EP3322775B1 - Use of copolymers in direct injection internal combustion engines - Google Patents
Use of copolymers in direct injection internal combustion engines Download PDFInfo
- Publication number
- 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
- Authority
- EP
- European Patent Office
- Prior art keywords
- diesel
- copolymers
- acid
- fuel
- deposits
- 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.)
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- PDEDQSAFHNADLV-UHFFFAOYSA-M potassium;disodium;dinitrate;nitrite Chemical compound [Na+].[Na+].[K+].[O-]N=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PDEDQSAFHNADLV-UHFFFAOYSA-M 0.000 description 1
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Images
Classifications
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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
- C10L1/18—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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- 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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- 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
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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
- C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
- C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—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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- 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
- C10L1/2364—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
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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
- C10L1/22—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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/236—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
-
- 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
- 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
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- 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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Description
Die vorliegende Erfindung betrifft neue Verwendungen von Copolymeren zur Entfernung und/oder Verringerung von Ablagerungen im Einspritzsystem von direkteinspritzenden Diesel- und/oder Benzinmotoren.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.
Die vorliegende Erfindung betrifft die Verwendung bestimmter Copolymere als Kraftstoffoder Schmierstoffadditiv; Verfahren zur Herstellung derartiger Additive, sowie damit additivierte Kraft- und Schmierstoffe; wie insbesondere als Detergensadditiv; Verwendung dieser Copolymere zur Verringerung oder Verhinderung von Ablagerungen in den Einspritzsystemen von direkteinspritzenden Dieselmotoren, insbesondere in Common-Rail-Einspritzsystemen, zur Verringerung des Kraftstoffverbrauches von direkteinspritzenden Dieselmotoren, insbesondere von Dieselmotoren mit Common-Rail-Einspritzsystemen, und zur Minimierung des Leistungsverlustes (power loss) in direkteinspritzenden Dieselmotoren, insbesondere in Dieselmotoren mit Common-Rail-Einspritzsystemen; sowie als Additiv für Ottokraftstoffe, insbesondere zum Betrieb von DISI Motoren.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.
Hintergrund der Erfindung:
Bei direkteinspritzenden Dieselmotoren wird der Kraftstoff durch eine direkt in den Brennraum des Motors reichende Mehrloch-Einspritzdüse eingespritzt und feinst verteilt (vernebelt), anstatt wie beim klassischen (Kammer-) Dieselmotor in eine Vor- oder Wirbelkammer eingeführt zu werden. Der Vorteil der direkteinspritzenden Dieselmotoren liegt in ihrer für Dieselmotoren hohen Leistung und einem dennoch geringen Verbrauch. Außerdem erreichen diese Motoren ein sehr hohes Drehmoment schon bei niedrigen Drehzahlen.Background of the invention:
In direct-injection diesel engines, the fuel is injected through a multi-hole injection nozzle that reaches directly into the combustion chamber of the engine and is finely distributed (atomized) instead of being introduced into a prechamber or swirl chamber as in the classic (chamber) diesel engine. The advantage of direct-injection diesel engines lies in their high performance for diesel engines and yet low consumption. In addition, these motors achieve a very high torque even at low speeds.
Zurzeit werden im Wesentlichen drei Verfahren eingesetzt, um den Kraftstoff direkt in den Brennraum des Dieselmotors einzuspritzen: die konventionelle Verteilereinspritzpumpe, das Pumpe-Düse-System (Unit-Injector-System bzw. Unit-Pump-System) und das Common-Rail-System.Currently, three main methods are used to inject the fuel directly into the combustion chamber of the diesel engine: the conventional distributor injection pump, the unit injector system and the common rail system .
