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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
• • 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
  • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
• • 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
  • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
  • C10L1/2462—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds
  • C10L1/2468—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds obtained by reactions involving only carbon to carbon unsaturated bonds; derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • 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
• • 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

Definitions

• the present invention relates to the use of homopolymers of ethylenically unsaturated esters to improve the effect of cold flow improvers for fuel oil compositions.
• the compound further relates to the use of an additive which comprises such a polymer and a customary cold flow improver for reducing the CFPP value and, if appropriate, furthermore for reducing the CFPP2 value and / or the aspiration value of a fuel oil composition.
• Mineral oils and crude oils containing paraffinic waxes show a marked deterioration in the flow properties when the temperature is lowered.
• the reason for this lies in the crystallization of longer-chain paraffins which occur from the temperature of the cloud point (cloud point) and form large platelet-shaped wax crystals. These wax crystals have a sponge-like structure and lead to the inclusion of other fuel components in the crystal structure.
• s ⁇ hon has long been added to mineral oils and crude oils in small concentrations, which often consist of a combination of nu ⁇ leators with the actual cold flow improvers.
• Nu ⁇ leators are Substances that generate crystal nuclei that promote the formation of tiny crystals.
• Cold flow improvers have similar crystallization properties to the paraffins contained in mineral oil or crude oil, but prevent their growth.
• Wax Anti Settling Additives WASA are added to the crude and mineral oils, which prevent the tiny crystals from sinking into the oils.
• CFPP Cold Filter Plugging Point
• a so-called aspiration value (a temperature value) can be determined for individual fuel oils, which expresses itself in the determination of the CFPP value according to EN 116 in the temporary increase in the filling time of the pipette, which then occurs before the actual CFPP value is reached progressively decreases again (see EN 116, German version 1997, points 10.1.9 and 10.2.6, note).
• this manifests itself in a significant decrease in the flow rate of the fuel through the fuel filter in a certain temperature range.
• Both CFPP2 and the aspiration value cause a reduction in fuel oil quality.
• GB 1,154,966 describes homo- or copolymers of monoolefinically unsaturated compounds having a linear saturated group with at least 18 carbon atoms as lowering points for fuels.
• Examples include vinyl and allyl esters of long-chain mono-carboxylic acids, (meth) acrylic acid esters of long-chain alcohols and di-carbonate esters of long-chain alcohols.
• GB 1,161,188 describes homo- and copolymers of ethylenically unsaturated compounds with aliphatic hydrocarbon side chains with at least 14 carbon atoms as cold flow improvers for crude oils.
• WO 99/27037 describes copolymers of various (meth) acrylic acid esters as cold flow improvers for rape oil ethyl ester.
• WO 01/48032 describes polyacrylates, their production and use as flow improvers in middle distillate oils.
• DE 2 022 588 describes polymer mixtures which contain components A and B in a ratio of 5: 1 to 1: 5.
• Component A comprises homopolymers or copolymers which have long-chain, essentially linear paraffin side chains. Homopolymers of unsaturated esters are not mentioned.
• Component B comprises copolymers of ethylene with ethylenically unsaturated compounds. The mixtures are used as pour point depressants for residue fuels such as heavy fuel oil and crude oil. An influence on the CFPP value is not described.
• a disadvantage of the additives of the prior art is that they sometimes do not or only slightly reduce the CFPP value of fuel oils, such as, in particular, heating oils, for example LCO-containing heating oils.
• the prior art does not describe any additives which have an effect on the CFPP2 and / or aspiration value of the fuel oils (see above).
• the object of the present invention was therefore to further improve the effect of conventional cold flow improvers.
• the additive should improve the effect of the cold flow improvers on reducing the CFPP value of fuel oil compositions and, if appropriate, lead to a reduction or elimination of the CFPP2 values and / or to avoid aspiration effects (see above).
• the additive enable the effective mixing of the cold flow improvers into the fuel oils even at low temperatures.
• the object was achieved by using a hoopoly- mer of an ethylenically unsaturated ester as a booster component to improve the effect of cold flow improvers for fuel oil compositions.
