EP3322775B1 - Utilisation de copolymères dans des moteurs à combustion interne à injection directe - Google Patents

Utilisation de copolymères dans des moteurs à combustion interne à injection directe Download PDF

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EP3322775B1
EP3322775B1 EP16738151.6A EP16738151A EP3322775B1 EP 3322775 B1 EP3322775 B1 EP 3322775B1 EP 16738151 A EP16738151 A EP 16738151A EP 3322775 B1 EP3322775 B1 EP 3322775B1
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diesel
copolymers
acid
fuel
deposits
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EP3322775A1 (fr
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Ivette Garcia Castro
Maxim Peretolchin
Jochen Mezger
Klaus Muehlbach
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—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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    • 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
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    • 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
    • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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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
    • C10M145/16—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
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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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    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
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    • 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
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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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    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2362—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing nitrile groups
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
    • C—CHEMISTRY; METALLURGY
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    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • 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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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2368—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing heterocyclic compounds containing nitrogen in the ring
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    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C10L2200/0446—Diesel
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines

Definitions

  • the present invention relates to new uses of copolymers for removing and / or reducing deposits in the injection system of direct injection diesel and / or gasoline engines.
  • the present invention relates to the use of certain copolymers as a fuel or lubricant additive; Process for the production of such additives, as well as fuels and lubricants with additives; such as, in particular, as a detergent additive; Use of these copolymers to reduce or prevent deposits in the injection systems of direct injection diesel engines, in particular in common rail injection systems, to reduce the fuel consumption of direct injection diesel engines, in particular diesel engines with common rail injection systems, and to minimize power loss ) in direct injection diesel engines, especially in diesel engines with common rail injection systems; and as an additive for petrol, especially for operating DISI engines.
  • the diesel fuel is conveyed by a pump with pressures of up to 2000 bar into a high pressure line, the common rail.
  • branch lines run to the various injectors, which inject the fuel directly into the combustion chamber.
  • There is always full pressure on the common rail which enables multiple injections or a special form of injection.
  • the other injection systems on the other hand, only a smaller variation of the injection is possible.
  • Injection in the common rail is essentially divided into three groups: (1.) Pre-injection, through which essentially a smoother combustion is achieved, so that hard combustion noises ("pounding") are reduced and the engine appears to run smoothly; (2.) main injection, which is responsible in particular for a good torque curve; and (3.) post-injection, especially for a low NO x value cares.
  • Pre-injection through which essentially a smoother combustion is achieved, so that hard combustion noises ("pounding") are reduced and the engine appears to run smoothly
  • (2.) main injection which is responsible in particular for a good torque curve
  • (3.) post-injection especially for a low NO x value cares.
  • the fuel is usually not burned, but evaporated by residual heat in the cylinder.
  • the resulting exhaust gas / fuel mixture is transported to the exhaust system, where the fuel acts as a reducing agent for the nitrogen oxides NO x in the presence of suitable catalysts.
  • variable, cylinder-specific injection can have a positive effect on the engine's pollutant emissions, such as nitrogen oxides (NO x ), carbon monoxide (CO) and, in particular, particles (soot).
  • NO x nitrogen oxides
  • CO carbon monoxide
  • particles particles
  • deposits can form on the injector openings that affect the injection behavior of the Negatively affect the fuel and thereby impair the performance of the engine, that is to say, in particular, reduce the output, but in some cases also worsen the combustion.
  • the formation of deposits is increased by further structural developments of the injectors, in particular by changing the geometry of the nozzles (narrower, conical openings with rounded outlets). In order for the engine and injectors to function optimally over the long term, such deposits in the nozzle openings must be prevented or reduced using suitable fuel additives.
  • injection system is understood to mean that part of the fuel system in motor vehicles from the fuel pump up to and including 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 WO 2011/146289 describes nitrogen-free additives made from a substituted hydrocarbon which has at least two carboxyl groups in free form or present as anhydride to improve the detergent effect in fuel systems.
  • nitrogen-free additives made from a substituted hydrocarbon which has at least two carboxyl groups in free form or present as anhydride to improve the detergent effect in fuel systems. Examples include hydrocarbyl-substituted succinic anhydrides and hydrolyzed forms thereof.
  • JP 2007-077216 describes oils containing partial esters of copolymers of maleic anhydride and ⁇ - olefins with alkylene glycols. An effect of the copolymer against deposits is not described.
  • WO 2011/161149 are copolymers of C 2 - to C 40 -alpha-olefins and certain mono- and dicarboxylic acids and their anhydrides, halides or esters, which are reacted with certain amines and used quaternized as an additive to remove deposits. Only the quaternized product is used in fuels.
  • the present invention is based on the object of providing a new class of copolymer-based additives for use in modern diesel and gasoline fuels.
  • copolymers have been shown to be effective in preventing and / or removing the following deposits in diesel and gasoline engines:
  • copolymers are particularly notable for the fact that they act against a wide variety of deposits that impair the performance of modern diesel engines.
  • the compounds according to the invention act, for example, against loss of performance both caused by the introduction of zinc and also caused by the introduction of sodium into the diesel fuel. This essentially eliminates or prevents deposits in the spray channels and the injector tip.
  • the compounds according to the invention also act against internal diesel injector deposits (IDID) caused by Na, Ca and / or K ions (so-called Na, Ca or K soaps IDID) and / or polymers Deposits.
  • IDID internal diesel injector deposits
  • Na, Ca and K soaps IDID are deposits that contain the metal ions in question with any counterions.
  • the polymeric deposits on the other hand, they are free of metal ions and are based on high molecular weight organic material that is little or insoluble in fuel.
  • Figure 1 shows the sequence of a one-hour engine test cycle according to CEC F-098-08.
  • the monomer (A) is at least one, preferably one to three, particularly preferably one or two and very particularly preferably exactly one anhydride of an ethylenically unsaturated dicarboxylic acid, very particularly preferably maleic anhydride.
  • C 1 -C 4 alkyl in the context of this specification means methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl understood, sec-butyl and tert-butyl, preferably methyl and ethyl, particularly preferably methyl .
