Classifications

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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
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  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/04—Mixtures of base-materials and additives
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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/04—Mixtures of base-materials and additives
  • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
  • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
  • C10L1/1835—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom having at least two hydroxy substituted non condensed benzene rings
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
  • C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
  • C10L1/1981—Condensation polymers of aldehydes or ketones
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/224—Amides; Imides carboxylic acid amides, imides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
  • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
  • C10M2205/022—Ethene
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/013—Iodine value
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/067—Unsaturated Compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/40—Low content or no content compositions
  • C10N2030/43—Sulfur free or low sulfur content compositions

Definitions

• the present invention relates to an additive, its use as a cold flow improver for vegetable or animal fuel oils and correspondingly fueled fuel oils.
• Oils obtained from animal or vegetable material are mainly metabolites comprising triglycerides of monocarboxylic acids, e.g. As acids having 10 to 25 carbon atoms, and the formula in which R is an aliphatic radical of 10 to 25 carbon atoms, which may be saturated or unsaturated.
• oils contain glycerides of a number of acids whose Number and variety varies with the source of the oil, and they may additionally contain phosphoglycerides.
• Such oils can be obtained by methods known in the art.
• EP-B-0 665 873 discloses a fuel oil composition
• a fuel oil composition comprising a biofuel, a petroleum-based fuel oil and an additive which comprises (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 substantially linear alkyl group having from 10 to 30 carbon atoms is bonded to a non-polymeric organic radical to provide at least one linear chain of atoms which includes the carbon atoms of the alkyl groups and one or more non-terminal oxygen atoms, or (e) one or more of the components ( a), (b), (c) and (d).
• EP-B-0 153 176 discloses the use of polymers based on unsaturated C 4 -C 8 dicarboxylic acid di-alkyl esters having average alkyl chain lengths of 12 to 14 as cold flow improvers for certain petroleum distillate fuel oils.
• Particularly suitable comonomers are vinyl esters, but also ⁇ -olefins.
• EP-B-0 153 177 discloses an additive concentrate comprising a combination of I) a copolymer having at least 25% by weight of an n-alkyl ester of a monoethylenically unsaturated C 4 -C 8 mono- or dicarboxylic acid, wherein the average number of carbon atoms in the n-alkyl radicals is 12- 14 and containing another unsaturated ester or olefin with II) another low temperature flow improver for distillate fuel oils.
• EP-A-0 282 342 teaches a fuel composition comprising a major portion of distillate fuel oil and a minor proportion of copolymer of (1) an alpha-olefin having from 2 to 17 carbon atoms per molecule or a substituted aromatic olefin having from 8 to 40 carbon atoms per molecule and (2) an ester; Ester is a mono- or di-alkyl fumarate, itaconate, citraconate, mesaconate, trans or cis glutanate in which the alkyl group has from 8 to 23 carbon atoms.
• Q has values from 24 to 26.
• the chain length distribution of the alcohols used is crucial.
• the degree of esterification is not taken into account.
• the molar ratio of olefins and ethylenically unsaturated Dicarboxylic acid esters are not included in the calculation of Q, since copolymerization of these monomers results in copolymers with approximately equal molar proportions of monomers.
• Suitable ethylene copolymers A) are those which contain from 8 to 21 mol% of vinyl and / or (meth) acrylic esters and 79 to 92% by weight of ethylene. Particularly preferred are ethylene copolymers with 10 to 18 mol% and especially 12 to 16 mol% of at least one vinyl ester. Suitable vinyl esters are derived from fatty acids with linear or branched alkyl groups having 1 to 30 carbon atoms.
• vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl heptanoate and vinyl octanoate and branched fatty acid based esters of vinyl alcohol such as vinyl isobutyrate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl neononanoate, vinyl neodecanoate and vinyl neoundecanoate.
• esters of acrylic and methacrylic acid having 1 to 20 C atoms in the alkyl radical such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n- and isobutyl (meth) acrylate, hexyl , Octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl (meth) acrylate and mixtures of two, three, four or more of these comonomers.
