WO2004069880A1 - Catalyst system for preparing styrene polymer and method for preparing of styrene polymer using the same - Google Patents
Catalyst system for preparing styrene polymer and method for preparing of styrene polymer using the same Download PDFInfo
- Publication number
- WO2004069880A1 WO2004069880A1 PCT/KR2004/000213 KR2004000213W WO2004069880A1 WO 2004069880 A1 WO2004069880 A1 WO 2004069880A1 KR 2004000213 W KR2004000213 W KR 2004000213W WO 2004069880 A1 WO2004069880 A1 WO 2004069880A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- styrene polymer
- preparing
- catalyst
- preparing styrene
- catalyst system
- Prior art date
Links
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
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
- C08F12/08—Styrene
-
- 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
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- 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
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- 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
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/904—Monomer polymerized in presence of transition metal containing catalyst at least part of which is supported on a polymer, e.g. prepolymerized catalysts
Definitions
- the present invention relates to a catalyst system for preparing styrene polymer
- syndiotactic styrene polymer in the. bulk method can be prevented. That is, no
- solvent should be at least 80 % of reactants, a process of solvent separation and
- reactors are used to polymerize syndiotactic styrene monomers, which increases
- US Patent No. 5,254,647 discloses a wiped surface reactor for preparing
- syndiotactic styrene polymer by connecting back-mixing reactors in series or in parallel.
- syndiotactic styrene polymer can be prepared
- styrene polymer capable of preventing polymer coagulation inside the reactor by fundamentally preventing the gelation problem and offering high conversion ratio by
- the present invention provides a catalyst system for
- the present invention also provides a method of preparing styrene polymer
- FIG. 1 is a schematic diagram of the styrene polymer preparing apparatus
- FIG. 2 is a schematic diagram of the continuous styrene polymer preparing
- the present inventors worked for a method of preparing styrene polymer
- styrene monomers in the present invention can be kept so much higher than that in
- styrene polymer comprising metallocene catalyst and cocatalyst supported on
- Said supported catalyst is prepared by polymerization in the presence of 100 to
- Styrene monomers used in the present invention are materials including the
- Ph is a phenyl group substituted by at least one hydrogen atom
- halogen atom carbon atom, oxygen atom, phosphorus atom, sulfur atom or tin atom.
- alkylstyrene halogenated styrene, halogen-substituted alkylstyrene, alkoxystyrene, vinylbiphenyl, vinylphenylnaphthalene, vinylphenylpyrene, vinylphenylanthracene,
- divinylbenzene may be used.
- alkylstyrene such as styrene
- halogenated styrene such as fluorostyrene, chlorostyrene and
- bromostyrene halogen-substituted styrene such as chloromethylstyr ⁇ ne and
- alkoxystyrene such as methoxystyrene, ethoxystyrene and
- vinylbiphenyl such as 4-vinylbiphenyl and 3-vinylbiphenyl
- vinylphenylnaphthalene such as 1-(4-vinylbiphenylnaphthalene), 2-(4-
- vinylbiphenylnaphthalene vinylbiphenylnaphthalene
- vinylphenylpyrene such as 1-(4-vinylphenyl)pyrene and 2-(4-
- vinylphenyl)pyrene vinylphenylanthracene such as 1-(4-vinylphenyl)anthracene and 2-
- alkylsilylstyrene such as o-trimethylsilylstyrene, m-
- triethylsilylstyrene and p-triethylsilylstyrene may be used.
- metallocene catalyst is comprised in 0.01 to 10 mol%, more
- tantalum (Ta)] compounds are preferable for the metallocene catalyst. Titanium
- alkylaluminoxane for said cocatalyst, alkylaluminoxane, alkylaluminum compound or borate
- alkylaluminoxane such as methylaluminoxane
- MAO modified methylaluminoxane
- MMAO modified methylaluminoxane
- alkylaluminum compound such as
- chloride triisobutylaluminum, tri(n-butyl)aluminum, tri(t?-propyl)aluminum and
- TIBAL triisopropylaluminum
- borate compound such as borane, triphenylcarbonium
- tetra(pentafluorophenyl)borate may be used.