  • dicarboxylic acids examples include maleic acid, fumaric acid, itaconic acid (2-methylenebutanedioic acid), citraconic acid (2-methylmaleic acid), glutaconic acid (pent-2-ene-1,5-dicarboxylic acid), 2,3-dimethylmaleic acid, 2-methylfumaric acid, 2,3 Dimethylfumaric acid, methylenemalonic acid and tetrahydrophthalic acid, preferably maleic acid and fumaric acid and particularly preferably maleic acid and its anhydrides.
  • 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, particularly preferably at least 16 and very particularly preferably at least 18 carbon atoms.
  • the ⁇ - olefins (B) preferably have up to and including 28, particularly preferably up to and including 26 and very particularly preferably up to and including 24 carbon atoms.
  • the ⁇ - olefins can 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-eicoses, 1-docoses, 1-tetracoses, 1-hexacoses , of which 1-octadecene, 1-eicosene, 1-docoses and 1-tetracoses, and mixtures thereof are preferred.
  • ⁇ - olefins are those olefins which are oligomers or polymers of C 2 to C 12 olefins, preferably of C 3 to C 10 olefins, particularly preferably of C 4 to C 6 olefins.
  • examples of these are ethene, propene, 1-butene, 2-butene, isobutene, pentene isomers and hexene isomers; preference is given to ethene, propene, 1-butene, 2-butene and isobutene.
  • ⁇ - olefins (B) are oligomers and polymers of propene, 1-butene, 2-butene, isobutene, and their mixtures, especially oligomers and polymers of propene or isobutene or mixtures of 1-butene and 2-butene.
  • the oligomers the trimers, tetramers, pentamers and hexamers and mixtures thereof are preferred.
  • At least one, preferably one to four, particularly preferably one to three, very particularly preferably one or two and in particular exactly one further aliphatic or cycloaliphatic olefin (C) having at least 4 carbon atoms, which is a other than (B) are polymerized into the copolymer according to the invention.
  • the olefins (C) can be olefins with a terminal ( ⁇ -) double bond or those with a non-terminal double bond, preferably with an ⁇ double bond.
  • the olefin (C) is preferably olefins having 4 to fewer 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 in the ⁇ position.
  • Examples of aliphatic olefins (C) are 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, ⁇ - or ⁇ - pinene and mixtures thereof, limonene and norbornene.
  • olefins (C) are polymers containing more than 30 carbon atoms of propene, 1-butene, 2-butene or isobutene or olefin mixtures containing such, preferably of isobutene or olefin mixtures containing such, particularly preferably having an average molecular weight M. w in the range from 500 to 5000 g / mol, preferably 650 to 3000, particularly preferably 800 to 1500 g / mol.
  • the oligomers or polymers containing isobutene in copolymerized form preferably have a high content of terminally arranged ethylenic double bonds ( ⁇ double bonds), for example at least 50 mol%, preferably at least 60 mol%, particularly preferably at least 70 mol% and very particularly preferably at least 80 mol%.
  • C4 raffinates in particular “raffinate 1”
  • C4 cuts from isobutane are suitable as isobutene sources for the production of such oligomers or polymers containing isobutene in copolymerized form -Dehydrogenation
  • a C4 hydrocarbon stream from an FCC refinery unit is also known as a "b / b" stream.
  • 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 generally 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 the said C4 hydrocarbon streams is typically in the range from 40 to 60% by weight.
  • Raffinate 1 generally consists essentially of 30 to 50% by weight isobutene, 10 to 50% by weight 1-butene, 10 to 40% by weight cis- and trans-2-butene and 2 to 35% by weight % Butanes; in the polymerization process according to the invention, the butenes not shown in raffinate 1 behave in the Usually practically inert and only the isobutene is polymerized.
  • the use of water as the sole initiator or as a further initiator has proven useful, especially when at temperatures from -20 ° C to + 30 ° C, in particular from 0 ° C to + 20 ° C, polymerized.
  • temperatures from -20 ° C. to + 30 ° C., in particular from 0 ° C. to + 20 ° C. the use of an initiator can also be dispensed with when using a raffinate 1 stream as the isobutene source.
  • the isobutene-containing monomer mixture mentioned can contain small amounts of contaminants such as water, carboxylic acids or mineral acids without there being any critical loss of yield or selectivity. 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.
  • 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 isobutene, and preferably at most 95% by weight, in particular preferably at most 90% by weight and in particular at most 80% by weight comonomers.
  • the mixture of olefins (B) and optionally (C), averaged over their amounts of substance has at least 12 carbon atoms, preferably at least 14, particularly preferably at least 16 and very particularly preferably at least 17 carbon atoms.
  • the upper limit is less relevant and is generally not more than 60 carbon atoms, preferably not more than 55, particularly preferably not more than 50, very particularly preferably not more than 45 and in particular not more than 40 carbon atoms.
  • vinyl esters (Da) are vinyl esters of C 2 to C 12 carboxylic acids, preferably vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pentanoate, vinyl hexanoate, vinyl octanoate, vinyl 2-ethylhexanoate, vinyl decanoate, and vinyl esters of Versatic acids 5 to 10, preferably Vinyl ester 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 ( Neooctanoic acid, Versatic acid 8), 2,2-dimethylheptanoic acid (neononanoic acid, Versatic acid 9) or 2,2-dimethyloctanoic acid (neodecanoic acid, Versatic acid 10).
  • 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.
  • 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-oc
  • Preferred (meth) acrylic acid esters (Dc) are (meth) acrylic acid esters of C 5 - to C 12 -alkanols, preferably of n-pentanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol ), 2-ethylhexanol or 2-propylheptanol. Pentyl acrylate, 2-ethylhexyl acrylate and 2-propylheptyl acrylate are particularly preferred.
  • Examples of monomers (Dd) are allyl alcohols and allyl ethers of C 2 - to C 12 -alkanols, preferably allyl ethers of methanol, ethanol, iso -propanol, n-propanol, n-butanol, iso- butanol, 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.
  • allylamines are allylamine, dialkylallylamine and trialkyl allylammonium halides.
  • Preferred monomers (D) are (Da), (Db), (Dc), (De) and / or (Df), particularly preferred (Da), (Db) and / or (Dc), very particularly preferred (Da) and / or (Dc) and in particular (Dc).
