Classifications

• • 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
  • C10L1/195—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 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
  • 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
  • C10L1/146—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 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
  • C10L1/192—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 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
  • C10L1/195—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 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
  • C10L1/195—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
• • 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
  • C10L1/195—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 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
  • 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

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.
• 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 include glycerides of a variety of acids, the number and variety of which varies with the source of the oil, and 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.
• Suitable comonomers are unsaturated esters, in particular vinyl acetate, 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.
• WO 95/22300 discloses comb polymers in which the alkyl radicals have on average less than 12 carbon atoms. These additives are particularly suitable for oils with cloud points of less than -10 ° C, where the oils may also be native hydrocarbon oils (page 21, line 16 ff.). However, native oils have cloud points from about -2 ° C upwards.
• WO 94/10267 teaches 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).
• 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
• EP-A-0 626 442 and EP-A-0 694 125 disclose fatty acid esters that contain pour point depressants to improve cold 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 -alky) (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 for improving the cold flow properties of fuel oils of animal or vegetable origin.
• R has values of 11.5 to 13.5 and especially 12.0 to 13.0.
• Suitable ethylene copolymers A) are those which contain from 8 to 21 mol% of one or more vinyl and / or (meth) acrylic esters and from 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 and preferably 1 to 18, especially 1 to 12 carbon atoms.
• vinyl acetate vinyl propionate, vinyl butyrate, vinyl hexanoate, Vinylheptanoat, vinyl octanoate, vinyl laurate and vinyl stearate and branched fatty acid based esters of vinyl alcohol such as vinyl isobutyrate, vinyl pivalate, vinyl 2-ethylhexanoate, iso-Nonanklarevinylester, Neononanklarevinylester, vinyl neodecanoate and Neoundecanklavinylester.
• vinyl acetate vinyl propionate, vinyl butyrate, vinyl hexanoate, Vinylheptanoat, vinyl octanoate, vinyl laurate and vinyl stearate and branched fatty acid based esters of vinyl alcohol such as vinyl isobutyrate, vinyl pivalate, vinyl 2-ethylhexanoate, iso-Nonanklarevinylester, Neononanklawrevinylester, vinyl neodecan
• 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 at least one 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, the melt viscosities at 140 ° C from 20 to 10,000 mPas in particular 30 to 5,000 mPas and especially 50 to 1,000 mPas correspond.
• 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 customary copolymerization processes such as, for example, suspension polymerization, solvent polymerization, Gas phase polymerization or high-pressure mass polymerization produced.
• 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 multizone reactor, wherein the temperature difference between the peroxide doses along the tubular reactor is kept as low as possible, ie ⁇ 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 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 permalate, 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 .-%, based on the
• 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.
• Preferred moderators are, for example, hydrogen, saturated and unsaturated hydrocarbons such as 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 as for example, butanol.
• the comonomers as well as the moderators can be metered into the reactor both together with ethylene and separately via side streams. In this case, 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 to 40% by weight of vinyl acetate and 60 to 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 / isobutyl vinyl
• the polymers underlying the mixtures differ in at least one characteristic.
• they may contain different comonomers, have different comonomer contents, molecular weights and / or degrees of branching.
• the Mixing ratio of the various ethylene copolymers 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 derived from alkyl acrylates, alkyl methacrylates, alkyl acrylamides, alkyl methacrylamides, alkyl vinyl esters, alkyl vinyl ethers, alkyl allyl ethers and alkyl diketenes having 8 to 16 carbon atoms in the alkyl radical. These comonomers are referred to below as comonomers B1).
• the copolymers constituting ingredient B are those containing comonomers derived from esters, amides and / or imides of ethylenically unsaturated monocarboxylic acids having from 3 to 8 carbon atoms with alcohols or amines, respectively, wherein 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 contain minor amounts of branched isomers of up to 30 mol%, preferably up to 20 mol% and in particular from 2 to 5 mol%.
• the proportion of the comonomers B1) and optionally B2) in the polymer is preferably more than 50 mol%, in particular more than 70 mol% and especially at least 80 mol%, for example 90 to 95 mol%.
• the proportion of the monomers B2), if present, is preferably less than 80 mol%, in particular less than 50 mol% and especially less than 20 mol%, for example from 2 to 10 mol% of the total amount of the monomers B1 ) and B2).
• the polymers B) consist only of the monomers B1) and optionally B2), which 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.
• Further preferred monomers are amides and optionally imides of these acids with octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine and mixtures thereof.
