen, nitrogen or sulfur atoms in the ring, these different cyclic radicals being directly linked ent to one or both of the phosphorus atoms or being bonded to one or both of the phosphorus atoms via a linear or branched alkylene radical having from 1 to 4 carbon atoms, the ring or rings which may be part of the divalent radical L may contain one or more substituents such as an alkyl group having 1 to 4 carbon atoms.
  • the preferred water-soluble phosphines are the phosphines of formula (I) or of formula (II) in which:
  • -COOM, -SO3M, -PO3M, M representing a mineral or organic cationic residue chosen from the proton, cations derived from sodium, potassium, calcium or barium, ammonium cations, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, cations derived from zinc, lead or tin,
  • R which are identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms
  • phosphines of general formula (i) By way of nonlimiting examples of phosphines of general formula (i), mention may in particular be made of alkali or alkaline-earth salts, ammonium salts, quaternary ammonium salts of (3-sulfo-4-methylphenyl) di (4-methylphenyl) -phosphine; (3-sulfo-4-methoxy phenyl) di (4-methoxy-phenyl) -phosphine; (3-chloro-4-phenyl) di (4-chloro-phenyl) -phosphine; di (3-sulfo phenyl) phenyl-phosphine; di (4-sulfo phenyl) phenylphosphine; di (3-sulfo-4-methylphenyl) (4-methyl-phenyl) -phosphine; di (3-sulfo-4-methoxy phenyl) phosphine; di
  • phosphines of general formula (II) there may be mentioned in particular the sodium salt of 2,2'-bis [di (sulfonatophenyl) phosphino] -1,1'- binaphthyl, the sodium salt 1,2-bis [di (sulfonatophenyl) phosphinomethyl] cyclobutane (CBDTS), 1,2-bis (dihydroxymethyl-phosphino) ethane, 1,3-bis (dihydroxymethylphosphino) propane, the sodium salt of 2,2 '- bis [di (sulfonatophenyl) phosphinomethyl] -1, l'-binaphtyl.
  • CBDTS 1,2-bis [di (sulfonatophenyl) phosphinomethyl] cyclobutane
  • 1,2-bis (dihydroxymethyl-phosphino) ethane 1,3-bis (dihydroxymethylphosphino) propane
  • the sulfonate groups for example, can be introduced by the reaction of SO3 in sulfuric acid.
  • the carboxylate, phosphonate and quaternary ammonium groups can likewise be introduced by applying the chemical methods known for this type of synthesis.
  • transition metal compounds compounds of nickel, cobalt, iron, palladium, platinum, rhodium and iridium are used, at least partially at a degree of oxidation different from 0. compounds soluble in water or capable of passing into solution under the conditions of the reaction.
  • the rest linked to the metal is not critical, as long as it satisfies these conditions.
  • the most preferred compounds are those of nickel. Mention may be made, by way of nonlimiting examples, of compounds such as nickel carboxylates (in particular acetate, formate, citrate), nickel carbonate, nickel bicarbonate, nickel borate, nickel bromide, nickel chloride, nickel iodide, nickel thiocyanate, nickel cyanide, nickel hydroxide, nickel hydrophosphite, phosphite nickel, nickel phosphate and derivatives, nickel nitrate, nickel sulfate, nickel sulfite, nickel aryl and alkyl sulfonates.
  • nickel carboxylates in particular acetate, formate, citrate
  • nickel carbonate nickel bicarbonate
  • nickel borate nickel bromide
  • nickel chloride nickel iodide
  • nickel thiocyanate nickel cyanide
  • nickel hydroxide nickel hydrophosphite
  • phosphite nickel nickel phosphate and derivatives
  • nickel nitrate nickel sulfate
  • the nickel compound need not itself be water soluble.
  • nickel cyanide poorly soluble in water dissolves well in an aqueous solution of water-soluble phosphine, in particular sulfonated.
  • the reduction by hydrogen of the transition metal compound, in the presence of at least one water-soluble phosphine monodentate or bidentate can be carried out in homogeneous phase, optionally in the presence of a homogeneous catalyst soluble in the reaction medium or in heterogeneous phase in the presence of a catalyst insoluble in the reaction medium.
  • catalysts of this type of catalysis such as for example water-soluble phosphine complexes of rhodium, iridium, cobalt, ruthenium, nickel or palladium.
  • heterogeneous catalyst it is possible to use the various metals or compounds of these metals, deposited on a support or not, which are generally used in catalytic hydrogenation.
  • these metals the most commonly used are the metals of group VIII of the Periodic Table of the Elements, as published in Ha ⁇ dbook of chemistry and physics, 51 st Edition (1970-1971) of The Chemical Rubber Co.
  • the metals of this group VIII which are more particularly suitable, mention may be made of platinum, palladium, ruthenium and nickel.
  • the supported catalysts are advantageously used.
  • the supports are very varied. Among them, non-limiting mention may be made of aluminas, carbon black, silicas, the various metal oxides such as cerine, zirconia, titanium dioxide, metal salts such as calcium carbonate, barium sulphate.
  • aluminas carbon black
  • silicas the various metal oxides such as cerine, zirconia, titanium dioxide, metal salts such as calcium carbonate, barium sulphate.
  • Raney nickel and Raney cobalt are preferably used. Raney nickel is particularly suitable.
  • the catalytic reduction is generally carried out under a hydrogen pressure measured at 25 ° C from 1 to 200 bars and at a temperature from 5 ° C to 200 ° C.
