Classifications

• • 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)
  • C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C)
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
  • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
• • 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
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
• • 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
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
  • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
• • 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
• • 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
  • C10L1/18—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

Definitions

• This invention involves a detergent composition, concentrate and fuel compositions that include the detergent composition, and a method that includes the fuel composition in controlling engine deposits in internal combustion engines.
• Hydrocarbon fuels generally contain numerous deposit-forming substances. When used in internal combustion engines, deposits tend to form on and around constricted areas of the engine in contact with the fuel. In diesel engines deposits tend to accumulate in the fuel injection system, thereby hampering good performance of the engine. In automobile engines deposits can build up on engine intake valves leading to progressive restriction of gaseous fuel mixture flow into the combustion chamber and also to valve sticking. It is common practice therefore to incorporate a detergent composition into a hydrocarbon fuel for the purpose of controlling engine deposits by inhibiting their formation and facilitating their removal, thereby maintaining or improving engine performance.
• U.S. Pat. Nos. 5,634,951 (Colucci et al., filed Jun. 7, 1996) and 5,725,612 (Malfer et al., filed Apr. 10, 1997) disclose Mannich condensation products which are effective detergents for use in spark ignition fuels and that are formed from a) a hydrocarbyl substituted hydroxyaromatic compound or a hydroxyaromatic compound having both a hydrocarbyl and a C 1-4 alkyl substituent, b) an aldehyde and c) an aliphatic polyamine having one and only one primary or secondary amino group capable of participating in the Mannich condensation reaction.
• U.S. Pat. Nos. 6,048,373 (Malfer et al., filed Nov. 30, 1998) and 5,697,988 (Malfer et al., filed Jun. 7, 1996) disclose Mannich compounds useful as detergents in fuel compositions which are derived from alkyl-substituted hydroxyaromatic compounds, an aldehyde, and an amine where the alkyl-substituted hydroxyaromatic compound can be an alkyl-substituted derivative of cresol, xylenol, hydroxydiphenyl, benzylphenol or phenethylphenol.
• the detergent composition of the present invention comprising a Mannich reaction product derived from a hydrocarbyl-substituted phenol having an ortho-alkyl substituent, unexpectedly provides significantly better detergency performance in a hydrocarbon fuel compared to a conventional Mannich reaction product derived from a hydrocarbyl-substituted phenol.
• Another object of the invention is to control deposits in a gasoline engine.
• a further object of this invention is to control deposits in a diesel engine.
• a detergent composition of this invention useful in hydrocarbon fuels comprises a Mannich reaction product prepared by adding an aldehyde to a mixture of a phenol (1) having a hydrocarbyl substituent and an ortho-alkyl substituent; and at least one amine selected from the group consisting of a primary monoamine, and a polyamine having at least two amino groups capable of undergoing a Mannich reaction wherein at least one of the amino groups is a primary amino group; and reacting the aldehyde; the phenol (1); and the at least one amine to form the Mannich reaction product.
• the Mannich reaction product of the above described detergent composition is derived from a mixture of the phenol (1) and a phenol (2) having a hydrocarbyl substituent where the phenol (1) is present in the mixture at about 50 mole % or higher.
• An additional embodiment of this invention is a concentrate composition comprising a solvent and the detergent composition of the present invention where the Mannich reaction product is derived from the phenol (1).
• Another embodiment of the present invention is a concentrate composition comprising a solvent and the detergent compositon of the present invention where the Mannich reaction product is derived from a mixture of the phenol (1) and the phenol (2).
• a fuel composition comprises a hydrocarbon fuel and the detergent composition of the present invention where the Mannich reaction product is derived from the phenol (1).
• a fuel composition comprises a hydrocarbon fuel and the detergent composition of the present invention where the Mannich reaction product is derived from a mixture of the phenol (1) and the phenol (2).
• a method for controlling deposits in an internal combustion engine comprises operating the engine with the fuel composition of the present invention that contains the detergent composition where the Mannich reaction product is derived from a mixture of the phenol (1) and the phenol (2).
• a detergent composition of the present invention useful in hydrocarbon fuels comprises a Mannich reaction product prepared by adding an aldehyde to a mixture of a phenol (1) having a hydrocarbyl substituent and an ortho-alkyl substituent; and at least one amine selected from the group consisting of a primary monoamine, and a polyamine having at least two amino groups capable of undergoing a Mannich reaction wherein at least one of the amino groups is a primary amino group; and reacting the aldehyde; the phenol (1); and the at least one amine to form the Mannich reaction product.