• the homopolymer of the ethylenically unsaturated ester preferably has the following structural formula I:
• Ri stands for COOR 5 or (CH 2 ) m OCOR 6 ,
• R 2 and R 3 each independently represent H or C 1 -C 4 alkyl, or together with the carbon atoms to which they are attached form a 5- to 7-membered ⁇ arbo- or hetero- ⁇ y ⁇ lis ⁇ hen ring,
• R 4 represents H or C 1 -C 4 alkylene or COOR 5 ,
• R 5 for -CC 4 o-al yl which is optionally interrupted by one or more groupings which are selected from CO, NR 5 , 0 and S, and / or by one or more radicals which are selected from NR 7 R 8 , OR 7 , SR 7 , COR 7 , COOR 7 , CONR 7 R 8 , aryl or heterocy ⁇ lyl is substituted,
• R 5 represents H or R 5 ,
• R 7 and R 8 each independently represent H or -CC 4 alkyl
• n stands for a number from 2 to 3000
• n 0 or 1.
• C 1 -C 40 -alkyl in particular represents methyl, ethyl, n-propyl, isopropyl, n-butyl, se ⁇ -butyl, isobutyl, tert-butyl, pentyl, hexyl, Heptyl, O ⁇ tyl, 2-Ethylhexyl, Nonyl, De ⁇ yl, Unde ⁇ yl, Dode ⁇ yl, Tride ⁇ yl, Tetrade ⁇ yl, Pentadade ⁇ yl, Hexade ⁇ yl, Heptade ⁇ yl, O ⁇ tade ⁇ yl, Nonade ⁇ yl, Ei ⁇ osyl, Do ⁇ osyl, Tri ⁇ osyl, Tetra ⁇ osyl, Penta ⁇ osyl, Penta O ⁇ ta ⁇ osyl, Nona ⁇ osyl, Squalyl and the higher homologues as
• C 1 -C 4 alkyl is in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, se ⁇ -butyl, isobutyl and tert-butyl.
• aryl preferably represents C 6 -Ci 4 -yl, such as phenyl, naphthyl, anthra ⁇ enyl and phenanthryl, where the aryl radical may be one or more radicals selected from C 1 -C 40 -alkyl , OR 7 , SR 7 , NR 7 R 8 , COOR 7 , CONR 7 R 8 and aryl.
• Hetero ⁇ y ⁇ lyl preferably represents a 5- to 7-membered saturated or unsaturated hetero ⁇ y ⁇ lis ⁇ hen radical with 1 to 4 heteroatoms selected from 0, N and S, which is optionally condensed with a further hetero ⁇ y ⁇ lus or carbo ⁇ y ⁇ lus.
• pyrrolidine tetrahydrofuran, piperidine, morpholine, pyrrole, furan, thiophene, pyrazole, imidazole, oxazole, thiazole, pyridine, pyran, pyrimidine, pyridazine, pyrazine, coumarone, indole and quinoline.
• R 5 preferably stands for Cj-Cao-alkyl, particularly preferably for CC 24 alkyl, such as for example C 8 -C 22 alkyl.
• the alkyl radical is preferably not very branched or linear, in particular linear.
• the alkyl radical is preferably either unsubstituted or substituted by OH, NH 2 or SH SHH.
• R 6 is preferably H or Ci-Cao-alkyl, particularly preferred for H or -CC 24 alkyl, for example C 8 -C 22 alkyl.
• the alkyl radical is preferably not very branched or linear, in particular linear.
• the alkyl radical is preferably not substituted by the groups listed above, and is not interrupted.
• R 2 and R 3 are preferably H.
• R 4 preferably stands for H or COOR 5 , the statements above regarding the preferred radicals R 5 correspondingly correspondingly. In particular, R 4 stands for H.
• Preferred compounds of the formula I also have a number-average molecular weight Mn in the range from about 1000 to 40,000, particularly preferably from 5000 to 35,000 and in particular from 10,000 to 30,000.
