EP1801187B2 - Huiles minérales contenant des additifs détergents avec capacité de fluidité au froid améliorée - Google Patents

Huiles minérales contenant des additifs détergents avec capacité de fluidité au froid améliorée Download PDF

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EP1801187B2
EP1801187B2 EP06025303.6A EP06025303A EP1801187B2 EP 1801187 B2 EP1801187 B2 EP 1801187B2 EP 06025303 A EP06025303 A EP 06025303A EP 1801187 B2 EP1801187 B2 EP 1801187B2
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alkyl
carbon atoms
oil
radical
alkenyl
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EP1801187B1 (fr
EP1801187A2 (fr
EP1801187A3 (fr
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Matthias Dr. Krull
Robert Dr. Janssen
Werner Dr. Reimann
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Clariant Produkte Deutschland GmbH
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Clariant Produkte Deutschland GmbH
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Priority claimed from DE200510061465 external-priority patent/DE102005061465B4/de
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—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
    • C10L1/19—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
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - 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
    • C10L1/22—Organic compounds containing nitrogen
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1981—Condensation polymers of aldehydes or ketones
    • 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
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • 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
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
    • 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
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/224—Amides; Imides carboxylic acid amides, imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)

Definitions

  • the present invention relates to the use of polyoxyalkylene compounds to improve the cold flowability of mineral oil distillates containing detergent additives, and the mineral oil distillates to which additives have been added.
  • paraffins contained in particular in middle distillates can crystallize out when the temperature of the oil decreases and sometimes agglomerate with the inclusion of oil. This crystallization and agglomeration can lead to clogging of the filters in engines and firing systems, especially in winter, which prevents reliable dosing of the fuel and, under certain circumstances, can lead to a complete interruption in the fuel supply.
  • the paraffin problem is also exacerbated by the hydrodesulfurization of fuel oils, which has to be carried out for environmental reasons in order to reduce the sulfur content, which leads to an increased proportion of paraffins in the fuel oil, which are critical at low temperatures.
  • cold flow improvers or flow improvers
  • middle distillates which modify the crystal structure and tendency of the precipitated paraffins to agglomerate, so that the oils with additives can still be pumped or used at temperatures that are often more than 20°C are lower than for oils without additives.
  • Oil-soluble copolymers of ethylene and unsaturated esters, oil-soluble polar nitrogen compounds and/or comb polymers are usually used as cold flow improvers.
  • more specific additives have also been proposed.
  • WO 03/042336 discloses additives for low-sulfur petroleum distillates comprising an ester of an alkoxylated polyol and a polar nitrogen-containing paraffin dispersant.
  • the additives can be used together with detergent additives.
  • WO 03/042337 discloses low-sulfur petroleum distillates having improved refrigeration properties comprising an ester of an alkoxylated polyol and a copolymer of ethylene and unsaturated esters.
  • the mineral oil distillates can also contain detergent additives.
  • WO 03/042 338 discloses combinations of polyoxyalkylene compounds and alkylphenolic resins as refrigeration additives for middle distillates having a sulfur content of less than 0.05% by weight.
  • the additives can be used together with detergent additives.
  • EP-A-0 973 848 discloses mixtures of esters of C 10 -C 40 carboxylic acids and alkoxylated monohydric alcohols having more than 10 carbon atoms with at least one other cold flow improver. These mixtures are used to improve the cold flow properties of fuel oils.
  • the additives can also contain detergent additives that are not specified further.
  • U.S. 5,522,906 discloses gasoline containing a nitrogenous detergent additive, a carrier oil based on alkylene oxide adducts of alcohols, and esters of polyhydric alcohols or their alkylene oxide adducts.
  • WO 03/078553 discloses gasoline detergent additives containing a nitrogenous detergent and optionally a polyether solvent.
  • WO 96/23855 discloses additive mixtures of ashless dispersing additives and carboxylic acids or their esters to improve the lubricity of low-sulphur middle distillates. This document does not give any indications of joint use with flow improvers.
  • detergent additives are being developed with ever greater effectiveness. In addition, they are often used at very high dosing rates. It is reported that this reduces the specific consumption of diesel fuels, for example, and increases engine performance.
  • these additives often have negative effects on the cold flowability of middle distillates and in particular on the effectiveness of known cold flow improvers. Particularly in the case of middle distillates with a low boiling point and, at the same time, a low aromatics content, it is often difficult or even impossible to set satisfactory cold flow behavior in the presence of modern detergent additives using conventional flow improvers.
  • paraffin dispersion established by paraffin dispersants is often impaired without being able to be restored by increasing the dosage of paraffin dispersant.
  • the filterability measured as CFPP with cold flow improvers added to oils is often significantly reduced in the cold and can only be compensated for by greatly increasing the dosage of the flow improver.
  • Detergent additives that differ from higher polyamines are particularly problematic derive and have very high molecular weights, for example due to multiple alkylation and/or acylation of these polyamines. Problems in cold additization are often also caused by the presence of nitrogen-containing detergent additives which are either derived from higher polyamines or which carry several polyamine groups on their hydrophobic radical and thus carry a comparatively large polar head group.
  • the object of the present invention was therefore to improve the response behavior of cold flow improvers in middle distillates containing detergent additives.
  • a further object of the invention was to provide a detergent additive which is improved over the prior art and which does not impair the response behavior of cold flow improvers.
  • the subject of the invention is thus the use according to claim 1 of at least one oil-soluble polyoxyalkylene compound, where this polyoxyalkylene compound is an oil-soluble ester, ether or ether/ester of alkoxylated polyols having at least three repetitive alkoxy units derived from alkylene oxides having 2 to 5 carbon atoms per OH group of the polyol, which has at least two aliphatic hydrocarbon radicals having 12 to 30 carbon atoms carries C-atoms, for improving the response behavior of mineral oil cold flow improvers in middle distillates which contain at least one ashless, nitrogenous detergent additive.
  • this polyoxyalkylene compound is an oil-soluble ester, ether or ether/ester of alkoxylated polyols having at least three repetitive alkoxy units derived from alkylene oxides having 2 to 5 carbon atoms per OH group of the polyol, which has at least two aliphatic hydrocarbon radicals having 12 to 30 carbon atoms carries C-atoms, for
  • Particularly degraded is the response of flow improvers in middle distillates containing more than 20 ppm and especially more than 40 ppm, such as 50 to 2000 ppm, of nitrogenous detergent additive.
  • the additives according to the invention preferably contain, based on one part by weight of the nitrogen-containing detergent additive, from 0.1 to 5 parts by weight, for example from 0.3 to 3 parts by weight, of the oil-soluble polyoxyalkylene compound.
  • Ashless means that the additives in question essentially only consist of elements that form gaseous reaction products during combustion.
  • the additives preferably consist essentially only of the elements carbon, hydrogen, oxygen and nitrogen.
  • ashless additives are essentially free of metals and metal salts.
  • 10 to 10,000 ppm and in particular 100 to 3,000 ppm of the nitrogen-containing detergent additives are preferably added to middle distillates.
  • the alkyl or alkenyl radical imparts oil solubility to the detergent additives.
  • Detergent additives whose alkyl radical has 20 to 500 carbon atoms and in particular 20 to 350 carbon atoms, for example 50 to 200 carbon atoms, are particularly problematic.
  • This alkyl radical can be linear or branched, in particular it is branched.
  • the alkyl radical is derived from oligomers of lower olefins having 3 to 6 carbon atoms, such as propene, butene, pentene or hexene and mixtures thereof.
  • Preferred isomers of these olefins are isobutene, 2-butene, 1-butene, 2-methyl-2-butene, 2,3-dimethyl-2-butene, 1-pentene, 2-pentene and isopentene as well as their mixtures.
  • Propene, isobutene, 2-butene, 2,3-dimethyl-2-butene and mixtures thereof are particularly preferred.
  • Preferred mixtures of polyolefins contain more than 50% by mole, in particular more than 70%, for example more than 90% by mole, of isobutene.
  • Particularly suitable for the production of such detergent additives are highly reactive low molecular weight polyolefins with a proportion of terminal double bonds of at least 75%, specifically at least 85% and in particular at least 90%, for example at least 95%.
  • Particularly preferred low molecular weight polyolefins are poly(isobutylene), poly(2-butene), poly(2-methyl-2-butene), poly(2,3-dimethyl-2-butene), poly(ethylene-co-isobutylene) and atactic poly(propylene).
