EP0342497B1 - Fuel for spark ignition engines - Google Patents

Fuel for spark ignition engines Download PDF

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Publication number
EP0342497B1
EP0342497B1 EP89108374A EP89108374A EP0342497B1 EP 0342497 B1 EP0342497 B1 EP 0342497B1 EP 89108374 A EP89108374 A EP 89108374A EP 89108374 A EP89108374 A EP 89108374A EP 0342497 B1 EP0342497 B1 EP 0342497B1
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EP
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Prior art keywords
copolymers
parts
acid
weight
fuel
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EP89108374A
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German (de)
French (fr)
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EP0342497A2 (en
EP0342497A3 (en
Inventor
Franz-Dieter Dr. Martischius
Hans-Henning Dr. Vogel
Norbert Dr. Greif
Knut Dr. Oppenlaender
Walter Denzinger
Heinrich Dr. Hartmann
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BASF SE
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BASF SE
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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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
    • 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
    • C10L1/24—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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/26—Organic compounds containing phosphorus
    • C10L1/2666—Organic compounds containing phosphorus macromolecular compounds
    • C10L1/2675—Organic compounds containing phosphorus 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
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B1/00—Engines characterised by fuel-air mixture compression
    • F02B1/02—Engines characterised by fuel-air mixture compression with positive ignition
    • F02B1/04—Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder

Definitions

  • the invention relates to fuels for gasoline engines containing copolymers of alkyl (meth) acrylates with 8 to 40 carbon atoms in the alkyl radical and / or vinyl esters of carboxylic acids containing 8 to 40 carbon atoms and monoethylenically unsaturated mono- and / or dicarboxylic acids with 3 to 12 carbon atoms, the carboxyl groups, also referred to below as acid groups, of the copolymers in whole or in part in the form of the alkali metal salts and the remaining radicals of the acid groups, if any, in the form of amide groups and / or ammonium salt groups.
  • FR 1 258 027 describes organic liquids, e.g. Also known are fuels which, in addition to a salt of a polyvalent metal and an alkylated salicylic acid, can also contain a copolymer with acid groups in salt form in order to increase the electrical conductivity. Alkali metal salts are not provided in this document.
  • the task therefore was to find substances which, in addition to preventing or reducing wear and tear on the valves of gasoline engines, also reduce corrosion in the gasoline engines.
  • the new fuel additives have the advantage that they do not impair the effect of conventional gasoline additives in the gasoline engines and at the same time the wear and tear on the valves prevent or at least greatly reduce and further surprisingly significantly reduce or even prevent the occurrence of corrosion in the gasoline engines.
  • the fuel additives according to the invention are expediently produced in two process stages.
  • the first process step is the preparation of the copolymers from alkyl (meth) acrylates with 8 to 40 C atoms in the alkyl radical and / or vinyl esters from carboxylic acids containing 8 to 40 C atoms and monoethylenically unsaturated mono- and / or dicarboxylic acids with 3 to 12 C. -Atoms.
  • the acid groups of the copolymers obtained are reacted in whole or in part with alkali to form the alkali metal salts.
  • the complete conversion of the acid groups of the copolymers to the alkali metal salts is expedient when the alkali metal salts of the copolymers obtained already have sufficient solubility in the fuels to which they are to be added. If the solubility is insufficient, the acid groups of the copolymers are expediently only partially reacted with alkali to form the alkali metal salts and the rest of the acid groups are reacted with ammonia and / or amines to give the corresponding amide groups and / or ammonium salts in order to obtain sufficient solubility.
  • alkyl (meth) acrylates and / or vinyl esters with a higher number of carbon atoms in the alkyl / carboxylic acid group for the preparation of the copolymers in the second process stage, amines with shorter alkyl chains or the proportion of the acid groups which is to be reacted with the amines.
  • the proportion of building blocks with acid function in the copolymer should be so large that the alkali metal salts of the copolymers, if appropriate also reacted with ammonia and / or amines to form amides and ammonium salts, are soluble in petrol. It is expedient to incorporate more of such molecules from a molecule containing large acid groups with few acid groups such as methacrylic acid than from a molecule with many acid groups such as maleic acid or maleic anhydride. Up to 60% by weight, preferably up to 30% by weight, of monomers containing acid groups are expediently polymerized into the copolymer.
  • Suitable alkyl (meth) acrylic esters are all esters of acrylic acid and methacrylic acid with straight-chain alcohols with 8 to 40 C atoms, e.g. 2-ethylhexyl acrylate, 2-ethylhexyl, n-decyl acrylate, n-decyl methacrylate, dodecyl acrylate, Dodecylmethalcrylat, isotridecyl, Isotridecylmethacrylat, tetradecyl acrylate, tetradecyl, C16 / C18-Talgfettalkoholmethacrylat, octadecyl acrylate, Octadpcylmethacrylat, n-eicosyl acrylate, n-eicosyl, n-docosyl acrylate, n-Docosyl methacrylate, tetracosyl acrylate, hexacosyl
  • C16 to C28 alkyl (meth) acrylates are preferred.
  • Suitable as vinyl esters are all based on branched and unbranched monocarboxylic acids with 8 to 40 carbon atoms.
  • vinyl 2-ethylhexanate, vinyl laurate, vinyl tallow fatty acid esters, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl oleate and mixtures with one another are suitable.
  • Suitable monoethylenically unsaturated mono- and / or dicarboxylic acids are those which have 3 to 12 carbon atoms in the molecule, for example acrylic acid, methacrylic acid, crotonic acid, vinyl lactic acid, allylacetic acid, propylidene acetic acid, ethyl acrylic acid, dimethylacrylic acid and the dicarboxylic acids maleic acid, fumaric acid, itaconic acid Glutaconic acid, methylene malonic acid, citraconic acid and tetrahydrophthalic acid.
  • the dicarboxylic acids in the form of the anhydrides, if available, in the copolymerization, for example maleic anhydride, itaconic anhydride, citraconic anhydride, methylene malonic anhydride and tetrahydrophthalic anhydride, since the anhydrides generally copolymerize better with the (meth) acrylates and vinyl esters .
  • the anhydride groups can then usually be reacted directly with the amines or also with the hydroxides of the alkali or alkaline earth metals without first converting the anhydride group into the acid with water.
  • the monoesters of the dicarboxylic acids mentioned from alcohols having 2 to 40 carbon atoms for example monoethyl maleate, monobutyl maleate, monododecyl maleate, monooctadecyl maleate, monotetracosyl maleate, monooctadecyl fumarate, monooktendeconate mixtures with one another.
  • Acrylic acid, methacrylic acid, maleic acid (anhydride) and itaconic acid (anhydride) are particularly preferred.
  • Such monoethylenically unsaturated N-alkyl acid amides are, for example, N-isotridecylacrylamide, N-di- (isotridecyl) acrylamide, N-stearylacrylamide, N-stearyl methacrylamide, maleic acid monoisotridecylamide, maleic acid diisotridecylamide, maleic acid monostearylamide, maleic acid distearyl amide.
  • the copolymers have molar masses of 500 to 20,000 g / mol, preferably 800 to 10,000 g / mol.
  • the preparation is carried out according to known conventional discontinuous and continuous polymerization processes such as bulk, suspension, precipitation and solution polymerization and initiation with conventional radical donors such as, for example, acetylcyclohexanesulfonyl peroxide, diacetyl peroxidicarbonate, dicyclohexyl peroxidicarbonate, di-2-ethylhexyl peroxidicarbonate, 2,2'-butylobutylate, tert-butyl butyl (4-methoxy-2,4-dimethylvaleronitrile), tert-butyl perpivalate, tert-butyl per-2-ethyl hexanoate, tert-butyl permaleinate, 2,2 ′ azobis (isobutyronitrile), bis (tert-butyl peroxide) cyclohexane, tert-butyl peroxyisopropyl carbonate, tert-butyl peracetate, dicum
  • the copolymerization is usually carried out at from 40 to 400 ° C., preferably from 80 to 300 ° C., with the use of (meth) acrylates and vinyl esters or solvents with boiling temperatures below Polymerization temperature is advantageously carried out under pressure.
  • the polymerization is expediently carried out with the exclusion of air, ie, if it is not possible to work under boiling conditions, with an inerting agent such as nitrogen, since atmospheric oxygen delays the polymerization.
  • the reaction can be accelerated by using redox coinitiators such as benzoin, dimethylaniline, ascorbic acid and organically soluble complexes of heavy metals such as copper, cobalt, manganese, iron, nickel and chromium.
  • the amounts usually used are 0.1 to 2000 ppm by weight, preferably 0.1 to 1000 ppm by weight.
  • the half-life of tert-butyl hydroperoxide is less than 3 hours.
  • the initiator system is 1% by weight.
  • tert-butyl hydroperoxide / 5 ppm by weight of copper (II) acetylacetonate has a polymerization behavior comparable to 1% by weight of tert-butyl hydroperoxide at 150 ° C. even at 100 ° C. If, for example, polymerization is carried out at a low temperature and polymerization is carried out at a higher temperature, 2 or more initiators are generally used.
  • regulators are, for example, allyl alcohols, such as buten-1-ol-3, organic mercapto compounds such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid, tert-butyl mercaptan, n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan and tert.- Dodecyl mercaptan, which are generally used in amounts of 0.1% by weight to 10% by weight.
  • the initiators, co-initiators, regulators and polymerization temperatures mentioned can be used equally for all polymerization methods.
  • Equipment suitable for the polymerization is e.g. Conventional stirred kettles with, for example, armature, blade, impeller or multi-stage impulse countercurrent stirrers and for the continuous production of stirred kettle cascades, tubular reactors and static mixers.
  • the simplest method of polymerization is bulk polymerization.
  • the (meth) acrylic esters and / or the vinyl esters and the acid group-containing monomer are polymerized in the presence of an initiator and in the absence of solvents.
  • This process is particularly suitable for those copolymers in which the (meth) acrylic ester and vinyl ester used have 12 or more carbon atoms.
  • all monomers are mixed in the desired composition and a small part, for example about 5 to 10%, is placed in the reactor, heated to the mixture with stirring desired polymerization temperature and metered in the remaining monomer mixture and the initiator and optionally coinitiator and regulator evenly within 1 to 10 hours, preferably 2 to 5 hours.
  • copolymer can then be converted to the fuel additive according to the invention directly in the melt or after dilution with a suitable solvent.
  • a continuous high-pressure process is also suitable for producing the desired copolymers, which permits space-time yields of 1 to 50 kg of polymer per liter of reactor and hour.
  • a polymerization apparatus e.g. a pressure vessel, a pressure vessel cascade, a pressure tube or a pressure vessel with a downstream reaction tube, which is provided with a static mixer, can be used.
  • the monomers are preferably polymerized from (meth) acrylic esters, vinyl esters and acid group-containing monoethylenically unsaturated compounds in at least 2 polymerization zones connected in series.
  • One reaction zone can consist of a pressure-tight vessel, the other of a heatable static mixer. You get sales of more than 99%.
  • a copolymer of stearyl acrylate and acrylic acid can be prepared, for example, by continuously feeding the monomers and a suitable initiator to a reactor or two reaction zones connected in series, for example a reactor cascade, and the reaction product after a residence time of 2 to 60, preferably 5 to 30 Minutes, continuously discharged from the reaction zone at temperatures between 200 and 400 ° C.
  • the polymerization is expediently carried out at pressures of more than 1 bar, preferably between 1 and 200 bar.
  • the copolymers obtained with solids contents of over 99% can then be further converted to the corresponding alkali metal salts or amides and ammonium salts.
  • Another method for the simple preparation of the copolymers is precipitation polymerization.
  • solvents are used in which the monomers are soluble and the copolymer formed is insoluble and fails.
  • solvents are for example ethers such as diethyl ether, dipropyl ether, dibutyl ether, methyl tert-butyl ether, diethylene glycol dimethyl ether and mixtures with one another.
  • ethers such as diethyl ether, dipropyl ether, dibutyl ether, methyl tert-butyl ether, diethylene glycol dimethyl ether and mixtures with one another.
  • a protective colloid are polymeric substances which are readily soluble in the solvents and which do not react with the monomers.
  • Copolymers of maleic anhydride are suitable, for example with vinyl alkyl ethers and / or olefins with 8 to 20 C atoms and their monoesters with C10 to C20 alcohols or mono- and diamides with C10 to C20 alkylamines and polyalkyl vinyl ethers whose alkyl group contains 1 to 20 C atoms, such as Polymethyl, polyethyl, polyisobutyl and polyoctadecyl vinyl ether.
  • the amounts of protective colloid added are usually 0.05 to 4% by weight (based on the monomers used), preferably 0.1 to 2% by weight, it often being advantageous to combine several protective colloids.
  • the solvent, the protective colloid and part of the monomer mixture in the reactor and to meter in the rest of the monomer mixture and the initiator and, if appropriate, the coinitiator and regulator at the selected polymerization temperature with vigorous stirring.
  • the feed times for monomer and initiator are generally between 1 and 10 hours, preferably 2 and 5 hours. It is also possible to polymerize all of the starting materials together in one reactor, but problems with heat dissipation can occur, so that such a procedure is less appropriate.
  • the concentrations of the monomers to be polymerized are between 20 and 80% by weight, preferably 30 to 70% by weight.
  • the polymers can be isolated directly from the polymer suspensions in evaporators, for example belt dryers, paddle dryers, spray dryers and fluidized bed dryers.
  • evaporators for example belt dryers, paddle dryers, spray dryers and fluidized bed dryers.
  • suitable solvents that can be added directly to fuels
  • the further conversion to the alkali or alkaline earth metal salt and amide and / or ammonium salt can be carried out directly in the suspension.
  • the preferred embodiment for the preparation of the copolymers is solution polymerization. It is carried out in solvents in which the monomers and the copolymers formed are soluble. All solvents that meet this requirement and that do not react with the monomers are suitable for this. For example, these are acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, aliphatic, cycloaliphatic and aromatic hydrocarbons such as n-octane, isooctane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, cumene, and tetrahydrofuran, tetrahydrofuran Copolymers xylene, ethylbenzene, cumene, tetrahydrofuran and dioxane are particularly
  • solvent and part of the monomer mixture for example about 5 to 20%
  • solvents and (meth) acrylic esters or vinyl esters can also be introduced into the polymerization reactor and then, after the polymerization temperature has been reached, the monomer containing acid groups, if appropriate dissolved in the solvent, and the initiator, and, if appropriate, coinitiator and regulator, are metered in.
  • concentrations of the too polymerizing monomers are between 20 and 80% by weight, preferably 30 and 70% by weight.
  • the solid copolymer can be isolated easily by evaporating the solvent. But here, too, it is expedient to choose a solvent in which the further conversion to the alkali salt and with ammonia and / or amines can take place.
  • the copolymers of (meth) acrylic esters and / or vinyl esters with monomers containing acid groups obtained in the first process step are then completely or partially converted to the alkali metal salts and, if the conversion to the alkali metal salts takes place only partially, with ammonia and / or amines to give the amides and / or ammonium salts implemented.
  • Amines with up to 50 carbon atoms are used to convert the copolymers to the amides and / or ammonium salts.
  • Suitable amines are, for example, di-2-ethylhexylamine, dioleylamine. Isotridecylamine and diisotridecylamine are used with particular advantage.
  • the acid groups of the copolymers are converted to the amides and / or ammonium salts.
  • the reaction of the copolymers of (meth) acrylates and / or vinyl esters with monomers containing acid groups with the amines is generally carried out in the melt or after dilution with a suitable solvent.
  • suitable solvents are: the solvents mentioned above for the preparation of the copolymers by precipitation and solution polymerization.
  • Aromatic, aliphatic or cycloaliphatic hydrocarbons are preferably used.
  • temperatures of 20 to 150 ° C. preferably 20 to 120 ° C., in particular 30 to 100 ° C., are generally used.
  • the reaction with the amines is carried out, for example, in such a way that the copolymer, e.g. in a reaction vessel, for example in molten form or in a solvent, and the amine is introduced with stirring at temperatures from 60 to 90 ° C. and reacted for 1 to 2 hours with stirring.
  • the copolymers which are derived from monoethylenically unsaturated dicarboxylic acids, the hemi-amide is obtained in which the remaining carboxyl group is present as the alkylammonium salt when excess amine is added.
  • the resulting amides and / or ammonium salts of the copolymers of (meth) acrylic esters and / or vinyl esters with monomers containing acid groups are used to convert the remaining carboxyl groups into the alkali metal salts with a basic alkali metal compound, e.g. the hydroxides, carbonates or alcoholates.
  • a basic alkali metal compound e.g. the hydroxides, carbonates or alcoholates.
  • the solvents and water formed are expediently removed in vacuo from the reaction mixture obtained.
  • the fuel additives according to the invention are used as alkali metal salts.
  • the alkali metal salts are the lithium, sodium, potassium, rubidium, cesium salts, the potassium salts being used with preference.
  • the proportion of alkali metal in the fuel additives according to the invention, based on the fuel additive, is generally at least 3% by weight, preferably 3 to 25% by weight, in particular 4 to 20% by weight, with particular advantage 4 to 15% by weight.
  • the new fuel additives are generally added to the fuels for gasoline engines in amounts of 10 to 2000 ppm by weight, preferably 50 to 1000 ppm by weight.
  • the fuels according to the invention can additionally contain known phenol- or amine-based antioxidants.
  • Residual oils from oxo alcohol synthesis have proven to be good solvents or solubilizers for the components to be added to the fuel.
  • Oxoalcohol residues from butanol, isobutanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol or dodecanol synthesis are preferably used.
  • the use of oxo alcohol residues from butanol synthesis is particularly advantageous.
  • other solvents or solvent mixtures can also be used which result in a homogeneous mixture of the components in the weight ratios mentioned above.
  • the effect of the gasoline additives according to the invention is not only limited to gasoline. It has been shown that they can also be used in aviation fuels, in particular in aviation fuels for piston engines.
  • the compounds according to the invention act not only in carburetor engines, but also in engines with fuel injection systems.
  • the fuels provided with the new additive can also contain other customary additives, e.g. additives to improve octane number or components containing oxygen, e.g. Contain methanol, ethanol or methyl tertiary butyl ether.
  • additives to improve octane number or components containing oxygen e.g. Contain methanol, ethanol or methyl tertiary butyl ether.
  • Examples 1 to 10 describe the preparation of the copolymers from (meth) acrylic esters and / or vinyl esters with monomers containing acid groups.
  • the parts specified are parts by weight.
  • the molecular weights were determined by gel permeation chromatography, using tetrahydrofuran as eluent and narrowly distributed fractions of polystyrene for calibration.
  • the procedure is as described in Example 4, but 90 parts of methacrylic acid are used instead of acrylic acid.
  • the solids content of the solution is 32.5%.
  • the molecular weight of the copolymer is 2050.
  • copolymers obtained in Examples 1 to 9 were converted according to Examples 10 to 18 into the fuel additives according to the invention by first reacting them with ammonia or amines to give the corresponding amides and / or ammonium salts and then to give the corresponding potassium salts, or by they have been completely converted into the potassium salts.