• Suitable ethylenically unsaturated esters are the vinyl, propenyl and allyl esters of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthate acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arraic acid, behenic acid, lignoeric acid, cerotic acid and melissic acid, the vinyl esters being preferred; also the esters of acrylic acid, methacrylic acid, crotonic acid, maleic acid and fumaric acid with methanol, ethanol, ethylene glycol, propanol, propanediol, butanol, butanediol, pentanol, hexanol, octanol, 2-ethylhexanediol, nonanol, de ⁇ anol, lauryl alcohol,
• the cold flow improvers are preferably selected from
• the monomer is preferably selected from alkenyl carboxylic acid esters, (meth) acrylic acid esters and olefins.
• Suitable olefins are, for example, those with 3 to 10 carbon atoms and with 1 to 3, preferably with 1 or 2, in particular with one, carbon-carbon double bond. In the latter case, the carbon-carbon double bond can be arranged both terminally ( ⁇ -olefin) and internally.
• ⁇ -olefins particularly preferably cc-olefins having 3 to 6 carbon atoms, such as propene, 1-butene, 1-pentene and 1-hexene.
• Suitable (meth) acrylate are, for example, esters of (meth) acrylic acid with C ⁇ -C ⁇ 0 alkanols, in particular methanol, ethanol, propanol, isopropanol, n-butanol, se ⁇ -butanol, isobutanol nol, tert-butanol, pentanol, hexanol , Heptanol, o ⁇ tanol, 2-ethylhexanol, nonanol and de ⁇ anol.
• esters of (meth) acrylic acid with C ⁇ -C ⁇ 0 alkanols in particular methanol, ethanol, propanol, isopropanol, n-butanol, se ⁇ -butanol, isobutanol nol, tert-butanol, pentanol, hexanol , Heptanol, o ⁇ tanol, 2-ethyl
• Suitable alkenyl carboxylic acid esters are, for example, the vinyl and propenyl esters of carboxylic acids having 2 to 20 carbon atoms, the hydrocarbon radical of which can be linear or branched. Among these, the vinyl esters are preferred.
• Preferred carboxylic acids with a branched hydrocarbon radical are those whose branching si ⁇ h is in the ⁇ position to the carboxyl group, the ⁇ carbon atom being particularly preferably tertiary, ie the carboxylic acid being a so-called Neo ⁇ arboxylic acid.
• the hydrocarbon residue of the carboxylic acid is preferably linear.
• alkenyl carboxylic acid esters examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodioate and the corresponding propenyl esters, with the vinyl esters being preferred.
• a particularly preferred alkenyl carboxylic acid ester is vinyl acetate.
• the ethylenically unsaturated monomer is particularly preferably selected from alkenyl carboxylic acid esters.
• the ethylenically unsaturated monomer is copolymerized in the copolymer in an amount of preferably 1 to 50 mol%, particularly preferably 10 to 50 mol% and in particular 5 to 20 mol%, based on the total copolymer.
• the copolymer a) preferably has a number-average molecular weight M n of 500 to 30,000, particularly preferably from 1,000 to 30,000 and in particular from 1,000 to 10,000.
• Comb polymers b) are, for example, those described in "Comb-Like Polymers. Structures and Properties", NA Plate and VP Shibaev, J. Poly. S ⁇ i. Ma ⁇ romole ⁇ ular Revs. 8, pages 117 to 253 (1974).
• Comb polymers of the formula II are suitable, for example, from those described there
• D represents R 7 , COOR 7 , OCOR 7 , R 8 , COOR 7 or OR 7 ,
• E represents H, CH 3 , D or R 8 ,
• G represents H or D
• J represents H, R 8 , R 8 COOR 7 'aryl or hetero ⁇ y ⁇ lyl
• K represents H, COOR 8 , OCOR 8 , OR 8 or COOH
• L represents H, R 8 COOR 8 , OCOR 8 , COOH or aryl
• R 7 represents a hydrocarbon radical with at least 10 carbon atoms, preferably with 10 to 30 carbon atoms,
• R 8 represents a hydrocarbon radical with at least one carbon atom, preferably with 1 to 30 carbon atoms,
• m stands for a Molenbru ⁇ h in the range from 1.0 to 0.4
• n stands for a Molenbru ⁇ h in the range from 0 to 0.6.
