EP0543356B1 - Procédé de fabrication des compositions avec un compostement amélioré à basse température - Google Patents

Procédé de fabrication des compositions avec un compostement amélioré à basse température Download PDF

Info

Publication number
EP0543356B1
EP0543356B1 EP92119657A EP92119657A EP0543356B1 EP 0543356 B1 EP0543356 B1 EP 0543356B1 EP 92119657 A EP92119657 A EP 92119657A EP 92119657 A EP92119657 A EP 92119657A EP 0543356 B1 EP0543356 B1 EP 0543356B1
Authority
EP
European Patent Office
Prior art keywords
esters
long
fatty acid
chain fatty
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP92119657A
Other languages
German (de)
English (en)
Other versions
EP0543356A3 (en
EP0543356A2 (fr
Inventor
Uwe Böhmke
Horst Dr. Pennewiss
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roehm GmbH Darmstadt
Original Assignee
Roehm GmbH Darmstadt
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 Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Publication of EP0543356A2 publication Critical patent/EP0543356A2/fr
Publication of EP0543356A3 publication Critical patent/EP0543356A3/de
Application granted granted Critical
Publication of EP0543356B1 publication Critical patent/EP0543356B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • C10L10/16—Pour-point depressants
    • 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
    • C10L1/195—Macromolecular compounds obtained 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
    • 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
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
    • 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
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/04—Fatty oil fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/34—Esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
    • C10M145/14—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/16—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate polycarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/06—Well-defined aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026—Butene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C10M2207/2815—Esters of (cyclo)aliphatic monocarboxylic acids used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/284—Esters of aromatic monocarboxylic acids
    • C10M2207/2845—Esters of aromatic monocarboxylic acids used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/286—Esters of polymerised unsaturated acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/401—Fatty vegetable or animal oils used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/404—Fatty vegetable or animal oils obtained from genetically modified species
    • C10M2207/4045—Fatty vegetable or animal oils obtained from genetically modified species used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/082—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type monocarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/106—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing four carbon atoms only