Abstract

The invention relates to fuels for spark-ignition engines, containing small quantities of copolymers of alkyl (meth)acrylates having 8 to 40 C atoms in the alkyl radical and/or vinyl esters of carboxylic acids containing 8 to 40 C atoms and monoethylenically unsaturated mono- and/or di-carboxylic acids having 3 to 12 C atoms and/or monoethylenically unsturated compounds with sulphonic and/or phosphonic acid groups, having a total molecular mass from 500 to 20,000 g per mole, the carboxyl groups, sulphonic acid groups and phosphonic acid groups of the copolymers having been wholly or partially reacted with alkali or an alkaline earth to form the alkali metal salts or alkaline earth metal salts and the remainder of the acid groups having been reacted with ammonia and/or amines having up to 50 C atoms to give the corresponding amide groups and/or ammonium salts.

Description

Die Erfindung betrifft Kraftstoffe für Ottomotoren mit einem Gehalt an Copolymeren aus Alkyl (meth) acrylaten mit 8 bis 40 C-Atomen im Alkylrest und/oder Vinylestern aus 8 bis 40 C-Atome enthaltenden Carbonsäuren und monoethylenisch ungesättigten Mono- und/oder Dicarbonsäuren mit 3 bis 12 C-Atomen, wobei die Carboxylgruppen, im folgenden auch als Säuregruppen bezeichnet, der Copolymeren ganz oder teilweise in Form der Alkalimetallsalze und der gegebenenfalls verbleibende Rest der Säuregruppen in Form von Amidgruppen und/oder Ammoniumsalzgruppen vorliegen.The invention relates to fuels for gasoline engines containing copolymers of alkyl (meth) acrylates with 8 to 40 carbon atoms in the alkyl radical and / or vinyl esters of carboxylic acids containing 8 to 40 carbon atoms and monoethylenically unsaturated mono- and / or dicarboxylic acids with 3 to 12 carbon atoms, the carboxyl groups, also referred to below as acid groups, of the copolymers in whole or in part in the form of the alkali metal salts and the remaining radicals of the acid groups, if any, in the form of amide groups and / or ammonium salt groups.

Aus der FR 1 258 027 sind organische Flüssigkeiten, z.B. auch Kraftstoffe, bekannt, die zur Erhöhung der elektrischen Leitfähigkeit neben einem Salz eines polyvalenten Metalls und einer alkylierten Salicylsäure auch ein Copolymer mit Säuregruppen in Salzform enthalten können. Alkalimetallsalze sind in dieser Druckschrift nicht vorgesehen.FR 1 258 027 describes organic liquids, e.g. Also known are fuels which, in addition to a salt of a polyvalent metal and an alkylated salicylic acid, can also contain a copolymer with acid groups in salt form in order to increase the electrical conductivity. Alkali metal salts are not provided in this document.

In der GB 802 589 sind Kraftstoffe beschrieben, die als Additive Copolymere enthalten, wobei diese Copolymere Carboxylgruppen aufweisen und die Carboxylgruppen z.T. in der Ester-, Amid-, Imid- oder Aminsalzform vorliegen. Metallsalze und insbesondere Alkalimetallsalze sind nicht erwähnt.In GB 802 589 fuels are described which contain copolymers as additives, these copolymers having carboxyl groups and some of the carboxyl groups. are in the ester, amide, imide or amine salt form. Metal salts and especially alkali metal salts are not mentioned.

Aus der DE-OS 36 20 651 ist bekannt, zur Verhinderung oder Minderung von Abnutzungserscheinungen an den Auslaßventilen oder Ventilsitzen von Ottomotoren, den Kraftstoffen geringe Mengen von Alkalimetall- oder Erdalkalimetallsalzen von bestimmten Derivaten der Bernsteinsäure zuzusetzen. Die Verbindungen haben jedoch den Nachteil, daß sie in den Ottomotoren nicht korrosionsmindernd wirken.From DE-OS 36 20 651 it is known to add small amounts of alkali metal or alkaline earth metal salts of certain derivatives of succinic acid to prevent or reduce wear and tear on the exhaust valves or valve seats of gasoline engines. However, the connections have the disadvantage that they do not reduce corrosion in the gasoline engines.

Es bestand daher die Aufgabe, Stoffe zu finden, die neben der Verhinderung oder Minderung von Abnutzungserscheinungen an den Ventilen von Ottomotoren gleichzeitig die Korrosion in den Ottomotoren vermindern.The task therefore was to find substances which, in addition to preventing or reducing wear and tear on the valves of gasoline engines, also reduce corrosion in the gasoline engines.