• Particularly preferred terpolymers of 2-ethylhexanoic acid vinyl ester, vinyl neononanoate or vinyl neodecanoate contain, in addition to ethylene, preferably 3.5 to 20 mol%, in particular 8 to 15 mol% vinyl acetate and 0.1 to 12 mol%, in particular 0.2 to 5 mol% of the respective long-chain vinyl ester, wherein the total comonomer content is between 8 and 21 mol%, preferably between 12 and 18 mol%.
• copolymers contain, in addition to ethylene and from 8 to 18 mol% of vinyl esters, from 0.5 to 10 mol% of olefins such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene and / or norbornene.
• olefins such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene and / or norbornene.
• the copolymers A preferably have molecular weights which correspond to melt viscosities at 140 ° C. of from 20 to 10,000 mPas, in particular from 30 to 5,000 mPas and especially from 50 to 1,000 mPas.
• the determined by 1 H NMR spectroscopy degrees of branching are preferably between 2 and 9 CH 3/100 CH 2 groups, in particular between 2.5 and 6 CH 3/100 CH 2 groups, which do not stem from the comonomers.
• the copolymers (A) can be prepared by the usual copolymerization methods such as suspension polymerization, solvent polymerization, gas phase polymerization or high-pressure bulk polymerization.
• the high-pressure mass polymerization is preferably carried out at pressures of from 50 to 400 MPa, preferably from 100 to 300 MPa, and at temperatures of from 100 to 300 ° C., preferably from 150 to 220 ° C.
• the polymerization takes place in a multi-zone reactor, wherein the temperature difference between the peroxide dosages along the tubular reactor is kept as low as possible, i. ⁇ 50 ° C, preferably ⁇ 30 ° C, in particular ⁇ 15 ° C.
• the temperature maxima in the individual reaction zones preferably differ by less than 30 ° C., more preferably by less than 20 ° C. and especially by less than 10 ° C.
• the reaction of the monomers is initiated by free radical initiators (free radical initiators).
• This class of substances includes, for example, oxygen, hydroperoxides, peroxides and azo compounds such as cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide carbonate, t-butyl perpivalate, t-butyl permaleinate, t-butyl perbenzoate, dicumyl peroxide, t-butylcumyl peroxide, di (t-butyl) peroxide, 2,2'- Azo-bis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile).
• the initiators are used individually or as a mixture of two or more substances in amounts of 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the monomer
• the high-pressure mass polymerization is carried out batchwise or continuously in known high-pressure reactors, for example autoclaves or tubular reactors, tube reactors have proven particularly useful. Solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, benzene or toluene may be present in the reaction mixture. Preferred is the substantially solvent-free operation.
• the comonomers can be metered into the reactor both together with ethylene and separately via side streams.
• the monomer streams can be composed differently ( EP-A-0 271 738 and EP-A-0 922 716 ).
• Suitable copolymers or terpolymers include, for example: ethylene-vinyl acetate copolymers with 10-40% by weight of vinyl acetate and 60-90% by weight of ethylene; from DE-A-34 43 475 known ethylene-vinyl acetate-hexene terpolymers; in the EP-B-0 203 554 described ethylene-vinyl acetate-diisobutylene terpolymers; from EP-B-0 254 284 known mixture of an ethylene-vinyl acetate-diisobutylene terpolymer and an ethylene / vinyl acetate copolymer; in the EP-B-0 405 270 disclosed blends of an ethylene-vinyl acetate copolymer and an ethylene-vinyl acetate-N-vinylpyrrolidone terpolymer; in the EP-B-0 463 518 described ethylene / vinyl acetate / iso-butyl vinyl
• the mixing ratio is preferably between 20: 1 and 1:20, preferably 10: 1 to 1:10, in particular 5: 1 to 1: 5.
