EP0342497B1 - Carburants pour moteurs à allumage par étincelle - Google Patents

Carburants pour moteurs à allumage par étincelle Download PDF

Info

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
Authority
EP
European Patent Office
Prior art keywords
copolymers
parts
acid
weight
fuel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP89108374A
Other languages
German (de)
English (en)
Other versions
EP0342497A3 (en
EP0342497A2 (fr
Inventor
Franz-Dieter Dr. Martischius
Hans-Henning Dr. Vogel
Norbert Dr. Greif
Knut Dr. Oppenlaender
Walter Denzinger
Heinrich Dr. Hartmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to AT89108374T priority Critical patent/ATE78508T1/de
Publication of EP0342497A2 publication Critical patent/EP0342497A2/fr
Publication of EP0342497A3 publication Critical patent/EP0342497A3/de
Application granted granted Critical
Publication of EP0342497B1 publication Critical patent/EP0342497B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Emergency Medicine (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fuel-Injection Apparatus (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Monitoring And Testing Of Transmission In General (AREA)

Claims (4)

1. Carburants pour moteurs à allumage par étincelle, comprenant de petites quantités de copolymères d'alkyl(méth)acrylates comprenant 8 à 10 atomes de carbone dans le reste alkyle et/ou d'esters vinyliques formés à partir d'acides carboxyliques comprenant 8 à 40 atomes de carbone et d'acides mono- et/ou dicarboxyliques monoéthylétiquement insaturés comprenant 3 à 12 atomes de carbone, ces copolymères ayant une masse molaire globale de 500 à 20 000 g par mole, les groupes carboxyle des copolymères ayant réagi en totalité ou en partie avec un alcali pour former des sels de métal alcalin et le reste des groupes acides ayant réagi avec de l'ammoniac et/ou des amines comprenant jusqu'à 50 atomes de carbone pour former les groupes amide correspondants et/ou les sels d'ammonium correspondants.
2. Carburants suivant la revendication 1, caractérisés par une teneur en les sels de métal alcalin des copolymères de 10 à 2000 ppm en poids.
3. Carburants suivant la revendication 1 ou 2, caractérisés en ce que les copolymères présentent une teneur en alcali inférieure à 3 °% en poids.
4. Carburants suivant l'une quelconque des revendications 1 à 3, caractérisés en ce que les groupes carboxyle des copolymères ont réagi avec formation de sels de potassium.
EP89108374A 1988-05-19 1989-05-10 Carburants pour moteurs à allumage par étincelle Expired - Lifetime EP0342497B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89108374T ATE78508T1 (de) 1988-05-19 1989-05-10 Kraftstoff fuer ottomotoren.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3817000 1988-05-19
DE3817000A DE3817000A1 (de) 1988-05-19 1988-05-19 Kraftstoffe fuer ottomotoren

Publications (3)

Publication Number Publication Date
EP0342497A2 EP0342497A2 (fr) 1989-11-23
EP0342497A3 EP0342497A3 (en) 1990-03-28
EP0342497B1 true EP0342497B1 (fr) 1992-07-22

Family

ID=6354656

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89108374A Expired - Lifetime EP0342497B1 (fr) 1988-05-19 1989-05-10 Carburants pour moteurs à allumage par étincelle

Country Status (7)

Country Link
US (1) US5009670A (fr)
EP (1) EP0342497B1 (fr)
JP (1) JPH0218495A (fr)
AT (1) ATE78508T1 (fr)
DD (1) DD283869A5 (fr)
DE (2) DE3817000A1 (fr)
ES (1) ES2043940T3 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3931039A1 (de) * 1989-09-16 1991-03-28 Basf Ag Verwendung von copolymerisaten auf basis von langkettigen ungesaettigten estern und ethylenisch ungesaettigten carbonsaeuren zum hydrophobieren von leder und pelzfellen
US5300126A (en) * 1992-10-19 1994-04-05 Mobil Oil Corporation Process for improving olefin etherification catalyst life
ES2082695B1 (es) * 1993-09-29 1996-12-16 Miralles Gines Marcos S Procedimiento para la obtencion de un aditivo quimico para combustibles liquidos.
ATE471362T1 (de) * 2003-07-03 2010-07-15 Infineum Int Ltd Kraftstoffzusammensetzung
DE10350063A1 (de) 2003-10-27 2005-05-25 Rohde & Schwarz Gmbh & Co. Kg Verfahren und Vorrichtung zur Messung von Funkstörpegeln mit Frequenznachführung
DE102005010882A1 (de) * 2005-03-09 2006-09-14 Rohde & Schwarz Gmbh & Co. Kg Verfahren und Vorrichtung zur Identifizierung von Funkstörpegeln asynchron zur Messung des Frequenzspektrums
DE102011076115A1 (de) * 2011-05-19 2012-11-22 Evonik Rohmax Additives Gmbh Poly(meth)acrylate als multifunktionales Additiv in Kunststoffen
FR3045366B1 (fr) * 2015-12-22 2019-03-29 L'oreal Polymere ethylenique phosphonique et ses applications en cosmetique
FR3064912B1 (fr) 2017-04-07 2019-04-05 L'oreal Procede de coloration des cheveux comprenant un polymere ethylenique phosphonique et un 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
US3126260A (en) * 1959-05-28 1964-03-24 Qgganic liquid composition
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 (nl) * 1966-03-17 1975-12-15 Shell Int Research Werkwijze voor het verlagen van het vloeipunt van een brandstofmengsel.
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 (de) * 1979-11-23 1984-05-15 Exxon Research And Engineering Company Kombinationen von zusaetzen und sie enthaltende brennstoffe.
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 (de) * 1984-02-17 1985-08-29 Bayer Ag, 5090 Leverkusen Copolymere auf basis von maleinsaeureanhydrid und (alpha), (beta)-ungesaettigten verbindungen, ein verfahren zu ihrer herstellung und ihre verwendung als paraffininhibitoren
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 (ja) * 1985-07-16 1987-01-27 Kao Corp 燃料油添加剤