• the Mannich reaction product of the detergent composition is derived from a mixture of the phenol (1) and a phenol (2) having a hydrocarbyl substituent where the phenol (1) is present in the mixture at about 50 mole % or higher, preferably at about 70 mole % or higher, and more preferably at about 80 mole % or higher.
• the hydrocarbyl substituent of the phenol (1) and the phenol (2) can have a number average molecular weight (Mn) of 200 to 5,000 or 200 to 750, preferably of 300 to 3,000 or 350 to 700, and more preferably of 400 to 1,500 or 450 to 650.
• the hydrocarbyl substituent is a univalent radical of carbon atoms that is predominantly hydrocarbon in nature but can have nonhydrocarbon substituent groups and can contain heteroatoms.
• the hydrocarbyl substituent can be derived from a polyolefin.
• the polyolefin can be a homopolymer from one olefin or a copolymer from two or more olefins.
• the polyolefin can be prepared from olefin monomers of 2 to about 10 carbon atoms to include ethylene, propylene, isomers of butene, isomers of decene and mixtures of two or more thereof.
• examples of polyolefins are polyethylenes, polypropylenes, polybutenes and copolymers of ethylene and propylene.
• a preferred polyolefin is a polyisobutene (PIB) derived from a refinery stream having a butene isomer content of about 35 to 75% by weight and an isobutene content of about 30 to 60% by weight.
• PIB polyisobutene
• a more preferred polyolefin is a polyisobutene having at least 70% of the olefinic double bonds at a terminal position on the carbon chain as the vinylidene type.
• Polyisobutenes having a high vinylidene content are highly reactive and are commercially available such as the Glissopal® series marketed by BASF.
• the ortho-alkyl substituent of the phenol (1) can be an alkyl group of 1 to about 10 carbon atoms.
• the hydrocarbyl-substituted ortho-alkyl substituted phenol (1) can be prepared by methods well known in the art including alkylation of an ortho-alkyl substituted phenol with a polyolefin using an acidic catalyst as detailed in the examples hereinbelow.
• Examples of commercially available ortho-alkylphenols which are useful in this invention include o-cresol, xylenols having an ortho methyl group, o-ethylphenol, o-propylphenol, o-isopropylphenol, o-butylphenol and 2-t-butylphenol.
• the aldehyde used to prepare the Mannich reaction product of the present invention can be an aldehyde having 1 to about 6 carbon atoms.
• formaldehyde can be used in one of its reagent forms such as paraformaldehyde and formalin.
• the aldehyde can have 2 to about 6 carbon atoms to include acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde and hexanal.
• the amine used to prepare the Mannich reaction product of this invention is capable of undergoing a Mannich reaction and in one embodiment where the aldehyde includes formaldehyde can be selected from the group consisting of a primary monoamine, and a polyamine having at least two amino groups capable of undergoing a Mannich reaction where at least one of the amino groups is a primary amino group.
• Primary monoamines can have 1 to about 22 carbon atoms and include amines such as ammonia, propylamine, and butylamine.
• Primary monoamines also include alkanolamines having a single amino group and one or more hydroxy groups such as ethanolamine and 1-amino-2-propanol.
• the polyamine can be an alkylenediamine to include amines such as ethylenediamine, N-methylethylenediamine, propylenediamine, and N-methylpropylenediamine.
• the polyamine can be a polyalkylenepolyamine such as diethylenetriamine.
• the polyamine can be an alkanolamine having one or more hydroxy groups and at least two amino groups as described above such as 2-(2-aminoethylamino)ethanol.
• the amine used to prepare the Mannich reaction product of this invention can be selected from the group consisting of a primary monoamine, a secondary monoamine, and a polyamine having at least two amino groups capable of undergoing a Mannich reaction.
• the secondary mono-amine can have 2 to about 22 carbon atoms and includes dimethylamine, diethylamine, dipropylamine and dibutylamine as well as alkanolamines having a single amino group and one or more hydroxy groups such as 2-(methylamino)-ethanol and diethanolamine; also included under polyamines in addition to those described above are N,N′-dimethylethylenediamine and N,N′-dimethylpropylene-diamine.
• the Mannich reaction product of this invention can be prepared by methods well known in the art, and can also be prepared by processes as detailed in the examples hereinbelow which form a part of this invention.
