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, 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
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  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
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  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
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  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—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, 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
  • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
  • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
  • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
  • C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
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  • 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
  • C10L1/22—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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—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
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  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/224—Amides; Imides carboxylic acid amides, imides

Definitions

• the present invention relates to an additive, its use as Cold flow improver for vegetable or animal fuel oils and accordingly additized fuel oils.
• renewable raw materials include, in particular, natural oils and fats of plant or animal origin. These are typically triglycerides of fatty acids with 10 to 24 C atoms, which have a calorific value comparable to conventional fuels, but at the same time are considered less harmful to the environment.
• Biofuels ie fuels derived from animal or plant material, are obtained from renewable sources and thus produce only as much CO 2 as was previously converted into biomass. It has been reported that combustion produces less carbon dioxide than equivalent amount of petroleum distillate fuel, eg, diesel fuel, and that very little sulfur dioxide is produced. In addition, they are biodegradable.
• Oils obtained from animal or vegetable material are mainly metabolites comprising triglycerides of monocarboxylic acids, eg 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 used in the prior art known methods are obtained.
• Triglycerides Due to the partially unsatisfactory physical properties of the Triglycerides, the technique has gone over to the naturally occurring Triglycerides in fatty acid esters of lower alcohols such as methanol or ethanol convict.
• EP-B-0 665 873 discloses a fuel oil composition
• a fuel oil composition comprising a A biofuel comprising 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 in the Substantially linear alkyl group having 10 to 30 carbon atoms with one not polymeric organic radical is connected to at least one linear chain of To provide atoms containing the carbon atoms of the alkyl groups and one or more includes non-terminal oxygen atoms, or (e) one or more of 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.
• Suitable comonomers are unsaturated esters, in particular vinyl acetate, but also ⁇ -olefins.
• WO 95/22300 discloses comb polymers in which the alkyl radicals have on average less than 12 C atoms. These additives are especially suitable for oils with cloud points of less than -10 ° C, where it is oils may also be native hydrocarbon oils (page 21, Line 16 ff.). However, native oils have cloud points from about -2 ° C upwards.
• EP-A-0 626 442 and EP-A-0 694 125 disclose fatty acid esters which contain pour point depressants for the purpose of improving the low-temperature properties.
• PPDs styrene-MSA copolymers esterified with a mixture of short-chain (butanol) and longer-chain C 10 -C 18 -alcohols neutralized with aminopropylmorpholine; Poly (C 4-24- alkyl (meth) acrylates and their copolymers with N-containing monomers; alkyl-bridged alkylaromatics.
• EP-A-1 032 620 discloses poly (alkyl (meth) acrylates) having broad C chain distribution and hydroxy-functional comonomers as an additive for mineral oil and biodiesel.
• Another object of the invention is an additive as defined above.
• Another object of the invention is the use of the above defined Additive to improve the cold flow properties of animal fuel oil or of vegetable origin.
• Another object of the invention is a method for improving the Cold flow properties of fuel oils of animal or vegetable origin, by giving fuel oils of animal or vegetable origin the above Adds defined additive.
• R has values of 11.5 to 13.5 and specifically 12.0 to 13.0.
• Suitable ethylene copolymers A) are those which contain from 8 to 21 mol% of one or more a plurality of vinyl and / or (meth) acrylic esters and 79 to 92 wt .-% ethylene.
• 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 and preferably 1 to 18, especially 1 to 12 C atoms, from.
• 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 iso-butyl (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-Ethylhexankladlesters, the Neononanoic or vinyl neodecanoate contain except Ethylene preferably 3.5 to 20 mol%, in particular 8 to 15 mol% of vinyl acetate and 0.1 to 12 mol%, in particular 0.2 to 5 mol% of at least one long-chain Vinylester, wherein the total comonomer content between 8 and 21 mol%, preferably between 12 and 18 mol%.