  • the hydrogen pressure measured at 25 ° C is from 1 to 150 bars and the temperature is from 10 "C to 120 ° C.
  • the solution of the transition metal compound to be reduced may further comprise compounds whose role is to supplement the catalyst prepared by the process of the invention.
  • These compounds are in particular Lewis acids.
  • Lewis acid is meant in the present text, according to the usual definition, compounds that accept electronic doublets. It is possible to use in particular the Lewis acids cited in the work edited by GA OLAH "Friedel-Crafts and related Reactions", volume I, pages 191 to 197 (1963).
  • the Lewis acids which can be used in the reaction mixture are chosen from the compounds of the elements of groups Ib, llb, lila, IIIb, IVa, IVb, Va, Vb, Vlb, Vllb and VIII of the Periodic Table of Elements , as published in Handbook of chemistry and physics, 51st Edition (1970-1971) of The Chemical Rubber Co, insofar as said compounds are at least partially soluble and stable in water or more generally in the aqueous solution to be treated .
  • salts especially halides, preferably chlorides and bromides, sulfates, nitrates, sulfonates, especially trifluoromethanesulfonates, carboxylates, acetyiacetonates, tetrafluoroborates and phosphates .
  • Lewis acids By way of nonlimiting examples of such Lewis acids, mention may be made of zinc chloride, zinc bromide, zinc iodide, zinc trifluoromethanesutfonate, zinc acetate, zinc nitrate, tetrafluoroborate zinc, manganese chloride, manganese bromide, nickel chloride, nickel bromide, nickel cyanide, nickel acetylacetonate, cadmium chloride, cadmium bromide, stannous chloride, bromide stannous, stannous sulfate, stannous tartrate, chlorides, bromides, sulfates, nitrates, carboxylates or trifluoromethane ⁇ sulfonates of rare earth elements like lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadoiinium, terbium, dysprosium, holmium, Perbium, thulium, y
  • the Lewis acid used generally represents from 0 to 50 moles per mole of transition metal compound, more particularly of nickel compound, and preferably from 0 to 10 moles per mole.
  • An interesting variant of the process of the invention consists in regenerating a spent catalyst, that is to say a catalyst which has been used and which has become at least partially inactive.
  • a catalyst based on water-soluble phosphine monodentate or bidentate and a transition metal with the oxidation state 0 or 1, optionally also containing one or more Lewis acids, used in the hydrocyanation reaction of butadiene and / or pentene-nitriles is gradually deactivated, in particular by oxidation of the transition metal.
  • This, and more particularly nickel is transformed at least in part into cyanide.
  • the aqueous phase containing in particular the water-soluble phosphine monodentate or bidentate and the compound of the transition metal at least partially at a degree of oxidation greater than 0, can be easily separated from the organic phase.
  • This aqueous phase can contain variable amounts of compounds initially introduced such as butadiene and / or pentene-nitriles or formed during the reaction such as adiponitrile, methyl-glutaronitrile, ethyl-succinonitrile, pentene-nitriles, methylbutene-nitriles.
  • the aqueous phase is treated as described above in order to regenerate the catalyst by reduction of the transition metal which is at a degree of oxidation greater than 0.
  • COD cyclo-octadiene
  • Example 11 reduction of Ni (CN) 2 on Pt / C and hydrocyanation of pentene-3 nitrile
  • CE2 * comparative test with a solution of Ni (CN) 2 (TPPTSNa3) 2 + ZnCl2 (0.5mol / kg) not treated with hydrogen.
  • the vial is placed in an autoclave which is pressurized to 100 bar of hydrogen and heated to 100 ° C (duration indicated in table 3).
  • the autoclave is decompressed and the analysis of the aqueous solution is carried out by polarography.
  • the nickel (0) concentration is calculated by the difference between the total nickel concentration and the residual nickel (II) concentration.
  • CE4 * comparative test with a solution of Ni (CN) 2 (TPPTSNa3) 2 + ZnCl2 (0.5mol / kg) not treated with hydrogen.
  • the ampoule is placed in an autoclave which is pressurized to 100 bar of hydrogen and stirred at room temperature (about 25 ° C) for 1 hour.
  • the reactor is decompressed and the analysis of the aqueous solution is carried out by poiarography.
  • the nickel (0) concentration is calculated by the difference between the total nickel concentration and the residual nickel (II) concentration. No nickel precipitate is observed and in each test the quantity of total nickel assayed corresponds, with the details close to the analysis, to the quantity introduced at the start of the test.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
EP96942425A 1995-12-29 1996-12-18 Procede de preparation par hydrogenation de catalyseurs a base de metal de transition et de phosphine Withdrawn EP0876214A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9515879A FR2743010B1 (fr) 1995-12-29 1995-12-29 Procede de preparation par hydrogenation de catalyseurs a base de metal de transition et de phosphine
FR9515879 1995-12-29
PCT/FR1996/002023 WO1997024183A1 (fr) 1995-12-29 1996-12-18 Procede de preparation par hydrogenation de catalyseurs a base de metal de transition et de phosphine

