EP1380634B1 - Lubricity additives stabilised against oxidation for highly desulphurised fuel oils. - Google Patents
Lubricity additives stabilised against oxidation for highly desulphurised fuel oils. Download PDFInfo
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- 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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Classifications
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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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- 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
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- 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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- 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
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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- 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
- C10L1/182—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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- 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
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- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
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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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- C10L1/195—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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- 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
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- 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
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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
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- 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
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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
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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
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- C10L1/14—Organic compounds
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- 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
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- 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
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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
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- 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
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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
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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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- 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
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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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
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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
- C10N2030/40—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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Abstract
Description
Die vorliegende Erfindung betrifft Additive aus Estern zwischen Polyolen und Fettsäuregemischen und Alkylphenolharzen mit verbesserter Oxidationsstabilität, sowie deren Verwendung zur Verbesserung der Schmierwirkung von hochentschwefelten Brennstoffölen.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.
Mineralöle und Mineralöldestillate, die als Brennstofföle verwendet werden, enthalten im allgemeinen 0,5 Gew.-% und mehr Schwefel, der bei der Verbrennung die Bildung von Schwefeldioxid verursacht. Um die daraus resultierenden Umweltbelastungen zu vermindern, wird der Schwefelgehalt von Brennstoffölen immer weiter abgesenkt. Die Dieseltreibstoffe betreffende Norm EN 590 schreibt in Europa seit November 1999 einen maximalen Schwefelgehalt von 350 ppm vor. Weitere Absenkungen des Schwefelgehalts sind in Vorbereitung. In Skandinavien kommen bereits Brennstofföle mit weniger als 50 ppm und in Ausnahmefällen mit weniger als 10 ppm Schwefel zur Anwendung. Diese Brennstofföle werden in der Regel dadurch hergestellt, dass man die aus dem Erdöl durch Destillation erhaltenen Fraktionen hydrierend raffiniert. Bei der Entschwefelung werden aber auch andere Substanzen entfernt, die den Brennstoffölen eine natürliche Schmierwirkung verleihen. Zu diesen Substanzen zählen unter anderem polyaromatische und polare Verbindungen.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.
Es hat sich nun aber gezeigt, dass die reibungs- und verschleißmindernden Eigenschaften von Brennstoffölen mit zunehmendem Entschwefelungsgrad schlechter werden. Oftmals sind diese Eigenschaften so mangelhaft, dass an den vom Kraftstoff geschmierten Materialien, wie z.B. den Verteiler-Einspritzpumpen von Dieselmotoren schon nach kurzer Zeit mit Fraßerscheinungen gerechnet werden muss. Der gemäß EN 590 seit dem Jahr 2000 festgesetzte Maximalwert für den 95%-Destillationspunkt von maximal 360°C und die mittlerweile in Skandinavien vorgenommene weitere Absenkung des 95%-Destillationspunkts auf unter 350°C und teilweise unter 330°C verschärft diese Problematik weiter.
Im Stand der Technik sind daher Ansätze beschrieben, die eine Lösung dieses Problems darstellen sollen (sogenannte Lubricity-Additive).However, it has now been shown that the friction and wear-reducing properties of fuel oils deteriorate with increasing degree of desulfurization. Often, these properties are so poor that on the lubricated by the fuel materials, such as the distributor injection pumps of diesel engines after a short time must be expected with feeding phenomena. The maximum value set for the 95% distillation point of maximum 360 ° C according to EN 590 since 2000 and the further lowering of the 95% distillation point to below 350 ° C, which has meanwhile been carried out in Scandinavia and sometimes below 330 ° C further aggravates this problem.
The prior art therefore describes approaches which are intended to provide a solution to this problem (so-called lubricity additives).
Die auf ungesättigten Fettsäuren und deren Derivaten basierenden Lubricity-Additive können bei längerer Lagerung des Additivs wie auch der additivierten Öle insbesondere unter erhöhter Temperatur zu nur noch bedingt öllöslichen Produkten verharzen. Dies kann zur Bildung von viskosen Ausscheidungen und Ablagerungen im Lagerbehälter des Additivs, im Brennstofföl wie auch im Motor führen. So stehen z. B. die Verbrennungs- und Kondensationsprodukte des Glycerins im Verdacht, für Koksrückstände und Ablagerungen an den Einspritzdüsen hochaufgeladener Dieselmotoren verantwortlich zu sein.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. For example, the combustion and condensation products of glycerin are suspected of being responsible for coke residues and deposits on the supercharged diesel engine injectors.
Die Wirksamkeit der derzeit eingesetzten Lubricity-Additive ist oftmals unbefriedigend, so daß entweder sehr hohe Dosierraten oder Synergisten eingesetzt werden müssen.The effectiveness of the currently used lubricity additives is often unsatisfactory, so that either very high dosing or synergists must be used.
Die auf kommerziellen Fettsäuremischungen basierenden Fettsäureester des Standes der Technik zeigen zudem in den mit ihnen additivierten Brennstoffölen eine ausgeprägte Emulgierneigung. Das bedeutet, dass bei Kontakt eines solchen Brennstofföls mit Wasser eine Emulgierung des Wassers im Brennstofföl stattfindet. Diese insbesondere an der Phasengrenze Öl/Wasser anzutreffenden Emulsionen lassen sich nicht oder nur unter großem Aufwand trennen. Da diese Emulsionen als solche nicht als Brennstofföle eingesetzt werden können, mindern sie den Wert der Produkte. Besonders stark tritt dieses Problem dann hervor, wenn auf natürlichen Fettsäuregemischen basierende Ester verwendet werden.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.
Aufgabe vorliegender Erfindung war daher, schmierverbessernde Zusätze für entschwefelte Brennstofföle zu finden, die eine gegenüber dem Stand der Technik verbesserte Oxidationsstabilität und gleichzeitig eine verbesserte Wirksamkeit als Lubricity-Additiv aufweisen.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.
Überraschenderweise wurde gefunden, dass Kombinationen von Partialestern aus ungesättigten Fettsäuren und Polyolen mit Alkylphenol-Aldehydharzen eine deutlich verbesserte Oxidationsstabilität aufweisen und bei ausgewählten Kombinationen aus Hydroxylzahl und Jodzahl eine besonders geringe Emulgierfähigkeit aufweisen. Des weiteren zeigen sie in schwefelarmen Brennstoffölen eine den Einzelbestandteilen überlegene Schmierwirkung.Surprisingly, it has been found that combinations of partial esters of unsaturated fatty acids and polyols with alkylphenol-aldehyde resins have a markedly improved oxidation stability and have a particularly low emulsifiability in selected combinations of hydroxyl number and iodine number. Of Further, they show in sulfur-poor fuel oils superior to the individual components lubricity.
Gegenstand der Erfindung ist daher ein Additiv zur Verbesserung der Schmierfähigkeit von Brennstoffölen mit einem Schwefelgehalt von maximal 0,035 Gew.-%, enthaltend
- A) mindestens einen Partialester aus einem zwei- oder mehrwertigen Alkohol und ungesättigten sowie gegebenenfalls gesättigten Fettsäuren, deren Kohlenstoffkettenlängen zwischen 8 und 30 Kohlenstoffatomen liegen, wobei mindestens 60% der Fettsäurereste mindestens eine Doppelbindung enthalten, und
- B) mindestens ein Alkylphenol-Aldehydharz, erhältlich durch die Kondensation von
- (i) mindestens einem Alkylphenol mit mindestens einem C6-C24-Alkyl oder C6-C24-Alkenylrest und
- (ii) mindestens einem Aldehyd oder Keton,
- A) at least one partial ester of a dihydric or polyhydric alcohol and unsaturated and optionally saturated fatty acids whose carbon chain lengths are between 8 and 30 carbon atoms, wherein at least 60% of the fatty acid residues contain at least one double bond, and
- B) at least one alkylphenol-aldehyde resin obtainable by the condensation of
- (i) at least one alkylphenol having at least one C 6 -C 24 -alkyl or C 6 -C 24 -alkenyl radical and
- (ii) at least one aldehyde or ketone,
Ein weiterer Gegenstand der Erfindung sind Brennstofföle mit maximal 0,035 Gew.-% Schwefelgehalt, die die erfindungsgemäßen Additive enthalten.Another object of the invention are fuel oils with a maximum of 0.035 wt .-% sulfur content containing the additives of the invention.
Ein weiterer Gegenstand der Erfindung ist die Verwendung der erfindungsgemäßen Additive zur Verbesserung der Schmierwirkung von Brennstoffölen mit höchstens 0,035 Gew.-% Schwefelgehalt.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.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Verbesserung der Schmierwirkung von Brennstoffölen mit einem Schwefelgehalt von maximal 0,035 Gew.-%, indem man den Brennstoffölen das erfindungsgemäße Additiv zusetzt.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.
Bevorzugte Fettsäuren, die Bestandteil der Ester A) sind, sind solche mit 10 bis 26 C-Atomen, insbesondere 12 bis 22 C-Atomen. Die Alkylreste bzw. Alkenylreste der Fettsäuren bestehen im wesentlichen aus Kohlenstoff und Wasserstoff. Sie können jedoch weitere Substituenten wie z.B. Hydroxy-, Halogen-, Amino- oder Nitrogruppen tragen, sofern diese den vorwiegenden Kohlenwasserstoffcharakter nicht beeinträchtigen. Die Fettsäuren enthalten vorzugsweise mindestens eine Doppelbindung. Sie können mehrere Doppelbindungen, beispielsweise 2 oder 3 Doppelbindungen, enthalten und natürlicher oder synthetischer Herkunft sein. Bei mehrfach ungesättigten Carbonsäuren können deren Doppelbindungen isoliert oder auch konjugiert sein. Bevorzugt sind Mischungen aus zwei oder mehr ungesättigten Fettsäuren mit 10 bis 26 C-Atomen. In besonders bevorzugten Fettsäuremischungen enthalten mindestens 50 Gew.-%, insbesondere mindestens 75 Gew.-%, speziell mindestens 90 Gew.-% der Fettsäuren eine oder mehrere Doppelbindungen. Die Jodzahlen der den erfindungsgemäßen Estern zugrunde liegenden Fettsäuren bzw. Fettsäuregemische liegen bevorzugt oberhalb 100 g J/100 g, besonders bevorzugt zwischen 105 und 190 g J/100 g, insbesondere zwischen 110 und 180 g J/100 g und speziell zwischen 120 und 180 g l/100 g Fettsäure bzw. Fettsäuregemisch.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. In particularly preferred fatty acid mixtures, at least 50% by weight, in particular at least 75% by weight, especially at least 90% by weight, of the fatty acids 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.
Geeignete ungesättigte Fettsäuren sind beispielsweise Öl-, Eruca-, Palmitolein-, Myristolein-, Linol-, Linolen-, Elaeosterin-, Arachidon- und/oder Ricinolsäure. Bevorzugt werden erfindungsgemäß aus natürlichen Fetten und Ölen gewonnene Fettsäuremischungen bzw. -fraktionen, wie z.B. Erdnussöl-, Fisch-, Leinöl-, Palmöl-, Rapsöl-, Ricinen-, Ricinusöl-, Rüböl-, Sojaöl-, Sonnenblumenöl-, Färberdistel- und Tallölfettsäure eingesetzt, die entsprechende Jodzahlen aufweisen.Suitable unsaturated fatty acids are, for example, oil, eruca, palmitoleic, myristoleic, linoleic, linolenic, elaeosterolic, arachidonic and / or ricinoleic acid. Preference is given to fatty acid mixtures or fractions obtained according to the invention from natural fats and oils, e.g. Peanut oil, fish, linseed oil, palm oil, rapeseed oil, ricinoleic, castor oil, rapeseed oil, soybean oil, sunflower oil, Färberdistel- and tall oil fatty acid having corresponding iodine numbers.
Als Fettsäuren ebenfalls geeignet sind Dicarbonsäuren, wie Dimerfettsäuren und Alkyl- sowie Alkenylbernsteinsäuren mit C8-C50-Alk(en)ylresten, bevorzugt mit C8-C40-, insbesondere mit C12-C22-Alkylresten. Die Alkylreste können linear wie auch verzweigt (oligomerisierte Alkene, Polyisobutylen) und gesättigt oder ungesättigt sein. Die Dicarbonsäuren können als solche oder in Mischungen mit Monocarbonsäuren eingesetzt werden, wobei in Mischungen Anteile der Dicarbonsäuren von bis zu 10 Gew.-%, insbesondere weniger als 5 Gew.-% bevorzugt sind.Also suitable as 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.
Daneben können die Fettsäuremischungen untergeordnete Mengen, d.h. bis zu 20 Gew.-%, bevorzugt weniger als 10%, insbesondere weniger als 5 % und speziell weniger als 2 % gesättigter Fettsäuren wie beispielsweise Laurin-, Tridecan-, Myristin-, Pentadecan-, Palmitin-, Margarin-, Stearin-, Isostearin-, Arachin- und Behensäure enthalten.In addition, 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.
Die Fettsäuren können weiterhin 1-40, speziell 1-25 Gew.-%, insbesondere 1-5 Gew.-% Harzsäuren enthalten.The fatty acids may further contain 1-40, especially 1-25 wt .-%, in particular 1-5 wt .-% resin acids.