- triisobutylaluminum is
- said cocatalyst is comprised in 1 to 2,000 times, more preferably 100
- cocatalyst content is below 1 mole, it is difficult to activate the metallocene catalyst. Otherwise, if it exceeds 2,000 moles, excess cocatalyst remains in the supported
- invention comprises metallocene catalyst and cocatalyst supported on syndiotactic
- said supported catalyst is prepared in inert organic
- nonane, decane, benzene, pentafluorobenzene or toluene may be used.
- benzene benzene, pentafluorobenzene or toluene
- the reaction is performed at a temperature ranging from 0 to 120 ° C, more preferably
- reaction time is 10 to 500 minutes, more preferably
- the reactor may have any shape if stirring can be performed uniformly.
- temperature through heat transfer fluid is preferable.
- the present invention also provides a method of preparing styrene polymer
- Said styrene polymer may be prepared by adding the catalyst system for
- syndiotactic styrene polymer and performing reaction for a given time or by adding the contents successively.
- said supported catalyst is the one dispersed in an inert organic
- said styrene monomers are comprised in 0.1 to 50 times,
- said cocatalyst is comprised in 10 to 1,000 times for 1 mole of
- metallocene supported catalyst may not be activated. Otherwise, if it exceeds 1 ,000
- polymerization of said styrene polymer is performed at a temperature
- the resultant styrene polymer has an average particle size of 0.05 to
- Said styrene polymer has a conversion ratio of 10 to 100 %, preferably 20 to
- said styrene polymer has a syndiotacticity of at least 75 %, more preferably at least 90 %, in C 13 NMR analysis.
- FIG. 1 is a schematic representation of FIG. 1 and FIG. 2.
- FIG. 2 is a schematic diagram of the continuous styrene polymer
- purified inert organic solvent 5 is added to a stirring reactor
- metallocene catalyst 4 diluted in inert organic solvent is added. Then, a supported metallocene catalyst 4 diluted in inert organic solvent is added. Then, a supported metallocene catalyst 4 diluted in inert organic solvent is added. Then, a supported metallocene catalyst 4 diluted in inert organic solvent is added. Then, a supported metallocene catalyst 4 diluted in inert organic solvent is added. Then, a supported
- FIG. 2 is a schematic diagram of the continuous styrene polymer preparing
- the supported catalyst solution 10 prepared in the reactor a is transferred to the reactor b through a pump 11.
- the reaction time is controlled so that the reaction product 9 is collected continuously
- styrene monomers 2 cocatalyst 3 and metallocene catalyst 4 are fed to the reactor a at
- the reactor inside was purged three times with high-purity argon gas. Then, the
- reactor was set at 25 TJ . 250 mL of purified n-heptane was added to the reactor, and
- Albemarle; 4.68 wt% AL) solution were added to the reactor. After stirring for 10
- Liquid phase polymerization product was collected through the valve at the
- Styrene polymer was obtained in the same manner of Example 1 except for
- the reactors was kept at 75 ° C and was cleaned by vacuuming for a day.
- reactors was purged three times with high-purity argon gas. Then, the 5 L reactor was set at 25 TJ and the 20 L reactor was set at 70 ° C .
- methylaluminoxane was added. Reaction was performed while stirring at 600 rpm.
- toluene were fed to the 5 L reactor at a flow rate of 30 mL/min, 0.10 mL/min, 0.45
- the total time was 10 hours for normal continuous operation.