Publications (1)

Publication Number Publication Date
EP0876214A1 true EP0876214A1 (fr) 1998-11-11

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EP96942425A Withdrawn EP0876214A1 (fr) 1995-12-29 1996-12-18 Procede de preparation par hydrogenation de catalyseurs a base de metal de transition et de phosphine

Country Status (10)

Country Link
US (1) US5908805A (zh)
EP (1) EP0876214A1 (zh)
JP (1) JP3320424B2 (zh)
KR (1) KR100482531B1 (zh)
CN (1) CN1099912C (zh)
BR (1) BR9612380A (zh)
CA (1) CA2240434C (zh)
FR (1) FR2743010B1 (zh)
RU (1) RU2167712C2 (zh)
WO (1) WO1997024183A1 (zh)

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JP5619753B2 (ja) 2008-10-14 2014-11-05 インヴィスタテクノロジーズ エスアエルエル ２−第二級−アルキル−４，５−ジ−（直鎖−アルキル）フェノール類を製造する方法
CN102471218B (zh) 2009-08-07 2014-11-05 因温斯特技术公司 用于形成二酯的氢化并酯化
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JPH11507297A (ja) 1999-06-29
CA2240434A1 (fr) 1997-07-10
CA2240434C (fr) 2001-09-18
CN1206357A (zh) 1999-01-27
RU2167712C2 (ru) 2001-05-27
CN1099912C (zh) 2003-01-29
WO1997024183A1 (fr) 1997-07-10
JP3320424B2 (ja) 2002-09-03
KR100482531B1 (ko) 2005-06-16
US5908805A (en) 1999-06-01
FR2743010B1 (fr) 1998-02-20
FR2743010A1 (fr) 1997-07-04
BR9612380A (pt) 1999-07-13
KR19990076853A (ko) 1999-10-25

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