Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or 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 acyloxy radical of a saturated carboxylic acid, of carbonic acid
  • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or 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 acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
  • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
  • C08G65/08—Saturated oxiranes
  • C08G65/10—Saturated oxiranes characterised by the catalysts used
  • C08G65/12—Saturated oxiranes characterised by the catalysts used containing organo-metallic compounds or metal hydrides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
  • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
  • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
  • C08G65/2645—Metals or compounds thereof, e.g. salts
  • C08G65/2663—Metal cyanide catalysts, i.e. DMC's
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)

Definitions

• the present invention relates to polyethers obtainable from 1-butene oxide and an alcohol using a double metal cyanide compound as a catalyst, the content of unsaturated components being 6 or more mol%, a process for the production of such a polyether and the use of a Polyether according to the invention as a carrier oil or in a carrier oil formulation, in particular in additive packages for petrol fuels, and carrier oil formulations and fuels, comprising a polyether according to the invention.
• polyethers based on 1-butene oxide are conventionally converted to monofunctional polyethers by basic catalysis, for example using potassium hydroxide, with long-chain fatty alcohols as starters. These monofunctional polyethers can be used as carrier oils for gasoline additives. These polyethers produced using basic catalysis have a certain degree of unsaturated compounds, generally between 0.5 and less than 6 mol%.
• WO 98/44022 discloses that polyethers produced by means of double metal cyanide catalysis a proportion of less than 6 mol% of unsaturated compounds have significantly improved properties as gasoline additives.
• polyethers obtainable from 1-butene oxide and an alcohol using a double metal cyanide compound as a catalyst, the polyether content of unsaturated components being 6 or more mol%.
• 1-butene oxide polyethers with a higher content of unsaturated compounds which were obtained by means of double metal cyanide catalysis, show very good properties as carrier oils.
• the lipophilic 1-butene oxide polyethers, which had an increased proportion of unsaturated compounds, were examined for their usability as a carrier oil for fuel additives. It was found that, contrary to the teaching of WO 98/44022, these lipophilic 1-butene oxide polyethers with an increased degree of unsaturated components showed no performance losses compared to conventionally produced carrier oils based on 1-butene oxide with a lower proportion of unsaturated components.
• polyethers with a content of unsaturated components of from 7 mol% to 50 mol%, for example from 8 mol% to 30 mol%, in particular from 9 mol% to 15 mol%, are particularly advantageous.
• the present invention therefore relates to polyethers with an unsaturated component content of from 7 mol% to 50
• alcohols having 2 to 24 carbon atoms in particular alcohols having 5 to 15 or for example having 8 to 13 carbon atoms, can be used to prepare the polyethers according to the invention.
• the present invention also relates to polyethers, in the production of which the alcohol used is an alcohol having 2 to 24 carbon atoms.
• the alcohol used for the preparation is advantageously a monofunctional alcohol in the context of the invention.
• the invention therefore relates to polyethers, in the production of which the alcohol used is a monofunctional alcohol.
• Alcohols suitable according to the invention are, for example, octanol, nonanol, decanol, undekanol, dodekanol, tridekanol, tetradecanol, pentadekanol, iso-octanol, iso-nonanol, iso-decanol, iso-undecanol, iso-dodekanol, iso-tridekanol and iso-tetradekanol , Iso-pentadecanol, preferably iso-decanol, 2-propylheptanol, tridekanol, iso-tridekanol or mixtures of C13 to C15 alcohols.
• the polyethers according to the invention have, for example, a viscosity at 40 ° C. of 20 to 330 mm 2 / sec, in particular of 30 to 300 mm 2 / sec.
• the oxygen content of the polyethers can vary according to the invention, but is at least 15.5%, in particular 16.5%.
• the invention thus relates to polyethers, at least one of the following properties (A) or (B) being fulfilled: (A) the polyether has a viscosity at 40 ° C of 20 to 330 m 2 / s;
• the polyether has an oxygen content of at least 15.5%.
• the present invention relates to a process for producing a polyether with an unsaturated component content of 6 or more mol%, in which 1-butene oxide and an alcohol are reacted with one another in the presence of a double metal cyanide compound as catalyst the.
• the method according to the invention can be carried out, for example, in a batch mode, but it is also possible according to the invention that the method is carried out semi-continuously or continuously.
• the present invention therefore relates to a method in which the alcohol used is a monofunctional alcohol having 2 to 24 carbon atoms.