  • the incorporation ratio of the monomers (A) and (B) and optionally (C) and optionally (D) in the copolymer obtained from reaction step (I) is generally 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, very particularly 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.
  • the molar ratio of the obligatory monomer (B) to the monomer (C), if 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, very particularly preferably from 1: 0.3 to 2.5 and especially 1: 0.5 to 1.5.
  • no optional monomer (C) is present in addition to monomer (B).
  • the proportion of one or more of the monomers (D), if present, based on the amount of 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%.
  • no optional monomer (D) is present.
  • the copolymer consists of monomers (A) and (B).
  • reaction step (II) the anhydride functionalities contained in the copolymer obtained from (I) can be partially hydrolyzed.
  • reaction step (II) anhydride functionalities are hydrolyzed and carboxylic acid ester functionalities are left essentially intact.
  • reaction step (II) more than 90% of the anhydride functionalities contained remain intact after reaction step (II), preferably at least 92%, particularly preferably at least 94%, very particularly preferably at least 95%, in particular at least 97% and especially at least 98%.
  • reaction step (II) it is possible that up to 99.9% of the anhydride functionalities contained remain intact after reaction step (II), preferably up to 99.8%, particularly preferably up to 99.7%, very particularly preferably up to 99.5% and especially up to 99%.
  • reaction step (II) is not carried out, so that 100% of the anhydride functionalities contained in the copolymer obtained from reaction step (I) remain intact.
  • the amount of water is added which corresponds to the desired degree of hydrolysis and the copolymer obtained from (I) is heated in the presence of the added water.
  • a temperature of preferably 20 to 150 ° C., preferably 60 to 100 ° C. is sufficient for this.
  • the reaction can be carried out under pressure in order to prevent the escape of water. Under these reaction conditions, the anhydride functionalities in the copolymer are generally converted selectively, whereas any carboxylic acid ester functionalities contained in the copolymer do not react or at least only react to a minor extent.
  • the copolymers obtained from step (II) still contain residues of acid anions, it may be preferred to remove these acid anions from the copolymer with the aid of an ion exchanger and preferably to replace them with hydroxide ions or carboxylate ions, particularly preferably hydroxide ions. This is particularly the case when the acid anions contained in the copolymer are halides, contain sulfur or contain nitrogen.
  • the copolymer obtained from reaction step (II) generally has a weight-average molecular weight Mw of 0.5 to 20 kDa, preferably 0.6 to 15, particularly preferably 0.7 to 7, very particularly preferably 1 to 7 and in particular 1, 5 to 54 kDa (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standards).
  • the number average molecular weight Mn is mostly from 0.5 to 10 kDa, preferably 0.6 to 5, particularly preferably 0.7 to 4, very particularly preferably 0.8 to 3 and in particular 1 up 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 reaction step (II) is preferably less than 5 mmol / g copolymer, particularly preferably less than 3, very particularly preferably less than 2 mmol / g copolymer and in particular less than 1 mmol / g.
  • the copolymers contain a high proportion of adjacent carboxylic acid groups, which is determined by measuring the adjacency. For this purpose, a sample of the copolymer is tempered for a period of 30 minutes at a temperature of 290 ° C. between two Teflon foils and an FTIR spectrum is recorded at a bubble-free point. The IR spectrum of Teflon is subtracted from the spectra obtained, the layer thickness is determined and the cyclic anhydride content is determined.
  • 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 fuel to which the copolymer according to the invention is added is a gasoline fuel or, in particular, a middle distillate fuel, especially a diesel fuel.
  • the fuel can contain other customary additives to improve effectiveness and / or suppress wear.
  • copolymers described are often used in the form of fuel additive mixtures, together with the usual additives: In the case of diesel fuels, these are primarily the usual detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors other than the copolymers described, demulsifiers, dehazers, antifoam agents, cetane number improvers, combustion improvers, antioxidants or stabilizers, metallocators, antioxidants , Dyes and / or solvents.
  • lubricity improvers In the case of petrol, these are primarily lubricity improvers (friction modifiers), corrosion inhibitors other than the copolymers described, demulsifiers, dehazers, antifoams, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and / or solvents.
  • the hydrophobic hydrocarbon radical in the above detergent additives which ensures sufficient solubility in the fuel, has a number-average molecular weight (M n ) of 85 to 20,000, preferably 113 to 10,000, particularly preferably 300 to 5,000, more preferably 300 to 3,000, even more preferably from 500 to 2,500 and in particular from 700 to 2,500, especially from 800 to 1500.
  • M n number-average molecular weight
  • a typical hydrophobic hydrocarbon radical especially in connection with the polar, in particular polypropenyl, polybutenyl and polyisobutenyl radicals with a number average molecular weight M n of preferably 300 to 5,000, particularly preferably 300 to 3,000, more preferably 500 to 2,500, even more preferably 700 to 2,500 and in particular 800 to 1,500 in each case.
  • the production route is by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to form carbonyl or Carboxyl compound and subsequent amination under reductive (hydrogenating) conditions.
  • amines such as. B. ammonia
  • monoamines or the abovementioned polyamines can be used.
  • Corresponding additives based on polypropene are in particular in the WO-A 94/24231 described.
  • Carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) containing additives are preferably copolymers of C 2 - to C 40 olefins with maleic anhydride with a total molecular weight of 500 to 20,000, the carboxyl groups wholly or partially to the alkali metal or alkaline earth metal salts and a remaining Rest of the carboxyl groups are reacted with alcohols or amines.
  • Such additives are in particular from EP-A 307 815 known.
  • Such additives are mainly used to prevent valve seat wear and can, as in the WO-A 87/01126 described, can be used with advantage in combination with conventional fuel detergents such as poly (iso) -butenamines or polyetheramines.
  • Additives containing sulfonic acid groups or their alkali metal or alkaline earth metal salts are preferably alkali metal or alkaline earth metal salts of an alkyl sulfosuccinate, as it is in particular in US Pat EP-A 639 632 is described.
  • Such additives are mainly used to prevent valve seat wear and can be used with advantage in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.
