EP3322780A1 - Inhibiteurs de corrosion pour carburants et lubrifiants - Google Patents

Inhibiteurs de corrosion pour carburants et lubrifiants

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Publication number
EP3322780A1
EP3322780A1 EP16736891.9A EP16736891A EP3322780A1 EP 3322780 A1 EP3322780 A1 EP 3322780A1 EP 16736891 A EP16736891 A EP 16736891A EP 3322780 A1 EP3322780 A1 EP 3322780A1
Authority
EP
European Patent Office
Prior art keywords
acid
use according
carbon atoms
olefin
anhydride
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.)
Granted
Application number
EP16736891.9A
Other languages
German (de)
English (en)
Other versions
EP3322780B1 (fr
Inventor
Jochen Mezger
Maxim Peretolchin
Ivette Garcia Castro
Klaus Muehlbach
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
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Application filed by BASF SE filed Critical BASF SE
Publication of EP3322780A1 publication Critical patent/EP3322780A1/fr
Application granted granted Critical
Publication of EP3322780B1 publication Critical patent/EP3322780B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/16—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate polycarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—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
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    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2366—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amine groups
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    • 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
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    • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
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    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
    • C10M145/14—Acrylate; Methacrylate
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    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
    • C10L1/1883—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom polycarboxylic acid
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
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    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • C—CHEMISTRY; METALLURGY
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    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines
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    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026—Butene
    • C—CHEMISTRY; METALLURGY
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C—CHEMISTRY; METALLURGY
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of saturated carboxylic or carbonic acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
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    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/022—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
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    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
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    • C10M2217/026—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrile group
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    • C10M2217/028—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
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    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition

Definitions

  • the present invention relates to new uses of corrosion inhibitors in fuels and lubricants.
  • Corrosion inhibitors are common additives in fuels and lubricants, often based on acid-containing structures, e.g. Dimer fatty acids.
  • a disadvantage of these corrosion inhibitors is that they tend to precipitate, especially in the presence of calcium ions, and as a result their corrosion-inhibiting action is reduced.
  • the deposits formed by these precipitations may also affect the operation of engines, engine components or parts of the fuel system, in particular the injection system, especially the injection pumps or nozzles.
  • injection system is understood to mean the part of the fuel system in motor vehicles from the fuel pump through the injector outlet.
  • fuel system is understood to mean the components of motor vehicles that are in contact with the respective fuel, preferably the area from the tank up to and including the injector outlet.
  • the compounds of the invention against deposits not only act in the injection system, but also in the rest of the fuel system, in particular against deposits in fuel filters and pumps.
  • US 3382056 teaches the use of low molecular weight copolymers containing olefins and succinic acid and their derivatives in copolymerized form as anti-rust additives in refined fuel compositions.
  • JP 55-085679 teaches the use of hydrolytically opened copolymers of molecular weight Mw from 2,000 to 30,000 of ⁇ -olefins having from 20 to 60 carbon atoms and maleic anhydride as oil-soluble rust inhibitors in mineral oil or lubricants. It is known from US Pat. No. 5,080,686 and EP 299120 that alkyl- and alkeny succinic acids and their derivatives as well as copolymers containing olefins and succinic acid and their derivatives in copolymerized form act as corrosion inhibitors in oxygenated fuel systems. None of these documents shows that the corrosion inhibitors according to the invention have an increased compatibility with calcium ions.
  • WO 96/28486 discloses copolymers of monoethylenically unsaturated C 4 -C 12 -dicarboxylic acids or their anhydrides with 1-olefins having 3 to 14 C atoms. Their reaction with amines leads to corrosion inhibitors, an effect of the copolymer alone against corrosion is not described.
  • JP 2007-077216 describes oils containing partial esters of copolymers of maleic anhydride and ⁇ -olefins with alkylene glycols. An effect of the copolymer alone against corrosion is not described.
  • the invention provides the use of copolymers obtainable by - in a first reaction step (I) copolymerization of
  • (C) optionally at least one further, at least 4 carbon atoms, aliphatic or cycloaliphatic olefin which is other than (B) and (D) optionally one or more other copolymerizable monomers other than the monomers (A), (B) and (C) selected from the group consisting of
  • N-vinyl compounds selected from the group consisting of vinyl compounds of heterocycles containing at least one nitrogen atom, N-vinylamides or N-vinyllactams, (Df) ethylenically unsaturated aromatics
  • reaction step (II) partial hydrolysis of the anhydride functionalities contained in the copolymer obtained from (I) and / or partial saponification of carboxylic acid ester functionalities contained in the copolymer obtained from (I), with the proviso that more than 90% of the anhydride and carboxylic acid ester functionalities remain intact after reaction step (II).
  • corrosion inhibitors in fuels or lubricants preferably in fuels, more preferably in fuels having a content of alkali and / or alkaline earth metals and / or zinc of at least 0.1 ppm by weight.
  • copolymers described have a particular advantage in fuels or lubricants, especially in fuels having a content of alkali and / or alkaline earth metals and / or zinc of at least 0.1 ppm by weight, more preferably at least 0.2 ppm by weight and very particularly preferably at least 0.3 ppm by weight and in particular at least 0.5
  • Ppm by weight a content of alkali metals and / or alkaline earth metals and / or zinc of at least 1 ppm by weight, preferably at least 2 and more preferably at least 3 ppm by weight.
  • alkali metals and / or alkaline earth metals and / or zinc preferably also in the presence of alkaline earth metals.
  • the content of alkali metals and / or alkaline earth metals in fuels is obtained, for example, by mixing with alkali and / or alkaline earth metal-containing lubricants, for example in the fuel pump.
  • alkali metals and / or alkaline earth metals may originate from unsatisfactorily or insufficiently desalted fuel additives, for example carrier oils.
  • a source of zinc for example, anti-wear additives.
  • alkali metals are sodium and potassium, in particular sodium.
  • alkaline earth metals are particularly magnesium and calcium, especially calcium.
  • the copolymers described are still active in the presence of calcium and show no precipitation.
  • alkali and / or alkaline earth metals and / or zinc in each case relate to individual metal species.
  • the monomer (A) is at least one, preferably one to three, more preferably one or two and most preferably exactly one ethylenically unsaturated, preferably ⁇ , ⁇ -ethylenically unsaturated mono- or dicarboxylic acid or derivatives thereof, preferably a dicarboxylic acid or their derivatives.
  • Mono- or dialkyl esters preferably mono- or di-C 1 -C 4 -alkyl esters, particularly preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters, and
  • mixed esters preferably mixed esters with different C 1 -C 4 alkyl components, more preferably mixed methyl ethyl esters.
