EP1380634B1 - Additifs lubrifiant stabilisés contre l'oxydation pour huiles combustibles hautement désulfurées. - Google Patents

Additifs lubrifiant stabilisés contre l'oxydation pour huiles combustibles hautement désulfurées. Download PDF

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Publication number
EP1380634B1
EP1380634B1 EP03013093A EP03013093A EP1380634B1 EP 1380634 B1 EP1380634 B1 EP 1380634B1 EP 03013093 A EP03013093 A EP 03013093A EP 03013093 A EP03013093 A EP 03013093A EP 1380634 B1 EP1380634 B1 EP 1380634B1
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EP
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Prior art keywords
additive
und
alkyl
oder
mol
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EP03013093A
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German (de)
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EP1380634A1 (fr
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Matthias Dr. Krull
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Clariant Produkte Deutschland GmbH
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Clariant Produkte Deutschland GmbH
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Priority claimed from DE2002152973 external-priority patent/DE10252973A1/de
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    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
    • 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
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    • 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
    • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • C10L1/1835—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom having at least two hydroxy substituted non condensed benzene rings
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
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    • C10L1/14—Organic compounds
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    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
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    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
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    • C10L1/00—Liquid carbonaceous fuels
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    • 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
    • C10L1/1966—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 poly-carboxylic
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    • C10L1/00—Liquid carbonaceous fuels
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    • 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
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
    • C10L1/1981—Condensation polymers of aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
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    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
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    • C10L1/00—Liquid carbonaceous fuels
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    • 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
    • C10L1/224—Amides; Imides carboxylic acid amides, imides
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    • 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
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
    • 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
    • C10M2205/022—Ethene
    • C—CHEMISTRY; METALLURGY
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    • 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
    • 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
    • C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/013—Iodine value
    • C—CHEMISTRY; METALLURGY
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    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/067—Unsaturated Compounds
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/43—Sulfur free or low sulfur content compositions

Definitions

  • the present invention relates to additives of esters between polyols and fatty acid mixtures and alkylphenol resins having improved oxidation stability, and to their use for improving the lubricity of highly desulfurized fuel oils.
  • Mineral oils and mineral oil distillates used as fuel oils generally contain 0.5% by weight and more sulfur which causes the formation of sulfur dioxide upon combustion. In order to reduce the resulting environmental impact, the sulfur content of fuel oils is lowered further and further.
  • the EN 590 standard relating to diesel fuels has prescribed a maximum sulfur content of 350 ppm in Europe since November 1999. Further reductions of the sulfur content are in preparation. In Scandinavia fuel oils of less than 50 ppm and in exceptional cases less than 10 ppm of sulfur are used. These fuel oils are usually prepared by hydrogenating the fractions obtained from the petroleum by distillation. In the desulfurization but other substances are removed, which give the fuel oils a natural lubricating effect. These substances include polyaromatic and polar compounds.
  • EP-A-0 680 506 discloses that esters of fatty acids impart improved lubricity to highly desulfurized fuel oils.
  • esters of fatty acids impart improved lubricity to highly desulfurized fuel oils.
  • glycerol monooleate and diisodecyl adipate are mentioned.
  • EP-A-0 739 970 discloses the suitability of glycerol ester blends for improving the lubricity of low sulfur fuel oils. Compositions of different degrees of esterification of the polyol and different degrees of saturation of the fatty acids are disclosed.
  • EP-A-0 839 174 discloses in its lubricity improved fuel oils which are low in sulfur and comprise a mixture of polyol esters with unsaturated fatty acids.
  • EP 0743972 discloses improved lubricity fuel oils comprising a lubricity enhancer and a nitrogen compound.
  • EP 0935645 discloses the use of C 1 -C 30 alkylphenol resins as lubricity additives for low sulfur diesel.
  • the examples used are C 18 and C 24 alkylphenol resins.
  • WO-99/61562 discloses blends of alkylphenol resins, nitrogen containing compounds and ethylene copolymers as refrigerants and lubricity additives for low sulfur diesel.