  • Additives containing polyoxy-C 2 -C 4 -alkylene groups are preferably polyethers or polyetheramines, which are obtained by reacting C 2 - to C 60 -alkanols, C 6 - to C 30 -alkanediols, mono- or di-C 2 - to C 30 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 the polyetheramines, can be obtained by subsequent reductive amination with ammonia, monoamines or polyamines.
  • Such products are particularly popular in the EP-A 310 875 , EP-A 356 725 , EP-A 700 985 and US-A-4,877,416 described.
  • polyethers such products also have carrier oil properties. Typical examples are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates and the corresponding reaction products with ammonia.
  • Additives containing carboxylic ester groups (Dg) are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, in particular those with a minimum viscosity of 2 mm 2 / s at 100 ° C., as in particular in the DE-A 38 38 918 are described.
  • Aliphatic or aromatic acids can be used as mono-, di- or tricarboxylic acids; long-chain representatives with, for example, 6 to 24 carbon atoms are particularly suitable as ester alcohols or polyols.
  • esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and iso-tridecanol. Such products also meet carrier oil properties.
  • the groupings with hydroxyl and / or amino and / or amido and / or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of di- or polyamines, which in addition to the amide function nor have free amine groups, succinic acid derivatives with an acid and an amide function, carboximides with monoamines, carboximides with di- or polyamines, which in addition to the imide function still have free amine groups, or diimides, which are formed by the reaction of di- or polyamines with two succinic acid derivatives will.
  • Such fuel additives are generally known and are described, for example, in documents (1) and (2).
  • reaction products of alkyl- or alkenyl-substituted succinic acids or derivatives thereof with amines are preferably the reaction products of polyisobutenyl-substituted succinic acids or derivatives thereof with amines.
  • reaction products with aliphatic polyamines such as, in particular, ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine and hexaethylene heptamine, which have an imide structure.
  • the compounds according to the invention can be combined with quaternized compounds, as described in WO 2012/004300 , there preferably page 5, line 18 to page 33, line 5, particularly preferably of preparation example 1, which is hereby expressly part of the present disclosure by reference.
  • the compounds according to the invention can be combined with quaternized compounds, as described in the unpublished international application with the file number PCT / EP2014 / 061834 and the filing date June 6, 2014, there preferably page 5, line 21 to page 47, line 34, particularly preferably the preparation examples 1 to 17.
  • the compounds according to the invention can be combined with quaternized compounds, as described in WO 11/95819 A1 , there preferably page 4, line 5 to page 13, line 26, particularly preferably preparation example 2.
  • the compounds according to the invention can be combined with quaternized compounds, as described in WO 11/110860 A1 , there preferably page 4, line 7 to page 16, line 26, particularly preferably of preparation examples 8, 9, 11 and 13.
  • the compounds according to the invention can be combined with quaternized compounds, as described in WO 06/135881 A2 , there preferably page 5, line 14 to page 12, line 14, particularly preferably examples 1 to 4.
  • the compounds according to the invention can be combined with quaternized compounds, as described in WO 10/132259 A1 , there preferably page 3, line 29 to page 10, line 21, particularly preferably example 3.
  • the compounds according to the invention can be combined with quaternized compounds, as described in WO 08/060888 A2 , there preferably page 6, line 15 to page 14, line 29, particularly preferably examples 1 to 4.
  • the compounds according to the invention can be combined with quaternized compounds, as described in GB 2496514 A , there preferably paragraphs [00012] to [00039], particularly preferably examples 1 to 3.
  • the compounds according to the invention can be combined with quaternized compounds, as described in WO 2013 070503 A1 , there preferably paragraphs [00011] to [00039], particularly preferably examples 1 to 5.
  • Additives containing (di) groups produced by the 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 ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine or dimethylaminopropylamine.
  • Such "polyisobutene Mannich bases" are particularly in the EP-A 831 141 described.
  • One or more of the detergent additives mentioned can be added to the fuel in such an amount that the metering rate of these detergent additives is preferably 25 to 2500 ppm by weight, in particular 75 to 1500 ppm by weight, especially 150 to 1000 ppm by weight .-ppm. B2) carrier oils
  • Carrier oils used can be of a mineral or synthetic nature.
  • Suitable mineral carrier oils are fractions obtained during petroleum processing, such as bright stocks or base oils with viscosities such as, for example, from class SN 500 to 2000, but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols.
  • a fraction known as "hydrocrack oil” and obtained in the refining of mineral oil can also be used (vacuum distillate cut with a boiling range of about 360 to 500 ° C., obtainable from natural mineral oil catalytically hydrogenated and isomerized and dewaxed under high pressure). Mixtures of the abovementioned mineral carrier oils are also suitable.
  • suitable synthetic carrier oils are polyolefins (polyalphaolefins or polyinternalolefins), (poly) esters, poly) alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-started polyethers, alkylphenol-started 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 obtained by reacting C 2 - to C 60 -alkanols, C 6 - to C 30 -alkanediols, mono- or di-C 2 - To C 30 -alkylamines, C 1 - to C 30 -alkyl-cyclohexanols 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 event the polyetheramines, are obtainable by subsequent reductive amination with ammonia, monoamines or polyamines.
  • Such products are particularly popular in the EP-A 310 875 , EP-A 356 725 , EP-A 700 985 and the US-A 4,877,416 described.
  • poly-C 2 - to C 6 -alkylene oxide amines or functional derivatives thereof can be used as polyether amines.
  • Typical examples are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and 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 they are in particular in US Pat DE-A 38 38 918 are described.
  • Aliphatic or aromatic acids can be used as mono-, di- or tricarboxylic acids, and especially long-chain representatives with, for example, 6 to 24 carbon atoms are suitable as ester alcohols or polyols.
  • esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, e.g. B. di- (n- or isotridecyl) phthalate.
  • particularly suitable synthetic carrier oils are alcohol-initiated polyethers with about 5 to 35, preferably about 5 to 30, particularly preferably 10 to 30 and in particular 15 to 30 C 3 to C 6 alkylene oxide units, e.g. B. propylene oxide, n-butylene oxide and isobutylene oxide units or mixtures thereof, per alcohol molecule.