  • the derivatives are preferably anhydrides in monomeric form or di-C 1 -C 4 -alkyl esters, more preferably anhydrides in monomeric form.
  • C 1 -C 4 -alkyl is understood to mean methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl and tert-butyl, preferably methyl and ethyl, particularly preferably methyl.
  • the ⁇ , ⁇ -ethylenically unsaturated mono- or dicarboxylic acid are those mono- or dicarboxylic acids or derivatives thereof in which the carboxyl group or, in the case of dicarboxylic acids, at least one carboxyl group, preferably both carboxyl groups, are conjugated with the ethylenically unsaturated double bond.
  • Examples of ethylenically unsaturated mono- or dicarboxylic acids which are not ⁇ , ⁇ -ethylenically unsaturated are cis-5-norbornene-endo-2,3-dicarboxylic anhydride, exo-3,6-epoxy-1,2,3,6- tetrahydrophthalic anhydride and cis-4-cyclohexene-1, 2-dicarboxylic anhydride.
  • ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids are acrylic acid, methacrylic acid, crotonic acid and ethylacrylic acid, preferably acrylic acid and methacrylic acid, referred to in this document as (meth) acrylic acid, and particularly preferably acrylic acid.
  • Particularly preferred derivatives of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids are methyl acrylate, ethyl acrylate, n-butyl acrylate and methyl methacrylate.
  • dicarboxylic acids examples include maleic acid, fumaric acid, itaconic acid (2-methylene-butanedioic acid), citraconic acid (2-methylmaleic acid), glutaconic acid (pent-2-ene-1, 5-dicarboxylic acid), 2,3-dimethylmaleic acid, 2-methylfumaric acid, 2,3 Dimethyl fumaric acid, methylene malonic acid and tetrahydrophthalic acid, preferably maleic acid and fumaric acid, and more preferably maleic acid and its derivatives.
  • the monomer (A) is maleic anhydride.
  • the monomer (B) is at least one, preferably one to four, particularly preferably one to three, very particularly preferably one or two and in particular exactly one olefin having from at least 12 up to and including 30 carbon atoms.
  • the ⁇ -olefins (B) preferably have at least 14, more preferably at least 16 and most preferably at least 18 carbon atoms.
  • the alpha-olefins (B) have up to and including 28, more preferably up to and including 26, and most preferably up to and including 24 carbon atoms.
  • the ⁇ -olefins may preferably be linear or branched, preferably linear, 1-alkenes.
  • Examples of these are 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonodecene, 1-eicosene, 1-docoses, 1-tetracoses, 1-hexacoses of which 1-octadecene, 1-eicosene, 1-docoses and 1-tetracoses, as well as their mixtures, are preferred.
  • ⁇ -olefin (B) are those olefins which are oligomers or polymers of C 2 to C 12 olefins, preferably C 3 to C 10 olefins, more preferably C 4 to C 6 olefins.
  • olefins which are oligomers or polymers of C 2 to C 12 olefins, preferably C 3 to C 10 olefins, more preferably C 4 to C 6 olefins.
  • Examples thereof are ethene, propene, 1-butene, 2-butene, isobutene, pentene isomers and hexene isomers, preferred are ethene, propene, 1-butene, 2-butene and isobutene.
  • ⁇ -olefins (B) may be mentioned oligomers and polymers of propene, 1-butene, 2-butene, isobutene, and mixtures thereof, especially oligomers and polymers of propene or isobutene or of mixtures of 1-butene and 2-butene.
  • the oligomers the trimers, tetramers, pentamers and hexamers and mixtures thereof are preferred.
  • the other than (B) is copolymerized in the copolymer of the invention.
  • the olefins (C) may be olefins with terminal (o) double bond or those with non-terminal double bond, preferably with a-double bond.
  • the olefin (C) is olefins having 4 to less than 12 or more than 30 carbon atoms. If the olefin (C) is an olefin having 12 to 30 carbon atoms, this olefin (C) has no ⁇ -double bond.
  • aliphatic olefins examples include 1-butene, 2-butene, isobutene, pentene isomers, hexene isomers, heptene isomers, octene isomers, nonene isomers, decene isomers, undecene isomers, and mixtures thereof ,
  • cycloaliphatic olefins are cyclopentene, cyclohexene, cyclooctene, cyclodecene, cyclododecene, o or ß-pinene and mixtures thereof, limonene and norbornene.
  • olefins (C) are polymers of propene, 1-butene, 2-butene or isobutene having more than 30 carbon atoms or olefin mixtures containing such, preferably isobutene or olefin mixtures containing such, more preferably having an average molecular weight Mw in the range of 500 to 5000 g / mol, preferably 650 to 3000, particularly preferably 800 to 1500 g / mol.
  • the iso-butene in polymerized form containing oligomers or polymers have a high content of terminal ethylenic double bonds (o double bonds), for example at least 50 mol%, preferably at least 60 mol%, more preferably at least 70 mol% and completely more preferably at least 80 moles
  • C4 raffinates in particular "raffinate 1"
  • C4 cuts from isobutane are suitable as isobutene source for the preparation of such isobutene in polymerized form containing oligomers or polymers
  • Dehydrogenation C4 cuts from steam crackers and fluid catalysed cracking (FCC) crackers provided that they are substantially free of 1,3-butadiene contained therein.
  • FCC fluid catalysed cracking
  • Suitable isobutene-containing C4 hydrocarbon streams are, for example, the product stream of a propylene-isobutane co-oxidation or the product stream from a metathesis unit, which are generally used after customary purification and / or concentration.
  • Suitable C4 hydrocarbon streams typically contain less than 500 ppm, preferably less than 200 ppm, butadiene. The presence of 1-butene and of cis- and trans-2-butene is largely uncritical.
  • the isobutene concentration in said C4 hydrocarbon streams is in the range of 40 to 60 weight percent.
  • refining nat 1 usually consists essentially of 30 to 50 wt .-% isobutene, 10 to 50 wt .-% 1-butene, 10 to 40 wt .-% cis- and trans-2-butene and 2 to 35 wt. % Butanes;
  • the unsubstituted butenes in the raffinate 1 are generally virtually inert and only the isobutene is polymerized.
  • the monomer used for the polymerization is a technical C 4 -hydrocarbon stream having an isobutene content of from 1 to 100% by weight, in particular from 1 to 99% by weight, especially from 1 to 90% by weight. , more preferably from 30 to 60% by weight, in particular a raffinate 1 stream, a b / b stream from an FCC refinery unit, a product stream from a propylene-isobutane co-oxidation or a product stream from a metathesis unit.