  • WO 01/19941 discloses partial esters of polyhydric alcohols with unsaturated fatty acids (pentaerythritol esterified with tall oil fatty acid) as lubricity additives with improved cold stability.
  • the lubricity additives based on unsaturated fatty acids and their derivatives can, on prolonged storage of the additive as well as of the additized oils, in particular, harden at elevated temperature to give only partially oil-soluble products. This can lead to the formation of viscous precipitates and deposits in the storage container of the additive, in the fuel oil as well as in the engine. So are z.
  • the combustion and condensation products of glycerin are suspected of being responsible for coke residues and deposits on the supercharged diesel engine injectors.
  • the fatty acid esters of the prior art based on commercial fatty acid mixtures also show marked emulsification tendency in the fuel oils additized with them. This means that when such a fuel oil comes in contact with water, emulsification of the water in the fuel oil takes place.
  • These emulsions which can be found in particular at the oil / water interface, can not be separated or can be separated only with great effort. Since these emulsions can not be used as such as fuel oils, they reduce the value of the products. This problem is particularly pronounced when esters based on natural fatty acid mixtures are used.
  • the object of the present invention was therefore to find lubricant-improving additives for desulfurized fuel oils, which have an improved oxidation stability compared to the prior art and at the same time an improved effectiveness as a lubricant additive.
  • Another object of the invention are fuel oils with a maximum of 0.035 wt .-% sulfur content containing the additives of the invention.
  • Another object of the invention is the use of the additives according to the invention for improving the lubricity of fuel oils with at most 0.035 wt .-% sulfur content.
  • Another object of the invention is a method for improving the lubricity of fuel oils having a sulfur content of not more than 0.035 wt .-% by adding the inventive additives to the fuel oils.
  • Preferred fatty acids which are part of the esters A) are those with 10 to 26 C atoms, in particular 12 to 22 C atoms.
  • the alkyl radicals or alkenyl radicals of the fatty acids consist essentially of carbon and hydrogen. However, they may carry other substituents such as hydroxy, halogen, amino or nitro groups, provided they do not affect the predominantly hydrocarbon character.
  • the fatty acids preferably contain at least one double bond. They may contain multiple double bonds, for example 2 or 3 double bonds, and be of natural or synthetic origin. In the case of polyunsaturated carboxylic acids, their double bonds may be isolated or else conjugated. Preference is given to mixtures of two or more unsaturated fatty acids having 10 to 26 carbon atoms.
  • fatty acids or fatty acid mixtures contain one or more double bonds.
  • the iodine numbers of the fatty acids or fatty acid mixtures on which the esters according to the invention are based are preferably above 100 g J / 100 g, more preferably between 105 and 190 g J / 100 g, in particular between 110 and 180 g J / 100 g and especially between 120 and 180 gl / 100 g fatty acid or fatty acid mixture.
  • Suitable unsaturated fatty acids are, for example, oil, eruca, palmitoleic, myristoleic, linoleic, linolenic, elaeosterolic, arachidonic and / or ricinoleic acid.
  • fatty acids are dicarboxylic acids, such as dimer fatty acids and alkyl- and alkenylsuccinic acids with C 8 -C 50 -alk (en) yl radicals, preferably with C 8 -C 40 -, in particular with C 12 -C 22 -alkyl radicals.
  • the alkyl radicals can be linear or branched (oligomerized alkenes, polyisobutylene) and saturated or unsaturated.
  • the dicarboxylic acids can be used as such or in mixtures with monocarboxylic acids, mixtures of dicarboxylic acids of up to 10% by weight, in particular less than 5% by weight, being preferred in mixtures.
  • the fatty acid mixtures may contain minor amounts, ie up to 20 wt .-%, preferably less than 10%, in particular less than 5% and especially less than 2% of saturated fatty acids such as lauric, tridecane, myristic, pentadecane, palmitic, margarine, stearic, isostearin , Arachin and behenic acid.
  • saturated fatty acids such as lauric, tridecane, myristic, pentadecane, palmitic, margarine, stearic, isostearin , Arachin and behenic acid.
