WO1998030602A1 - Procede pour polymeriser les olefines - Google Patents

Procede pour polymeriser les olefines Download PDF

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Publication number
WO1998030602A1
WO1998030602A1 PCT/NL1997/000695 NL9700695W WO9830602A1 WO 1998030602 A1 WO1998030602 A1 WO 1998030602A1 NL 9700695 W NL9700695 W NL 9700695W WO 9830602 A1 WO9830602 A1 WO 9830602A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
olefins
polymerization
transition
aryl
Prior art date
Application number
PCT/NL1997/000695
Other languages
English (en)
Inventor
Maurits Frederik Hendrik Van Tol
Adrianus Henricus Joseph Franciscus De Keijzer
Gerhard Willem Klumpp
Original Assignee
Dsm N.V.
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 Dsm N.V. filed Critical Dsm N.V.
Priority to JP53077098A priority Critical patent/JP2002514246A/ja
Priority to CA002277909A priority patent/CA2277909A1/fr
Priority to EP97950490A priority patent/EP0954539A1/fr
Priority to AU53474/98A priority patent/AU5347498A/en
Priority to EA199900651A priority patent/EA199900651A1/ru
Publication of WO1998030602A1 publication Critical patent/WO1998030602A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged

Definitions

  • the invention relates to a process for polymerizing olefins by bringing olefins into contact with a transition metal catalyst and a cocatalyst.
  • a transition metal catalyst usually a co-catalyst is required to obtain an active catalyst system.
  • Ziegler-Natta catalysts have been used for the polymerization of olefins since the Fifties. In order for these olefin polymerizations to proceed satisfactory with these Ziegler-Natta catalysts, co- catalysts need to be added. Usually aluminium- containing co-catalysts, such as, for example diethyl aluminium chloride, are used in combination with Ziegler-Natta catalysts.
  • transition-metal catalysts such as for example metallocene catalysts
  • metallocene catalysts have also been used for the polymerization of olefins.
  • metallocene catalysts In order for olefin polymerizations with the aid of metallocene catalysts to proceed satisfactory, it is also necessary to use a co-catalyst.
  • Aluminoxanes are used as co-catalysts in combination with metallocene catalysts.
  • An example of an aluminoxane is methylaluminoxane (MAO) .
  • a disadvantage of the use of aluminoxanes as co-catalysts in the polymerization of olefins with the aid of a metallocene catalyst is that a very large excess of the aluminoxane relative to the metallocene catalyst has to be applied in order for an active catalyst system to be obtained.
  • the polyolefin produced contains a high concentration of aluminium, so that the aluminium will often need to be washed out of the polyolefin.
  • the object of the invention is to provide co- catalysts suitable for use in combination with a transition-metal catalyst for the polymerization of olefins which do not have this disadvantage.
  • the invention relates to a cocatalyst having the formula XR 4 , wherein X represents Si or Ge and R represents an alkyl, aryl, arylalkyl or alkylaryl group, or to a cocatalyst having the formula [XR 5 ] ⁇ [Y] + , wherein X represents Si, Ge, Sn or Pb and R represents hydrogen or an alkyl, aryl, arylalkyl or alkylaryl group and Y represents a cation.
  • an active catalyst system consisting of a transition-metal catalyst with one of the compounds according to the invention as co-catalyst is obtained which is suitable for the polymerization of olefins.
  • the compounds according to the invention are used as co-catalyst for the polymerization of olefins, the required quantity of co-catalyst relative to the transition-metal catalyst is much smaller than when an aluminoxane is used a co-catalyst.
  • Lewis acids or ion complexes are also used as coatalysts in combination with metallocene catalysts.
  • Lewis acids are boranes, such as tris (pentafluorophenyl) borane
  • ion complexes are borates, such as dimethylaniliniumtetrakis- (pentafluorophenyl) borate, triphenylcarbeniumtetrakis- (pentafluorophenyl) borate and trityltetrakis (3 , 5-trifluoromethylphenyl) borate .
  • Boron-containing co-catalysts of this kind are described in for example EP-A-426 , 637 , EP-A-277,003 and EP-A-277, 004.
  • Another advantage of the use of compounds according to the invention as co-catalysts in the polymerization of olefins is that the use of these compounds is generally cheaper than the use of aluminoxanes, boranes or borates.
  • X is an atom from Group 14 of the Periodic Table of the Elements and can be chosen from the group comprising Si, Ge, Sn and Pb .
  • X is Si, as Si is non- toxic.
  • the R groups may be identical or different and can be chosen from the group comprising hydrogen and alkyl , aryl, arylalkyl or alkylaryl groups.
  • the R group is preferably a hydrocarbon group containing 1-20 carbon atoms. Examples of suitable R groups are methyl, ethyl, propyl, isopropyl, hexyl, decyl and phenyl .
  • two R groups may together form a bridged R 2 -group, for example a biphenyl-2,2' -diyl group and a diphenyl-2 , 2 ' - diylmethane group .
  • at least two R groups together form a bridged aryl group.
  • the compound having the formula XR 4 or [XR S ] " [Y] + contains two of such bridged aryl groups .
  • the cation Y is for example a Bronsted acid which can donate a proton, a cation of an alkali metal or a carbene.