Geeignete Alkohole enthalten vorzugsweise 2 bis 6, insbesondere 3 bis 4 Kohlenstorfatome, und 2 bis 5, insbesondere 3 bis 4 Hydroxylgruppen, jedoch maximal eine Hydroxylgruppe pro Kohlenstoffatom. Besonders geeignete Alkohole sind Ethylenglykol, Diethylenglykol, Propylenglykol, Glycerin, Trimethylolpropan, Neopentylglykol und Pentaerythritol sowie die daraus durch Kondensation zugänglichen Oligomere mit 2 bis 10 Monomereinheiten, wie beispielsweise Polyglycerin.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.
Die Partialester sind aus Alkoholen und Fettsäuren in bekannter Weise durch Veresterung herstellbar. Alternativ ist auch die partielle Verseifung natürlich vorkommender Fette und Öle möglich. Erfindungsgemäße Ester sind solche, die aus einem zwei- oder mehrwertigen Alkohol und einer Fettsäure oder einem Gemisch von Fettsäuren herstellbar sind. Hierbei sind sowohl Mischungen beispielsweise aus Mono-, Di- und/oder Triestern, oder ggf. höheren Estern, eines Alkohols mit verschiedenen Fettsäuren, aus Mono-, Di- und/oder Triestern, oder ggf. höheren Estern, verschiedener Alkohole mit verschiedenen Fettsäuren, als auch aus Mischungen von Mono-, Di- und/oder Triestern, oder ggf. höheren Estern, eines oder mehrerer Alkohole mit verschiedenen Fettsäuren umfasst. Bevorzugt sind solche Ester, die aus einem Fettsäuregemisch herstellbar sind.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.
Bevorzugt weisen die erfindungsgemäßen Ester Jodzahlen von mehr als 50 g l/100 g Ester auf, besonders bevorzugt liegen sie zwischen 90 und 200 g l/100 g Ester, insbesondere zwischen 100 und 180 g l/100 g Ester und speziell zwischen 110 und 150 g l/100 g Ester. Die Jodzahlen ergeben sich aus der Jodzahl des zugrundeliegenden Fettsäuregemischs und dem zur Veresterung verwendeten Alkohol in stöchiometrischer Weise.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.
Bevorzugt sind ebenfalls Partialester, deren OH-Zahlen zwischen 10 und 200 mg KOH/g Ester liegen, besonders bevorzugt zwischen 100 und 200, insbesondere zwischen 110 und 195, speziell zwischen 130 und 190 mg KOH/g Ester. In der Regel handelt es sich dabei um Mischungen verschiedener Ester, z. B. um Mischungen aus Mono- Di- und Triglyceriden, Mischungen, wie sie bei der Veresterung von Polyolen entstehen.Also preferred are 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. In general, these are mixtures of different esters, eg. As mixtures of mono-, di- and triglycerides, mixtures, such as those resulting from the esterification of polyols.
Die Partialester mit OH-Zahlen zwischen 110 und 200 mg KOH/g Ester zeichnen sich insbesondere in Kombination mit den Alkylphenolharzen B) durch eine sehr geringe Emulgierneigung aus. Vermutlich bewirkt dabei der durch die OH-Zahl begrenzte HLB-Bereich der Additive eine reduzierte Affinität der amphiphilen Wirkstoffe zu Wasser; gleichzeitig wird die Ausbildung oberflächenaktiver und micellarer Strukturen durch die mittels Jodzahl charakterisierte Anzahl an Doppelbindungen in den Alkylresten gestört.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 Emulgierneigung. Presumably, the limited by the OH number HLB range of additives causes a reduced affinity of the amphiphilic agents to water; At the same time, 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.
Die im erfindungsgemäßen Additiv enthaltenen Alkylphenol-Aldehyd-Harze (B) sind prinzipiell bekannt und beispielsweise im Römpp Chemie Lexikon, 9. Auflage, Thieme Verlag 1988-92, Band 4, S. 3351ff. beschrieben. Die Alkyl- oder Alkenylreste des Alkylphenols besitzen 6 - 24, bevorzugt 8 - 22, insbesondere 9-18 Kohlenstoffatome. Sie können linear oder bevorzugt verzweigt sein, wobei die Verzweigung sekundäre wie auch tertiäre Strukturen enthalten kann. Bevorzugt handelt es sich um n- und iso-Hexyl, n- und iso-Octyl, n- und iso-Nonyl, n- und iso-Decyl, n- und iso-Dodecyl, Tetradecyl, Hexadecyl, Octadecyl, Eicosyl sowie Tripropenyl, Tetrapropenyl, Pentapropenyl und Polyisobutenyl bis C24. Der Präfix iso bedeutet hier, daß die Alkylkette eine oder mehrere sekundäre Verzweigungen enthält. Das Alkylphenol-Aldehyd-Harz kann auch bis zu 20 mol-% Phenoleinheiten und/oder Alkylphenole mit kurzen Alkyketten wie z. B. Butylphenol enthalten. Für das Alkylphenol-Aldehydharz können gleiche oder verschiedene Alkylphenole verwendet werden.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. 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. B. butylphenol. For the alkylphenol-aldehyde resin, the same or different alkylphenols may be used.
Der Aldehyd im Alkylphenol-Aldehyd-Harz besitzt 1 bis 10, bevorzugt 1 bis 4 Kohlenstoffatome und kann weitere funktionelle Gruppen tragen. Bevorzugt ist er ein aliphatischer Aldehyd, besonders bevorzugt ist er Formaldehyd.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.
Das Molekulargewicht der Alkylphenol-Aldehyd-Harze beträgt vorzugsweise 350 - 10.000, insbesondere 400 - 5000 g/mol. Bevorzugt entspricht dies einem Kondensationsgrad n von 3 bis 40, insbesondere von 4 bis 20. Voraussetzung ist hierbei, dass die Harze öllöslich sind.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.
In einer bevorzugten Ausführungsform der Erfindung handelt es sich bei diesen Alkylphenol-Formaldehydharzen um solche, die Oligo- oder Polymere mit einer repetitiven Struktureinheit der Formel
Die Herstellung der Alkylphenol-Aldehyd-Harze erfolgt in bekannter Weise durch basische Katalyse, wobei Kondensationsprodukte vom Resoltyp entstehen, oder durch saure Katalyse, wobei Kondensationsprodukte vom Novolaktyp entstehen.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.
Die nach beiden Arten gewonnenen Kondensate sind für die erfindungsgemäßen Zusammensetzungen geeignet. Bevorzugt ist die Kondensation in Gegenwart von sauren Katalysatoren.The condensates obtained according to both types are suitable for the compositions according to the invention. Preferably, the condensation is in the presence of acidic catalysts.
Zur Herstellung der Alkylphenol-Aldehyd-Harze werden ein Alkylphenol mit 6 - 24, bevorzugt 8 - 22, insbesondere 9 - 18 C-Atomen je Alkylgruppe, oder Gemische hiervon und mindestens ein Aldehyd miteinander umgesetzt, wobei pro mol Alkylphenolverbindung etwa 0,5 - 2 mol, vorzugsweise 0,7- 1,3 mol und insbesondere äquimolare Mengen Aldehyd eingesetzt werden.For the preparation of the alkylphenol-aldehyde resins, 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.
Geeignete Alkylphenole sind insbesondere n- und iso-Hexylphenol, n- und isoOctylphenol, n- und iso- Nonylphenol, n- und iso-Decylphenol, n- und iso-Dodecylphenol, Tetradecylphenol, Hexadecylphenol, Octadecylphenol, Eicosylphenol, Tripropenylphenol, Tetrapropenylphenol und Polyi(isobutenyl)phenol bis C24.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 .
Die Alkylphenole sind vorzugsweise para-substituiert. Die Alkylphenole können einen oder mehrere Alkylreste tragen. Vorzugsweise sind sie zu höchstens 5 mol-%, insbesondere zu höchstens 20 mol-% und speziell höchstens 40 mol-% mit mehr als einer Alkylgruppe substituiert. Bevorzugt tragen höchstens 40 mol-%, insbesondere höchstens 20 mol-% der eingesetzten Alkylphenole in ortho-Position einen Alkylrest. Speziell sind die Alkylphenole in ortho-Position zur Hydroxylgruppe nicht mit tertiären Alkylgruppen substituiert.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.
Der Aldehyd kann ein Mono- oder Dialdehyd sein und weitere funktionelle Gruppen wie -COOH tragen. Besonders geeignete Aldehyde sind Formaldehyd, Acetaldehyd, Butyraldehyd, Glutardialdehyd und Glyoxalsäure, bevorzugt ist Formaldehyd. Der Formaldehyd kann in Form von Paraformaldehyd oder in Form einer vorzugsweise 20 - 40 gew.-%igen wässrigen Formalinlösung eingesetzt werden. Es können auch entsprechende Mengen an Trioxan verwendet werden.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.
Die Umsetzung von Alkylphenol und Aldehyd erfolgt üblicherweise in Gegenwart von alkalischen Katalysatoren, beispielsweise Alkalihydroxiden oder Alkylaminen, oder von sauren Katalysatoren, beispielsweise anorganischen oder organischen Säuren, wie Salzsäure, Schwefelsäure, Phosphorsäure, Sulfonsäure, Sulfamidosäuren oder Halogenessigsäuren. Die Kondensation wird bevorzugt lösemittelfrei bei 90 bis 200°C, bevorzugt bei 100 bis 160°C durchgeführt. In einer weiteren bevorzugten Ausführungsform erfolgt die Umsetzung in Gegenwart eines mit Wasser ein Azeotrop bildenden organischen Lösungsmittels, beispielsweise Toluol, Xylol, höheren Aromaten oder Gemischen hiervon. Das Reaktionsgemisch wird auf eine Temperatur von 90 bis 200°C, bevorzugt 100 - 160°C erhitzt, wobei das entstehende Reaktionswasser während der Umsetzung durch azeotrope Destillation entfernt wird. Lösungsmittel, die unter den Bedingungen der Kondensation keine Protonen abspalten, können nach der Kondensationsreaktion in den Produkten bleiben. Die Harze können direkt oder nach Neutralisation des Katalysators eingesetzt werden, gegebenenfalls nach weiterer Verdünnung der Lösung mit aliphatischen und/oder aromatischen Kohlenwasserstoffen oder Kohlenwasserstoffgemischen, z.B. Benzinfraktionen, Kerosin, Decan, Pentadecan, Toluol, Xylol, Ethylbenzol oder Lösungsmitteln wie ® Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol, ® ISOPAR- und ® Shellsol D-Typen.The reaction of 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. The condensation is preferably carried out solvent-free at 90 to 200 ° C, preferably at 100 to 160 ° C. In a further preferred embodiment, 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.
Die Gewichtsanteile der Bestandteile A) und B) in den erfindungsgemäßen Additiven können je nach Anwendungsfall in weiten Grenzen variieren. Sie liegen vorzugsweise zwischen 10 und 99,999 Gew.-% A) zu 90 bis 0,001 Gew.-% B), insbesondere zwischen 20 und 99,995 Gew.-% A) zu 80 bis 0,005 Gew.-% B). Dabei werden zur Stabilisierung der Fettsäuren bevorzugt kleinere Anteile der Komponenten B von 0,001 bis 10 Gew.-%, bevorzugt 0,005 bis 5 Gew.-% B) eingesetzt, wogegen zur Optimierung der Schmierfähigkeit größere Anteile B von beispielsweise 5 bis 90 Gew.-%, bevorzugt 10 bis 80 Gew.-% und insbesondere 25 bis 75 Gew.-% eingesetzt werden.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). In this case, for the stabilization of the fatty acids 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.
Überraschenderweise wurde ebenfalls gefunden, dass eine weitere Steigerung der Wirksamkeit als Lubricity-Additiv erzielt wird, wenn die erfindungsgemäßen Mischungen zusammen mit stickstoffhaltigen Paraffindispergatoren eingesetzt werden. Paraffindispergatoren sind Additive, die bei Abkühlung des Öls die Größe der ausfallenden Paraffinkristalle reduzieren und darüber hinaus bewirken, dass die Paraffinpartikel sich nicht absetzen, sondern kolloidal mit deutlich reduziertem Sedimentationsbestreben, dispergiert bleiben.Surprisingly, it has also been found that a further increase in the effectiveness as a lubricant additive is achieved when the mixtures according to the invention are used together with nitrogen-containing paraffin dispersants. 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.
Bei den stickstoffhaltigen Paraffindispergatoren handelt es sich vorzugsweise um niedermolekulare oder polymere, öllösliche Stickstoffverbindungen, z.B. Aminsalze, Imide und/oder Amide, die durch Reaktion aliphatischer oder aromatischer Amine, vorzugsweise langkettiger aliphatischer Amine, mit aliphatischen oder aromatischen Mono-, Di-, Tri-, Tetra- und/oder Polycarbonsäuren oder deren Anhydriden erhalten werden. Besonders bevorzugte Paraffindispergatoren enthalten Umsetzungsprodukte sekundärer Fettamine mit 8 bis 36 C-Atomen, insbesondere Dicocosfettamin, Ditalgfettamin und Distearylamin. Andere Paraffindispergatoren sind Copolymere des Maleinsäureanhydrids und α,β-ungesättigten Verbindungen, die gegebenenfalls mit primären Monoalkylaminen und/oder aliphatischen Alkoholen umgesetzt werden können, die Umsetzungsprodukte von Alkenylspirobislactonen mit Aminen und Umsetzungsprodukte von Terpolymerisaten auf Basis α,β-ungesättigter Dicarbonsäureanhydride, α,β-ungesättigter Verbindungen und Polyoxyalkylenether niederer ungesättigter Alkohole mit Aminen und/oder Alkoholen. Im folgenden werden einige geeignete Paraffindispergatoren aufgeführt.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. Other paraffin dispersants are copolymers of maleic anhydride and α, β-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 α, β-unsaturated dicarboxylic anhydrides, α, β-unsaturated compounds and polyoxyalkylene of lower unsaturated alcohols with amines and / or alcohols. In the following, some suitable paraffin dispersants are listed.