  • Said isobutene-containing monomer mixture may contain small amounts of contaminants such as water, carboxylic acids or mineral acids, without resulting in critical yield or selectivity losses. It is expedient to avoid an accumulation of these impurities by removing such pollutants from the isobutene-containing monomer mixture, for example by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.
  • monomer mixtures of isobutene or of the isobutene-containing hydrocarbon mixture can also be reacted with olefinically unsaturated monomers which are copolymerizable with isobutene.
  • the monomer mixture preferably contains at least 5% by weight, particularly preferably at least 10% by weight and in particular at least 20% by weight of isobutene, and preferably at most 95% by weight. , particularly preferably at most 90% by weight and in particular at most 80% by weight of comonomers.
  • the substance mixture of the olefins (B) and optionally (C) averaged to their substance amounts at least 12 carbon atoms, preferably at least 14, more preferably at least 16 and most preferably at least 17 carbon atoms.
  • the upper limit is less relevant and is usually not more than 60 carbon atoms, preferably not more than 55, more preferably not more than 50, most preferably not more than 45 and especially not more than 40 carbon atoms.
  • the optional monomer (D) is at least one monomer, preferably one to three, more preferably one or two and most preferably exactly one monomer selected from the group consisting of
  • N-vinyl compounds selected from the group consisting of vinyl compounds of at least one nitrogen-containing heterocycles, N-vinyl amides or N-vinyl lactams, (Df) ethylenically unsaturated aromatics and
  • vinyl esters (Da) are vinyl esters of C 2 -C 12 -carboxylic acids, preferably vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pentanoate, vinyl hexanoate, vinyl octanoate, vinyl 2-ethylhexanoate, vinyl decanoate, as well as vinyl esters of versatic acids 5 to 10 Vinyl esters of 2,2-dimethylpropionic acid (pivalic acid, versatic acid 5), 2,2-dimethylbutyric acid (neohexanoic acid, versatic acid 6), 2,2-dimethylpentanoic acid (neoheptanoic acid, versatic acid 7), 2,2- Dimethylhexanoic acid (neoctanoic acid, versatic acid 8), 2,2-dimethylheptanoic acid (neononanoic acid, versatic acid 9) or 2,2-dimethyloctanoic acid (neo-decanoic acid, versatic acid
  • vinyl ethers (Db) are vinyl ethers of C 1 to C 12 -alkanols, preferably vinyl ethers of methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-hexanol , n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol) or 2-ethylhexanol.
  • Preferred (meth) acrylic esters (De) are (meth) acrylic esters of C5 to C12 alkanols, preferably of n-pentanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol ), 2-ethylhexanol or 2-propylheptanol. Particular preference is given to acrylic acid pentyl esters, 2-ethylhexyl acrylate, 2-propylheptyl acrylate.
  • Examples of monomers (Dd) are allyl alcohols and allyl ethers of C 2 - to C 12 -alkanols, preferably allyl ethers of methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n Hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol) or 2-ethylhexanol.
  • Examples of vinyl compounds (De) of heterocycles containing at least one nitrogen atom are N-vinylpyridine, N-vinylimidazole and N-vinylmorpholine.
  • Preferred compounds (De) are N-vinylamides or N-vinyllactams:
  • N-vinylamides or N-vinyllactams are N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone and N-vinylcaprolactam.
  • ethylenically unsaturated aromatics are styrene and ⁇ -methylstyrene.
  • Examples of ⁇ , ⁇ -ethylenically unsaturated nitriles (Dg) are acrylonitrile and methacrylonitrile.
  • Examples of (meth) acrylic acid amides (Dh) are acrylamide and methacrylamide.
  • Examples of allylamines (di) are allylamine, dialkylallylamine and trialkyl allylammonium halide.
  • Preferred monomers (D) are (Da), (Db), (De), (De) and / or (Df), particularly preferably (Da), (Db) and / or (De), very particularly preferably (Da) and / or (De) and in particular (De).
  • the incorporation ratio of the monomers (A) and (B) and optionally (C) and optionally (D) in the polymer obtained from the reaction step (I) is usually as follows:
  • the molar ratio of (A) / ((B) and (C)) (in total) is generally from 10: 1 to 1:10, preferably 8: 1 to 1: 8, particularly preferably 5: 1 to 1 : 5, most preferably 3: 1 to 1: 3, in particular 2: 1 to 1: 2 and especially 1, 5: 1 to 1: 1, 5.
  • the molar incorporation ratio of maleic anhydride to monomers ((B) and (C)) (in total) is about 1: 1.
  • maleic anhydride in a slight excess over the ⁇ -olefin, for example 1, 01-1, 5: 1, preferably 1, 02-1, 4: 1, particularly preferably 1 , 05-1, 3: 1, very particularly preferably 1, 07-1, 2: 1 and especially 1, 1-1, 15: 1.
  • the molar ratio of the obligate monomer (B) to the monomer (C), as far as it is present, is generally from 1: 0.05 to 10, preferably from 1: 0.1 to 6, particularly preferably from 1: 0, 2 to 4, most preferably from 1: 0.3 to 2.5 and especially 1: 0.5 to 1.5.
  • the proportion of one or more of the monomers (D), if present, based on the amount of the monomers (A), (B) and optionally (C) (in total) is generally 5 to 200 mol%, preferably 10 to 150 mol%, particularly preferably 15 to 100 mol%, very particularly preferably 20 to 50 mol% and in particular 0 to 25 mol%. In a preferred embodiment, no optional monomer (D) is present.
  • the copolymer consists of the monomers (A) and (B).
  • reaction step (II) the anhydride or carboxylic ester functionalities contained in the copolymer obtained from (I) can be partially hydrolyzed and / or saponified.
  • reaction step (II) anhydride functionalities are hydrolyzed and carboxylic acid ester functionalities are left substantially intact.
  • reaction step (II) more than 90% of the anhydride and carboxylic acid ester functionalities present remain intact after reaction step (II), preferably at least 92%, more preferably at least 94%, even more preferably at least 95%, especially at least 97% and especially at least 98%.
  • reaction step (II) it is possible that up to 99.9% of the anhydride and carboxylic acid ester functionalities present remain intact after reaction step (II), preferably up to 99.8%, more preferably up to 99.7%, most preferably up to 99, 5% and in particular up to 99%.
  • reaction step (II) is not carried out so that 100% of the anhydride and carboxylic acid ester functionalities contained in the copolymer obtained from reaction step (I) remain intact.