• Preferred comb polymers are, for example, the copolymerization of maleic anhydride or fu aric acid with another ethylenically unsaturated monomer, for example with an ⁇ -olefin or an unsaturated ester such as vinyl acetate, and subsequent esterification of the anhydride or acid function with one Alcohol with at least 10 carbon atoms available.
• Further preferred comb polymers are copolymers of ⁇ -olefins and esterified comonomers, for example esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid.
• comb polymers are suitable.
• Comb polymers can also be polyfumarates or polymaleinates his.
• Homopolymers and copolymers of vinyl ethers are also suitable comb polymers.
• Suitable polyoxyalkylenes ⁇ ) are, for example, polyoxyalkylene esters, ethers, esters / ethers and mixtures thereof.
• the polyoxyalkylene compounds preferably contain at least one, particularly preferably at least two, linear alkyl groups with 10 to 30 carbon atoms and a polyoxyalkylene group with a molecular weight of up to 5000.
• the alkyl group of the polyoxyalkylene radical preferably contains 1 to 4 carbon atoms.
• Such polyoxyalkylene compounds are described, for example, in EP-A-0 061 895 and in US 4,491,455, to which reference is hereby made in full.
• Preferred polyoxyalkylene esters, ethers and esters / ethers have the general formula III
• R 9 and R 10 each independently represent R 11 , R 11_C0- , R i ⁇ _0-C0 (CH 2 ) z - or R H -0-CO (CH 2 ) z -CO-,
• y represents a number from 1 to 4,
• x represents a number from 2 to 200
• z represents a number from 1 to 4.
• Preferred polyoxyalkylene compounds of the formula III in which both R 9 and R 10 are R 11 , are polyethylene glycols and polypropylene glycols with a number average molecular weight from 100 to 5000.
• Preferred polyoxyalkylenes of the formula III in which one of the radicals R 9 is R 11 and the other stands for R xl -C0-, are polyoxyalkylene esters of fatty acids with 10 to 30 carbon atoms, such as stearic acid or behenic acid.
• Preferred polyoxyalkylene compounds in which both R 9 and R 10 represent a radical R ii -CO- are diesters of fatty acids having 10 to 30 carbon atoms, preferably stearic or behenic acid.
• the polar nitrogen compounds d), which are suitably oil-soluble, can be both ionic and non-ionic and preferably have at least one, particularly preferably at least 2, substituents of the formula> NR 12 , where R 12 is a C 8 -C 4o -Carbon residue stands.
• the nitrogen substituents can also be quaternized, i.e. in cationic form, lie.
• An example of such nitrogen compounds are ammonium salts and / or amides which are obtainable by the reaction of at least one amine substituted with at least one hydrocarbon radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof.
• the amines preferably contain at least one linear C 8 -C 40 alkyl radical.
• Suitable primary amines are, for example, o ⁇ tylamine, nonylamine, decylamine, unde ⁇ ylamine, dode ⁇ ylamine, tetrad ⁇ ylamine and the higher linear homologues.
• Suitable secondary amines are, for example, dio ⁇ tade ⁇ ylamine and methylbehenylamine.
• amine mixtures in particular large amine mixtures, such as fatty amines or hydrogenated tallamines, as described, for example, in Ullmann's En ⁇ y ⁇ lopedia of Industrial Architecture, 6th edition, 2000 ele ⁇ troni ⁇ release, chapter "Amines, aliphati ⁇ ".
• Acids suitable for the reaction are, for example, c- ⁇ lohexane-1,2-di ⁇ arboxylic acid, cyclohexene-1, 2-di ⁇ arboxylic acid, cycloshexane-l, 2-di ⁇ arboxylic acid, naphthalenedi ⁇ arboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and succinic acids substituted with long-chain hydrocarbon radicals.