  • the molecular weight of particularly preferred polyolefins is between 500 and 3000 g/mol.
  • Such oligomers of lower olefins are accessible, for example, by polymerization using Lewis acids such as BF 3 and AlCl 3 , using Ziegler catalysts and in particular using metallocene catalysts.
  • the polar fraction of the detergent additives which are particularly problematic for the response behavior of known cold additives, is derived from polyamines having 2 to 20 N atoms.
  • polyamines correspond, for example, to the formula (R 9 ) 2 N-[AN(R 9 )] q -(R 9 ) wherein each R 9 is independently hydrogen, an alkyl or hydroxyalkyl radical having up to 24 carbon atoms, a polyoxyalkylene radical -(AO) r - or polyiminoalkylene radical -[AN(R 9 )] s -(R 9 ) with, however at least one R 9 is hydrogen, q is an integer from 1 to 19, A is an alkylene radical having 1 to 6 carbon atoms, r and s are independently 1 to 50.
  • polyamines usually mixtures of polyamines and in particular mixtures of poly(ethylene amines) and/or poly(propylene amines).
  • examples which may be mentioned are: ethylenediamine, 1,2-propylenediamine, dimethylaminopropylamine, diethylenetriamine (DETA), dipropylenetriamine, triethylenetetramine (TETA), tripropylenetetramine, tetraethylenepentamine (TEPA), tetrapropylenepentamine, pentaethylenehexamine (PEHA), pentapropylenehexamine and heavy polyamines.
  • Heavy polyamines are generally understood to be mixtures of polyalkylenepolyamines which, in addition to small amounts of TEPA and PEHA, mainly contain oligomers having 7 or more nitrogen atoms, two or more of which are in the form of primary amino groups. These polyamines often also contain structural elements branched via tertiary amino groups.
  • Suitable amines are those which comprise cyclic structural units derived from piperazine.
  • the piperazine units can preferably carry hydrogen, an alkyl or hydroxyalkyl radical having up to 24 carbon atoms or a polyiminoalkylene radical —[AN(R 9 )] s -(R 9 ) on one or both nitrogen atoms, where A, R 9 and s have the meanings given above.
  • Suitable amines include alicyclic diamines such as 1,4-di(aminomethyl)cyclohexane and heterocyclic nitrogen compounds such as imidazolines and N-aminoalkylpiperazines such as N-(2-aminoethyl)piperazine.
  • Detergent additives whose polar fraction is derived from polyamines bearing hydroxyl groups, from polyamines substituted with heterocycles and from aromatic polyamines are also problematic. Examples which may be mentioned are: N-(2-hydroxyethyl)ethylenediamine, N, N1 -bis-(2-hydroxyethyl)ethylenediamine, N-(3-hydroxybutyl)tetra(methylene)diamine, N-2-aminoethylpiperazine, N-2- and N-3-aminopropylmorpholine, N-3-(dimethylamino)propylpiperazine, 2-heptyl-3-(2-aminopropyl)imidazoline, 1,4-bis(2-aminoethyl)piperazine, 1-(2-hydroxyethyl)piperazine, various isomers of phenylenediamine and naphthalenediamine and mixtures of these amines.
  • Detergent additives based on heavy polyamines in which R 9 in the above formula is hydrogen and q has values of at least 3, in particular at least 4, for example 5, 6, 7 or higher, are particularly critical for cold additization of middle distillates.
  • Mixtures of polyamines which contain at least 40% by weight and in particular at least 60% by weight, for example at least 80% by weight, of higher polyamines having 5 or more nitrogen atoms are particularly problematic.
  • the heavy polyamines, which are particularly efficient for the dispersing behavior but are particularly problematic for cold additization are generally understood as meaning mixtures of polyalkylenepolyamines which, in addition to TEPA and PEHA, contain larger amounts, i.e. at least 10% by weight and in particular at least 30% by weight, specifically at least 50% by weight, such as more than 70% by weight, of oligomers containing 7 or more nitrogen atoms.
  • the oil-soluble alkyl group and the polar head group of the detergent additives can be linked either directly through a C-N bond or through an ester, amide, or imide bond.
  • preferred detergent additives are alkyl poly(amines), Mannich reaction products, hydrocarbon-substituted succinic acid amides and imides, and mixtures of these substance classes.
  • the detergent additives linked via CN bonds are preferably alkyl poly(amines), which can be obtained, for example, by reacting polyisobutylenes with polyamines, for example by hydroformylation and subsequent reductive amination with the abovementioned polyamines.
  • alkyl poly(amines) can be obtained, for example, by reacting polyisobutylenes with polyamines, for example by hydroformylation and subsequent reductive amination with the abovementioned polyamines.
  • One or more alkyl radicals can be attached to the polyamine.
  • Detergent additives based on higher polyamines having more than 4 N atoms, such as those having 5, 6, 7 or more N atoms, are particularly critical for cold additivation.
  • Detergent additives containing amide or imide bonds can be obtained, for example, by reacting alkenylsuccinic anhydrides with polyamines. Alkenylsuccinic anhydride and polyamine are preferably reacted in a molar ratio of about 1:0.5 to about 1:1.
  • the underlying alkenylsuccinic anhydrides are usually prepared by addition of ethylenically unsaturated polyolefins or chlorinated polyolefins onto ethylenically unsaturated dicarboxylic acids.
  • alkenyl succinic anhydrides can be prepared by reacting chlorinated polyolefins with maleic anhydride.
  • production can also be achieved by thermal addition of polyolefins to maleic anhydride in an "ene reaction".
  • Particularly suitable here are highly reactive olefins with a high proportion of, for example, more than 75% and specifically more than 85 mol %, based on the total number of polyolefin molecules, of isomers with a terminal double bond.
  • the molar ratio of the two reactants in the reaction between maleic anhydride and polyolefin can vary within wide limits. Preferably, it may be between 10:1 and 1:5, with molar ratios of 6:1 to 1:1 being particularly preferred.
  • Maleic anhydride is preferably used in a stoichiometric excess, for example 1.1 to 3 moles of maleic anhydride per mole of polyolefin. Excess maleic anhydride can be removed from the reaction mixture, for example by distillation.
  • the reaction products obtainable in this way have an average degree of maleation of more than 1, preferably about 1.01 to 2.0 and in particular 1.1 to 1.8 dicarboxylic acid units per alkyl radical. Products with significantly increased effectiveness as detergent additives are formed from this by reaction with the above-mentioned amines.
  • alkenylsuccinic anhydrides with polyamines leads to products which can carry one or more amide and/or imide bonds per polyamine and, depending on the degree of maleation, one or two polyamines per alkyl radical.
  • alkenylsuccinic anhydride and polyamine are reacted in equimolar amounts.
  • Typical and particularly preferred acylated nitrogen compounds are obtained by reacting poly(isobutylene), poly(2-butenyl), poly(2-methyl-2-butenyl), poly(2,3-dimethyl-2-butenyl) or Poly(propenyl)succinic anhydrides having an average of about 1.2 to 1.5 anhydride groups per alkyl radical, the alkylene radicals of which have between 50 and 400 carbon atoms, with a mixture of poly(ethyleneamines) having at least 3 and preferably about 4 to 12 such as for example 5 to 7 nitrogen atoms and at least 2 and preferably about 3 to 11 such as 4 to 6 ethylene units.
  • Oil-soluble Mannich reaction products based on polyolefin-substituted phenols and polyamines also impair the effectiveness of conventional cold flow improvers.
  • Such Mannich bases can be prepared by known methods, for example by alkylating phenol and/or salicylic acid with the polyolefins described above, such as poly(isobutylene), poly(2-butene), poly(2-methyl-2-butene), poly( 2,3-dimethyl-2-butene) or atactic poly(propylene) and subsequent condensation of the alkylphenol with aldehydes having 1 to 6 carbon atoms such as formaldehyde or its reactive equivalents such as formalin or paraformaldehyde and the polyamines described above such as TEPA, PEHA or heavy polyamines.
  • the average molecular weight determined by vapor pressure osmometry which is particularly efficient but at the same time also particularly critical for the cold additization of middle distillates, is above 800 g/mol and in particular between 2,000 and 20,000 g/mol, for example between 3,000 and 15,000 g/mol (measured by GPC against poly (styrene) standards in THF).
  • the average molecular weight of the detergent additives described above can also be increased via crosslinking agents and adapted to the intended use.
  • Suitable crosslinking agents are for example dialdehydes such as glutardialdehyde, bisepoxides derived for example from bisphenol A, dicarboxylic acids and their reactive derivatives such as maleic anhydride and alkenylsuccinic anhydrides and higher polybasic carboxylic acids and their derivatives such as trimellitic acid, trimellitic anhydride and pyromellitic dianhydride.
  • the oil-soluble polyoxyalkylene compounds have at least 3, such as for example 4, 5 or more aliphatic hydrocarbon residues.
  • These radicals independently of one another, preferably have 16 to 26 carbon atoms, for example 17 to 24 carbon atoms.
  • the aliphatic hydrocarbon radicals can be linear or branched; they are preferably linear. Furthermore, they are preferably largely saturated; in particular, these are alkyl radicals. Esters are particularly preferred.
  • particularly suitable polyols are polyethylene glycols, polypropylene glycols, polybutylene glycols and their copolymers with a molecular weight of about 100 to about 5000 g/mol, preferably 200 to 2000 g/mol.
  • the oil-soluble polyoxyalkylene compounds are derived from polyols having 3 or more OH groups, preferably from polyols having 3 to about 50 OH groups, for example 4 to 10 OH groups, in particular from neopentyl glycol, glycerol, trimethylolethane, trimethylolpropane , sorbitan, pentaerythritol, and the oligomers accessible therefrom by condensation with 2 to 10 monomer units such as polyglycerol.