  • suitable starter alcohols are long-chain alkanols or long-chain alkyl-substituted phenols, the long-chain alkyl radical in particular being a straight-chain or branched C 6 - to C 18 -alkyl radical.
  • Tridecanol and nonylphenol should be mentioned as special examples.
  • Particularly preferred alcohol-initiated polyethers are the reaction products (polyetherification products) of monohydric aliphatic C 6 to C 18 alcohols with C 3 to C 6 alkylene oxides.
  • monohydric aliphatic C 6 -C 18 alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol and their constitution and constitution Positional isomers.
  • the alcohols can be used both in the form of the pure isomers and in the form of technical mixtures.
  • a particularly preferred alcohol is tridecanol.
  • Examples of C 3 - to C 6 -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.
  • Particularly preferred are among them C 3 - to 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 in particular.
  • Special 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 1 to 1000 ppm by weight, particularly preferably 10 to 500 ppm by weight and in particular 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. Appropriately, they must have sufficient oil solubility.
  • the cold flow improvers (“middle distillate flow improvers”, “MDFI”) used for middle distillates of fossil origin, that is to say for conventional mineral diesel fuels, are suitable for this purpose.
  • MDFI middle distillate flow improvers
  • organic compounds can also be used which, when used in conventional diesel fuels, have partly or predominantly the properties of a wax anti-settling additive ("WASA"). They can also act partly or mainly as nucleators.
  • WASA wax anti-settling additive
  • Suitable C 2 to C 40 olefin monomers for the copolymers of class (K1) are, for example, those with 2 to 20, in particular 2 to 10 carbon atoms and with 1 to 3, preferably 1 or 2, in particular with a carbon-carbon Double bond.
  • 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 alkenyl carboxylates, (meth) acrylic acid esters and further olefins.
  • further olefins are also polymerized in, these are preferably higher molecular weight than the above-mentioned C 2 to C 40 olefin base monomers. If, for example, ethylene or propene is used as the base olefin monomer, suitable further olefins are, in particular, C 10 -C 40 ⁇ - olefins. In most cases, other olefins are only also incorporated into the polymerization when monomers with carboxylic acid ester functions are also used.
  • Suitable (meth) acrylic acid esters are, for example, esters of (meth) acrylic acid with C 1 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 acid alkenyl esters are, for example, C 2 - to C 14 -alkenyl esters, for example the vinyl and propenyl esters, of carboxylic acids having 2 to 21 carbon atoms, the hydrocarbon radical of which can be linear or branched. Of these, the vinyl esters are preferred.
  • carboxylic acids with a branched hydrocarbon radical preference is given to those whose branches are in the ⁇ -position to the carboxyl group, the ⁇ -carbon atom being particularly preferably tertiary, ie the carboxylic acid being what is known as a neocarboxylic acid.
  • the hydrocarbon radical of the carboxylic acid is preferably linear.
  • alkenyl carboxylates 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 alkenyl carboxylate is vinyl acetate; typical copolymers of group (K1) resulting therefrom are the ethylene-vinyl acetate copolymers ("EVA”) used most frequently.
  • copolymers of class (K1) are those which contain two or more 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 C 2 to C 40 ⁇ - olefin, a C 1 to C 20 alkyl ester of an ethylenically unsaturated monocarboxylic acid with 3 to 15 carbon atoms and a C 2 to C 14 alkenyl ester of a saturated monocarboxylic acid with 2 to 21 Carbon atoms are suitable as class (K1) copolymers.
  • Such terpolymers are in the WO 2005/054314 described.
  • a typical such terpolymer is made up of ethylene, 2-ethylhexyl acrylate and vinyl acetate.
  • the at least one or the further ethylenically unsaturated monomers are present in the copolymers of class (K1) in an amount of preferably 1 to 50% by weight, in particular 10 to 45% by weight and especially 20 to 40% by weight .-%, based on the total copolymer, polymerized.
  • the majority by weight of the monomer units in the copolymers of class (K1) thus generally originate from the C 2 to C 40 base olefins.
  • the copolymers of class (K1) preferably have a number average molecular weight M n 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, through 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 with at least 10 carbon atoms available.
  • Further 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 can also be polyfumarates or polymaleinates.
  • homo- and copolymers of vinyl ethers are suitable comb polymers.
  • Comb polymers suitable as components of class (K2) are, for example, also those in the WO 2004/035715 and in " Comb-Like Polymers. Structure and Properties, "NA Plate and VP Shibaev, J. Poly. Sci. Macromolecular Revs. 8, pp. 117-253 (1974 ) ". Mixtures of comb polymers are also suitable.
  • Polyoxyalkylenes suitable as components of class (K3) are, for example, polyoxyalkylene 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 10 to 30 carbon atoms and one polyoxyalkylene group with a number average molecular weight of up to 5000. Such polyoxyalkylene compounds are, for example, in EP-A 061 895 as well as in the U.S. 4,491,455 described. Special polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols with a number average molecular weight of 100 to 5000. Furthermore, polyoxyalkylene mono- and diesters of fatty acids with 10 to 30 carbon atoms such as stearic acid or behenic acid are suitable.
  • Polar nitrogen compounds suitable as component of class (K4) can be both ionic and non-ionic in nature and preferably have at least one in particular at least two substituents in the form of a tertiary nitrogen atom of the general formula> NR 7 , in which R 7 is a C 8 to C 40 hydrocarbon radical.
  • the nitrogen substituents can also be present in quaternized form, that is to say in cationic form. Examples of such nitrogen compounds are ammonium salts and / or amides which can be obtained by reacting at least one amine substituted by at least one hydrocarbon radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof.
  • the amines preferably contain at least one linear C 8 - to C 40 -alkyl radical.
  • Primary amines suitable for the production of the polar nitrogen compounds mentioned are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues; secondary amines suitable for this purpose are, for example, dioctadecylamine and methylbehenylamine.
  • Amine mixtures are also suitable for this purpose, in particular amine mixtures available on an industrial scale, such as fatty amines or hydrogenated tall amines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, in the chapter "Amines, aliphatic".
  • Acids suitable 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 with long-chain hydrocarbon radicals.
  • the component of class (K4) is an oil-soluble reaction product of poly (C 2 to C 20 carboxylic acids) having at least one tertiary amino group with primary or secondary amines.