Also Published As

Publication number Publication date
DE58901869D1 (de) 1992-08-27
US5009670A (en) 1991-04-23
ES2043940T3 (es) 1994-01-01
ATE78508T1 (de) 1992-08-15
EP0342497A3 (en) 1990-03-28
DE3817000A1 (de) 1989-11-23
EP0342497A2 (fr) 1989-11-23
DD283869A5 (de) 1990-10-24
JPH0218495A (ja) 1990-01-22

Similar Documents

Publication Publication Date Title
EP0307815B1 (fr) Combustibles pour moteurs à allumage par étincelle
EP0485773B1 (fr) Distillat moyen de pétrole à propriétés d'écoulement au froid améliorées
EP0606055B1 (fr) Terpolymères à base d'anhydrydes d'acides dicarboxyliques alpha, bêta insaturés, de composés alpha, bêta insaturés et de polyoxyalkylène éther d'alcools inférieurs insaturés
EP0744413B1 (fr) Préparation de dérivés de l'acide polyalkényl succinique et leur application comme additifs de combustibles ou de lubrifiants
EP0418661B1 (fr) Utilisation de copolymérisates à base d'esters non saturés à longue chaîne et d'acides carboxyliques à liaison éthylénique pour hydrophober du cuir ou des peaux
CA1060206A (fr) Agents azotes ameliorant l'ecoulement a froid des fractions moyennes de distillation
DE1044409B (de) Verfahren zur Herstellung von wasserempfindlichen Partialestern und Partialamiden eines Polymerisats
EP0486608B1 (fr) Utilisation de copolymerisats a base d'ethers vinyliques d'alkyle a chaines longues et d'anhydrides d'acide dicarboxylique ethyleniquement insatures pour impermeabiliser des cuirs et des peaux
EP0342497B1 (fr) Carburants pour moteurs à allumage par étincelle
EP0436151B1 (fr) Distillat moyen de pétrole stable au froid contenant des copolymères comme dispersants de paraffine
DE3905681A1 (de) Konzentrierte mischungen von pfropfcopolymerisaten aus estern von ungesaettigten saeuren und ethylen-vinylester-copolymerisaten
EP0486836B1 (fr) Distillat moyen de pétrole à propriétés d'écoulement au froid améliorées
EP0485774B1 (fr) Distillat moyen de pétrole à propriétés d'écoulement au froid améliorées
DE3730885A1 (de) Kraftstoffe fuer ottomotoren
DE1025670B (de) Kraftstoffgemisch
DE3733172A1 (de) Kraftstoffe fuer ottomotoren
EP0751963B1 (fr) Copolymeres a base de dicetenes, d'acides dicarboxyliques insatures ethyleniquement ou de leurs derives et d'hydrocarbures insatures ethyleniquement
DE19856270C2 (de) Polymermischung zur Verbesserung der Schmierwirkung von Mitteldestillaten
EP0475052A1 (fr) Distillats moyens de pétrole stables au froid, contenant des polymères comme dispersants de paraffine
EP0925274B1 (fr) Ameliorateur d'ecoulement pour distillats moyens de petrole brut
DE19719689A1 (de) Fließverbesserer für Erdölmitteldestillate
AT229569B (de) Verfahren zur Copolymerisation von Olefinen
DE2718248A1 (de) Additive zur verbesserung des viskositaetsindex
DE1811576B2 (de) Kohlenwasserstoffhaltige zubereitung
DE1039682B (de) Schmieroel

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE DE ES FR GB IT NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE DE ES FR GB IT NL SE

17P Request for examination filed

Effective date: 19900308

17Q First examination report despatched

Effective date: 19910114

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE DE ES FR GB IT NL SE

REF Corresponds to:

Ref document number: 78508

Country of ref document: AT

Date of ref document: 19920815

Kind code of ref document: T

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

REF Corresponds to:

Ref document number: 58901869

Country of ref document: DE

Date of ref document: 19920827

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2043940

Country of ref document: ES

Kind code of ref document: T3

EAL Se: european patent in force in sweden

Ref document number: 89108374.3

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19960424

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19960425

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19960501

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19960507

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19960514

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19960515

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19960520

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19960528

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19970510

Ref country code: AT

Effective date: 19970510

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19970511

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970512

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19970521

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19970531

BERE Be: lapsed

Owner name: BASF A.G.

Effective date: 19970531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19971201

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19970510

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980130

EUG Se: european patent has lapsed

Ref document number: 89108374.3

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19971201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 19990405

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050510