  • polyols such as sorbitol, sucrose, glucose, fructose and their oligomers such as cyclodextrin are also suitable as polyols provided their esterified or etherified alkoxylates are oil-soluble at least in application-relevant amounts.
  • Preferred polyoxyalkylene compounds thus have a branched polyoxyalkylene nucleus to which are attached a plurality of alkyl groups imparting oil solubility.
  • the polyols are generally reacted with 3 to 70 moles of alkylene oxide, preferably 4 to 50 moles, in particular 5 to 20 moles, of alkylene oxide per hydroxyl group of the polyol.
  • Preferred alkylene oxides are ethylene oxide, propylene oxide and/or butylene oxide.
  • the alkoxylation is carried out by known methods.
  • the fatty acids suitable for the esterification of the alkoxylated polyols preferably have 12 to 30 and in particular 16 to 26 carbon atoms.
  • the alkyl radicals of the fatty acids can be branched or linear; preferred fatty acids carry linear alkyl radicals.
  • Suitable fatty acids are, for example, lauric, tridecanoic, myristic, pentadecanoic, palmitic, margaric, stearic, isostearic, arachidic and behenic acid, oleic and erucic acid, palmitoleic, myristoleic, ricinoleic acid, and from natural fats and oils derived fatty acid mixtures.
  • Preferred fatty acid mixtures contain more than 50 mol % of fatty acids with at least 20 carbon atoms. Preferably less than 50 mol % of the fatty acids used for the esterification contain double bonds, in particular less than 10 mol %; specifically, they are largely saturated.
  • the esterification can also be carried out starting from reactive derivatives of fatty acids such as esters with lower alcohols (e.g. methyl or ethyl ester) or anhydrides.
  • largely saturated is understood as meaning an iodine number of the fatty acid or fatty alcohol used of up to 5 g I per 100 g of fatty acid or fatty alcohol.
  • polybasic carboxylic acids can also be used to esterify the alkoxylated polyols.
  • suitable polybasic carboxylic acids are dimer fatty acids, alkenylsuccinic acids and aromatic polycarboxylic acids and their derivatives such as anhydrides and C 1 to C 5 esters.
  • Alkenylsuccinic acid and its derivatives with alkyl radicals having 8 to 200, in particular 10 to 50, carbon atoms are preferred.
  • Examples are dodecenyl, octadecenyl and poly(isobutenyl) succinic anhydride.
  • the polybasic carboxylic acids are preferably used here in minor proportions of up to 30 mol %, preferably 1 to 20 mol %, in particular 2 to 10 mol %.
  • Ester and fatty acid are used for the esterification in a ratio of 1.5:1 to 1:1.5, preferably in a ratio of 1.1:1 to 1:1.1 and in particular equimolar, based on the content of hydroxyl groups on the one hand and carboxyl groups on the other.
  • the terminal hydroxyl groups are converted into terminal carboxyl groups, for example by oxidation or by reaction with dicarboxylic acids.
  • Polyoxyalkylene esters according to the invention are likewise obtained by reaction with fatty alcohols having 8 to 50, in particular 12 to 30, especially 16 to 26 carbon atoms.
  • Preferred fatty alcohols or fatty alcohol mixtures contain more than 50 mol % fatty alcohols with at least 20 carbon atoms.
  • Preferably less than 50 mol % of the fatty alcohols used for the esterification contain double bonds, in particular less than 10 mol %; specifically, they are largely saturated.
  • esters of alkoxylated fatty alcohols with fatty acids which contain the abovementioned proportions of poly(alkylene oxides) and whose fatty alcohol and fatty acid have the abovementioned alkyl chain lengths and degrees of saturation.
  • the esterification is carried out according to customary methods.
  • the reaction of polyol alkoxylate with fatty acid if appropriate in the presence of catalysts such as, for example, para-toluenesulfonic acid, C 2 - to C 50 -alkylbenzenesulfonic acids, methanesulfonic acid or acidic ion exchangers, has proven particularly useful.
  • the water of reaction can be removed by distillation by direct condensation or preferably by azeotropic distillation in the presence of organic solvents, in particular aromatic solvents such as toluene, xylene or higher-boiling mixtures such as ®Shellsol A, ®Shellsol B, ®Shellsol AB or solvent naphtha.
  • the esterification is preferably essentially complete, ie 1.0 to 1.5 mol of fatty acid per mol of hydroxyl groups are used for the esterification.
  • the acid number of the esters is generally below 15 mg KOH/g, preferably below 10 mg KOH/g, specifically below 5 mg KOH/g.
  • the OH number of the esters is preferably below 20 mg KOH/g and specifically below 10 mg KOH/g.
  • alkoxylated polyols described above can be converted into polyoxyalkylene compounds suitable according to the invention by etherification with fatty alcohols having 8 to 50, in particular 12 to 30, especially 16 to 26 carbon atoms.
  • the fatty alcohols preferred for this purpose are linear and largely saturated.
  • the etherification preferably takes place completely or at least as completely as possible. The etherification is carried out according to known methods.
  • Particularly preferred polyoxyalkylene compounds are derived from polyols having 3, 4 and 5 OH groups, which carry about 5 to 10 mol of structural units derived from ethylene oxide per hydroxyl group of the polyol and are largely completely esterified with largely saturated C 17 -C 24 fatty acids.
  • Other particularly preferred polyoxyalkylene compounds are polyethylene glycols esterified with largely saturated C 17 -C 24 fatty acids and having molecular weights of about 350 to 1000 g/mol.
  • polyoxyalkylene compounds are polyethylene glycols esterified with stearic acid and in particular behenic acid and having molecular weights between 350 and 800 g/mol; neopentyl glycol 14-ethylene oxide distearate (neopentyl glycol alkoxylated with 14 moles of ethylene oxide and then esterified with 2 moles of stearic acid) and in particular neopentyl glycol 14-ethylene oxide dibehenate; glycerol 20-ethylene oxide tristearate, glycerol 20-ethylene oxide dibehenate and in particular glycerol 20-ethylene oxide tribehenate; trimethylolpropane-22-ethylene oxide tribehenate; sorbitan 25-ethylene oxide tristearate, sorbitan 25-ethylene oxide tetrastearate, sorbitan 25-ethylene oxide tribehenate and in particular sorbitan 25-ethylene oxide tetrabehenate; pentaerythritol 30-ethylene oxide tribehenate,
  • the quantitative ratio between detergent additive and polyoxyalkylene compound in the oil containing the additive can vary within wide limits.
  • Flow improvers used in the middle distillates according to the invention are in particular one or more of the following substance classes III to VII, ethylene copolymers (component III) or mixtures thereof with one or more of components IV to VII being preferably used.
  • ethylene copolymers (component III) and alkylphenol-aldehyde resins (component V) are preferably used.
  • component III alkylphenol-aldehyde resins
  • component VI comb polymers
  • ethylene copolymers component III and olefin (co )polymers
  • Mixtures of ethylene copolymers (component III) with components IV and V or components IV and VI have proven particularly suitable for the paraffin dispersion.
  • Preferred cold flow improvers as component III are copolymers of ethylene and olefinically unsaturated compounds.
  • Particularly suitable ethylene copolymers are those which, in addition to ethylene, contain 8 to 21 mol %, in particular 10 to 18 mol %, of olefinically unsaturated compounds as comonomers.
  • the olefinically unsaturated compounds are preferably vinyl esters, acrylic esters, methacrylic esters, alkyl vinyl ethers and/or alkenes, it being possible for the compounds mentioned to be substituted with hydroxyl groups.
  • One or more comonomers can be contained in the polymer.
  • R 1 is C 1 to C 30 alkyl, preferably C 4 to C 16 alkyl, especially C 6 to C 12 alkyl.
  • the alkyl groups mentioned can be substituted with one or more hydroxyl groups.
  • R 1 is a branched alkyl group or a neoalkyl group having 7 to 11 carbon atoms, in particular having 8, 9 or 10 carbon atoms.
  • Particularly preferred vinyl esters are derived from secondary and in particular tertiary carboxylic acids whose branching is in the alpha position to the carbonyl group.
  • Suitable vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl hexanoate, vinyl heptanoate, vinyl octanoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate and versatic esters such as vinyl neononanoate, vinyl neodecanoate, vinyl neoundecanoate.
  • these ethylene copolymers contain vinyl acetate and at least one other vinyl ester of the formula 1 where R 1 is C 4 to C 30 alkyl, preferably C 4 to C 16 alkyl, especially C 6 to C 12 alkyl .
  • Suitable acrylic esters include, for example, 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 these comonomers.
  • the alkyl groups mentioned can be substituted with one or more hydroxyl groups.
  • An example of such an acrylic ester is hydroxyethyl methacrylate.
  • the alkenes are preferably monounsaturated hydrocarbons having 3 to 30 carbon atoms, more preferably 4 to 16 carbon atoms and especially 5 to 12 carbon atoms.
  • Suitable alkenes include propene, butene, isobutylene, pentene, hexene, 4-methylpentene, octene, diisobutylene, and norbornene and its derivatives such as methyl norbornene and vinyl norbornene.
  • the alkyl groups mentioned can be substituted with one or more hydroxyl groups.
  • terpolymers which, in addition to ethylene, contain 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 longer-chain and preferably branched Contain vinyl esters such as vinyl 2-ethylhexanoate, vinyl neononanoate or vinyl neodecanoate, the total comonomer content of the terpolymers preferably being between 8 and 21 mol%, in particular between 12 and 18 mol%.
  • other particularly preferred copolymers also contain 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.
  • These ethylene co- and terpolymers preferably have melt viscosities at 140° C. of from 20 to 10,000 mPas, in particular from 30 to 5000 mPas, especially from 50 to 2000 mPas.
  • the degrees of branching determined by means of 1 H-NMR spectroscopy are preferably between 1 and 9 CH 3 /100 CH 2 groups, in particular between 2 and 6 CH 3 /100 CH 2 groups, which do not originate from the comonomers.
