EP1473353A1 - Demulsifiers for blends of middle distillates and fuel oils of animal or vegetable origin - Google Patents

Demulsifiers for blends of middle distillates and fuel oils of animal or vegetable origin Download PDF

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Publication number
EP1473353A1
EP1473353A1 EP04008585A EP04008585A EP1473353A1 EP 1473353 A1 EP1473353 A1 EP 1473353A1 EP 04008585 A EP04008585 A EP 04008585A EP 04008585 A EP04008585 A EP 04008585A EP 1473353 A1 EP1473353 A1 EP 1473353A1
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EP
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Prior art keywords
oil
acid
mol
copolymer
oils
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EP04008585A
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German (de)
French (fr)
Inventor
Bettina Dr. Siggelkow
Werner Dr. Reimann
Ulrike Neuhaus
Renate Braun
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Clariant Produkte Deutschland GmbH
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Clariant GmbH
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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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds 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 an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1988—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 epoxy resins and derivatives; natural resins, e.g. colophony

Definitions

  • the present invention relates to the use of an additive as a demulsifier for Mixtures of middle distillates with vegetable or animal fuel oils and appropriately additive fuel oils.
  • Oils obtained from animal or vegetable material are mainly metabolic products which comprise triglycerides of monocarboxylic acids, for example acids with 10 to 25 carbon atoms, and of the formula correspond in which R is an aliphatic radical having 10 to 25 carbon atoms, which may be saturated or unsaturated.
  • oils contain glycerides from a number of acids, the Number and variety varies with the source of the oil and they can be added Contain phosphoglycerides.
  • Such oils can be found in the prior art known methods can be obtained.
  • Triglyceride Due to the partially unsatisfactory physical properties of the Triglyceride has become the technique of naturally occurring Triglycerides in fatty acid esters of lower alcohols such as methanol or ethanol convict. Mixtures of middle distillates also belong to the prior art with oils of vegetable or animal origin (hereinafter also referred to as "biofuel oils” called).
  • EP-B-0 665 873 discloses a fuel oil composition
  • a fuel oil composition comprising one Biofuel, a petroleum-based fuel oil and an additive which (a) an oil-soluble ethylene copolymer or (b) a comb polymer or (c) a polar Nitrogen compound or (d) a compound in which at least one in essential linear alkyl group having 10 to 30 carbon atoms with one not polymeric organic residue is linked to at least one linear chain of To deliver atoms that are the carbon atoms of the alkyl groups and one or more does not include terminal oxygen atoms, or (e) one or more of the Components (a), (b), (c) and (d).
  • the object of this invention was therefore to provide a suitable demulsifier for Find mixtures of middle distillates and biofuel oils.
  • Another object of the invention is the use of that defined under C) Copolymers as a demulsifier in mixtures of middle distillate fuel oils Biofuel oils.
  • Another object of the invention is a method for demulsifying Mixtures of middle distillate fuel oils with biofuel oils by the Mixtures the copolymer defined above.
  • Middle distillate fuel oils are used as component A). So called one particularly such mineral oils obtained by distillation of crude oil and boil in the range of 120 to 450 ° C, for example kerosene, jet fuel, Diesel and heating oil. Middle distillates are preferably used which less than 350 ppm sulfur, particularly preferably less than 200 ppm sulfur in particular less than 50 ppm sulfur and in special cases less than 10 contain ppm of sulfur. These are generally such Middle distillates which have been subjected to hydrogenation refining and therefore only contain small amounts of polyaromatic and polar compounds. These are preferably middle distillates, the 95% distillation points below 370 ° C, especially 350 ° C and in special cases below Have 330 ° C. The middle distillates preferably have aromatic contents of below 28% by weight, in particular below 20% by weight.
  • Biofuel oils are used as component B).
  • the biofuel oil which is often also called “Biodiesel” or “biofuel” is called to make fatty acid alkyl esters Fatty acids with 14 to 24 carbon atoms and alcohols with 1 to 4 carbon atoms. Usually Most of the fatty acids contain one, two or three double bonds. It is particularly preferably e.g. around rapeseed oleic acid methyl ester and specifically to mixtures containing rapeseed, sunflower and / or soybean oil fatty acid methyl esters contain.
  • oils derived from animal or vegetable material and the can be used in the composition according to the invention Rapeseed oil, coriander oil, cottonseed oil, sunflower oil, castor oil, olive oil, Peanut oil, corn oil, almond oil, palm kernel oil, coconut oil, soybean oil, mustard seed oil, Beef tallow, bone oil and fish oils.
  • oils can be used, which are made from used waste oils, how frying oil was obtained.
  • Rapeseed oil which is a mixture of partial glycerin esterified fatty acids is preferred because it is available in large quantities and in is easily obtained by pressing rapeseed. Furthermore are the also widely used oils of sunflower and soy and their Mixtures with rapeseed oil are preferred.
  • the lower alkyl esters of fatty acids are the following, for example as commercially available mixtures: the ethyl, propyl, butyl and in particular methyl esters of fatty acids with 12 to 22 carbon atoms, for example of lauric acid, myristic acid, palmitic acid, palmitolic acid, Stearic acid, oleic acid, elaidic acid, petroselinic acid, ricinoleic acid, Elaeostearic acid, linoleic acid, linolenic acid, eicosanoic acid, gadoleic acid, Docosanoic acid or erucic acid, which preferably has an iodine number of 50 to 150, in particular have 90 to 125.
  • the ethyl, propyl, butyl and in particular methyl esters of fatty acids with 12 to 22 carbon atoms for example of lauric acid, myristic acid, palmitic acid, palmitolic acid, Stea
  • Mixtures with particularly beneficial ones Properties are those that are primarily, i.e. H. at least 50% by weight, Methyl esters of fatty acids with 16 to 22 carbon atoms and 1, 2 or 3 Double bonds included.
  • the preferred lower alkyl esters of fatty acids are the methyl esters of oleic acid, linoleic acid, linolenic acid and erucic acid.
  • Component C) is an ethylene copolymer.
  • the copolymer has an OH number of 20 to 250, in particular 25 to 200 mg KOH / g.
  • the Copolymer an average molecular weight Mw of 700 to 10,000 g / mol.
  • the olefinically unsaturated compounds which in addition to ethylene in the copolymer are contained, it is preferably vinyl esters, acrylic esters, mono- and Diesters of ethylenically unsaturated carboxylic acids, methacrylic esters, alkyl vinyl ethers and / or alkenes which are hydroxyalkyl, hydroxyalkenyl, hydroxycycloalkyl or Wear hydroxyaryl residues. These residues contain at least one hydroxyl group, the can be anywhere on the rest, but preferably at the chain end ( ⁇ position) or in the para position for ring systems.
  • Suitable vinyl esters include 2-hydroxyethyl vinyl esters, ⁇ -hydroxypropyl vinyl esters, 3-hydroxypropyl vinyl esters and 4-hydroxybutyl vinyl esters as well as diethylene glycol monovinyl esters.
  • Suitable acrylic esters include hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, hydroxyisopropyl acrylate, 4-hydroxybutyl acrylate and glycerol monoacrylate.
  • the corresponding esters of methacrylic acid and also esters of ethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid with diols are equally suitable.
  • Suitable alkyl vinyl ethers include 2-hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hexanediol monovinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether and cyclohexanedimethanol monovinyl ether.
  • the alkenes are preferably monounsaturated Hydroxy hydrocarbons with 3 to 30 carbon atoms, especially 4 to 16 carbon atoms and especially 5 to 12 carbon atoms.
  • Copolymers are also included for use as a demulsifier Structural units derived from ethylene and vinyl alcohol are suitable. Copolymers of this type can be prepared by using a copolymer partially containing structural units derived from ethylene and vinyl acetate or fully hydrolyzed.
  • copolymers can be carried by ethylene and glycidyl residues Monomers such as Derive glycidyl (meth) acrylate or glycidyl allyl ether after Hydrolysis with water, alcohols, such as methanol or glycol or amines, e.g. Ammonia, methylamine, ethanolamine or diethanolamine according to the invention be used.
  • Monomers such as Derive glycidyl (meth) acrylate or glycidyl allyl ether after Hydrolysis with water, alcohols, such as methanol or glycol or amines, e.g. Ammonia, methylamine, ethanolamine or diethanolamine according to the invention be used.
  • Demulsification in the manner according to the invention can furthermore be achieved by using ethylene copolymers which contain oxalkylated acid groups.
  • Suitable ethylene copolymers are, for example, those with acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid or maleic anhydride.
  • these copolymers containing acid groups are oxalkylated on the acid groups with C 1 -C 10 -alkylene oxides.
  • Preferred alkylene oxides are ethylene oxide, propylene oxide and butylene oxide.
  • the oxyalkylation is preferably carried out using 0.5 to 10 mol, in particular 1 to 5 mol and especially 1 to 2 mol of alkylene oxide per mol of acid group.
  • the molar proportion of hydroxy-functionalized comonomers in the copolymer is preferably 0.5 to 15%, in particular 1 to 12%.
  • the melt viscosities of the copolymers according to the invention are 140 ° C. preferably below 10,000 mPas, in particular between 10 and 1000 mPas and especially between 15 and 500 mPas.
  • the copolymers according to the invention contain at least one Comonomer with hydroxyl groups. You can add more, for example one or two or contain three further olefinically unsaturated comonomers.
  • Such olefinic unsaturated comonomers are, for example, vinyl esters, acrylic acid, Methacrylic acid, acrylic ester, methacrylic ester, vinyl ether or olefins.
  • Especially preferred vinyl esters are vinyl acetate, vinyl propionate and vinyl esters from Neocarboxylic acids with 8, 9, 10, 11 or 12 carbon atoms.
  • acrylic and methacrylic esters are those with alcohols with 1 to 20 carbon atoms, especially of methanol, ethanol, propanol, n-butanol, iso-butanol and tert-butanol.
  • Particularly preferred vinyl ethers are Hydroxy vinyl ether.
  • Particularly preferred olefins are those with 3 to 10 carbon atoms, especially propene, isobutylene, diisobutylene, norbornene, 4-methylpentene-1 and hexene.
  • Terpolymers of ethylene are particularly preferred, a hydroxy functionalized comonomer and either vinyl acetate or one Vinyl ester of a neocarboxylic acid with 8 to 12 carbon atoms. Contain the Copolymers another comonomer, so its molar proportion preferably up to 18%, in particular up to 12%.
  • the comonomers are copolymerized by known processes (cf. for this e.g. Ullmann's Encyclopedia of Technical Chemistry, 4th Edition, Vol. 19, Pages 169 to 178). Polymerization in solution, in suspension, in the gas phase and high pressure bulk polymerization. Preferably one turns high-pressure bulk polymerization, which is carried out at pressures of 50 to 400 MPa, preferably 100 to 300 MPa and temperatures of 50 to 350 ° C, preferably 100 to 300 ° C, is carried out.
  • the reaction of the comonomers is determined by Radical initiators (radical chain initiators) initiated. To this Substance classes belong e.g.
  • Oxygen, hydroperoxides, peroxides and Azo compounds such as cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, Dibenzoyl peroxide, bis (2-ethylhexyl) peroxidicarbonate, t-butyl permaleinate, t-butyl perbenzoate, dicumyl peroxide, t-butylcumyl peroxide, di- (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile).
  • the initiators are used individually or as a mixture of two or more substances in quantities of 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Comonomer mixture used.
  • the desired melt viscosity of the copolymers is given Composition of the comonomer mixture by varying the Reaction parameters pressure and temperature and optionally by adding Moderators hired.
  • Hydrogen, saturated or unsaturated hydrocarbons e.g. Propane, aldehydes, e.g. propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones, e.g. Acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone or alcohols, e.g. Butanol, proven.
  • the moderators in quantities up to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Comonomer mixture used.
  • High pressure bulk polymerization is carried out in known high pressure reactors, e.g. Autoclaves or tube reactors are carried out batchwise or continuously, Tube reactors have proven particularly useful. Solvents such as aliphatic Hydrocarbons or hydrocarbon mixtures, benzene or toluene, can be contained in the reaction mixture, although the solvent-free Working method has proven particularly successful.
  • the Polymerization is the mixture of the comonomers, the initiator and, if used, the moderator, a tubular reactor via the reactor inlet and via one or more side branches fed.
  • the comonomer streams be composed differently (EP-B-0 271 738).
  • the copolymers C) are the A) and B) containing mixtures in amounts of 0.001 to 5% by weight, preferably 0.005 to 1% by weight and especially 0.01 to 0.05 wt .-% added. They can be used as such or they can be solved or dispersed in solvents such as e.g. aliphatic and / or aromatic Hydrocarbons or hydrocarbon mixtures such as e.g.
  • copolymers C) can according to the oil to be additiv in the prior art known methods are supplied. If more than one copolymer component Such components can be used together or separately in any combination can be introduced into the oil.
  • Copolymers C) also together with one or more oil-soluble co-additives are used that already have the properties of crude oils, Improve lubricating oils or fuel oils.
  • oil-soluble co-additives are polar Compounds that cause paraffin dispersion (paraffin dispersants), Alkylphenol-aldehyde resins, polymeric cold flow improvers and oil-soluble ones Amphiphiles.
  • the additives according to the invention in a mixture with ethylene / vinyl acetate / vinyl 2-ethylhexanoate terpolymers, Ethylene / vinyl acetate / neononanoic acid vinyl ester terpolymers and / or ethylene vinyl acetate / vinyl neodecanoate terpolymers to improve the flowability and lubrication of Mineral oils or mineral oil distillates.
  • vinyl neodecanoic acid contains 8 to 40% by weight of vinyl acetate and 1 to 40 wt .-% of the respective long-chain vinyl ester. More preferred In addition to ethylene and 10 to 40% by weight, copolymers contain vinyl esters and / or 1 to 40 wt .-% long-chain vinyl esters still 0.5 to 20 wt .-% olefin with 3 to 10 Carbon atoms such as Isobutylene, diisobutylene, propylene, methylpentene or Norbornene.
  • paraffin dispersants are preferably low molecular weight or polymeric, oil-soluble compounds with ionic or polar groups such as e.g. Amine salts, imides and / or amides.
  • Particularly preferred paraffin dispersants contain reaction products of secondary fatty amines with 8 to 36 carbon atoms, especially dicocos fatty amine, ditallow fatty amine and distearyl amine. Tried and tested have become paraffin dispersants, which by reaction aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their Anhydrides can be obtained (cf. US 4 211 534).
  • paraffin dispersants are Copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds which optionally with primary monoalkylamines and / or aliphatic alcohols can be implemented (cf. EP-A-0 154 177), the reaction products of Alkenylspirobislactones with amines (cf. EP-A-0 413 279 B1) and according to EP-A-0 606 055 A2 Reaction products of terpolymers based on ⁇ , ⁇ -unsaturated Dicarboxylic anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxylalkylene ethers lower unsaturated alcohols.
  • esters suitable are esters suitable. These esters are derived from polyols with 3 or more OH groups, in particular of glycerol, trimethylolpropane, pentaerythritol and those derived therefrom Oligomers with 2 to 10 monomer units, e.g. Polyglycerol.
  • the polyols are generally with 1 to 100 mol of alkylene oxide, preferably 3 to 70, in particular 5 to 50, mol of alkylene oxide per mol of polyol.
  • Preferred alkylene oxides are ethylene oxide, propylene oxide and butylene oxide.
  • the Alkoxylation takes place according to known processes.
  • fatty acids suitable for the esterification of the alkoxylated polyols preferably 8 to 50, in particular 12 to 30, especially 16 to 26 carbon atoms.
  • Suitable fatty acids are, for example, lauric, tridecane, myristic, pentadecane, Palmitic, margarine, stearic, isostearic, arachic and behenic acid, oleic and Erucic acid, palmitoleic, myristolein, ricinoleic acid, as well as from natural fats and Oil-derived fatty acid mixtures.
  • Preferred fatty acid mixtures contain more than 50% fatty acids with at least 20 carbon atoms.
  • the esterification can also starting from reactive derivatives of fatty acids such as esters with lower Alcohols (e.g. methyl or ethyl esters) or anhydrides.
  • polyvalent carboxylic acids can also be used to esterify the alkoxylated polyols.
  • suitable polyvalent carboxylic acids are dimer fatty acids, alkenyl succinic acids and aromatic polycarboxylic acids and their derivatives such as anhydrides and C 1 to C 5 esters.
  • Alkenylsuccinic acids and their derivatives with alkyl radicals having 8 to 200, in particular 10 to 50, carbon atoms are preferred.
  • Examples are dodecenyl, octadecenyl and poly (isobutenyl) succinic anhydride.
  • the polyvalent carboxylic acids are preferably used in minor proportions of up to 30 mol%, preferably 1 to 20 mol%, in particular 2 to 10 mol%.
  • Ester and fatty acid are based on the content of the esterification Hydroxyl groups on the one hand and carboxyl groups on the other hand in a ratio of 1.5: 1 used up to 1: 1.5, preferably 1.1: 1 to 1: 1.1, in particular equimolar.
  • the Paraffin-dispersing effect is particularly pronounced when using a Acid excess of up to 20 mol%, especially up to 10 mol%, especially up to 5 mol% is worked.
  • the esterification is carried out using customary methods.
  • the reaction of polyol alkoxylate with fatty acid has proven particularly useful, if appropriate in the presence of catalysts such as, for example, para-toluenesulfonic acid, C 2 -C 50 -alkylbenzenesulfonic acids, methanesulfonic acid or acidic ion exchangers.
  • the water of reaction can be separated off by direct condensation or preferably by azeotropic distillation in the presence of organic solvents, in particular aromatic solvents such as toluene, xylene or else higher-boiling mixtures such as ® Shellsol A, Shellsol B, Shellsol AB or Solvent Naphtha.
  • the esterification is preferably carried out completely, ie 1.0 to 1.5 mol of fatty acid per mol of hydroxyl groups are used for the esterification.
  • the acid number of the esters is generally below 15 mg KOH / g, preferably below 10 mg KOH / g, especially below 5 mg KOH / g.
  • paraffin dispersants are prepared by reacting compounds containing an acyl group with an amine.
  • the paraffin dispersants can be added to the copolymers C) or separately be added to the middle distillate to be added.
  • Alkylphenol-aldehyde resins are known in principle and are described, for example, in the Römpp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, Volume 4, pp. 3351ff. described.
  • the alkyl or alkenyl radicals of the alkylphenol have 6-24, preferably 8-22, in particular 9-18, carbon atoms. They can be linear or preferably branched, the branching being able to contain secondary as well as tertiary structural elements.
  • the alkylphenol-aldehyde resin can also contain up to 20 mol% phenol units and / or alkylphenols with short alkyl chains such as e.g. B. contain butylphenol. The same or different alkylphenols can be used for the alkylphenol-aldehyde resin.
  • the aldehyde in the alkylphenol-aldehyde resin has 1 to 10, preferably 1 to 4 Carbon atoms and can carry other functional groups. It is preferably a aliphatic aldehyde, particularly preferably it is formaldehyde.
  • the molecular weight of the alkylphenol-aldehyde resins is preferably 350- 10,000, in particular 400 - 5000 g / mol. This preferably corresponds to one Degree of condensation n from 3 to 40, in particular from 4 to 20. Prerequisite here that the resins are oil-soluble.
  • the alkylphenol-aldehyde resins are prepared in a known manner by basic catalysis, whereby condensation products of the resol type arise, or by acidic catalysis, producing condensation products of the novolak type.
  • 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, tripropetraphenylphenol, tripropenylphenol (isobutenyl) phenol to C 24 .
  • the alkylphenols are preferably para-substituted.
  • the alkylphenols can be one or carry several alkyl radicals. They are preferably at most 5 mol%, in particular at most 20 mol% and especially at most 40 mol% with more than an alkyl group. Preferably carry at most 40 mol%, in particular not more than 20 mol% of the alkylphenols used in the ortho position an alkyl radical. Specifically, the alkylphenols ortho to the hydroxyl group are not tertiary Alkyl groups substituted.
  • the aldehyde can be a mono- or dialdehyde and other functional groups wear like -COOH.
  • Particularly suitable aldehydes are formaldehyde, acetaldehyde, Butyraldehyde, glutardialdehyde and glyoxalic acid, formaldehyde is preferred.
  • the Formaldehyde can be in the form of paraformaldehyde or in the form of a preferred 20 - 40 wt .-% aqueous formalin solution can be used. It can too appropriate amounts of trioxane can be used.
  • alkylphenol and aldehyde usually takes place in the presence of alkaline catalysts, for example alkali 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 Halogenacetic acids, and in the presence of an azeotrope with water organic solvent, for example toluene, xylene, higher aromatics or Mixtures of these.
  • the reaction mixture is at a temperature of 90 to 200 ° C, preferably 100 - 160 ° C heated, the water of reaction formed is removed by azeotropic distillation during the 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, e.g. Petroleum fractions, Kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or solvents such as ® Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol, ® ISOPARund ® Shellsol D types.
  • Hydrocarbons or hydrocarbon mixtures e.g. Petroleum fractions, Kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or solvents such as ® Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol, ® ISOPARund ® Shellsol
  • the additives according to the invention are used together with comb polymers.
  • comb polymers This is understood to mean polymers in which hydrocarbon radicals having at least 8, in particular at least 10, carbon atoms are bonded to a polymer backbone. They are preferably homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms. In the case of copolymers, 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 an NC 6 -C 22 -alkylmaleimide (cf. EP-A-0 320 766), also esterified olefin / maleic anhydride copolymers, polymers and copolymers of ⁇ -olefins and esterified copolymers of styrene and maleic anhydride.
  • fumarate / vinyl acetate copolymers cf. EP 0 153 176 A1
  • copolymers of a C 6 -C 24 - ⁇ -olefin and an NC 6 -C 22 -alkylmaleimide cf. EP-A-0 320 766
  • esterified olefin / maleic anhydride copolymers polymers and copo
  • the mixing ratio (in parts by weight) of the copolymers C) with polymers Cold flow improvers, paraffin dispersants, comb polymers or resins each 1:10 to 20: 1, preferably 1: 1 to 10: 1.
  • copolymers C) can be used alone or together with other additives are used, e.g. B. with other pour point depressors or Dewaxing agents, with corrosion inhibitors, antioxidants, lubricity additives Mud inhibitors, dehazers and additives to lower the cloud point.
  • additives e.g. B. with other pour point depressors or Dewaxing agents, with corrosion inhibitors, antioxidants, lubricity additives Mud inhibitors, dehazers and additives to lower the cloud point.
  • the CFPP value is determined in accordance with EN 116, the boiling data in accordance with ASTM D-86 and the cloud point in accordance with ISO 3015.
  • the OH numbers are determined in accordance with DIN 53240 by reaction with a defined amount of excess acetic anhydride and subsequent titration of the acetic acid formed.
  • Characterization of the copolymers polymer vinyl acetate Content in% by weight V 140 , mPas OH number VeoVa 10 Hydroxy comonomer P1 29.1 - 4.2 53 20 P2 - 23.6 34.8 135 121 P3 22.2 - 13.7 88 66 P4 24.1 - 7.3 99 35 P5 21 - 11.5 96 71 P6 11.3 - 36.6 169 112 P7 26.4 - 0.77 131 5 P8 32 - - 125 0 P9 31 8th - 110 0 P10 31.5 4.1 - 170 0
  • a middle distillate with a CFPP of -7 ° C. and its mixture with 5% of the described biofuel (CFPP of the mixture also -7 ° C.) with cold flow improvers and copolymers containing hydroxyl groups were investigated Influencing the cold flow properties by copolymers containing hydroxyl groups example fuel oil copolymers 300 ppm P8 300 ppm P9 300 ppm P8 + 10ppmP4 300 ppm P9 + 10 ppm P4 33 (V) middle distillate - 16th - 15th - 17th - 17th 34 Middle distillate + biofuel - 17th - 16th - 17th - 16th