Die nachfolgend genannten Paraffindispergatoren werden zum Teil durch Reaktion von Verbindungen, die eine Acylgruppe enthalten, mit einem Amin hergestellt. Bei diesem Amin handelt es sich um eine Verbindung der Formel NR6R7R8, worin R6, R7 und R8 gleich oder verschieden sein können, und wenigstens eine dieser Gruppen für C8-C36-Alkyl, C6-C36-Cycloalkyl, C8-C36-Alkenyl, insbesondere C12-C24-Alkyl, C12-C24-Alkenyl oder Cyclohexyl steht, und die übrigen Gruppen entweder Wasserstoff, C1-C36-Alkyl, C2-C36-Alkenyl, Cyclohexyl, oder eine Gruppe der Formeln - (A-O)x-E oder -(CH2)n-NYZ bedeuten, worin A für eine Ethylen- oder Propylengruppe steht, x eine Zahl von 1 bis 50, E = H, C1-C30-Alkyl, C5-C12-Cycloalkyl oder C6-C30-Aryl, und n 2, 3 oder 4 bedeuten, und Y und Z unabhängig voneinander H, C1-C30-Alkyl oder -(A-O)x bedeuten. Unter Acylgruppe wird hier eine funktionelle Gruppe folgender Formel verstanden:
>C=O
- 1. Umsetzungsprodukte von Alkenylspirobislactonen der Formel
EP-A-0 413 279 - 2. Amide bzw. Ammoniumsalze von Aminoalkylenpolycarbonsäuren mit sekundären Aminen der Formeln
R10 einen geradkettigen oder verzweigten Alkylenrest mit 2 bis 6 Kohlenstoffatomen oder den Rest der Formel
Die Amide bzw. Amid-Ammoniumsalze bzw. Ammoniumsalze z.B. der Nitrilotriessigsäure, der Ethylendiamintetraessigsäure oder der Propylen-1,2-diamintetraessigsäure werden durch Umsetzung der Säuren mit 0,5 bis 1,5 Mol Amin, bevorzugt 0,8 bis 1,2 Mol Amin pro Carboxylgruppe erhalten. Die Umsetzungstemperaturen betragen etwa 80 bis 200°C, wobei zur Herstellung der Amide eine kontinuierliche Entfernung des entstandenen Reaktionswasser erfolgt. Die Umsetzung muss jedoch nicht vollständig zum Amid geführt werden, vielmehr können 0 bis 100 Mol-% des eingesetzten Amins in Form des Ammoniumsalzes vorliegen. Unter analogen Bedingungen können auch die unter B1) genannten Verbindungen hergestellt werden.
Als Amine der Formel - 3. Quartäre Ammoniumsalze der Formel
+NR6R7R8R11 X-
wobei R6, R7, R8 die oben gegebene Bedeutung haben und R11 für C1-C30-Alkyl, bevorzugt C1-C22-Alkyl, C1-C30-Alkenyl, bevorzugt C1-C22-Alkenyl, Benzyl oder einen Rest der Formel -(CH2-CH2-O)n-R12 steht, wobei R12 Wasserstoff oder ein Fettsäurerest der Formel C(O)-R13 ist, mit R13 = C6-C40-Alkenyl, n eine Zahl von 1 bis 30 und X für Halogen, bevorzugt Chlor, oder ein Methosulfat steht.
Beispielhaft für derartige quartäre Ammoniumsalze seien genannt: Dihexadecyl-dimethylammoniumchlorid, Distearyldimethylammoniumchlorid, Quaternisierungsprodukte von Estern des Di- und Triethanolamins mit langkettigen Fettsäuren (Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, Behensäure, Ölsäure und Fettsäuremischungen, wie Cocosfettsäure, Talgfettsäure, hydrierte Talgfettsäure, Tallölfettsäure), wie N-Methyltriethanolammonium-distearylester-chlorid, N-Methyltriethanolammoniumdistearylester-methosulfat, N,N-Dimethyldiethanolammoniumdistearylesterchlorid, N-Methyltriethanolammonium-dioleylester-chlorid, N-Methyltriethanolammoniumtrilaurylestermethosulfat, N-Methyltriethanolammoniumtristearylestermethosulfat und deren Mischungen. - 4. Verbindungen der Formel
Bevorzugte Carbonsäuren bzw. Säurederivate sind Phthalsäure(anhydrid), Trimellit, Pyromellitsäure(dianhydrid), Isophthalsäure, Terephthalsäure, Cyclohexan-dicarbonsäure(anhydrid), Maleinsäure(anhydrid), Alkenylbernsteinsäure(anhydrid). Die Formulierung (anhydrid) bedeutet, dass auch die Anhydride der genannten Säuren bevorzugte Säurederivate sind. Wenn die Verbindungen obiger Formel Amide oder Aminsalze sind, sind sie vorzugsweise von einem sekundären Amin, das eine Wasserstoff und Kohlenstoff enthaltende Gruppe mit mindestens 10 Kohlenstoffatomen enthält, erhalten.
Es ist bevorzugt, dass R17 10 bis 30, insbesondere 10 bis 22, z.B. 14 bis 20 Kohlenstoffatome enthält und vorzugsweise geradkettig oder an der 1- oder 2-Position verzweigt ist. Die anderen Wasserstoff und Kohlenstoff enthaltenden Gruppen können kürzer sein, z.B. weniger als 6 Kohlenstoffatome enthalten, oder können, falls gewünscht, mindestens 10 Kohlenstoffatome aufweisen. Geeignete Alkylgruppen schließen Methyl, Ethyl, Propyl, Hexyl, Decyl, Dodecyl, Tetradecyl, Eicosyl und Docosyl (Behenyl) ein.
Des weiteren sind Polymere geeignet, die mindestens eine Amid- oder Ammoniumgruppe direkt an das Gerüst des Polymers gebunden enthalten, wobei die Amid- oder Ammoniumgruppe mindestens eine Alkylgruppe von mindestens 8 C-Atomen am Stickstoffatom trägt. Derartige Polymere können auf verschiedene Arten hergestellt werden. Eine Art ist, ein Polymer zu verwenden, das mehrere Carbonsäure oder -Anhydridgruppen enthält, und dieses Polymer mit einem Amin der Formel NHR6R7 umzusetzen, um das gewünschte Polymer zu erhalten.
Als Polymere sind dazu allgemein Copolymere aus ungesättigten Estern wie C1-C40-Alkyl(meth)acrylaten, Fumarsäuredi(C1-C40-alkylestern), C1-C40-Alkylvinylethern, C1-C40-Alkylvinylestern oder C2-C40-Olefinen (linear, verzweigt, aromatisch) mit ungesättigten Carbonsäuren bzw. deren reaktiven Derivaten, wie z.B. Carbonsäureanhydriden (Acrylsäure, Methacrylsäure, Maleinsäure, Fumarsäure, Tetrahydrophthalsäure, Citraconsäure, bevorzugt Maleinsäureanhydrid) geeignet.
Carbonsäuren werden vorzugsweise mit 0,1 bis 1,5 mol, insbesondere 0,5 bis 1,2 mol Amin pro Säuregruppe, Carbonsäureanhydride vorzugsweise mit 0,1 bis 2,5, insbesondere 0,5 bis 2,2 mol Amin pro Säureanhydridgruppe umgesetzt, wobei je nach Reaktionsbedingungen Amide, Ammoniumsalze, Amid-Ammoniumsalze oder Imide entstehen. So ergeben Copolymere, die ungesättigte Carbonsäureanhydride enthalten, bei der Umsetzung mit einem sekundären Amin auf Grund der Reaktion mit der Anhydridgruppe zur Hälfte Amid und zur Hälfte Aminsalze. Durch Erhitzen kann unter Bildung des Diamids Wasser abgespalten werden.
Besonders geeignete Beispiele amidgruppenhaltiger Polymere zur erfindungsgemäßen Verwendung sind: - 5. Copolymere (a) eines Dialkylfumarats, -maleats, -citraconats oder -itaconats mit Maleinsäureanhydrid, oder (b) von Vinylestern, z.B. Vinylacetat, Vinylpropionat, Vinyl-2-ethylhexanoat oder Vinylstearat mit Maleinsäureanhydrid, oder (c) eines Dialkylfumarats, -maleats, -citraconats oder -itaconats mit Maleinsäureanhydrid und Vinylacetat.
Besonders geeignete Beispiele für diese Polymere sind Copolymere von Didodecylfumarat, Vinylacetat und Maleinsäureanhydrid; Ditetradecylfumarat, Vinylacetat und Maleinsäureanhydrid; Di-hexadecylfumarat, Vinylacetat und Maleinsäureanhydrid; oder den entsprechenden Copolymeren, bei denen anstelle des Fumarats das ltaconat verwendet wird.
In den oben genannten Beispielen geeigneter Polymere wird das gewünschte Amid durch Umsetzung des Polymers, das Anhydridgruppen enthält, mit einem sekundären Amin der Formel HNR6R7 (gegebenenfalls außerdem mit einem Alkohol, wenn ein Esteramid gebildet wird) erhalten. Wenn Polymere, die eine Anhydridgruppe enthalten, umgesetzt werden, werden die resultierenden Aminogruppen Ammoniumsalze und Amide sein. Solche Polymere können verwendet werden, mit der Maßgabe, dass sie mindestens zwei Amidgruppen enthalten.
Es ist wesentlich, dass das Polymer, das mindestens zwei Amidgruppen enthält, mindestens eine Alkylgruppe mit mindestens 10 Kohlenstoffatomen enthält. Diese langkettige Gruppe, die eine geradkettige oder verzweigte Alkylgruppe sein kann, kann über das Stickstoffatom der Amidgruppe gebunden vorliegen.
Die dafür geeigneten Amine können durch die Formel R6R7NH und die Polyamine durch R6NH[R19NH]xR7 wiedergegeben werden, wobei R19 eine zweiwertige Kohlenwasserstoffgruppe, vorzugsweise eine Alkylen- oder kohlenwasserstoffsubstituierte Alkylengruppe, und x eine ganze Zahl, vorzugsweise zwischen 1 und 30 ist. Vorzugsweise enthalten einer der beiden oder beide Reste R6 und R7 mindestens 10 Kohlenstoffatome, beispielsweise 10 bis 20 Kohlenstoffatome, zum Beispiel Dodecyl, Tetradecyl, Hexadecyl oder Octadecyl.
Beispiele geeigneter sekundärer Amine sind Dioctylamin und solche, die Alkylgruppen mit mindestens 10 Kohlenstoffatomen enthalten, beispielsweise Didecylamin, Didodecylamin, Dicocosamin (d.h. gemischte C12-C14-Amine), Dioctadecylamin, Hexadecyloctadecylamin, Di-(hydriertes Talg)-Amin (annähernd 4 Gew.-% n-C14-Alkyl, 30 Gew.-% n-C10-Alkyl, 60 Gew.-% n-C18-Alkyl, der Rest ist ungesättigt).
Beispiele geeigneter Polyamine sind N-Octadecylpropandiamin, N,N'-Dioctadecylpropandiamin, N-Tetradecylbutandiamin und N,N'-Dihexadecylhexandiamin. N-Cocospropylendiamin (C12/C14-Alkylpropylen-diamin), N-Talgpropylendiamin (C16/C18-Alkylpropylendiamin).
Die amidhaltigen Polymere haben üblicherweise ein durchschnittliches Molekulargewicht (Zahlenmittel) von 1000 bis 500 000, zum Beispiel 10 000 bis 100 000. - 6. Copolymere des Styrols, seiner Derivate oder aliphatischer Olefine mit 2 bis 40 C-Atomen, bevorzugt mit 6 bis 20 C-Atomen und olefinisch ungesättigten Carbonsäuren oder Carbonsäureanhydriden, die mit Aminen der Formel HNR6R7 umgesetzt sind. Die Umsetzung kann vor oder nach der Polymerisation vorgenommen werden.
Im einzelnen leiten sich die Struktureinheiten der Copolymere von z.B. Maleinsäure, Fumarsäure, Tetrahydrophthalsäure, Citraconsäure, bevorzugt Maleinsäureanhydrid ab. Sie können sowohl in Form ihrer Homopolymeren als auch der Copolymeren eingesetzt werden. Als Comonomere sind geeignet: Styrol und Alkylstyrole, geradkettige und verzweigte Olefine mit 2 bis 40 Kohlenstoffatomen, sowie deren Mischungen untereinander. Beispielsweise seien genannt: Styrol, α-Methylstyrol, Dimethylstyrol, α-Ethylstyrol, Diethylstyrol, i-Propylstyrol, tert.-Butylstyrol, Ethylen, Propylen, n-Butylen, Diisobutylen, Decen, Dodecen, Tetradecen, Hexadecen, Octadecen. Bevorzugt sind Styrol und Isobuten, besonders bevorzugt ist Styrol.