  • reaction step (II) Hydrolysis in reaction step (II) is then carried out when an anhydride, preferably the anhydride of a dicarboxylic acid, is used as the derivative of the monomer (A), whereas saponification or hydrolysis can be carried out when an ester is used as the monomer (A).
  • an anhydride preferably the anhydride of a dicarboxylic acid
  • the amount of water is added which corresponds to the desired degree of hydrolysis and which heats the copolymer obtained from (I) in the presence of the added water.
  • a temperature of preferably 20 to 150 ° C. is sufficient for this, preferably 60 to 100 ° C.
  • the reaction can be carried out under pressure to prevent the escape of water.
  • the anhydride functionalities are usually selectively reacted in the copolymer, whereas any carboxylic acid ester functionalities present in the copolymer do not react or at least react only in a subordinate manner.
  • the copolymer is reacted with an amount of a strong base in the presence of water, which corresponds to the desired degree of saponification.
  • Preferred strong bases are hydroxides, oxides, carbonates or bicarbonates of alkali metals or alkaline earth metals.
  • the copolymer obtained from (I) is then heated in the presence of the added water and strong base.
  • a temperature of preferably 20 to 130 ° C is sufficient, preferably 50 to 1 10 ° C. If necessary, the reaction can be carried out under pressure.
  • acids are mineral, carbon, sulfone or phosphorus-containing acids having a pKa of not more than 5, more preferably not more than 4.
  • acetic acid formic acid, oxalic acid, salicylic acid, substituted succinic acids, aromatic or unsubstituted benzenesulfonic acids, sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid.
  • acidic ion exchanger resins is also conceivable.
  • the copolymer obtained from (I) is then heated in the presence of the added water and the acid.
  • a temperature of preferably 40 to 200 ° C. is sufficient for this, preferably 80 to 150 ° C. If necessary, the reaction can be carried out under pressure.
  • the copolymers obtained from step (II) still contain residues of acid anions, it may be preferable to remove these acid anions from the copolymer with the aid of an ion exchanger and to exchange them preferably for hydroxide ions or carboxylate ions, more preferably hydroxide ions. This is especially the case when the acid anions contained in the copolymer are halides, sulfur-containing or nitrogen-containing.
  • the copolymer obtained from reaction step (II) generally has a weight-average molecular weight Mw of from 0.5 to 20 kDa, preferably from 0.6 to 15, more preferably from 0.7 to 7, very particularly preferably from 1 to 7 and in particular 1, 5 to 4 kDa (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).
  • the number average molecular weight Mn is usually from 0.5 to 10 kDa, preferably from 0.6 to 5, particularly preferably from 0.7 to 4, very particularly preferably from 0.8 to 3 and in particular from 1 to 2 kDa (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).
  • the polydispersity is generally from 1 to 10, preferably from 1, 1 to 8, particularly preferably from 1, 2 to 7, very particularly preferably from 1, 3 to 5 and in particular from 1, 5 to 3.
  • the content of free Acid groups in the copolymer after passing through the reaction step (II) is preferably less than 5 mmol / g copolymer, more preferably less than 3, most preferably less than 2 mmol / g copolymer and especially less than 1 mmol / g copolymer.
  • the copolymers contain a high proportion of adjacent carboxylic acid groups as determined by an adjuacy measurement.
  • a sample of the copolymer is tempered for 30 minutes at a temperature of 290 ° C between two Teflon films and recorded at a bubble-free FTIR spectrum. From the spectra obtained, the IR spectrum of Teflon is subtracted, determines the layer thickness and determines the content of cyclic anhydride.
  • the adjacency is at least 10%, preferably at least 15%, particularly preferably at least 20%, very particularly preferably at least 25% and in particular at least 30%.
  • the use according to the invention relates to the inhibition of the corrosion of iron, steel and / or non-ferrous metal surfaces.
  • non-ferrous metals copper and its alloys are preferred.
  • the corrosion of steel surfaces is inhibited.
  • copolymers described are generally added to fuels having the above-specified content of alkali metals and / or alkaline earth metals and / or zinc in amounts of from 1 to 60, preferably from 4 to 50, ppm by weight and more preferably from 10 to 40 ppm by weight.
  • the copolymers described are used in the form of fuel additive mixtures, together with customary additives:
  • these are primarily conventional detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors other than the copolymers described, demulsifiers, dehazers, defoamers, cetane number improvers, combustion improvers, antioxidants or stabilizers, antistatics , Metallocenes, metal deactivators, dyes and / or solvents.
  • the usual detergent additives are preferably amphiphilic substances which have at least one hydrophobic hydrocarbon radical having a number-average molecular weight (M n ) of from 85 to 20 000 and at least one polar group selected from:
  • the hydrophobic hydrocarbon radical in the above detergent additives which provides sufficient solubility in the fuel has a number average molecular weight (M n ) of from 85 to 20,000, preferably from 1 13 to 10,000, more preferably from 300 to 5,000, more preferably from 300 up to 3,000, more preferably from 500 to 2,500 and especially from 700 to 2,500, especially from 800 to 1,500.
  • M n number average molecular weight
  • hydrophobic hydrocarbon radical in particular in combination with the polar, in particular polypropenyl, polybutenyl and polyisobutenyl radicals having a number average molecular weight M n of preferably in each case from 300 to 5,000, particularly preferably from 300 to 3,000, more preferably from 500 to 2,500, even more preferably from 700 to 2,500 and in particular from 800 to 1,500.
  • M n number average molecular weight of preferably in each case from 300 to 5,000, particularly preferably from 300 to 3,000, more preferably from 500 to 2,500, even more preferably from 700 to 2,500 and in particular from 800 to 1,500.
  • monoamino (Da) -containing additives are the compounds obtained from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DE-A 196 20 262.
  • these reaction products are mixtures of pure nitropolyisobutenes (for example ⁇ , ⁇ -dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (for example ⁇ -nitro- ⁇ -hydroxy polyisobutene).
  • Carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) containing additives are preferably copolymers of C2 to C 4 o-olefins with maleic anhydride having a total molecular weight of 500 to 20,000, the carboxyl groups wholly or partly to the alkali metal. metal or alkaline earth metal salts and a remaining radical of the carboxyl groups are reacted with alcohols or amines.
  • Such additives are known in particular from EP-A 307 815. Such additives are mainly used to prevent valve seat wear and, as described in WO-A 87/01 126, can be advantageously used in combination with conventional fuel detergents such as poly (iso) -butene amines or polyetheramines.