• the alcohol and 1-butene oxide are reacted with one another in a molar ratio of at least 1: 3 to a maximum of 1: 100, for example from 1: 5 to 1:80, in particular from 1:10 to 1:50.
• a double metal cyanide compound is used as catalyst in the process according to the invention.
• DMC compounds suitable as catalysts are described, for example, in WO 99/16775 and DE 10117273.7.
• special double metal cyanide compound of the general formula I used as a catalyst for the process according to the invention:
• M 1 at least one metal ion selected from the group consisting of Zn 2+ , Fe 2+ , Fe 3+ , Co 3+ , Ni 2+ , Mn 2+ , Co 2+ , Sn 2+ , Pb 2+ , Mo 4 + , Mo 6+ , Al 3+ , V 4+ , V 5+ , Sr 2 *, ⁇ + , W 6+ , Cr 2+ , Cr 3+ , Cd 2+ , Hg 2+ , Pd 2+ ,
• M 2 at least one metal ion selected from the group consisting of Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Mn 2+ , Mn 3+ , V 4+ , V 5+ , Cr 2 "1 " , Cr 3+ ,
• Rh 3+ , Ru 2+ , Ir 3+ is,
• a and X independently of one another are an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate,
• L is a water-miscible ligand selected from the group consisting of alcohols, aldehydes, ketones, ethers, polyethers, esters, polyesters, polycarbonate, ureas, amides, primary, secondary and tertiary amines, ligands with pyridine Nitrogen, nitriles, sulfides, phosphides, phosphates, phosphines, phosphonates and phosphates,
• k is a fractional or whole number greater than or equal to zero
• P is an organic additive
• e the number of ligand molecules is a fractional or whole number greater than 0 or 0,
• organic additives P are mentioned: polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyakylene glycol glycidyl ethers, polyacrylamide, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylamide-co-maleic acid), polyacrylonitrile, polyalkylacrylates, polyalkyl methacrylates, Polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinylpyrrolidone, poly (N-vinylpyrrolidone-co-acrylic acid), polyvinyl methyl ketone, poly (4-vinylphenol), poly (acrylic acid-co-styrene), oxazoline polymers, polyalkylnimines , Maleic acid and maleic anhydride copolymers, hydroxyethyl cellulose, polyacetates, ionic surface and surface-active compounds
• These catalysts can be crystalline or amorphous. In the event that k is zero, crystalline double metal cyanide compounds are preferred. In the event that k is greater than zero, both crystalline, partially crystalline and substantially amorphous catalysts are preferred.
• a preferred embodiment are catalysts of the formula ( ⁇ ), where k is greater than zero.
• the preferred catalyst then contains at least one double metal cyanide compound, at least one organic ligand and at least one organic additive P.
• k is zero, optionally e is also zero and X is exclusively a carboxylate, preferably formate, acetate and propionate.
• crystalline double metal cyanide catalysts are preferred.
• double metal cyanide catalysts as described in WO 00/74845, which are crystalline and platelet-shaped.
• the modified catalysts are produced by combining a metal salt solution with a cyanometalate solution, which can optionally contain both an organic ligand L and an organic additive P.
• the organic ligand and optionally the organic additive are then added.
• an inactive double metal cyanide phase is first produced and this is then converted into an active double metal cyanide phase by primary crystallization, as described in PCT / EP01 / 01893.
• f, e and k are not equal to zero.
• double metal cyanide catalysts which contain a water-miscible organic ligand (generally in amounts from 0.5 to 30% by weight) and an organic additive (generally in amounts from 5 to 80% by weight) such as described in WO 98/06312.
• the catalysts can either be produced with vigorous stirring (24,000 rpm with Turax) or with stirring (US Pat. No. 5,158,922).
• Double metal cyanide compounds which contain zinc, cobalt or iron or two thereof are particularly suitable as catalysts for the process according to the invention. Berlin blue, for example, is particularly suitable.
• crystalline DMC compounds preference is given to using crystalline DMC compounds; in a preferred embodiment, a crystalline DMC compound of the Zn-Co type is used as the catalyst, which contains zinc acetate as a further metal salt component.
• a crystalline DMC compound of the Zn-Co type is used as the catalyst, which contains zinc acetate as a further metal salt component.
• Such compounds crystallize in a monoclinic structure and have a platelet-like habit.
• Such compounds are described for example in WO 00/74845 or PCT / EP01 / 01893.
• DMC compounds suitable as catalysts for the process according to the invention can in principle be prepared in all ways known to the person skilled in the art.
• the DMC compounds can be produced by direct precipitation, the “incipient wetness” method, by preparation of a precursor phase and subsequent recrystallization.
• the DMC compounds can be used for the process according to the invention as a powder, paste or suspension or deformed into a shaped body, introduced into shaped bodies, foams or the like or applied to shaped bodies, foams or the like.