  • the fatty acids may further contain 1-40, especially 1-25 wt .-%, in particular 1-5 wt .-% resin acids.
  • Suitable alcohols preferably contain 2 to 6, in particular 3 to 4 Kohlenstorfatome, and 2 to 5, in particular 3 to 4 hydroxyl groups, but at most one hydroxyl group per carbon atom.
  • Particularly suitable alcohols are ethylene glycol, diethylene glycol, propylene glycol, glycerol, trimethylolpropane, neopentyl glycol and pentaerythritol and the oligomers having from 2 to 10 monomer units obtainable therefrom by condensation, such as, for example, polyglycerol.
  • the partial esters can be prepared from alcohols and fatty acids in a known manner by esterification. Alternatively, the partial saponification of naturally occurring fats and oils is possible.
  • Esters according to the invention are those which can be prepared from a dihydric or polyhydric alcohol and a fatty acid or a mixture of fatty acids. In this case, mixtures of, for example, mono-, di- and / or triesters, or optionally higher esters, of an alcohol with different fatty acids, of mono-, di- and / or triesters, or optionally higher esters, of different alcohols with different fatty acids , as well as mixtures of mono-, di- and / or triesters, or optionally higher esters, of one or more alcohols with different fatty acids. Preference is given to those esters which can be prepared from a fatty acid mixture.
  • the esters according to the invention preferably have iodine numbers of more than 50 g / 100 g of ester, more preferably between 90 and 200 g / 100 g of ester, in particular between 100 and 180 g / 100 g of ester and especially between 110 and 150 g / 100 g ester.
  • the iodine numbers result from the iodine value of the basic fatty acid mixture and the alcohol used for the esterification in a stoichiometric manner.
  • partial esters whose OH numbers are between 10 and 200 mg KOH / g ester, more preferably between 100 and 200, in particular between 110 and 195, especially between 130 and 190 mg KOH / g ester.
  • these are mixtures of different esters, eg. As mixtures of mono-, di- and triglycerides, mixtures, such as those resulting from the esterification of polyols.
  • the partial esters with OH numbers between 110 and 200 mg KOH / g ester are characterized in particular in combination with the alkylphenol resins B) by a very low Emulgierneist.
  • the limited by the OH number HLB range of additives causes a reduced affinity of the amphiphilic agents to water;
  • the formation of surface-active and micellar structures is disturbed by the number of double bonds in the alkyl radicals which are characterized by iodine number.
  • the alkylphenol-aldehyde resins (B) contained in the additive according to the invention are known in principle and, for example, in the Römpp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, Volume 4, p 3351ff. described.
  • the alkyl or alkenyl radicals of the alkylphenol have 6-24, preferably 8-22, in particular 9-18, carbon atoms. They may be linear or preferably branched, wherein the branch may contain secondary as well as tertiary structures.
  • n- and iso-hexyl Preference is given to n- and iso-hexyl, n- and iso-octyl, n- and iso-nonyl, n- and iso-decyl, n- and iso-dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and tripropenyl, Tetrapropenyl, pentapropenyl and polyisobutenyl to C 24 .
  • the prefix iso here means that the alkyl chain contains one or more secondary branches.
  • the alkylphenol-aldehyde resin can also be up to 20 mol% of phenol units and / or alkylphenols with short alkyl chains such.
  • the same or different alkylphenols may be used.
  • the aldehyde in the alkylphenol-aldehyde resin has 1 to 10, preferably 1 to 4, carbon atoms and may carry further functional groups. It is preferably an aliphatic aldehyde, more preferably it is formaldehyde.
  • the molecular weight of the alkylphenol-aldehyde resins is preferably 350 to 10,000, in particular 400 to 5000, g / mol. This preferably corresponds to a condensation degree n of from 3 to 40, in particular from 4 to 20.
  • the prerequisite here is that the resins are oil-soluble.
  • these alkylphenol-formaldehyde resins are those which are oligomers or polymers having a repeating structural unit of the formula wherein R A is C 6 -C 24 alkyl or alkenyl and n is a number from 2 to 50.