  • Sulfonic acid groups or their alkali metal or alkaline earth metal salts (De) containing additives are preferably alkali metal or alkaline earth metal salts of a Sulfobern- steinklaklalesters, as described in particular in EP-A 639 632.
  • Such additives are mainly used to prevent valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly (iso) buteneamines or polyetheramines.
  • Polyoxy-C2-C4-alkylene (Df) containing additives are preferably polyether or polyetheramines, which by reaction of C2 to C6o-alkanols, C6 to C30 alkanediols, mono- or D1-C2 to C3o-alkylamines, Cr to C3o-alkylcyclo-hexanols or C1- to C3o-alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines are available.
  • Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416.
  • polyethers such products also fulfill carrier oil properties. Typical examples thereof are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and also polyisobutenol butoxylates and propoxylates, and the corresponding reaction products with ammonia.
  • Carboxyl ester groups (Dg) -containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, especially those having a minimum viscosity of 2 mm 2 / s at 100 ° C, as described in particular in DE-A 38 38 918 are described.
  • mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 C atoms.
  • esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and of isotridecanol. Such products also meet carrier oil properties.
  • the moieties having hydroxy and / or amino and / or amido and / or imido groups they are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of diamines or polyamines which, in addition to the amide function, still have free amine groups, succinic acid derivatives having an acid and an amide function, carboximides with monoamines, carboximides with diamines or polyamines, in addition to the imide function still have free amine groups, or diimides formed by the reaction of di- or polyamines with two succinic acid derivatives.
  • Such fuel additives are well known and described, for example, in documents (1) and (2).
  • reaction products of alkyl- or alkenyl-substituted succinic acids or derivatives thereof with amines and particularly preferably to the reaction products of polyisobutenyl-substituted succinic acids or derivatives thereof with amines.
  • reaction products with aliphatic polyamines polyalkyleneimines
  • ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine which have an imide structure.
  • Mannich-containing additives produced by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine ,
  • Such "polyisobutene-Mannich bases" are described in particular in EP-A 831 141.
  • One or more of said detergent additives may be added to the fuel in such an amount that the metering rate of these detergent additives is preferably from 25 to 2500 ppm by weight, in particular from 75 to 1500 ppm by weight, especially from 150 to 1000% by weight . ppm.
  • Co-used carrier oils may be mineral or synthetic.
  • Suitable mineral carrier oils are fractions obtained in petroleum processing, such as bright stock or base oils having viscosities such as from class SN 500 to 2000, but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. It is also useful as a "hydrocrack oil” known and obtained in the refining of mineral oil fraction (Vakuumdestillatites with a boiling range of about 360 to 500 ° C, available from high pressure catalytically hydrogenated and isomerized and dewaxed natural mineral oil). Also suitable are mixtures of the abovementioned mineral carrier oils.
  • suitable synthetic carrier oils are polyolefins (polyalphaolefins or polyternal olefins), (poly) esters, poly) alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-initiated polyethers, alkylphenol-initiated polyetheramines and carboxylic acid esters of long-chain alkanols.
  • suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C 2 - to C 4 -alkylene groups which are prepared by reacting C 2 - to C 60 -alkanols, C 6 - to C 3 -alkanediols, mono- or C 1 - to C 20 -alkylamines, C 1 to C 30 -alkylcyclohexanols or C 1 to C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines are available.
  • P0IV-C2 to C6 alkylene oxide amines or functional derivatives thereof may be used as the polyether amines.
  • Typical examples thereof are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and also polyisobutenol butoxylates and propoxylates and the corresponding reaction products with ammonia.
  • carboxylic acid esters of long-chain alkanols are, in particular, esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as described in particular in DE-A 38 38 918.
  • mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 carbon atoms.
  • suitable representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and of isotridecanol, eg.
  • B di- (n- or isotridecyl) phthalate.
  • suitable carrier oil systems are described, for example, in DE-A 38 26 608, DE-A 41 42 241, DE-A 43 09 074, EP-A 452 328 and EP-A 548 617.
  • particularly suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, preferably about 5 to 30, particularly preferably 10 to 30 and in particular 15 to 30 C3 to C6 alkylene oxide units, for.
  • suitable starter alcohols are long-chain alkanols or long-chain alkyl-substituted phenols, where the long-chain alkyl radical is in particular a straight-chain or branched Ce to Cie-alkyl radical.
  • Specific examples include tridecanol and nonylphenol.
  • Particularly preferred alcohol-started polyethers are the reaction products (polyetherification products) of monohydric C6- to Cis-aliphatic alcohols with C3- to C6-alkylene oxides.
  • monohydric C6-C8 aliphatic alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol and their constitution and position isomers.
  • the alcohols can be used both in the form of pure isomers and in the form of technical mixtures.
  • a particularly preferred alcohol is tridecanol.
  • C3 to C6 alkylene oxides are propylene oxide, such as 1, 2-propylene oxide, butylene oxide, such as 1, 2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran, pentylene oxide and hexylene oxide.
  • propylene oxide such as 1, 2-propylene oxide
  • butylene oxide such as 1, 2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran, pentylene oxide and hexylene oxide.
  • C 3 -C 4 -alkylene oxides ie propylene oxide, such as 1,2-propylene oxide and butylene oxide such as 1,2-butylene oxide, 2,3-butylene oxide and isobutylene oxide.
  • butylene oxide is used.
  • suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A 10 102 913.
  • carrier oils are synthetic carrier oils, the alcohol-initiated polyethers described above being particularly preferred.
  • the carrier oil or the mixture of different carrier oils is added to the fuel in an amount of preferably from 1 to 1000 ppm by weight, more preferably from 10 to 500 ppm by weight and in particular from 20 to 100 ppm by weight.
  • Suitable cold flow improvers are in principle all organic compounds which are able to improve the flow behavior of middle distillate fuels or diesel fuels in the cold. Conveniently, they must have sufficient oil solubility.
  • middle distillates of fossil origin ie for conventional mineral diesel fuels
  • used cold flow improvers (“middle distillate flow improvers", "MDFI") come into consideration.
  • MDFI middle distillate flow improvers
  • WASA wax anti-settling additive
  • the cold flow improver is selected from:
  • Suitable C 2 - to C 4 -olefin monomers for the copolymers of class (K1) are, for example, those having 2 to 20, in particular 2 to 10 carbon atoms and having 1 to 3, preferably 1 or 2, in particular a carbon-carbon double pelitati.
  • the carbon-carbon double bond can be arranged both terminally ( ⁇ -olefins) and internally.
  • ⁇ -olefins particularly preferably olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene and, above all, ethylene.