  • cations are Li + , K + , Na + , H + , triphenylcarbenium, anilinium, guanidinium, glycinium, ammonium or a substituted ammonium cation, in which at most three hydrogen atoms have been replaced by a hydrocarbyl radical having 1-20 carbon atoms, or a substituted hydrocarbyl radical having 1-20 carbon atoms , in which one or more of the hydrogen atoms has or have been replaced by a halogen atom, phosphonium radicals, substituted phosphonium radicals, in which at most three hydrogen atoms have been replaced by a hydrocarbyl radical having 1-20 carbon atoms or a substituted hydrocarbyl radical having 1-20 carbon atoms, in which one or more of the hydrogen atoms has or have been replaced by a
  • the cation is preferably dimethylanilinium, triphenylcarbenium or Li + .
  • Compounds having the formula XR 4 are known from, for example, 'The chemistry of organic silicon compounds, E.S. Patai et al . , Wiley and Sons, 1989' . Anionic organosilicates were demonstrated for the first time in Angew. Chem. Int. Ed. Engl . 1996, 35, no. 10.
  • lithium (2, 2' - biphenyldiyltrimethylsilicate) .4THF lithium (2 , 2 ' - biphenyldiyldimethylphenylsilicate) .4THF, lithium (2 , 2 ' - biphenyldiyldimethyl-t-butylsilicate) .4THF and lithium (pentaphenylsilicate) .4HMPA are mentioned.
  • THF is tetrahydrofuran and HMPA is hexamethylphosphorus triamide.
  • the above-mentioned compounds having the formula XR 4 can for example be synthesized according to the synthesis methods described in the above-mentioned publications .
  • the compounds according to the invention can also be used on a carrier as co-catalysts in the polymerization of olefins.
  • Si0 2 , A1 2 0 3 , MgCl 2 and polymer particles, such as polystyrene spherules can be mentioned as suitable carrier materials.
  • These carrier materials can also be modified with for example silanes and/or aluminoxanes and/or aluminium alkyls .
  • the supported co-catalysts can be synthesized prior to the polymerization, but they can also be formed in situ.
  • Transition-metal catalysts are suitable as catalysts for the polymerization of olefins. Examples of such catalysts are described in US-A-5 , 096, 867 , WO- A-92/00333, EP-A-347 , 129 , EP-A-344 , 887 , EP-A-129 , 368 ,
  • Supported transition-metal catalysts can be used. Si0 2 , Al 2 0 3 , MgCl 2 and polymer particles, such as polystyrene spherules, can be mentioned as suitable carrier materials. These carrier materials can also be modified with for example silanes and/or aluminoxanes and/or aluminium alkyls.
  • the supported transition-metal catalysts can be synthesized prior to the polymerization, but they can also be formed in situ.
  • metallocene catalysts are used for the polymerization of olefins in combination with a cocatalyst according to the invention.
  • Metallocene catalysts are characterized by the presence in the transition-metal catalyst of one or more ⁇ -bound ligands, such as cyclopentadiene ligands (Cp) or cyclopentadiene-related ligands, for example indene and fluorene .
  • Cp cyclopentadiene ligands
  • Cp-related ligands for example indene and fluorene .
  • transition-metal catalyst in which the transition metal is in a reduced oxidation state, as described in WO-A-96/13529, is more preferred.
  • olefins for example ethylene, propylene, butene, hexene, octene and mixtures thereof and combinations with dienes
  • olefins for example ethylene, propylene, butene, hexene, octene and mixtures thereof and combinations with dienes
  • the catalyst system described above can also be used for the polymerization of vinylaromatic monomers, such as styrene and p-methylstyrene, for the polymerization of polar vinyl monomers, such as for example monomers containing alcohol, amine, alkyl halide, ether, amide, imine or anhydride groups, and for the polymerization of cyclic olefins, such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, norbornene, dimethanooctahydronaphthalene and substituted norbornenes.
  • the amount of co-catalyst used relative to the amount of transition-metal catalyst (mol:mol) is normally 1:100-1000:1, preferably 1:5-250:1.
  • the polymerizations can be carried out in the known manner and the use of the co-catalyst according to the invention does not necessitate any essential modification of these processes.
  • the known polymerizations are carried out in suspension, solution, emulsion, gas phase or as bulk polymerization .
  • the co-catalyst is used in suspension or gas-phase polymerization it is to be preferred to use the transition-metal catalyst or the co-catalyst according to the invention on a support. It is also possible to use both the catalyst and the co-catalyst on a support.
  • the polymerizations are carried out at temperatures between -50°C and +350°C. Preferably between 50°C and 250°C.
  • the pressures used generally lie between atmospheric pressure and 250 Mpa; for bulk polymerizations more in particular between 50 and 250 MPa, for the other polymerization processes between 0.5 and 25 MPa.
  • dispersants and solvents substituted and unsubstituted hydrocarbons can for example be used, such as pentane, heptane and mixtures thereof. Aromatic, possibly perfluorinated hydrocarbons can also be considered.
  • a monomer to be used in the polymerization can also be used as dispersant.
  • the catalyst/cocatalyst mixture was introduced.
  • the ethylene pressure was kept constant at 20 bars during the polymerisation. After 20 minutes the polymerization was stopped, the polymer was removed from the reactor and the yield was determined to be 3.63 g.