Es wurde nun überraschenderweise gefunden, daß diese Aufgabe gelöst wird mit Kraftstoffen für Ottomotoren, enthaltend geringe Mengen von Copolymeren aus Alkyl(meth)acrylaten mit 8 bis 40 C-Atomen im Alkylrest und/oder Vinylestern aus 8 bis 40 C-Atome enthaltenden Carbonsäuren und monoethylenisch ungesättigten Mono- und/oder Dicarbonsäuren mit 3 bis 12 C-Atomen mit einer Gesamt-Molmasse von 500 bis 20 000 g pro Mol, wobei die Carboxylgruppen der Copolymeren ganz oder teilweise mit Alkali unter Bildung der Alkalimetallsalze umgesetzt sind und der Rest der Säuregruppen mit Ammoniak und/oder Aminen mit bis zu 50 C-Atomen zu den entsprechenden Amidgruppen und/oder Ammoniumsalzen umgesetzt ist.It has now surprisingly been found that this object is achieved with fuels for gasoline engines containing small amounts of copolymers of alkyl (meth) acrylates with 8 to 40 carbon atoms in the alkyl radical and / or vinyl esters of carboxylic acids containing 8 to 40 carbon atoms and monoethylenically unsaturated mono- and / or dicarboxylic acids with 3 to 12 carbon atoms with a total molecular weight of 500 to 20,000 g per mole, the carboxyl groups of the copolymers being fully or partially reacted with alkali to form the alkali metal salts and the rest of the acid groups is reacted with ammonia and / or amines having up to 50 carbon atoms to give the corresponding amide groups and / or ammonium salts.

Die neuen Kraftstoffzusätze haben den Vorteil, daß sie die Wirkung üblicher Benzinadditive in den Ottomotoren nicht beeinträchtigen und gleichzeitig das Auftreten von Abnutzungserscheinungen an den Ventilen verhindern oder zumindest stark herabsetzen und weiter überraschenderweise das Auftreten von Korrosion in den Ottomotoren beträchtlich mindern oder gar verhindern.The new fuel additives have the advantage that they do not impair the effect of conventional gasoline additives in the gasoline engines and at the same time the wear and tear on the valves prevent or at least greatly reduce and further surprisingly significantly reduce or even prevent the occurrence of corrosion in the gasoline engines.

Die erfindungsgemäßen Kraftstoffzusätze werden zweckmäßig in zwei Verfahrensstufen hergestellt. Die erste Verfahrensstufe ist die Herstellung der Copolymeren aus Alkyl(meth)acrylaten mit 8 bis 40 C-Atomen im Alkylrest und/oder Vinylestern aus 8 bis 40 C-Atome enthaltenden Carbonsäuren und monoethylenisch ungesättigten Mono- und/oder Dicarbonsäuren mit 3 bis 12 C-Atomen. In der zweiten Verfahrensstufe werden die Säuregruppen der erhaltenen Copolymeren ganz oder teilweise mit Alkali unter Bildung der Alkalimetallsalze umgesetzt. Die vollstäntige Umsetzung der Säuregruppen der Copolymeren zu den Alkalimetallsalzen erfolgt zweckmäßig dann, wenn die erhaltenen Alkalimetallsalze der Copolymeren bereits eine hinreichende Löslichkeit in den Kraftstoffen, denen sie zugesetzt werden sollen, aufweisen. Falls die Löslichkeit nicht ausreicht, wird man die Säuregruppen der Copolymeren zweckmäßig nur teilweise mit Alkali unter Bildung der Alkalimetallsalze umsetzen und den Rest der Säuregruppen mit Ammoniak und/oder Aminen zu den entsprechenden Amidgruppen und/oder Ammoniumsalzen umsetzen, um die hinreichende Löslichkeit zu erhalten. Um die erforderliche Löslichkeit der Kraftstoffzusätze zu erreichen, wird man weiter zweckmäßig so vorgehen, daß man bei der Herstellung der Copolymeren aus Alkyl(meth)acrlyaten und/oder Vinylestern mit geringer Zahl von C-Atomen in der Alkyl/Carbonsäuregruppe in der zweiten Verfahrensstufe bei der weiteren Umsetzung mit Aminen längerkettige Amine verwendet und/oder gegebenenfalls den Anteil der Säuregruppen, der mit den Aminen umzusetzen ist, erhöht. Entsprechend kann man bei der Verwendung von Alkyl(meth)acrylaten und/oder Vinylestern mit höherer Zahl von C-Atomen in der Alkyl/Carbonsäuregruppe für die Herstellung der Copolymeren in der zweiten Verfahrensstufe Amine mit kürzeren Alkylketten verwenden bzw. den Anteil der Säuregruppen, der mit den Aminen umzusetzen ist, erniedrigen.The fuel additives according to the invention are expediently produced in two process stages. The first process step is the preparation of the copolymers from alkyl (meth) acrylates with 8 to 40 C atoms in the alkyl radical and / or vinyl esters from carboxylic acids containing 8 to 40 C atoms and monoethylenically unsaturated mono- and / or dicarboxylic acids with 3 to 12 C. -Atoms. In the second process stage, the acid groups of the copolymers obtained are reacted in whole or in part with alkali to form the alkali metal salts. The complete conversion of the acid groups of the copolymers to the alkali metal salts is expedient when the alkali metal salts of the copolymers obtained already have sufficient solubility in the fuels to which they are to be added. If the solubility is insufficient, the acid groups of the copolymers are expediently only partially reacted with alkali to form the alkali metal salts and the rest of the acid groups are reacted with ammonia and / or amines to give the corresponding amide groups and / or ammonium salts in order to obtain sufficient solubility. In order to achieve the required solubility of the fuel additives, one will proceed appropriately so that in the preparation of the copolymers from alkyl (meth) acrylicates and / or vinyl esters with a small number of carbon atoms in the alkyl / carboxylic acid group in the second process step in the further reaction with amines, longer-chain amines are used and / or, if appropriate, the proportion of acid groups to be reacted with the amines is increased. Correspondingly, when using alkyl (meth) acrylates and / or vinyl esters with a higher number of carbon atoms in the alkyl / carboxylic acid group for the preparation of the copolymers in the second process stage, amines with shorter alkyl chains or the proportion of the acid groups which is to be reacted with the amines.

Der Anteil an Bausteinen mit Säurefunktion im Copolymeren soll so groß sein, daß die Alkalimetallsalze der Copolymeren, gegebenenfalls noch mit Ammoniak und/oder Aminen zu Amiden und Ammonsalzen umgesetzt, in Otto-Kraftstoffen löslich sind. Von einem großen Säuregruppen enthaltenden Molekül mit wenig Säuregruppen wie Methacrylsäure ist es zweckmäßig, mehr solcher Moleküle einzubauen als von einem Molekül mit viel Säuregruppen wie Maleinsäure bzw. Maleinsäureanhydrid. Zweckmäßigerweise werden bis zu 60 Gew.%, vorzugsweise bis zu 30 Gew.%, an säuregruppenhaltigen Monomeren in das Copolymere einpolymerisiert.The proportion of building blocks with acid function in the copolymer should be so large that the alkali metal salts of the copolymers, if appropriate also reacted with ammonia and / or amines to form amides and ammonium salts, are soluble in petrol. It is expedient to incorporate more of such molecules from a molecule containing large acid groups with few acid groups such as methacrylic acid than from a molecule with many acid groups such as maleic acid or maleic anhydride. Up to 60% by weight, preferably up to 30% by weight, of monomers containing acid groups are expediently polymerized into the copolymer.

Als Alkyl(meth)acrylester sind alle Ester der Acrylsäure und Methacrylsäure mit geradkettigen Alkoholen mit 8 bis 40 C-Atomen geeignet, z.B. 2-Ethylhexylacrylat, 2-Ethylhexylmethacrylat, n-Decylacrylat, n-Decylmethacrylat, Dodecylacrylat, Dodecylmethalcrylat, Isotridecylacrylat, Isotridecylmethacrylat, Tetradecylacrylat, Tetradecylmethacrylat, C₁₆/C₁₈-Talgfettalkoholmethacrylat, Octadecylacrylat, Octadpcylmethacrylat, n-Eicosylacrylat, n-Eicosylmethacrylat, n-Docosylacrylat, n-Docosylmethacrylat, Tetracosylacrylat, Hexacosylacrylat, Hexacosylmethacrylat, Octocosylacrylat, Octocosylmethacrylat und Mischungen untereinander, wie beispielsweise C₁₈-C₂₂-Alkylacrylat. Bevorzugt sind C₁₆- bis C₂₈-Alkyl(meth)acrylate. Als Vinylester sind alle auf Basis verzweigter und unverzweigter Monocarbonsäuren mit 8 bis 40 C-Atomen geeignet. Beispielsweise seien geeignet Vinyl-2-ethylhexanat, Vinyllaurat, Vinyltalgfettsäureester, Vinylmyristat, Vinylpalmitat, Vinylstearat, Vinyloleat sowie Mischungen untereinander.Suitable alkyl (meth) acrylic esters are all esters of acrylic acid and methacrylic acid with straight-chain alcohols with 8 to 40 C atoms, e.g. 2-ethylhexyl acrylate, 2-ethylhexyl, n-decyl acrylate, n-decyl methacrylate, dodecyl acrylate, Dodecylmethalcrylat, isotridecyl, Isotridecylmethacrylat, tetradecyl acrylate, tetradecyl, C₁₆ / C₁₈-Talgfettalkoholmethacrylat, octadecyl acrylate, Octadpcylmethacrylat, n-eicosyl acrylate, n-eicosyl, n-docosyl acrylate, n-Docosyl methacrylate, tetracosyl acrylate, hexacosyl acrylate, hexacosyl methacrylate, octocosyl acrylate, octocosyl methacrylate and mixtures with one another, such as C₁₈-C₂₂ alkyl acrylate. C₁₆ to C₂₈ alkyl (meth) acrylates are preferred. Suitable as vinyl esters are all based on branched and unbranched monocarboxylic acids with 8 to 40 carbon atoms. For example, vinyl 2-ethylhexanate, vinyl laurate, vinyl tallow fatty acid esters, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl oleate and mixtures with one another are suitable.

Als monoethylenisch ungesättigte Mono- und/oder Dicarbonsäuren kommen solche in Frage, die 3 bis 12 C-Atome im Molekül besitzen, z.B. Acrylsäure, Methacrylsäure, Crotonsäure, Vinylmilchsäure, Allylessigsäure, Propylidenessigsäure, Ethylacrylsäure, Dimethylacrylsäure sowie die Dicarbonsäuren Maleinsäure, Fumarsäure, Itaconsäure, Glutaconsäure, Methylenmalonsäure, Citraconsäure und Tetrahydrophthalsäure. In der Regel ist es von Vorteil, die Dicarbonsäuren in Form der Anhydride, soweit verfügbar, bei der Copolymerisation einzusetzen, z.B. Maleinsäureanhydrid, Itaconsäureanhydrid, Citraconsäureanhydrid, Methylenmalonsäureanhydrid und Tetrahydrophthalsäureanhydrid, da die Anhydride in der Regel besser mit den (Meth)acrylaten und Vinylestern copolymerisieren. Die Anhydridgruppen können dann meist direkt mit den Aminen oder auch mit den Hydroxiden der Alkali- oder Erdalkalimetalle umgesetzt werden, ohne vorher die Anhydridgruppe mit Wasser in die Säure überzuführen. Manchmal ist es aus Löslichkeitsgründen von Vorteil, die Monoester der genannten Dicarbonsäuren aus Alkoholen mit 2 bis 40 C-Atomen einzusetzen, beispielsweise Monoethylmaleinat, Monobutylmaleinat, Monododecylmaleinat, Monooctadecylmaleinat, Monotetracosylmaleinat, Monooktadecylfumarat, Monooktendecylitaconat und Mischungen untereinander. Besonders bevorzugt sind Acrylsäure, Methacrylsäure, Maleinsäure(anhydrid) und Itaconsäure-(anhydrid).Suitable monoethylenically unsaturated mono- and / or dicarboxylic acids are those which have 3 to 12 carbon atoms in the molecule, for example acrylic acid, methacrylic acid, crotonic acid, vinyl lactic acid, allylacetic acid, propylidene acetic acid, ethyl acrylic acid, dimethylacrylic acid and the dicarboxylic acids maleic acid, fumaric acid, itaconic acid Glutaconic acid, methylene malonic acid, citraconic acid and tetrahydrophthalic acid. As a rule, it is advantageous to use the dicarboxylic acids in the form of the anhydrides, if available, in the copolymerization, for example maleic anhydride, itaconic anhydride, citraconic anhydride, methylene malonic anhydride and tetrahydrophthalic anhydride, since the anhydrides generally copolymerize better with the (meth) acrylates and vinyl esters . The anhydride groups can then usually be reacted directly with the amines or also with the hydroxides of the alkali or alkaline earth metals without first converting the anhydride group into the acid with water. Sometimes, for reasons of solubility, it is advantageous to use the monoesters of the dicarboxylic acids mentioned from alcohols having 2 to 40 carbon atoms, for example monoethyl maleate, monobutyl maleate, monododecyl maleate, monooctadecyl maleate, monotetracosyl maleate, monooctadecyl fumarate, monooktendeconate mixtures with one another. Acrylic acid, methacrylic acid, maleic acid (anhydride) and itaconic acid (anhydride) are particularly preferred.