Als Polymere seien beispielsweise im einzelnen genannt: Polymaleinsäure, ein equimolares, alternierend aufgebautes Styrol/Maleinsäure-Copolymer, statistisch aufgebaute Styrol/Maleinsäure-Copolymere im Verhältnis 10:90 und ein alternierendes Copolymer aus Maleinsäure und i-Buten. Die molaren Massen der Polymeren betragen im allgemeinen 500 g/mol bis 20 000 g/mol, bevorzugt 700 bis 2000 g/mol.
Die Umsetzung der Polymeren oder Copolymeren mit den Aminen erfolgt bei Temperaturen von 50 bis 200°C im Verlauf von 0,3 bis 30 Stunden. Das Amin wird dabei in Mengen von ungefähr einem Mol pro Mol einpolymerisiertem Dicarbonsäureanhydrid, d.i. ca.0,9 bis 1,1 Mol/Mol, angewandt. Die Verwendung größerer oder geringerer Mengen ist möglich, bringt aber keinen Vorteil. Werden größere Mengen als ein Mol angewandt, erhält man zum Teil Ammoniumsalze, da die Bildung einer zweiten Amidgruppierung höhere Temperaturen, längere Verweilzeiten und Wasserauskreisen erfordert. Werden geringere Mengen als ein Mol angewandt, findet keine vollständige Umsetzung zum Monoamid statt und man erhält eine dementsprechend verringerte Wirkung.
Anstelle der nachträglichen Umsetzung der Carboxylgruppen in Form des Dicarbonsäureanhydrids mit Aminen zu den entsprechenden Amiden kann es manchmal von Vorteil sein, die Monoamide der Monomeren herzustellen und dann bei der Polymerisation direkt einzupolymerisieren. Meist ist das jedoch technisch viel aufwendiger, da sich die Amine an die Doppelbindung der monomeren Mono- und Dicarbonsäure anlagern können und dann keine Copolymerisation mehr möglich ist. - 7. Copolymere, bestehend aus 10 bis 95 Mol-% eines oder mehrerer Alkylacrylate oder Alkylmethacrylate mit C1-C26-Alkylketten und aus 5 bis 90 Mol-% einer oder mehrerer ethylenisch ungesättigter Dicarbonsäuren oder deren Anhydriden, wobei das Copolymere weitgehend mit einem oder mehreren primären oder sekundären Aminen zum Monoamid oder Amid/Ammoniumsalz der Dicarbonsäure umgesetzt ist.
Die Copolymeren bestehen zu 10 bis 95 Mol-%, bevorzugt zu 40 bis 95 Mol-% und besonders bevorzugt zu 60 bis 90 Mol-% aus Alkyl(meth)acrylaten und zu 5 bis 90 Mol-%, bevorzugt zu 5 bis 60 Mol-% und besonders bevorzugt zu 10 bis 40 Mol-% aus den olefinisch ungesättigten Dicarbonsäurederivaten. Die Alkylgruppen der Alkyl(meth)acrylate enthalten aus 1 bis 26, bevorzugt 4 bis 22 und besonders bevorzugt 8 bis 18 Kohlenstoffatome. Sie sind bevorzugt geradkettig und unverzweigt. Es können jedoch auch bis zu 20 Gew.-% cyclische und/oder verzweigte Anteile enthalten sein.
Beispiele für besonders bevorzugte Alkyl(meth)acrylate sind n-Octyl(meth)acrylat, n-Decyl(meth)acrylat, n-Dodecyl(meth)acrylat, n-Tetradecyl(meth)acrylat, n-Hexadecyl(meth)acrylat und n-Octadecyl(meth)acrylat sowie Mischungen davon.
Beispiele ethylenisch ungesättigter Dicarbonsäuren sind Maleinsäure, Tetrahydrophthalsäure, Citraconsäure und Itaconsäure bzw. deren Anhydride sowie Fumarsäure. Bevorzugt ist Maleinsäureanhydrid.
Als Amine kommen Verbindungen der Formel HNR6R7 in Betracht.
In der Regel ist es von Vorteil, die Dicarbonsäuren in Form der Anhydride, soweit verfügbar, bei der Copolymerisation einzusetzen, z.B. Maleinsäureanhydrid, Itaconsäureanhydrid, Citraconsäureanhydrid und Tetrahydrophthalsäureanhydrid, da die Anhydride in der Regel besser mit den (Meth)acrylaten copolymerisieren. Die Anhydridgruppen der Copolymeren können dann direkt mit den Aminen umgesetzt werden.
Die Umsetzung der Polymeren mit den Aminen erfolgt bei Temperaturen von 50 bis 200°C im Verlauf von 0,3 bis 30 Stunden. Das Amin wird dabei in Mengen von ungefähr einem bis zwei. Mol pro Mol einpolymerisiertem Dicarbonsäureanhydrid, d.i. ca. 0,9 bis 2,1 Mol/Mol angewandt. Die Verwendung größerer oder geringerer Mengen ist möglich, bringt aber keinen Vorteil. Werden größere Mengen als zwei Mol angewandt, liegt freies Amin vor. Werden geringere Mengen als ein Mol angewandt, findet keine vollständige Umsetzung zum Monoamid statt und man erhält eine dementsprechend verringerte Wirkung.
In einigen Fällen kann es von Vorteil sein, wenn die Amid/Ammoniumsalzstruktur aus zwei unterschiedlichen Aminen aufgebaut wird. So kann beispielsweise ein Copolymer aus Laurylacrylat und Maleinsäureanhydrid zuerst mit einem sekundären Amin, wie hydriertem Ditalgfettamin zum Amid umgesetzt werden, wonach die aus dem Anhydrid stammende freie Carboxylgruppe mit einem anderen Amin, z.B. 2-Ethylhexylamin zum Ammoniumsalz neutralisiert wird. Genauso ist die umgekehrte Vorgehensweise denkbar: Zuerst wird mit Ethylhexylamin zum Monoamid, dann mit Ditalgfettamin zum Ammoniumsalz umgesetzt. Vorzugsweise wird dabei mindestens ein Amin verwendet, welches mindestens eine geradkettige, unverzweigte Alkylgruppe mit mehr als 16 Kohlenstoffatomen besitzt. Es ist dabei nicht erheblich, ob dieses Amin am Aufbau der Amidstruktur oder als Ammoniumsalz der Dicarbonsäure vorliegt.
Anstelle der nachträglichen Umsetzung der Carboxylgruppen bzw. des Dicarbonsäureanhydrids mit Aminen zu den entsprechenden Amiden oder Amid/Ammoniumsalzen, kann es manchmal von Vorteil sein, die Monoamide bzw. Amid/Ammoniumsalze der Monomeren herzustellen und dann bei der Polymerisation direkt einzupolymerisieren. Meist ist das jedoch technisch viel aufwendiger, da sich die Amine an die Doppelbindung der monomeren Dicarbonsäure anlagern können und dann keine Copolymerisation mehr möglich ist. - 8. Terpolymere auf Basis von α,β-ungesättigten Dicarbonsäureanhydriden, α,β-ungesättigten Verbindungen und Polyoxyalkylenethern von niederen, ungesättigten Alkoholen, die dadurch gekennzeichnet sind, dass sie 20 - 80, bevorzugt 40 - 60 Mol-% an bivalenten Struktureinheiten der Formeln 1 und/oder 3, sowie gegebenenfalls 2 enthalten, wobei die Struktureinheiten 2 von nicht umgesetzten Anhydridresten stammen,
R22 und R23 unabhängig voneinander Wasserstoff oder Methyl,
a, b gleich Null oder Eins und a + b gleich Eins,
R24 und R25 gleich oder verschieden sind und für die Gruppen -NHR6, N(R6)2 und/oder -OR27 stehen, und R27 für ein Kation der Formel H2N(R6)2 oder
H3NR6 steht, 19 - 80 Mol-%, bevorzugt 39-60 Mol-% an bivalenten
Struktureinheiten der Formel 4
R28 Wasserstoff oder C1-C4-Alkyl und
R29 C6-C60-Alkyl oder C6-C18-Aryl bedeuten und
1 - 30 Mol-%, bevorzugt 1 - 20 Mol-% an bivalenten Struktureinheiten der Formel 5
R30 Wasserstoff oder Methyl,
R31 Wasserstoff oder C1-C4-Alkyl,
R33 C1-C4-Alkylen,
m eine Zahl von 1 bis 100,
R32 C1-C24-Alkyl, C5-C20-Cycloalkyl, C6-C18-Aryl oder -C(O)-R34, wobei
R34 C1-C40-Alkyl, C5-C10-Cycloalkyl oder C6-C18-Aryl, enthalten.
Die vorgenannten Alkyl-, Cycloalkyl- und Arylreste können gegebenenfalls substituiert sein. Geeignete Substituenten der Alkyl- und Arylreste sind beispielsweise (C1-C6)-Alkyl, Halogene, wie Fluor, Chlor, Brom und Jod, bevorzugt Chlor und (C1-C6)-Alkoxy.
Alkyl steht hier für einen geradkettigen oder verzweigten Kohlenwasserstoffrest. Im einzelnen seien genannt: n-Butyl, tert.-Butyl, n-Hexyl, n-Octyl, Decyl, Dodecyl, Tetradecyl, Hexadecyl, Octadecyl, Dodecenyl, Tetrapropenyl, Tetradecenyl, Pentapropenyl, Hexadecenyl, Octadecenyl und Eicosanyl oder Mischungen, wie Cocosalkyl, Talgfettalkyl und Behenyl.
Cycloalkyl steht hier für einen cyclischen aliphatischen Rest mit 5 - 20 Kohlenstoffatomen. Bevorzugte Cycloalkylreste sind Cyclopentyl und Cyclohexyl.
Aryl steht hier für einen gegebenenfalls substituiertes aromatisches Ringsystem mit 6 bis 18 Kohlenstoffatomen.
Die Terpolymere bestehen aus den bivalenten Struktureinheiten der Formeln 1 und 3 sowie 4 und 5 und ggf. 2. Sie enthalten lediglich noch in an sich bekannter Weise die bei der Polymerisation durch Initiierung, Inhibierung und Kettenabbruch entstandenen Endgruppen.
Im einzelnen leiten sich Struktureinheiten der Formeln 1 bis 3 von α,β-ungesättigten Dicarbonsäureanhydriden der Formeln 6 und 7
Die Struktureinheiten der Formel 4 leiten sich von den α,β-ungesättigten Verbindungen der Formel 8 ab.
Die Struktureinheiten der Formel 5 leiten sich von Polyoxyalkylenethern niederer, ungesättigter Alkohole der Formel 9 ab.
Die Polyoxyalkylenether (R32 = H) lassen sich nach bekannten Verfahren z.B. durch Anlagerung von α-Olefinoxiden, wie Ethylenoxid, Propylenoxid und/oder Butylenoxid an polymerisierbare niedere, ungesättigte Alkohole der Formel 10
Als zur Herstellung der Terpolymere geeignete primäre Amine seien beispielsweise die folgenden genannt:- n-Hexylamin, n-Octylamin, n-Tetradecylamin, n-Hexadecylamin,
- n-Stearylamin oder auch N,N-Dimethylaminopropylendiamin, Cyclohexylamin, Dehydroabietylamin sowie deren Mischungen.
Die Terpolymeren besitzen K-Werte (gemessen nach Ubbelohde in 5 gew.-%iger Lösung in Toluol bei 25°C) von 8 bis 100, bevorzugt 8 bis 50, entsprechend mittleren Molekulargewichten (Mw) zwischen ca. 500 und 100.000. Geeignete Beispiele sind inEP 606 055 - 9. Umsetzungsprodukte von Alkanolaminen und/oder Polyetheraminen mit Polymeren enthaltend Dicarbonsäureanhydridgruppen, dadurch gekennzeichnet, dass sie 20 - 80, bevorzugt 40 - 60 Mol-% an bivalenten Struktureinheiten der Formeln 13 und 15 und gegebenenfalls 14
R22 und R23 unabhängig voneinander Wasserstoff oder Methyl,
a, b gleich Null oder 1 und a + b gleich 1,
R37 = -OH, -O-[C1-C30-Alkyl], -NR6R7, OsNrR6R7H2
R38 = R37oderNR6R39
R39 = -(A-O)x-E
mit
A = Ethylen- oder Propylengruppe
x = 1 bis 50
E = H, C1-C30-Alkyl, C5-C12-Cycloalkyl oder C6-C30-Aryl bedeuten, und 80 - 20 Mol-%, bevorzugt 60 - 40 Mol-% an bivalenten Struktureinheiten der Formel 4 enthalten.
Im einzelnen leiten sich die Struktureinheiten der Formeln 13, 14 und 15 von α,β-ungesättigten Dicarbonsäureanhydriden der Formeln 6 und/oder 7 ab.
Die Struktureinheiten der Formel 4 leiten sich von den α,β-ungesättigten Olefinen der Formel 8 ab. Die vorgenannte Alkyl-, Cycloalkyl- und Arylreste haben die gleichen Bedeutungen wie unter 8.