Definitions

  • the invention relates to a process for the production of compositions with improved low-temperature behavior for use as fuels or lubricants based on longer-chain fatty acid alkyl esters, in particular rape oil methyl esters.
  • PAMA polyalkyl (meth) acrylates
  • CFPP Gold Filter Plugging Point
  • PP Pour Point
  • rapeseed oil / rapeseed oil in its average composition has about 51% by weight erucic acid, 22% by weight linoleic acid, 18% by weight oleic acid, 2% by weight palmitic acid and in each case less than 1% by weight myristyl as fatty acid components -, stearyl and palmitolic acid. Newer breeds, on the other hand, have a low erucic acid content.
  • the task was therefore to provide additives for improving the low-temperature behavior, in particular the cold filter plugging point of fatty acid esters of monohydric alcohols, especially the rape oil methyl ester.
  • the aim was to reduce the CFPP from -15 degrees C to -22 degrees C.
  • the additives should be in the range ⁇ 0.1% by weight.
  • the additives should also belong to a class other than that of the triglycerides.
  • the long-chain fatty acid esters FAE The long-chain fatty acid esters FAE
  • the expedient field of application of the method according to the invention results from the low-temperature behavior, in particular the values of the CFPP of the long-chain fatty acid esters from natural sources.
  • esters of fatty acids derived from liquid vegetable oils with monohydric C1-C6 alcohols especially the methyl esters (usually in the proportions of the natural occurrence of the acids).
  • they do not contain any noteworthy C10 fatty acid fractions, C12 fractions mostly only in traces and also relatively little C14 fractions, so that the main fractions are to be found in the area of saturated / unsaturated C16-C24 fatty acids, with a focus on unsaturated ones C18-C20 fatty acids.
  • the long-chain fatty acid esters FA-E are formed at least 95% by weight from C12-C26 fatty acids.
  • the fatty acid alkyl esters to be used according to the invention are prepared from the naturally occurring esters, especially the triglycerides, by processes known per se.
  • the naturally occurring fatty acid esters, in particular the triglycerides can be converted, for example, by transesterification.
  • the procedure can be such that the triglycerides are stirred with a 0.5 to 2-fold excess of the monohydric alcohol, for example methanol in about 1 atmosphere and about 50-100 degrees C. and in the presence of a preferably alkaline catalyst such as alkali hydroxide and / or alkali alkoxide in amounts of 0.05 to 0.2 parts by weight per 100 parts by weight of triglyceride.
  • the working-up usually takes place by stripping off the excess alcohol, washing the residue one or more times with water or dilute acid and drying the ester after separating off the aqueous phase (cf. also AT-A 387 399).
  • the rape oil methyl ester is of particular interest in the context of the present invention.
  • the following explanations exemplified are therefore preferably concerned with this ester, but they can easily be transferred to other fatty acid esters of the type claimed.
  • the rape oil methyl esters are commercially available (source: e.g. from CASTROL, Austria; from HENKEL, Düsseldorf).
  • a commercially available rape oil methyl ester can e.g. have the following composition: approx. 65% by weight oleic acid ester, approx. 19% by weight linoleic acid ester, approx. 2% by weight stearic acid ester, approx. 4% by weight palmitine ester, approx. 4% by weight ⁇ C14- Ester, approx. 6% by weight> C20 ester.
  • Such an ester is hereinafter referred to as FEA-1.
  • pour point depressants are generally the polymers used in particular, in particular those which are produced by a large number of long-chain ones Alkyl residues in the molecule are characterized or have a polyalkylene structure (cf. Ullmanns Encyclopadie der Technischen Chemie, 4th edition, vol. 20, pp. 548/549 Verlag Chemie 19; HF Mark et al. In Encyclopedia of Polymer Science and Engineering loc.cit. pg. 26 - 27)
  • the polymers ⁇ ) - ⁇ ) mentioned can by definition be present as homopolymers or copolymers. They generally have the molecular weights recognized as appropriate in the conventional additives, generally in the range from 800 to 2,000,000 daltons. They can also be used in the form of graft (co) polymers, block polymers, but also as polymer mixtures. Mixtures with suitable alcohols, esters and / or carboxylic acids should also be considered.
  • the content of the additives PPD is in the range from 0.0001 to 10% by weight, preferably in the range from 0.1 to 0.5% by weight, based on the esters to be added.
  • the rape oil-methyl ester compositions produced according to the invention are distinguished by a significantly improved low-temperature behavior.
  • the CFPP can be reduced from -15 degrees C to -22 degrees C with a maximum of 0,1 0.1% by weight of additive to the beet oil methyl ester.
  • Polyalkyl (meth) acrylates are particularly preferred in the context of the present invention.
  • the PAMA additives used as improvers in low-temperature behavior correspond to those used in the prior art. In particular, they are polymers with molecular weights Mw in the range 800-1,000,000 daltons, in particular in the range 800-400,000 daltons (determination by gel permeation chromatography, cf. HF Mark et al. In "Encyclopedia of Polymer Science 2nd Ed. Vol. 10 , pg. 1-19, J.
  • Suitable PAMA polymers are described, for example, in US Pat. No. 4,867,894.
  • the alkyl radicals of the ester units are in the C1-C28 range, with at least 75% by weight if the proportions of lower alkyl esters are in the C1-C2-alkyl range preferably ⁇ 85% by weight of the monomers alkyl radicals above C6, while if the proportion of lower alkyl esters is in the C3-C6 range, the proportion of long-chain alkyl esters from C6 can be up to ⁇ 40% by weight.
  • They are preferably C12-C18-alkyl esters of (meth) acrylic acid.
  • the monomers to be used to prepare the PAMA additives are known.
  • the polymerization is usually free radical.
  • the radical polymerization is advantageously carried out in a compatible solvent, for example in mineral oil.
  • Usual polymerization initiators such as per compounds, especially peresters such as tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl perbenzoate and the like are used. in the usual amounts, for example 0.1 to 5, preferably 0.3 to 1% by weight, based on the monomers (cf. Th. Völker, H. Rauch-Puntigam, acrylic and methacrylic compounds, Springer-Verlag 1967).
  • Molecular weight regulators in particular sulfur regulators, special mercaptans such as, for example, dodecyl mercaptan, can also be added to the batches in the usual amounts, for example 0.01 to 2% by weight, based on the monomers, in a manner known per se. It is expedient to work under a protective gas such as CO 2 .
  • the procedure is advantageously such that the monomers are dissolved in the solvent in a suitable polymerization vessel equipped with a stirrer, if appropriate together with the regulator and initiator and first degassed, for example by means of CO 2 snow, and then warmed. For example, 80 ⁇ 10 degrees C can be used as a guide.
  • the initiator can also be added to the heated mixture in some cases.
  • the temperature usually continues to rise, for example to 140 ⁇ 10 degrees C. If necessary, suitable conditions for the postpolymerization can be established by adding heat and / or further addition of initiator.
  • the total polymerization time is generally less than 12 hours.
  • the amounts added when adding the rapeseed methyl ester are 10 to 0.0001% by weight, preferably 0.1 to 0.05% by weight.
  • step c) the process according to the invention provides for the removal of unsaturated and saturated fatty acid methyl esters of the C12-C30 acids. These fatty acid methyl esters tend to separate at low temperatures.
  • the separation is expediently carried out in the temperature range 0 to -50 degrees C, in particular at -20 to -30 degrees C, by mechanical separation processes such as filtering, centrifuging, decanting and the like.
  • the filtrate thus obtained has a cold filter plugging point from -23 to -41 degrees C, among others. depending on the oil provenance and the concentration of the additives.
  • the C12-C30 fatty acid methyl esters can also be separated off by fractional distillation. For economic reasons, however, the fractional Crystallization is preferred according to the procedure outlined above.
  • the residues (preferably by filtration) are composed of unsaturated and saturated C12-C26 fatty acid methyl esters. These residues can advantageously be reused elsewhere.
  • the PPD additives are preferably incorporated by mixing in, expediently with stirring into the beet oil methyl ester before separating off the fatty acid methyl ester according to c).
  • compositions produced according to the invention can, in addition to the components mentioned, also other relevant polymers used, as well as low molecular weight compounds such as alcohols, long-chain iso-alcohols, fatty acid esters (esters of long-chain iso-alcohols) and the like. contain.
  • beet oil-methyl ester compositions to be regarded as paradigmatic and produced by the process according to the invention come close to the technical requirements with regard to the “cold filter plugging point” or the “pour point”. They are environmentally friendly, sulfur-free additional fuels with higher efficiency than diesel fuel (see e.g. BE-A 889 140). It can be considered particularly advantageous that a soot filter can be dispensed with. But they are also suitable as lubricants or additives Lubricant components, the setting of the required viscosity is within the experience of the expert. The application in tribology follows the state of the art (see “State of the art").
  • the process according to the present invention which is exemplified by the rape oil methyl ester, can also be used for other esters of naturally occurring fatty acids with monobasic alcohols having 1 to 4 carbon atoms. These can also be prepared so that they can be used, for example, as a fuel substitute or as a lubricant.
  • the FAN products obtained by separation are suitable - if necessary. after appropriate preparation for the production of nutrients and / or for the substitution of the unsaturated fatty acids desired in the diet.
  • the CFPP is determined according to DIN 51 428, the "pour point" in a HERZOG PP apparatus MC 850.
  • Mw U stands for the non-uniformity U: Mw Mn -1 (See Vieweg-Esser, Kunststoff-Handbuch, Volume IX, p. 24, Carl Hanser 1975).
  • the pore size of the filter is specified according to ISO 4793. Filters P40 or P100 are preferred as pore sizes.
  • the viscosity ⁇ is determined according to DIN 51 398 / ASTM D 2183.
  • the yield is 92%.
  • the CFPP improved to -19 degrees C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Combustion & Propulsion (AREA)
  • Lubricants (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fats And Perfumes (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Claims (10)