Anstelle der nachträglichen Umsetzung der Säuregruppen, mit Aminen zu den entsprechenden Amiden und gegebenenfalls Ammonsalzen kann es manchmal von Vorteil sein, die entsprechenden N-Alkylamide der monoethylenisch ungesättigten Mono- und Dicarbonsäuren bereits in Form der Monomeren herzustellen und dann bei der Polymerisation direkt einzupolymerisieren. Meist ist das jedoch technisch viel aufwendiger, da sich die Amine an die Doppelbindung der monomeren Mono- und Dicarbonsäure anlagern können und dann das Einpolymerisieren verhindern. Solche monoethylenisch ungesättigte N-Alkylsäureamide sind beispielsweise N-Isotridecylacrylamid, N-Di-(Isotridecyl)acrylamid, N-Stearylacrylamid, N-Stearylmethacrylamid, Maleinsäuremonoisotridecylamid, Maleinsäurediisotridecylamid, Maleinsäuremonostearylamid, Maleinsäuredistearylamid.Instead of the subsequent reaction of the acid groups, with amines to give the corresponding amides and optionally ammonium salts, it can sometimes be advantageous to prepare the corresponding N-alkylamides of the monoethylenically unsaturated mono- and dicarboxylic acids already in the form of the monomers and then to copolymerize them directly during the polymerization. In most cases, however, this is technically much more complex, since the amines can attach to the double bond of the monomeric mono- and dicarboxylic acid and then prevent polymerization. Such monoethylenically unsaturated N-alkyl acid amides are, for example, N-isotridecylacrylamide, N-di- (isotridecyl) acrylamide, N-stearylacrylamide, N-stearyl methacrylamide, maleic acid monoisotridecylamide, maleic acid diisotridecylamide, maleic acid monostearylamide, maleic acid distearyl amide.

Die Copolymeren weisen Molmassen von 500 bis 20 000 g/mol, vorzugsweise 800 bis 10 000 g/mol, auf.The copolymers have molar masses of 500 to 20,000 g / mol, preferably 800 to 10,000 g / mol.

Die Herstellung erfolgt nach bekannten üblichen diskontinuierlichen und kontinuierlichen Polymerisationsverfahren wie Masse-, Suspensions-, Fällungs- und Lösungspolymerisation und Initiierung mit üblichen Radikalspendern wie beispielsweise Acetylcyclohexansulfonylperoxid, Diacetylperoxidicarbonat, Dicyclohexylperoxidicarbonat, Di-2-ethylhexylperoxidicarbonat, tert.-Butylperneodecanoat, 2,2′Azobis(4-methoxi-2,4-dimethylvaleronitril), tert.-Butylperpivalat, tert.-Butylper-2-ethyl-hexanoat, tert.-Butylpermaleinat, 2,2′ Azobis(isobutyronitril), Bis-(tert.-butylperoxid)cyclohexan, tert.-Butylperoxiisopropylcarbonat, tert.-Butylperacetat, Dicumylperoxid, Di-tert.-amylperoxid, Di-tert.-butylperoxid, p-Methanhydroperoxid, Cumolhydroperoxid und tert.-Butylhydroperoxid und Mischungen untereinander. Üblicherweise werden diese Initiatoren in Mengen von 0,1 bis 10 Gew.%, vorzugsweise 0,2 bis 5 Gew.%, berechnet auf die Monomeren, eingesetzt.The preparation is carried out according to known conventional discontinuous and continuous polymerization processes such as bulk, suspension, precipitation and solution polymerization and initiation with conventional radical donors such as, for example, acetylcyclohexanesulfonyl peroxide, diacetyl peroxidicarbonate, dicyclohexyl peroxidicarbonate, di-2-ethylhexyl peroxidicarbonate, 2,2'-butylobutylate, tert-butyl butyl (4-methoxy-2,4-dimethylvaleronitrile), tert-butyl perpivalate, tert-butyl per-2-ethyl hexanoate, tert-butyl permaleinate, 2,2 ′ azobis (isobutyronitrile), bis (tert-butyl peroxide) cyclohexane, tert-butyl peroxyisopropyl carbonate, tert-butyl peracetate, dicumyl peroxide, di-tert-amyl peroxide, di-tert-butyl peroxide, p-methane hydroperoxide, cumene hydroperoxide and tert-butyl hydroperoxide and mixtures with one another. These initiators are usually used in amounts of 0.1 to 10% by weight, preferably 0.2 to 5% by weight, based on the monomers.

Üblicherweise erfolgt die Copolymerisation bei Temperaturen von 40 bis 400°C, vorzugsweise 80 bis 300°C, wobei bei Verwendung von (Meth)acrylaten und Vinylestern oder Lösungsmitteln mit Siedetemperaturen unterhalb der Polymerisationstemperatur zweckmäßig unter Druck gearbeitet wird. Die Polymerisation wird zweckmäßig unter Luftausschluß, d.h., wenn nicht unter Siedebedingungen gearbeitet werden kann, unter Inertisierungsmittel wie beispielsweise Stickstoff durchgeführt, da Luftsauerstoff die Polymerisation verzögert. Durch Mitverwendung von Redox-Coinitiatoren wie beispielsweise Benzoin, Dimethylanilin, Ascorbinsäure sowie organisch lösliche Komplexe von Schwermetallen wie Kupfer, Kobalt, Mangan, Eisen, Nickel und Chrom kann die Reaktion beschleunigt werden. Die üblicherweise eingesetzten Mengen liegen bei 0,1 bis 2000 Gew.-ppm, vorzugsweise 0,1 bis 1000 Gew.-ppm. Bei der Wahl des Initiators bzw. des Initiatorsystems ist es zweckmäßig, bei der gewählten Polymerisationstemperatur darauf zu achten, daß die Halbwertszeit des Initiators oder des Initiatorsystems weniger als 3 Std. beträgt. Bei 150°C ist beispielsweise die Halbwertszeit von tert.-Butylhydroperoxid weniger als 3 Std. Das Initiatorsystem 1 Gew.%. tert.-Butylhydroperoxid/5 Gew.-ppm Kupfer-II-Acetylacetonat besitzt dagegen schon bei 100°C ein vergleichbares Polymerisationsverhalten wie 1 Gew.% tert.-Butylhydroperoxid bei 150°C. Wird beispielsweise bei niedriger Temperatur anpolymerisiert und bei höherer Temperatur auspolymerisiert, wird in der Regel mit 2 oder mehr Initiatoren gearbeitet.The copolymerization is usually carried out at from 40 to 400 ° C., preferably from 80 to 300 ° C., with the use of (meth) acrylates and vinyl esters or solvents with boiling temperatures below Polymerization temperature is advantageously carried out under pressure. The polymerization is expediently carried out with the exclusion of air, ie, if it is not possible to work under boiling conditions, with an inerting agent such as nitrogen, since atmospheric oxygen delays the polymerization. The reaction can be accelerated by using redox coinitiators such as benzoin, dimethylaniline, ascorbic acid and organically soluble complexes of heavy metals such as copper, cobalt, manganese, iron, nickel and chromium. The amounts usually used are 0.1 to 2000 ppm by weight, preferably 0.1 to 1000 ppm by weight. When choosing the initiator or the initiator system, it is advisable to ensure at the chosen polymerization temperature that the half-life of the initiator or the initiator system is less than 3 hours. At 150 ° C., for example, the half-life of tert-butyl hydroperoxide is less than 3 hours. The initiator system is 1% by weight. In contrast, tert-butyl hydroperoxide / 5 ppm by weight of copper (II) acetylacetonate has a polymerization behavior comparable to 1% by weight of tert-butyl hydroperoxide at 150 ° C. even at 100 ° C. If, for example, polymerization is carried out at a low temperature and polymerization is carried out at a higher temperature, 2 or more initiators are generally used.

Zur Erzielung niedermolekularer Copolymeren ist es oftmals zweckmäßig, in Gegenwart von Reglern zu arbeiten. Geeignete Regler sind beispielsweise Allylalkohole, wie Buten-1-ol-3, organische Merkaptoverbindungen wie 2-Merkaptoethanol, 2-Merkaptopropanol, Merkaptoessigsäure, Merkaptopropionsäure, tert.-Butylmerkaptan, n-Butylmerkaptan, n-Octylmerkaptan, n-Dodecylmerkaptan und tert.-Dodecylmerkaptan, die im allgemeinen in Mengen von 0,1 Gew.% bis 10 Gew.% eingesetzt werden.To achieve low molecular weight copolymers, it is often advisable to work in the presence of regulators. Suitable regulators are, for example, allyl alcohols, such as buten-1-ol-3, organic mercapto compounds such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid, tert-butyl mercaptan, n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan and tert.- Dodecyl mercaptan, which are generally used in amounts of 0.1% by weight to 10% by weight.

Die genannten Initiatoren, Co-Initiatoren, Regler und Polymerisationstemperaturen sind für alle Polymerisationsmethoden gleichermaßen einsetzbar. Für die Polymerisation geeignete Apparaturen sind z.B. übliche Rührkessel mit beispielsweise Anker-, Blatt-, Impeller- oder Mehrstufenimpuls-Gegenstrom-Rührer und für die kontinuierliche Herstellung Rührkesselkaskaden, Rohrreaktoren und statische Mischer.The initiators, co-initiators, regulators and polymerization temperatures mentioned can be used equally for all polymerization methods. Equipment suitable for the polymerization is e.g. Conventional stirred kettles with, for example, armature, blade, impeller or multi-stage impulse countercurrent stirrers and for the continuous production of stirred kettle cascades, tubular reactors and static mixers.