Die Reste R37 und R38 in Formel 13 bzw. R39 in Formel 15 leiten sich von Polyetheraminen oder Alkanolaminen der Formeln 16 a) und b), Aminen der Formel NR6R7R8 sowie gegebenenfalls von Alkoholen mit 1 bis 30 Kohlenstoffatomen ab.- R53
- Wasserstoff, C6-C40-Alkyl oder
- R54
- Wasserstoff, C1-C4-Alkyl
- R55
- Wasserstoff, C1- bis C4-Alkyl, C5- bis C12-Cycloalkyl oder C6- bis C30-Aryl
- R56, R57
- unabhängig voneinander Wasserstoff, C1- bis C22-Alkyl, C2- bis C22-Alkenyl oder Z - OH
- Z
- C2- bis C4-Alkylen
- n
- eine Zahl zwischen 1 und 1000.
Eine weitere Möglichkeit zur Derivatisierung der Struktureinheiten der Formeln 6 und 7 besteht darin, dass anstelle der Polyetheramine ein Alkanolamin der Formeln 16a) oder 16b) eingesetzt und nachfolgend einer Oxalkylierung unterworfen wird.
Pro Mol Anhydrid werden 0,01 bis 2 Mol, bevorzugt 0,01 bis 1 Mol Alkanolamin eingesetzt. Die Reaktionstemperatur beträgt zwischen 50 und 100°C (Amidbildung). Im Falle von primären Aminen erfolgt die Umsetzung bei Temperaturen oberhalb 100°C (lmidbildung).
Die Oxalkylierung erfolgt üblicherweise bei Temperaturen zwischen 70 und 170°C unter Katalyse von Basen, wie NaOH oder NaOCH3, durch Aufgasen von Alkylenoxiden, wie Ethylenoxid (EO) und/oder Propylenoxid (PO). Üblicherweise werden pro Mol Hydroxylgruppen 1 bis 500, bevorzugt 1 bis 100 Mol Alkylenoxid zugegeben.
Als geeignete Alkanolamine seien beispielsweise genannt:- Monoethanolamin, Diethanolamin, N-Methylethanolamin, 3-Aminopropanol,
- Isopropanol, Diglykolamin, 2-Amino-2-methylpropanol und deren Mischungen.
- n-Hexylamin, n-Octylamin, n-Tetradecylamin, n-Hexadecylamin,
- n-Stearylamin oder auch N,N-Dimethylaminopropylendiamin, Cyclohexylamin, Dehydroabietylamin sowie deren Mischungen.
- Didecylamin, Ditetradecylamin, Distearylamin, Dicocosfettamin, Ditalgfettamin und deren Mischungen.
- Methanol, Ethanol, Propanol, lsopropanol, n-, sek.-, tert.-Butanol, Octanol,
- Tetradecanol, Hexadecanol, Octadecanol, Talgfettalkohol, Behenylalkohol und deren Mischungen. Geeignete Beispiele sind in
EP-A-688 796
- 10. Co- und Terpolymere von N-C6-C24-Alkylmaleinimid mit C1-C30-Vinylestern, Vinylethern und/oder Olefinen mit 1 bis 30 C-Atomen, wie z.B. Styrol oder α-Olefinen. Diese sind zum einen durch Umsetzung eines Anhydridgruppen enthaltenden Polymers mit Aminen der Formel H2NR6 oder durch Imidierung der Dicarbonsäure und anschließende Copolymerisation zugänglich. Bevorzugte Dicarbonsäure ist dabei Maleinsäure bzw. Maleinsäureanhydrid. Bevorzugt sind dabei Copolymere aus 10 bis 90 Gew.-% C6-C24-α-Olefinen und 90 bis 10 Gew.-% N-C6-C22-Alkylmaleinsäureimid.
> C = O
- 1. Reaction products of Alkenylspirobislactonen the formula
EP-A-0 413 279 - 2. Amides or ammonium salts of aminoalkylene polycarboxylic acids with secondary amines of the formulas
R 10 is a straight-chain or branched alkylene radical having 2 to 6 carbon atoms or the radical of the formula
The amides or amide ammonium salts or ammonium salts of, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diaminetetraacetic acid are obtained by reacting the acids with 0.5 to 1.5 moles of amine, preferably 0.8 to 1.2 moles of amine per carboxyl group. The reaction temperatures are about 80 to 200 ° C, wherein for the preparation of the amides a continuous removal of the resulting water of reaction takes place. However, the reaction does not have to be completely led to the amide, but may be 0 to 100 mol% of the amine used in the form of the ammonium salt. Under analogous conditions, the compounds mentioned under B1) can also be prepared.
As amines of the formula - 3. Quaternary ammonium salts of the formula
+ NR 6 R 7 R 8 R 11 X -
where R 6 , R 7 , R 8 have the abovementioned meaning and R 11 is C 1 -C 30 -alkyl, preferably C 1 -C 22 -alkyl, C 1 -C 30 -alkenyl, preferably C 1 -C 22 - Alkenyl, benzyl or a radical of the formula - (CH 2 -CH 2 -O) n -R 12 wherein R 12 is hydrogen or a fatty acid radical of the formula C (O) -R 13 , with R 13 = C 6 -C 40 alkenyl, n is a number from 1 to 30 and X is halogen, preferably chlorine, or a methosulfate.
Examples of such quaternary ammonium salts include: dihexadecyldimethylammonium chloride, distearyldimethylammonium chloride, Quaternization products of esters of di- and triethanolamine with long-chain fatty acids (lauric, myristic, palmitic, stearic, behenic, oleic and fatty acid mixtures such as coconut fatty acid, tallow fatty acid, hydrogenated tallow fatty acid, tall oil fatty acid) such as N-methyltriethanolammonium distearyl ester chloride, N-methyltriethanolammonium distearyl ester methosulfate, N, N-dimethyldiethanolammonium distearyl ester chloride, N-methyltriethanolammonium dioleyl ester chloride, N-methyltriethanolammonium trilauryl ester methosulfate, N-methyltriethanolammonium tristearyl ester methosulfate, and mixtures thereof. - 4. Compounds of the formula
Preferred carboxylic acids or acid derivatives are phthalic acid (anhydride), trimellit, pyromellitic acid (dianhydride), isophthalic acid, terephthalic acid, cyclohexane-dicarboxylic acid (anhydride), maleic acid (anhydride), alkenylsuccinic acid (anhydride). The formulation (anhydride) means that the anhydrides of said acids are also preferred acid derivatives. When the compounds of the above formula are amides or amine salts, they are preferably obtained from a secondary amine containing a hydrogen and carbon containing group having at least 10 carbon atoms.
It is preferred that R 17 contains from 10 to 30, in particular from 10 to 22, for example from 14 to 20 carbon atoms and is preferably straight-chain or branched at the 1- or 2-position. The other hydrogen and carbon containing groups may be shorter, eg containing less than 6 carbon atoms, or may have at least 10 carbon atoms if desired. Suitable alkyl groups include methyl, ethyl, propyl, hexyl, decyl, dodecyl, tetradecyl, eicosyl and docosyl (behenyl).
Furthermore, polymers are suitable which contain at least one amide or ammonium group bound directly to the skeleton of the polymer, wherein the amide or ammonium group carries at least one alkyl group of at least 8 C atoms on the nitrogen atom. Such polymers can be prepared in various ways. One way is to use a polymer containing several carboxylic acid or anhydride groups and react this polymer with an amine of the formula NHR 6 R 7 to obtain the desired polymer.
As polymers are generally copolymers of unsaturated esters such as C 1 -C 40 alkyl (meth) acrylates, fumaric di (C 1 -C 40 alkyl esters), C 1 -C 40 alkyl vinyl ethers, C 1 -C 40 alkyl vinyl esters or C. C 2 -C 40 -olefins (linear, branched, aromatic) with unsaturated carboxylic acids or their reactive derivatives, such as carboxylic acid anhydrides (acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, citraconic acid, preferably maleic anhydride) suitable.
Carboxylic acids are preferably reacted with from 0.1 to 1.5 mol, in particular from 0.5 to 1.2 mol of amine per acid group, carboxylic anhydrides, preferably with from 0.1 to 2.5, in particular from 0.5 to 2.2, mol of amine per acid anhydride group Depending on the reaction conditions, amides, ammonium salts, amide-ammonium salts or imides are formed. Thus, copolymers containing unsaturated carboxylic acid anhydrides, upon reaction with a secondary amine, yield half amide and half amine salts by reaction with the anhydride group. By heating, the formation of the Diamids water are split off.
Particularly suitable examples of amide group-containing polymers for use according to the invention are: - 5. Copolymers of (a) a dialkyl fumarate, maleate, citraconate or itaconate with maleic anhydride, or (b) vinyl esters, for example vinyl acetate, vinyl propionate, vinyl 2-ethylhexanoate or vinyl stearate with maleic anhydride, or (c) a dialkyl fumarate, maleate, citraconate or itaconate with maleic anhydride and vinyl acetate.
Particularly suitable examples of these polymers are copolymers of didodecyl fumarate, vinyl acetate and maleic anhydride; Ditetradecyl fumarate, vinyl acetate and maleic anhydride; Di-hexadecyl fumarate, vinyl acetate and maleic anhydride; or the corresponding copolymers in which the ltaconate is used instead of the fumarate.
In the above examples of suitable polymers, the desired amide is obtained by reacting the polymer containing anhydride groups with a secondary amine of the formula HNR 6 R 7 (optionally also with an alcohol when forming an ester amide). When polymers containing an anhydride group are reacted, the resulting amino groups will be ammonium salts and amides. Such polymers may be used provided that they contain at least two amide groups.
It is essential that the polymer containing at least two amide groups contains at least one alkyl group having at least 10 carbon atoms. This long-chain group, which may be a straight-chain or branched alkyl group, may be bonded via the nitrogen atom of the amide group.
The suitable amines can be represented by the formula R 6 R 7 NH and the polyamines by R 6 NH [R 19 NH] x R 7 , wherein R 19 is a divalent hydrocarbon group, preferably an alkylene or hydrocarbyl-substituted alkylene group, and x is an integer, preferably between 1 and 30. Preferably, one of the two or both R 6 and R 7 contains at least 10 carbon atoms, for example 10 to 20 carbon atoms, for example dodecyl, tetradecyl, hexadecyl or octadecyl.
Examples of suitable secondary amines are dioctylamine and those containing alkyl groups of at least 10 carbon atoms, for example, didecylamine, didodecylamine, dicocosamine (ie, mixed C 12 -C 14 amines), dioctadecylamine, hexadecyloctadecylamine, di (hydrogenated tallow) amine (approx Wt% nC 14 alkyl, 30 wt% nC 10 alkyl, 60 wt% nC 18 alkyl, the remainder is unsaturated).
Examples of suitable polyamines are N-octadecylpropanediamine, N, N'-dioctadecylpropanediamine, N-tetradecylbutanediamine and N, N'-dihexadecylhexanediamine. N-Cocospropylenediamine (C 12 / C 14 -alkylpropylenediamine), N-tallowpropylenediamine (C 16 / C 18 -alkylpropylenediamine).
The amide-containing polymers usually have a number average molecular weight of from 1,000 to 500,000, for example 10,000 to 100,000. - 6. Copolymers of styrene, its derivatives or aliphatic olefins having 2 to 40 carbon atoms, preferably having 6 to 20 carbon atoms and olefinically unsaturated carboxylic acids or carboxylic anhydrides, which are reacted with amines of the formula HNR 6 R 7 . The reaction can be carried out before or after the polymerization.
In detail, the structural units of the copolymers are derived from, for example, maleic acid, fumaric acid, tetrahydrophthalic acid, citraconic acid, preferably maleic anhydride. They can be used both in the form of their homopolymers and the copolymers. Suitable comonomers are: styrene and alkylstyrenes, straight-chain and branched olefins with 2 to 40 carbon atoms, as well as their mixtures with each other. Examples which may be mentioned: styrene, α-methylstyrene, dimethylstyrene, α-ethylstyrene, diethylstyrene, i-propylstyrene, tert-butylstyrene, ethylene, propylene, n-butylene, diisobutylene, decene, dodecene, tetradecene, hexadecene, octadecene. Preference is given to styrene and isobutene, particular preference to styrene.
Examples of polymers which may be mentioned are: polymaleic acid, an equimolar, styrene / maleic acid copolymer of alternating construction, random copolymers of styrene / maleic acid in a ratio of 10:90 and an alternating copolymer of maleic acid and i-butene. The molar masses of the polymers are generally 500 g / mol to 20,000 g / mol, preferably 700 to 2000 g / mol.
The reaction of the polymers or copolymers with the amines is carried out at temperatures of 50 to 200 ° C in the course of 0.3 to 30 hours. The amine is applied in amounts of about one mole per mole of copolymerized dicarboxylic anhydride, ie about 0.9 to 1.1 mol / mol. The use of larger or smaller amounts is possible, but brings no advantage. If larger amounts than one mole are used, ammonium salts are sometimes obtained because the formation of a second amide group requires higher temperatures, longer residence times, and water recirculation. If amounts smaller than one mole are used, complete conversion to the monoamide does not take place and a correspondingly reduced effect is obtained.