• double metal cyanide compound is used in an amount of 5 ppm to 5000 ppm, for example from 100 ppm to 1000 ppm, in particular from 20 ppm to 500 ppm, based on the final quantity structure.
• the present invention therefore relates to a process in which the double metal cyanide compound is used in an amount of 5 ppm to 5000 ppm, based on the final quantity structure.
• the method it is possible, for example, to carry out the method in batch mode, in semi-batch mode or continuously.
• conventional vacuum dewatering of the starter / DMC mixture can take place first.
• the vacuum can then be broken by means of nitrogen and the epoxide can be metered in under increased pressure from about 1 bar to about 2 bar.
• the invention it is also possible that the vacuum is not completely released and the internal reactor pressure at the start of the epoxidation is less than 1 bar.
• the present invention also relates to the use of a polyether according to the invention as a carrier oil or in a carrier oil formulation, in particular in an additive package for petrol.
• a carrier oil formulation means a composition comprising at least one carrier oil according to the invention.
• a carrier oil is understood to mean a substance which is used, for example, in an additive package for petrol fuels and which has the task of suppressing the tendency of a further additive to add to the carrier oil formulation, for example a detergent, and / or to improve the properties of an additive package in terms of keeping the intake system and intake valves in line.
• an additive package for petrol fuels is understood to mean a composition which can be added to petrol fuels in order to achieve an improved property profile of the petrol fuel.
• an additive package for Otto fuels contains at least one carrier oil according to the invention or a carrier oil formulation according to the invention.
• the carrier oil formulations in particular the additive packages for petrol fuels, can, in addition to a carrier oil, for example also the following lü ⁇
• the additives contain: at least one detergent, at least one solvent, at least one anticorrosive agent, at least one demulsifier, at least one lubrication improver, at least one conductivity improver, at least one coloring or marking agent.
• polyisobutenamine prepared via hydroformylation of polyisobutene and subsequent hydrogenating amination
• PIBA manufactured by nitriding polyisobutene and then hydrogenating amination
• PIBA manufactured by epoxidation of polyisobutene and subsequent hydrogenating amination
• PIBA produced by alkylation of phenol (cresol) with polyisobutene and subsequent Mannich synthesis with mono- and / or polyamines
• polyisobutene succinimide prepared via maleination of polyisobutene and subsequent imidation with mono- and / or polyamines.
• the present invention therefore relates to the use of a polyether according to the invention or a polyether which can be prepared by a process according to the invention as carrier oil, and to the use of a polyether according to the invention or a polyether which can be prepared by a process according to the invention in a carrier oil formulation, in particular in an additive package for Otto fuels ,
• the carrier oils, carrier oil formulations and additive packages for petrol fuels according to the invention have the advantage, for example, that they can be produced particularly inexpensively by the DMC compounds used in the production of the polyethers according to the invention.
• the carrier oil formulations, in particular the additive packages for petrol fuels have a content of at least one detergent of at least 10%.
• Polyisobutenamine or Mannich PIBA are preferably used as detergents for the additive packages according to the invention for Otto fuels.
• the present invention therefore relates to the use of a polyether according to the invention or a polyether which can be prepared by a process according to the invention in a carrier oil formulation, in particular in an additive package for petrol fuels, the carrier oil formulation or the additive package for petrol fuels containing at least one detergent, preferably polyisobutenamine or Mannich PIBA, of at least 10%.
• the carrier oil formulations according to the invention in particular the additive packages according to the invention, can also contain mixtures of one or more of the detergents mentioned.
• the present invention also relates to carrier oil formulations, in particular additive packages for Otto fuels themselves, which comprise a polyether according to the invention, and to a fuel which comprises a polyether according to the invention or a carrier oil formulation according to the invention, in particular an additive package according to the invention for Otto fuels.
• the present invention relates to a carrier oil formulation which is an additive package for petrol fuels.
• a carrier oil formulation according to the invention or an additive package according to the invention for petrol fuels can be added to a fuel, for example in amounts of 100 to 2000 mg / kg of fuel.
• Table 2 Emulsion test according to DIN 51415 (dosage: 600 mg / kg in petrol according to DIN EN 228)
• Table 4 Storage stability at -20 ° C, 0 ° C and + 35 ° C