• a further example of polar nitrogen compounds are ring systems which carry at least two substituents of the formula -A-NR 13 R 14 , in which A stands for a linear or branched aliphatic hydrocarbon group, which may be replaced by one or more groups which are selected from 0 , S, NR and CO, is interrupted, and R 13 and R 14 stand for a Cg-C 4 o -hydrocarbon radical which may be one or more groups selected from 0, S, NR 5 and CO, interrupted and / or by one or more substituents selected from OH, SH and NR 5 R 6 , where R 5 and R 6 are as defined above.
• A is preferably a methylene or polymethylene group having 2 to 20 methylene units.
• radicals R 13 and R 14 are 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-ketopropyl, ethoxyethyl and propoxypropyl.
• the ⁇ yclic system can be both homocy ⁇ lis ⁇ he, hetero-ro ⁇ y ⁇ lis ⁇ he, condensed poly ⁇ y ⁇ lis ⁇ he or not condensed poly ⁇ yclis ⁇ he systems.
• the ring system is preferably ⁇ arbo- or heteroaromatic, in particular ⁇ arboaromatic.
• poly ⁇ y ⁇ lis ⁇ he ring systems examples include condensed benzoid structures, such as naphthalene, anthracene, phenanthrene and pyrene, condensed nonbenzoic structures, such as azulene, indene, hydrindens and fluorene, not condensed polycylene, such as diphenyl, hetero ⁇ yolene, such as quinoline, such as quinoline, such as quinoline Benzofuran, coumarin, iso ⁇ umarin, benzthiophene, carbazole, diphenylene oxide and diphenylene sulfide, non-aromatic or partially saturated
• Ring systems such as De ⁇ alin
• three-dimensional structures such as ⁇ - Pinene, Camphene, Bornylene, Norbonan, Norbonen, Bi ⁇ y ⁇ looctan and Bi ⁇ y ⁇ loo ⁇ ten.
• Suitable polar nitrogen compounds are condensates of long-chain primary or secondary amines with carboxyl-containing polymers.
• Suitable polar nitrogen compounds are e.g. also described in DE-A-198 48 621, DE-A-196 22 052 or EP-B-398 101, to which reference is hereby made.
• Suitable sulfoarboxylic acids / sulfonic acids or their derivatives e) are, for example, those of the general formula IV
• R 15 represents a hydrocarbon radical
• R 16 and R 17 represent alkyl, alkoxyalkyl or polyalkoxyalkyl with at least 10 carbon atoms in the main chain,
• R 18 represents C 0 -C 5 alkylene
• Z- stands for an anion equivalent and A and B represent alkyl, alkenyl or two substituted hydrocarbon radicals or together with the carbon atoms to which they are attached form an aromatic or ⁇ y ⁇ loaliphatis ⁇ hes ring system.
• Suitable poly (meth) acrylic acid esters f) are both homo- and also copolymers of acrylic and methacrylic acid esters, the homopolymers being different from the compounds of the formula I used according to the invention.
• Preferred are copolymers of at least two different (meth) acrylic acid esters which differ from each other with respect to the condensed alcohol.
• the copolymer no ⁇ h polymerized another, different olefinically unsaturated monomer.
• the weight-average molecular weight of the polymer is preferably 50,000 to 500,000.
• a particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated C 4 and C 15 alcohols, the acid groups being neutralized with hydrogenated valley laminate.
• Suitable poly (meth) acrylic acid esters are described, for example, in WO 00/44857, to which reference is hereby made in full.
• Copolymers of ethylene with at least one further ethylenically unsaturated monomer a) are preferably used as cold flow improvers.
• preferred copolymers reference is made to the statements made above.
• Mixtures of copolymers a) with at least one of the cold flow improvers b) to f) are also suitable.
• Fuel oil compositions are preferably fuels. Suitable fuels are petrol and middle distillates, such as diesel fuels, heating oil or kerosene, with diesel fuel and heating oil being preferred.
• the heating oils are, for example, low-sulfur or low-sulfur petroleum refines or hard or lignite distillates, which usually have a boiling range of 150 to 400 ° C.
• the heating oils are preferably low-sulfur heating oils, for example those with a sulfur content of at most 0.1% by weight, preferably at most 0.05% by weight, particularly preferably at most 0.005% by weight, and in particular of at most 0.001% by weight.