Beim Common-Rail-System wird der Dieselkraftstoff von einer Pumpe mit Drücken bis zu 2000 bar in eine Hochdruckleitung, die Common-Rail gefördert. Ausgehend von der Common-Rail laufen Stichleitungen zu den verschiedenen Injektoren, die den Kraftstoff direkt in den Brennraum injizieren. Dabei liegt auf der Common-Rail stets der volle Druck an, was eine Mehrfacheinspritzung oder eine spezielle Einspritzform ermöglicht. Bei den anderen Injektionssystemen ist dagegen nur eine geringere Variation der Einspritzung möglich. Die Einspritzung beim Common-Rail wird im Wesentlichen in drei Gruppen unterteilt: (1.) Voreinspritzung, durch die im Wesentlichen eine weichere Verbrennung erreicht wird, so dass harte Verbrennungsgeräusche ("Nageln") vermindert werden und der Motorlauf ruhig erscheint; (2.) Haupteinspritzung, die insbesondere für einen guten Drehmomentverlauf verantwortlich ist; und (3.) Nacheinspritzung, die insbesondere für einen geringen NOx-Wert sorgt. Bei dieser Nacheinspritzung wird der Kraftstoff in der Regel nicht verbrannt, sondern durch Restwärme im Zylinder verdampft. Das dabei gebildete Abgas-/Kraftstoffgemisch wird zur Abgasanlage transportiert, wo der Kraftstoff in Gegenwart geeigneter Katalysatoren als Reduktionsmittel für die Stickoxide NOx wirkt.In the common rail system, the diesel fuel is conveyed by a pump with pressures of up to 2000 bar into a high pressure line, the common rail. Starting from 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. With 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. With this post-injection, 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.
Durch die variable, zylinderindividuelle Einspritzung kann beim Common-Rail-Einspritzsystem der Schadstoffausstoß des Motors, z.B. der Ausstoß von Stickoxiden (NOx), Kohlenmonoxid (CO) und insbesondere von Partikeln (Ruß), positiv beeinflusst werden. Dies ermöglicht beispielsweise, dass mit Common-Rail-Einspritzsystemen ausgerüstete Motoren der Euro 4-Norm theoretisch auch ohne zusätzlichen Partikelfilter genügen können.With the common rail injection system, the 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). This enables, for example, engines equipped with common rail injection systems to theoretically meet the Euro 4 standard even without an additional particle filter.
In modernen Common-Rail-Dieselmotoren können sich unter bestimmten Bedingungen, beispielsweise bei Verwendung von biodieselhaltigen Kraftstoffen oder von Kraftstoffen mit Metall-Verunreinigungen wie Zink-Verbindungen, Kupfer-Verbindungen, Bleiverbindungen und weiteren Metallverbindungen, an den Injektoröffnungen Ablagerungen bilden, die das Einspritzverhalten des Kraftstoffs negativ beeinflussen und dadurch die Performance des Motors beeinträchtigen, d.h. insbesondere die Leistung verringern, aber zum Teil auch die Verbrennung verschlechtern. Die Bildung von Ablagerungen wird durch bauliche Weiterentwicklungen der Injektoren, insbesondere durch die Veränderung der Geometrie der Düsen (engere, konische Öffnungen mit abgerundetem Auslass) noch verstärkt. Für eine dauerhaft optimale Funktionsweise von Motor und Injektoren müssen solche Ablagerungen in den Düsenöffnungen durch geeignete Kraftstoffadditive verhindert oder reduziert werden.In modern common rail diesel engines, under certain conditions, for example when using fuels containing biodiesel or fuels with metal impurities such as zinc compounds, copper compounds, lead compounds and other metal compounds, 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.
In den Einspritzsystemen moderner Dieselmotoren verursachen Ablagerungen signifikante Performance-Probleme. Weit verbreitet ist die Erkenntnis, dass derartige Ablagerungen in den Sprühkanälen zu einer Verringerung des Kraftstoffflusses und damit zu Leistungsverlusten (power loss) führen können. Ablagerungen an der Injektorspitze beeinträchtigen dagegen die optimale Ausbildung von Kraftstoff-Sprühnebel und bedingen dadurch eine verschlechterte Verbrennung und damit verbunden höhere Emissionen und vermehrten Kraftstoffverbrauch. Im Gegensatz zu diesen herkömmlichen, "äußeren" Ablagerungsphänomenen bereiten auch "interne" Ablagerungen (zusammengefasst als innere Diesel-Injektor-Ablagerungen (IDID)) in bestimmten Teilen der Injektoren, besonders an der Düsennadel, am Steuerkolben, am Ventilkolben, am Ventilsitz, an der Ansteuereinheit und an den Führungen dieser Komponenten, zunehmend Performance-Probleme. Herkömmliche Additive zeigen eine unzureichende Wirkung gegen diese IDIDs.In the injection systems of modern diesel engines, deposits cause significant performance problems. It is widely recognized that such deposits in the spray channels can lead to a reduction in the flow of fuel and thus to power loss. Deposits on the injector tip, on the other hand, impair the optimal formation of fuel spray and thus cause poor combustion and the associated higher emissions and increased fuel consumption. In contrast to these conventional, "external" deposit phenomena, "internal" deposits (summarized as internal diesel injector deposits (IDID)) also form in certain parts of the injectors, especially on the nozzle needle, on the control piston, on the valve piston, on the valve seat the control unit and on the guides of these components, increasing performance problems. Conventional additives show insufficient effectiveness against these IDIDs.