  • the preparation of the alkylphenol-aldehyde resins is carried out in a known manner by basic catalysis, resulting in resol-type condensation products, or by acid catalysis to form novolac-type condensation products.
  • the condensates obtained according to both types are suitable for the compositions according to the invention.
  • the condensation is in the presence of acidic catalysts.
  • an alkylphenol having 6-24, preferably 8-22, in particular 9-18, carbon atoms per alkyl group, or mixtures thereof, and at least one aldehyde are reacted with each other, wherein about 0.5 mol per mol of alkylphenol compound. 2 mol, preferably 0.7 to 1.3 mol and in particular equimolar amounts of aldehyde are used.
  • Suitable alkylphenols are in particular n- and iso-hexylphenol, n- and iso-octylphenol, n- and iso-nonylphenol, n- and iso-decylphenol, n- and iso-dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, tripropenylphenol, tetrapropenylphenol and polyis (isobutenyl) phenol to C 24 .
  • the alkylphenols are preferably para-substituted.
  • the alkylphenols may carry one or more alkyl radicals. Preferably, they are substituted at most 5 mol%, in particular at most 20 mol% and especially at most 40 mol% with more than one alkyl group. Preferably, at most 40 mol%, in particular at most 20 mol% of the alkylphenols used in the ortho position carry an alkyl radical. Specifically, the alkylphenols ortho to the hydroxyl group are not substituted with tertiary alkyl groups.
  • the aldehyde can be a mono- or dialdehyde and carry other functional groups such as -COOH.
  • Particularly suitable aldehydes are formaldehyde, acetaldehyde, butyraldehyde, glutaric dialdehyde and glyoxylic acid, with formaldehyde being preferred.
  • the formaldehyde can be used in the form of paraformaldehyde or in the form of a preferably 20-40% strength by weight aqueous formalin solution.
  • Corresponding amounts of trioxane can also be used.
  • alkylphenol and aldehyde is usually carried out in the presence of alkaline catalysts, for example alkali metal hydroxides or alkylamines, or of acidic catalysts, for example inorganic or organic acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acid, sulfamido acids or haloacetic acids.
  • alkaline catalysts for example alkali metal hydroxides or alkylamines
  • acidic catalysts for example inorganic or organic acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acid, sulfamido acids or haloacetic acids.
  • the condensation is preferably carried out solvent-free at 90 to 200 ° C, preferably at 100 to 160 ° C.
  • the reaction takes place in the presence of an organic solvent which forms an azeotrope with water, for example toluene, xylene, higher aromatics or mixtures thereof.
  • the reaction mixture is heated to a temperature of 90 to 200 ° C, preferably 100 to 160 ° C, wherein the resulting reaction water is removed during the reaction by azeotropic distillation. Solvents that do not release protons under condensation conditions may remain in the products after the condensation reaction.
  • the resins can be used directly or after neutralization of the catalyst, optionally after further dilution of the solution with aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, for example gasoline fractions, kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or solvents such as ® Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol, ® ISOPAR and ® Shellsol D types.
  • aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures for example gasoline fractions, kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or solvents such as ® Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol, ® ISOPAR
  • the proportions by weight of constituents A) and B) in the additives according to the invention can vary within wide limits, depending on the application. They are preferably between 10 and 99.999% by weight of A) to 90 to 0.001% by weight of B), in particular of 20 to 99.995% by weight of A) to 80 to 0.005% by weight of B).
  • preferably smaller proportions of components B from 0.001 to 10 wt .-%, preferably 0.005 to 5 wt .-% B) are used, whereas to optimize the lubricity greater proportions B of, for example, 5 to 90 wt .-% , preferably 10 to 80 wt .-% and in particular 25 to 75 wt .-% are used.
  • Paraffin dispersants are additives which reduce the size of the precipitated wax crystals as the oil cools and, moreover, cause the paraffin particles to not settle but remain colloidally dispersed with significantly reduced sedimentation tendency.