Abstract

Procédé pour polymériser les oléfines, selon lequel on met des oléfines en contact avec un catalyseur contenant un métal de transition et avec un cocatalyseur. Le procédé est caractérisé par le fait que le cocatalyseur est un composé de formule XR4, dans laquelle X représente Si ou Ge, et R représente un groupe alkyle, aryle, arylalkyle ou alkylaryle; ou bien le cocatalyseur est un composé de formule [XR5]-[Y]+, dans laquelle X représente Si, Ge, Sn ou Pb, R représente hydrogène ou un groupe alkyle, aryle, arylalkyle ou alkylaryle, et Y représente un cation.
PCT/NL1997/000695 1997-01-14 1997-12-15 Procede pour polymeriser les olefines WO1998030602A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP53077098A JP2002514246A (ja) 1997-01-14 1997-12-15 オレフィン重合法
CA002277909A CA2277909A1 (fr) 1997-01-14 1997-12-15 Procede pour polymeriser les olefines
EP97950490A EP0954539A1 (fr) 1997-01-14 1997-12-15 Procede pour polymeriser les olefines
AU53474/98A AU5347498A (en) 1997-01-14 1997-12-15 A process for polymerizing olefins
EA199900651A EA199900651A1 (ru) 1997-01-14 1997-12-15 Способ полимеризации олефинов

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
NL1004992A NL1004992C2 (nl) 1997-01-14 1997-01-14 Toepassing van verbindingen die Si, Ge, Sn of Pb bevatten als cokatalysator bij de polymerisatie van olefinen.
NL1004992 1997-01-14
US60/041,598 1997-03-17

Publications (1)

Publication Number Publication Date
WO1998030602A1 true WO1998030602A1 (fr) 1998-07-16

Family

ID=19764208

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1997/000695 WO1998030602A1 (fr) 1997-01-14 1997-12-15 Procede pour polymeriser les olefines

Country Status (8)