Unter dem "Einspritzsystem" wird dabei der Teil des Kraftstoffsystems in Kraftfahrzeugen von Kraftstoffpumpe bis einschließlich Injektorauslass verstanden. Als "Kraftstoffsystem" werden dabei die Bauteile von Kraftfahrzeugen verstanden, die mit dem jeweiligen Kraftstoff in Kontakt stehen, bevorzugt der Bereich von Tank bis einschließlich Injektorauslass.The “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. The term “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.
Es stelle eine Ausführungsform der vorliegenden Erfindung dar, daß die erfindungsgemäßen Verbindungen gegen Ablagerungen im Einspritzsystem wirken.It is an embodiment of the present invention that the compounds according to the invention act against deposits in the injection system.
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Aus der Internationalen Patentanmeldung mit dem Aktenzeichen
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Es wird die Wirkung der Zugabe dieser Copolymere zu verschiedenen Zwecken in den Kraftstoffen beschrieben, jedoch nicht zur Beseitigung von Ablagerungen im Einspritzsystem von Motoren.The effect of adding these copolymers to the fuels for various purposes is described, but not for removing deposits in the injection system of engines.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, eine neue Klasse von Copolymer - basierten Additiven für den Einsatz in modernen Diesel- und Ottokraftstoffen bereit zu stellen.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.
Die Aufgabe wird gelöst durch die Verwendung von Copolymeren, erhältlich durch
- in einem ersten Reaktionsschritt (I) Copolymerisation von
- (A) mindestens einem Anhydrid einer ethylenisch ungesättigten Dicarbonsäure,
- (B) mindestens einem α -Olefin mit von mindestens 12 bis zu
einschließlich 30 Kohlenstoffatomen, - (C) optional mindestens einem weiteren, mindestens 4 Kohlenstoffatome aufweisenden, aliphatischen oder cycloaliphatischen Olefin, das ein anderes als (B) ist und
- (D) optional eines oder mehrerer weiterer copolymerisierbarer Monomere, die verschieden von den Monomeren (A), (B) und (C) sind, ausgewählt aus der Gruppe bestehend aus
- (Da) Vinylestern,
- (Db) Vinylethern,
- (Dc) (Meth)acrylsäureestern von Alkoholen, die mindestens 5 Kohlenstoffatome aufweisen,
- (Dd) Allylalkoholen oder deren Ether,
- (De) N-Vinylverbindungen, ausgewählt aus der Gruppe bestehend aus Vinylverbindungen von mindestens ein Stickstoffatom enthaltenden Heterocyclen, N-Vinylamide oder N-Vinyllactame,
- (Df) ethylenisch ungesättigte Aromaten
- (Dg) α,β -ethylenisch ungesättigte Nitrilen,
- (Dh) (Meth)acrylsäureamiden und
- (Di) Allylaminen,
- in einem zweiten optionalen Reaktionsschritt (II) teilweise Hydrolyse der im aus (I) erhaltenen Copolymer enthaltenen Anhydridfunktionalitäten, mit der Maßgabe, daß mehr als 90% der enthaltenen Anhydridfunktionalitäten nach dem Reaktionsschritt (II) intakt bleiben, zur Entfernung und/oder Verhinderung von Ablagerungen im Einspritzsystem von direkteinspritzenden Diesel- und/oder Benzinmotoren.