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Abstract

A fuel oil contains (1) a major amount of (i) a middle distillate fuel oil and (ii) a bio-fuel oil; and (2) a minor amount of (iii) an oil-soluble ethylene/0.2-35 mol.% further olefinically-unsaturated compound copolymer containing a free OH group and having an OH number of 10-300 mg KOH/g.

Description

Die vorliegende Erfindung betrifft die Verwendung eines Additivs als Demulgator für Mischungen aus Mitteldestillaten mit pflanzlichen oder tierischen Brennstoffölen und entsprechend additivierte Brennstofföle.The present invention relates to the use of an additive as a demulsifier for Mixtures of middle distillates with vegetable or animal fuel oils and appropriately additive fuel oils.

Im Zuge abnehmender Welterdölreserven und der Diskussion um die Umwelt beeinträchtigenden Konsequenzen des Verbrauchs fossiler und mineralischer Brennstoffe steigt das Interesse an alternativen, auf nachwachsenden Rohstoffen basierenden Energiequellen. Dazu gehören insbesondere native Öle und Fette pflanzlichen oder tierischen Ursprungs. Dies sind in der Regel Triglyceride von Fettsäuren mit 10 bis 24 C-Atomen, die einen den herkömmlichen Brennstoffen vergleichbaren Heizwert haben, aber gleichzeitig als biologisch abbaubar und umweltverträglich eingestuft werden. ,In the course of decreasing world oil reserves and the discussion about the environment adverse consequences of fossil and mineral consumption Fuels are becoming more and more interested in alternative, renewable raw materials based energy sources. These include, in particular, native oils and fats of vegetable or animal origin. These are usually triglycerides from Fatty acids with 10 to 24 carbon atoms, which are the same as conventional fuels have a comparable calorific value, but at the same time as biodegradable and be classified as environmentally friendly. .