Country Link
EP (1) EP0954539A1 (fr)
JP (1) JP2002514246A (fr)
CN (1) CN1248980A (fr)
AU (1) AU5347498A (fr)
CA (1) CA2277909A1 (fr)
EA (1) EA199900651A1 (fr)
NL (1) NL1004992C2 (fr)
WO (1) WO1998030602A1 (fr)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002100866A1 (fr) * 2001-06-12 2002-12-19 Dsm N.V. Compose de formule (xr5-)(y+) et procede de synthese
WO2004046214A2 (fr) 2002-10-15 2004-06-03 Exxonmobil Chemical Patents Inc. Systeme catalyseur multiple pour la polymerisation d'olefines et polymeres ainsi produits
WO2005113622A1 (fr) 2004-04-15 2005-12-01 Exxonmobil Chemical Patents Inc. Systeme a catalyseurs et reacteurs multiples pour la polymerisation d'olefines et polymeres produits au moyen de ce systeme
EP1624000A1 (fr) 1999-05-06 2006-02-08 Univation Technologies, LLC procédé de polymérisation pour la production de polymères plus faciles à traiter
WO2006049699A1 (fr) 2004-10-29 2006-05-11 Exxonmobil Chemical Patents Inc Compose catalytique contenant un ligand tridente divalent
EP1803747A1 (fr) 2005-12-30 2007-07-04 Borealis Technology Oy Catalyseur de polymérisation à surface modifiée pour réduire la formation de gels dans des films
WO2010071798A1 (fr) 2008-12-18 2010-06-24 Univation Technologies, Llc Procédé de traitement d'un lit d'ensemencement pour une réaction de polymérisation
WO2011048527A1 (fr) 2009-10-19 2011-04-28 Sasol Technology (Pty) Limited Oligomérisation de composés oléfiniques avec formation réduite de polymère
WO2012074709A1 (fr) 2010-11-30 2012-06-07 Univation Technologies, Llc Procédés pour la polymérisation d'oléfines avec des sels carboxylate de métal extraits
WO2012074710A1 (fr) 2010-11-30 2012-06-07 Univation Technologies, Llc. Composition de catalyseur ayant des caractéristiques d'écoulement améliorées, et ses procédés de fabrication et d'utilisation
WO2012158260A1 (fr) 2011-05-13 2012-11-22 Univation Technologies, Llc Compositions de catalyseur séchées par pulvérisation et procédés de polymérisation utilisant celles-ci
WO2014109832A1 (fr) 2013-01-14 2014-07-17 Univation Technologies, Llc Procédés de préparation de systèmes de catalyseurs ayant une productivité accrue
WO2014120494A1 (fr) 2013-01-30 2014-08-07 Univation Technologies, Llc Procédés de fabrication de compositions catalytiques ayant un écoulement amélioré
WO2015153082A1 (fr) 2014-04-02 2015-10-08 Univation Technologies, Llc Compositions de continuité et leurs procédés de fabrication et d'utilisation
WO2016145179A1 (fr) 2015-03-10 2016-09-15 Univation Technologies, Llc Compositions de catalyseur séchées par pulvérisation, procédés de préparation et d'utilisation dans des procédés de polymérisation d'oléfines
WO2016172097A1 (fr) 2015-04-20 2016-10-27 Univation Technologies, Llc Ligands bi-aromatiques pontés et catalyseurs de polymérisation d'oléfines préparés à partir de ceux-ci
WO2016172110A1 (fr) 2015-04-20 2016-10-27 Univation Technologies, Llc Ligands bi-aromatiques pontés et composés à base de métaux de transition préparés à partir de ceux-ci
WO2016176135A1 (fr) 2015-04-27 2016-11-03 Univation Technologies, Llc Compositions de catalyseur supporté aux propriétés de coulabilité améliorées et leur préparation
EP3372311A1 (fr) 2007-10-22 2018-09-12 Univation Technologies, LLC Film contenant une compositions de polyéthylène dotées de propriétés améliorées

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WO1996013532A1 (fr) * 1994-10-31 1996-05-09 W.R. Grace & Co.-Conn. Deshydroxylation in situ de supports et preparation de catalyseurs polyolefiniques a alliage organometallique sur support

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US3332927A (en) * 1966-02-14 1967-07-25 Cabot Corp Process for polymerization
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WO1996013532A1 (fr) * 1994-10-31 1996-05-09 W.R. Grace & Co.-Conn. Deshydroxylation in situ de supports et preparation de catalyseurs polyolefiniques a alliage organometallique sur support