  1. Procédé de préparation de compositions ayant un comportement à basse température amélioré en vue de leur utilisation comme carburants ou lubrifiants, à partir des esters des acides gras à longue chaîne tirés de substances naturelles avec des monoalcools en C1-C6 (FAE),
       caractérisé en ce que
    a) on ajoute des additifs PPD ("Pour Point Depressant" = additif abaissant le point d'écoulement) en soi connus, utilisés pour améliorer le comportement à basse température d'huiles minérales, dans des proportions de 0,0001 à 10% en poids par rapport aux esters d'acides gras à longue chaîne FAE,
    b) on refroidit à une température inférieure au Cold Filter Plugging Point (= point de bouchage de filtre au froid, déterminé suivant la norme DIN 51 458) des esters d'acides gras à longue chaîne FAE non additionnés d'additif et
    c) on sépare le précipité (FAN) formé.
  2. Procédé selon la revendication 1, caractérisé en ce que les acides gras à longue chaîne qui sont présents dans les esters ont été obtenus à partir d'huiles végétales liquides.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que les esters d'acides gras à longue chaîne (FAE) sont formés d'acide:- gras en C12-C26 pour au moins 95% en poids.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que les esters d'acides gras à longue chaîne (FAE) sont des esters méthyliques.
  5. Procédé selon la revendication 4, caractérisé en ce que les esters d'acides gras à longue chaîne (FAE) sont des esters méthyliques d'huile de colza.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le Cold Filter Plugging Point de l'ester méthylique d'huile de colza est abaissé de -15°C à -22°C.
  7. Procédé selon la revendication 1, caractérisé en ce que les additifs PPD sont des composés polymères comportant un grand nombre de chaînes alkyle latérales à 8-40 atomes de carbone.
  8. Procédé selon la revendication 7, caractérisé en ce que les additifs PPD sont des polyesters alkyliques d'acide (méth)acrylique (PAMA).
  9. Procédé selon la revendication 8, caractérisé en ce que les polyesters alkyliques d'acide (méth)acrylique sont composés d'esters monomères d'alcools en C1-G28, 40% en poids au moins des monomères comportant des restes alkyle au-dessus de C8.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que les étapes opératoires b) et c) sont exécutées dans la gamme de température de -20 à -30°C.
EP92119657A 1991-11-22 1992-11-19 Procédé de fabrication des compositions avec un compostement amélioré à basse température Expired - Lifetime EP0543356B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4138429A DE4138429A1 (de) 1991-11-22 1991-11-22 Verfahren zur herstellung von kompositionen mit verbessertem tieftemperaturverhalten
DE4138429 1991-11-22