  • the poly (C 2 to C 20 carboxylic acids) on which this reaction product is based contain at least one tertiary amino group and 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 linked to the polycarboxylic acids in a suitable manner, usually via one or more carbon and / or nitrogen atoms. They are preferably attached to tertiary nitrogen atoms which, in the case of several nitrogen atoms, are linked via hydrocarbon chains.
  • the component of class (K4) is preferably an oil-soluble reaction product based on poly (C 2 to C 20 carboxylic acids) of the general formula IIa or IIb having at least one tertiary amino group in which the variable A is a straight-chain or branched C 2 - to C 6 -alkylene group or the grouping of the formula III and the variable B denotes a C 1 to C 19 alkylene group.
  • the compounds of the general formulas IIa and IIb in particular have the properties of a WASA.
  • the preferred oil-soluble reaction product of component (K4) in particular that of the 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 have been 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, 2-methyl-1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene (hexamethylene) and especially 1,2-ethylene.
  • the variable A preferably comprises 2 to 4, in particular 2 or 3, carbon atoms.
  • C 1 - to C 19 alkylene groups of the variable B are, for example, 1,2-ethylene, 1,3-propylene, 1,4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene and in particular their methylene.
  • the variable B preferably 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 component (K4) are usually monoamines, in particular aliphatic monoamines. These primary and secondary amines can be selected from a large number of amines which - optionally linked to one another - carry hydrocarbon radicals.
  • these amines on which the oil-soluble reaction products of component (K4) are based are secondary amines and have the general formula HN (R 8 ) 2 , in which the two variables R 8 are, independently of one another, straight-chain or branched C 10 - to C 30 -alkyl radicals, in particular C 14 - to C 24 -alkyl radicals.
  • These longer-chain alkyl radicals are preferably straight-chain or only slightly branched.
  • the secondary amines mentioned are derived from natural with regard to their longer-chain alkyl radicals occurring fatty acids or their derivatives.
  • the two radicals R 8 are preferably the same.
  • the secondary amines mentioned can be bound to the polycarboxylic acids by means of amide structures or in the form of the ammonium salts; only some can also be present as amide structures and some as ammonium salts. Preferably there are few or no free acid groups.
  • the oil-soluble reaction products of component (K4) are preferably 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-diamine tetraacetic acid, each with 0.5 to 1.5 mol per carboxyl group, in particular 0.8 to 1.2 mol per carboxyl group, dioleylamine , Dipalmitinamine, dicoconut fatty amine, distearylamine, dibehenylamine or especially ditallow fatty amine.
  • a particularly preferred component (K4) is the reaction product of 1 mol of ethylenediaminetetraacetic acid and 4 mol 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 mole of phthalic anhydride and 2 moles of ditallow fatty amine, the latter being hydrogenated or non-hydrogenated , and the reaction product of 1 mole of an alkenyl spirobislactone with 2 moles of a dialkylamine, for example ditallow fatty amine and / or tallow fatty amine, the latter two being hydrogenated or non-hydrogenated.
  • Sulphocarboxylic acids, sulphonic acids or their derivatives suitable as cold flow improvers of the component of class (K5) are, for example, the oil-soluble carboxamides and carboxylic esters of ortho-sulphobenzoic acid, in which the sulphonic acid function is present as a sulphonate with alkyl-substituted ammonium cations, as described in US Pat EP-A 261 957 to be discribed.
  • Poly (meth) acrylic acid esters suitable as cold flow improvers of the component of class (K6) are both homo- and copolymers of acrylic and methacrylic acid esters. Preference is given to copolymers of at least two (meth) acrylic acid esters which are different from one another and which differ with regard to the alcohol which has condensed in.
  • the copolymer may contain a further, different olefinically unsaturated monomer in copolymerized form.
  • the weight average molecular weight of the polymer is preferably 50,000 to 500,000.
  • a particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated C 14 and C 15 alcohols, the acid groups being neutralized with hydrogenated tallamine.
  • Suitable poly (meth) acrylic acid esters are, for example, in WO 00/44857 described.
  • the cold flow improver or the mixture of different cold flow improvers is added to the middle distillate fuel or diesel fuel in a total amount of preferably 10 to 5000 ppm by weight, particularly preferably 20 to 2000 ppm by weight, more preferably 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, are added.
  • Suitable lubricity improvers or friction modifiers are usually based on fatty acids or fatty acid esters. Typical examples are tall oil fatty acid, such as in WO 98/004656 and glycerol monooleate. Even those in the US 6,743,266 B2 The reaction products described from natural or synthetic oils, for example triglycerides, and alkanolamines are suitable as such lubricity improvers.
  • Suitable corrosion inhibitors include BernsteinTexreester, in particular with polyols, fatty acid derivatives, for example ⁇ l Listereester, oligomerized fatty acids, substituted ethanol amines and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany), Irgacor ® L12 (BASF SE) or HiTEC 536 (Ethyl Corporation).
  • Suitable demulsifiers are, for example, the alkali metal or alkaline earth metal salts of alkyl-substituted phenol and naphthalene sulfonates and the alkali metal or alkaline earth metal salts of fatty acids, as well as neutral compounds such as alcohol alkoxylates, e.g. alcohol ethoxylates, phenol alkoxylates, e.g. tert-butylphenol ethoxylates, e.g.
  • tert-butylphenol ethoxylate or tert-pentylphenol ethoxylates Alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), for example also in the form of EO / PO block copolymers, polyethyleneimines or polysiloxanes.
  • EO ethylene oxide
  • PO propylene oxide
  • Suitable dehazers are, for example, alkoxylated phenol-formaldehyde condensates, such as the products available under the trade name NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite).
  • Suitable antifoam agents are, for example, polyether-modified polysiloxanes, such as, for example, the products available under the trade name TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc).
  • Suitable cetane number improvers are, for example, aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate and peroxides such as di-tert-butyl peroxide.
  • Suitable antioxidants are, for example, 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, for example, salicylic acid derivatives such as N, N'-disalicylidene-1,2-propanediamine.