  • the nitrogen-containing paraffin dispersants are preferably low molecular weight or polymeric, oil-soluble nitrogen compounds, for example amine salts, imides and / or amides, which are obtained by reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri- or amines. , Tetra- and / or polycarboxylic acids or their anhydrides are obtained.
  • Particularly preferred paraffin dispersants contain reaction products of secondary fatty amines having 8 to 36 carbon atoms, in particular dicoco fatty amine, ditallow fatty amine and distearylamine.
  • paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols can be reacted, the reaction products of Alkenylspirobislactonen with amines and reaction products of terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkylene of lower unsaturated alcohols with amines and / or alcohols.
  • some suitable paraffin dispersants are listed.
  • the polar nitrogen-containing paraffin dispersants can be admixed with the additives according to the invention or added separately to the middle distillate to be added.
  • the amount ratio between paraffin dispersants and the additives according to the invention is between 5: 1 and 1: 5 and preferably between 3: 1 and 1: 3.
  • the Additives according to the invention can also be used together with one or more oil-soluble co-additives which on their own improve the lubricating and / or cold-flow properties of crude oils, lubricating oils or fuel oils.
  • oil-soluble co-additives are vinyl acetate-containing copolymers or terpolymers of ethylene, comb polymers and oil-soluble amphiphiles.
  • the additives according to the invention are mixed with ethylene / vinyl acetate / vinyl 2-ethylhexanoate terpolymers, ethylene / vinyl acetate / vinyl neononanoate terpolymers and / or ethylene / vinyl acetate / vinyl neodecanoate terpolymers to simultaneously improve flowability and lubricity of mineral oils or mineral oil distillates.
  • the terpolymers of vinyl 2-ethylhexanoate, vinyl neononanoate or vinyl neodecanoate contain, in addition to ethylene, 10 to 35% by weight of vinyl acetate and 1 to 25% by weight of the particular long-chain vinyl ester.
  • Other preferred copolymers contain in addition to ethylene and 10 to 35 wt .-% vinyl esters or 0.5 to 20 wt .-% of olefin having 3 to 10 carbon atoms such.
  • isobutylene, diisobutylene, 4-methylpentene or norbornene isobutylene, diisobutylene, 4-methylpentene or norbornene.
  • the additives according to the invention are used together with comb polymers.
  • This term refers to polymers in which hydrocarbon radicals having at least 8, in particular at least 10, carbon atoms are bonded to a polymer backbone.
  • they are homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms.
  • at least 20%, preferably at least 30% of the monomers have side chains (cf., Comb-like Polymers-Structure and Properties; NA Platé and VP Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff ).
  • Suitable comb polymers are, for example, fumarate / vinyl acetate copolymers (cf. EP 0 153 176 A1 ), Copolymers of a C 6 -C 24 - ⁇ -olefin and a NC 6 -C 22 -alkylmaleimide (cf. EP 0 320 766 Further, esterified olefin / maleic anhydride copolymers, polymers and copolymers of ⁇ -olefins and esterified copolymers of styrene and maleic anhydride.
  • the mixing ratio (in parts by weight) of the additives according to the invention with ethylene copolymers or comb polymers is in each case 1:10 to 20: 1, preferably 1: 1 to 10: 1.
  • the additives according to the invention are added to oils in amounts of 0.0001 to 1% by weight, preferably 0.001 to 0.1% by weight and especially 0.002 to 0.05% by weight. They may be used as such or dissolved in solvents, such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures such as toluene, xylene, ethylbenzene, decane, pentadecane, gasoline fractions, diesel, kerosene or commercial solvent mixtures such as Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol, ® Isopar and ® Shellsol D grades, as well as polar solvents such as Alcohols, glycols and esters such as fatty acid alkyl esters and in particular rapeseed oil methyl ester (RME) can be used.
  • solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures such as to
  • the additives of the invention can be stored at elevated temperature for a long time without aging effects, without causing aging phenomena such as resinification and the formation of insoluble structures or deposits in storage containers and / or engine parts.