• the copolymers making up Component B contain comonomers which are esters and / or ethers of ethylenically unsaturated alcohols of 2 to 10 carbon atoms, and carboxylic acids or alcohols bearing alkyl groups of 8 to 16 carbon atoms.
• 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 mixtures thereof.
• Further preferred monomers of the copolymers B) are, for example, ethers of allyl and in particular vinyl alcohol with octanol, nonanol, decanol, undecanol, dodecanol, n-tridecanol, isotridecanol, tetradecanol, pentadecanol, hexadecanol and mixtures thereof.
• comonomers B2 are olefins having 10 to 20 carbon atoms, preferably having 12 to 18 carbon atoms and in particular having 10 to 16 carbon atoms. These are preferably linear ⁇ -olefins with terminal double bond. In a further preferred embodiment, it is branched olefins such as in particular oligomers of isobutylene and propylene having 10 to 20 carbon atoms.
• alkyl (meth) acrylates alkyl (meth) acrylates, alkyl vinyl esters, alkyl vinyl ethers having 1 to 5 carbon atoms in the alkyl radical and ethylenically unsaturated free carboxylic acids such as 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.
• comonomers which are copolymerizable with the stated monomers, for example allyl polyglycol ethers, vinylaromatics and relatively high molecular weight olefins such as poly ( isobutylene).
• the polymers according to the invention can be prepared by direct polymerization from the monomers mentioned in known polymerization processes such as bulk, solution, emulsion, suspension or precipitation polymerization.
• They can also be prepared by derivatization of a base polymer carrying acid or hydroxyl groups, for example, with corresponding fatty acids, fatty alcohols or fatty amines having 8 to 16 C atoms in the alkyl radical.
• the esterifications, etherifications, amidations and / or imidations are carried out by known condensation methods. In this case, the derivatization be complete or partial.
• Partially esterified or amidated acid-based polymers (solvent-free) preferably have acid numbers of 60-140 mg KOH / g and in particular 80-120 mg KOH / g. Copolymers with acid numbers of 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 of 40 to 200 mg KOH / g, preferably 60 to 150 mg KOH / g; Copolymers having hydroxyl numbers less than 60 and especially less than 40 mg KOH / g are considered fully derivatized. Particularly preferred are partially derivatized polymers.
• suitable acid-bearing polymers are homo- and copolymers of 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 Methyl methacrylate and maleic anhydride with each other as well as with other monomers copolymerizable with these acids.
• 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 Methyl methacrylate and maleic anhydride with each other as well as with other 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 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 .-% branched alkyl radicals.
• the branches are preferably in the 1- or 2-position. Shorter as well as longer-chain fatty alcohols or fatty amines can be used, but their proportion is 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.
• Preferred are Monoamines.
• Especially preferred as 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.
• Polymers which are particularly suitable for derivatization with fatty acids and / or fatty alcohols to esters and / or ethers are homopolymers and copolymers of monomers carrying hydroxyl groups, 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 substantially linear but can also be minor amounts, e.g. B. up to 30 wt .-%, preferably up to 20 wt .-% and especially up to 10 wt .-% of branched isomers.
• Nonadecanklare and mixtures thereof are nonanoic, decanoic, undecanoic, dodecanoic, tridecanoic, tetradecanoic, pentadecanoic, hexadecanoic, heptadecanoic and octadecanoic and Nonadecanklare and mixtures thereof.
• the effectiveness of the additives according to the invention can be further limited to specific Fatty acid ester compositions are adjusted.
• the molecular weights of the copolymers B according to the invention are between 1,000 and 100,000, in particular 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 must be oil-soluble in practice-relevant dosing quantities, ie they must dissolve in the oil to be additized at 50 ° C. without residue.
• mixtures of the copolymers B according to the invention are used, with the proviso that the mean value of the R values of the mixture components in turn has values of from 11 to 14, preferably from 11.5 to 13.5 and in particular values from 12.0 to 13 , 0 takes.
• 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 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 as e.g.
• they are dissolved in fuel oil of animal or vegetable origin based on fatty acid alkyl esters.
• the additives according to the invention contain 1-80%, especially 10-70%, in particular 25-60% (m / m) of solvent.
• the fuel oil which is often referred to as “biodiesel” or “biofuel”
• biodiesel is fatty acid alkyl esters of fatty acids having 12 to 24 carbon atoms and alcohols having 1 to 4 carbon atoms.
• fatty acids having 12 to 24 carbon atoms and alcohols having 1 to 4 carbon atoms.