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Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1624000A1 (fr) 1999-05-06 2006-02-08 Univation Technologies, LLC procédé de polymérisation pour la production de polymères plus faciles à traiter
WO2002100866A1 (fr) * 2001-06-12 2002-12-19 Dsm N.V. Compose de formule (xr5-)(y+) et procede de synthese
WO2004046214A2 (fr) 2002-10-15 2004-06-03 Exxonmobil Chemical Patents Inc. Systeme catalyseur multiple pour la polymerisation d'olefines et polymeres ainsi produits
WO2005113622A1 (fr) 2004-04-15 2005-12-01 Exxonmobil Chemical Patents Inc. Systeme a catalyseurs et reacteurs multiples pour la polymerisation d'olefines et polymeres produits au moyen de ce systeme
WO2006049699A1 (fr) 2004-10-29 2006-05-11 Exxonmobil Chemical Patents Inc Compose catalytique contenant un ligand tridente divalent
EP1803747A1 (fr) 2005-12-30 2007-07-04 Borealis Technology Oy Catalyseur de polymérisation à surface modifiée pour réduire la formation de gels dans des films
EP3372311A1 (fr) 2007-10-22 2018-09-12 Univation Technologies, LLC Film contenant une compositions de polyéthylène dotées de propriétés améliorées
EP3597294A1 (fr) 2007-10-22 2020-01-22 Univation Technologies, LLC Compositions de polyéthylène dotées de propriétés améliorées
WO2010071798A1 (fr) 2008-12-18 2010-06-24 Univation Technologies, Llc Procédé de traitement d'un lit d'ensemencement pour une réaction de polymérisation
WO2011048527A1 (fr) 2009-10-19 2011-04-28 Sasol Technology (Pty) Limited Oligomérisation de composés oléfiniques avec formation réduite de polymère
WO2012074709A1 (fr) 2010-11-30 2012-06-07 Univation Technologies, Llc Procédés pour la polymérisation d'oléfines avec des sels carboxylate de métal extraits
WO2012074710A1 (fr) 2010-11-30 2012-06-07 Univation Technologies, Llc. Composition de catalyseur ayant des caractéristiques d'écoulement améliorées, et ses procédés de fabrication et d'utilisation
WO2012158260A1 (fr) 2011-05-13 2012-11-22 Univation Technologies, Llc Compositions de catalyseur séchées par pulvérisation et procédés de polymérisation utilisant celles-ci
WO2014109832A1 (fr) 2013-01-14 2014-07-17 Univation Technologies, Llc Procédés de préparation de systèmes de catalyseurs ayant une productivité accrue
WO2014120494A1 (fr) 2013-01-30 2014-08-07 Univation Technologies, Llc Procédés de fabrication de compositions catalytiques ayant un écoulement amélioré
WO2015153082A1 (fr) 2014-04-02 2015-10-08 Univation Technologies, Llc Compositions de continuité et leurs procédés de fabrication et d'utilisation
EP3747913A1 (fr) 2014-04-02 2020-12-09 Univation Technologies, LLC Compositions de continuité et procédé de polymérisation d'oléfines l'utilisant
WO2016145179A1 (fr) 2015-03-10 2016-09-15 Univation Technologies, Llc Compositions de catalyseur séchées par pulvérisation, procédés de préparation et d'utilisation dans des procédés de polymérisation d'oléfines
WO2016172097A1 (fr) 2015-04-20 2016-10-27 Univation Technologies, Llc Ligands bi-aromatiques pontés et catalyseurs de polymérisation d'oléfines préparés à partir de ceux-ci
WO2016172110A1 (fr) 2015-04-20 2016-10-27 Univation Technologies, Llc Ligands bi-aromatiques pontés et composés à base de métaux de transition préparés à partir de ceux-ci
WO2016176135A1 (fr) 2015-04-27 2016-11-03 Univation Technologies, Llc Compositions de catalyseur supporté aux propriétés de coulabilité améliorées et leur préparation

Also Published As

Publication number Publication date
JP2002514246A (ja) 2002-05-14
EA199900651A1 (ru) 1999-12-29
CA2277909A1 (fr) 1998-07-16
AU5347498A (en) 1998-08-03
EP0954539A1 (fr) 1999-11-10
CN1248980A (zh) 2000-03-29
NL1004992C2 (nl) 1998-07-15

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