  • they improve the oxidation stability of the additized oils with simultaneously reduced emulsification tendency. This is particularly advantageous for oils containing larger amounts of cracking process oils.
  • a further advantage of the additives according to the invention is their crystallization temperature which is lower than the fatty acid esters used according to the prior art as lubricity additives. So they can be used even at low temperatures of, for example, 0 ° C to -20 ° C and sometimes also lower without problems.
  • the additives of the invention are particularly well suited for use in middle distillates.
  • middle distillates are in particular those mineral oils which are obtained by distillation of crude oil and boil in the range of 120 to 450 ° C, for example kerosene, jet fuel, diesel and fuel oil.
  • the oils may also contain or consist of alcohols such as methanol and / or ethanol.
  • the additives of the present invention are used in middle distillates containing less than 350 ppm sulfur, more preferably less than 200 ppm sulfur, and in special cases less than 50 ppm and less than 10 ppm sulfur, respectively.
  • middle distillates which have been subjected to a hydrogenating refining, and therefore only small proportions of polyaromatic and polar compounds which give them a natural lubricating effect.
  • the additives according to the invention are furthermore preferably used in middle distillates which have 95% distillation points below 370.degree. C., in particular 350.degree. C. and in special cases below 330.degree.
  • the same are the additives of the invention for use in synthetic fuels with also low lubricity, as z. B. can be produced in the Fischer-Tropsch erozess suitable.
  • the lubricity-enhanced oils have a wear scar diameter measured by the HFRR test of preferably less than 460 ⁇ m, especially less than 450 ⁇ m.
  • the additives according to the invention can also be used as components in lubricating oils.
  • the mixtures can be used alone or together with other additives, e.g. with pour point depressants, corrosion inhibitors, antioxidants, sludge inhibitors, dehazers, conductivity improvers, lubricity additives, and cloud point depressant additives. Furthermore, they are successfully used in conjunction with additive packages, which i.a. known ashless dispersing additives, detergents, defoamers, antioxidants, dehazers, demulsifiers and corrosion inhibitors.
  • Test oil 1 Test oil 2
  • Test oil 3 distillation IBP [° C] 202 182 164 20% [° C] 237 221 214 90% [° C] 321 280 342
  • FBP [° C] 348 304 367 Cloud Point [° C] -5.9 -29.7 -7.7 CFPP [° C] -8th -33 -13
  • the additives used are characterized.
  • the OH numbers were determined according to DIN 53240 by reaction with a defined amount of excess acetic anhydride and subsequent titration of the acetic acid formed.
  • Iodine numbers are determined by Kaufmann. For this purpose, the sample is mixed with a defined amount of a methanolic bromine solution, wherein an equivalent amount of bromine is added to the content of double bonds. The excess of bromine is back titrated with sodium thiosulfate.
  • a mixture of 9 g A 7, 1 g B1 and 2 g C2 gave after three days of storage at 90 ° C and subsequent dilution with 500 ml of test oil 3, a clear solution and a filtration time of 65 s.
  • the lubricating effect of the additives was tested by means of an HFRR instrument from PCS Instruments on additized oils at 60 ° C.
  • the high frequency Reciprocating Rig Test (HFRR) is described in D. Wei, H. Spikes, Wear, Vol. 2, p. 217, 1986 , The results are given as coefficient of friction and Wear Scar (WS 1.4).
  • a low Wear Scar and a low friction coefficient (Friction) show a good lubricating effect.
  • Wear Scar values of less than 460 ⁇ m are considered an indication of a sufficient lubricating effect, although values of less than 400 ⁇ m are desired in practice.
  • the dosing rates in Table 6 are based on the amount of dosed active ingredient.