• a major part of the fatty acids contains one, two or three double bonds.
• 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, fish oils and used edible 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.
• Particularly suitable as biofuels are lower alkyl esters of fatty acids.
• lower alkyl esters of fatty acids are, for example, commercially available mixtures of ethyl, propyl, butyl and especially methyl esters of fatty acids having 14 to 22 carbon atoms, for example of lauric, myristic, palmitic, palmitolic, stearic, oleic, elaidic, petroselic, ricinoleic, elaeostearic, linoleic, linolenic , Eicosanoic acid, gadoleic acid, docosanoic acid or erucic acid, which preferably have an iodine value of from 50 to 150, in particular from 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.
• a biofuel is an oil obtained from plant or animal matter or both, or a derivative thereof, which can be used as a fuel and especially as a diesel or fuel oil.
• 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 methyl rapeseed oil, methyl sunflower oil and soybean oil methyl ester being most preferred.
• particularly preferred biofuel or as a component in the biofuel are also old fat esters such as, for example, used fat methyl ester.
• 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.
• the pour point of biodiesel is reduced by the addition of the additives according to the invention.
• the additives according to the invention are particularly advantageous in problematic oils which have a high content of esters of saturated fatty acids of more than 4%, in particular more than 5% and especially 7 to 25%, for example 8 to 20%, as is the case, for example, in oils Sunflowers and soy are included.
• Such oils are characterized by cloud points above -5 ° C and especially above -3 ° C.
• the additives according to the invention also to adjust mixtures of Rapsölklaremethylester and sunflower and / or soybean oil fatty acid methyl ester to CFPP values of -20 ° C and below.
• 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 cause a paraffin dispersion (paraffin dispersants) and oil-soluble amphiphiles.
• 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.
• Suitable paraffin dispersants are both low molecular weight and polymeric, oil-soluble compounds having ionic or polar groups, such as amine salts and / or amides have proven.
• Particularly preferred paraffin dispersants contain reaction products of secondary fatty amines having 20 to 44 carbon atoms, in particular dicocoamine, ditallow fatty amine, distearylamine and dibehenylamine with carboxylic acids and derivatives thereof.
• Paraffin dispersants which have been 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 have proven particularly suitable (cf. US 4 211 534 ).
• amides and ammonium salts of aminoalkylene polycarboxylic acids such as nitrilotriacetic acid or ethylenediaminetetraacetic acid with secondary amines are suitable as paraffin dispersants (cf. EP 0 398 101 ).
• 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 ) and the reaction products of alkenyl spiro-bis-lactones with amines (cf. EP 0 413 279 B1 ) and after EP 0 606 055 A2 Reaction products of terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols.
• the mixing ratio (in parts by weight) of the additives according to the invention with paraffin dispersants is 1:10 to 20: 1, preferably 1: 1 to 10: 1.
• the additives can be used alone or together with other additives, for example with other pour point depressants or dewaxing aids, with antioxidants, cetane number improvers, dehazers, demulsifiers, detergents, dispersants, defoamers, dyes, corrosion inhibitors, conductivity improvers, sludge inhibitors, odorants, and / or additives Humiliation of the cloud point.
• other pour point depressants or dewaxing aids with antioxidants, cetane number improvers, dehazers, demulsifiers, detergents, dispersants, defoamers, dyes, corrosion inhibitors, conductivity improvers, sludge inhibitors, odorants, and / or additives 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.
• 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 3 Characterization of the ethylene copolymers used example Comonomer (s) V140 CH 3 / 100CH 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
• CFPP value (according to EN 116, in ° C) of various biofuels according to the above table after addition of 1200 ppm, 1500 ppm and 2000 ppm additive mixture was determined. 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.
• Table 5 CFPP testing in test oil E1 Ex.
• 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. It are consecutively run through 6 of these cycles (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.
• Table 9 Chilling resistance of the additized oil: additive CFPP before storage CFPP after storage example Ethylene copolymer A Comb polymer B metering below ⁇ CFPP (below) center ⁇ CFPP (middle) above ⁇ CFPP (above) 37 80% A1 20% B2 1500 ppm -24 ° C -23 ° C + 1K -24 ° C 0K -24.5 ° C -0.5K 38 80% A4 20% B9 1500 ppm -24 ° C -23.5 ° C 0.5K -24 ° C 0K -25 ° C -1K 39 (V) A4 --- 2500 ppm -20 ° C -12 ° C 8K -12.5 ° C 7.5K -14 ° C 6K The CFPP values given are average values of a double determination

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