• An example of heating oil is, in particular, heating oil for domestic oil firing systems or heating oil Called EL.
• the quality requirements for such heating oils are specified, for example, in DIN 51-603-1 (cf.au ⁇ h Ullmann's En ⁇ y ⁇ lopedia of Industrial Chemistry, 5th edition, Vol. A12, p. 617 ff., To which express reference is made here).
• the diesel fuels are, for example, petroleum refines, which usually have a boiling range of 100 to 400 ° C. These are mostly distillates with a 95% point up to 360 ° C or beyond. However, these can also be so-called “ultra low sulfur diesel” or "city diesel", characterized by a 95% point of, for example, a maximum of 345 ° C. and a sulfur content of a maximum of 0.005% by weight or by a 95% point of, for example 285 ° C and a maximum sulfur content of 0.001% by weight.
• those available through coal gasification or gas liquefaction (“gas to liquid” (GTL) fuels) are suitable.
• GTL gas to liquid
• Fuel oil compositions preferably added according to the invention are, in particular, middle distillates, such as heating oils, with an LCO content of up to 30% by weight, such as e.g. 2 to 20% by weight, or 5 to 15% by weight or 8 to 12% by weight, in each case based on the total weight of the composition.
• middle distillates such as heating oils
• LCO is a distillate fraction obtained in the usual way in the catalytic cracking of petroleum.
• an LCO fraction without being limited to it, e.g. have a boiling range of about 170 to 370 ° C and a specific density of about 0.9 (at 16 ° C).
• the additive mixture according to the invention is also preferred for additizing diesel fuels with a low sulfur content, that is to say with a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, in particular less than 0.005% by weight .-% and especially less than 0.001% by weight sulfur, or for the additive of heating oil with a low sulfur content, for example with a sulfur content of at most 0.1% by weight, preferably at most 0.05% by weight, particularly preferably of at most 0.005% by weight, and in particular of at most 0.001% by weight.
• the hoopolymer of ethylenically unsaturated esters is preferably used in a proportion, based on the total amount of the fuel oil composition, which, for itself, has essentially no effect on the cold flow properties. has the fuel oil compositions.
• the action improver is particularly preferably used in an amount of 0.0001 to 0.005% by weight, in particular 0.0001 to 0.001% by weight, based on the total amount of the fuel oil composition.
• the weight ratio of effectiveness improver to cold flow improver is preferably 1: 1 to 1: 500, particularly preferably 1: 5 to 1: 500, more preferably 1: 6 to 1: 500, no ⁇ h more preferably 1:10 to 1: 500, in particular 1:20 to 1: 500 and especially 1:20 to 1: 350, e.g. B. 1:20, 1:80, 1: 100, 1: 200 or 1: 300.
• Another object of the present invention is the use of an additive mixture comprising
• component A at least one homopolymer of an ethylenically unsaturated ester
• component B at least one conventional cold flow improver
• Another object of the present invention is the use of an additive mixture comprising
• component A at least one homopolymer of an ethylenically unsaturated ester
• component B at least one conventional cold flow improver
• the weight ratio of component A to component B is preferably from 1: 1 to 1: 500, particularly preferably 1: 5 to 1: 500, more preferably 1: 6 to 1: 500, no ⁇ h more preferably 1:10 to 1: 500, in particular 1:20 to 1: 500 and especially 1:20 to 1: 350, e.g. B. 1:20, 1:80, 1: 100, 1: 200 or 1: 300.
• homopolymers of ethylenically unsaturated esters, cold flow improvers and fuel oil compositions are examples of ethylenically unsaturated esters, cold flow improvers and fuel oil compositions.
• the additive mixtures used according to the invention preferably serve to improve the cold flow properties of fuel oil compositions, such as, for example, lowering the cloud point, the pour point, the viscosity and in particular the CFPP value.