• copolymers contain, in addition to ethylene and 8 to 18 mol% vinyl esters, 0.5 to 10 mol% 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 1 and 9 CH 3/100 CH 2 groups, especially between 2 and 6 CH 3/100 CH 2 groups, such as 2.5 to 5 CH 3/100 CH 2 groups not derived from the comonomers.
• the copolymers (A) are prepared by conventional copolymerization methods such as for example suspension polymerization, solvent polymerization, Gas phase polymerization or high-pressure mass polymerization produced. Preference is given to high pressure bulk polymerization at pressures of 50 to 400 MPa, preferably 100 to 300 MPa and temperatures of 100 to 300 ° C, preferably 150 to 220 ° C performed. In a particularly preferred production variant the polymerization takes place in a multizone reactor, wherein the Temperature difference between the Peroxiddostechniken along the tube reactor is kept as low as possible, i. ⁇ 50 ° C, preferably ⁇ 30 ° C, in particular ⁇ 15 ° C. Preferably, the temperature maxima differ in the individual reaction zones less than 30 ° C, more preferably less than 20 ° C and especially around less than 10 ° C.
• the reaction of the monomers is by free-radical initiators (Radical chain starter) initiated.
• This class of substance includes e.g. 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 per-maleate, t-butyl perbenzoate, dicumyl peroxide, t-butyl cumyl 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 amounts of 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-
• High pressure bulk polymerization is used in known high pressure reactors, e.g. Autoclaves or tube reactors, discontinuous or continuous, Tube reactors have proven particularly useful.
• Solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, benzene or toluene, may be included in the reaction mixture.
• the polymerization is the mixture of the monomers, the initiator and, if used, the moderator, a tubular reactor via the reactor inlet and above supplied to one or more side branches.
• Preferred moderators are for example, hydrogen, saturated and unsaturated hydrocarbons such as for example, propane or propene, aldehydes such as propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones such as acetone, Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and alcohols such for example, butanol.
• the comonomers as well as the moderators can do it both together with ethylene and separated via side streams in the reactor be dosed.
• the monomer streams can be different be composed (EP-A-0 271 738 and EP-A-0 922 716).
• Suitable copolymers or terpolymers include, for example: ethylene-vinyl acetate copolymers with 10 to 40% by weight of vinyl acetate and 60 to 90% by weight of ethylene; the ethylene-vinyl acetate-hexene terpolymers known from DE-A-34 43 475; the ethylene-vinyl acetate-diisobutylene terpolymers described in EP-B-0 203 554; the mixture known from EP-B-0 254 284 comprising an ethylene-vinyl acetate-diisobutylene terpolymer and an ethylene-vinyl acetate copolymer; the blends disclosed in EP-B-0 405 270 of an ethylene-vinyl acetate copolymer and an ethylene-vinyl acetate-N-vinylpyrrolidone terpolymer; the ethylene / vinyl acetate / iso-butyl vinyl ether terpolymers described
• the mixtures differ based on the mixtures lying polymers in at least one characteristic.
• the Mixing ratio of the different ethylene copolymers is preferred between 20: 1 and 1:20, preferably 10: 1 to 1:10, in particular 5: 1 to 1: 5.
• the copolymers B are derived from alkyl acrylates, alkyl methacrylates, Alkylacrylamides, alkylmethacrylamides, alkylvinylesters, alkylvinylethers, Alkylallyl ethers and Alkyldiketenen having 8 to 16 carbon atoms in the alkyl radical. These Comonomers are referred to below as comonomers B1).
• the copolymers which are Component B to those containing comonomers derived from Esters, amides and / or imides of ethylenically unsaturated monocarboxylic acids with 3 to 8 carbon atoms are derived with alcohols or amines, wherein the Alcohols or amines carry alkyl radicals having 8 to 16 carbon atoms.
• the copolymers B) may also contain comonomers B2) which comprise i) esters, amides and / or imides of ethylenically unsaturated dicarboxylic acids having 4 to 8 C atoms and alcohols or amines having 8 to 16 C atoms in the alkyl radicals and / or or ii) C 10 to C 20 olefins.