  • Suitable are, for example, non-polar organic solvents such as aromatic and aliphatic hydrocarbons, for example toluene, xylenes, "white spirit” and products sold 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 get into the diesel fuel together with the aforementioned additives and co-additives, which they are intended to dissolve or dilute for better handling.
  • the additive according to the invention is outstandingly suitable as a fuel additive and can in principle be used in any fuel. It has a number of beneficial effects when operating internal combustion engines with fuels.
  • the quaternized additive according to the invention is preferably used in middle distillate fuels, in particular diesel fuels.
  • the present invention therefore also relates to fuels, in particular middle distillate fuels, with an effective content as an additive to achieve advantageous effects in the operation of internal combustion engines, for example diesel engines, in particular direct-injection diesel engines, especially diesel engines with common rail injection systems on the quaternized additive according to the invention.
  • This effective content (dosing rate) is usually 10 to 5000 ppm by weight, preferably 20 to 1500 ppm by weight, in particular 25 to 1000 ppm by weight, especially 30 to 750 ppm by weight, each based on the total amount of fuel.
  • the use according to the invention relates in principle to any fuel, preferably diesel and petrol.
  • Middle distillate fuels such as diesel fuels or heating oils are preferably petroleum raffinates, which usually have a boiling range of 100 to 400.degree. These are mostly distillates with a 95% point up to 360 ° C or even more. However, these can also be so-called "Ultra Low Sulfur Diesel” or "City Diesel", characterized by a 95% point of, for example, a maximum of 345 ° C. and a sulfur content of a maximum of 0.005% by weight or a 95% point of for example 285 ° C. and a maximum sulfur content of 0.001% by weight.
  • mineral middle distillate fuels or diesel fuels obtainable through refining
  • mineral middle distillate fuels or diesel fuels there are also those that are produced through coal gasification or gas liquefaction ["gas to liquid” (GTL) fuels] or through biomass liquefaction ["biomass to liquid” (BTL) fuels] are available, suitable.
  • GTL gas to liquid
  • BTL biomass liquefaction
  • Mixtures of the aforementioned middle distillate fuels or diesel fuels with regenerative fuels such as biodiesel or bioethanol are also suitable.
  • middle distillate fuels of fossil, vegetable or animal origin which essentially represent hydrocarbon mixtures
  • biofuel oils biodiesel
  • middle distillate fuel Such mixtures are encompassed by the term "middle distillate fuel”. They are commercially available and usually contain the biofuel oils in minor amounts, typically in amounts from 1 to 30% by weight, in particular from 3 to 10% by weight, based on the total amount of middle distillate of fossil, vegetable or animal origin and biofuel oil.
  • Biofuel oils are generally based on fatty acid esters, preferably essentially on alkyl esters of fatty acids which are derived from vegetable and / or animal oils and / or fats.
  • Alkyl esters are usually understood to mean lower alkyl esters, in particular C 1 to C 4 alkyl esters, which are obtained by transesterification of the glycerides, in particular triglycerides, which occur in vegetable and / or animal oils and / or fats, by means of lower alcohols, for example ethanol or, in particular, methanol (“ FAME ”) are available.
  • Typical lower alkyl esters based on vegetable and / or animal oils and / or fats, which are used as biofuel oil or components for this, are, 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, that is to say with a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, in particular less than 0.005 wt% and especially less than 0.001 wt% sulfur.
  • gasoline fuel compositions can be used as gasoline.
  • the common Eurosuper base fuel according to EN 228 should be mentioned as a typical representative.
  • gasoline fuel compositions are also in accordance with the specification WO 00/47698 possible fields of application for the present invention.
  • the quaternized additive according to the invention is particularly suitable as a fuel additive in fuel compositions, in particular in diesel fuels, to overcome the problems described at the outset in direct-injection diesel engines, especially those with common rail injection systems.
  • test methods mentioned below are part of the general disclosure of the application and are not restricted to the specific exemplary embodiments.
  • the mass-average Mw and number-average molecular weight Mn of the copolymers were measured by means of gel permeation chromatography (GPC). GPC separation was carried out using two PLge Mixed B columns (Agilent) in tetrahydrofuran at 35 ° C. Calibration was carried out using a narrowly distributed polystyrene standard (PSS, Germany) with a molecular weight of 162-50400 Da. Hexylbenzene was used as a low molecular weight marker.
  • the olefin or the mixture of olefins with or without a solvent was initially introduced into a reactor with an anchor stirrer.
  • the mixture was heated to the indicated temperature under a stream of nitrogen and with stirring.
  • the specified free-radical initiator (optionally diluted in the same solvent) and molten maleic anhydride (1 equivalent based on olefin monomer) were added.
  • the reaction mixture was stirred at the same temperature for the specified reaction time and then cooled.
  • the specified amount of water was then added and the mixture was stirred either at 95 ° C. for 10-14 hours or under pressure at 110 ° C. for 3 hours.
  • the IDID engine test was used as a further test method, in which the exhaust gas temperatures of the cylinders at the cylinder outlet were determined when the DW10 engine was cold started.
  • a direct-injection diesel engine with a common rail system from the manufacturer Peugeot was used in accordance with test methods CEC F-098-08.
  • a commercially available B7 diesel fuel in accordance with EN 590 from Aral was used as the fuel. 1 ppm by weight of sodium naphthenate and 20 ppm by weight of dodecenylsuccinic acid were added to this to artificially stimulate the formation of deposits.
  • the engine was cooled down and started again.
  • the exhaust temperature from each cylinder was recorded. The smaller the differences between the determined exhaust gas temperatures, the lower the amount of IDID formed.
  • the compounds according to the present invention are very effective for prevention / removal in direct injection engines, as seen on the Peugeot DW10 engine in a test similar to CEC F-98-08, but with 1 ppm by weight Na in the form of sodium naphthenate and 20 ppm by weight of dodecenyl succinic acid.