Aus tierischem oder pflanzlichem Material erhaltene Öle sind hauptsächlich Stoffwechselprodukte, die Triglyceride von Monocarbonsäuren umfassen, z.B. Säuren mit 10 bis 25 Kohlenstoffatomen, und der Formel

Figure 00010001
entsprechen, in der R ein aliphatischer Rest mit 10 bis 25 Kohlenstoffatomen ist, der gesättigt oder ungesättigt sein kann.Oils obtained from animal or vegetable material are mainly metabolic products which comprise triglycerides of monocarboxylic acids, for example acids with 10 to 25 carbon atoms, and of the formula
Figure 00010001
correspond in which R is an aliphatic radical having 10 to 25 carbon atoms, which may be saturated or unsaturated.

Im allgemeinen enthalten solche Öle Glyceride von einer Reihe von Säuren, deren Anzahl und Sorte mit der Quelle des Öls variiert, und sie können zusätzlich Phosphoglyceride enthalten. Solche Öle können nach im Stand der Technik bekannten Verfahren erhalten werden.Generally, such oils contain glycerides from a number of acids, the Number and variety varies with the source of the oil and they can be added Contain phosphoglycerides. Such oils can be found in the prior art known methods can be obtained.

Auf Grund der teilweise unbefriedigenden physikalischen Eigenschaften der Triglyceride ist die Technik dazu übergegangen, die natürlich vorkommenden Triglyceride in Fettsäureester niederer Alkohole wie Methanol oder Ethanol zu überführen. Zum Stand der Technik gehören auch Mischungen aus Mitteldestillaten mit Ölen pflanzlicher oder tierischer Herkunft (im folgenden auch "Biobrennstofföle" genannt).Due to the partially unsatisfactory physical properties of the Triglyceride has become the technique of naturally occurring Triglycerides in fatty acid esters of lower alcohols such as methanol or ethanol convict. Mixtures of middle distillates also belong to the prior art with oils of vegetable or animal origin (hereinafter also referred to as "biofuel oils" called).

EP-B-0 665 873 offenbart eine Brennstoffölzusammensetzung, die einen Biobrennstoff, ein Brennstofföl auf Erdölbasis und ein Additiv umfasst, welches (a) ein öllösliches Ethylencopolymer oder (b) ein Kammpolymer oder (c) eine polare Stickstoffverbindung oder (d) eine Verbindung, in der mindestens eine im wesentlichen lineare Alkylgruppe mit 10 bis 30 Kohlenstoffatomen mit einem nicht polymeren organischen Rest verbunden ist, um mindestens eine lineare Kette von Atomen zu liefern, die die Kohlenstoffatome der Alkylgruppen und ein oder mehrere nicht endständige Sauerstoffatome einschließt, oder (e) eine oder mehrere der Komponenten (a), (b), (c) und (d) umfasst.EP-B-0 665 873 discloses a fuel oil composition comprising one Biofuel, a petroleum-based fuel oil and an additive which (a) an oil-soluble ethylene copolymer or (b) a comb polymer or (c) a polar Nitrogen compound or (d) a compound in which at least one in essential linear alkyl group having 10 to 30 carbon atoms with one not polymeric organic residue is linked to at least one linear chain of To deliver atoms that are the carbon atoms of the alkyl groups and one or more does not include terminal oxygen atoms, or (e) one or more of the Components (a), (b), (c) and (d).

Ein Hindernis für die Verwendung von Mischungen aus Mitteldestillaten und Biobrennstoffölen ist deren starke Neigung, mit Wasser stabile Emulsionen einzugehen. Solche Emulsionen bewirken in der Verteilungskette der Brennstofföle sowie bei deren Verwendung in Kraftfahrzeugen Korrosionsprobleme.An obstacle to the use of mixtures of middle distillates and Biofuel oils have a strong tendency to emulsions that are stable with water enter into. Such emulsions cause in the distribution chain of the fuel oils and corrosion problems when used in motor vehicles.

Aufgabe dieser Erfindung war es somit, einen geeigneten Demulgator für Mischungen aus Mitteldestillaten und Biobrennstoffölen zu finden.The object of this invention was therefore to provide a suitable demulsifier for Find mixtures of middle distillates and biofuel oils.

Überraschenderweise wurde nun gefunden, dass Ethylencopolymere, die hydrophile Substituenten enthalten, ausgezeichnete Demulgatoren für solche Mischungen sind.Surprisingly, it has now been found that ethylene copolymers, the hydrophilic Containing substituents that are excellent demulsifiers for such mixtures.

Gegenstand der Erfindung ist ein Brennstofföl, enthaltend einen größeren Anteil einer Mischung aus

  • A) einem Mitteldestillat-Brennstofföl, und
  • B) einem Biobrennstofföl,
    sowie einem kleineren Anteil
  • C) eines öllöslichen Copolymers aus Ethylen und mindestens 0,2 bis 35 mol-% einer weiteren olefinisch ungesättigten Verbindung, die mindestens eine freie Hydroxylgruppe enthält, und das eine OH-Zahl von 10 bis 300 mg KOH/g aufweist.
    • The invention relates to a fuel oil containing a larger proportion of a mixture
  • A) a middle distillate fuel oil, and
  • B) a biofuel oil,
    as well as a smaller proportion
  • C) an oil-soluble copolymer of ethylene and at least 0.2 to 35 mol% of a further olefinically unsaturated compound which contains at least one free hydroxyl group and which has an OH number of 10 to 300 mg KOH / g.

    • Ein weiterer Gegenstand der Erfindung ist die Verwendung des unter C) definierten Copolymers als Demulgator in Mischungen aus Mitteldestillat-Brennstoffölen mit Biobrennstoffölen.Another object of the invention is the use of that defined under C) Copolymers as a demulsifier in mixtures of middle distillate fuel oils Biofuel oils.

    Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Demulgierung von Mischungen aus Mitteldestillat-Brennstoffölen mit Biobrennstoffölen, indem man den Mischungen das oben definierte Copolymer zusetzt.Another object of the invention is a method for demulsifying Mixtures of middle distillate fuel oils with biofuel oils by the Mixtures the copolymer defined above.

    Als Bestandteil A) werden Mitteldestillat-Brennstofföle verwendet. Damit 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. Vorzugsweise werden solche Mitteldestillate verwendet, die weniger als 350 ppm Schwefel, besonders bevorzugt weniger als 200 ppm Schwefel insbesondere weniger als 50 ppm Schwefel und in speziellen Fällen 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. Vorzugsweise handelt es sich um solche Mitteldestillate, die 95 %-Destillationspunkte unter 370°C, insbesondere 350°C und in Spezialfällen unter 330°C aufweisen. Vorzugsweise haben die Mitteldestillate Aromatengehalte von unter 28 Gew.-%, insbesondere unter 20 Gew.-%.Middle distillate fuel oils are used as component A). So called one particularly such mineral oils obtained by distillation of crude oil and boil in the range of 120 to 450 ° C, for example kerosene, jet fuel, Diesel and heating oil. Middle distillates are preferably used which less than 350 ppm sulfur, particularly preferably less than 200 ppm sulfur in particular less than 50 ppm sulfur and in special cases less than 10 contain ppm of sulfur. These are generally such Middle distillates which have been subjected to hydrogenation refining and therefore only contain small amounts of polyaromatic and polar compounds. These are preferably middle distillates, the 95% distillation points below 370 ° C, especially 350 ° C and in special cases below Have 330 ° C. The middle distillates preferably have aromatic contents of below 28% by weight, in particular below 20% by weight.

    Als Bestandteil B) werden Biobrennstofföle verwendet. In einer bevorzugten Ausführungsform handelt es sich bei dem Biobrennstofföl, das häufig auch als "Biodiesel" oder "Biokraftstoff" bezeichnet wird, um Fettsäurealkylester aus Fettsäuren mit 14 bis 24 C-Atomen und Alkoholen mit 1 bis 4 C-Atomen. Gewöhnlich enthält ein größerer Teil der Fettsäuren ein, zwei oder drei Doppelbindungen. Besonders bevorzugt handelt es sich z.B. um Rapsölsäuremethylester und speziell um Mischungen, die Raps-, Sonnenblumen- und/oder Sojaölfettsäuremethylester enthalten.Biofuel oils are used as component B). In a preferred one Embodiment is the biofuel oil, which is often also called "Biodiesel" or "biofuel" is called to make fatty acid alkyl esters Fatty acids with 14 to 24 carbon atoms and alcohols with 1 to 4 carbon atoms. Usually Most of the fatty acids contain one, two or three double bonds. It is particularly preferably e.g. around rapeseed oleic acid methyl ester and specifically to mixtures containing rapeseed, sunflower and / or soybean oil fatty acid methyl esters contain.

    Beispiele für Öle, die sich von tierischem oder pflanzlichem Material ableiten, und die in der erfindungsgemäßen Zusammensetzung verwendet werden können, sind Rapsöl, Korianderöl, Baumwollsamenöl, Sonnenblumenöl, Ricinusöl, Olivenöl, Erdnussöl, Maisöl, Mandelöl, Palmkernöl, Kokosnussöl, Sojaöl, Senfsamenöl, Rindertalg, Knochenöl und Fischöle. Weitere Beispiele schließen Öle ein, die sich von Weizen, Jute, Sesam, Scheabaumnuß, Arachisöl und Leinöl ableiten und können aus diesen nach im Stand der Technik bekannten Verfahren abgeleitet werden. Außerdem können Öle verwendet werden, welche aus gebrauchten Altölen, wie Fritieröl gewonnen wurden. Rapsöl, das eine Mischung von mit Glycerin partiell veresterten Fettsäuren ist, ist bevorzugt, da es in großen Mengen erhältlich ist und in einfacher Weise durch Auspressen von Rapssamen erhältlich ist. Des weiteren sind die ebenfalls weit verbreiteten Öle von Sonnenblumen und Soja sowie deren Mischungen mit Rapsöl bevorzugt.Examples of oils derived from animal or vegetable material and the can be used in the composition according to the invention Rapeseed oil, coriander oil, cottonseed oil, sunflower oil, castor oil, olive oil, Peanut oil, corn oil, almond oil, palm kernel oil, coconut oil, soybean oil, mustard seed oil, Beef tallow, bone oil and fish oils. Other examples include oils that are derive from wheat, jute, sesame, shea nut, arachis oil and linseed oil and can be derived from these by methods known in the art become. In addition, oils can be used, which are made from used waste oils, how frying oil was obtained. Rapeseed oil, which is a mixture of partial glycerin esterified fatty acids is preferred because it is available in large quantities and in is easily obtained by pressing rapeseed. Furthermore are the also widely used oils of sunflower and soy and their Mixtures with rapeseed oil are preferred.

    Als niedrigere Alkylester von Fettsäuren kommen die folgenden in Betracht, beispielsweise als handelsübliche Mischungen: Die Ethyl-, Propyl-, Butyl- und insbesondere Methylester von Fettsäuren mit 12 bis 22 Kohlenstoffatomen, beispielsweise von Laurinsäure, Myristinsäure, Palmitinsäure, Palmitolsäure, Stearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Ricinolsäure, Elaeostearinsäure, Linolsäure, Linolensäure, Eicosansäure, Gadoleinsäure, Docosansäure oder Erucasäure, die bevorzugt eine lodzahl von 50 bis 150, insbesondere 90 bis 125 haben. Mischungen mit besonders vorteilhaften Eigenschaften sind solche, die hauptsächlich, d. h. zu mindestens 50 Gew.-%, Methylester von Fettsäuren mit 16 bis 22 Kohlenstoffatomen und 1, 2 oder 3 Doppelbindungen enthalten. Die bevorzugten niedrigeren Alkylester von Fettsäuren sind die Methylester von Ölsäure, Linolsäure, Linolensäure und Erucasäure.The lower alkyl esters of fatty acids are the following, for example as commercially available mixtures: the ethyl, propyl, butyl and in particular methyl esters of fatty acids with 12 to 22 carbon atoms, for example of lauric acid, myristic acid, palmitic acid, palmitolic acid, Stearic acid, oleic acid, elaidic acid, petroselinic acid, ricinoleic acid, Elaeostearic acid, linoleic acid, linolenic acid, eicosanoic acid, gadoleic acid, Docosanoic acid or erucic acid, which preferably has an iodine number of 50 to 150, in particular have 90 to 125. Mixtures with particularly beneficial ones Properties are those that are primarily, i.e. H. at least 50% by weight, Methyl esters of fatty acids with 16 to 22 carbon atoms and 1, 2 or 3 Double bonds included. The preferred lower alkyl esters of fatty acids are the methyl esters of oleic acid, linoleic acid, linolenic acid and erucic acid.