Instead of the subsequent reaction of the carboxyl groups in the form of the dicarboxylic anhydride with amines to the corresponding amides, it may sometimes be advantageous to prepare the monoamides of the monomers and then to copolymerize them directly in the polymerization. In most cases, however, this is technically much more complicated because the amines can attach to the double bond of the monomeric mono- and dicarboxylic acid and then no copolymerization is possible. - 7. Copolymers consisting of 10 to 95 mol% of one or more alkyl acrylates or alkyl methacrylates with C 1 -C 26 alkyl chains and from 5 to 90 mol% of one or more ethylenically unsaturated dicarboxylic acids or their anhydrides, wherein the copolymer is largely with a or more primary or secondary amines to the monoamide or amide / ammonium salt of the dicarboxylic acid is reacted.
The copolymers consist of 10 to 95 mol%, preferably 40 to 95 mol% and particularly preferably 60 to 90 mol% of alkyl (meth) acrylates and 5 to 90 mol%, preferably 5 to 60 mol -% and particularly preferably from 10 to 40 mol% of the olefinically unsaturated dicarboxylic acid derivatives. The alkyl groups of the alkyl (meth) acrylates contain from 1 to 26, preferably 4 to 22 and more preferably 8 to 18 carbon atoms. They are preferably straight-chain and unbranched. However, it may also contain up to 20 wt .-% cyclic and / or branched portions.
Examples of particularly preferred alkyl (meth) acrylates are n-octyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-hexadecyl (meth) acrylate and n-octadecyl (meth) acrylate and mixtures thereof.
Examples of ethylenically unsaturated dicarboxylic acids are maleic acid, tetrahydrophthalic acid, citraconic acid and itaconic acid or their anhydrides and fumaric acid. Preference is given to maleic anhydride.
Suitable amines are compounds of the formula HNR 6 R 7 .
As a rule, it is advantageous to use the dicarboxylic acids in the form of the anhydrides, if available, in the copolymerization, for example maleic anhydride, itaconic anhydride, citraconic anhydride and tetrahydrophthalic anhydride, since the anhydrides generally copolymerize better with the (meth) acrylates. The anhydride groups of the copolymers can then be reacted directly with the amines.
The reaction of the polymers with the amines takes place at temperatures of 50 to 200 ° C in the course of 0.3 to 30 hours. The amine is in amounts of about one to two. Moles per mole of polymerized dicarboxylic anhydride, ie applied about 0.9 to 2.1 mol / mol. The use of larger or smaller amounts is possible, but brings no advantage. If amounts greater than two moles are used, free amine is present. If amounts smaller than one mole are used, complete conversion to the monoamide does not take place and a correspondingly reduced effect is obtained.
In some cases, it may be advantageous for the amide / ammonium salt structure to be built up from two different amines. For example, a copolymer of lauryl acrylate and maleic anhydride may first be reacted with a secondary amine such as hydrogenated di-tallow fatty amine to form the amide, after which the free carboxyl group derived from the anhydride is neutralized with another amine, eg 2-ethylhexylamine, to the ammonium salt. Likewise, the reverse procedure is conceivable: first with ethylhexylamine to the monoamide, then reacted with Ditalgfettamin to the ammonium salt. Preferably, at least one amine is used which has at least one straight-chain, unbranched alkyl group having more than 16 carbon atoms. It is not significant whether this amine is present in the structure of the amide structure or as the ammonium salt of the dicarboxylic acid.
Instead of the subsequent reaction of the carboxyl groups or of the dicarboxylic anhydride with amines to the corresponding amides or amide / ammonium salts, it may sometimes be advantageous to prepare the monoamides or amide / ammonium salts of the monomers and then to copolymerize them directly in the polymerization. However, this is usually technically much more complicated because the amines can attach to the double bond of the monomeric dicarboxylic acid and then no copolymerization is possible. - 8. terpolymers based on α, β-unsaturated dicarboxylic acid anhydrides, α, β-unsaturated compounds and polyoxyalkylene ethers of lower, unsaturated alcohols, which are characterized in that they contain 20-80, preferably 40- 60 mol% of bivalent structural units of the formulas 1 and / or 3, and optionally 2, wherein the Structural units 2 are derived from unreacted anhydride residues,
R 22 and R 23 independently of one another are hydrogen or methyl,
a, b is zero or one and a + b is one,
R 24 and R 25 are the same or different and the groups -NHR 6 , N (R 6 ) 2 and / or -OR 27 , and R 27 is a cation of the formula H 2 N (R 6 ) 2 or
H 3 NR 6 is, 19-80 mol%, preferably 39-60 mol% of bivalent
Structural units of the formula 4
R 28 is hydrogen or C 1 -C 4 -alkyl and
R 29 is C 6 -C 60 -alkyl or C 6 -C 18 -aryl and
1 - 30 mol%, preferably 1 - 20 mol% of bivalent structural units of the formula 5
R 30 is hydrogen or methyl,
R 31 is hydrogen or C 1 -C 4 -alkyl,
R 33 is C 1 -C 4 -alkylene,
m is a number from 1 to 100,
R 32 is C 1 -C 24 -alkyl, C 5 -C 20 -cycloalkyl, C 6 -C 18 -aryl or -C (O) -R 34 , wherein
R 34 is C 1 -C 40 -alkyl, C 5 -C 10 -cycloalkyl or C 6 -C 18 -aryl.
The abovementioned alkyl, cycloalkyl and aryl radicals may optionally be substituted. Suitable substituents of the alkyl and aryl radicals are, for example, (C 1 -C 6 ) -alkyl, halogens, such as fluorine, chlorine, bromine and iodine, preferably chlorine and (C 1 -C 6 ) -alkoxy.
Alkyl here stands for a straight-chain or branched hydrocarbon radical. Specific examples which may be mentioned are: n-butyl, tert-butyl, n-hexyl, n-octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, dodecenyl, tetrapropenyl, tetradecenyl, pentapropenyl, hexadecenyl, octadecenyl and eicosanyl or mixtures such as cocoalkyl , Tallow fatty alkyl and behenyl.
Cycloalkyl here stands for a cyclic aliphatic radical having 5 to 20 carbon atoms. Preferred cycloalkyl radicals are cyclopentyl and cyclohexyl.
Aryl here stands for an optionally substituted aromatic ring system having 6 to 18 carbon atoms.
The terpolymers consist of the bivalent structural units of the formulas 1 and 3 and 4 and 5 and optionally 2. They contain only in a conventional manner the end groups formed in the polymerization by initiation, inhibition and chain termination.
In detail, structural units of the formulas 1 to 3 are derived from α, β-unsaturated dicarboxylic acid anhydrides of the formulas 6 and 7
The structural units of the formula 4 are derived from the α, β-unsaturated compounds of the formula 8.
The structural units of the formula 5 are derived from polyoxyalkylene ethers of lower, unsaturated alcohols of the formula 9.
The polyoxyalkylene ethers (R 32 = H) can be prepared by known processes, for example by addition of α-olefin oxides such as ethylene oxide, propylene oxide and / or butylene oxide to polymerizable lower unsaturated alcohols of the formula 10
Examples of suitable primary amines for the preparation of the terpolymers are the following:- n-hexylamine, n-octylamine, n-tetradecylamine, n-hexadecylamine,
- N-stearylamine or N, N-dimethylaminopropylenediamine, cyclohexylamine, dehydroabietylamine and mixtures thereof.
The terpolymers have K values (measured according to Ubbelohde in 5% strength by weight solution in toluene at 25 ° C.) of 8 to 100, preferably 8 to 50, corresponding to average molecular weights (M w ) of between about 500 and 100,000. Suitable examples are inEP 606,055 - 9. Reaction products of alkanolamines and / or polyetheramines with polymers containing dicarboxylic anhydride groups, characterized in that they contain 20-80, preferably 40-60, mol% of bivalent structural units of the formulas 13 and 15 and optionally 14
R 22 and R 23 independently of one another are hydrogen or methyl,
a, b is zero or 1 and a + b is 1,
R 37 = -OH, -O- [C 1 -C 30 -alkyl], -NR 6 R 7 , O s N r R 6 R 7 H 2
R 38 = R 37 or NR 6 R 39
R 39 = - (AO) x -E
With
A = ethylene or propylene group
x = 1 to 50
E = H, C 1 -C 30 -alkyl, C 5 -C 12 -cycloalkyl or C 6 -C 30 -aryl, and 80-20 mol%, preferably 60-40 mol% of bivalent structural units of the formula 4 contain.
In detail, the structural units of the formulas 13, 14 and 15 are derived from α, β-unsaturated dicarboxylic acid anhydrides of the formulas 6 and / or 7.
The structural units of the formula 4 are derived from the α, β-unsaturated olefins of the formula 8. The abovementioned alkyl, cycloalkyl and aryl radicals have the same meanings as under 8.
The radicals R 37 and R 38 in formula 13 or R 39 in formula 15 are derived from polyetheramines or alkanolamines of the formulas 16 a) and b), amines of the formula NR 6 R 7 R 8 and optionally of alcohols having 1 to 30 carbon atoms from.- R 53
- Hydrogen, C 6 -C 40 -alkyl or
- R 54
- Hydrogen, C 1 -C 4 -alkyl
- R 55
- Is hydrogen, C 1 - to C 4 -alkyl, C 5 - to C 12 -cycloalkyl or C 6 - to C 30 -aryl
- R 56 , R 57
- independently of one another hydrogen, C 1 - to C 22 -alkyl, C 2 - to C 22 -alkenyl or Z - OH
- Z
- C 2 - to C 4 -alkylene
- n
- a number between 1 and 1000.
A further possibility for derivatizing the structural units of the formulas 6 and 7 is that, instead of the polyether amines, an alkanolamine of the formula 16a) or 16b) is used and subsequently subjected to alkoxylation.
From 0.01 to 2 mol, preferably from 0.01 to 1 mol of alkanolamine are used per mole of anhydride. The reaction temperature is between 50 and 100 ° C (amide formation). In the case of primary amines, the reaction takes place at temperatures above 100 ° C (imide formation).
The alkoxylation is usually carried out at temperatures between 70 and 170 ° C with catalysis of bases, such as NaOH or NaOCH 3 , by gassing of alkylene oxides, such as ethylene oxide (EO) and / or propylene oxide (PO). Usually, 1 to 500, preferably 1 to 100, moles of alkylene oxide are added per mole of hydroxyl groups.
Examples of suitable alkanolamines include:- Monoethanolamine, diethanolamine, N-methylethanolamine, 3-aminopropanol,
- Isopropanol, diglycolamine, 2-amino-2-methylpropanol and mixtures thereof.
- n-hexylamine, n-octylamine, n-tetradecylamine, n-hexadecylamine,
- N-stearylamine or N, N-dimethylaminopropylenediamine, cyclohexylamine, dehydroabietylamine and mixtures thereof.
- Didecylamine, ditetradecylamine, distearylamine, dicocosfettamine, ditallow fatty amine and mixtures thereof.
- Methanol, ethanol, propanol, isopropanol, n-, sec-, tert-butanol, octanol,
- Tetradecanol, hexadecanol, octadecanol, tallow fatty alcohol, behenyl alcohol and mixtures thereof. Suitable examples are in
EP-A-688 796
- 10. Co- and terpolymers of NC 6 -C 24 -alkylmaleinimid with C 1 -C 30 vinyl esters, vinyl ethers and / or olefins having 1 to 30 carbon atoms, such as styrene or α-olefins. These are accessible on the one hand by reacting an anhydride-containing polymer with amines of the formula H 2 NR 6 or by imidization of the dicarboxylic acid and subsequent copolymerization. Preferred dicarboxylic acid is maleic acid or maleic anhydride. Copolymers of 10 to 90% by weight of C 6 -C 24 -α-olefins and 90 to 10% by weight of NC 6 -C 22 -alkylmaleimide are preferred.
Die polaren stickstoffhaltigen Paraffindispergatoren können den erfindungsgemäßen Additiven beigemischt oder separat dem zu additivierenden Mitteldestillat zugesetzt werden. Das Mengenverhältnis zwischen Paraffindispergatoren und den erfindungsgemäßen Additiven liegt zwischen 5:1 und 1:5 und bevorzugt zwischen 3:1 und 1:3.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.
Zur Herstellung von Additivpaketen für spezielle Problemlösungen können die erfindungsgemäßen Additive auch zusammen mit einem oder mehreren öllöslichen Co-Additiven eingesetzt werden, die für sich allein die Schmierwirkung und/oder die Kaltfließeigenschaften von Rohölen, Schmierölen oder Brennstoffölen verbessern. Beispiele solcher Co-Additive sind Vinylacetat enthaltende Copolymerisate oder Terpolymerisate des Ethylens, Kammpolymere sowie öllösliche Amphiphile.For the production of additive packages for special problem solutions, 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. Examples of such co-additives are vinyl acetate-containing copolymers or terpolymers of ethylene, comb polymers and oil-soluble amphiphiles.