- the reactor inside was purged three times with high-purity argon gas. Then, the
- Albemarle; 4.68 wt% AL) solution were added to the reactor. After stirring for 10
- the polymerization product was collected and washed with excess methanol containing
- Example was only about 75%. That is, the catalyst system of the present invention
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT04708517T ATE528325T1 (en) | 2003-02-05 | 2004-02-05 | CATALYST SYSTEM FOR PRODUCING STYRENE POLYMER AND METHOD FOR PRODUCING STYRENE POLYMER USING THE CATALYST SYSTEM |
JP2005501714A JP2006506517A (en) | 2003-02-05 | 2004-02-05 | Catalyst for producing styrenic polymer and method for producing styrenic polymer using the same |
EP04708517A EP1590375B1 (en) | 2003-02-05 | 2004-02-05 | Catalyst system for preparing styrene polymer and method for preparing of styrene polymer using the same |
US10/505,915 US7084220B2 (en) | 2003-02-05 | 2004-02-05 | Catalyst system for preparing styrene polymer and method for preparing of styrene polymer using the same |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20030007170 | 2003-02-05 | ||
KR10-2003-0007170 | 2003-02-05 | ||
KR10-2004-0007310 | 2004-02-04 | ||
KR1020040007310A KR100561076B1 (en) | 2003-02-05 | 2004-02-04 | Catalyst system for preparing styrene polymer and method for preparing of styrene polymer using the same |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004069880A1 true WO2004069880A1 (en) | 2004-08-19 |
Family
ID=32852794
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2004/000213 WO2004069880A1 (en) | 2003-02-05 | 2004-02-05 | Catalyst system for preparing styrene polymer and method for preparing of styrene polymer using the same |
Country Status (4)
Country | Link |
---|---|
US (1) | US7084220B2 (en) |
EP (1) | EP1590375B1 (en) |
JP (1) | JP2006506517A (en) |
WO (1) | WO2004069880A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006107162A1 (en) | 2005-04-02 | 2006-10-12 | Lg Chem, Ltd. | Method of producing styren polymers using high speed catalytic dispersion technology |
JP2008534733A (en) * | 2005-04-02 | 2008-08-28 | エルジー・ケム・リミテッド | Method for producing styrenic polymer using high-speed catalyst dispersion method |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5942589A (en) * | 1996-08-02 | 1999-08-24 | Basf Aktiengesellschaft | Preparation of semicrystalline syndiotactic polymers of vinylaromatic monomers |
US6096677A (en) * | 1997-10-17 | 2000-08-01 | Sri International | Supported metallocene catalysts |
US6100214A (en) * | 1997-06-05 | 2000-08-08 | Exxon Chemical Patents Inc. | Polymeric supported catalysts for olefin polymerization |
US6228795B1 (en) * | 1997-06-05 | 2001-05-08 | Exxon Chemical Patents, Inc. | Polymeric supported catalysts |
US20010047065A1 (en) * | 1999-06-03 | 2001-11-29 | Sun-Chueh Kao | Method for preparing a supported catalyst system and its use in a polymerization process |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2735596B2 (en) | 1989-01-20 | 1998-04-02 | 出光石油化学株式会社 | Method for producing styrenic polymer |
JP2911501B2 (en) | 1989-09-29 | 1999-06-23 | 出光興産株式会社 | Method for producing styrenic polymer |
US5473020A (en) * | 1994-06-30 | 1995-12-05 | Phillips Petroleum Company | Polymer bound ligands, polymer bound metallocenes, catalyst systems, preparation, and use |
RU2166513C2 (en) * | 1994-11-17 | 2001-05-10 | Дзе Дау Кемикал Компани | Carrier-based catalyst component, method of preparing thereof, and polyaddition method |
US5484862A (en) | 1995-03-10 | 1996-01-16 | The Dow Chemical Company | Liquid phase powder bed syndiotactic vinylaromatic polymerization |
DE69807497T2 (en) * | 1997-08-27 | 2003-04-24 | Dow Chemical Co | SYNDIOTACTIC VINYLAROMATIC POLYMERIZATION USING MULTI-STAGE SERIES REACTORS |
CN1230557A (en) * | 1998-03-30 | 1999-10-06 | 中国石油化工总公司 | Carrier for homogenous carried syndiotactic polymerization of styrene |
US6040261A (en) * | 1999-04-15 | 2000-03-21 | Equistar Chemicals, Lp | Supported single-site catalyst and olefin polymerization process |
KR20020012346A (en) * | 2000-08-07 | 2002-02-16 | 유현식 | Supported Catalyst for Producing a Syndiotactic Styrene Polymer with High Productivity and Reduced Reactor Fouling |
-
2004
- 2004-02-05 EP EP04708517A patent/EP1590375B1/en not_active Expired - Lifetime
- 2004-02-05 US US10/505,915 patent/US7084220B2/en not_active Expired - Lifetime
- 2004-02-05 JP JP2005501714A patent/JP2006506517A/en active Pending