Publications (3)

Publication Number Publication Date
EP0543356A2 EP0543356A2 (fr) 1993-05-26
EP0543356A3 EP0543356A3 (en) 1993-10-20
EP0543356B1 true EP0543356B1 (fr) 1997-02-12

Family

ID=6445352

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92119657A Expired - Lifetime EP0543356B1 (fr) 1991-11-22 1992-11-19 Procédé de fabrication des compositions avec un compostement amélioré à basse température

Country Status (5)

Country Link
EP (1) EP0543356B1 (fr)
AT (1) ATE148915T1 (fr)
DE (2) DE4138429A1 (fr)
DK (1) DK0543356T3 (fr)
ES (1) ES2098425T3 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006022719B4 (de) * 2006-05-16 2008-10-02 Clariant International Limited Kaltfließverbesserer für pflanzliche oder tierische Brennstofföle
DE102006022698B4 (de) * 2006-05-16 2008-10-02 Clariant International Limited Zusammensetzung von Brennstoffölen
DE102006022718B4 (de) * 2006-05-16 2008-10-02 Clariant International Limited Zusammensetzung von Brennstoffölen
DE102006022720B4 (de) * 2006-05-16 2008-10-02 Clariant International Limited Kaltfließverbesserer für pflanzliche oder tierische Brennstofföle
CN101205489B (zh) * 2006-12-18 2012-01-25 中国石油化工股份有限公司 一种燃料油添加剂组合物、其制备方法及其应用