• the copolymers B are preferably derived from dicarboxylic acids and their derivatives, such as esters and anhydrides. Preference is given to maleic acid, fumaric acid, itaconic acid and especially maleic anhydride. Monoolefins having 10 to 20, in particular 12 to 18, carbon atoms are particularly suitable as comonomers. These are preferably linear and the double bond is preferably terminal such as in dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene and octadecene.
• the ratio of maleic anhydride to olefin or olefins in the polymer is preferably in the range 1: 1.5 to 1.5: 1, especially equimolar.
• further comonomers which are copolymerizable with maleic anhydride and the olefins mentioned, such as, for example, shorter and longer-chain olefins, allyl polyglycol ethers, C 1 -C 30 -alkyl (meth) acrylates, vinylaromatics or C 1 - C 20 alkyl vinyl ether.
• Alkyl polyglycol ethers correspond to the general formula wherein R 1 Hydrogen or methyl, R 2 Hydrogen or C 1 -C 4 -alkyl, m a number from 1 to 100, R 3 C 1 -C 24 -alkyl, C 5 -C 20 -cycloalkyl, C 6 -C 18 -aryl or -C (O) -R 4 , R 4 C 1 -C 40 alkyl, C 5 -C 10 cycloalkyl or C 6 -C 18 aryl.
• the preparation of the copolymers B) according to the invention is preferably carried out at temperatures between 50 and 220 ° C, in particular 100 to 190 ° C, especially 130 to 170 ° C.
• the preferred method of preparation is solvent-free bulk polymerization, but it is also possible to carry out the polymerization in the presence of aprotic solvents such as benzene, toluene, xylene or higher-boiling aromatic, aliphatic or isoaliphatic solvents or solvent mixtures such as kerosene or solvent naphtha.
• the polymerization is particularly preferably in moderately moderating, aliphatic or isoaliphatic solvents.
• the proportion of solvent in the polymerization mixture is generally between 10 and 90 wt .-%, preferably between 35 and 60 wt .-%.
• the reaction temperature can be set particularly easily by the boiling point of the solvent or by working under reduced or elevated pressure.
• the reaction of the monomers is initiated by free radical initiators (free radical initiators).
• This class of substance includes e.g. Oxygen, hydroperoxides and peroxides such as e.g. Cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide carbonate, t-butyl perpivalate, t-butyl permalate, t-butyl perbenzoate, dicumyl peroxide, t-butyl cumyl peroxide, di (t-butyl) peroxide, and azo compounds such as eg 2,2'-azobis (2-methylpropanonitrile) or 2,2'-azobis (2-methylbutyronitrile).
• the initiators are used individually or as a mixture of two or more substances in amounts of 0.01 to 20 wt .-%, preferably 0.05 to 10 w
• the copolymers can be prepared either by esterification of maleic, fumaric and / or itaconic acid with the corresponding alcohols and subsequent copolymerization or by copolymerization of olefin or olefins with itaconic and / or maleic anhydride and subsequent esterification.
• a copolymerization with anhydrides is carried out and esterified the resulting copolymer after preparation.
• This esterification takes place in both cases, for example by reaction with 0.8 to 2.5 moles of alcohol per mole of anhydride, preferably with 1.0 to 2.0 moles of alcohol per mole of anhydride at 50 to 300 ° C.
• esterification temperatures of about 70 to 120 ° C are preferred.
• larger amounts of alcohol preferably 2 moles of alcohol per mole of anhydride formed at 100 - 300 ° C, preferably 120 - 250 ° C diester.
• the water of reaction can be distilled off by means of an inert gas stream or discharged in the presence of an organic solvent by means of azeotropic distillation.
• half esters copolymers having acid numbers of 30-70 mg KOH / g, preferably 40-60 mg KOH / g, are considered here. Copolymers with acid numbers of less than 40, especially less than 30 mg KOH / g are considered as diesters. Particularly preferred are half esters.
• the resulting in the incomplete esterification acid may be present in the additive preferably as such or as a salt.
• Preferred cations are ammonium ions of primary, secondary and tertiary amines.