  • the polymers on which the mixtures are based particularly preferably differ in at least one characteristic.
  • they can contain different comonomers, have different comonomer contents, molecular weights and/or degrees of branching.
  • the mixing ratio between the additives according to the invention and ethylene copolymers as component III can vary within wide limits depending on the application, the ethylene copolymers III often representing the larger proportion.
  • Such additive and oil mixtures preferably contain 0.1 to 25, preferably 0.5 to 10, parts by weight of ethylene copolymers per part by weight of the additive combination according to the invention.
  • Oil-soluble polar nitrogen compounds are suitable as further cold flow improvers. These are preferably reaction products of fatty amines with compounds containing an acyl group.
  • the preferred amines are compounds of the formula NR 6 R 7 R 8 , in which R 6 , R 7 and R 8 can be the same or different, and at least one of these groups is C 8 -C 36 -alkyl, C 6 - C 36 -cycloalkyl, C 8 -C 36 -alkenyl, in particular C 12 -C 24 -alkyl, C 12 -C 24 -alkenyl or cyclohexyl, and the other groups are either hydrogen, C 1 -C 36 -alkyl, C 2 -C 36 -alkenyl, cyclohexyl, or a group of the formulas -(AO) x -E or -(CH 2 ) n -NYZ, in which A represents an ethyl or propyl group, x
  • the alkyl and alkenyl radicals can be linear or branched and contain up to two double bonds. They are preferably linear and largely saturated, ie they have iodine values of less than 75 gl 2 /g, preferably less than 60 gl 2 /g and in particular between 1 and 10 gl 2 /g. Particular preference is given to secondary fatty amines in which two of the groups R 6 , R 7 and R 8 are C 8 -C 36 alkyl, C 6 -C 36 cycloalkyl, C 8 -C 36 alkenyl, in particular C 12 -C C 24 -alkyl, C 12 -C 24 -alkenyl or cyclohexyl.
  • Suitable fatty amines are octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, behenylamine, didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine, dioctadecylamine, diicosylamine, dibehenylamine and mixtures thereof.
  • the amines contain chain cuts based on natural raw materials such as coconut fatty amine, tallow fatty amine, hydrogenated tallow fatty amine, dicocos fatty amine, ditallow fatty amine and di(hydrogenated tallow fatty amine).
  • Particularly preferred amine derivatives are amine salts, imides and/or amides such as, for example, amide-ammonium salts of secondary fatty amines, in particular of dicoco fatty amine, ditallow fatty amine and distearyl amine.
  • Carbonyl compounds suitable for the reaction with amines are both monomeric and polymeric Compounds with one or more carboxyl groups. In the case of the monomeric carbonyl compounds, those having 2, 3 or 4 carbonyl groups are preferred. They can also contain heteroatoms such as oxygen, sulfur and nitrogen.
  • Suitable carboxylic acids are, for example, maleic, fumaric, crotonic, itaconic, succinic, C 1 -C 40 -alkenylsuccinic, adipic, glutaric, sebacic and malonic acid and also benzoic, phthalic, trimellitic and pyromellitic acid, nitrilotriacetic acid , ethylenediaminetetraacetic acid and its reactive derivatives such as esters, anhydrides and acid halides.
  • copolymers of ethylenically unsaturated acids such as, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid have proven to be polymeric carbonyl compounds, with copolymers of maleic anhydride being particularly preferred.
  • Suitable comonomers are those which impart oil solubility to the copolymer. Oil-soluble is understood here to mean that the copolymer, after reaction with the fatty amine, dissolves without leaving any residue in the middle distillate to be additized at dosing rates relevant in practice.
  • Suitable comonomers are olefins, alkyl esters of acrylic acid and methacrylic acid, alkyl vinyl esters and alkyl vinyl ethers having 2 to 75, preferably 4 to 40 and in particular 8 to 20 carbon atoms in the alkyl radical.
  • the carbon number refers to the alkyl group attached to the double bond.
  • the molecular weights of the polymeric carbonyl compounds are preferably between 400 and 20,000, particularly preferably between 500 and 10,000, for example between 1,000 and 5,000.
  • Oil-soluble polar nitrogen compounds which are obtained by reacting aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides (cf. U.S. 4,211,534 ).
  • amides and ammonium salts of aminoalkylenepolycarboxylic acids such as nitrilotriacetic acid or ethylenediaminetetraacetic acid with secondary amines are suitable as oil-soluble polar nitrogen compounds (cf. EP 0 398 101 ).
  • oil-soluble polar nitrogen compounds are copolymers of maleic anhydride with ⁇ , ⁇ -unsaturated compounds, which can optionally be reacted with primary monoalkylamines and/or aliphatic alcohols (cf. EP-A-0 154 177 , EP 0 777 712 ), the reaction products of alkenylspirobislactones with amines (cf. EP-A-0 413 279 B1) and after EP-A-0 606 055 A2 Reaction products of terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic acid anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols.
  • the mixing ratio between the ethylene copolymers III according to the invention and oil-soluble polar nitrogen compounds as component IV can vary depending on the application.
  • Such additive mixtures preferably contain, based on the active substances, 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, of at least one oil-soluble polar nitrogen compound per part by weight of the additive combination according to the invention.
  • alkylphenol-aldehyde resins as component V. These are, in particular, those alkylphenol-aldehyde resins which are derived from alkylphenols having one or two alkyl radicals in the ortho and/or para position to the OH group. Particularly preferred starting materials are alkylphenols which have at least two hydrogen atoms on the aromatic compound which are capable of condensing with aldehydes, and in particular monoalkylated phenols. The alkyl radical is particularly preferably in the para position to the phenolic OH group.
  • the alkyl radicals (which are generally understood to mean hydrocarbon radicals according to the definition below) can be the same or different, they can be saturated or unsaturated and have 1-200, preferably 1-20, especially 4-16 such as 6-12 carbon atoms; preferably it is n-, iso- and tert-butyl, n- and isopentyl, n- and iso-hexyl, n- and iso-octyl, n- and isononyl, n- and isodecyl, n- and isododecyl, tetradecyl, hexadecyl, octadecyl, tripropenyl, tetrapropenyl, poly(propenyl) and poly(isobutenyl) radicals.
  • mixtures of alkylphenols with different alkyl radicals are used to prepare the alkylphenol resins.
  • resins based on butylphenol on the one hand and octyl-, nonyl- and/or dodecylphenol in a molar ratio of 1:10 to 10:1 on the other hand have proven particularly useful.
  • Suitable alkylphenol resins can also contain or consist of structural units of other phenol analogues such as salicylic acid, hydroxybenzoic acid and their derivatives such as esters, amides and salts.
  • Suitable aldehydes for the alkylphenol-aldehyde resins are those having 1 to 12 carbon atoms and preferably those having 1 to 4 carbon atoms such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2-ethylhexanal, benzaldehyde, glyoxylic acid and their reactive equivalents such as paraformaldehyde and trioxane.
  • Formaldehyde in the form of paraformaldehyde and in particular formalin is particularly preferred.
  • the molecular weight of the alkylphenol-aldehyde resins measured by gel permeation chromatography against poly(styrene) standards in THF is preferably 500-25,000 g/mol, particularly preferably 800-10,000 g/mol and especially 1,000-5,000 g/mol, such as 1500-3,000 g/mol.
  • the prerequisite here is that the alkylphenol-aldehyde resins are oil-soluble at least in application-relevant concentrations of 0.001 to 1% by weight.
  • these are alkylphenol-formaldehyde resins, the oligomers or polymers with a repetitive structural unit of the formula wherein R 11 is C 1 -C 200 alkyl or alkenyl, OR 10 or OC(O)-R 10 , R 10 is C 1 -C 200 alkyl or alkenyl and n is a number from 2 to 100, contain.
  • R 10 is preferably C 1 -C 20 -alkyl or alkenyl and in particular C 4 -C 16 -alkyl or alkenyl such as, for example, C 6 -C 12 -alkyl or alkenyl.
  • R 11 is particularly preferably C 1 -C 20 -alkyl or alkenyl and in particular C 4 -C 16 -alkyl or alkenyl, for example C 6 -C 12 -alkyl or alkenyl.
  • n is preferably a number from 2 to 50 and especially a number from 3 to 25, for example a number from 5 to 15.
  • alkylphenol-aldehyde resins can be obtained by known processes, for example by condensing the corresponding alkylphenols with formaldehyde, ie with 0.5 to 1.5 mol, preferably 0.8 to 1.2 mol, of formaldehyde per mole of alkylphenol.
  • the condensation can be carried out without a solvent, but it is preferably carried out in the presence of an inert organic solvent which is immiscible or only partially water-miscible, such as mineral oils, alcohols, ethers and the like. Solvents which can form azeotropes with water are particularly preferred.
  • Aromatics such as toluene, xylene, diethylbenzene and higher-boiling commercial solvent mixtures such as ®Shellsol AB and solvent naphtha are used in particular as such solvents.
  • Fatty acids and their derivatives such as esters with lower alcohols having 1 to 5 carbon atoms such as ethanol and in particular methanol are also suitable as solvents.
  • the condensation preferably takes place between 70 and 200°C, for example between 90 and 160°C. It is usually catalyzed by 0.05 to 5% by weight of bases or preferably by 0.05 to 5% by weight of acids.
  • carboxylic acids such as acetic acid and oxalic acid
  • particularly strong mineral acids such as hydrochloric acid, phosphoric acid and sulfuric acid and also sulfonic acids are customary as acidic catalysts.
  • Particularly suitable catalysts are sulfonic acids which contain at least one sulfonic acid group and at least one saturated or unsaturated, linear, branched and/or cyclic hydrocarbon radical having 1 to 40 carbon atoms and preferably having 3 to 24 carbon atoms.