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Claims (11)

  1. Utilisation de copolymères, pouvant être obtenus par
    - dans une première étape de réaction (I), la copolymérisation de
    (A) au moins un anhydride d'un acide dicarboxylique éthyléniquement insaturé,
    (B) au moins une α-oléfine contenant d'au moins 12 jusqu'à 30 atomes de carbone inclus,
    (C) optionnellement au moins une oléfine aliphatique ou cycloaliphatique supplémentaire, comprenant au moins 4 atomes de carbone, qui est autre que (B), et
    (D) optionnellement un ou plusieurs monomères copolymérisables supplémentaires, qui sont différents des monomères (A), (B) et (C), choisis dans le groupe constitué par
    (Da) les esters de vinyle,
    (Db) les éthers de vinyle,
    (Dc) les esters de l'acide (méth)acrylique d'alcools, qui comprennent au moins 5 atomes de carbone,
    (Dd) les alcools allyliques ou leurs éthers,
    (De) les composés de N-vinyle, choisis dans le groupe constitué par les composés de vinyle d'hétérocycles contenant au moins un atome d'azote, les N-vinylamides ou les N-vinyllactames,
    (Df) les composés aromatiques éthyléniquement insaturés,
    (Dg) les nitriles α,β-éthyléniquement insaturés,
    (Dh) les amides de l'acide (méth)acrylique et
    (Di) les allylamines,
    suivie par
    - dans une deuxième étape de réaction optionnelle (II), l'hydrolyse partielle des fonctionnalités anhydride contenues dans le copolymère obtenu en (I), à condition que plus de 90 % des fonctionnalités anhydride contenues restent intactes après l'étape de réaction (II), pour éliminer et/ou empêcher des dépôts dans le système d'injection de moteurs diesel et/ou à essence à injection directe.
  2. Utilisation des copolymères tels que décrits dans la revendication 1 en tant qu'additif pour réduire la consommation de carburant de moteurs diesel à injection directe, notamment de moteurs diesel à systèmes d'injection à rampe commune.
  3. Utilisation des copolymères tels que décrits dans la revendication 1 en tant qu'additif pour minimiser la perte de puissance (powerloss) de moteurs diesel à injection directe, notamment de moteurs diesel à systèmes d'injection à rampe commune.
  4. Utilisation selon la revendication 3 en tant qu'additif pour minimiser la perte de puissance (powerloss) causée par des ions K, Zn, Ca et/ou Na (dite perte de puissance K, Zn, Ca ou Na).
  5. Utilisation des copolymères tels que décrits dans la revendication 1 en tant qu'additif d'essence automobile pour réduire des dépôts dans le système d'admission d'un moteur automobile, tel que notamment des moteurs DISI et PFI (Port Fuel Injector).
  6. Utilisation selon la revendication 1 en tant qu'additif de carburant diesel pour réduire et/ou éviter des dépôts dans les systèmes d'injection, tels que notamment les dépôts d'injecteur diesel internes (IDID) et/ou les adhésions de soupapes dans des moteurs diesel à injection directe, notamment dans des systèmes d'injection à rampe commune.
  7. Utilisation selon la revendication 6 en tant qu'additif de carburant diesel pour réduire et/ou éviter les dépôts d'injecteur diesel internes (IDID) causés par des ions Na, Ca et/ou K (dits IDID de savons Na, Ca ou K).
  8. Utilisation selon la revendication 6 en tant qu'additif de carburant diesel pour réduire et/ou éviter les dépôts d'injecteur diesel internes (IDID) causés par des dépôts polymères.
  9. Utilisation selon la revendication 1, dans laquelle le carburant est choisi parmi les carburants diesel, les carburants biodiesel, les essences automobiles et les essences automobiles contenant de l'alcanol.
  10. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que de l'anhydride de l'acide maléique est utilisé en tant que composant (A) et l'étape de réaction optionnelle (II) n'est pas réalisée.
  11. Utilisation selon l'une quelconque des revendications 1 à 9, caractérisée en ce que de l'anhydride de l'acide maléique est utilisé en tant que composant (A) et plus de 90 % et jusqu'à 99,9 % des fonctionnalités anhydride restent intactes dans l'étape de réaction (II).
EP16738151.6A 2015-07-16 2016-07-12 Utilisation de copolymères dans des moteurs à combustion interne à injection directe Active EP3322775B1 (fr)

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PCT/EP2016/066465 WO2017009305A1 (fr) 2015-07-16 2016-07-12 Copolymères utilisés en tant qu'additifs pour carburants et lubrifiants

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US8992636B1 (en) 2013-10-08 2015-03-31 Afton Chemical Corporation Alkoxylated quaternary ammonium salts and fuels containing them
WO2015113681A1 (fr) * 2014-01-29 2015-08-06 Basf Se Additifs à base d'acide polycarbonique, destinés à des carburants et à des lubrifiants
AU2015212878B2 (en) 2014-01-29 2018-03-29 Basf Se Corrosion inhibitors for fuels and lubricants
KR20180019106A (ko) 2015-06-17 2018-02-23 바스프 에스이 윤활유를 포함하는 전도성 페이스트 및 반도체 소자
EP3322774A1 (fr) 2015-07-15 2018-05-23 Basf Se Utilisation d'inhibiteurs de corrosion pour carburants et lubrifiants
BR112018000797A2 (pt) 2015-07-16 2018-09-04 Basf Se uso de copolímeros.
EP3192857A1 (fr) 2016-01-13 2017-07-19 Basf Se Utilisation de copolymères de poly (méth) acrylate avec des chaînes alkyles c17 ramifiées dans des compositions d'huile lubrifiante
US11078418B2 (en) 2016-07-05 2021-08-03 Basf Se Corrosion inhibitors for fuels and lubricants
WO2018007192A1 (fr) 2016-07-05 2018-01-11 Basf Se Inhibiteurs de corrosion pour carburants et lubrifiants
WO2018007375A1 (fr) 2016-07-07 2018-01-11 Basf Se Copolymères utilisés en tant qu'additifs pour carburants et lubrifiants
ES2948483T3 (es) 2016-12-15 2023-09-13 Basf Se Polímeros como aditivos de combustible diésel para motores diésel de inyección directa

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WO2017009305A1 (fr) 2017-01-19
CN107849471B (zh) 2021-07-16
RU2018105763A (ru) 2019-08-16
US20180201855A1 (en) 2018-07-19
US11085001B2 (en) 2021-08-10
EP3322775A1 (fr) 2018-05-23
CN107849471A (zh) 2018-03-27

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