• the alkyl radicals of the amines preferably have 1 to 20 C atoms and may contain heteroatoms such as nitrogen, oxygen or sulfur.
• Further suitable cations are alkali ions such as e.g. Sodium and potassium, alkaline earth ions such as e.g. Calcium and magnesium as well as transition metal ions such as chromium, manganese, cerium and iron.
• Suitable alcohols are particularly linear, but they can also minor amounts, eg. B. up to 30 wt .-%, preferably up to 20 wt .-% and especially up to 10 wt .-% (in 1- or 2-position) branched alcohols. Particularly preferred are octanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol and hexadecanol.
• the effectiveness can be further adapted to specific fatty acid ester compositions.
• the additives may also contain polymers and copolymers based on C 10 -C 24 -alkyl acrylates or methacrylates (component C).
• These poly (alkyl acrylates) and methacrylates have molecular weights of 800 to 1,000,000 g / mol, and are preferably derived from caprylic, capric, undecyl, lauryl, myristyl, cetyl, palmitoleyl, stearyl alcohol or the like Mixtures such as coconut, palm, tallow or behenyl from.
• mixtures of the copolymers B according to the invention are used, with the proviso that the mean value of the Q values of the In turn, mixture components will assume values of 23 to 27 and preferably values of 24 to 26.
• the mixing ratio of the additives A and B according to the invention is (in parts by weight) 20: 1 to 1:20, preferably 10: 1 to 1:10, in particular 5: 1 to 1: 2.
• the proportion of component C in the formulations of A, B and C may be up to 40% by weight; it is preferably less than 20% by weight, in particular between 1 and 10% by weight.
• the additives of the invention are added to oils in amounts of 0.001 to 5 wt .-%, preferably 0.005 to 1 wt .-% and especially 0.01 to 0.5 wt .-%. They may be dissolved as such or dissolved or dispersed in solvents, e.g. aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures such.
• toluene xylene, ethylbenzene, decane, pentadecane, gasoline fractions, kerosene, naphtha, diesel, fuel oil, isoparaffins or commercial solvent mixtures such as solvent naphtha, ®Shellsol AB, ®Solvesso 150, ®Solvesso 200, ®Exxsol-, ®Isopar- and ® Shellsol D types are used.
• solvent naphtha ®Shellsol AB, ®Solvesso 150, ®Solvesso 200, ®Exxsol-, ®Isopar- and ® Shellsol D types
• they are dissolved in fuel oil of animal or vegetable origin based on fatty acid alkyl esters.
• the additives according to the invention preferably contain 1 to 80%, especially 10 to 70%, in particular 25 to 60%, of solvent.
• the fuel oil which is often referred to as “biodiesel” or “biofuel” to fatty acid alkyl esters of fatty acids having 14 to 24 carbon atoms and alcohols having 1 to 4 carbon atoms.
• fatty acids Usually, a major part of the fatty acids contains one, two or three double bonds.
• Particularly preferred are, for example, Rapsölklaremethylester and especially mixtures containing rapeseed, sunflower and / or soybean oil fatty acid methyl ester.
• the additives according to the invention can be used with equal success in mixtures of fatty acid methyl esters and mineral oil diesel. Such mixtures contain up to 25 wt .-%, in particular up to 10 wt .-%, especially up to 5 wt .-% of fuel oil of animal or vegetable origin.
• oils derived from animal or vegetable material and in which the additive according to the invention can be used are rapeseed oil, coriander oil, soybean oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, corn oil, almond oil, palm kernel oil, coconut oil, mustard seed oil, Beef tallow, bone oil and fish oils.
• oils derived from wheat, jute, sesame, shea nut, arachis oil and linseed oil can be derived from these oils by methods known in the art.
• Rapeseed oil which is a mixture of glycerol partially esterified fatty acids, is preferred because it is available in large quantities and is readily available by squeezing rapeseed. Furthermore, the also widespread oils of sunflower and soybeans and their mixtures with rapeseed oil are preferred.