  • Aromatic sulfonic acids specifically alkylaromatic monosulfonic acids having one or more C 1 -C 28 -alkyl radicals and in particular those having C 3 -C 22 -alkyl radicals, are particularly preferred.
  • Suitable examples are methanesulfonic acid, butanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, 2-mesitylenesulfonic acid, 4-ethylbenzenesulfonic acid, isopropylbenzenesulfonic acid, 4-butylbenzenesulfonic acid, 4-octylbenzenesulfonic acid; Dodecylbenzenesulfonic acid, Didodecylbenzenesulfonic acid, Naphthalenesulfonic acid.
  • Suitable comb polymers are, for example, copolymers of ethylenically unsaturated dicarboxylic acids such as maleic or fumaric acid with other ethylenically unsaturated monomers such as olefins or vinyl esters such as vinyl acetate.
  • Particularly suitable olefins are ⁇ -olefins having 10 to 24 carbon atoms, such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and mixtures thereof.
  • n-tetradecan-1-ol and n-hexadecan-1-ol are particularly preferred.
  • comb polymers are poly(alkyl acrylates), poly(alkyl methacrylates) and poly(alkyl vinyl ethers) derived from alcohols having 12 to 20 carbon atoms, and poly(vinyl esters) derived from fatty acids having 12 to 20 carbon atoms .
  • Also suitable as flow improvers are homo- and copolymers of olefins having 2 to 30 carbon atoms (component VII). These can be derived directly from monoethylenically unsaturated monomers or can be prepared indirectly by hydrogenating polymers derived from polyunsaturated monomers such as isoprene or butadiene. In addition to ethylene, preferred copolymers contain structural units which are derived from ⁇ -olefins having 3 to 24 carbon atoms and have molecular weights of up to 120,000 g/mol.
  • Preferred ⁇ -olefins are propylene, butene, isobutene, n-hexene, isohexene, n-octene, isooctene, n-decene, isodecene.
  • the comonomer content of olefins is preferably between 15 and 50 mol %, particularly preferably between 20 and 35 mol % and especially between 30 and 45 mol %.
  • These copolymers may also contain small amounts, e.g., up to 10 mole percent, of other comonomers such as non-terminal olefins or non-conjugated olefins. Ethylene-propylene copolymers are particularly preferred.
  • copolymers of different olefins having 5 to 30 carbon atoms such as poly(hexene-co-decene).
  • the olefin homo- and copolymers can be prepared by known methods, e.g., using Ziegler or metallocene catalysts.
  • Suitable olefin copolymers are block copolymers containing blocks of olefinically unsaturated, aromatic monomers A and blocks of hydrogenated polyolefins B.
  • the mixing ratio between the additives according to the invention and the other components V, VI and VII is generally between 1:10 and 10:1, preferably between 1:5 and 5:1.
  • the additives according to the invention are preferably used as concentrates which contain 10 to 95% by weight and preferably 20 to 80% by weight, for example 25 to 60% by weight, of solvent.
  • Preferred solvents are high-boiling, low-viscosity aliphatic, aromatic and alkylaromatic hydrocarbons, alcohols, esters, ethers and mixtures thereof.
  • Preferably such concentrates contain 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, such as 0.3 to 3 parts by weight of the polyoxyalkylene compound per part by weight of detergent additive.
  • the polyoxyalkylene compounds according to the invention improve the response behavior of middle distillates containing detergent additives, such as kerosene, jet fuel, diesel and heating oil, for conventional flow improvers in terms of lowering the pour point and CFPP value and improving the paraffin dispersion.
  • detergent additives such as kerosene, jet fuel, diesel and heating oil
  • Middle distillates refers in particular to those mineral oils which are obtained by distillation of crude oil, boil in the range from about 150 to 450° C. and in particular in the range from about 170 to 390° C., for example kerosene, jet fuel, diesel and heating oil.
  • Middle distillates usually contain about 5 to 50% by weight, for example about 10 to 35% by weight, of n-paraffins, of which the longer-chain ones can crystallize out on cooling and impair the flowability of the middle distillate.
  • the compositions according to the invention are particularly advantageous in middle distillates with a low aromatics content of less than 21% by weight, such as less than 19% by weight.
  • compositions according to the invention are particularly advantageous in middle distillates with a low boiling point, i.e. in those middle distillates which have 90% distillation points below 360° C., in particular 350° C. and in special cases below 340° C. and also in those middle distillates which have boiling ranges between 20 and 90%.
  • Aromatic compounds are taken to mean the sum of mono-, di- and polycyclic aromatic compounds, as can be determined using HPLC in accordance with DIN EN 12916 (2001 edition).
  • the middle distillates can also contain minor amounts, such as up to 40 % by volume, preferably 1 to 20% by volume, especially 2 to 15% by volume, for example 3 to 10% by volume, of the oils of animal and/or vegetable origin described in more detail below, for example fatty acid methyl esters.
  • compositions according to the invention are also suitable for improving the low-temperature properties of fuels containing detergent additives and based on renewable raw materials (biofuels).
  • Biofuels are oils obtained from animal and preferably vegetable material or both, as well as derivatives thereof, which can be used as fuel and in particular as diesel or heating oil.
  • These are in particular triglycerides of fatty acids having 10 to 24 carbon atoms and the fatty acid esters of lower alcohols such as methanol or ethanol which can be obtained from them by transesterification.
  • biofuels examples include canola 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.
  • Other examples include oils derived from wheat, jute, sesame, shea nut, arachis oil and linseed oil.
  • the fatty acid alkyl esters, also referred to as biodiesel can be derived from these oils by methods known in the art.
  • Rapeseed oil which is a mixture of fatty acids esterified with glycerol, is preferred because it is available in large quantities and is easily obtained by pressing rapeseeds.
  • the oils from sunflowers, palm trees and soybeans, which are also widespread, and their mixtures with rapeseed oil are preferred.
  • Lower alkyl esters of fatty acids are particularly suitable as biofuels.
  • biofuels are, for example, commercial mixtures of ethyl, propyl, butyl and especially 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.
  • lauric acid myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselinic acid, ricinoleic acid, elaeostearic acid, linoleic acid, l
  • Preferred esters have an iodine value of from 50 to 150 and in particular from 90 to 125.
  • Mixtures with particularly advantageous properties are those which mainly, i. H. contain at least 50% by weight of 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.
  • the additives can be used alone or together with other additives, for example with other pour point depressants or dewaxing aids, with other detergents, with antioxidants, cetane number improvers, dehazers, demulsifiers, dispersants, defoamers, dyes, corrosion inhibitors, lubricity additives, sludge inhibitors, and odorants /or additions to lower the cloud point.
  • other pour point depressants or dewaxing aids with other detergents, with antioxidants, cetane number improvers, dehazers, demulsifiers, dispersants, defoamers, dyes, corrosion inhibitors, lubricity additives, sludge inhibitors, and odorants /or additions to lower the cloud point.
  • Detergent additives (A) with various polyoxyalkylene compounds (B) and ethylene copolymers (C) and paraffin dispersants (D) with the characteristics given below were used to assess the effect of the additives according to the invention on the cold flow properties of middle distillates.
  • the lower 20% by volume is isolated directly after cold storage and the cloud point is determined in accordance with IP 3015. Only a small deviation of the cloud point of the lower phase (CP KS ) from the oil blank value indicates good paraffin dispersion.
  • Table 1 Characterization of the test oils: Current middle distillates from European refineries were used as test oils. The CFPP value was determined in accordance with EN 116 and the cloud point was determined in accordance with ISO 3015.
  • Example B1 the numbers -20-, -28- and -30- indicate the number of moles of alkylene oxide per mole of glycerol.
  • Example B4 the number -600- indicates the molecular weight of the polyethylene glycol used for the esterification.
  • CFPP values in test oil 1 were determined after adding 200 ppm C2 and 150 ppm D1 to the oil.
  • Table 2 Cold flow improvement in test oil 1 example Detergent additive (DA) Dosing rate DA/ppm CFPP in test oil 1/°C polyolefin Mw polyolefin polyamine mol SA / mol polyamine without DA with DNA with DA +50ppm
  • DA Detergent additive
  • PIB 700 TEPA 1.0 150 -29 -25 -28 2
  • PIB 700 TEPA 1.4 150 -29 -26 -28 3
  • PIB 1000 PEHA 1.0 150 -29 -22 -29 4
  • DA detergent additive
  • P2B poly(butene) from a mixture of different butene isomers with a proportion of 2-butene of about 80%;
  • TEPA tetraethylenepentamine;
  • PEHA pentaethylene hexamine;
  • PAM heavy polyamine
  • Example 3 the reaction product of poly(isobutenyl)succinic anhydride and pentaethylenehexamine according to Table 2
  • Example 4 the reaction product of poly(isobutenyl)succinic anhydride and pentaethylenehexamine according to Table 2
  • Example 4 and as detergent additive A2 the reaction product of poly(butenyl)succinic anhydride and heavy polyamines according to Table 2
  • Example 18 was used as detergent additive A3.
  • Table 3 Cold flow improvement in test oil 2 example additives Test oil 2 CFPP [°C] A B C D 19 (cf.) - - 75ppm C2 - -14 20 (cf.) - - 100ppm C2 - -19 21 (cf.) - - 150ppm C1 - -20 22 (cf.) - - 75ppm C1 150 D1 -21 23 (cf.) - - 100ppm C1 150 D1 -29 24 (cf.) - - 150ppm C1 150 D1 -31 25 (cf.) 50 A1 - 75ppm C1 150 D1 -14 26 (cf.) 50 A1 - 100ppm C1 150 D1 -19 27 (cf.) 50 A1 - 150ppm C1 150 D1 -20 28 (cf.) 50 A1 - 150ppm C1 250 D1 -20 29 50 A1 25B1 75ppm C1 150 D1 -23 30 50 A1 25B1