    Handelsübliche Mischungen der genannten Art werden beispielsweise durch Spaltung und Veresterung von tierischen und pflanzlichen Fetten und Ölen durch ihre Umesterung mit niedrigeren aliphatischen Alkoholen erhalten. Zur Herstellung von niedrigeren Alkylestern von Fettsäuren ist es vorteilhaft, von Fetten und Ölen mit hoher lodzahl auszugehen, wie beispielsweise Sonnenblumenöl, Rapsöl, Korianderöl, Castoröl (Ricinusöl), Sojaöl, Baumwollsamenöl, Erdnussöl oder Rindertalg. Niedrigere Alkylester von Fettsäuren auf Basis einer neuen Rapsölsorte, deren Fettsäurekomponente zu mehr als 80 Gew.-% von ungesättigten Fettsäuren mit 18 Kohlenstoffatomen abgeleitet ist, sind bevorzugt.Commercial mixtures of the type mentioned are, for example, by Cleavage and esterification of animal and vegetable fats and oils by get their transesterification with lower aliphatic alcohols. For the production of lower alkyl esters of fatty acids it is advantageous to use fats and oils high iodine number, such as sunflower oil, rapeseed oil, Coriander oil, castor oil (castor oil), soybean oil, cottonseed oil, or peanut oil Beef tallow. Lower alkyl esters of fatty acids based on a new type of rapeseed oil, their fatty acid component to more than 80 wt .-% of unsaturated fatty acids derived with 18 carbon atoms are preferred.

    Das Mischungsverhältnis der Bestandteile A und B kann beliebig variieren. Es liegt vorzugsweise zwischen A:B = 99,9:0,1 und 0,1:99,9, insbesondere 99:1 und 1:99, speziell 95:5 und 5:95, beispielhaft 85:15 und 15:85 oder 80:20 und 20:80.The mixing ratio of components A and B can vary as desired. It lies preferably between A: B = 99.9: 0.1 and 0.1: 99.9, in particular 99: 1 and 1:99, specifically 95: 5 and 5:95, for example 85:15 and 15:85 or 80:20 and 20:80.

    Bestandteil C) ist ein Ethylencopolymer. In einer bevorzugten Ausführungsform der Erfindung weist das Copolymer eine OH-Zahl von 20 bis 250, insbesondere 25 bis 200 mg KOH/g auf. In einer weiteren bevorzugten Ausführungsform weist das Copolymer ein mittleres Molekulargewicht Mw von 700 bis 10.000 g/mol auf.Component C) is an ethylene copolymer. In a preferred embodiment of the Invention, the copolymer has an OH number of 20 to 250, in particular 25 to 200 mg KOH / g. In a further preferred embodiment, the Copolymer an average molecular weight Mw of 700 to 10,000 g / mol.

    Bei den olefinisch ungesättigten Verbindungen, die neben Ethylen im Copolymer enthalten sind, handelt es sich vorzugsweise um Vinylester, Acrylester, Mono- und Diester ethylenisch ungesättigter Carbonsäuren, Methacrylester, Alkylvinylether und/oder Alkene, die Hydroxyalkyl-, Hydroxyalkenyl-, Hydroxycycloalkyl- oder Hydroxyarylreste tragen. Diese Reste enthalten wenigstens eine Hydroxylgruppe, die an einer beliebigen Stelle des Restes stehen kann, bevorzugt aber am Kettenende (ω-Stellung) bzw. in para-Stellung bei Ringsystemen steht.In the case of the olefinically unsaturated compounds, which in addition to ethylene in the copolymer are contained, it is preferably vinyl esters, acrylic esters, mono- and Diesters of ethylenically unsaturated carboxylic acids, methacrylic esters, alkyl vinyl ethers and / or alkenes which are hydroxyalkyl, hydroxyalkenyl, hydroxycycloalkyl or Wear hydroxyaryl residues. These residues contain at least one hydroxyl group, the can be anywhere on the rest, but preferably at the chain end (ω position) or in the para position for ring systems.

    Bei den Vinylestern handelt es sich vorzugsweise um solche der Formel 1 CH2 = CH - OCOR1 worin R1 C1-C30-Hydroxyalkyl, vorzugsweise C1-C12-Hydroxyalkyl, speziell C2-C6-Hydroxyalkyl sowie die entsprechenden Hydroxyoxalkylreste bedeutet. Geeignete Vinylester umfassen 2-Hydroxyethylvinylester, α-Hydroxypropylvinylester, 3-Hydroxypropylvinylester und 4-Hydroxybutylvinylester sowie Diethylenglykolmonovinylester. The vinyl esters are preferably those of the formula 1 CH 2 = CH - OCOR 1 wherein R 1 is C 1 -C 30 hydroxyalkyl, preferably C 1 -C 12 hydroxyalkyl, especially C 2 -C 6 hydroxyalkyl, and the corresponding hydroxyoxalkyl radicals. Suitable vinyl esters include 2-hydroxyethyl vinyl esters, α-hydroxypropyl vinyl esters, 3-hydroxypropyl vinyl esters and 4-hydroxybutyl vinyl esters as well as diethylene glycol monovinyl esters.

    Bei den Acrylestern handelt es sich vorzugsweise um solche der Formel 2 CH2 = CR2 - COOR3 worin R2 Wasserstoff oder Methyl und R3 C1-C30-Hydroxyalkyl, vorzugsweise C1-C12-Hydroxyalkyl, speziell C2-C6-Hydroxyalkyl sowie die entsprechenden Hydroxyoxalkylreste bedeutet. Geeignete Acrylester umfassen Hydroxyethylacrylat, Hydroxyethylmethacrylat, 2-Hydroxypropylacrylat, 3-Hydroxypropylacrylat, 3-Hydroxypropylmethacrylat, Hydroxyisopropylacrylat, 4-Hydroxybutylacrylat und Glycerinmonoacrylat. Genauso geeignet sind die entsprechenden Ester der Methacrylsäure, sowie Ester von ethylenisch ungesättigten Dicarbonsäuren wie Maleinsäure, Fumarsäure oder Itaconsäure mit Diolen.The acrylic esters are preferably those of the formula 2 CH 2 = CR 2 - COOR 3 wherein R 2 is hydrogen or methyl and R 3 is C 1 -C 30 hydroxyalkyl, preferably C 1 -C 12 hydroxyalkyl, especially C 2 -C 6 hydroxyalkyl and the corresponding hydroxyoxalkyl radicals. Suitable acrylic esters include hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, hydroxyisopropyl acrylate, 4-hydroxybutyl acrylate and glycerol monoacrylate. The corresponding esters of methacrylic acid and also esters of ethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid with diols are equally suitable.

    Bei den Alkylvinylethern handelt es sich vorzugsweise um Verbindungen der Formel 3 CH2 = CH - OR4 worin R4 C1-C30-Hydroxyalkyl, vorzugsweise C1-C12-Hydroxyalkyl, speziell C2-C6-Hydroxyalkyl sowie die entsprechenden Hydroxyoxalkylreste bedeutet. Geeignete Alkylvinylether umfassen 2-Hydroxyethylvinylether, Hydroxypropylvinylether, Hexandiolmonovinylether, 4-Hydroxybutylvinylether, Diethylenglykolmonovinylether und Cyclohexandimethanolmonovinylether.The alkyl vinyl ethers are preferably compounds of the formula 3 CH 2 = CH - OR 4 wherein R 4 is C 1 -C 30 hydroxyalkyl, preferably C 1 -C 12 hydroxyalkyl, especially C 2 -C 6 hydroxyalkyl and the corresponding hydroxyoxalkyl radicals. Suitable alkyl vinyl ethers include 2-hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hexanediol monovinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether and cyclohexanedimethanol monovinyl ether.

    Bei den Alkenen handelt es sich vorzugsweise um einfach ungesättigte Hydroxykohlenwasserstoffe mit 3 bis 30 Kohlenstoffatomen, insbesondere 4 bis 16 Kohlenstoffatomen und speziell 5 bis 12 Kohlenstoffatomen. Geeignete Alkene umfassen Dimethylvinylcarbinol (= 2-Methyl-3-buten-2-ol), Allyloxypropandiol, 2-Buten-1,4-diol, 1-Buten-3-ol, 3-Buten-1-ol, 2-Buten-1-ol, 1-Penten-3-ol, 1-Penten-4-ol, 2-Methyl-3-buten-1-ol, 1-Hexen-3-ol, 5-Hexen-1-ol und 7-Octen-1,2-diol.The alkenes are preferably monounsaturated Hydroxy hydrocarbons with 3 to 30 carbon atoms, especially 4 to 16 carbon atoms and especially 5 to 12 carbon atoms. Suitable alkenes include dimethylvinylcarbinol (= 2-methyl-3-buten-2-ol), allyloxypropanediol, 2-butene-1,4-diol, 1-butene-3-ol, 3-butene-1-ol, 2-butene-1-ol, 1-penten-3-ol, 1-penten-4-ol, 2-methyl-3-buten-1-ol, 1-hexen-3-ol, 5-hexen-1-ol and 7-octene-1,2-diol.

    Zur Verwendung als Demulgator sind ebenfalls Copolymere, enthaltend Struktureinheiten, die sich aus Ethylen und Vinylalkohol ableiten, geeignet. Copolymere dieser Art können hergestellt werden, indem man ein Copolymer, enthaltend Struktureinheiten, die sich von Ethylen und Vinylacetat ableiten, teilweise oder vollständig hydrolysiert.Copolymers are also included for use as a demulsifier Structural units derived from ethylene and vinyl alcohol are suitable. Copolymers of this type can be prepared by using a copolymer partially containing structural units derived from ethylene and vinyl acetate or fully hydrolyzed.

    Desgleichen können Copolymere, die sich von Ethylen und Glycidylresten tragenden Monomeren, wie z.B. Glycidyl(meth)acrylat oder Glycidylallylether ableiten, nach Hydrolyse mit Wasser, Alkoholen, wie Methanol oder Glykol bzw. Aminen, wie z.B. Ammoniak, Methylamin, Ethanolamin oder Diethanolamin erfindungsgemäß verwendet werden.Likewise, copolymers can be carried by ethylene and glycidyl residues Monomers such as Derive glycidyl (meth) acrylate or glycidyl allyl ether after Hydrolysis with water, alcohols, such as methanol or glycol or amines, e.g. Ammonia, methylamine, ethanolamine or diethanolamine according to the invention be used.

    Weiterhin lässt sich eine Demulgierung in erfindungsgemäßer Weise durch Verwendung von Ethylencopolymeren erzielen, die oxalkylierte Säuregruppen enthalten. Dazu geeignete Ethylencopolymere sind beispielsweise solche mit Acrylsäure, Methacrylsäure, Itaconsäure, Fumarsäure, Maleinsäure oder Maleinsäureanhydrid. Dazu werden diese säuregruppenhaltigen Copolymere an den Säuregruppen mit C1- bis C10-Alkylenoxiden oxalkyliert. Bevorzugte Alkylenoxide sind Ethylenoxid, Propylenoxid und Butylenoxid. Die Oxalkylierung erfolgt vorzugsweise mit einem Einsatz von 0,5 bis 10 mol, insbesondere 1 bis 5 mol und speziell 1 bis 2 mol Alkylenoxid pro mol Säuregruppe.Demulsification in the manner according to the invention can furthermore be achieved by using ethylene copolymers which contain oxalkylated acid groups. Suitable ethylene copolymers are, for example, those with acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid or maleic anhydride. For this purpose, these copolymers containing acid groups are oxalkylated on the acid groups with C 1 -C 10 -alkylene oxides. Preferred alkylene oxides are ethylene oxide, propylene oxide and butylene oxide. The oxyalkylation is preferably carried out using 0.5 to 10 mol, in particular 1 to 5 mol and especially 1 to 2 mol of alkylene oxide per mol of acid group.

    Der molare Anteil an hydroxyfunktionalisierten Comonomeren am Copolymeren beträgt vorzugsweise 0,5 bis 15 %, insbesondere 1 bis 12 %.The molar proportion of hydroxy-functionalized comonomers in the copolymer is preferably 0.5 to 15%, in particular 1 to 12%.

    Die Schmelzviskositäten der erfindungsgemäßen Copolymere bei 140°C liegen vorzugsweise unterhalb 10.000 mPas, insbesondere zwischen 10 und 1000 mPas und speziell zwischen 15 und 500 mPas.The melt viscosities of the copolymers according to the invention are 140 ° C. preferably below 10,000 mPas, in particular between 10 and 1000 mPas and especially between 15 and 500 mPas.