• lower alkyl esters of fatty acids the following are suitable, for example as commercial mixtures: The ethyl, propyl, butyl and especially methyl esters of fatty acids having 12 to 22 carbon atoms, for example of lauric acid, myristic acid, palmitic acid, palmitoleic 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 have an iodine value of 50 to 150, in particular 90 to 125.
• Mixtures with particularly advantageous properties are those which are mainly d. H. at least 50 wt .-%, contain methyl esters of fatty acids having 16 to 22 carbon atoms and 1, 2 or 3 double bonds.
• the preferred lower alkyl esters of fatty acids are the methyl esters of oleic, linoleic, linolenic and erucic acids.
• oils according to the invention which can be used as biofuels.
• Biofuels i. Fuels derived from animal or vegetable material are considered to be less harmful to the environment when incinerated and are obtained from a renewable source. It has been reported that on combustion, less carbon dioxide than by equivalent amount of petroleum distillate fuel, e.g. Diesel fuel is formed and that very little sulfur dioxide is formed. Certain derivatives of vegetable oil, e.g. those obtained by saponification and reesterification with a monohydric alkyl alcohol can be used as a substitute for diesel fuel. Similarly, used cooking oils are also suitable as fuels.
• rapeseed esters such as rapeseed oil methyl ester (RME)
• RME rapeseed oil methyl ester
• the additives according to the invention are also suitable for such mixtures.
• a biofuel is an oil obtained from vegetable or animal matter or both, or a derivative thereof, which can be used as a fuel.
• oils may be used as biofuels
• vegetable oil derivatives are preferred, with particularly preferred biofuels being alkyl ester derivatives of rapeseed oil, cottonseed oil, soybean oil, sunflower oil, olive oil or palm oil, with rapeseed oil methyl ester genz being particularly preferred.
• the additive may be added to the oil to be treated according to methods known in the art. If more than one additive component or co-additive component is to be used, such components may be incorporated into the oil together or separately in any combination.
• the CFPP value of biodiesel can be adjusted to values below -20 ° C. and sometimes to values below -25 ° C., as required for marketing in particular for use in winter. This also applies to problematic oils that contain a high proportion of sunflower and soybean oils.
• the so-additive oils have a good resistance to cold, that is, the CFPP value remains constant even when stored under wintry conditions.
• the additives according to the invention can also be used together with one or more oil-soluble co-additives, which in themselves improve the cold flow properties of crude oils, lubricating oils or fuel oils.
• oil-soluble co-additives are polar compounds which produce a paraffin dispersion (paraffin dispersants) and oil-soluble amphiphiles:
• the additives of the invention can be used in admixture with paraffin dispersants.
• Paraffin dispersants reduce the size of the paraffin crystals and cause the paraffin particles to not settle but remain colloidally dispersed with significantly reduced sedimentation effort.
• oil-soluble polar compounds having ionic or polar groups e.g. For example, amine salts and / or amides which are obtained by reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides (cf. US 4 211 534 ).
• paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds, which can optionally be reacted with primary monoalkylamines and / or aliphatic alcohols (cf. EP 0 154 177 ), the reaction products of Alkenylspirobislactonen with amines (see. EP 0 413 279 B1 ) and after EP 0 606 055 A2 Reaction products of terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic acid anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols.
• Paraffin dispersants are 1:10 to 20: 1, preferably 1: 1 to 10: 1.
• the middle distillate is in particular those mineral oils which are obtained by distillation of crude oil and boil in the range of 120 to 450 ° C, for example kerosene, jet fuel, diesel and fuel oil.
• such middle distillates are used which contain 0.05% by weight of sulfur and less, more preferably less than 350 ppm of sulfur, in particular less than 200 ppm of sulfur and in special cases less than 50 ppm of sulfur.
• These are generally those middle distillates which have been subjected to a hydrogenating refining, and therefore contain only small amounts of polyaromatic and polar compounds.
• middle distillates which have 95% distillation points below 370.degree. C., in particular 350.degree. C. and in special cases below 330.degree.