• comonomers B2 comprise i) esters, amides and / or imides of ethylenically unsaturated dicarboxylic acids having 4 to 8 C atoms and alcohols or amines having 8 to 16 C atoms in the alkyl radicals and / or or ii) C 10 to C 20 olefins.
• the alkyl radicals of the comonomers B1 and B2 are preferably linear, but may also be minor amounts of branched isomers of up to 30 mol%, preferably up to 20 mol% and especially 2 to 5 mol%.
• the proportion of comonomers B1) and optionally B2) is preferably Polymer more than 50 mol%, especially more than 70 mol% and especially at least 80 mol%, such as 90 to 95 mol%.
• the proportion of monomers B2), if present, is preferably less than 80 mol%, in particular less than 50 mole% and especially less than 20 mole% such as 2 to 10 mol% of the total amount of monomers B1) and B2).
• the polymers B) consist only of the monomers B1) and optionally B2), the then add up to 100 mol%.
• Preferred monomers of the copolymers B) are esters of acrylic acid, Methacrylic acid, maleic acid, fumaric acid and itaconic acid with octanol, nonanol, Decanol, undecanol, dodecanol, n-tridecanol, iso-tridecanol, tetradecanol, Pentadecanol, hexadecanol and mixtures thereof.
• Preferred monomers are furthermore amides and optionally imides of these acids with octylamine, nonylamine, Decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, Pentadecylamine, hexadecylamine and mixtures thereof.
• the copolymers containing component B Comonomers which esters and / or ethers of ethylenic unsaturated alcohols having 2 to 10 carbon atoms, and carboxylic acids or Alcohols bearing alkyl radicals of 8 to 16 carbon atoms are.
• Such preferred monomers of the copolymers B) are, for example, esters of Vinyl alcohol with octanoic acid, 2-ethylhexanoic acid, nonanoic acid, neononanoic acid, Decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, Tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid and their Mixtures.
• Further preferred monomers of the copolymers B) are, for example, ethers of Allyl and especially the vinyl alcohol with octanol, nonanol, decanol, Undecanol, dodecanol, n-tridecanol, isotridecanol, tetradecanol, pentadecanol, Hexadecanol and mixtures thereof.
• comonomers B2 are also olefins having 10-20 carbon atoms, preferably with 12-18 C atoms and in particular with 10-16 C atoms suitable. This is it preferably linear ⁇ -olefins with terminal double bond.
• branched olefins such as in particular oligomers of isobutylene and of propylene having 10 to 20 C atoms.
• alkyl (meth) acrylates alkyl (meth) acrylates, alkyl vinyl esters, alkyl vinyl ethers with 1 to 5 C atoms in the alkyl radical and ethylenically unsaturated free carboxylic acids such as for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and functional groups such as -OH, -SH, -N-, -CN-bearing Monomers may be present in minor amounts of ⁇ 20 mol%, ⁇ 10 mol%, ⁇ 5 mol%, also be present in the copolymer B.
• Quantities of up to 20 mol%, preferably ⁇ 10 mol%, especially ⁇ 5 mol% can also contain other comonomers containing those monomers copolymerizable, e.g. Allyl polyglycol ethers, vinyl aromatics and higher molecular weight olefins such as poly (isobutylene).
• the polymers of the invention can be prepared by direct polymerization from the mentioned monomers in known polymerization processes such as mass, Solution, emulsion, suspension or precipitation polymerization.
• Acid or Hydroxyl-bearing base polymer with corresponding fatty acids, Fatty alcohols or fatty amines having 8 to 16 carbon atoms in the alkyl radical become.
• the esterifications, etherifications, amidations and / or imidations done by known condensation methods.
• the derivatization be complete or partial.
• Partially esterified or amidated, acid-based Polymers have (solvent-free) preferably acid numbers of 60-140 mg KOH / g and in particular from 80 to 120 mg KOH / g. Copolymers with acid numbers less than 80, especially less than 60 mg KOH / g are considered to be fully derivatized.