Die einfachste Polymerisationsmethode ist die Massepolymerisation. Dabei werden die (Meth)acrylester und/oder die Vinylester und das säuregruppenhaltige Monomere in Gegenwart eines Initiators und in Abwesenheit von Lösungsmitteln polymerisiert. Dieses Verfahren ist besonders geeignet für solche Copolymeren, bei denen der verwendete (Meth)acrylester und Vinylester 12 und mehr C-Atome besitzen. Zweckmäßigerweise mischt man alle Monomeren in der gewünschten Zusammensetzung und legt einen kleinen Teil, z.B. ca. 5 bis 10 %, im Reaktor vor, erhitzt unter Rühren auf die gewünschte Polymerisationstemperatur und dosiert die restliche Monomerenmischung und den Initiator und gegebenenfalls Coinitiator sowie Regler innerhalb 1 bis 10 Std., vorzugsweise 2 bis 5 Std., gleichmäßig zu. Es ist dabei zweckmäßig, den Initiator sowie den Coinitiator getrennt in Form von Lösungen in einer kleinen Menge eines geeigneten Lösungsmittels zuzudosieren. Das Copolymere läßt sich dann zum erfindungsgemäßen Kraftstoffzusatz direkt in der Schmelze oder auch nach Verdünnen mit einem geeigneten Lösungsmittel umsetzen.The simplest method of polymerization is bulk polymerization. The (meth) acrylic esters and / or the vinyl esters and the acid group-containing monomer are polymerized in the presence of an initiator and in the absence of solvents. This process is particularly suitable for those copolymers in which the (meth) acrylic ester and vinyl ester used have 12 or more carbon atoms. Advantageously, all monomers are mixed in the desired composition and a small part, for example about 5 to 10%, is placed in the reactor, heated to the mixture with stirring desired polymerization temperature and metered in the remaining monomer mixture and the initiator and optionally coinitiator and regulator evenly within 1 to 10 hours, preferably 2 to 5 hours. It is expedient to meter in the initiator and the coinitiator separately in the form of solutions in a small amount of a suitable solvent. The copolymer can then be converted to the fuel additive according to the invention directly in the melt or after dilution with a suitable solvent.

Geeignet zur Herstellung der gewünschten Copolymeren ist auch ein kontinuierliches Hochdruckverfahren, das Raum-Zeit-Ausbeuten von 1 bis 50 kg Polymer pro Liter Reaktor und Stunde zuläßt. Als Polymerisationsapparatur kann z.B. ein Druckkessel, eine Druckkesselkaskade, ein Druckrohr oder auch ein Druckkessel mit einem nachgeschalteten Reaktionsrohr, das mit einem statischen Mischer versehen ist, verwendet werden. Vorzugsweise polymerisiert man die Monomeren aus (Meth)acrylestern, Vinylestern und säuregruppenhaltigen monoethylenisch ungesättigten Verbindungen in mindestens 2 hintereinander geschalteten Polymerisationszonen. Dabei kann die eine Reaktionszone aus einem druckdichten Kessel, die andere aus einem beheizbaren statischen Mischer bestehen. Man erhält dabei Umsätze von mehr als 99 %. Ein Copolymerisat aus Stearylacrylat und Acrylsäure kann beispielsweise dadurch hergestellt werden, daß man die Monomeren und einen geeigneten Initiator einem Reaktor oder zwei hintereinandergeschalteten Reaktionszonen, beispielsweise einer Reaktorkaskade, kontinuierlich zuführt, und das Reaktionsprodukt nach einer Verweilzeit von 2 bis 60, vorzugsweise von 5 bis 30 Minuten, bei Temperaturen zwischen 200 und 400°C kontinuierlich aus der Reaktionszone ausschleust. Die Polymerisation wird zweckmäßig bei Drücken von mehr als 1 bar, vorzugsweise zwischen 1 und 200 bar, durchgeführt. Die erhaltenen Copolymeren mit Feststoffgehalten von über 99 % können dann weiter zu den entsprechenden Alkalisalzen bzw. Amiden und Ammonsalzen umgesetzt werden.A continuous high-pressure process is also suitable for producing the desired copolymers, which permits space-time yields of 1 to 50 kg of polymer per liter of reactor and hour. As a polymerization apparatus, e.g. a pressure vessel, a pressure vessel cascade, a pressure tube or a pressure vessel with a downstream reaction tube, which is provided with a static mixer, can be used. The monomers are preferably polymerized from (meth) acrylic esters, vinyl esters and acid group-containing monoethylenically unsaturated compounds in at least 2 polymerization zones connected in series. One reaction zone can consist of a pressure-tight vessel, the other of a heatable static mixer. You get sales of more than 99%. A copolymer of stearyl acrylate and acrylic acid can be prepared, for example, by continuously feeding the monomers and a suitable initiator to a reactor or two reaction zones connected in series, for example a reactor cascade, and the reaction product after a residence time of 2 to 60, preferably 5 to 30 Minutes, continuously discharged from the reaction zone at temperatures between 200 and 400 ° C. The polymerization is expediently carried out at pressures of more than 1 bar, preferably between 1 and 200 bar. The copolymers obtained with solids contents of over 99% can then be further converted to the corresponding alkali metal salts or amides and ammonium salts.

Eine weitere Methode zur einfachen Herstellung der Copolymeren ist die Fällungspolymerisation. Bei der Fällungspolymerisation werden solche Lösungsmittel eingesetzt, in denen die Monomeren löslich und das gebildete Copolymere unlöslich ist und ausfällt. Solche Lösungsmittel sind beispielsweise Ether wie Diethylether, Dipropylether, Dibutylether, Methyltert.-butylether, Diethylenglykoldimethylether und Mischungen untereinander. Bei der Durchführung der Fällungspolymerisation ist es zweckmäßig, besonders wenn bei Konzentrationen von über 40 Gew.% gearbeitet wird, in Gegenwart eines Schutzkolloids zu arbeiten zur Verhinderung der Aggregatbildung. Als Schutzkolloide sind polymere Stoffe geeignet, die in den Lösungsmitteln gut löslich sind und keine Reaktion mit den Monomeren eingehen. Geeignet sind beispielsweise Copolymere des Maleinsäureanhydrids mit Vinylalkylethern und/oder Olefinen mit 8 bis 20 C-Atomen sowie deren Monoester mit C₁₀- bis C₂₀-Alkoholen oder Mono- und Diamide mit C₁₀- bis C₂₀-Alkylaminen sowie Polyalkylvinylether, deren Alkylgruppe 1 bis 20 C-Atome enthält, wie beispielsweise Polymethyl-, Polyethyl-, Polyisobutyl- sowie Polyoktadecylvinylether. Die zugesetzten Mengen an Schutzkolloid liegen üblicherweise bei 0,05 bis 4 Gew.% (berechnet auf eingesetzte Monomere), vorzugsweise 0,1 bis 2 Gew.%, wobei es oftmals von Vorteil ist, mehrere Schutzkolloide zu kombinieren. Bei der Polymerisation ist es zweckmäßig, das Lösungsmittel, das Schutzkolloid und einen Teil der Monomerenmischung im Reaktor vorzulegen und bei gewählter Polymerisationstemperatur unter intensivem Rühren den Rest der Monomerenmischung und den Initiator sowie gegebenenfalls den Coinitiator und Regler zuzudosieren. Die Zulaufzeiten für Monomer und Initiator sind im allgemeinen zwischen 1 und 10 Std., vorzugsweise 2 und 5 Std. Es ist auch möglich, alle Einsatzstoffe gemeinsam in einem Reaktor zu polymerisieren, wobei jedoch Probleme mit der Wärmeabführung auftreten können, so daß eine solche Arbeitsweise weniger zweckmäßig ist. Die Konzentrationen der zu polymerisierenden Monomeren liegen zwischen 20 und 80 Gew.%, bevorzugt 30 bis 70 Gew.%. Aus den Polymerisatsuspensionen können direkt in Verdampfern, beispielsweise Bandtrocknern, Schaufeltrocknern, Sprühtrocknern und Wirbelbett-Trocknern, die Polymeren isoliert werden. Beim Arbeiten in geeigneten Lösungsmitteln, die Kraftstoffen direkt zugesetzt werden können, kann die weitere Umsetzung zum Alkali- bzw. Erdalkalisalz und Amid und/oder Ammoniumsalz direkt in der Suspension durchgeführt werden.Another method for the simple preparation of the copolymers is precipitation polymerization. In the case of precipitation polymerization, solvents are used in which the monomers are soluble and the copolymer formed is insoluble and fails. Such solvents are for example ethers such as diethyl ether, dipropyl ether, dibutyl ether, methyl tert-butyl ether, diethylene glycol dimethyl ether and mixtures with one another. When carrying out the precipitation polymerization, it is expedient, especially when working at concentrations of more than 40% by weight, to work in the presence of a protective colloid to prevent the formation of aggregates. Suitable protective colloids are polymeric substances which are readily soluble in the solvents and which do not react with the monomers. Copolymers of maleic anhydride are suitable, for example with vinyl alkyl ethers and / or olefins with 8 to 20 C atoms and their monoesters with C₁₀ to C₂₀ alcohols or mono- and diamides with C₁₀ to C₂₀ alkylamines and polyalkyl vinyl ethers whose alkyl group contains 1 to 20 C atoms, such as Polymethyl, polyethyl, polyisobutyl and polyoctadecyl vinyl ether. The amounts of protective colloid added are usually 0.05 to 4% by weight (based on the monomers used), preferably 0.1 to 2% by weight, it often being advantageous to combine several protective colloids. In the case of the polymerization, it is expedient to put the solvent, the protective colloid and part of the monomer mixture in the reactor and to meter in the rest of the monomer mixture and the initiator and, if appropriate, the coinitiator and regulator at the selected polymerization temperature with vigorous stirring. The feed times for monomer and initiator are generally between 1 and 10 hours, preferably 2 and 5 hours. It is also possible to polymerize all of the starting materials together in one reactor, but problems with heat dissipation can occur, so that such a procedure is less appropriate. The concentrations of the monomers to be polymerized are between 20 and 80% by weight, preferably 30 to 70% by weight. The polymers can be isolated directly from the polymer suspensions in evaporators, for example belt dryers, paddle dryers, spray dryers and fluidized bed dryers. When working in suitable solvents that can be added directly to fuels, the further conversion to the alkali or alkaline earth metal salt and amide and / or ammonium salt can be carried out directly in the suspension.

Die bevorzugte Ausführungsform für die Herstellung der Copolymeren ist die Lösungspolymerisation. Sie wird durchgeführt in Lösungsmitteln, in denen die Monomeren und die gebildeten Copolymeren löslich sind. Es sind hierfür alle Lösungsmittel geeignet, die diese Vorgabe erfüllen und die mit den Monomeren keine Reaktionen eingehen. Beispielsweise sind dies Aceton, Methylethylketon, Diethylketon, Methylisobutylketon, Ethylacetat, Butylacetat, aliphatische, cycloaliphatische und aromatische Kohlenwasserstoffe wie n-Oktan, Isooktan, Cyclohexan, Methylcyclohexan, Benzol, Toluol, Xylol, Ethylbenzol, Cumol, Tetrahydrofuran und Dioxan, wobei zur Erzielung niedermolekularer Copolymerer Xylol, Ethylbenzol, Cumol, Tetrahydrofuran und Dioxan besonders gut geeignet sind. Wie bei der Masse- und Fällungspolymerisation ist es auch hier zweckmäßig, das Lösungsmittel und einen Teil der Monomerenmischung (z.B. ca. 5 bis 20 %) vorzulegen und den Rest der Monomerenmischung mit dem Initiator und gegebenenfalls Co-Initiator und Regler zuzudosieren. Es können auch Lösungsmittel und (Meth)acrylester oder Vinylester im Polymerisationsreaktor vorgelegt und nach Erreichen der Polymerisationstemperatur dann das säuregruppenhaltige Monomere, gegebenenfalls gelöst im Lösungsmittel, und der Initiator sowie gegebenenfalls Coinitiator und Regler zudosiert werden. Die Konzentrationen der zu polymerisierenden Monomeren liegen zwischen 20 und 80 Gew.%, bevorzugt 30 und 70 Gew.%. Das feste Copolymer kann problemlos durch Verdampfen des Lösungsmittels isoliert werden. Aber auch hier ist es zweckmäßig, ein Lösungsmittel zu wählen, in dem die weitere Umsetzung zum Alkalisalz und mit Ammoniak und/oder Aminen erfolgen kann.The preferred embodiment for the preparation of the copolymers is solution polymerization. It is carried out in solvents in which the monomers and the copolymers formed are soluble. All solvents that meet this requirement and that do not react with the monomers are suitable for this. For example, these are acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, aliphatic, cycloaliphatic and aromatic hydrocarbons such as n-octane, isooctane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, cumene, and tetrahydrofuran, tetrahydrofuran Copolymers xylene, ethylbenzene, cumene, tetrahydrofuran and dioxane are particularly suitable. As with bulk and precipitation polymerization, it is also expedient here to introduce the solvent and part of the monomer mixture (for example about 5 to 20%) and to meter in the rest of the monomer mixture with the initiator and, if appropriate, co-initiator and regulator. Solvents and (meth) acrylic esters or vinyl esters can also be introduced into the polymerization reactor and then, after the polymerization temperature has been reached, the monomer containing acid groups, if appropriate dissolved in the solvent, and the initiator, and, if appropriate, coinitiator and regulator, are metered in. The concentrations of the too polymerizing monomers are between 20 and 80% by weight, preferably 30 and 70% by weight. The solid copolymer can be isolated easily by evaporating the solvent. But here, too, it is expedient to choose a solvent in which the further conversion to the alkali salt and with ammonia and / or amines can take place.