• Synthetic fuels such as those obtainable by the Fischer-Tropsch process, are also suitable as middle distillates.
• the additives can be used alone or together with other additives, for example with other pour point depressants or dewaxing aids, with corrosion inhibitors, antioxidants, sludge inhibitors, dehazems and additives for lowering the cloud point.
• the CFPP value is determined in accordance with EN 116 and the determination of the cloud point in accordance with ISO 3015.
• Table 1 Characterization of the test oils used Oil no. CP CFPP E 1 Rapsölklaremethylester -2.3 -14 ° C E 2 80% rapeseed oil methyl ester + 20% sunflower oil methyl ester -1.6 -10 ° C E 3 90% rapeseed oil methyl ester + 10% soybean oil methyl ester -2.0 -8 ° C
• the ethylene copolymers used are commercial products having the characteristics given in Table 2. The products were used as 65% and 50% (A3) settings in kerosene, respectively.
• Table 2 Characterization of the ethylene copolymers used example Comonomer (s) V140 CH 3/100 CH 2 A1 13.6 mole% vinyl acetate 130 mPas 3.7 A2 13.7 mole percent vinyl acetate and 1.4 mole percent vinyl neodecanoate 105 mPas 5.3 A3 (V) 11.2 mol% vinyl acetate 220 mPas 6.2 A4 (V) Mixture of EVA copolymer with 16 mol% vinyl acetate and EVA with 5 mol% vinyl acetate in the ratio 13: 1 95 mPas / 350 mPas 3.2 / 5.7
• the esterifications are carried out in the presence of solvent naphtha (40-50 wt .-%) at 90 - 100 ° C for half ester and at 160 - 180 ° C with azeotropic culling of water of reaction to the diester.
• the degree of esterification is inversely proportional to the acid number.
• poly (alkyl (meth) acrylate As poly (alkyl (meth) acrylate), the compounds listed in the table were used as 50% settings in higher-boiling solvents. The K values are determined according to Ubbelohde at 25 ° C. in 5% strength toluene solution. Table 4: Characterization of the poly (acrylates) used C1 Poly (octadecyl acrylate), K value 32 C2 Poly (dodecyl acrylate), K value 35.6 C3 Poly (phenyl acrylate), K value 22.4
• the CFPP value (according to EN 116, in ° C) of various biofuels according to the above table was determined after addition of 1200 ppm, 1500 ppm and 2000 ppm of additive mixture. Percentages refer to parts by weight in the respective mixtures.
• Tables 5 to 7 show that comb polymers with the factor Q according to the invention already at low dosing rates achieve excellent CFPP reductions and offer additional potential at higher dosing rates.
• Table 5 CFPP testing in test oil E1 Ex.
• the CFPP value according to DIN EN 116 is compared before and after a standardized cold-change treatment.
• test oil E1 500 ml of biodiesel (test oil E1) are treated with the appropriate cold additive, placed in a cylinder and stored in a programmable cold chamber for one week. During this time, a program is run through which repeatedly cools to -13 ° C and then warms up again to -3 ° C. 6 cycles are consecutively run through (Table 8).
• Cooling program for determining the resistance to cold chill section begin The End duration description A ⁇ B + 5 ° C -3 ° C 8 h Pre-cooling to cycle start temperature B ⁇ C -3 ° C -3 ° C 2 h stationary temperature, start of cycle C ⁇ D -3 ° C -13 ° C 14 h Temperature reduction, incipient crystal formation D ⁇ E -13 ° C - 13 ° C 2 h Stationary temperature, crystal growth E ⁇ F -13 ° C -3 ° C 6 h Temperature increase, melting of the crystals F ⁇ B Another 6 cycles B ⁇ F are carried out.
• the additiviere oil sample is reheated to room temperature without shaking. From each of the upper, middle and lower sections of the cylinder a sample of 50 ml is drawn for CFPP measurements.
• the CFPP values given are average values of a double determination

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