• Partially esterified or etherified hydroxyl-bearing polymers have OH numbers from 40 to 200 mg KOH / g, preferably 60 to 150 mg KOH / g; Copolymers with Hydroxyl numbers of less than 60 and in particular less than 40 mg KOH / g are considered fully derivatized. Particularly preferred are partial derivatized polymers.
• suitable acid group-bearing polymers are homopolymers and copolymers ethylenically unsaturated carboxylic acids such as acrylic acid, Methacrylic acid, maleic acid, fumaric acid, itaconic acid or their reactive Equivalents such as lower esters or anhydrides such as Methacrylates and maleic anhydride with each other as well as with further monomers copolymerizable with these acids.
• suitable examples are poly (acrylic acid), poly (methacrylic acid), poly (maleic acid), Poly (maleic anhydride), poly (acrylic acid-co-maleic acid).
• Suitable fatty alcohols and fatty amines are especially linear, but they can also minor amounts, z. B. up to 30 wt .-%, preferably up to 20 wt .-% and especially up to 10 wt .-% of branched alkyl radicals.
• the branches are preferably in the 1- or 2-position. Shorter as well as longer-chained Fatty alcohols or fatty amines can be used, but their share preferably below 20 mol% and especially below 10 mol%, such as between 1 and 5 mol% based on the total amount of amines used.
• Particularly preferred fatty alcohols are octanol, decanol, undecanol, dodecanol, Tridecanol, tetradecanol, pentadecanol and hexadecanol.
• Suitable amines are primary and secondary amines having one or two C 8 -C 16 alkyl radicals. They can carry one, two or three amino groups which are linked via alkylene radicals having two or three carbon atoms. Preference is given to monoamines.
• primary amines are octylamine, 2-ethylhexylamine, decylamine, undecylamine, dodecylamine, n-tridecylamine, iso-tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine and mixtures thereof.
• Preferred secondary amines are dioctylamine, dinonylamine, didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine, and amines having different alkyl chain lengths such as N-octyl-N-decylamine, N-decyl-N-dodecylamine, N-decyl-N-tetradecylamine, N-decyl N-hexadecylamine, N-dodecyl-N-tetradecylamine, N-dodecyl-N-hexadecylamine, N-tetradecyl-N-hexadecylamine.
• Secondary amines which, in addition to a C 8 -C 16 -alkyl radical, bear shorter side chains having 1 to 5 C atoms, for example methyl or ethyl groups, are suitable according to the invention.
• the alkyl chain length n is taken into account as the mean value of the alkyl chain lengths of C 8 to C 16 for the calculation of the Q factor.
• Shorter and longer alkyl radicals, if present, are not included in the calculation because they do not contribute to the effectiveness of the additives. Therefore, the proportion of shorter and longer alkyl chains is preferably below 20 mol%, preferably below 10 mol%, based on the total amount of amine used.
• Particularly preferred are amides derived from primary monoamines and imides.
• hydroxyl-bearing polymers are homo- and Copolymers of hydroxyl-bearing monomers such as vinyl alcohol, allyl alcohol or hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and Hydroxypropyl methacrylate.
• Suitable fatty acids have 8 to 16 carbon atoms in the alkyl radical.
• the alkyl radical is essentially linear but may also be secondary Quantities, e.g. B.
• Nonanoic acid decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, Tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid and Octadecanoic and nonadecanoic acid and mixtures thereof.
• the molecular weights of the inventive copolymers B are in between 1,000 and 100,000, especially between 2,000 and 50,000 and in particular between 2,500 and 25,000 g / mol, measured by gel permeation chromatography (GPC) against poly (styrene).
• Copolymers of the invention B must be oil-soluble in practice-relevant dosage quantities, that means they have to be in the oil to be added at 50 ° C without residue.
• mixtures of the invention Copolymers B provided that the average of the R values of the In turn, mixture components have values from 11 to 14, preferably from 11.5 to 13.5 and in particular assumes values of 12.0 to 13.0.