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4040317A1 (de) * 1990-12-17 1992-06-25 Henkel Kgaa Mischungen von fettsaeureniedrigalkylestern mit verbesserter kaeltestabilitaet
CN1054155C (zh) * 1996-03-21 2000-07-05 中国石油化工总公司石油化工科学研究院 一种复合钡基润滑脂及其制备方法
EP1032620B1 (fr) * 1997-11-21 2004-03-03 Rohmax Additives GmbH Additif pour biodiesels et biocarburants
ES2399626T3 (es) 2002-07-09 2013-04-02 Clariant Produkte (Deutschland) Gmbh Agente mejorador de la fluidez en frío para aceites combustibles de procedencia vegetal o animal
DE10349850C5 (de) 2003-10-25 2011-12-08 Clariant Produkte (Deutschland) Gmbh Kaltfließverbesserer für Brennstofföle pflanzlichen oder tierischen Ursprungs
DE10349851B4 (de) 2003-10-25 2008-06-19 Clariant Produkte (Deutschland) Gmbh Kaltfließverbesserer für Brennstofföle pflanzlichen oder tierischen Ursprungs
DE10357878C5 (de) 2003-12-11 2013-07-25 Clariant Produkte (Deutschland) Gmbh Brennstofföle aus Mitteldestillaten und Ölen pflanzlichen oder tierischen Ursprungs mit verbesserten Kälteeigenschaften
DE10357880B4 (de) 2003-12-11 2008-05-29 Clariant Produkte (Deutschland) Gmbh Brennstofföle aus Mitteldestillaten und Ölen pflanzlichen oder tierischen Ursprungs mit verbesserten Kälteeigenschaften

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR846829A (fr) * 1938-06-02 1939-09-26 Raffinage Cie Francaise Procédé de préparation d'huiles de filage très actives et produits en résultant
FR976997A (fr) * 1942-06-02 1951-03-27 Raffinage Cie Francaise Amélioration de la combustion des huiles grasses
US2610915A (en) * 1950-07-24 1952-09-16 Swift & Co Winterized glyceride oil and process of producing the same
GB1354749A (en) * 1971-07-14 1974-06-05 Exxon Research Engineering Co Palm oil compositions
FR2492402A1 (fr) * 1980-10-21 1982-04-23 Inst Francais Du Petrole Compositions combustibles renfermant des esters d'acides gras, utilisables comme carburants diesel
AT387399B (de) * 1987-04-03 1989-01-10 Gaskoks Vertrieb Ges Mit Besch Verfahren und vorrichtung zur herstellung von fettsaeureestern und deren verwendung
DE4040317A1 (de) * 1990-12-17 1992-06-25 Henkel Kgaa Mischungen von fettsaeureniedrigalkylestern mit verbesserter kaeltestabilitaet

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006022719B4 (de) * 2006-05-16 2008-10-02 Clariant International Limited Kaltfließverbesserer für pflanzliche oder tierische Brennstofföle
DE102006022698B4 (de) * 2006-05-16 2008-10-02 Clariant International Limited Zusammensetzung von Brennstoffölen
DE102006022718B4 (de) * 2006-05-16 2008-10-02 Clariant International Limited Zusammensetzung von Brennstoffölen
DE102006022720B4 (de) * 2006-05-16 2008-10-02 Clariant International Limited Kaltfließverbesserer für pflanzliche oder tierische Brennstofföle
CN101205489B (zh) * 2006-12-18 2012-01-25 中国石油化工股份有限公司 一种燃料油添加剂组合物、其制备方法及其应用

Also Published As

Publication number Publication date
EP0543356A3 (en) 1993-10-20
EP0543356A2 (fr) 1993-05-26
ATE148915T1 (de) 1997-02-15
DE4138429A1 (de) 1993-05-27
ES2098425T3 (es) 1997-05-01
DK0543356T3 (da) 1997-08-18
DE59208037D1 (de) 1997-03-27