    Die erfindungsgemäßen Copolymere enthalten neben Ethylen mindestens ein Comonomer mit Hydroxylgruppen. Sie können noch weitere, beispielsweise ein, zwei oder drei weitere olefinisch ungesättigte Comonomere enthalten. Solche olefinisch ungesättigten Comonomere sind beispielsweise Vinylester, Acrylsäure, Methacrylsäure, Acrylester, Methacrylester, Vinylether oder Olefine. Besonders bevorzugte Vinylester sind Vinylacetat, Vinylpropionat und Vinylester von Neocarbonsäuren mit 8, 9, 10, 11 oder 12 Kohlenstoffatomen. Besonders bevorzugte Acryl- und Methacrylester sind solche mit Alkoholen mit 1 bis 20 Kohlenstoffatomen, insbesondere von Methanol, Ethanol, Propanol, n-Butanol, iso-Butanol und tert.-Butanol. Besonders bevorzugte Vinylether, sind Hydroxyvinylether. Besonders bevorzugte Olefine sind solche mit 3 bis 10 Kohlenstoffatomen, speziell Propen, Isobutylen, Diisobutylen, Norbornen, 4-Methylpenten-1 und Hexen. Besonders bevorzugt sind Terpolymere aus Ethylen, einem hydroxyfunktionalisierten Comonomer und entweder Vinylacetat oder einem Vinylester einer Neocarbonsäure mit 8 bis 12 Kohlenstoffatomen. Enthalten die Copolymeren ein weiteres Comonomer, so beträgt dessen molarer Anteil vorzugsweise bis zu 18 %, insbesondere bis zu 12 %.In addition to ethylene, the copolymers according to the invention contain at least one Comonomer with hydroxyl groups. You can add more, for example one or two or contain three further olefinically unsaturated comonomers. Such olefinic unsaturated comonomers are, for example, vinyl esters, acrylic acid, Methacrylic acid, acrylic ester, methacrylic ester, vinyl ether or olefins. Especially preferred vinyl esters are vinyl acetate, vinyl propionate and vinyl esters from Neocarboxylic acids with 8, 9, 10, 11 or 12 carbon atoms. Especially preferred acrylic and methacrylic esters are those with alcohols with 1 to 20 carbon atoms, especially of methanol, ethanol, propanol, n-butanol, iso-butanol and tert-butanol. Particularly preferred vinyl ethers are Hydroxy vinyl ether. Particularly preferred olefins are those with 3 to 10 carbon atoms, especially propene, isobutylene, diisobutylene, norbornene, 4-methylpentene-1 and hexene. Terpolymers of ethylene are particularly preferred, a hydroxy functionalized comonomer and either vinyl acetate or one Vinyl ester of a neocarboxylic acid with 8 to 12 carbon atoms. Contain the Copolymers another comonomer, so its molar proportion preferably up to 18%, in particular up to 12%.

    Die Copolymerisation der Comonomeren erfolgt nach bekannten Verfahren (vgl. hierzu z.B. Ullmanns Encyclopädie der Technischen Chemie, 4. Auflage, Bd. 19, Seiten 169 bis 178). Geeignet sind die Polymerisation in Lösung, in Suspension, in der Gasphase und die Hochdruckmassepolymerisation. Vorzugsweise wendet man die Hochdruckmassepolymerisation an, die bei Drücken von 50 bis 400 MPa, vorzugsweise 100 bis 300 MPa und Temperaturen von 50 bis 350°C, vorzugsweise 100 bis 300°C, durchgeführt wird. Die Reaktion der Comonomeren wird durch Radikale bildende Initiatoren (Radikalkettenstarter) eingeleitet. Zu dieser Substanzklasse gehören z.B. Sauerstoff, Hydroperoxide, Peroxide und Azoverbindungen wie Cumolhydroperoxid, t-Butylhydroperoxid, Dilauroylperoxid, Dibenzoylperoxid, Bis(2-ethylhexyl)-peroxidicarbonat, t-Butylpermaleinat, t-Butylperbenzoat, Dicumylperoxid, t-Butylcumylperoxid, Di-(t-butyl)peroxid, 2,2'-Azo-bis(2-methylpropanonitril), 2,2'-Azo-bis(2-methylbutyronitril). Die Initiatoren werden einzeln oder als Gemisch aus zwei oder mehr Substanzen in Mengen von 0,01 bis 20 Gew.-%, vorzugsweise 0,05 bis 10 Gew.-%, bezogen auf das Comonomerengemisch, eingesetzt.The comonomers are copolymerized by known processes (cf. for this e.g. Ullmann's Encyclopedia of Technical Chemistry, 4th Edition, Vol. 19, Pages 169 to 178). Polymerization in solution, in suspension, in the gas phase and high pressure bulk polymerization. Preferably one turns high-pressure bulk polymerization, which is carried out at pressures of 50 to 400 MPa, preferably 100 to 300 MPa and temperatures of 50 to 350 ° C, preferably 100 to 300 ° C, is carried out. The reaction of the comonomers is determined by Radical initiators (radical chain initiators) initiated. To this Substance classes belong e.g. Oxygen, hydroperoxides, peroxides and Azo compounds such as cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, Dibenzoyl peroxide, bis (2-ethylhexyl) peroxidicarbonate, t-butyl permaleinate, t-butyl perbenzoate, dicumyl peroxide, t-butylcumyl peroxide, di- (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile). The initiators are used individually or as a mixture of two or more substances in quantities of 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Comonomer mixture used.

    Die gewünschte Schmelzviskosität der Copolymerisate wird bei gegebener Zusammensetzung des Comonomerengemisches durch Variation der Reaktionsparameter Druck und Temperatur und gegebenenfalls durch Zusatz von Moderatoren eingestellt. Als Moderatoren haben sich Wasserstoff, gesättigte oder ungesättigte Kohlenwasserstoffe, z.B. Propan, Aldehyde, z.B. Propionaldehyd, n-Butyraldehyd oder Isobutyraldehyd, Ketone, z.B. Aceton, Methylethylketon, Methylisobutylketon, Cyclohexanon oder Alkohole, z.B. Butanol, bewährt. In Abhängigkeit von der angestrebten Viskosität werden die Moderatoren in Mengen bis zu 20 Gew.-%, vorzugsweise 0,05 bis 10 Gew.-%, bezogen auf das Comonomerengemisch, angewandt.The desired melt viscosity of the copolymers is given Composition of the comonomer mixture by varying the Reaction parameters pressure and temperature and optionally by adding Moderators hired. Hydrogen, saturated or unsaturated hydrocarbons, e.g. Propane, aldehydes, e.g. propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones, e.g. Acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone or alcohols, e.g. Butanol, proven. In Depending on the desired viscosity, the moderators in quantities up to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Comonomer mixture used.

    Die Hochdruckmassepolymerisation wird in bekannten Hochdruckreaktoren, z.B. Autoklaven oder Rohrreaktoren diskontinuierlich oder kontinuierlich durchgeführt, besonders bewährt haben sich Rohrreaktoren. Lösungsmittel wie aliphatische Kohlenwasserstoffe oder Kohlenwasserstoffgemische, Benzol oder Toluol, können im Reaktionsgemisch enthalten sein, wenngleich sich die lösungsmittelfreie Arbeitsweise besonders bewährt hat. Nach einer bevorzugten Ausführungsform der Polymerisation wird das Gemisch aus den Comonomeren, dem Initiator und, sofern eingesetzt, dem Moderator, einem Rohrreaktor über den Reaktoreingang sowie über einen oder mehrere Seitenäste zugeführt. Hierbei können die Comonomerenströme unterschiedlich zusammengesetzt sein (EP-B-0 271 738).High pressure bulk polymerization is carried out in known high pressure reactors, e.g. Autoclaves or tube reactors are carried out batchwise or continuously, Tube reactors have proven particularly useful. Solvents such as aliphatic Hydrocarbons or hydrocarbon mixtures, benzene or toluene, can be contained in the reaction mixture, although the solvent-free Working method has proven particularly successful. According to a preferred embodiment of the Polymerization is the mixture of the comonomers, the initiator and, if used, the moderator, a tubular reactor via the reactor inlet and via one or more side branches fed. Here, the comonomer streams be composed differently (EP-B-0 271 738).

    Die Copolymere C) werden den A) und B) enthaltenden Mischungen in Mengen von 0,001 bis 5 Gew.-%, bevorzugt 0,005 bis 1 Gew.-% und speziell 0,01 bis 0,05 Gew.-% zugesetzt. Dabei können sie als solche oder auch gelöst bzw. dispergiert in Lösemitteln, wie z.B. aliphatischen und/oder aromatischen Kohlenwasserstoffen oder Kohlenwasserstoffgemischen wie z.B. Toluol, Xylol, Ethylbenzol, Decan, Pentadecan, Benzinfraktionen, Kerosin, Naphtha, Diesel, Heizöl, Isoparaffine oder kommerziellen Lösemittelgemischen wie Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol-, ® Isopar- und ® Shellsol D-Typen eingesetzt werden. Bevorzugt sind sie in Brennstofföl tierischen oder pflanzlichen Ursprungs auf Basis von Fettsäurealkylestern gelöst. Bevorzugt enthalten die erfindungsgemäßen Additive 1 - 80 %, speziell 10 - 70 %, insbesondere 25 - 60 % Lösemittel.The copolymers C) are the A) and B) containing mixtures in amounts of 0.001 to 5% by weight, preferably 0.005 to 1% by weight and especially 0.01 to 0.05 wt .-% added. They can be used as such or they can be solved or dispersed in solvents such as e.g. aliphatic and / or aromatic Hydrocarbons or hydrocarbon mixtures such as e.g. Toluene, xylene, Ethylbenzene, decane, pentadecane, gasoline fractions, kerosene, naphtha, diesel, Heating oil, isoparaffins or commercial solvent mixtures such as solvent naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol, ® Isopar and ® Shellsol D types be used. They are preferably animal or in fuel oil vegetable origin based on fatty acid alkyl esters. Prefers contain the additives according to the invention 1-80%, especially 10-70%, especially 25 - 60% solvent.

    Die Copolymere C) können dem zu additivierenden Öl gemäß im Stand der Technik bekannten Verfahren zugeführt werden. Wenn mehr als eine Copolymerkomponente verwendet werden soll, können solche Komponenten zusammen oder separat in beliebiger Kombination in das Öl eingebracht werden.The copolymers C) can according to the oil to be additiv in the prior art known methods are supplied. If more than one copolymer component Such components can be used together or separately in any combination can be introduced into the oil.

    Zur Herstellung von Additivpaketen für spezielle Problemlösungen können die Copolymere C) auch zusammen mit einem oder mehreren öllöslichen Co-Additiven eingesetzt werden, die bereits für sich allein die Eigenschaften von Rohölen, Schmierölen oder Brennölen verbessern. Beispiele solcher Co-Additive sind polare Verbindungen, die eine Paraffindispergierung bewirken (Paraffindispergatoren), Alkylphenol-Aldehydharze, polymere Kaltfließverbesserer sowie öllösliche Amphiphile.For the production of additive packages for special problem solutions the Copolymers C) also together with one or more oil-soluble co-additives are used that already have the properties of crude oils, Improve lubricating oils or fuel oils. Examples of such co-additives are polar Compounds that cause paraffin dispersion (paraffin dispersants), Alkylphenol-aldehyde resins, polymeric cold flow improvers and oil-soluble ones Amphiphiles.

    So haben sich Mischungen der Copolymere C) mit solchen 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 8 bis 40 Gew.-% Vinylacetat und 1 bis 40 Gew.-% des jeweiligen langkettigen Vinylesters. Weitere bevorzugte Copolymere enthalten neben Ethylen und 10 bis 40 Gew.-% Vinylestern und/oder 1 bis 40 Gew.-% langkettige Vinylester noch 0,5 bis 20 Gew.-% Olefin mit 3 bis 10 C-Atomen wie z.B. Isobutylen, Diisobutylen, Propylen, Methylpenten oder Norbornen.So have mixtures of copolymers C) with such copolymers excellent proven, the 10 to 40 wt .-% vinyl acetate and 60 to 90 wt .-% Contain ethylene. According to a further embodiment of the invention, the additives according to the invention in a mixture with ethylene / vinyl acetate / vinyl 2-ethylhexanoate terpolymers, Ethylene / vinyl acetate / neononanoic acid vinyl ester terpolymers and / or ethylene vinyl acetate / vinyl neodecanoate terpolymers to improve the flowability and lubrication of Mineral oils or mineral oil distillates. The terpolymers of vinyl 2-ethylhexanoate, Vinyl neononanoate or In addition to ethylene, vinyl neodecanoic acid contains 8 to 40% by weight of vinyl acetate and 1 to 40 wt .-% of the respective long-chain vinyl ester. More preferred In addition to ethylene and 10 to 40% by weight, copolymers contain vinyl esters and / or 1 to 40 wt .-% long-chain vinyl esters still 0.5 to 20 wt .-% olefin with 3 to 10 Carbon atoms such as Isobutylene, diisobutylene, propylene, methylpentene or Norbornene.