So haben sich Mischungen der erfindungsgemäßen Additive mit Copolymerisaten hervorragend bewährt, die 10 bis 40 Gew.-% Vinylacetat und 60 bis 90 Gew.-% Ethylen enthalten. Nach einer weiteren Ausgestaltung der Erfindung setzt man die erfindungsgemäßen Additive in Mischung mit Ethylen/Vinylacetat/Vinyl-2-ethylhexanoat-Terpolymeren, Ethylen/Vinylacetat/ Neononansäurevinylester-Terpolymeren und/oder Ethylen-Vinylacetat/ Neodecansäurevinylester-Terpolymeren zur gleichzeitigen Verbesserung der Fließfähigkeit und Schmierwirkung von Mineralölen oder Mineralöldestillaten ein. Die Terpolymerisate der 2-Ethylhexansäurevinylester, Neononansäurevinylester bzw. der Neodecansäurevinylester enthalten außer Ethylen 10 bis 35 Gew.-% Vinylacetat und 1 bis 25 Gew.-% des jeweiligen langkettigen Vinylesters. Weitere bevorzugte Copolymere enthalten neben Ethylen und 10 bis 35 Gew.-% Vinylestern noch 0,5 bis 20 Gew.-% Olefin mit 3 bis 10 C-Atomen wie z. B. Isobutylen, Diisobutylen, 4-Methylpenten oder Norbornen.For example, mixtures of the additives according to the invention with copolymers which have 10 to 40% by weight of vinyl acetate and 60 to 90% by weight of ethylene have proven outstanding. According to a further embodiment of the invention, 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. As isobutylene, diisobutylene, 4-methylpentene or norbornene.
Schließlich werden in einer weiteren Ausführungsform der Erfindung die erfindungsgemäßen Additive zusammen mit Kammpolymeren verwendet. Hierunter versteht man Polymere, bei denen Kohlenwasserstoffreste mit mindestens 8, insbesondere mindestens 10 Kohlenstoffatomen an einem Polymerrückgrat gebunden sind. Vorzugsweise handelt es sich um Homopolymere, deren Alkylseitenketten mindestens 8 und insbesondere mindestens 10 Kohlenstoffatome enthalten. Bei Copolymeren weisen mindestens 20 %, bevorzugt mindestens 30 % der Monomeren Seitenketten auf (vgl. Comb-like Polymers-Structure and Properties;
Kammpolymere können beispielsweise durch die Formel
- A
- R', COOR', OCOR', R"-COOR' oder OR';
- D
- H, CH3, A oder R;
- E
- H oder A;
- G
- H, R", R"-COOR', einen Arylrest oder einen heterocyclischen Rest;
- M
- H, COOR", OCOR", OR" oder COOH;
- N
- H, R", COOR", OCOR, COOH oder einen Arylrest;
- R'
- eine Kohlenwasserstoffkette mit 8-150 Kohlenstoffatomen;
- R"
- eine Kohlenwasserstoffkette mit 1 bis 10 Kohlenstoffatomen;
- m
- eine Zahl zwischen 0,4 und 1,0; und
- n
- eine Zahl zwischen 0 und 0,6.
- A
- R ', COOR', OCOR ', R "-COOR' or OR ';
- D
- H, CH 3, A or R;
- e
- H or A;
- G
- H, R ", R" -COOR ', an aryl radical or a heterocyclic radical;
- M
- H, COOR ", OCOR", OR "or COOH;
- N
- H, R ", COOR", OCOR, COOH or an aryl radical;
- R '
- a hydrocarbon chain of 8-150 carbon atoms;
- R "
- a hydrocarbon chain of 1 to 10 carbon atoms;
- m
- a number between 0.4 and 1.0; and
- n
- a number between 0 and 0.6.
Das Mischungsverhältnis (in Gewichtsteilen) der erfindungsgemäßen Additive mit Ethylencopolymeren bzw. Kammpolymeren beträgt jeweils 1:10 bis 20:1, vorzugsweise 1:1 bis 10:1.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.
Die erfindungsgemäßen Additive werden ölen in Mengen von 0,0001 bis 1 Gew.-%, bevorzugt 0,001 bis 0,1 Gew.-% und speziell 0,002 bis 0,05 Gew.-% zugesetzt. Dabei können sie als solche oder auch gelöst in Lösemitteln, wie z.B. aliphatischen und/oder aromatischen Kohlenwasserstoffen oder Kohlenwasserstoffgemischen wie z.B. Toluol, Xylol, Ethylbenzol, Decan, Pentadecan, Benzinfraktionen, Diesel, Kerosin oder kommerziellen Lösemittelgemischen wie Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol-, ® Isopar- und ® Shellsol D-Typen, sowie polaren Lösungsmitteln wie Alkoholen, Glykolen und Estern wie beispielsweise Fettsäurealkylestern und insbesondere Rapsölsäuremethylester (RME), eingesetzt werden. Bevorzugt enthalten die erfindungsgemäßen Additive bis zu 70 %, speziell 5 - 60 %, insbesondere 10 - 40 Gew.-% Lösemittel.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. Preferably, the additives of the invention contain up to 70%, especially 5 to 60%, in particular 10 to 40% by weight of solvent.
Die erfindungsgemäßen Additive können bei erhöhter Temperatur über längere Zeit ohne Alterungseffekte gelagert werden, ohne dass es zu Alterungserscheinungen wie Verharzung und der Bildung unlöslicher Strukturen oder Ablagerungen in Lagerbehältern und/oder Motorteilen kommt. Darüber hinaus verbessern sie die Oxidationsstabilität der additivierten Öle bei gleichzeitig verminderter Emulgierneigung. Dies ist insbesondere bei Ölen, die größere Anteile an Ölen aus Crack-Prozessen enthalten, von Vorteil.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. In addition, 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.
Des weiteren zeigen sie eine den Einzelkomponenten überlegene Verbesserung der Lubricity von Mitteldestillaten. Damit kann die für die Einstellung der Spezifikation erforderliche Dosierrate abgesenkt werden.Furthermore, they show a superior to the individual components improvement of the Lubricity of middle distillates. Thus, the dosage rate required for setting the specification can be lowered.
Ein weiterer Vorteil der erfindungsgemäßen Additive ist ihre gegenüber den gemäß dem Stand der Technik als Lubricity-Additive eingesetzten Fettsäureestern abgesenkte Kristallisationstemperatur. So können sie auch bei niedrigen Temperaturen von beispielsweise 0°C bis -20°C und teilweise auch niedriger problemlos eingesetzt werden.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.
Die erfindungsgemäßen Additive sind für die Verwendung in Mitteldestillaten besonders gut geeignet. Als Mitteldestillate bezeichnet man insbesondere solche Mineralöle, die durch Destillation von Rohöl gewonnen werden und im Bereich von 120 bis 450°C sieden, beispielsweise Kerosin, Jet-Fuel, Diesel und Heizöl. Die Öle können auch Alkohole wie Methanol und/oder Ethanol enthalten oder aus diesen bestehen. Vorzugsweise werden die erfindungsgemäßen Additive in solchen Mitteldestillaten verwendet, die weniger als 350 ppm Schwefel, insbesondere weniger als 200 ppm Schwefel und in speziellen Fällen weniger als 50 ppm bzw. weniger als 10 ppm Schwefel enthalten. Es handelt sich dabei im allgemeinen um solche Mitteldestillate, die einer hydrierenden Raffination unterworfen wurden, und die daher nur geringe Anteile an polyaromatischen und polaren Verbindungen enthalten, die ihnen eine natürliche Schmierwirkung verleihen. Die erfindungsgemäßen Additive werden weiterhin vorzugsweise in solchen Mitteldestillaten verwendet, die 95 %-Destillationspunkte unter 370°C, insbesondere 350°C und in Spezialfällen unter 330°C aufweisen. Des gleichen sind die erfindungsgemäßen Additive für die Verwendung in synthetischen Kraftstoffen mit ebenfalls geringer Schmierfähigkeit, wie sie z. B. im Fischer-Tropsch-erozeß hergestellt werden können, geeignet. Die in ihrer Schmierfähigkeit verbesserten Öle besitzen einen im HFRR-Test gemessenen Wear Scar Diameter von bevorzugt weniger als 460 µm, speziell weniger als 450 µm. Die erfindungsgemäßen Additive können auch als Komponenten in Schmierölen eingesetzt werden.The additives of the invention are particularly well suited for use in middle distillates. As 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. Preferably, 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. These are generally those 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 μm, especially less than 450 μm. The additives according to the invention can also be used as components in lubricating oils.
Die Mischungen können allein oder auch zusammen mit anderen Additiven verwendet werden, z.B. mit Stockpunkterniedrigern, Korrosionsinhibitoren, Antioxidantien, Schlamminhibitoren, Dehazern, Leitfähigkeitsverbesserern, Lubricity-Additiven, und Zusätzen zur Erniedrigung des Cloud-Points. Des weiteren werden sie erfolgreich zusammen mit Additivpaketen eingesetzt, die u.a. bekannte aschefreie Dispergieradditive, Detergenzien, Entschäumer, Antioxidantien, Dehazer, Demulgatoren und Korrosionsinhibitoren enthalten.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.
Die Vorteile der erfindungsgemäßen Additive werden durch die nachfolgenden Beispiele näher erläutert.The advantages of the additives according to the invention are explained in more detail by the following examples.
Im folgenden werden die eingesetzten Additive charakterisiert. Die OH-Zahlen wurden gemäß DIN 53240 durch Umsetzung mit einer definierten Menge überschüssigem Acetanhydrid und anschließende Titration der gebildeten Essigsäure bestimmt.In the following, 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.
Jodzahlen werden nach Kaufmann bestimmt. Dazu wird die Probe mit einer definierten Menge einer methanolischen Bromlösung versetzt, wobei sich eine dem Gehalt an Doppelbindungen equivalente Menge Brom anlagert. Der Überschuss an Brom wird mit Natriumthiosulfat zurücktitriert.
In einen 500 ml Erlenmeyerkolben werden 10 g des zu überprüfenden Additiv(gemisch)s eingewogen. Der Kolben wird drei Tage bei einer Temperatur von 90 °C im Trockenschrank gelagert, wobei täglich die über dem Additiv stehende Atmosphäre durch Überleiten eines Luftstroms ausgetauscht wird.
Nach der Konditionierung lässt man die Mischung eine Stunde bei Raumtemperatur abkühlen. Anschließend wird mit 500 ml Dieselkraftstoff (Testöl 3) versetzt und gut durchmischt. Nach zwei Stunden Standzeit wird die Mischung visuell auf eventuelle Ausscheidungen, Trübungen, unlösliche Anteile u.s.w. beurteilt, die Hinweise auf oxidative Veränderungen geben (visuelle Beurteilung). Sodann wird über ein 0,8 µm Filter bei einer Druckdifferenz von 800 mbar filtriert. Die Gesamtmenge muss innerhalb von 2 Minuten filtrierbar sein, ansonsten wird das nach 2 Minuten filtrierte Volumen notiert.
After conditioning, the mixture is allowed to cool for one hour at room temperature. Then 500 ml of diesel fuel (test oil 3) are added and thoroughly mixed. After two hours of use, the mixture is visually assessed for any precipitations, turbidity, insoluble matter, etc., which indicate oxidative changes (visual assessment). It is then filtered through a 0.8 micron filter at a pressure difference of 800 mbar. The total amount must be filterable within 2 minutes, otherwise the volume filtered after 2 minutes is noted.
Eine Mischung aus 9 g A 7, 1 g B1 und 2 g C2 ergab nach dreitägiger Lagerung bei 90°C und anschließender Verdünnung mit 500 ml Testöl 3 eine klare Lösung und eine Filtrationszeit von 65 s.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.
Verschiedene Ester wurden jeweils 5 Tage bei 15°C, +5°C und -5°C gelagert und nach 3 bzw. 5 Tagen visuell auf Fließfähigkeit und evtl. Ausscheidungen bzw. Trübungen beurteilt. Die Bewertungen haben folgende Bedeutung:
- +
- fließfähig und klar
- O
- fließfähig aber trüb bzw. mit Ausscheidungen
- ―
- fest
- +
- flowable and clear
- O
- flowable but cloudy or with excretions
- -
- firmly
Die Schmierwirkung der Additive wurde mittels eines HFRR-Geräts der Firma PCS Instruments an additivierten Ölen bei 60°C geprüft. Der High Frequency
Reciprocating Rig Test (HFRR) ist beschrieben in
Reciprocating Rig Test (HFRR) is described in
Claims (13)
- An additive for improving the lubricity of fuel oils having a maximum sulfur content of 0.035% by weight, comprisingA) at least one partial ester composed of a di- or polyhydric alcohol and unsaturated and optionally also saturated fatty acids whose carbon chain lengths are between 8 and 30 carbon atoms, at least 60% of the fatty acid radicals containing at least one double bond, andB) at least one alkylphenol-aldehyde resin, obtainable by the condensation ofto a degree of condensation of between 2 and 50 alkylphenol units.(i) at least one alkylphenol having at least one C6-C24-alkyl or C6-C24-alkenyl radical and(ii) at least one aldehyde or ketone,
- An additive as claimed in claim 1, wherein the iodine number of constituent A) is more than 50 g of 1/100 g of ester.
- An additive as claimed in claim 1 and/or 2, wherein the OH number of constituent A) is between 10 and 200 mg of KOH/g of ester.
- An additive as claimed in one or more of claims 1 to 3, wherein the fatty acids which are a constituent of the fatty acid mixture contain from 10 to 26 carbon atoms.