- in a first reaction step (I) copolymerization of
- (A) at least one anhydride of an ethylenically unsaturated dicarboxylic acid,
- (B) at least one α- olefin having from at least 12 up to and including 30 carbon atoms,
- (C) optionally at least one further aliphatic or cycloaliphatic olefin which has at least 4 carbon atoms and which is other than (B) and
- (D) optionally one or more further copolymerizable monomers, which are different from the monomers (A), (B) and (C), selected from the group consisting of
- (There) vinyl esters,
- (Db) vinyl ethers,
- (Dc) (meth) acrylic acid esters of alcohols which have at least 5 carbon atoms,
- (Dd) allyl alcohols or their ethers,
- (De) N-vinyl compounds selected from the group consisting of vinyl compounds of heterocycles containing at least one nitrogen atom, N-vinyl amides or N-vinyl lactams,
- (Df) ethylenically unsaturated aromatics
- (Dg) α , β -ethylenically unsaturated nitriles,
- (Dh) (meth) acrylic acid amides and
- (Di) allylamines,
- in a second optional reaction step (II) partial hydrolysis of the anhydride functionalities contained in the copolymer obtained from (I), with the proviso that more than 90% of the anhydride functionalities contained remain intact after reaction step (II), in order to remove and / or prevent deposits in the injection system of direct injection diesel and / or gasoline engines.
Derartige Copolymere haben sich als wirksam in der Unterbindung und/oder Beseitigung der folgenden Ablagerungen in Diesel- und Ottomotoren erwiesen:Such copolymers have been shown to be effective in preventing and / or removing the following deposits in diesel and gasoline engines:
Diese Copolymere zeichnen sich insbesondere dadurch aus, dass sie gegen verschiedenste Ablagerungen wirken, die die Leistungsfähigkeit von modernen Dieselmotoren beeinträchtigen. Die erfindungsgemäßen Verbindungen wirken beispielsweise gegen Leistungsverlust sowohl hervorgerufen durch Zinkeintrag als auch hervorgerufen durch Natriumeintrag in den Dieselkraftstoff. Hierbei werden im Wesentlichen Ablagerungen in den Sprühkanälen und der Injektorspitze beseitigt bzw. vermieden. Andererseits wirken die erfindungsgemäßen Verbindungen aber auch gegen innere Diesel-Injektor-Ablagerungen (IDID), bedingt durch Na-, Ca- und/oder K-Ionen (so genannte Na-, Ca- bzw. K- Seifen IDID) und/oder polymere Ablagerungen. Bei Na-, Ca- bzw. K- Seifen IDID handelt es sich um Ablagerungen, die die betreffenden Metallionen mit beliebigen Gegenionen enthalten. Die polymeren Ablagerungen dagegen sind frei von Metallionen und auf hochmolekulares und im Kraftstoff wenig oder unlösliches organisches Material zurückzuführen.These 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. On the other hand, 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. 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.
Spezielle Ausführungsformen der Erfindung sind:
- 1. Verwendung von Copolymeren, erhältlich durch
- in einem ersten Reaktionsschritt (I) Copolymerisation von
- (A) mindestens einem Anhydrid einer ethylenisch ungesättigten Dicarbonsäure,
- (B) mindestens einem α -Olefin
mit von mindestens 12bis zu einschließlich 30 Kohlenstoffatomen, - (C) optional mindestens einem weiteren,
mindestens 4 Kohlenstoffatome aufweisenden, aliphatischen oder cycloaliphatischen Olefin, das ein anderes als (B) ist und - (D) optional eines oder mehrerer weiterer copolymerisierbarer Monomere, die verschieden von den Monomeren (A), (B) und (C) sind, ausgewählt aus der Gruppe bestehend aus
- (Da) Vinylestern,
- (Db) Vinylethern,
- (Dc) (Meth)acrylsäureestern von Alkoholen, die
mindestens 5 Kohlenstoffatome aufweisen, - (Dd) Allylalkoholen oder deren Ether,
- (De) N-Vinylverbindungen, ausgewählt aus der Gruppe bestehend aus Vinylverbindungen von mindestens ein Stickstoffatom enthaltenden Heterocyclen, N-Vinylamide oder N-Vinyllactame,
- (Df) ethylenisch ungesättigte Aromaten
- (Dg) α,β -ethylenisch ungesättigte Nitrilen,
- (Dh) (Meth)acrylsäureamiden und
- (Di) Allylaminen,
- in einem zweiten optionalen Reaktionsschritt (II) teilweise Hydrolyse der im aus (I) erhaltenen Copolymer enthaltenen Anhydridfunktionalitäten, mit der Maßgabe, daß mehr als 90% der enthaltenen Anhydridfunktionalitäten nach dem Reaktionsschritt (II) intakt bleiben, als Kraftstoff- oder Schmierstoffadditiv, insbesondere Dieselkraftstoffadditiv.