• the present invention furthermore relates to an additive mixture comprising
• the weight ratio of component A to component B is preferably 1: 1 to 1: 500, particularly preferably 1: 5 to 1: 500, more preferably 1: 6 to 1: 500, no ⁇ h more preferably 1:10 to 1: 500, in particular 1:20 to 1: 500 and especially 1:20 to 1: 350, e.g. B. 1:20, 1: '80, 1: 100, 1: 200 or 1: 300.
• the present invention also relates to a fuel oil composition
• a fuel oil composition comprising a main amount of a hydrocarbon fuel and an effective amount of an additive mixture as defined above and optionally at least one further conventional additive.
• the present application also relates to an additive concentrate containing an additive mixture as defined above and at least one diluent and, if appropriate, at least one further additive.
• Suitable diluents are, for example, fractions obtained in petroleum processing, such as kerosene, naphtha or Brightsto ⁇ k. Aromatic and aliphatic hydrocarbons and alkoxyalkanols are also suitable. Preferred for middle distillates, especially for diesel fuels and heating oils Diluents used are naphtha, kerosene, diesel fuels, aromatic hydrocarbons, such as solvent naphtha s ⁇ hwer, Solvesso ® or Shellsol ®, and mixtures of these solvents and diluents.
• the additive mixture according to the invention is preferably present in the concentrates in an amount of 0.1 to 80% by weight, particularly preferably 1 to 70% by weight and in particular 20 to 60% by weight, based on the total weight of the concentrate, in front.
• Suitable additives which can be contained in the fuel or concentrate according to the invention in addition to the additive mixtures according to the invention, in particular for diesel fuels and heating oils, include detergents, corrosion inhibitors, dehazers, demulsifiers, foam inhibitors ("antifoam”), antioxidants, metal deactivators, multifunctional stabilizers , Get number improvers, combustion improvers, dyes, markers, solubilizers, antistatic agents, lubricity improvers, of the abovementioned various additives which improve the cold properties, such as nucleators, flow improvers (“MDFI"), paraffin dispersants (“WASA”) and the combination of the latter two Additives (“WAFI").
• detergents corrosion inhibitors, dehazers, demulsifiers, foam inhibitors ("antifoam”), antioxidants, metal deactivators, multifunctional stabilizers , Get number improvers, combustion improvers, dyes, markers, solubilizers, antistatic agents, lubricity improvers, of the abovementione
• the use of homopolymers of ethylenically unsaturated esters leads to an improved effect of conventional cold flow improvers on the cold flow properties of fuel oil compositions, in particular to a more effective reduction in the CFPP value.
• the cold flow improvers can be used in significantly smaller quantities than previously required.
• the effect improvers lead to better solubility of conventional cold flow improvers in the fuel compositions at low temperatures.
• middle distillates were mixed with different cold flow improvers alone or in a mixture with homopolymers of ethylenically unsaturated esters and the CFPP value according to EN 116 was determined.
• the following middle distillates were used
• IBP initial boiling point
• FBP final boiling point
• LCO Light ⁇ y ⁇ le oil
• HGO Heavy gas oil
• HOB Heating oil blend
• MDFI cold flow improvers
• MDFI 1 Ethylene vinyl acetate based polymer mixture (Keroflux ES 35 6100)
• MDFI 2 Ethylene vinyl acetate based polymer mixture (Keroflux ES 6204)
• MDFI 4 Ethylene vinyl acetate-based polymer mixture (Keroflux ES 6103) 45 The following polymeric esters (PE) were used to improve the effect:
• the CFPP values were determined in accordance with EN 116.
• a commercially available automatic CFPP analysis device e.g. available from WalterHerzog GmbH, Lauda-Königshofen, Germany, type MP 842. Compare the operating instructions for determining the CFPP 2 value.
• the mixing behavior of MDFI 1 in different fuels was determined at two different temperatures.
• the additive MDFI 1 or MDFI 1 with We - Improved PE
• the additive was added to the fuel, the mixture was heated at 45 ° C. for 15 minutes and the CFPP value was then determined. The results are shown in the table below.
• the cold flow improver MDFI 1 alone is not fully effective.
• the full effectiveness is achieved even when mixed in at a low temperature.

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