• 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 additives according to the invention are oils in amounts of from 0.001 to 5% by weight, preferably 0.005 to 1 wt .-% and especially added 0.01 to 0.5 wt .-%. there they may be dissolved as such or dissolved in solvents, e.g. aliphatic and / or aromatic hydrocarbons or Hydrocarbon mixtures such as e.g.
• they are based on fuel oil of animal or vegetable origin dissolved by fatty acid alkyl esters.
• the fuel oil is the often referred to as "biodiesel” or “biofuel” to Fatty acid alkyl esters of fatty acids having 12 to 24 carbon atoms and alcohols having 1 to 4 C-atoms. Usually a major part of the fatty acids contains one, two or three Double bonds.
• oils derived from animal or vegetable material examples include 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, fish oils and used cooking oils.
• the fatty acid alkyl esters, also referred to as biodiesel can be made from these oils be derived by methods known in the art.
• Rapeseed oil that is a mixture of glycerol partially esterified fatty acids, is preferred because it is available in large quantities and in a simple manner by pressing out of Rapeseed is available. Furthermore, the also widely used oils of Sunflowers and soybeans and their mixtures with rapeseed oil preferred.
• Particularly suitable as biofuels are lower alkyl esters of fatty acids.
• commercial mixtures of ethyl, propyl, butyl and in particular methyl esters of fatty acids having 14 to 22 carbon atoms for example, 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, preferably having an iodine value of 50 to 150, especially 90 to 125 have.
• Mixtures with particularly advantageous Properties are those that are mainly, i. H. at least 50% by weight, Methyl esters of fatty acids having 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.
• a biofuel is an oil derived from vegetable or animal material or is obtained or a derivative thereof, which as fuel and especially as diesel or heating oil can be used.
• oils can be used as biofuels are vegetable oil derivatives with particularly preferred biofuels alkyl ester derivatives of rapeseed oil, Cottonseed oil, soybean oil, sunflower oil, olive oil or palm oil are, being Rapsölchuremethylester, sunflower oil and Sojaölchuremethylester are very particularly preferred.
• biofuel or as a component in biofuel are also Altfettester such as Altfettmethylester.
• the additive may be added to the oil to be treated according to art known in the art Procedures are introduced. If more than one additive component or Coadditive component should be used, such components be introduced together or separately in any combination in the oil.
• the CFPP value of biodiesel can be on Set values below -20 ° C and sometimes to values below -25 ° C, as they do be required for marketing for use especially in winter.
• the pour point of biodiesel by the addition of the invention Additives are minimized.
• the additives of the invention are particularly advantageous in problematic oils containing a high proportion of esters of saturated fatty acids of more than 4% in particular more than 5% and especially with 7 to 25% like For example, with 8 to 20%, as for example in oils from sunflowers and Soy included. Such oils are characterized by cloud points of over -5 ° C and especially above -3 ° C.
• the additives according to the invention also together with one or more oil-soluble Co-additives are used, which already by themselves the cold flow properties of crude oils, lubricating oils or fuel oils.
• oil-soluble Co-additives are polar compounds that cause paraffin dispersion (Paraffin dispersants) and oil-soluble amphiphiles.
• Paraffin dispersants reduce the size of the paraffin crystals and cause The paraffin particles do not settle, but colloidly with significantly reduced Sedimentation tendency, remain dispersed.
• paraffin dispersants have become both low molecular weight and polymeric, oil-soluble compounds with ionic or polar groups, e.g. Amine salts and / or amides proven.
• Especially preferred paraffin dispersants contain reaction products of secondary Fatty amines containing 20 to 44 carbon atoms, in particular dicocosamine, ditallow fatty amine, Distearylamine and dibehenylamine with carboxylic acids and their derivatives.
• Paraffin dispersants which have proved particularly suitable by reaction aliphatic or aromatic amines, preferably long-chain aliphatic Amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides are obtained (see US 4 211 534).
• Amides and ammonium salts of aminoalkylene polycarboxylic acids such as Nitrilotriacetic acid or ethylenediaminetetraacetic acid with secondary amines as Paraffin dispersants are suitable (compare EP 0 398 101).
• paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols can be implemented (see EP 0 154 177) and the reaction products of Alkenylspirobislactones with amines (see EP 0 413 279 B1) and according to EP 0 606 055 A2 Reaction products of terpolymers based on ⁇ , ⁇ -unsaturated Dicarboxylic acid anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkylene ethers lower unsaturated alcohols.
• Paraffin dispersants are 1:10 to 20: 1, preferably 1: 1 to 10: 1.
• the additives can be used alone or together with other additives be, e.g. with other pour point depressants or dewaxing aids, with Antioxidants, cetane improvers, dehazers, demulsifiers, detergents, Dispersants, defoamers, dyes, corrosion inhibitors, Conductivity improvers, sludge inhibitors, odorants, and / or additives to Humiliation of the cloud point.
• other pour point depressants or dewaxing aids with Antioxidants, cetane improvers, dehazers, demulsifiers, detergents, Dispersants, defoamers, dyes, corrosion inhibitors, Conductivity improvers, sludge inhibitors, odorants, and / or additives to Humiliation of 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. Characterization of the used test oils 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% of soybean oil methyl ester -2.0 -8 ° C C chain distribution of the fatty acid methyl esters used for the preparation of the test oils (main constituents, FI .-% according to GC): C 16 C 16 ' C 18 C 18 ' C 18 '' C 18 '' C 20 C 20 ' C 22 ⁇ saturated RME 4.4 0.4 1.6 57.8 21.6 8.8 1.5 0.7 0.2 7.7 SBME 6.0 0.1 3.8 28.7 58.7 0.1 0.3 0.3 0.7 10.8 SojaME 10.4 0.1 4.1 24.8 51.3 6.
• 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. Characterization of the ethylene copolymers used example Comonomer (s) V140 CH 3/100 CH 2 A1 13.6 mol% vinyl acetate 130 mPas 3.7 A2 13.7 mol% of vinyl acetate and 1.4 mol% of vinyl neodecanoate 105 mPas 5.3 A3 9.4 mol% vinyl acetate 220 mPas 6.2 A4 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 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 additive mixtures.
• Tables 5 to 7 show that comb polymers with the factor R according to the invention achieve excellent CFPP reductions even at low dosing rates and offer additional potential at higher dosing rates.
• Ethylene copolymer A Comb polymer B CFPP in test oil 1 1200 ppm 1500 ppm 2000 ppm 1 80% A1 20% B1 -20 -23 -24 2 80% A1 20% B2 -21 -24 -27 3 80% A1 20% B3 -21 -24 -26 4 80% A1 20% B4 -20 -23 -25 5 80% A1 20% B5 -20 -21 -23 6 80% A1 20% B6 -19 -20 -22 7 80% A1 20% B7 -21 -24 -28 8th 80% A1 20% B8 -21 -25 -27 9 80% A1 20% B9 -21 -24 -28 10 (Cf.) 80% A3 20% B9 -19 -19 -21 11 (Cf.) 80% A1 20% B10 -17 -17 -18 12 (Cf.) 80% A1 20% B12 -18 -17 -19 13 (Cf.) 80% A1 20% B13 -18 -17 -17 14 (Cf.) 100% A1
• Ethylene copolymer A Comb polymer B CFPP in test oil E3 1500 ppm 2000 ppm 30 70% A2 30% B2 -20 -25 31 70% A2 30% B3 -19 -24 32 70% A2 30% B4 -20 -26 33 70% A2 30% B9 -20 -25 34 (Cf.) 70% A2 30% B11 -16 -17 35 (Cf.) 70% A2 30% B12 -16 -13 36 (See) 70% A2 30% B13 -15 -15 36 (See) 100% A2 --- -14 -13
• the CFPP value according to DIN EN 116 is compared before and after a standardized cold-change treatment.
• 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. A difference between the mean values of the CFPP values after storage to the CFPP value before storage and between the individual phases of less than 3 K shows a good resistance to cold flashes.

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