Die in der ersten Verfahrensstufe erhaltenen Copolymeren aus (Meth)acrylestern und/oder Vinylestern mit Säuregruppen enthaltenden Monomeren werden anschließend ganz oder teilweise zu den Alkalimetallsalzen umgesetzt und, falls die Umsetzung zu den Alkalimetallsalzen nur teilweise erfolgt, mit Ammoniak und/oder Aminen zu den Amiden und/oder Ammoniumsalzen umgesetzt. Es ist jedoch ebenso möglich, die anschließende Umsetzung der Copolymeren in umgekehrter Reihenfolge durchzuführen, indem die Copolymeren zunächst mit Aminen zu den entsprechenden Amiden und/oder Ammoniumsalzen umgesetzt werden und danach in die Akalimetallsalze übergeführt werden.The copolymers of (meth) acrylic esters and / or vinyl esters with monomers containing acid groups obtained in the first process step are then completely or partially converted to the alkali metal salts and, if the conversion to the alkali metal salts takes place only partially, with ammonia and / or amines to give the amides and / or ammonium salts implemented. However, it is also possible to carry out the subsequent reaction of the copolymers in reverse order by first reacting the copolymers with amines to give the corresponding amides and / or ammonium salts and then converting them to the alkali metal salts.

Für die Umsetzung der Copolymeren zu den Amiden und/oder Ammoniumsalzen werden Amine mit bis zu 50 C-Atomen verwendet. In der Regel werden Amine der allgemeinen Formel

Figure imgb0001

verwendet, in der R¹ und R² gleiche oder unterschiedliche unsubstituierte oder substituierte, gegebenenfalls einfach olefinisch ungesättigte Kohlenwasserstoffreste bedeuten, die im allgemeinen 1 bis 25, vorzugsweise 5 bis 25 C-Atome aufweisen, oder in der R¹ für H- steht und R² einen unsubstituierten oder substituierten, gegebenenfalls einfach olefinisch ungesättigten Kohlenwasserstoffrest mit im allgemeinen 1 bis 50, vorzugsweise 5 bis 50, insbesondere 8 bis 30 C-Atomen bedeutet. Geeignete Amine sind z.B. Di-2-ethylhexylamin, Dioleylamin. Mit besonderem Vorteil werden Isotridecylamin und Diisotridecylamin verwendet.Amines with up to 50 carbon atoms are used to convert the copolymers to the amides and / or ammonium salts. As a rule, amines of the general formula
Figure imgb0001
used in which R¹ and R² are the same or different unsubstituted or substituted, optionally simply olefinically unsaturated hydrocarbon radicals which generally have 1 to 25, preferably 5 to 25, carbon atoms, or in which R¹ is H- and R² is an unsubstituted or Substituted, optionally simply olefinically unsaturated hydrocarbon radical having in general 1 to 50, preferably 5 to 50, in particular 8 to 30, carbon atoms. Suitable amines are, for example, di-2-ethylhexylamine, dioleylamine. Isotridecylamine and diisotridecylamine are used with particular advantage.

Im allgemeinen werden die Säuregruppen der Copolymeren zu 5 bis 80 %, vorzugsweise 10 bis 70 %, insbesondere 15 bis 60 % zu den Amiden und/oder Ammoniumsalzen umgesetzt. Die Umsetzung der Copolymeren aus (Meth)acrylaten und/oder Vinylestern mit säuregruppenhaltigen Monomeren mit den Aminen erfolgt im allgemeinen in der Schmelze oder nach Verdünnen mit einem geeigneten Lösungsmittel. Als Lösungsmittel kommen beispielsweise die vorstehend für die Herstellung der Copolymeren durch Fällungs- und Lösungspolymerisation genannten Lösungsmittel in Betracht. Vorzugsweise werden aromatische, aliphatische oder cycloaliphatische Kohlenwasserstoffe eingesetzt.In general, 5 to 80%, preferably 10 to 70%, in particular 15 to 60%, of the acid groups of the copolymers are converted to the amides and / or ammonium salts. The reaction of the copolymers of (meth) acrylates and / or vinyl esters with monomers containing acid groups with the amines is generally carried out in the melt or after dilution with a suitable solvent. Examples of suitable solvents are: the solvents mentioned above for the preparation of the copolymers by precipitation and solution polymerization. Aromatic, aliphatic or cycloaliphatic hydrocarbons are preferably used.

Bei der Umsetzung mit den Aminen werden im allgemeinen Temperaturen von 20 bis 150°C, vorzugsweise 20 bis 120°C, insbesondere 30 bis 100°C angewendet.In the reaction with the amines, temperatures of 20 to 150 ° C., preferably 20 to 120 ° C., in particular 30 to 100 ° C., are generally used.

Im einzelnen geht man beispielsweise bei der Umsetzung mit den Aminen so vor, daß man das Copolymere, z.B. in einem Reaktionsgefäß, beispielsweise in geschmolzener Form oder in einem Lösungsmittel, vorlegt und unter Rühren bei Temperaturen von 60 bis 90°C das Amin einträgt und 1 bis 2 Std. unter Rühren umsetzt. Dabei erhält man in der Regel bei den Copolymeren, die sich von monoethylenisch ungesättigten Dicarbonsäuren ableiten, das Halbamid, bei dem bei überschüssiger Aminzugabe die verbleibende Carboxylgruppe als Alkylammoniumsalz vorliegt.In particular, the reaction with the amines is carried out, for example, in such a way that the copolymer, e.g. in a reaction vessel, for example in molten form or in a solvent, and the amine is introduced with stirring at temperatures from 60 to 90 ° C. and reacted for 1 to 2 hours with stirring. In the case of the copolymers which are derived from monoethylenically unsaturated dicarboxylic acids, the hemi-amide is obtained in which the remaining carboxyl group is present as the alkylammonium salt when excess amine is added.

Die erhaltenen Amide und/oder Ammoniumsalze der Copolymeren aus (Meth)acrylestern und/oder Vinylestern mit Säuregruppen enthaltenden Monomeren werden zur Überführung der verbleibenden Carboxylgruppen in die Alkalimetallsalze mit einer basischen Alkalimetallverbindung, z.B. den Hydroxiden, Carbonaten oder Alkoholaten, umgesetzt. Beispielsweise werden zur Herstellung der Kaliummetallsalze die Lösungen der Amide und/oder Ammoniumsalze der Copolymeren mit der berechneten Menge Kaliumverbindung, z.B. einer Lösung von KOH oder KOCH₃ zweckmäßig in Alkoholen, z.B. einem C₁- bis C₆-Alkohol wie Methanol, Ethanol, Propanol, Butanol, umgesetzt. Aus dem erhaltenen Reaktionsgemisch werden die Lösungsmittel und gebildetes Wasser zweckmäßig im Vakuum abgezogen.The resulting amides and / or ammonium salts of the copolymers of (meth) acrylic esters and / or vinyl esters with monomers containing acid groups are used to convert the remaining carboxyl groups into the alkali metal salts with a basic alkali metal compound, e.g. the hydroxides, carbonates or alcoholates. For example, the solutions of the amides and / or ammonium salts of the copolymers with the calculated amount of potassium compound, e.g. a solution of KOH or KOCH₃ suitably in alcohols, e.g. a C₁ to C₆ alcohol such as methanol, ethanol, propanol, butanol, implemented. The solvents and water formed are expediently removed in vacuo from the reaction mixture obtained.

Die erfindungsgemäßen Kraftstoffzusätze werden als Alkalimetallsalze verwendet. Als Alkalimetallsalze kommen die Lithium-, Natrium-, Kalium-, Rubidium-, Cäsiumsalze in Betracht, wobei die Kaliumsalze bevorzugt verwendet werden. Der Alkalimetallanteil in den erfindungsgemäßen Kraftstoffzusätzen beträgt, bezogen auf den Kraftstoffzusatz im allgemeinen mindestens 3 Gew.%, vorzugsweise 3 bis 25 Gew.%, insbesondere 4 bis 20 Gew.%, mit besonderem Vorteil 4 bis 15 Gew.%.The fuel additives according to the invention are used as alkali metal salts. The alkali metal salts are the lithium, sodium, potassium, rubidium, cesium salts, the potassium salts being used with preference. The proportion of alkali metal in the fuel additives according to the invention, based on the fuel additive, is generally at least 3% by weight, preferably 3 to 25% by weight, in particular 4 to 20% by weight, with particular advantage 4 to 15% by weight.

Die neuen Kraftstoffzusätze werden den Kraftstoffen für Ottomotoren in der Regel in Mengen von 10 bis 2000 Gew.-ppm, vorzugsweise von 50 bis 1000 Gew.-ppm zugegeben.The new fuel additives are generally added to the fuels for gasoline engines in amounts of 10 to 2000 ppm by weight, preferably 50 to 1000 ppm by weight.

Die erfindungsgemäßen Kraftstoffe können neben den Alkalimetallsalzen zusätzlich noch bekannte Antioxidantien auf Phenol- oder Aminbasis enthalten. Insbesondere ist es vorteilhaft, Kraftstoffzusätze zur Reinigung und Reinhaltung des Einlaßsystems mit phenolischen Antioxidantien zur Erhöhung der Lagerstabilität der Kraftstoffe zu kombinieren.In addition to the alkali metal salts, the fuels according to the invention can additionally contain known phenol- or amine-based antioxidants. In particular, it is advantageous to combine fuel additives for cleaning and keeping the intake system clean with phenolic antioxidants to increase the storage stability of the fuels.

Als gute Lösungsmittel bzw. Lösungsvermittler für die genannten, den Kraftstoff zuzusetzenden Komponenten haben sich Rückstandsöle aus der Oxoalkoholsynthese erwiesen.Residual oils from oxo alcohol synthesis have proven to be good solvents or solubilizers for the components to be added to the fuel.

Vorzugsweise verwendet man Oxoalkoholrückstände aus der Butanol-, Isobutanol-, Pentanol-, Hexanol-, Heptanol-, Oktanol-, Nonanol-, Dekanol-, Undekanol- oder Dodekanolsynthese. Besonders vorteilhaft ist die Verwendung von Oxoalkoholrückständen aus der Butanolsynthese. Daneben sind auch andere Lösungsmittel bzw. Lösungsmittelgemische verwendbar, die eine homogene Mischung der Komponenten in den weiter oben genannten Gewichtsverhältnissen ergeben. Die Wirkung der erfindungsgemäßen Benzinzusätze ist nicht nur auf Fahrbenzine beschränkt. Es hat sich gezeigt, daß man sie auch in Flugbenzinen verwenden kann, insbesondere in Flugbenzinen für Kolbenmotoren. Desgleichen wirken die erfindungsgemäßen Verbindungen nicht nur in Vergasermotoren, sondern auch bei Motoren mit Einspritzanlagen für den Kraftstoff.Oxoalcohol residues from butanol, isobutanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol or dodecanol synthesis are preferably used. The use of oxo alcohol residues from butanol synthesis is particularly advantageous. In addition, other solvents or solvent mixtures can also be used which result in a homogeneous mixture of the components in the weight ratios mentioned above. The effect of the gasoline additives according to the invention is not only limited to gasoline. It has been shown that they can also be used in aviation fuels, in particular in aviation fuels for piston engines. Likewise, the compounds according to the invention act not only in carburetor engines, but also in engines with fuel injection systems.