    Bei den Paraffindispergatoren handelt es sich vorzugsweise um niedermolekulare oder polymere, öllösliche Verbindungen mit ionischen oder polaren Gruppen wie z.B. Aminsalze, Imide und/oder Amide. Besonders bevorzugte Paraffindispergatoren enthalten Umsetzungsprodukte sekundärer Fettamine mit 8 bis 36 C-Atomen, insbesondere Dicocosfettamin, Ditalgfettamin und Distearylamin. Besonders bewährt haben sich Paraffindispergatoren, die durch Reaktion aliphatischer oder aromatischer Amine, vorzugsweise langkettiger aliphatischer Amine, mit aliphatischen oder aromatischen Mono-, Di-, Tri- oder Tetracarbonsäuren oder deren Anhydriden erhalten werden (vgl. US 4 211 534). Andere Paraffindispergatoren sind Copolymere des Maleinsäureanhydrids und α,β-ungesättigter Verbindungen, die gegebenenfalls mit primären Monoalkylaminen und/oder aliphatischen Alkoholen umgesetzt werden können (vgl. EP-A-0 154 177), die Umsetzungsprodukte von Alkenylspirobislactonen mit Aminen (vgl. EP-A-0 413 279 B1 ) und nach EP-A-0 606 055 A2 Umsetzungsprodukte von Terpolymeren auf Basis α,β-ungesättigter Dicarbonsäureanhydride, α,β-ungesättigter Verbindungen und Polyoxylalkylenether niederer ungesättigter Alkohole.The paraffin dispersants are preferably low molecular weight or polymeric, oil-soluble compounds with ionic or polar groups such as e.g. Amine salts, imides and / or amides. Particularly preferred paraffin dispersants contain reaction products of secondary fatty amines with 8 to 36 carbon atoms, especially dicocos fatty amine, ditallow fatty amine and distearyl amine. Tried and tested have become paraffin dispersants, which by reaction aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their Anhydrides can be obtained (cf. US 4 211 534). Other paraffin dispersants are Copolymers of maleic anhydride and α, β-unsaturated compounds which optionally with primary monoalkylamines and / or aliphatic alcohols can be implemented (cf. EP-A-0 154 177), the reaction products of Alkenylspirobislactones with amines (cf. EP-A-0 413 279 B1) and according to EP-A-0 606 055 A2 Reaction products of terpolymers based on α, β-unsaturated Dicarboxylic anhydrides, α, β-unsaturated compounds and polyoxylalkylene ethers lower unsaturated alcohols.

    Als Co-Additive, die eine Paraffindispergierung bewirken sind beispielsweise Ester geeignet. Diese Ester leiten sich von Polyolen mit 3 oder mehr OH-Gruppen ab, insbesondere von Glycerin, Trimethylolpropan, Pentaerythrit sowie die daraus durch Kondensation zugänglichen Oligomere mit 2 bis 10 Monomereinheiten wie z.B. Polyglycerin. Die Polyole sind im allgemeinen mit 1 bis 100 mol Alkylenoxid, bevorzugt 3 bis 70, insbesondere 5 bis 50 mol Alkylenoxid pro mol Polyol umgesetzt. Bevorzugte Alkylenoxide sind Ethylenoxid, Propylenoxid und Butylenoxid. Die Alkoxylierung erfolgt nach bekannten Verfahren.Examples of co-additives which effect paraffin dispersion are esters suitable. These esters are derived from polyols with 3 or more OH groups, in particular of glycerol, trimethylolpropane, pentaerythritol and those derived therefrom Oligomers with 2 to 10 monomer units, e.g. Polyglycerol. The polyols are generally with 1 to 100 mol of alkylene oxide, preferably 3 to 70, in particular 5 to 50, mol of alkylene oxide per mol of polyol. Preferred alkylene oxides are ethylene oxide, propylene oxide and butylene oxide. The Alkoxylation takes place according to known processes.

    Die für die Veresterung der alkoxylierten Polyole geeigneten Fettsäuren haben vorzugsweise 8 bis 50, insbesondere 12 bis 30, speziell 16 bis 26 C-Atome. Geeignete Fettsäuren sind beispielsweise Laurin-, Tridecan-, Myristin-, Pentadecan-, Palmitin-, Margarin-, Stearin-, Isostearin-, Arachin- und Behensäure, Öl- und Erucasäure, Palmitolein-, Myristolein, Ricinolsäure, sowie aus natürlichen Fetten und Ölen gewonnene Fettsäuremischungen. Bevorzugte Fettsäuremischungen enthalten mehr als 50% Fettsäuren mit mindestens 20 C-Atomen. Bevorzugt enthalten weniger als 50 % der zur Veresterung verwendeten Fettsäuren Doppelbindungen, insbesondere weniger als 10 %; speziell sind sie weitestgehend gesättigt. Unter weitestgehend gesättigt soll hier eine lodzahl der verwendeten Fettsäure von bis zu 5 g l pro 100 g Fettsäure verstanden werden. Die Veresterung kann auch ausgehend von reaktiven Derivaten der Fettsäuren wie Estern mit niederen Alkoholen (z.B. Methyl- oder Ethylester) oder Anhydriden erfolgen.Have the fatty acids suitable for the esterification of the alkoxylated polyols preferably 8 to 50, in particular 12 to 30, especially 16 to 26 carbon atoms. Suitable fatty acids are, for example, lauric, tridecane, myristic, pentadecane, Palmitic, margarine, stearic, isostearic, arachic and behenic acid, oleic and Erucic acid, palmitoleic, myristolein, ricinoleic acid, as well as from natural fats and Oil-derived fatty acid mixtures. Preferred fatty acid mixtures contain more than 50% fatty acids with at least 20 carbon atoms. Preferably contain less than 50% of the fatty acids used for esterification double bonds, especially less than 10%; in particular, they are largely saturated. Under To a large extent saturated, an iodine number of the fatty acid used should be up to 5 g l per 100 g fatty acid can be understood. The esterification can also starting from reactive derivatives of fatty acids such as esters with lower Alcohols (e.g. methyl or ethyl esters) or anhydrides.

    Zur Veresterung der alkoxylierten Polyole können auch Gemische obiger Fettsäuren mit fettlöslichen, mehrwertigen Carbonsäuren eingesetzt werden. Beispiele für geeignete mehrwertige Carbonsäuren sind Dimerfettsäuren, Alkenylbernsteinsäuren und aromatische Polycarbonsäuren sowie deren Derivate wie Anhydride und C1- bis C5-Ester. Bevorzugt sind Alkenylbernsteinsäuren und deren Derivate mit Alkylresten mit 8 bis 200, insbesondere 10 bis 50 C-Atomen. Beispiele sind Dodecenyl-, Octadecenyl- und Poly(isobutenyl)bernsteinsäureanhydrid. Bevorzugt werden die mehrwertigen Carbonsäuren dabei zu untergeordneten Anteilen von bis zu 30 Mol-%, bevorzugt 1 bis 20 Mol-%, insbesondere 2 bis 10 Mol-% eingesetzt.Mixtures of the above fatty acids with fat-soluble, polyvalent carboxylic acids can also be used to esterify the alkoxylated polyols. Examples of suitable polyvalent carboxylic acids are dimer fatty acids, alkenyl succinic acids and aromatic polycarboxylic acids and their derivatives such as anhydrides and C 1 to C 5 esters. Alkenylsuccinic acids and their derivatives with alkyl radicals having 8 to 200, in particular 10 to 50, carbon atoms are preferred. Examples are dodecenyl, octadecenyl and poly (isobutenyl) succinic anhydride. The polyvalent carboxylic acids are preferably used in minor proportions of up to 30 mol%, preferably 1 to 20 mol%, in particular 2 to 10 mol%.

    Ester und Fettsäure werden für die Veresterung bezogen auf den Gehalt an Hydroxylgruppen einerseits und Carboxylgruppen andererseits im Verhältnis 1,5:1 bis 1:1,5 eingesetzt, bevorzugt 1,1:1 bis 1:1,1, insbesondere equimolar. Die paraffindispergierende Wirkung ist besonders ausgeprägt, wenn mit einem Säureüberschuss von bis zu 20 Mol-%, speziell bis zu 10 Mol-%, insbesondere bis zu 5 Mol-% gearbeitet wird.Ester and fatty acid are based on the content of the esterification Hydroxyl groups on the one hand and carboxyl groups on the other hand in a ratio of 1.5: 1 used up to 1: 1.5, preferably 1.1: 1 to 1: 1.1, in particular equimolar. The Paraffin-dispersing effect is particularly pronounced when using a Acid excess of up to 20 mol%, especially up to 10 mol%, especially up to 5 mol% is worked.

    Die Veresterung wird nach üblichen Verfahren durchgeführt. Besonders bewährt hat sich die Umsetzung von Polyolalkoxylat mit Fettsäure, gegebenenfalls in Gegenwart von Katalysatoren wie z.B. para-Toluolsulfonsäure, C2- bis C50-Alkylbenzolsulfonsäuren, Methansulfonsäure oder sauren Ionenaustauschern. Die Abtrennung des Reaktionswassers kann destillativ durch Direktkondensation oder bevorzugt mittels azeotroper Destillation in Anwesenheit organischer Lösemittel, insbesondere aromatischer Lösemittel wie Toluol, Xylol oder auch höher siedender Gemische wie ® Shellsol A, Shellsol B, Shellsol AB oder Solvent Naphtha erfolgen. Die Veresterung erfolgt bevorzugt vollständig, d.h. für die Veresterung werden 1,0 bis 1,5 mol Fettsäure pro mol Hydroxylgruppen eingesetzt. Die Säurezahl der Ester liegt im allgemeinen unter 15 mg KOH/g, bevorzugt unter 10 mg KOH/g speziell unter 5 mg KOH/g.The esterification is carried out using customary methods. The reaction of polyol alkoxylate with fatty acid has proven particularly useful, if appropriate in the presence of catalysts such as, for example, para-toluenesulfonic acid, C 2 -C 50 -alkylbenzenesulfonic acids, methanesulfonic acid or acidic ion exchangers. The water of reaction can be separated off by direct condensation or preferably by azeotropic distillation in the presence of organic solvents, in particular aromatic solvents such as toluene, xylene or else higher-boiling mixtures such as ® Shellsol A, Shellsol B, Shellsol AB or Solvent Naphtha. The esterification is preferably carried out completely, ie 1.0 to 1.5 mol of fatty acid per mol of hydroxyl groups are used for the esterification. The acid number of the esters is generally below 15 mg KOH / g, preferably below 10 mg KOH / g, especially below 5 mg KOH / g.

    Besonders bevorzugte Paraffindispergatoren werden 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 Particularly preferred paraffin dispersants are prepared by reacting compounds containing an acyl group with an amine. This amine is a compound of the formula NR 6 R 7 R 8 , in which R 6 , R 7 and R 8 can be the same or different, and at least one of these groups for C 8 -C 36 alkyl, C 6 - C 36 cycloalkyl, C 8 -C 36 alkenyl, in particular C 12 -C 24 alkyl, C 12 -C 24 alkenyl or cyclohexyl, and the remaining groups are either hydrogen, C 1 -C 36 alkyl, C 2 -C 36 alkenyl, cyclohexyl, or a group of the formulas - (AO) x -E or - (CH 2 ) n -NYZ, where A is an ethylene or propylene group, x is a number from 1 to 50, E = H, C 1 -C 30 alkyl, C 5 -C 12 cycloalkyl or C 6 -C 30 aryl, and n is 2, 3 or 4, and Y and Z independently of one another are H, C 1 -C 30 - Alkyl or - (AO) x mean. Acyl group is understood here to mean a functional group of the following formula: > C = O

    Die Paraffindispergatoren können den Copolymeren C) beigemischt oder separat dem zu additivierenden Mitteldestillat zugesetzt werden.The paraffin dispersants can be added to the copolymers C) or separately be added to the middle distillate to be added.

    Alkylphenol-Aldehyd-Harze 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 Strukturelemente 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. Das Alkylphenol-Aldehyd-Harz kann auch bis zu 20 Mol-% Phenoleinheiten und/oder Alkylphenole mit kurzen Alkylketten wie z. B. Butylphenol enthalten. Für das Alkylphenol-Aldehydharz können gleiche oder verschiedene Alkylphenole verwendet werden.Alkylphenol-aldehyde resins are known in principle and are described, for example, in the Römpp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, Volume 4, pp. 3351ff. described. The alkyl or alkenyl radicals of the alkylphenol have 6-24, preferably 8-22, in particular 9-18, carbon atoms. They can be linear or preferably branched, the branching being able to contain secondary as well as tertiary structural elements. It is preferably 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 alkylphenol-aldehyde resin can also contain up to 20 mol% phenol units and / or alkylphenols with short alkyl chains such as e.g. B. contain butylphenol. The same or different alkylphenols can be used for the alkylphenol-aldehyde resin.

    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 can carry other functional groups. It is preferably a aliphatic aldehyde, particularly 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- 10,000, in particular 400 - 5000 g / mol. This preferably corresponds to one Degree of condensation n from 3 to 40, in particular from 4 to 20. Prerequisite here 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

    Figure 00140001
    sind, worin RA für C6-C24-Alkyl oder -Alkenyl, RB für OH oder O-(A-O)x-H mit A = C2-C4-Alkylen und x = 1 bis 50, und n für eine Zahl von 2 bis 50, insbesondere 5 bis 40 steht.In a preferred embodiment of the invention, these alkylphenol-formaldehyde resins are those which contain oligomers or polymers with a repetitive structural unit of the formula
    Figure 00140001
    are in which R A for C 6 -C 24 alkyl or alkenyl, R B for OH or O- (AO) x -H with A = C 2 -C 4 alkylene and x = 1 to 50, and n for is a number from 2 to 50, in particular 5 to 40.