  • the at least one further ethylenically unsaturated monomer is preferably selected from carboxylic alkenyl esters, (meth) acrylic esters and further olefins. If further olefins are polymerized in, these are preferably higher molecular weight than the abovementioned C 2 - to C 4 -olefin base monomers. If, for example, ethylene or propene is used as the olefin base monomer, suitable further olefins are, in particular, C 10 - to C 40 -alpha-olefins. Other olefins are polymerized in most cases only when monomers with carboxylic acid ester functions are used.
  • Suitable (meth) acrylic acid esters are, for example, esters of (meth) acrylic acid with C 2 to C 20 alkanols, in particular C 1 to C 10 alkanols, especially with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert Butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol and structural isomers thereof.
  • Suitable carboxylic alkenyl esters are, for example, C2 to C-u-alkenyl esters, e.g. the vinyl and propenyl esters of carboxylic acids having from 2 to 21 carbon atoms, the hydrocarbon radical of which may be linear or branched. Preferred among these are the vinyl esters.
  • carboxylic acids having a branched hydrocarbon radical preference is given to those whose branching is in the ⁇ -position relative to the carboxyl group, the ⁇ -carbon atom being particularly preferably tertiary, ie. H. the carboxylic acid is a so-called neocarboxylic acid.
  • the hydrocarbon radical of the carboxylic acid is linear.
  • carboxylic alkenyl esters examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, the vinyl esters being preferred.
  • a particularly preferred carboxylic acid alkenyl ester is vinyl acetate; typical resulting copolymers of group (K1) are the most commonly used ethylene-vinyl acetate copolymers ("EVA").
  • Suitable copolymers of class (K1) are also those which contain two or more mutually different carboxylic acid alkenyl esters in copolymerized form, these differing in the alkenyl function and / or in the carboxylic acid group. Also suitable are copolymers which, in addition to the carboxylic acid alkenyl ester (s), contain at least one olefin and / or at least one (meth) acrylic acid ester in copolymerized form.
  • Terpolymers of a C2 to C4o- ⁇ -olefin, a C to C2o-alkyl ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a C2 to C14 alkenyl ester of a saturated monocarboxylic acid having 2 to 21 carbon atoms are also known as copolymers.
  • polymers of class (K1) are suitable.
  • Such terpolymers are described in WO 2005/054314.
  • a typical such terpolymer is composed of ethylene, 2-ethylhexyl acrylate and vinyl acetate.
  • the at least one or the other ethylenically unsaturated monomers are present in the copolymers of class (K1) in an amount of preferably from 1 to 50% by weight, in particular from 10 to 45% by weight and especially from 20 to 40% by weight .-%, based on the total copolymer, copolymerized.
  • the majority by weight of the monomer units in the copolymers of class (K1) thus usually comes from the C2 to C4o-based olefins.
  • the copolymers of class (K1) preferably have a number average molecular weight M n of from 1000 to 20,000, particularly preferably from 1000 to 10,000 and in particular from 1000 to 8000.
  • Typical comb polymers of component (K2) are, for example, by the copolymerization of maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an ⁇ -olefin or an unsaturated ester such as vinyl acetate, and subsequent esterification of the anhydride or acid function with an alcohol having at least 10 carbon atoms available.
  • Other suitable comb polymers are copolymers of olefins and esterified comonomers, for example esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid.
  • Suitable comb polymers may also be polyfumarates or polymaleinates.
  • homopolymers and copolymers of vinyl ethers are suitable comb polymers.
  • Comb polymers suitable as component of class (K2) are, for example, those described in WO 2004/035715 and in "Comb-Like Polymers, Structure and Properties", N.A. Plate and V.P. Shibaev, J. Poly. Be. Macromolecular Revs. 8, pages 1 17 to 253 (1974). "Mixtures of comb polymers are also suitable.
  • Polyoxyalkylenes suitable as a component of class (K3) are, for example, polyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester ethers and mixtures thereof. These polyoxyalkylene compounds preferably contain at least one, preferably at least two, linear alkyl groups each having from 10 to 30 carbon atoms and a polyoxyalkylene group having a number average molecular weight of up to 5,000. Such polyoxyalkylene compounds are described, for example, in EP-A 061 895 and in US Pat. No. 4,491,455 described. Particular polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a number average molecular weight of 100 to 5000.
  • Polar nitrogen compounds suitable as a component of class (K4) may be of both ionic and nonionic nature, and preferably have at least one, especially at least two, tertiary nitrogen substituent of the general formula> NR 7 , wherein R 7 is Cs to C 40 Hydrocarbon residue stands.
  • the nitrogen substituents may also be quaternized, ie in cationic form.
  • nitrogen compounds are ammonium salts and / or amides obtainable by reacting at least one amine substituted with at least one hydrocarbyl radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof.
  • the amines contain at least one linear Ce to C4o-alkyl radical.
  • suitable primary amines for preparing said polar nitrogen compounds are octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues, secondary amines which are suitable for this purpose are, for example, dioctadecylamine and methylbehenylamine.
  • amine mixtures in particular industrially available amine mixtures such as fatty amines or hydrogenated tallamines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, in the chapter "Amines, aliphatic".
  • Suitable acids for the reaction are, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and succinic acids substituted by long-chain hydrocarbon radicals.
  • the component of class (K4) is an oil-soluble reaction product of poly (C 2 - to C 20 -carboxylic acids) containing at least one tertiary amino group with primary or secondary amines.
  • the poly (C 2 - to C 20 -carboxylic acids) which have at least one tertiary amino group and are based on this reaction product preferably contain at least 3 carboxyl groups, in particular 3 to 12, especially 3 to 5, carboxyl groups.
  • the carboxylic acid units in the polycarboxylic acids preferably have 2 to 10 carbon atoms, in particular they are acetic acid units.
  • the carboxylic acid units are suitably linked to the polycarboxylic acids, usually via one or more carbon and / or nitrogen atoms. Preferably, they are attached to tertiary nitrogen atoms, which are connected in the case of several nitrogen atoms via hydrocarbon chains.
  • the component of the class (K4) is preferably an oil-soluble reaction product based on poly (C 2 - to C 20 -carboxylic acids) having the general formula IIa or IIb and having at least one tertiary amino group
  • variable A is a straight-chain or branched C 2 - to C 6 -alkylene group or the grouping of the formula III
  • CH 2 -CH 2 - and the variable B denotes a C to Cig-alkylene group.
  • the compounds of the general formula IIa and IIb have in particular the properties of a WASA.