Similar Documents

Publication Publication Date Title
EP0543356B1 (fr) Procédé de fabrication des compositions avec un compostement amélioré à basse température
EP0418610B1 (fr) Produit améliorant l'indice de viscosité, à action dispersante
DE69516154T2 (de) Verfahren zur herstellung eines synthetischen esters aus pflanzlichem öl
EP3224285B1 (fr) Copolymère et son utilisation pour réduire la cristallisation de cristaux de paraffine dans les carburants
DE2740449C2 (de) Verfahren zur Herstellung von Schmierölzusätzen
EP0807643B1 (fr) Terpolymères de l'éthylène, leur préparation et leur utilisation pour les distillats d'huile minérale
EP0140274A2 (fr) Additifs pour huile lubrifiante
DE2810364A1 (de) Paraffinhaltiges erdoeldestillatgemisch mit fliessfaehigkeitsverbesserndem kombinationszusatz aus oelloeslichen aliphatischen copolymeren mit stickstoffderivaten von kohlenwasserstoffsubstituierten bernsteinsaeureverbindungen
EP1526167A2 (fr) Agent d'amélioration de l'écoulement à froid pour huiles combustibles d'origine végétale ou animale
EP4095217A1 (fr) Copolymère et son utilisation pour réduire la cristallisation des cristaux de paraffine dans les carburants
EP2376609A1 (fr) Compositions de carburant ayant un point de trouble amélioré et des propriétés améliorées au stockage
EP0406684B1 (fr) Additif pour combustible diesel
DE2307600B2 (de) Hochdruckschmiermittelzusatz
DE3725059A1 (de) Polymere fliessverbesserer fuer mitteldestillate
DE1014694B (de) Schmierfett und Verfahren zu seiner Herstellung
EP0880572A1 (fr) Desemulsifiants
DE69309926T2 (de) Ölzusätze und zusammensetzungen
EP1358306A1 (fr) Procede de transesterification de matiere grasse et/ou d'huile par alcoolyse
EP0485774B1 (fr) Distillat moyen de pétrole à propriétés d'écoulement au froid améliorées
DE3933376A1 (de) Verfahren zur entparaffinierung von wachshaltigen erdoelprodukten
DE1444817A1 (de) Mineralisches oder synthetisches Schmieroel
EP0407906B1 (fr) Huiles minérales à comportement modifié à l'écoulement
DE2056903A1 (de) Copolymere, Verfahren zu ihrer Her stellung und ihre Verwendung ais Zusatz stoffe in Schmierstoffen
DE2810248A1 (de) Oelloesliches produkt und seine verwendung
DE2231162A1 (de) Verfahren zur herstellung kaeltebestaendiger ester hoeherer fluessiger fettsaeuren mit mehrwertigen alkoholen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE DK ES FR GB IT LI NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE DK ES FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19931103

17Q First examination report despatched

Effective date: 19950704

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB IT LI NL SE

REF Corresponds to:

Ref document number: 148915

Country of ref document: AT

Date of ref document: 19970215

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 59208037

Country of ref document: DE

Date of ref document: 19970327

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2098425

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: BOVARD AG PATENTANWAELTE

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19970424

ET Fr: translation filed
REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
NLT1 Nl: modifications of names registered in virtue of documents presented to the patent office pursuant to art. 16 a, paragraph 1

Owner name: ROEHM GMBH & CO. KG

REG Reference to a national code

Ref country code: FR

Ref legal event code: CJ

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20031029

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20031030

Year of fee payment: 12

Ref country code: CH

Payment date: 20031030

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20031103

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 20031104

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20031105

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20031107

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20031119

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20031209

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041119

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041119

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041120

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041120

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041130

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041130

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041130

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041130

BERE Be: lapsed

Owner name: *ROHM G.M.B.H.

Effective date: 20041130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050601

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

EUG Se: european patent has lapsed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20041119

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050729

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20050601

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051119

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20041120

BERE Be: lapsed

Owner name: *ROHM G.M.B.H.

Effective date: 20041130

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20081121

Year of fee payment: 17

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100601