- An additive as claimed in one or more of claims 1 to 4, wherein the fatty acid mixtures comprise up to 20% by weight of saturated fatty acids.
- An additive as claimed in one or more of claims 1 to 5, wherein the fatty acid mixtures comprise one or more dicarboxylic acids.
- An additive as claimed in one or more of claims 1 to 6, wherein the alcohols contain from 2 to 6 carbon atoms.
- An additive as claimed in one or more of claims 1 to 7, wherein the alcohols contain from 2 to 5 hydroxyl groups, but a maximum of one hydroxyl group per carbon atom.
- An additive as claimed in one or more of claims 1 to 8, which also comprises at least one nitrogen-containing paraffin dispersant.
- An additive as claimed in one or more of claims 1 to 9, which also comprises at least one ethylene copolymer.
- An additive as claimed in one or more of claims 1 to 10, which also comprises at least one comb polymer.
- A fuel oil having a maximum sulfur content of 0.035% by weight, comprising an additive as claimed in one or more of claims 1 to 11 in amounts of from 0.001 to 0.5% by weight, based on the fuel oil.
- The use of an additive as claimed in one or more of claims 1 to 11 in amounts of from 0.001 to 0.5% by weight, based on the fuel oil, for improving the lubricity of fuel oils having a maximum sulfur content of 0.035% by weight.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10230771 | 2002-07-09 | ||
DE10230771 | 2002-07-09 | ||
DE10252973 | 2002-11-14 | ||
DE2002152973 DE10252973A1 (en) | 2002-11-14 | 2002-11-14 | Lubricity additive for low-sulfur fuel oils, e.g. diesel fuel, comprises a polyol fatty acid partial ester and an alkylphenol resin |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1380634A1 EP1380634A1 (en) | 2004-01-14 |
EP1380634B1 true EP1380634B1 (en) | 2007-08-15 |
Family
ID=29737617
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03013093A Revoked EP1380634B1 (en) | 2002-07-09 | 2003-06-11 | Lubricity additives stabilised against oxidation for highly desulphurised fuel oils. |
Country Status (7)
Country | Link |
---|---|
US (2) | US20040010965A1 (en) |
EP (1) | EP1380634B1 (en) |
JP (1) | JP4484458B2 (en) |
AT (1) | ATE370214T1 (en) |
CA (1) | CA2431749C (en) |
DE (1) | DE50307929D1 (en) |
ES (1) | ES2291562T3 (en) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040010965A1 (en) * | 2002-07-09 | 2004-01-22 | Clariant Gmbh | Oxidation-stabilized lubricant additives for highly desulfurized fuel oils |
CA2431748C (en) * | 2002-07-09 | 2010-11-09 | Clariant Gmbh | Oxidation-stabilized oily liquids based on vegetable or animal oils |
AU2004321204A1 (en) * | 2004-07-02 | 2006-01-12 | Monsanto S.A.S. | A new biofuel composition |
US20060046941A1 (en) * | 2004-08-26 | 2006-03-02 | Laurent Chambard | Lubricating oil compositions |
EP1997870A1 (en) | 2004-08-26 | 2008-12-03 | Infineum International Limited | Lubricating oil compositions |
US20080306314A1 (en) * | 2005-05-26 | 2008-12-11 | The Lubrizol Corporation | Hydrocarbyl- and Hydroxy-Substituted Aromatic Condensate |
DE102005035277B4 (en) * | 2005-07-28 | 2007-10-11 | Clariant Produkte (Deutschland) Gmbh | Mineral oils with improved conductivity and cold flowability |
DE102005035275B4 (en) * | 2005-07-28 | 2007-10-11 | Clariant Produkte (Deutschland) Gmbh | Mineral oils with improved conductivity and cold flowability |
DE102005045134B4 (en) * | 2005-09-22 | 2010-12-30 | Clariant Produkte (Deutschland) Gmbh | Alkylphenol-aldehyde resins, compositions containing them for improving the low-flowability and lubricity of fuel oils and their use |
ES2544239T3 (en) * | 2005-12-15 | 2015-08-28 | Infineum International Limited | Use of a corrosion inhibitor of a lubricating oil composition |
EP2036962A1 (en) * | 2007-09-14 | 2009-03-18 | Cognis Oleochemicals GmbH | Additives for water-based drilling fluids |
EP2036963A1 (en) * | 2007-09-14 | 2009-03-18 | Cognis Oleochemicals GmbH | Lubricants for drilling fluids |
EP2036964A1 (en) * | 2007-09-14 | 2009-03-18 | Cognis Oleochemicals GmbH | Thickener for oil-based drilling fluids |
FR2969620B1 (en) * | 2010-12-23 | 2013-01-11 | Total Raffinage Marketing | MODIFIED ALKYLPHENOL ALDEHYDE RESINS, THEIR USE AS ADDITIVES IMPROVING THE COLD PROPERTIES OF LIQUID HYDROCARBON FUELS AND FUELS |
Family Cites Families (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2499365A (en) * | 1947-03-07 | 1950-03-07 | Petrolite Corp | Chemical manufacture |
NL130122C (en) * | 1962-05-01 | |||
US4211534A (en) * | 1978-05-25 | 1980-07-08 | Exxon Research & Engineering Co. | Combination of ethylene polymer, polymer having alkyl side chains, and nitrogen containing compound to improve cold flow properties of distillate fuel oils |
EP0061894B1 (en) | 1981-03-31 | 1985-09-11 | Exxon Research And Engineering Company | Two-component flow improver additive for middle distillate fuel oils |
US4612880A (en) * | 1982-12-20 | 1986-09-23 | Union Oil Company Of California | Method for control of octane requirement increase in an internal combustion engine having manifold and/or combustion surfaces which inhibit the formation of engine deposits |
DE3405843A1 (en) * | 1984-02-17 | 1985-08-29 | Bayer Ag, 5090 Leverkusen | COPOLYMERS BASED ON MALEINIC ACID ANHYDRIDE AND (ALPHA), (BETA) -UNAUSAUTED COMPOUNDS, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS PARAFFIN INHIBITORS |
EP0153177B1 (en) * | 1984-02-21 | 1991-11-06 | Exxon Research And Engineering Company | Middle distillate compositions with improved low temperature properties |
CA1271895A (en) | 1985-05-29 | 1990-07-17 | Wolfgang Payer | The use of ethylene terpolymers as additives in mineral oil and miniral oil distillates |
US5039437A (en) * | 1987-10-08 | 1991-08-13 | Exxon Chemical Patents, Inc. | Alkyl phenol-formaldehyde condensates as lubricating oil additives |
DE3742630A1 (en) * | 1987-12-16 | 1989-06-29 | Hoechst Ag | POLYMER BLENDS FOR IMPROVING THE FLOWABILITY OF MINERAL OIL DISTILLATES IN THE COLD |
DE3921279A1 (en) | 1989-06-29 | 1991-01-03 | Hoechst Ag | METHOD FOR IMPROVING THE FLOWABILITY OF MINERAL OILS AND MINERAL OIL DISTILLATES |
DE3926992A1 (en) * | 1989-08-16 | 1991-02-21 | Hoechst Ag | USE OF TRANSPARENT PRODUCTS OF ALKENYL SPIROBISLACTONES AND AMINES AS PARAFFINDISPERGATORS |
DE4020640A1 (en) * | 1990-06-29 | 1992-01-02 | Hoechst Ag | TERPOLYMERISATES OF ETHYLENE, THEIR PRODUCTION AND THEIR USE AS ADDITIVES FOR MINERAL OIL DISTILLATES |
DE4040317A1 (en) * | 1990-12-17 | 1992-06-25 | Henkel Kgaa | MIXTURES OF FATTY ACID LOW ALKYL ESTERS WITH IMPROVED COLD TESTABILITY |
DE4042206A1 (en) * | 1990-12-29 | 1992-07-02 | Hoechst Ag | ETHYLENE TERPOLYMERISES, THEIR PREPARATION AND THEIR USE AS ADDITIVES FOR MINERALOLE DISTILLATES |
GB9204709D0 (en) | 1992-03-03 | 1992-04-15 | Exxon Chemical Patents Inc | Additives for oils |
GB9222458D0 (en) * | 1992-10-26 | 1992-12-09 | Exxon Chemical Patents Inc | Oil additives and compositions |
DK0606055T3 (en) * | 1993-01-06 | 1998-04-14 | Clariant Gmbh | Terpolymers on the basis of alpha, beta-unsaturated dicarboxylic acid anhydrides, alpha-beta-unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols |
GB9301119D0 (en) | 1993-01-21 | 1993-03-10 | Exxon Chemical Patents Inc | Fuel composition |
IT1270954B (en) * | 1993-07-21 | 1997-05-26 | Euron Spa | DIESEL COMPOSITION |
DE4422159A1 (en) * | 1994-06-24 | 1996-01-04 | Hoechst Ag | Reaction products of polyetheramines with polymers alpha, beta-unsaturated dicarboxylic acids |
DE69515318D1 (en) * | 1994-08-30 | 2000-04-06 | Procter & Gamble | IMPROVED PHOTOBLEACHING WITH CHELATE IMAGES |
KR100420430B1 (en) * | 1994-12-13 | 2004-06-24 | 엑손 케미칼 패턴츠 인코포레이티드 | Fuel oil composition |
GB9514480D0 (en) * | 1995-07-14 | 1995-09-13 | Exxon Chemical Patents Inc | Additives and fuel oil compositions |
JP3379866B2 (en) * | 1995-04-24 | 2003-02-24 | 花王株式会社 | Gas oil additive and gas oil composition |
US5882364A (en) * | 1995-07-14 | 1999-03-16 | Exxon Chemical Patents Inc. | Additives and fuel oil compositions |
DE19620118C1 (en) * | 1996-05-18 | 1997-10-23 | Hoechst Ag | Terpolymers of ethylene, their preparation and their use as additives for mineral oil distillates |
DE19620119C1 (en) * | 1996-05-18 | 1997-10-23 | Hoechst Ag | Terpolymers of ethylene, their production and their use as additives for mineral oil distillates |
GB9621231D0 (en) * | 1996-10-11 | 1996-11-27 | Exxon Chemical Patents Inc | Low sulfer fuels with lubricity additive |
ES2183073T5 (en) * | 1997-01-07 | 2007-10-16 | Clariant Produkte (Deutschland) Gmbh | IMPROVEMENT OF THE FLUIDITY OF MINERAL AND DISTILLED OILS OF MINERAL OILS BY MEASURING USE OF RENT-PHENOLS AND ALDEHIDS RESINS. |
DE19732915C1 (en) * | 1997-07-30 | 1998-12-10 | Siemens Ag | Manufacturing method for chip-module e.g. for credit card |
DE19739271A1 (en) * | 1997-09-08 | 1999-03-11 | Clariant Gmbh | Additive to improve the flowability of mineral oils and mineral oil distillates |
JPH11293262A (en) * | 1998-04-03 | 1999-10-26 | Yushiro Chem Ind Co Ltd | Lubricating additive for gas oil and gas oil composition |
GB9810994D0 (en) * | 1998-05-22 | 1998-07-22 | Exxon Chemical Patents Inc | Additives and oil compositions |
JP4103218B2 (en) * | 1998-12-15 | 2008-06-18 | コスモ石油株式会社 | Light oil composition |
EP1088880A1 (en) * | 1999-09-10 | 2001-04-04 | Fina Research S.A. | Fuel composition |
DE10000649C2 (en) * | 2000-01-11 | 2001-11-29 | Clariant Gmbh | Multi-functional additive for fuel oils |
CA2431746C (en) * | 2002-07-09 | 2011-11-01 | Clariant Gmbh | Cold flow improvers for fuel oils of vegetable or animal origin |
US20040010965A1 (en) * | 2002-07-09 | 2004-01-22 | Clariant Gmbh | Oxidation-stabilized lubricant additives for highly desulfurized fuel oils |
-
2003
- 2003-06-11 US US10/459,180 patent/US20040010965A1/en not_active Abandoned
- 2003-06-11 JP JP2003166760A patent/JP4484458B2/en not_active Expired - Fee Related
- 2003-06-11 EP EP03013093A patent/EP1380634B1/en not_active Revoked
- 2003-06-11 ES ES03013093T patent/ES2291562T3/en not_active Expired - Lifetime
- 2003-06-11 DE DE50307929T patent/DE50307929D1/en not_active Expired - Lifetime
- 2003-06-11 CA CA2431749A patent/CA2431749C/en not_active Expired - Fee Related
- 2003-06-11 AT AT03013093T patent/ATE370214T1/en not_active IP Right Cessation
-
2006
- 2006-03-28 US US11/391,643 patent/US7815696B2/en not_active Expired - Fee Related
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ATE370214T1 (en) | 2007-09-15 |
ES2291562T3 (en) | 2008-03-01 |
US7815696B2 (en) | 2010-10-19 |
CA2431749C (en) | 2010-12-14 |
CA2431749A1 (en) | 2004-01-09 |
JP4484458B2 (en) | 2010-06-16 |
JP2004043801A (en) | 2004-02-12 |
EP1380634A1 (en) | 2004-01-14 |
DE50307929D1 (en) | 2007-09-27 |
US20040010965A1 (en) | 2004-01-22 |
US20060162241A1 (en) | 2006-07-27 |
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