Die mit dem neuen Zusatz versehenen Kraftstoffe können noch weitere, übliche Zusätze, z.B. oktanzahlverbessernde Zusätze oder auch sauerstoffhaltige Komponenten, z.B. Methanol, Ethanol oder Methyltertiärbutylether enthalten.The fuels provided with the new additive can also contain other customary additives, e.g. additives to improve octane number or components containing oxygen, e.g. Contain methanol, ethanol or methyl tertiary butyl ether.

Die nachfolgenden Beispiele erläutern die ErfindungThe following examples illustrate the invention

In den Beispielen 1 bis 10 wird die Herstellung der Copolymeren aus (Meth)acrylestern und/oder Vinylestern mit Säuregruppen enthaltenen Monomeren beschrieben.Examples 1 to 10 describe the preparation of the copolymers from (meth) acrylic esters and / or vinyl esters with monomers containing acid groups.

Die angegebenen Teile sind Gewichtsteile. Die Molmassen wurden durch Gelpermeationschromatographie bestimmt, wobei als Elutionsmittel Tetrahydrofuran und zur Eichung eng verteilte Fraktionen von Polystyrol eingesetzt wurden.The parts specified are parts by weight. The molecular weights were determined by gel permeation chromatography, using tetrahydrofuran as eluent and narrowly distributed fractions of polystyrene for calibration.

Beispiel 1example 1

In einem Glasrührkolben mit Rückflußkühler werden 318,8 Teile einer 80 gew.%igen Lösung eines C₁₈-C₂₂-Alkylacrylats in Toluol, 585 Teile o-Xylol, 4,5 Teile Buten-1-ol-3, 15 Teile 2-Merkaptoethanol bis zum Sieden auf ca. 135°C erhitzt und innerhalb 2 Stunden eine Lösung aus 45 Teilen Acrylsäure und 15 Teilen o-Xylol und innerhalb 3 Stunden eine Lösung aus 9 Teilen Di-tert.-butylperoxid in 81 Teilen o-Xylol zudosiert. Anschließend wird noch 2 Stunden am Rückfluß gekocht. Der Feststoffgehalt der Lösung beträgt 32,1 %. Die Molmasse des Copolymeren beträgt 7600.In a glass stirred flask with a reflux condenser, 318.8 parts of an 80% by weight solution of a C₁₈-C₂₂ alkyl acrylate in toluene, 585 parts of o-xylene, 4.5 parts of buten-1-ol-3, 15 parts of 2-mercaptoethanol bis heated to boiling at approx. 135 ° C. and a solution of 45 parts of acrylic acid and 15 parts of o-xylene and a solution of 9 parts of di-tert-butyl peroxide in 81 parts of o-xylene were metered in within 3 hours. The mixture is then refluxed for a further 2 hours. The solids content of the solution is 32.1%. The molecular weight of the copolymer is 7600.

Beispiel 2Example 2

In einem Glasrührkolben mit Rückflußkühler werden 255 Teile Dodecylacrylat, 385 Teile o-Xylol, 4,5 Teile Buten-1-ol-3 und 15 Teile 2-Mercaptoethanol zum Sieden erhitzt und innerhalb 2 Stunden eine Lösung aus 45 Teilen Acrylsäure und 15 Teilen Xylol und innerhalb 3 Stunden eine Lösung aus 9 Teilen Di-tert.-butylperoxid in 81 Teilen Xylol zudosiert. Anschließend wird noch 2 Stunden am Rückfluß erhitzt. Der Feststoffgehalt der Lösung beträgt 32,9 %. Die Molmasse des Copolymeren beträgt 2600.In a glass stirred flask with a reflux condenser, 255 parts of dodecyl acrylate, 385 parts of o-xylene, 4.5 parts of buten-1-ol-3 and 15 parts of 2-mercaptoethanol are heated to boiling and a solution of 45 parts of acrylic acid and 15 parts of xylene is heated within 2 hours and a solution of 9 parts of di-tert-butyl peroxide in 81 parts of xylene was metered in over the course of 3 hours. The mixture is then heated under reflux for a further 2 hours. The solids content of the solution is 32.9%. The molecular weight of the copolymer is 2600.

Beispiel 3Example 3

In einem Rührkolben mit Rückflußkühler werden 255 Teile Oktadecylacrylat, 585 Teile o-Xylol, 4,5 Teile Buten-1-ol-3, 15 Teile 2-Mercaptoethanol bis zum Sieden erhitzt und innerhalb 2 Stunden eine Lösung aus 45 Teilen Acrylsäure und 15 Teilen o-Xylol und innerhalb 3 Stunden eine Lösung von 9 Teilen Di-tert.-butylperoxid und 81 Teilen o-Xylol zudosiert. Anschließend wird noch 2 Stunden am Rückfluß gekocht. Der Feststoffgehalt der Lösung beträgt 32,6 %. Die Molmasse des Copolymeren beträgt 2700.In a stirred flask with a reflux condenser, 255 parts of octadecyl acrylate, 585 parts of o-xylene, 4.5 parts of buten-1-ol-3, 15 parts of 2-mercaptoethanol are heated to boiling and a solution of 45 parts of acrylic acid and 15 parts within 2 hours o-xylene and within 3 hours a solution of 9 parts of di-tert-butyl peroxide and 81 parts of o-xylene. The mixture is then refluxed for a further 2 hours. The solids content of the solution is 32.6%. The molecular weight of the copolymer is 2700.

Beispiel 4Example 4

In einem Rührkolben mit Rückflußkühler werden 210 Teile Oktadecylacrylat, 585 Teile o-Xylol, 4,5 Teile Buten-1-ol-3, 15 Teile Mercaptoethanol zum Sieden erhitzt und innerhalb 2 Stunden eine Lösung aus 90 Teilen Acrylsäure und 15 Teilen o-Xylol und innerhalb 3 Stunden eine Lösung aus 9 Teilen Di-tert.-butylperoxid und 81 Teilen o-Xylol zudosiert. Anschließend wird noch 2 Stunden am Rückfluß gekocht. Der Feststoffgehalt der Lösung beträgt 32,7 %. Die Molmasse des Copolymeren beträgt 1500.210 parts of octadecyl acrylate, 585 parts of o-xylene, 4.5 parts of buten-1-ol-3, 15 parts of mercaptoethanol are heated to boiling in a stirred flask with reflux condenser and a solution of 90 parts of acrylic acid and 15 parts of o-xylene is heated within 2 hours and a solution of 9 parts of di-tert-butyl peroxide and 81 parts of o-xylene was metered in within 3 hours. The mixture is then refluxed for a further 2 hours. The solids content of the solution is 32.7%. The molecular weight of the copolymer is 1500.

Beispiel 5Example 5

Man verfährt wie in Beispiel 4 beschrieben, wobei jedoch anstelle von Acrylsäure 90 Teile Methacrylsäure eingesetzt werden. Der Feststoffgehalt der Lösung beträgt 32,5 %. Die Molmasse des Copolymeren beträgt 2050.The procedure is as described in Example 4, but 90 parts of methacrylic acid are used instead of acrylic acid. The solids content of the solution is 32.5%. The molecular weight of the copolymer is 2050.

Beispiel 6Example 6

In einem Rührkolben mit Rückflußkühler werden 281,25 Teile einer 80 gew.%igen Lösung eines C₁₈-C₂₂-Alkylmethacrylates (Methacrylester eines C₁₈-C₂₂-Alkoholgemisches (Alfol 1822) der Firma Condea Chemie, Hamburg) in Xylol, 525 Teile o-Xylol, 4,5 Teile Buten-1-ol-3, 15 Teile 2-Mercaptoethanol zum Sieden erhitzt und innerhalb 2 Stunden eine Lösung von 75 Teilen Acrylsäure und 15 Teilen o-Xylol und innerhalb 3 Stunden eine Lösung von 9 Teilen Di-tert.-butylperoxid und 81 Teilen o-Xylol zudosiert. Anschließend wird noch 2 Stunden am Rückfluß gekocht. Der Feststoffgehalt der Lösung beträgt 32,8 %. Die Molmasse der Copolymeren beträgt 3000.In a stirred flask with reflux condenser, 281.25 parts of an 80% by weight solution of a C₁₈-C₂₂-alkyl methacrylate (methacrylic ester of a C₁₈-C₂₂-alcohol mixture (Alfol 1822) from Condea Chemie, Hamburg) in xylene, 525 parts of o-xylene , 4.5 parts of buten-1-ol-3, 15 parts of 2-mercaptoethanol heated to boiling and within 2 hours a solution of 75 parts of acrylic acid and 15 parts of o-xylene and within 3 hours a solution of 9 parts of di-tert. -butyl peroxide and 81 parts of o-xylene are metered in. The mixture is then refluxed for a further 2 hours. The solids content of the solution is 32.8%. The molecular weight of the copolymers is 3000.

Beispiel 7Example 7

In einem Rührkolben mit Rückflußkühler werden 300 Teile einer 80 %igen Lösung eines C₁₈-C₂₂-Alkylmethacrylates in o-Xylol, 525 Teile o-Xylol, 4,5 Teile Buten-1-ol-3, 15 Teile 2-Mercaptoethanol bis zum Sieden erhitzt und innerhalb 2 Stunden eine Lösung aus 60 Teilen Methacrylsäure und 15 Teilen o-Xyol und innerhalb 3 Stunden eine Lösung aus 9 Teilen Di-tert.-butylperoxid und 81 Teilen o-Xylol zudosiert. Anschließend wird noch 2 Stunden am Rückfluß gekocht. Der Feststoffgehalt der Lösung beträgt 32,4 %. Die Molmasse des Copolymeren beträgt 2700.In a stirred flask with a reflux condenser, 300 parts of an 80% solution of a C₁₈-C₂₂-alkyl methacrylate in o-xylene, 525 parts of o-xylene, 4.5 parts of buten-1-ol-3, 15 parts of 2-mercaptoethanol until boiling heated and within 2 hours a solution of 60 parts of methacrylic acid and 15 parts of o-xylene and within 3 hours a solution of 9 parts of di-tert-butyl peroxide and 81 parts of o-xylene. The mixture is then refluxed for a further 2 hours. The solids content of the solution is 32.4%. The molecular weight of the copolymer is 2700.

Beispiel 8Example 8

In einem Rührkolben mit Rückflußkühler werden 210 Teile Octadecylacrylat, 585 Teile o-Xylol, 4,5 Teile Buten-1-ol-3, 15 Teile 2-Mercaptoethanol bis zum Sieden auf ca. 136°C erhitzt und innerhalb 2 Stunden eine 60°C heiße Lösung aus 90 Teilen Maleinsäureanhydrid und 15 Teilen o-Xyol und innerhalb 3 Stunden eine Lösung aus 9 Teilen Di-tert.-butylperoxid und 81 Teilen o-Xylol zudosiert. Anschließend wird noch 2 Stunden am Rückfluß gekocht. Der Feststoffgehalt der Lösung beträgt 32,6 %. Die Molmasse des Copolymeren beträgt 1700.In a stirred flask with a reflux condenser, 210 parts of octadecyl acrylate, 585 parts of o-xylene, 4.5 parts of buten-1-ol-3, 15 parts of 2-mercaptoethanol are heated to boiling at about 136 ° C. and 60 ° within 2 hours C hot solution of 90 parts of maleic anhydride and 15 parts of o-xylene and within 3 hours a solution of 9 parts of di-tert-butyl peroxide and 81 parts of o-xylene. The mixture is then refluxed for a further 2 hours. The solids content of the solution is 32.6%. The molecular weight of the copolymer is 1700.