• the reaction of a hydrocarbyl-substituted phenol with an aldehyde and an amine such as ethylenediamine can result in several product components being formed.
• a PIB-substituted phenol is reacted with formaldehyde and ethylenediamine, about three product components can be formed.
• the PIB phenol can undergo a single Mannich condensation with formaldehyde and the amine to form a “Mono” product component as depicted by Formula 1 below.
• this Mono product component can condense with a second PIB phenol and formaldehyde to form a “Bis” product component as depicted by Formula 2.
• the Mono product component can undergo a second condensation with formaldehyde and the amine to form a “Diamine” product component as depicted in Formula 3.
• all three product components will be formed in a Mannich reaction although it is possible to increase the formation of more of one of these product components by modifying the reaction conditions such as sequence of addition, dilution level, solvent selection and the molar ratio of the reactants.
• the Mannich reaction product of this invention is derived from a hydrocarbyl-substituted ortho-alkyl substituted phenol (1), such as a PIB-substituted ortho-cresol, so that Mono and Bis product components are formed while the Diamine product component is not formed since the phenol (1) reactant has only one ortho site available for a Mannich condensation reaction.
• the Mannich reaction product is derived from a mixture of the phenol (1) and a hydrocarbyl-substituted phenol (2), such as a PIB-substituted phenol, so that the Diamine product component is formed in only a limited amount depending on the amount of the phenol (2) present in the mixture.
• the mole ratio of reactants in the present invention can be about 1-2 of phenol (1) or of mixture of phenol (1) and phenol (2):1-2 of aldehyde:1 of amine with a preferred ratio being about 1:1:1.
• the aldehyde includes formaldehyde
• the Mannich reaction product can be prepared by adding the aldehyde to a mixture of the phenol (1) or of the phenol (1) and the phenol (2); and the at least one amine; and reacting the aldehyde; the phenol (1) or the phenol (1) and phenol (2); and the at least one amine to form the Mannich reaction product.
• the temperature of the mixture of the phenol or phenols and the amine to which the aldehyde is added will generally be elevated to a temperature at which the Mannich reaction can occur such as about 50-160° C., preferably about 70-140° C., more preferably about 100-130° C.
• the at least one amine can be added to a mixture of the phenol or phenols and the aldehyde.
• the Mannich reaction product can be prepared as described above or by any other of the well known methods for preparation.
• An additive package or concentrate composition of the present invention comprises the detergent composition as described above, a solvent and optionally a carrier fluid.
• the detergent composition is preferably present in a fuel composition as an additive package or concentrate composition.
• the additive package can be present in the fuel composition at about 50 to 5,000 ppm, preferably at about 125 to 3,000 ppm, and more preferably at about 200 to 900 ppm.
• the detergent composition is generally present in the additive package at about 5 to 40% by weight.
• Suitable carrier fluids include alkylphenols, optionally alkoxylated; esters of carboxylic acids with alcohols, polyols and glycol ethers to include vegetable oils and where the acids can be saturated or unsaturated; phthalate esters; trimellitate esters; alkoxylated alcohols or polyols; polyalkylene glycols; polyetheramines such as cynaoethylated and hydrogenated alkoxylated alcohols or polyalkylene glycols; amine alkoxylates and mineral oils.
• Suitable solvents may include most known aromatic or aliphatic hydrocarbons, glycol ethers, alcohols and mixtures thereof that result in a fluid, homogeneous composition.
• a fuel composition of the present invention comprises a hydrocarbon fuel and the detergent composition as described above comprising a Mannich reaction product derived from a hydrocarbyl-substituted ortho-alkyl substituted phenol (1) where the ortho-alkyl substituent has 1 to 10 carbon atoms.
• a fuel composition comprises a hydrocarbon fuel and the above described detergent composition where the Mannich reaction product is derived from a mixture of the phenol (1) and the phenol (2) where the phenol (1) is present in the mixture at 50 mole % or higher.
• the invention in a still further aspect is a fuel composition comprising a hydrocarbon fuel and the above-described additive package or concentrate composition containing the detergent composition of the present invention.
• the detergent composition can be present in the fuel composition from 10 to 1,000 ppm, preferably from 30 to 500 ppm, and more preferably from 50 to 250 ppm.