  • the preferred oil-soluble reaction product of component (K4) in particular that of general formula IIa or IIb, is an amide, an amide ammonium salt or an ammonium salt in which no, one or more carboxylic acid groups are converted into amide groups.
  • Straight-chain or branched C 2 - to C 6 -alkylene groups of the variable A are, for example, 1, 1-ethylene, 1, 2-propylene, 1, 3-propylene, 1, 2-butylene, 1, 3-butylene, 1, 4-butylene ethylene, 2-methyl-1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene (hexa-1-propylene), methylene) and in particular 1, 2-ethylene.
  • the variable A comprises 2 to 4, in particular 2 or 3 carbon atoms.
  • C to Ci9-alkylene groups of the variable B are, for example, 1, 2-ethylene, 1, 3-propylene, 1, 4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, Tetradecamethyl- en, hexadecamethylene, octadecamethylene, Nonadecamethylen and especially methylene.
  • the variable B comprises 1 to 10, in particular 1 to 4, carbon atoms.
  • the primary and secondary amines as reaction partners for the polycarboxylic acids to form the component (K4) are usually monoamines, in particular aliphatic monoamines. These primary and secondary amines may be selected from a variety of amines bearing hydrocarbon radicals, optionally linked together.
  • amines which are the oil-soluble reaction products of component (K4) are secondary amines and have the general formula HN (R 8 ) 2 in which the two variables R 8 independently of one another each represent straight-chain or branched C 10 - to C 30 -alkyl radicals, in particular C 14 - to C24-alkyl radicals mean.
  • These longer-chain alkyl radicals are preferably straight-chain or only slightly branched.
  • the abovementioned secondary amines are derived, with regard to their longer-chain alkyl radicals, from naturally occurring fatty acids or from their derivatives.
  • the two radicals R 8 are the same.
  • the abovementioned secondary amines can be bound to the polycarboxylic acids by means of amide structures or in the form of the ammonium salts, and only one part can be present as amide structures and another part as ammonium salts. Preferably, there are few or none free acid groups.
  • the oil-soluble reaction products of component (K4) are completely in the form of the amide structures.
  • Typical examples of such components (K4) are reaction products of nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diaminetetraacetic acid with in each case 0.5 to 1.5 mol per carboxyl group, in particular 0.8 to 1.2 mol per carboxyl group, dioleylamine, dipalmitinamine, dicoco fatty amine, distearylamine, dibehenylamine or especially ditallow fatty amine.
  • a particularly preferred component (K4) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated ditallow fatty amine.
  • component (K4) are the N, N-dialkylammonium salts of 2-N ', N'-dialkylamidobenzoates, for example the reaction product of 1 mol of phthalic anhydride and 2 mol of ditallow fatty amine, the latter hydrogenated or unhydrogenated and the reaction product of 1 mole of an alkenyl spiro-bis-lactone with 2 moles of a dialkylamine, for example, ditallow fatty amine and / or tallow fatty amine, the latter two of which may be hydrogenated or unhydrogenated.
  • 2-N ', N'-dialkylamidobenzoates for example the reaction product of 1 mol of phthalic anhydride and 2 mol of ditallow fatty amine, the latter hydrogenated or unhydrogenated and the reaction product of 1 mole of an alkenyl spiro-bis-lactone with 2 moles of a dialkylamine, for example, ditallow fatty amine and / or tallow
  • component of the class (K4) are cyclic compounds having tertiary amino groups or condensates of long-chain primary or secondary amines with carboxylic acid-containing polymers, as described in WO 93/181 15.
  • Sulfocarboxylic acids, sulfonic acids or their derivatives which are suitable as cold flow improvers of the component of class (K5) are, for example, the oil-soluble carboxamides and carboxylic acid esters of ortho-sulfobenzoic acid in which the sulfonic acid function is present as sulfonate with alkyl-substituted ammonium cations, as described in EP-A 261 957 to be discribed.
  • suitable poly (meth) acrylic acid esters are both homo- and copolymers of acrylic and methacrylic acid esters.
  • Preferred are copolymers of at least two mutually different (meth) acrylic acid esters, which differ with respect to the fused alcohol.
  • the copolymer contains a further, different of which olefinically unsaturated monomer copolymerized.
  • the weight-average molecular weight of the polymer is preferably 50,000 to 500,000.
  • a particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated C14 and Cis alcohols, wherein the acid groups are neutralized with hydrogenated talla- min.
  • Suitable poly (meth) acrylic esters are described, for example, in WO 00/44857.
  • the middle distillate fuel or diesel fuel is the cold flow improver or the mixture of various cold flow improvers in a total amount of preferably 10 to 5000 ppm by weight, more preferably from 20 to 2000 ppm by weight, more preferably from 50 to 1000 ppm by weight and in particular from 100 to 700 ppm by weight, for example from 200 to 500 ppm by weight.
  • Suitable lubricity improvers are usually based on fatty acids or fatty acid esters. Typical examples are tall oil fatty acid, as described for example in WO 98/004656, and glycerol monooleate.
  • the reaction products of natural or synthetic oils, for example triglycerides, and alkanolamines described in US Pat. No. 6,743,266 B2 are also suitable as such lubricity improvers. B5) Other corrosion inhibitors than the described copolymer
  • Suitable corrosion inhibitors are e.g. Succinic esters, especially with polyols, fatty acid derivatives, e.g. Oleic acid esters, oligomerized fatty acids, substituted ethanolamines and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany), Irgora® L12 (BASF SE) or HiTEC 536 (Ethyl Corporation).
  • Succinic esters especially with polyols, fatty acid derivatives, e.g. Oleic acid esters, oligomerized fatty acids, substituted ethanolamines and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany), Irgora® L12 (BASF SE) or HiTEC 536 (Ethyl Corporation).
  • Suitable demulsifiers are e.g. the alkali or alkaline earth salts of alkyl-substituted phenol and naphthalenesulfonates and the alkali or alkaline earth salts of fatty acids, as well as neutral compounds such as alcohol alkoxylates, e.g. Alcohol ethoxylates, phenol alkoxylates, e.g. tert-butylphenolethoxylate or tert-pentylphenolethoxylate, fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), e.g. also in the form of EO / PO block copolymers, polyethyleneimines or polysiloxanes.
  • EO ethylene oxide
  • PO propylene oxide
  • Suitable dehazers are e.g. alkoxylated phenol-formaldehyde condensates such as the NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite) products available under the tradename.
  • Suitable antifoams are e.g. Polyether-modified polysiloxanes such as the TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc) products available under the tradename.