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Claims (26)

  1. Utilisation d'au moins un composé de polyoxyalkylène soluble dans l'huile,
    ce composé de polyoxyalkylène étant un ester, un éther ou un éther/ester de polyols alcoxylés soluble dans l'huile contenant au moins trois unités alcoxy répétitives, dérivant d'oxydes d'alkylène de 2 à 5 atomes C, par groupe OH du polyol, qui porte au moins deux radicaux hydrocarbonés aliphatiques de 12 à 30 atomes C, pour améliorer la réactivité au regard de l'abaissement du point d'écoulement et du CFPP et de l'amélioration de la dispersion des paraffines dans des distillats moyens contenant au moins un additif détergent azoté sans cendres, avec des agents d'amélioration de l'écoulement à froid des huiles minérales choisis parmi
    III) les copolymères d'éthylène et 8 à 21 % en moles de composés oléfiniquement insaturés, les composés oléfiniquement insaturés étant choisis parmi un ou plusieurs esters vinyliques, esters acryliques, esters méthacryliques, éthers d'alkyle et de vinyle et/ou alcènes, qui peuvent être substitués avec des groupes hydroxyle ;
    IV) les composés azotés polaires solubles dans l'huile, qui sont des produits de réaction d'amines de formule NR6R7R8, R6, R7 et R8 pouvant être identiques ou différents, et au moins un de ces groupes représentant alkyle en C8-C36, cycloalkyle en C6-C36, alcényle en C8-C36, notamment alkyle en C12-C24, alcényle en C12-C24 ou cyclohexyle, et les autres groupes signifiant soit hydrogène, alkyle en C1-C36, alcényle en C2-C36, cyclohexyle soit un groupe de formule -(A-O)x-E ou-(CH2)n-NYZ, A représentant un groupe éthyle ou propyle, x un nombre de 1 à 50, E = H, alkyle en C1-C30, cycloalkyle en C5-C12 ou aryle en C6-C30, et n = 2, 3 ou 4, et Y et Z signifiant indépendamment l'un de l'autre H, alkyle en C1-C30 ou -(A-O)x, avec des composés contenant un groupe acyle ;
    V) les résines d'alkylphénol-formaldéhyde, qui sont des oligomères ou des polymères contenant une unité
    structurale répétitive de formule
    Figure imgb0015
     dans laquelle R11 représente alkyle ou alcényle en C1-C200, O-R10 ou O-C(O)-R10, R10 représente alkyle ou alcényle en C1-C200, et n représente un nombre de 2 à 100 ;
    VI) les polymères en peigne de formule
    Figure imgb0016
     dans laquelle
    A signifie R', COOR', OCOR', R"-COOR', OR' ;
    D signifie H, CH3, A ou R" ;
    E signifie H, A ;
    G signifie H, R", R"-COOR', un radical aryle ou un radical hétérocyclique ;
    M signifie H, COOR", OCOR", OR", COOH ;
    N signifie H, R", COOR", OCOR, un radical aryle ;
    R' signifie une chaîne hydrocarbonée de 8 à 50 atomes de carbone ;
    R" signifie une chaîne hydrocarbonée de 1 à 10 atomes de carbone ;
    m signifie un nombre compris entre 0,4 et 1,0 ; et
    n signifie un nombre compris entre 0 et 0,6 ;
    VII) les homo- et copolymères d'oléfines contenant 2 à 30 atomes C, qui présentent des poids moléculaires de jusqu'à 120 000 g/mol,
    l'additif détergent étant un composé amphiphile soluble dans l'huile qui comprend au moins un radical alkyle ou alcényle qui est relié à un groupe polaire, le radical alkyle ou alcényle comprenant 20 à 500 atomes C et le groupe polaire comprenant 2 atomes d'azote ou plus, et le groupe polaire des additifs détergents dérivant de polyamines de formule