- in einem ersten Reaktionsschritt (I) Copolymerisation von
- 2. Verwendung nach der Ausführungsform 1 als Additiv zur Verringerung des Kraftstoffverbrauches von direkteinspritzenden Dieselmotoren, insbesondere von Dieselmotoren mit Common-Rail-Einspritzsystemen.
- 3. Verwendung nach einer der Ausführungsformen als Additiv zur Minimierung des Leistungsverlustes (powerloss) in direkteinspritzenden Dieselmotoren, insbesondere in Dieselmotoren mit Common-Rail-Einspritzsystemen.
- 4. Verwendung nach einer der Ausführungsformen als Additiv zur Minimierung des Leistungsverlustes (powerloss) bedingt durch K-, Zn-, Ca- und/oder Na-Ionen (so genannter K-, Zn-, Ca- bzw. Na-powerloss).
- 5. Verwendung nach einer der Ausführungsformen als Ottokraftstoffadditiv zur Verringerung von Ablagerungen im Einlasssystem eines Ottomotors, wie insbesondere DISI und PFI (Port Fuel Injector) -Motoren.
- 6. Verwendung nach einer der Ausführungsformen als Dieselkraftstoffadditiv zur Verringerung und/oder Vermeidung von Ablagerungen in den Einspritzsystemen, wie insbesondere der Internal Diesel Injector Deposits (IDID) und / oder von Ventilkleben in direkteinspritzenden Dieselmotoren, insbesondere in Common-Rail-Einspritzsystemen.
- 7. Verwendung nach einer der Ausführungsformen als Dieselkraftstoffadditiv zur Verringerung und/oder Vermeidung der Internal Diesel Injector Deposits (IDID) bedingt durch Na-, Ca.- und/oder K-Ionen (so genannte Na-, Ca- bzw. K- Seifen IDID).
- 8. Verwendung nach einer der Ausführungsformen als Dieselkraftstoffadditiv zur Verringerung und/oder Vermeidung der Internal Diesel Injector Deposits (IDID) bedingt durch polymere Ablagerungen.
- 9. Verwendung nach einer der vorhergehenden Ausführungsformen, wobei der Kraftstoff ausgewählt unter Dieselkraftstoffen, Biodieselkraftstoffen, Ottokraftstoffen, und Alkanol-haltigen Ottokraftstoffen.
- 1. Use of copolymers obtainable from
- in a first reaction step (I) copolymerization of
- (A) at least one anhydride of an ethylenically unsaturated dicarboxylic acid,
- (B) at least one α- olefin having from at least 12 up to and including 30 carbon atoms,
- (C) optionally at least one further aliphatic or cycloaliphatic olefin which has at least 4 carbon atoms and which is other than (B) and
- (D) optionally one or more further copolymerizable monomers, which are different from the monomers (A), (B) and (C), selected from the group consisting of
- (There) vinyl esters,
- (Db) vinyl ethers,
- (Dc) (meth) acrylic acid esters of alcohols which have at least 5 carbon atoms,
- (Dd) allyl alcohols or their ethers,
- (De) N-vinyl compounds selected from the group consisting of vinyl compounds of heterocycles containing at least one nitrogen atom, N-vinyl amides or N-vinyl lactams,
- (Df) ethylenically unsaturated aromatics
- (Dg) α , β -ethylenically unsaturated nitriles,
- (Dh) (meth) acrylic acid amides and
- (Di) allylamines,
- in a second optional reaction step (II) partial hydrolysis of the anhydride functionalities contained in the copolymer obtained from (I), with the proviso that more than 90% of the anhydride functionalities contained after the reaction step (II) remain intact, as a fuel or lubricant additive, especially a diesel fuel additive.