  • Polyether-modified polysiloxanes such as the TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc) products available under the tradename.
  • Cetane number improvers are, for example, aliphatic nitrates, such as 2-ethylhexyl nitrate and cyclohexyl nitrate, and peroxides, such as di-tert-butyl peroxide.
  • aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate
  • peroxides such as di-tert-butyl peroxide.
  • Suitable antioxidants are e.g. substituted phenols such as 2,6-di-tert-butylphenol and 6-di-tert-butyl-3-methylphenol and phenylenediamines such as N, N'-di-sec-butyl-p-phenylenediamine.
  • Suitable metal deactivators are e.g. Salicylic acid derivatives such as N, N'-disalicylidene-1,2-propanediamine.
  • Suitable ones are e.g. nonpolar organic solvents such as aromatic and aliphatic hydrocarbons, for example, toluene, xylenes, white spirit, and products marketed under the trade names SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (ExxonMobil), as well as polar organic solvents; For example, alcohols such as 2-ethylhexanol, decanol and isotridecanol.
  • solvents usually arrive together with the aforementioned additives and co-additives which they are intended to dissolve or dilute for better handling into the diesel fuel.
  • the use according to the invention relates in principle to any fuels, preferably diesel and gasoline fuels.
  • Middle distillate fuels such as diesel fuels or fuel oils
  • mineral middle distillate fuels or diesel fuels obtainable by refining
  • mineral middle distillate fuels or diesel fuels there are also those produced by coal gasification or gas liquefaction [GTL] or by biomass liquefaction [BTL].
  • - Fuels are available, suitable. Also suitable are mixtures of the abovementioned middle distillate fuels or diesel fuels with regenerative fuels, such as biodiesel or bioethanol.
  • middle distillate fuels of fossil, vegetable or animal origin, which are essentially hydrocarbon mixtures, also relates to mixtures of such middle distillates with biofuel oils (biodiesel). Such mixtures are encompassed by the term "middle distillate fuel”.
  • biofuel oils are commercially available and usually contain the biofuel oils in minor amounts, typically in amounts of 1 to 30 wt .-%, in particular from 3 to 10 wt .-%, based on the total amount of middle distillate of fossil, vegetable or animal origin and biofuel.
  • Biofuel oils are generally based on fatty acid esters, preferably substantially on alkyl esters of fatty acids derived from vegetable and / or animal oils and / or fats.
  • Alkyl esters are usually lower alkyl esters, especially C 1 to C 4 alkyl esters, understood by transesterification of occurring in vegetable and / or animal oils and / or fats glycerides, especially triglycerides, by means of lower alcohols, for example ethanol or especially methanol (“FAME ”) are available.
  • Typical low-alkyl esters based on vegetable and / or animal oils and / or fats which are used as biofuel oil or components thereof include, for example, sunflower methyl ester, palm oil methyl ester ("PME"), soybean oil methyl ester ("SME”) and in particular rapeseed oil methyl ester ( "RME”).
  • the middle distillate fuels or diesel fuels are particularly preferably those with a low sulfur content, ie with a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, in particular less as 0.005 wt .-% and especially less than 0.001 wt .-% sulfur.
  • gasoline fuels are all commercially available gasoline fuel compositions into consideration.
  • a typical representative here is the market-standard basic fuel of Eurosuper according to EN 228.
  • gasoline compositions of the specification according to WO 00/47698 are also possible fields of use for the present invention. The following examples are intended to illustrate the present invention without limiting it.
  • the weight average Mw and number average molecular weight Mn of the polymers were measured by gel permeation chromatography (GPC). GPC separation was achieved via two PLge Mixed B columns (Agilent) in tetrahydrofuran at 35 ° C. The calibration was carried out by means of a narrowly distributed polystyrene standard (PSS, Germany) with molecular weight 162-50400 Da. Hexylbenzene was used as a low molecular weight marker.
  • FIG. 1 shows the clear oil with the copolymer according to Synthesis Example 1 (40% strength in solvent naphtha) on the right.
  • Dimer fatty acid (dimeric oleic acid, CAS: 61788-89-4, 20% in Solvent Naphtha) was used in the middle beaker. One recognizes a clearly visible turbidity. From the above Synthesis Examples, the following additive formulations were prepared by blending with polyisobuteneamine (molecular weight 1000), polypropylene glycol as carrier oil and solvent and dehazer and used in the application examples (compositions in parts by weight):
  • the fuel used was commercially available commercial fuel E0 CEC RF-12-09 from Garrmann and additized with an additive package of polyisobutenamine and carrier oil as indicated above.
  • To formulate the corrosion inhibitors indicated in the following table (each 40% in Solvent Naphtha) were added and subjected to a corrosion test according to ASTM D 665 B.
  • dimer fatty acid was used as a corrosion inhibitor (dimeric oleic acid, CAS: 61788-89-4, 40% strength in solvent naphtha).
  • the anticorrosion agent of formulation 5 is a comparison of 2- (8-heptadecen-1-yl) -4,5-dihydro-1H-imidazole-1-ethanol, CAS-No. 95-38-5, active ingredient 90 - 100%.

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Abstract

La présente invention concerne de nouvelles utilisations d'inhibiteurs de corrosion dans des carburants et des lubrifiants.
EP16736891.9A 2015-07-16 2016-07-12 Inhibiteurs de corrosion pour carburants Active EP3322780B1 (fr)

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US11168273B2 (en) 2014-01-29 2021-11-09 Basf Se Polycarboxylic acid-based additives for fuels and lubricants
US11085001B2 (en) 2015-07-16 2021-08-10 Basf Se Copolymers as additives for fuels and lubricants
US11078418B2 (en) 2016-07-05 2021-08-03 Basf Se Corrosion inhibitors for fuels and lubricants
CN110088253B (zh) 2016-12-15 2022-03-18 巴斯夫欧洲公司 作为燃料添加剂的聚合物
US10927319B2 (en) 2016-12-20 2021-02-23 Basf Se Use of a mixture of a complex ester with a monocarboxylic acid to reduce friction
JP2023508906A (ja) * 2019-12-18 2023-03-06 ザ ルブリゾル コーポレイション ポリマー界面活性剤化合物
ES2964845T3 (es) * 2020-07-14 2024-04-09 Basf Se Inhibidores de corrosión para combustibles y lubricantes
US20240034941A1 (en) * 2020-11-20 2024-02-01 Basf Se New mixtures for improving or boosting the separation of water from fuels

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JPS5922791B2 (ja) * 1978-12-25 1984-05-29 三菱化学株式会社 防錆剤
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