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Emergency Medicine (AREA)
• Toxicology (AREA)
• Combustion & Propulsion (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Polyethers (AREA)
• Catalysts (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Detergent Compositions (AREA)
• Fats And Perfumes (AREA)

Priority Applications (14)

Applications Claiming Priority (2)

Publications (1)

Family

ID=27771165

Family Applications (1)

Country Status (20)

Families Citing this family (7)

Citations (2)

Family Cites Families (12)

• 2002
  • 2002-03-11 DE DE10210596A patent/DE10210596A1/de not_active Withdrawn
• 2003
  • 2003-03-10 CA CA2478669A patent/CA2478669C/en not_active Expired - Fee Related
  • 2003-03-10 WO PCT/EP2003/002411 patent/WO2003076492A1/de not_active Ceased
  • 2003-03-10 MX MXPA04008700A patent/MXPA04008700A/es active IP Right Grant
  • 2003-03-10 HR HR20040922A patent/HRP20040922A2/xx not_active Application Discontinuation
  • 2003-03-10 US US10/506,601 patent/US7470823B2/en not_active Expired - Lifetime
  • 2003-03-10 AU AU2003215645A patent/AU2003215645B2/en not_active Ceased
  • 2003-03-10 DK DK03743859T patent/DK1485424T3/da active
  • 2003-03-10 JP JP2003574706A patent/JP4421899B2/ja not_active Expired - Fee Related
  • 2003-03-10 CN CNB038079925A patent/CN100506885C/zh not_active Expired - Fee Related
  • 2003-03-10 NZ NZ535150A patent/NZ535150A/en unknown
  • 2003-03-10 ES ES03743859T patent/ES2271616T5/es not_active Expired - Lifetime
  • 2003-03-10 AT AT03743859T patent/ATE336534T1/de not_active IP Right Cessation
  • 2003-03-10 BR BR0308324-1A patent/BR0308324A/pt not_active IP Right Cessation
  • 2003-03-10 DE DE50304661T patent/DE50304661D1/de not_active Expired - Lifetime
  • 2003-03-10 EP EP03743859A patent/EP1485424B2/de not_active Expired - Lifetime
  • 2003-03-10 KR KR1020047014213A patent/KR100959601B1/ko not_active Expired - Fee Related
  • 2003-03-10 PT PT03743859T patent/PT1485424E/pt unknown
  • 2003-03-10 PL PL372939A patent/PL212551B1/pl not_active IP Right Cessation
• 2004
  • 2004-09-10 ZA ZA200407277A patent/ZA200407277B/en unknown
  • 2004-09-28 NO NO20044115A patent/NO20044115L/no not_active Application Discontinuation

Patent Citations (2)

Also Published As

Similar Documents

Legal Events