            (R9)2N- [A-N(R9)]q-(R9)

    dans laquelle les R9 représentent chacun indépendamment les uns des autres l'hydrogène, un radical alkyle ou hydroxyalkyle contenant jusqu'à 24 atomes C, un radical polyoxyalkylène -(A-O)r- ou un radical polyiminoalkylène -[A-N(R9)]s- (R9), au moins un R9 représentant toutefois l'hydrogène, q représente un nombre entier de 1 à 19, A représente un radical alkylène de 1 à 6 atomes C, r et s représentent indépendamment l'un de l'autre un nombre entier de 1 à 50, et
    les distillats moyens contenant plus de 10 ppm d'au moins un additif détergent azoté sans cendres, et
    par rapport à une partie en poids de l'additif détergent azoté sans cendres, 0,01 à 10 parties en poids d'au moins un composé de polyoxyalkylène soluble dans l'huile étant utilisées.
  2. Utilisation selon la revendication 1, dans laquelle le radical alkyle ou alcényle de l'additif détergent dérive d'oligomères d'oléfines inférieures contenant 3 à 6 atomes C.
  3. Utilisation selon une ou plusieurs des revendications 1 et 2, dans laquelle l'additif détergent dérive d'un anhydride d'acide alcénylsuccinique qui présente un degré de maléinisation, par rapport aux fractions de poly(oléfines) mises en réaction avec des acides carboxyliques insaturés, en moyenne de plus de 1 unité acide dicarboxylique par radical alkyle.
  4. Utilisation selon une ou plusieurs des revendications 1 à 3, dans laquelle le groupe polaire des additifs détergents dérive de polyamines de formule

            (R9)2N-[A-N(R9)]q-(R9)

    dans laquelle R9 représente l'hydrogène, q représente un nombre entier de 3 à 19, A représente un radical alkylène de 1 à 6 atomes C, et r et s représentent indépendamment l'un de l'autre un nombre entier de 1 à 50.
  5. Utilisation selon une ou plusieurs des revendications 1 à 4, dans laquelle la polyamine de laquelle l'additif détergent dérive contient des éléments structuraux dérivés de pipérazine.
  6. Utilisation selon une ou plusieurs des revendications 1 à 5, dans laquelle la polyamine de laquelle l'additif détergent dérive contient au moins un groupe amino primaire.
  7. Utilisation selon la revendication 4, dans laquelle la polyamine de laquelle l'additif détergent dérive contient plus de 10 % en poids d'amines dans lesquelles q est égal à 4 ou supérieur à 4.
  8. Utilisation selon une ou plusieurs des revendications 1 à 7, dans laquelle les composés de polyoxyalkylène solubles dans l'huile comprennent au moins 3 radicaux hydrocarbonés aliphatiques.
  9. Utilisation selon une ou plusieurs des revendications 1 à 8, dans laquelle les composés de polyoxyalkylène solubles dans l'huile dérivent de polyols contenant 3 groupes OH ou plus.
  10. Utilisation selon une ou plusieurs des revendications 1 à 9, dans laquelle les composés de polyoxyalkylène solubles dans l'huile sont des esters, des éthers et/ou des éthers/esters dans lesquels moins de 50 % en moles des acides gras utilisés pour l'estérification comprennent des doubles liaisons.
  11. Utilisation selon une ou plusieurs des revendications 1 à 10, dans laquelle l'agent d'amélioration de l'écoulement à froid comprend des copolymères d'éthylène et 8 à 21 % en moles de composés oléfiniquement insaturés, les composés oléfiniquement insaturés étant choisis parmi un ou plusieurs esters vinyliques, esters acryliques, esters méthacryliques, éthers d'alkyle et de vinyle et/ou alcènes, qui peuvent être substitués avec des groupes hydroxyle.
  12. Utilisation selon une ou plusieurs des revendications 1 à 11, dans laquelle l'agent d'amélioration de l'écoulement à froid comprend des composés azotés polaires solubles dans l'huile, qui sont des produits de réaction d'amines de formule NR6R7R8, R6, R7 et R8 pouvant être identiques ou différents, et au moins un de ces groupes représentant alkyle en C8-C36, cycloalkyle en C6-C36, alcényle en C8-C36, notamment alkyle en C12-C24, alcényle en C12-C24 ou cyclohexyle, et les autres groupes signifiant soit hydrogène, alkyle en C1-C36, alcényle en C2-C36, cyclohexyle soit un groupe de formule -(A-O)x-E ou -(CH2)n-NYZ, A représentant un groupe éthyle ou propyle, x un nombre de 1 à 50, E = H, alkyle en C1-C30, cycloalkyle en C5-C12 ou aryle en C6-C30, et n = 2, 3 ou 4, et Y et Z signifiant indépendamment l'un de l'autre H, alkyle en C1-C30 ou -(A-O)x, avec des composés contenant un groupe acyle.
  13. Utilisation selon une ou plusieurs des revendications 1 à 12, dans laquelle l'agent d'amélioration de l'écoulement à froid comprend des résines d'alkylphénol-formaldéhyde qui sont des oligomères ou des polymères contenant une unité structurale répétitive de formule
    Figure imgb0017
     dans laquelle R11 représente alkyle ou alcényle en C1-C200, O-R10 ou O-C(O)-R10, R10 représente alkyle ou alcényle en C1-C200, et n représente un nombre de 2 à 100.
  14. Utilisation selon une ou plusieurs des revendications 1 à 13, dans laquelle l'agent d'amélioration de l'écoulement à froid comprend des polymères en peigne de formule
    Figure imgb0018
     dans laquelle
    A signifie R', COOR', OCOR', R''-COOR', OR' ;
    D signifie H, CH3, A ou R" ;
    E signifie H, A ;
    G signifie H, R", R"-COOR', un radical aryle ou un radical hétérocyclique ;
    M signifie H, COOR", OCOR", OR", COOH ;
    N signifie H, R", COOR", OCOR, un radical aryle ;
    R' signifie une chaîne hydrocarbonée de 8 à 50 atomes de carbone ;
    R" signifie une chaîne hydrocarbonée de 1 à 10 atomes de carbone ;
    m signifie un nombre compris entre 0,4 et 1,0 ; et
    n signifie un nombre compris entre 0 et 0,6.
  15. Utilisation selon une ou plusieurs des revendications 1 à 14, dans laquelle l'agent d'amélioration de l'écoulement à froid comprend des homopolymères et des copolymères d'oléfines contenant 2 à 30 atomes C, qui présentent des poids moléculaires de jusqu'à 120 000 g/mol.
  16. Utilisation selon une ou plusieurs des revendications 1 à 15, qui a lieu dans des distillats moyens ayant une teneur en soufre de moins de 100 ppm et une plage d'ébullition par distillation entre 20 et 90 % en volume de moins de 120 °C.
  17. Compositions, contenant
    a) au moins un additif détergent azoté sans cendres, qui est un composé amphiphile soluble dans l'huile qui comprend au moins un radical alkyle ou alcényle qui est relié à un groupe polaire, le radical alkyle ou alcényle comprenant 20 à 500 atomes C et le groupe polaire comprenant 2 atomes d'azote ou plus, et
    le groupe polaire des additifs détergents dérivant de polyamines de formule