- 2004-02-05 WO PCT/KR2004/000213 patent/WO2004069880A1/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5942589A (en) * | 1996-08-02 | 1999-08-24 | Basf Aktiengesellschaft | Preparation of semicrystalline syndiotactic polymers of vinylaromatic monomers |
US6100214A (en) * | 1997-06-05 | 2000-08-08 | Exxon Chemical Patents Inc. | Polymeric supported catalysts for olefin polymerization |
US6228795B1 (en) * | 1997-06-05 | 2001-05-08 | Exxon Chemical Patents, Inc. | Polymeric supported catalysts |
US6096677A (en) * | 1997-10-17 | 2000-08-01 | Sri International | Supported metallocene catalysts |
US20010047065A1 (en) * | 1999-06-03 | 2001-11-29 | Sun-Chueh Kao | Method for preparing a supported catalyst system and its use in a polymerization process |
Non-Patent Citations (1)
Title |
---|
See also references of EP1590375A4 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006107162A1 (en) | 2005-04-02 | 2006-10-12 | Lg Chem, Ltd. | Method of producing styren polymers using high speed catalytic dispersion technology |
EP1866348A1 (en) * | 2005-04-02 | 2007-12-19 | LG Chem. Ltd. | Method of producing styren polymers using high speed catalytic dispersion technology |
JP2008534733A (en) * | 2005-04-02 | 2008-08-28 | エルジー・ケム・リミテッド | Method for producing styrenic polymer using high-speed catalyst dispersion method |
EP1866348A4 (en) * | 2005-04-02 | 2010-02-17 | Lg Chemical Ltd | Method of producing styren polymers using high speed catalytic dispersion technology |
JP4733176B2 (en) * | 2005-04-02 | 2011-07-27 | エルジー・ケム・リミテッド | Method for producing styrenic polymer using high-speed catalyst dispersion method |
Also Published As
Publication number | Publication date |
---|---|
EP1590375A4 (en) | 2008-11-26 |
JP2006506517A (en) | 2006-02-23 |
EP1590375B1 (en) | 2011-10-12 |
US20050171308A1 (en) | 2005-08-04 |
US7084220B2 (en) | 2006-08-01 |
EP1590375A1 (en) | 2005-11-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2597375B2 (en) | Vinylcyclohexane-based polymer and method for producing the same | |
CA1288887C (en) | Process for production of styrene polymers | |
JPH0593015A (en) | Production of styrenic polymer | |
JPH04249504A (en) | Preparation of styrenic polymer and catalyst therefor | |
JP2948630B2 (en) | Production of styrene polymer | |
JP3369294B2 (en) | Transition metal compound, polymerization catalyst using the same, and method for producing styrenic polymer using the polymerization catalyst | |
US6369173B1 (en) | Process for preparing syndiotactic styrenic polymers by recycling the products | |
US6245865B1 (en) | Polymerization process for preparing syndiotactic polystyrenes through microfluidization | |
JP3814148B2 (en) | Supported catalysts to produce syndiotactic polystyrene in high yield and reduce reactor deposits | |
US7084220B2 (en) | Catalyst system for preparing styrene polymer and method for preparing of styrene polymer using the same | |
JPH09183811A (en) | Production of crystalline aromatic vinyl polymer predominant in syndiotactic structure | |
EP0838481B1 (en) | Process for the production of vinyl-aromatic polymers with a high degree of syndiotacticity | |
KR100561076B1 (en) | Catalyst system for preparing styrene polymer and method for preparing of styrene polymer using the same | |
EP0796875B1 (en) | Process for the preparation of crystalline vinylaromatic polymers with a predominant syndiotactic structure | |
JP3860751B2 (en) | A novel metallocene supported catalyst for syndiotactic styrenic polymer polymerization | |
EP1866348B1 (en) | Method of producing styren polymers using high speed catalytic dispersion technology | |
EP1777239B1 (en) | Half-metallocene catalyst and process for preparing syndiotactic styrene polymer using the same | |
JP3306400B2 (en) | Method for producing styrenic polymer using microfluidic method | |
JPH0359012A (en) | Purification of styrene polymer | |
KR100690352B1 (en) | Method of producing styrenic polymers using high speed catalytic dispersion technology | |
JPH0813852B2 (en) | Method for producing styrene polymer and its catalyst |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 2004708517 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 20048000330 Country of ref document: CN |
|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
WWE | Wipo information: entry into national phase |
Ref document number: 10505915 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2005501714 Country of ref document: JP |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWP | Wipo information: published in national office |
Ref document number: 2004708517 Country of ref document: EP |