Beispiel 9Example 9

In einem Rührkolben werden 270 Teile Octadecylacrylat, 30 Teile Maleinsäureanhydrid, 600 Teile o-Xylol, 9 Teile Buten-1-ol-3 auf ca. 140°C bis zum Sieden erhitzt und innerhalb 3 Stunden eine Lösung aus 9 Teilen Di-tert.-butylperoxid und 81 Teilen o-Xylol zudosiert. Anschließend wird noch 2 Stunden am Rückfluß gekocht. Der Feststoffgehalt der Lösung beträgt 34,1 %. Die Molmasse des Copolymeren beträgt 6200.In a stirred flask, 270 parts of octadecyl acrylate, 30 parts of maleic anhydride, 600 parts of o-xylene, 9 parts of buten-1-ol-3 are heated to boiling at approx. 140 ° C. and a solution of 9 parts of di-tert is added within 3 hours. -butyl peroxide and 81 parts of o-xylene are metered in. The mixture is then refluxed for a further 2 hours. The solids content of the solution is 34.1%. The molecular weight of the copolymer is 6200.

Beispiele 10 bis 18 (siehe Tabelle)Examples 10 to 18 (see table)

Die in den Beispielen 1 bis 9 erhalten Copolymeren wurden gemäß den Beispielen 10 bis 18 in die erfindungsgemäßen Kraftestoffsusätze übergeführt, indem sie zunächst mit Ammoniak oder Aminen zu den entsprechenden Amiden und/oder Ammonium-Salzen und danach zu den entsprechenden Kaliumsalzen umgesetzt wurden, oder indem sie vollständig in die Kaliumsalze übergeführt wurden.The copolymers obtained in Examples 1 to 9 were converted according to Examples 10 to 18 into the fuel additives according to the invention by first reacting them with ammonia or amines to give the corresponding amides and / or ammonium salts and then to give the corresponding potassium salts, or by they have been completely converted into the potassium salts.

Zur Herstellung der Kaliumsalze wurden Lösungen der Copolymeren bzw. die Amide und/oder Ammonium-Salze der Copolymeren mit 20 gew.%iger ethanolischer KOH-Lösung, die die berechnete KOH-Menge enthielt, versetzt, und aus dem erhaltenen Gemisch wurden im Vakuum bei Temperaturen von 70 bis 90°C das Lösungsmittel und das gebildete Wasser abdestilliert.To prepare the potassium salts, solutions of the copolymers or the amides and / or ammonium salts of the copolymers were admixed with 20% by weight ethanolic KOH solution, which contained the calculated amount of KOH, and the mixture obtained was used in vacuo Temperatures of 70 to 90 ° C the solvent and the water formed distilled off.

In der Tabelle sind die Einzelheiten der Reaktionsbedingungen für die Beispiele 10 bis 18 angegeben. Die Mol-Angaben beziehen sich auf 100 g Copolymeres.

Figure imgb0002
The details of the reaction conditions for Examples 10 to 18 are given in the table. The molar data relate to 100 g of copolymer.
Figure imgb0002

Beispiel 19Example 19

Um den günstigen Einfluß der erfindungsgemäßen Kraftstoffe auf das Korrosionsverhalten von Ottomotoren zu zeigen, wird unverbleiter, nicht additivierter Super-Ottokraftstoff (SOK) (Produkt der Erdölraffinerie Mannheim) einer Korrosionsprüfung gemäß DIN 51 585 bzw. ASTM D 665-60 bzw. IP 135/64 bei einer Temperatur von 23°C und einer Prüfzeit von 24 h unterworfen, wobei die erfindungsgemäßen Kraftstoffzusätze aus den Beispielen 10 bis 18 dem Kraftstoff jeweils in Mengen von 10 Gew.-ppm, bezogen auf Kalium, zugesetzt werden. Bei den erfindungsgemäßen Kraftstoffen wird am Stahlfinger keinerlei Korrosion festgestellt. Dagegen wird beim nicht additivierten Kraftstoff der Korrosionsgrad 3 festgestellt.In order to show the favorable influence of the fuels according to the invention on the corrosion behavior of gasoline engines, unleaded, non-additive super gasoline (SOK) (product of the petroleum refinery in Mannheim) is subjected to a corrosion test in accordance with DIN 51 585 or ASTM D 665-60 or IP 135 / 64 at a temperature of 23 ° C. and a test time of 24 h, the fuel additives according to the invention from Examples 10 to 18 being added to the fuel in each case in amounts of 10 ppm by weight, based on potassium. No corrosion is found on the steel finger of the fuels according to the invention. In contrast, the degree of corrosion 3 is determined for the non-additive fuel.

Beispiel 20Example 20

Bei der motorischen Prüfung auf einem Opel Kadett-Motor gemäß CEC F-02-C-79 mit einem Kraftstoff gemäß Beispiel 19, der einen Zusatz von 10 Gew.-ppm, bezogen auf Kalium, der Verbindung gemäß Beispiel 14 enthält, werden die Ventilablagerungen von durchschnittlich 386 mg/Einlaßventil auf 237 mg/Einlaßventil gesenkt. Hierdurch wird der übliche Additivbedarf zum Schutz und zur Reinhaltung der Einlaßsysteme erheblich gesenkt.When testing the engine on an Opel Kadett engine according to CEC F-02-C-79 with a fuel according to Example 19 which contains an addition of 10 ppm by weight, based on potassium, of the compound according to Example 14, the valve deposits reduced from an average of 386 mg / inlet valve to 237 mg / inlet valve. As a result, the usual need for additives to protect and keep the inlet systems clean is considerably reduced.

Claims (4)

1. A fuel for gasoline engines, containing small amounts of copolymers of alkyl (meth)acrylates where the alkyl radical is of 8 to 40 carbon atoms and/or vinyl esters of carboxylic acids of 8 to 40 carbon atoms and monoethylenically unsaturated mono- and/or dicarboxylic acids of 3 to 12 carbon atoms having a total molecular weight of from 500 to 20 000 g per mole, some or all of the carboxyl groups of the copolymers having been reacted with an alkali with formation of the alkali metal salts and the remainder of the acid groups having been reacted with ammonia and/or amines of not more than 50 carbon atoms to give the corresponding amide groups and/or ammonium salts.
2. A fuel as claimed in claim 1, which contains from 10 to 2 000 ppm by weight of the alkali metal salts of the copolymers.
3. A fuel as claimed in claim 1 or 2, wherein the copolymers contain not less than 3% by weight of the alkali.
4. A fuel as claimed in any of claims 1 to 3, wherein the carboxyl groups of the copolymers have been reacted with formation of the potassium salts.
EP89108374A 1988-05-19 1989-05-10 Fuel for spark ignition engines Expired - Lifetime EP0342497B1 (en)

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DE3817000A DE3817000A1 (en) 1988-05-19 1988-05-19 FUELS FOR OTTO ENGINES

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DE3931039A1 (en) * 1989-09-16 1991-03-28 Basf Ag USE OF COPOLYMERISATS BASED ON LONG-CHAIN UNSATURATED ESTERS AND ETHYLENICALLY UNSATURATED CARBONIC ACIDS FOR THE HYDROPHOBICATION OF LEATHER AND FUR SKINS
US5300126A (en) * 1992-10-19 1994-04-05 Mobil Oil Corporation Process for improving olefin etherification catalyst life
ES2082695B1 (en) * 1993-09-29 1996-12-16 Miralles Gines Marcos S PROCEDURE FOR OBTAINING A CHEMICAL ADDITIVE FOR LIQUID FUELS.
DE602004027686D1 (en) * 2003-07-03 2010-07-29 Infineum Int Ltd Fuel composition
DE10350063A1 (en) 2003-10-27 2005-05-25 Rohde & Schwarz Gmbh & Co. Kg Radio interference levels measuring method e.g. for RF circuits, involves measuring level of signal and in each case with limit value compared and during excess of limit value by measuring level, respective measuring frequency is marked
DE102005010882A1 (en) * 2005-03-09 2006-09-14 Rohde & Schwarz Gmbh & Co. Kg Method and apparatus for identifying radio interference levels asynchronously for measuring the frequency spectrum
DE102011076115A1 (en) * 2011-05-19 2012-11-22 Evonik Rohmax Additives Gmbh Poly (meth) acrylates as a multifunctional additive in plastics
FR3045366B1 (en) * 2015-12-22 2019-03-29 L'oreal PHOSPHONIC ETHYLENE POLYMER AND COSMETIC APPLICATIONS THEREOF
FR3064912B1 (en) 2017-04-07 2019-04-05 L'oreal HAIR COLORING PROCESS COMPRISING A PHOSPHONIC ETHYLENE POLYMER AND A PIGMENT

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2851345A (en) * 1955-02-02 1958-09-09 Armour & Co Fuel oil compositions
GB802589A (en) * 1955-03-22 1958-10-08 California Research Corp Compounded hydrocarbon fuels
US3397145A (en) * 1958-12-29 1968-08-13 Universal Oil Prod Co Hydrocarbon oils containing alkylthiophosphoric acid salts of polymeric condensation products
NL239642A (en) * 1959-05-28
US3100695A (en) * 1960-10-18 1963-08-13 Exxon Research Engineering Co Middle distillate pour point depressants
US3342734A (en) * 1961-11-22 1967-09-19 Rohm & Haas Phosphorous-containing graft copolymers as dispersants in lubricating and fuel compositions
US3256073A (en) * 1963-03-22 1966-06-14 Cities Service Oil Co Liquid hydrocarbon compositions having antistatic properties
NL148099B (en) * 1966-03-17 1975-12-15 Shell Int Research PROCEDURE FOR REDUCING THE FLOOD POINT OF A FUEL MIXTURE.
US3506625A (en) * 1967-12-01 1970-04-14 Sinclair Research Inc Oil-soluble metal salts of partial imides of monovinyl monomer - maleic anhydride copolymers
US3807976A (en) * 1969-08-13 1974-04-30 Du Pont Multi-functional gasoline additives and gasolines containing them
US3658493A (en) * 1969-09-15 1972-04-25 Exxon Research Engineering Co Distillate fuel oil containing nitrogen-containing salts or amides as was crystal modifiers
JPS5650996A (en) * 1979-10-04 1981-05-08 Sekiguchi:Kk Apparatus for producing emulsified fuel oil
ATE7151T1 (en) * 1979-11-23 1984-05-15 Exxon Research And Engineering Company COMBINATIONS OF ADDITIVES AND FUELS CONTAINING THEM.
US4489194A (en) * 1982-08-09 1984-12-18 The Lubrizol Corporation Carboxylic acylating agents substituted with olefin polymers of high/low molecular weight mono-olefins, derivatives thereof, and fuels and lubricants containing same
DE3405843A1 (en) * 1984-02-17 1985-08-29 Bayer Ag, 5090 Leverkusen COPOLYMERS BASED ON MALEINIC ACID ANHYDRIDE AND (ALPHA), (BETA) -UNAUSAUTED COMPOUNDS, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS PARAFFIN INHIBITORS
US4620855A (en) * 1984-11-07 1986-11-04 The Lubrizol Corp. Amino sulfonic acid derivatives of carboxylic acid-containing interpolymers, and fuels, lubricants and aqueous systems containing said derivatives
GB8515974D0 (en) * 1985-06-24 1985-07-24 Shell Int Research Gasoline composition
JPS6218494A (en) * 1985-07-16 1987-01-27 Kao Corp Additive for fuel oil

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