    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 alkylphenol-aldehyde resins are prepared in a known manner by basic catalysis, whereby condensation products of the resol type arise, or by acidic catalysis, producing condensation products of the novolak type.

    Die nach beiden Arten gewonnenen Kondensate sind für die erfindungsgemäßen Zusammensetzungen geeignet. Bevorzugt ist die Kondensation in Gegenwart von sauren Katalysatoren.The condensates obtained in both ways are for the inventive ones Suitable compositions. The condensation 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.To prepare the alkylphenol-aldehyde resins, an alkylphenol with 6 - 24, preferably 8-22, in particular 9-18, carbon atoms per alkyl group, or mixtures thereof and at least one aldehyde reacted with one another, with per mol Alkylphenol compound about 0.5 - 2 mol, preferably 0.7 - 1.3 mol and in particular equimolar amounts of aldehyde can be 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, tripropetraphenylphenol, tripropenylphenol (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 can be one or carry several alkyl radicals. They are preferably at most 5 mol%, in particular at most 20 mol% and especially at most 40 mol% with more than an alkyl group. Preferably carry at most 40 mol%, in particular not more than 20 mol% of the alkylphenols used in the ortho position an alkyl radical. Specifically, the alkylphenols ortho to the hydroxyl group are not tertiary Alkyl groups substituted.

    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 other functional groups wear like -COOH. Particularly suitable aldehydes are formaldehyde, acetaldehyde, Butyraldehyde, glutardialdehyde and glyoxalic acid, formaldehyde is preferred. The Formaldehyde can be in the form of paraformaldehyde or in the form of a preferred 20 - 40 wt .-% aqueous formalin solution can be used. It can too appropriate amounts of trioxane can 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, und 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, ® ISOPARund ® Shellsol D-Typen. The reaction of alkylphenol and aldehyde usually takes place in the presence of alkaline catalysts, for example alkali 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 Halogenacetic acids, and in the presence of an azeotrope with water organic solvent, for example toluene, xylene, higher aromatics or Mixtures of these. The reaction mixture is at a temperature of 90 to 200 ° C, preferably 100 - 160 ° C heated, the water of reaction formed is removed by azeotropic distillation during the reaction. Solvent, that cannot release protons under the conditions of condensation 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, e.g. Petroleum fractions, Kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or solvents such as ® Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol, ® ISOPARund ® Shellsol D types.

    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; N.A. Platé and V.P. Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8,117 ff). Beispiele für geeignete Kammpolymere sind z.B. Fumarat/Vinylacetat-Copolymere (vgl. EP 0 153 176 A1 ), Copolymere aus einem C6-C24-α-Olefin und einem N-C6-C22-Alkylmaleinsäureimid (vgl. EP-A-0 320 766), ferner veresterte Olefin/Maleinsäureanhydrid-Copolymere, Polymere und Copolymere von α-Olefinen und veresterte Copolymere von Styrol und Maleinsäureanhydrid.Finally, in a further embodiment of the invention, the additives according to the invention are used together with comb polymers. This is understood to mean polymers in which hydrocarbon radicals having at least 8, in particular at least 10, carbon atoms are bonded to a polymer backbone. They are preferably homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms. In the case of copolymers, 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). Examples of suitable comb polymers are, for example, fumarate / vinyl acetate copolymers (cf. EP 0 153 176 A1), copolymers of a C 6 -C 24 -α-olefin and an NC 6 -C 22 -alkylmaleimide (cf. EP-A-0 320 766), also esterified olefin / maleic anhydride copolymers, polymers and copolymers of α-olefins and esterified copolymers of styrene and maleic anhydride.

    Kammpolymere können beispielsweise durch die Formel

    Figure 00160001
    beschrieben werden. Darin bedeuten

    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.
    Comb polymers can, for example, by the formula
    Figure 00160001
    to be discribed. Mean in it
    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 with 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 Copolymere C) mit polymeren Kaltfließverbesserern, Paraffindispergatoren, Kammpolymeren bzw. Harzen beträgt jeweils 1:10 bis 20:1, vorzugsweise 1:1 bis 10:1.The mixing ratio (in parts by weight) of the copolymers C) with polymers Cold flow improvers, paraffin dispersants, comb polymers or resins each 1:10 to 20: 1, preferably 1: 1 to 10: 1.

    Die Copolymere C) können allein oder auch zusammen mit anderen Additiven verwendet werden, z. B. mit anderen Stockpunkterniedrigern oder Entwachsungshilfsmitteln, mit Korrosionsinhibitoren, Antioxidantien, Lubricity-Additiven Schlamminhibitoren, Dehazern und Zusätzen zur Erniedrigung des Cloud-Points.The copolymers C) can be used alone or together with other additives are used, e.g. B. with other pour point depressors or Dewaxing agents, with corrosion inhibitors, antioxidants, lubricity additives Mud inhibitors, dehazers and additives to lower the cloud point.

    BeispieleExamples Charakterisierung der Testöle:Characterization of the test oils:

    Die Bestimmung des CFPP-Werts erfolgt gemäß EN 116, die der Siedekenndaten gemäß ASTM D-86 und die Bestimmung des Cloud Points gemäß ISO 3015. Analyse des verwendeten Biodiesel (im Folgenden auch "RME" genannt) Kettenlängen Anteil Vorlauf 0,12 C12 0,01 C13 + iso C14 0,01 C14: 0 0,05 C14:1 0,0 C15 + iso-C16 0,05 C16: 0 4,64 C16: 1/2/3 0,28 C17 + iSO-C18 0,11 C18: 0 0,37 C18: 1 trans + cis 61,72 C18: 2 trans + cis 19,16 C18: 3 9,01 C19 + iso-C20 0,29 C20: 0 0,70 C20:1/2/3 1,57 C21 + iso C22 0,26 C22: 0 0,36 C22: 1/2/3 0,39 C24 0 0,15 C23 + iSO C24 0,16 C24: 1/2/3 0,18 Nachlauf 0,41 100,00 Jod-Zahl errechnet aus GC   116 Charakterisierung der verwendeten Mitteldestillate F1 F2 F3 F4 Schwefelgehalt, ppm 7,9 4,9 32,0 900 Dichte, g/cm3 0,8436 0,8306 0,8348 0,8487 Siedebeginn, °C 209,9 143,9 209,1 203,7 Siedeende, °C 334,6 363,2 347,8 365,6 Siedebereich (90-20), °C 63,5 87,6 83,8 94,9 Aromatengehalt, Gew.-% 25,7 16,5 20,5 29,9 The CFPP value is determined in accordance with EN 116, the boiling data in accordance with ASTM D-86 and the cloud point in accordance with ISO 3015. Analysis of the biodiesel used (hereinafter also referred to as "RME") chain lengths proportion of leader 0.12 C 12 0.01 C 13 + iso C 14 0.01 C 14 : 0 0.05 C 14 : 1 0.0 C 15 + iso-C 16 0.05 C 16 : 0 4.64 C 16 : 1/2/3 0.28 C 17 + iSO-C 18 0.11 C 18 : 0 0.37 C18: 1 trans + cis 61.72 C 18 : 2 trans + cis 19.16 C 18 : 3 9.01 C 19 + iso-C 20 0.29 C 20 : 0 0.70 C 20 : 1/2/3 1.57 C 21 + iso C 22 0.26 C 22 : 0 0.36 C 22 : 1/2/3 0.39 C 24 0 0.15 C 23 + iSO C 24 0.16 C 24 : 1/2/3 0.18 trailing 0.41 100.00 Iodine number calculated from GC 116 Characterization of the middle distillates used F1 F2 F3 F4 Sulfur content, ppm 7.9 4.9 32.0 900 Density, g / cm 3 .8436 0.8306 .8348 .8487 Initial boiling point, ° C 209.9 143.9 209.1 203.7 End of boiling, ° C 334.6 363.2 347.8 365.6 Boiling range (90-20), ° C 63.5 87.6 83.8 94.9 Aromatics content,% by weight 25.7 16.5 20.5 29.9

    Charakterisierung der CopolymereCharacterization of the copolymers

    Folgende Copolymere wurden verwendet: P1 E/VA 4-Hydroxybutylvinylether (4-HBVE)-Terpolymer (3577) P2 E/VeoVa-10/Hydroxypropylacrylat (HPA)-Terpolymer (3365) P3 E/VA/Hydroxybutylvinylether (HBVE)- Terpolymer (3659) P4 E/VA/Hydroxybutylvinylether (HBVE)- Terpolymer (3636) P5 ENA/Hydroxyethylvinylether (HEVE)- Terpolymer (3691) P6 E/VA/Hydroxypropylmethacrylat-Terpolymer (3373) P7 E/VA/2-Metyl-3-buten-2-ol-Terpolymer (3503) P8 E/VA-Copolymer (3905) P9 E/VA/VeoVa10-Terpolymer (4134) P10 E/VA/VeoVa10-Terpolymer (4302) VA = Vinylacetat VeoVa 10 = Neodecansäurevinylester The following copolymers were used: P1 E / VA 4-hydroxybutyl vinyl ether (4-HBVE) terpolymer (3577) P2 E / VeoVa-10 / hydroxypropyl acrylate (HPA) terpolymer (3365) P3 E / VA / Hydroxybutyl vinyl ether (HBVE) terpolymer (3659) P4 E / VA / Hydroxybutyl vinyl ether (HBVE) terpolymer (3636) P5 ENA / hydroxyethyl vinyl ether (HEVE) terpolymer (3691) P6 E / VA / hydroxypropyl methacrylate terpolymer (3373) P7 E / VA / 2-metyl-3-buten-2-ol terpolymer (3503) P8 E / VA copolymer (3905) P9 E / VA / VeoVa10 terpolymer (4134) P10 E / VA / VeoVa10 terpolymer (4302) VA = vinyl acetate VeoVa 10 = neodecanoic acid vinyl ester

    Die OH-Zahlen werden für die Zwecke vorliegender Erfindung gemäß DIN 53240 durch Umsetzung mit einer definierten Menge überschüssigem Acetanhydrid und anschließende Titration der gebildeten Essigsäure bestimmt. Charakterisierung der Copolymere Polymer Vinylacetat Gehalte in Gew.-% an V140, mPa·s OH-Zahl VeoVa 10 Hydroxy-Comonomer P1 29,1 - 4,2 53 20 P2 - 23,6 34,8 135 121 P3 22,2 - 13,7 88 66 P4 24,1 - 7,3 99 35 P5 21 - 11,5 96 71 P6 11,3 - 36,6 169 112 P7 26,4 - 0,77 131 5 P8 32 - - 125 0 P9 31 8 - 110 0 P10 31,5 4,1 - 170 0 For the purposes of the present invention, the OH numbers are determined in accordance with DIN 53240 by reaction with a defined amount of excess acetic anhydride and subsequent titration of the acetic acid formed. Characterization of the copolymers polymer vinyl acetate Content in% by weight V 140 , mPas OH number VeoVa 10 Hydroxy comonomer P1 29.1 - 4.2 53 20 P2 - 23.6 34.8 135 121 P3 22.2 - 13.7 88 66 P4 24.1 - 7.3 99 35 P5 21 - 11.5 96 71 P6 11.3 - 36.6 169 112 P7 26.4 - 0.77 131 5 P8 32 - - 125 0 P9 31 8th - 110 0 P10 31.5 4.1 - 170 0