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  • Lubricants (AREA)

Claims (13)

  1. Additifs pour améliorer le pouvoir lubrifiant d'huiles combustibles avec une teneur en soufre de 0,035 % en poids au maximum, contenant
    A) au moins un ester partiel d'un alcool di- ou polyhydroxylé et des acides gras insaturés ou éventuellement saturés, dont les longueurs des chaînes hydrocarbonées se situent entre 8 et 30 atomes de carbone, dans lequel au moins 60 % des radicaux acide gras contiennent au moins une double liaison, et
    B) au moins une résine alkylphénol-aldéhyde, pouvant être obtenue par condensation de
    (i) au moins un alkylphénol avec au moins un radical alkyle en C6 à C24 ou alcényle en C6 à C24 et
    (ii) au moins un aldéhyde ou une cétone
    dans laquelle le degré de condensation est entre 2 et 50 unités alkylphénol.
  2. Additif selon la revendication 1, dans lequel l'indice d'iode du constituant A) est supérieur à 50 g 1/100 g ester.
  3. Additif selon la revendication 1 et/ou 2, dans lequel l'indice OH du constituant A) se situe entre 10 et 200 mg KOH/g ester.
  4. Additif selon une ou plusieurs des revendications 1 à 3, dans lequel les acides gras, qui sont le constituant du mélange d'acides gras, contiennent 10 à 26 atomes de carbone.
  5. Additif selon une ou plusieurs des revendications 1 à 4, dans lequel les mélanges d'acides gras contiennent jusqu'à 20 % en poids d'acides gras saturés.
  6. Additif selon une ou plusieurs des revendications 1 à 5, dans lequel les mélanges d'acides gras contiennent un ou plusieurs acides dicarboxyliques.
  7. Additif selon une ; ou plusieurs des revendications 1 à 6, dans lequel les alcools contiennent 2 à 6 atomes de carbone.
  8. Additif selon une ou plusieurs des revendications 1 à 7, dans lequel les alcools contiennent 2 à 5 groupes hydroxyle, cependant au maximum un groupe hydroxyle par atome de carbone.
  9. Additif selon une ou plusieurs des revendications 1 à 8, qui contient en outre au moins un agent dispersant azoté de la paraffine.
  10. Additif selon une ou plusieurs des revendications 1 à 9, qui contient en outre au moins un copolymère d'éthylène.
  11. Additif selon une ou plusieurs des revendications 1 à 10, qui contient en outre au moins un polymère en peigne.
  12. Huiles combustibles avec une teneur en soufre au maximum de 0,035 % en poids, contenant un additif selon un ou plusieurs des revendications 1 à 11 en quantités de 0,001 à 0,5 % en poids par rapport à l'huile combustible.
  13. Utilisation d'un additif selon une ou plusieurs des revendications 1 à 11 en quantités de 0,001 à 0,5 % en poids par rapport à l'huile combustible, pour améliorer le pouvoir lubrifiant d'huiles combustibles avec une teneur en soufre au maximum de 0,035 % en poids.
EP03013093A 2002-07-09 2003-06-11 Additifs lubrifiant stabilisés contre l'oxydation pour huiles combustibles hautement désulfurées. Revoked EP1380634B1 (fr)

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DE10000649C2 (de) * 2000-01-11 2001-11-29 Clariant Gmbh Mehrfunktionelles Additiv für Brennstofföle
CA2431746C (fr) * 2002-07-09 2011-11-01 Clariant Gmbh Ameliorant de l'ecoulement a froid pour des huiles combustibles d'origine vegetale ou animale
JP4484458B2 (ja) * 2002-07-09 2010-06-16 クラリアント・プロドゥクテ・（ドイチュラント）・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング 高度に脱硫された燃料油用の酸化安定性潤滑剤添加剤

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US20060162241A1 (en) 2006-07-27
ATE370214T1 (de) 2007-09-15
CA2431749A1 (fr) 2004-01-09
DE50307929D1 (de) 2007-09-27
US7815696B2 (en) 2010-10-19
ES2291562T3 (es) 2008-03-01
CA2431749C (fr) 2010-12-14
JP2004043801A (ja) 2004-02-12
EP1380634A1 (fr) 2004-01-14
JP4484458B2 (ja) 2010-06-16
US20040010965A1 (en) 2004-01-22

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