• the hydrocarbon fuel of the present invention may suitably comprise a hydrocarbon fraction boiling in the gasoline range or a hydrocarbon fraction boiling in the diesel range.
• gasolines suitable for use in spark ignition engines generally boil in the range from 30 to 230° C.
• Such gasolines may comprise mixtures of saturated, olefinic and aromatic hydrocarbons. They may be derived from straight-run gasoline, synthetically produced aromatic hydrocarbon mixtures, thermally or catalytically cracked hydrocarbon feedstocks, hydrocracked petroleum fractions or catalytically reformed hydrocarbons.
• the octane number of the base fuel is not critical and will generally be above 65.
• hydrocarbons may be replaced in part by alcohols, ethers, ketones or esters, typically in an amount up to 20% by weight.
• liquid hydrocarbon fuel there may be used any fuel suitable for operating spark compression engines, such as those which may be found in road vehicles, ships and the like.
• a diesel fuel will boil in the range from about 140° C. to about 400° C. (at atmospheric pressure), particularly in the range from about 150 to 390° C., especially from about 175 to 370° C.
• Such fuels may be obtained directly from crude oil (straight-run) or from a catalytically or thermally cracked product or a hydrotreated product, or from a mixture of the aforesaid.
• a biofuel for example, rape seed methyl ester.
• the cetane number will typically be in the range from 25 to 60.
• the hydrocarbon fuel can also be a mixture of a diesel fuel and a biofuel.
• the fuel composition contains the detergent composition of this invention in an amount sufficient to provide detergency. Typically in a gasoline fuel this amount will be in the range from 10 to 1000 ppm w/w based on the total weight of the composition. Typically in a diesel fuel this amount will be in the range from 20 to 500 ppm w/w based on the total weight of the composition.
• the fuel composition and concentrate composition may suitably be prepared by blending the various components until the mixture is homogeneous.
• the fuel composition and concentrate composition in addition to the detergent composition may contain known additives.
• the nature of the additives will depend to some extent on the end-use of the fuel composition.
• Diesel fuel compositions may contain nitrates or nitrites as a cetane improver and copolymers of ethylene and vinyl esters, e.g. vinyl acetate, as a cold flow improver.
• Gasoline fuel compositions may contain a lead compound as an anti-knock additive, an antioxidant, e.g.
• additives that can be present in the fuel and concentrate compositions include corrosion inhibitors such as alkenylsuccinic acids, anti-static agents, biocidal additives, smoke suppressants, antifoam agents such as silicone fluids, lubricity additives such as tall oil fatty acid, and demulsifiers such as alkoxylated alkylphenols. These additives may be blended directly into the fuel composition or may be incorporated by way of a concentrate composition.
• the method of the present invention of controlling deposits in an internal combustion engine comprises operating the engine with the fuel composition of the present invention as described above.
• the internal combustion engine in one instance is a gasoline engine and in another instance is a diesel engine.
• Ethylenediamine (7.1 g, 0.118 mol), formaldehyde solution 37% wt. (10.5 g, 0.130 mol) and 2-Ethylhexanol (225 g, solvent) were charged to a round-bottomed flask and heated rapidly to 100° C.
• the polyisobutene-substituted o-Cresol from Example 2 (112.2 g, 0.101 mol) was dissolved in 2-etylhexanol (450 g, solvent) and added to the reaction via a pressure equalising dropping funnel over a two hour period. The reaction was heated to 130° C. over two hours and 9.1 ml of aqueous distillate was collected.
• reaction was then refluxed at 130° C. for 2.5 hours prior to vacuum distillation at 27′′Hg vacuum and 130° C.
• product of reaction was washed with 2 ⁇ 100 ml of hot water to remove any unreacted residual amine. Analysis revealed 1.209% nitrogen, alkalinity value of 8.84 mgKOH/g.

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• Health & Medical Sciences (AREA)
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• Polymers & Plastics (AREA)
• Solid Fuels And Fuel-Associated Substances (AREA)
• Detergent Compositions (AREA)

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• 2002
  • 2002-05-02 EP EP02734157A patent/EP1385924A2/de not_active Withdrawn
  • 2002-05-02 AU AU2002305344A patent/AU2002305344A1/en not_active Abandoned
  • 2002-05-02 WO PCT/US2002/013949 patent/WO2002090471A2/en not_active Ceased
  • 2002-05-02 US US10/474,653 patent/US20040168364A1/en not_active Abandoned

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