    Wirksamkeit als DemulgatorEfficacy as a demulsifier

    Die Prüfung der Emulgierneigung von Additiven erfolgt gemäß ASTM D 1094-85. 80 ml eines Dieselkraftstoffs werden in einem 100 ml Standzylinder mit 250 ppm des zu testenden Additivs versetzt und 15 Minuten bei 60°C temperiert und dann geschüttelt. Nach Abkühlen auf Raumtemperatur werden 2 ml Pufferlösung hinzugegeben und 2 Minuten geschüttelt. Nach 5 Minuten wird die Probe optisch nach folgenden Kriterien beurteilt: Bewertung der Trennschicht Bewertung der Phasentrennung 1 Klar und sauber 1 Komplette Abwesenheit aller Emulsionen und/oder Abscheidungen in beiden Phasen oder oben auf der Öl-Phase. 1b kleine, klare Blasen, die schätzungsweise nicht mehr als 50 % der Trennschicht bedecken. Keine Schlieren, keine Filmbildung oder sonstige Benetzung an der Trennschicht. 2 Wie (1), aber zusätzlich kleine Luftbläschen oder kleine Wassertröpfchen in der Öl-Phase. 2 Schlieren, Filmbildung oder sonstige Benetzung an der Trennschicht 3 Emulsionen und/oder Niederschläge in beiden Phasen oder oben auf der Öl-Phase, und/oder Tropfen in der Wasser-Phase oder an der Wandung anhaftend (ausgenommen die Wandung über der Öl-Phase). In Klammern gesetzt: Menge der Wasserphase 3 Schmaler Saum oder leichte Schaumbildung, oder beides 4 Dichter Saum oder starke Schaumbildung, oder beides Wirksamkeit von Copolymeren als Demulgator in einer Mischung aus 95 Gew.-% F2 und 5 Gew.-% Biodiesel Bsp. Nr. Copolymer optische Beurteilung Dosierung Wirkstoff ppm Trennschicht Phasentrennung Öl-Phase Wasser-Phase 1 (V) ohne 3-4 14 ml 3 trübe klar - 2 (V) P8 3 18 ml 3 trübe klar 250 3 (V) P9 4 16 ml 3 trübe klar 250 4 (V) P10 3 18 ml 3 trübe klar 250 5 P1 1b 20 ml 3 trübe klar 250 6 P2 1 20 ml 3 trübe klar 250 7 P3 1 20 ml 3 trübe klar 250 8 P6 1 20 ml 3 trübe klar 250 9 P7 1 20 ml 3 trübe klar 250 10 P3 1 20 ml 3 trübe klar 250 11 P3 1 20 ml 3 trübe klar 100 12 P3 1 20 ml 3 trübe klar 50 13 P3 1 20 ml 3 trübe klar 25 14 P3 1 20 ml 3 trübe klar 10 15 P6 1 20 ml 3 trübe klar 250 16 P6 1b 20 ml 3 trübe klar 100 17 P6 1b 20 ml 3 trübe klar 50 18 P6 1b 20 ml 3 trübe klar 25 19 P6 2 20 ml 3 trübe klar 10 20 P2 1 20 ml 3 trübe klar 250 21 P2 1b 20 ml 3 trübe klar 50 22 P7 1b 20 ml 3 trübe klar 250 23 P7 1b 20 ml 3 trübe klar 50

    Figure 00220001
    The tendency of additives to emulsify is tested in accordance with ASTM D 1094-85. 80 ml of a diesel fuel are mixed in a 100 ml standing cylinder with 250 ppm of the additive to be tested and tempered for 15 minutes at 60 ° C. and then shaken. After cooling to room temperature, 2 ml of buffer solution are added and shaken for 2 minutes. After 5 minutes, the sample is assessed optically according to the following criteria: Evaluation of the interface Assessment of phase separation 1 Clear and clean 1 Complete absence of all emulsions and / or deposits in both phases or on top of the oil phase. 1b small, clear bubbles that are estimated to cover no more than 50% of the interface. No streaks, no film formation or other wetting at the interface. 2 Like (1), but with small air bubbles or small water droplets in the oil phase. 2 Streaks, film formation or other wetting at the interface 3 Emulsions and / or precipitates in both phases or on top of the oil phase, and / or drops in the water phase or adhering to the wall (except the wall above the oil phase). In brackets: amount of water phase 3 Narrow hem or slight foaming, or both 4 Thick hem or heavy foaming, or both Effectiveness of copolymers as a demulsifier in a mixture of 95% by weight of F2 and 5% by weight of biodiesel Example No. copolymer optical assessment Dosage active ingredient ppm Interface phase separation Oil phase Water phase 1 (V) without 3-4 14 ml 3 cloudy clear - 2 (V) P8 3 18 ml 3 cloudy clear 250 3 (V) P9 4 16 ml 3 cloudy clear 250 4 (V) P10 3 18 ml 3 cloudy clear 250 5 P1 1b 20 ml 3 cloudy clear 250 6 P2 1 20 ml 3 cloudy clear 250 7 P3 1 20 ml 3 cloudy clear 250 8th P6 1 20 ml 3 cloudy clear 250 9 P7 1 20 ml 3 cloudy clear 250 10 P3 1 20 ml 3 cloudy clear 250 11 P3 1 20 ml 3 cloudy clear 100 12 P3 1 20 ml 3 cloudy clear 50 13 P3 1 20 ml 3 cloudy clear 25 14 P3 1 20 ml 3 cloudy clear 10 15 P6 1 20 ml 3 cloudy clear 250 16 P6 1b 20 ml 3 cloudy clear 100 17 P6 1b 20 ml 3 cloudy clear 50 18 P6 1b 20 ml 3 cloudy clear 25 19 P6 2 20 ml 3 cloudy clear 10 20 P2 1 20 ml 3 cloudy clear 250 21 P2 1b 20 ml 3 cloudy clear 50 22 P7 1b 20 ml 3 cloudy clear 250 23 P7 1b 20 ml 3 cloudy clear 50
    Figure 00220001

    Einfluss des hydroxylgruppenhaltigen Copolymers auf die Wirkung von KaltfließeigenschaftenInfluence of the copolymer containing hydroxyl groups on the effect of Cold flow properties

    Es wurden ein Mitteldestillat mit einem CFPP von -7°C und dessen Mischung mit 5 % des beschriebenen Biokraftstoffs (CFPP der Mischung ebenfalls -7°C) mit Kaltfließverbesserer und hydroxylgruppenhaltigen Copolymeren untersucht Beeinflussung der Kaltfließeigenschaften durch hydroxylgruppenhaltige Copolymere Beispiel Brennstofföl Copolymere 300 ppm P8 300 ppm P9 300 ppm P8 +10ppmP4 300 ppm P9 + 10 ppm P4 33 (V) Mitteldestillat - 16 - 15 - 17 - 17 34 Mitteldestillat + Biokraftstoff - 17 - 16 - 17 - 16 A middle distillate with a CFPP of -7 ° C. and its mixture with 5% of the described biofuel (CFPP of the mixture also -7 ° C.) with cold flow improvers and copolymers containing hydroxyl groups were investigated Influencing the cold flow properties by copolymers containing hydroxyl groups example fuel oil copolymers 300 ppm P8 300 ppm P9 300 ppm P8 + 10ppmP4 300 ppm P9 + 10 ppm P4 33 (V) middle distillate - 16th - 15th - 17th - 17th 34 Middle distillate + biofuel - 17th - 16th - 17th - 16th

    Einfluss der hydroxylgruppenhaltigen Copolymeren auf das Emulgierverhalten der Diesel/Biodiesel-Mischung in Anwesenheit von FließverbesserernInfluence of the copolymers containing hydroxyl groups on the emulsifying behavior of the Diesel / biodiesel mixture in the presence of flow improvers

    Das Emulgierverhalten des Öls F4 mit Zusatz von 5 Gew.-% Biokraftstoff wurde durch die Zugabe von 10 ppm P4 deutlich geändert und zeigte kaum Emulgierneigung trotz Anwesenheit von 300 ppm eines Fließverbesserers. Einfluss von Kaltfließverbesserern auf die Emulgierneigung mit und ohne Copolymer C) Bsp. Öl optische Beurteilung Dosierung Wirkstoff ppm Trennschicht Phasentrennung Öl-Phase Wasser-Phase 35 (V) F4 1b 20 ml 3 trüb klar - 36 (V) F4+RME 3 18 ml 3 trüb klar - 37 F4+RME 1* 20 ml 3 trüb klar 10 38 (V) F4+RME 3 18 ml 3 trüb klar 250 39 F4+RME 1b 20 ml 3 trüb klar 10 40 (V) F4+RME 3 18 ml 3 trüb klar 250 41 F4+RME 1b 20 ml 3 trüb klar 10 The emulsification behavior of the oil F4 with the addition of 5% by weight of biofuel was significantly changed by the addition of 10 ppm P4 and showed little tendency to emulsify despite the presence of 300 ppm of a flow improver. Influence of cold flow improvers on the tendency to emulsify with and without copolymer C) E.g. oil optical assessment Dosage active ingredient ppm Interface phase separation Oil phase Water phase 35 (V) F4 1b 20 ml 3 cloudy clear - 36 (V) F4 + RME 3 18 ml 3 cloudy clear - 37 F4 + RME 1* 20 ml 3 cloudy clear 10 38 (V) F4 + RME 3 18 ml 3 cloudy clear 250 39 F4 + RME 1b 20 ml 3 cloudy clear 10 40 (V) F4 + RME 3 18 ml 3 cloudy clear 250 41 F4 + RME 1b 20 ml 3 cloudy clear 10

    Claims (9)

    Brennstofföl, enthaltend einen größeren Anteil einer Mischung aus A) einem Mitteldestillat-Brennstofföl, und B) einem Biobrennstofföl,
    sowie einem kleineren Anteil     C) eines öllöslichen Copolymers aus Ethylen und mindestens 0,2 bis 35 Mol-% einer weiteren olefinisch ungesättigten Verbindung, die mindestens eine freie Hydroxylgruppe enthält, und das eine OH-Zahl von 10 bis 300 mg KOH/g aufweist.     Fuel oil containing a large proportion of a mixture A) a middle distillate fuel oil, and B) a biofuel oil,
    as well as a smaller proportion     C) an oil-soluble copolymer of ethylene and at least 0.2 to 35 mol% of a further olefinically unsaturated compound which contains at least one free hydroxyl group and which has an OH number of 10 to 300 mg KOH / g.     Brennstoffe) nach Anspruch 1, worin das Mischungsverhältnis A) : B) bei 99:1 bis 1:99 liegt.Fuels) according to claim 1, wherein the mixing ratio A): B) at 99: 1 to 1:99. Brennstofföl nach Anspruch 1 und/oder 2, worin die OH-Zahl des Copolymers C) zwischen 20 und 250 liegt.A fuel oil according to claim 1 and / or 2, wherein the OH number of the copolymer C) is between 20 and 250. Brennstofföl nach einem oder mehreren der Ansprüche 1 bis 3, worin das Copolymer ein mittleres Molekulargewicht von 700 bis 10.000 g/mol aufweist.Fuel oil according to one or more of claims 1 to 3, wherein the Copolymer has an average molecular weight of 700 to 10,000 g / mol. Brennstofföl nach einem oder mehreren der Ansprüche 1 bis 4, worin der Anteil des hydroxyfunktionellen Comonomeren am Copolymeren zwischen 0,5 und 15 Mol-% liegt.Fuel oil according to one or more of claims 1 to 4, wherein the Proportion of the hydroxy-functional comonomer in the copolymer between 0.5 and 15 mol% is. Brennstofföl nach einem oder mehreren der Ansprüche 1 bis 5, worin das Copolymer C) neben Ethylen und mindestens einem hydroxyfunktionellen Comonomer noch mindestens ein weiteres Comonomer enthält, welches aus der Gruppe bestehend aus Vinylestern, Acrylsäure, Methacrylsäure, Acrylester, Methacrylester, Vinylether oder Olefinen ausgewählt ist.Fuel oil according to one or more of claims 1 to 5, wherein the Copolymer C) in addition to ethylene and at least one hydroxy-functional one Comonomer contains at least one other comonomer, which from the Group consisting of vinyl esters, acrylic acid, methacrylic acid, acrylic esters, Methacrylic ester, vinyl ether or olefins is selected. Brennstofföl nach einem oder mehreren der Ansprüche 1 bis 6, worin der Gehalt der aus A) und B) bestehenden Mischung an C) von 0,001 bis 5 Gew.-% beträgt. Fuel oil according to one or more of claims 1 to 6, wherein the C) content of the mixture consisting of A) and B) from 0.001 to 5% by weight is. Brennstofföle nach einem oder mehreren der Ansprüche 1 bis 7, welche zusätzlich zu den Bestandteilen A), B) und C) noch mindestens ein Alkylphenol-Formaldehydharz der Formel
    Figure 00260001
    enthalten, worin RA für C6-C24-Alkyl oder -Alkenyl, RB für OH oder O-(A-O)x-H mit A = C2-C4-Alkylen und x = 1 bis 50, und n für eine Zahl von 2 bis 50, insbesondere 5 bis 40 steht.    Fuel oils according to one or more of claims 1 to 7, which, in addition to components A), B) and C), also contain at least one alkylphenol-formaldehyde resin of the formula
    Figure 00260001
    contain, wherein R A for C 6 -C 24 alkyl or alkenyl, R B for OH or O- (AO) x -H with A = C 2 -C 4 alkylene and x = 1 to 50, and n for is a number from 2 to 50, in particular 5 to 40.         Verwendung eines öllöslichen Copolymers aus Ethylen und mindestens 0,2 bis 35 Mol-% einer weiteren olefinisch ungesättigten Verbindung, die mindestens eine freie Hydroxylgruppe enthält, und das eine OH-Zahl von 10 bis 300 mg KOH/g aufweist, als Demulgator in Mischungen aus Mitteldestillat-Brennstoffölen mit Biobrennstoffölen.Use of an oil-soluble copolymer of ethylene and at least 0.2 up to 35 mol% of a further olefinically unsaturated compound which at least contains a free hydroxyl group, and that has an OH number of 10 to 300 mg KOH / g has as a demulsifier in mixtures of middle distillate fuel oils Biofuel oils.
    EP04008585A 2003-04-28 2004-04-08 Demulsifiers for blends of middle distillates and fuel oils of animal or vegetable origin Withdrawn EP1473353A1 (en)

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