            (R9)2N-[A-N(R9)]q-(R9)

    dans laquelle les R9 représentent chacun indépendamment les uns des autres l'hydrogène, un radical alkyle ou hydroxyalkyle contenant jusqu'à 24 atomes C, un radical polyoxyalkylène -(A-O)r- ou un radical polyiminoalkylène -[A-N(R9)]s-(R9), au moins un R9 représentant toutefois l'hydrogène, q représente un nombre entier de 1 à 19, A représente un radical alkylène de 1 à 6 atomes C, r et s représentent indépendamment l'un de l'autre un nombre entier de 1 à 50,
    et lesquels dérivent de polyols contenant au moins 3 groupes OH,
    b) au moins un composé de polyoxyalkylène soluble dans l'huile, qui est un ester, un éther ou un éther/ester de polyols alcoxylés soluble dans l'huile contenant au moins trois unités alcoxy répétitives, dérivant d'oxydes d'alkylène de 2 à 5 atomes C, par groupe OH du polyol, qui porte au moins deux radicaux hydrocarbonés aliphatiques de 12 à 30 atomes C, contenant 0,01 à 10 parties en poids d'au moins un composé de polyoxyalkylène soluble dans l'huile par partie en poids de l'additif détergent azoté sans cendres.
  18. Compositions selon la revendication 17, contenant 5 à 90 % en poids des constituants a) et b), ainsi que 10 à 95 % en poids de solvant.
  19. Compositions selon une ou plusieurs des revendications 17 et 18, dans lesquelles le radical alkyle ou alcényle de l'additif détergent dérive d'oligomères d'oléfines inférieures contenant 3 à 6 atomes C.
  20. Compositions selon une ou plusieurs des revendications 17 à 19, dans lesquelles l'additif détergent dérive d'un anhydride d'acide alcénylsuccinique qui présente un degré de maléinisation, par rapport aux fractions de poly(oléfines) mises en réaction avec des acides carboxyliques insaturés, en moyenne de plus de 1 unité acide dicarboxylique par radical alkyle.
  21. Compositions selon une ou plusieurs des revendications 17 à 20, dans lesquelles le groupe polaire des additifs détergents dérive de polyamines de formule

            (R9)2N-[A-N(R9)]q-(R9)

    dans laquelle R9 représente l'hydrogène, q représente un nombre entier de 3 à 19, A représente un radical alkylène de 1 à 6 atomes C, r et s représentent indépendamment l'un de l'autre un nombre entier de 1 à 50.
  22. Compositions selon une ou plusieurs des revendications 17 à 21, dans lesquelles la polyamine de laquelle l'additif détergent dérive contient des éléments structuraux dérivés de pipérazine.
  23. Distillats moyens ayant une teneur en soufre de moins de 100 ppm et une plage d'ébullition par distillation entre 20 et 90 % en volume de moins de 120 °C, contenant 10 à 10 000 ppm d'une composition selon une ou plusieurs des revendications 17 à 22, ainsi qu'au moins un agent d'amélioration de l'écoulement à froid des huiles minérales choisi parmi
    III) les copolymères d'éthylène et 8 à 21 % en moles de composés oléfiniquement insaturés, les composés oléfiniquement insaturés étant choisis parmi un ou plusieurs esters vinyliques, esters acryliques, esters méthacryliques, éthers d'alkyle et de vinyle et/ou alcènes, qui peuvent être substitués avec des groupes hydroxyle ;
    IV) les composés azotés polaires solubles dans l'huile, qui sont des produits de réaction d'amines de formule NR6R7R8, R6, R7 et R8 pouvant être identiques ou différents, et au moins un de ces groupes représentant alkyle en C8-C36, cycloalkyle en C6-C36, alcényle en C8-C36, notamment alkyle en C12-C24, alcényle en C12-C24 ou cyclohexyle, et les autres groupes signifiant soit hydrogène, alkyle en C1-C36, alcényle en C2-C36, cyclohexyle soit un groupe de formule -(A-O)x-E ou-(CH2)n-NYZ, A représentant un groupe éthyle ou propyle, x un nombre de 1 à 50, E = H, alkyle en C1-C30, cycloalkyle en C5-C12 ou aryle en C6-C30, et n = 2, 3 ou 4, et Y et Z signifiant indépendamment l'un de l'autre H, alkyle en C1-C30 ou -(A-O)x, avec des composés contenant un groupe acyle ;
    V) les résines d'alkylphénol-formaldéhyde, qui sont des oligomères ou des polymères contenant une unité structurale répétitive de formule
    Figure imgb0019
     dans laquelle R11 représente alkyle ou alcényle en C1-C200, O-R10 ou O-C(O)-R10, R10 représente alkyle ou alcényle en C1-C200, et n représente un nombre de 2 à 100 ;
    VI) les polymères en peigne de formule
    Figure imgb0020
     dans laquelle
    A signifie R', COOR', OCOR', R''-COOR', OR' ;
    D signifie H, CH3, A ou R" ;
    E signifie H, A ;
    G signifie H, R", R"-COOR', un radical aryle ou un radical hétérocyclique ;
    M signifie H, COOR", OCOR", OR", COOH ;
    N signifie H, R", COOR", OCOR, un radical aryle ;
    R' signifie une chaîne hydrocarbonée de 8 à 50 atomes de carbone ;
    R" signifie une chaîne hydrocarbonée de 1 à 10 atomes de carbone ;
    m signifie un nombre compris entre 0,4 et 1,0 ; et
    n signifie un nombre compris entre 0 et 0,6 ;
    VII) les homopolymères et copolymères d'oléfines contenant 2 à 30 atomes C, qui présentent des poids moléculaires de jusqu'à 120 000 g/mol.
  24. Distillats moyens selon la revendication 23, contenant plus de 10 ppm d'au moins un additif détergent azoté sans cendres et, par rapport à une partie en poids de l'additif détergent azoté sans cendres, 0,01 à 10 parties en poids d'au moins un composé de polyoxyalkylène soluble dans l'huile.
  25. Distillats moyens selon la revendication 23, dans lesquels l'agent d'amélioration de l'écoulement à froid d'huiles minérales est un mélange de 0,1 à 10 parties en poids de III) par partie en poids de IV).
  26. Distillats moyens selon une ou plusieurs des revendications 23 à 25, dans lesquels le rapport en poids entre la teneur totale en additif détergent azoté sans cendres et en composé de polyoxyalkylène soluble dans l'huile d'une part et la teneur totale en agents d'amélioration de l'écoulement à froid d'huiles minérales d'autre part est compris entre 10:1 et 1:10.
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CA2572166A1 (fr) 2007-06-22
KR20070066987A (ko) 2007-06-27
JP2007169648A (ja) 2007-07-05
EP1801187B1 (fr) 2015-10-21
ES2554978T3 (es) 2015-12-28
KR101385485B1 (ko) 2014-04-24
HUE028316T2 (en) 2016-12-28
PL1801187T3 (pl) 2016-04-29
EP1801187A2 (fr) 2007-06-27
CA2572166C (fr) 2014-01-14
JP5590759B2 (ja) 2014-09-17
EP1801187A3 (fr) 2008-07-02
US8153567B2 (en) 2012-04-10
US20070149417A1 (en) 2007-06-28

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