- in a first reaction step (I) copolymerization of
- 2. Use according to
embodiment 1 as an additive for reducing the fuel consumption of direct injection diesel engines, in particular diesel engines with common rail injection systems. - 3. Use according to one of the embodiments as an additive to minimize power loss in direct-injection diesel engines, in particular in diesel engines with common rail injection systems.
- 4. Use according to one of the embodiments as an additive to minimize the power loss (powerloss) caused by K, Zn, Ca and / or Na ions (so-called K, Zn, Ca or Na powerloss).
- 5. Use according to one of the embodiments as a gasoline additive for reducing deposits in the intake system of a gasoline engine, such as in particular DISI and PFI (Port Fuel Injector) engines.
- 6. Use according to one of the embodiments as a diesel fuel additive to reduce and / or avoid deposits in the injection systems, such as in particular the Internal Diesel Injector Deposits (IDID) and / or valve sticking in direct-injection diesel engines, especially in common rail injection systems.
- 7. Use according to one of the embodiments as a diesel fuel additive to reduce and / or avoid Internal Diesel Injector Deposits (IDID) caused by Na, Ca and / or K ions (so-called Na, Ca or K soaps IDID).
- 8. Use according to one of the embodiments as a diesel fuel additive to reduce and / or avoid Internal Diesel Injector Deposits (IDID) caused by polymeric deposits.
- 9. Use according to one of the preceding embodiments, wherein the fuel is selected from diesel fuels, biodiesel fuels, petrol, and alkanol-containing petrol.
Bei dem Monomer (A) handelt es sich um mindestens eine, bevorzugt ein bis drei, besonders bevorzugt ein oder zwei und ganz besonders bevorzugt genau ein Anhydrid einer ethylenisch ungesättigten Dicarbonsäure, ganz besonders bevorzugt Maleinsäureanhydrid. Unter C1-C4-Alkyl wird im Rahmen dieser Schrift Methyl, Ethyl, iso-Propyl, n-Propyl, n-Butyl, iso-Butyl, sek-Butyl und tert-Butyl verstanden, bevorzugt Methyl und Ethyl, besonders bevorzugt Methyl.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. Among 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 .
Beispiele für Dicarbonsäuren sind Maleinsäure, Fumarsäure, Itaconsäure (2-Methylenbutandisäure), Citraconsäure (2-Methylmaleinsäure), Glutaconsäure (Pent-2-en-1,5-dicarbonsäure), 2,3-Dimethylmaleinsäure, 2-Methylfumarsäure, 2,3-Dimethylfumarsäure, Methylenmalonsäure und Tetrahydrophthalsäure, bevorzugt um Maleinsäure und Fumarsäure und besonders bevorzugt um Maleinsäure und deren Anhydride.Examples of dicarboxylic acids are 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.
Insbesondere handelt es sich bei dem Monomer (A) um Maleinsäureanhydrid.In particular, the monomer (A) is maleic anhydride.
Bei dem Monomer (B) handelt es sich um mindestens ein, bevorzugt ein bis vier, besonders bevorzugt ein bis drei, ganz besonders bevorzugt ein oder zwei und insbesondere genau ein α -Olefin mit von mindestens 12 bis zu einschließlich 30 Kohlenstoffatomen. Die α -Olefine (B) weisen bevorzugt mindestens 14, besonders bevorzugt mindestens 16 und ganz besonders bevorzugt mindestens 18 Kohlenstoffatome auf. Bevorzugt weisen die α -Olefine (B) bis einschließlich 28, besonders bevorzugt bis einschließlich 26 und ganz besonders bevorzugt bis einschließlich 24 Kohlenstoffatome auf.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 α- olefin having from at least 12 up to and including 30 carbon atoms. The α- olefins (B) preferably have at least 14, particularly preferably at least 16 and very particularly preferably at least 18 carbon atoms. The α- 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.
Bevorzugt kann es sich bei den α -Olefinen um lineare oder verzweigte, bevorzugt lineare 1-Alkene handeln. The α- olefins can preferably be linear or branched, preferably linear 1-alkenes.
Beispiele dafür sind 1-Dodecen, 1-Tridecen, 1-Tetradecen, 1-Pentadecen, 1-Hexadecen, 1-Heptadecen, 1- Octadecen, 1-Nonodecen, 1-Eicosen, 1-Docosen, 1-Tetracosen, 1-Hexacosen, wovon 1- Octadecen, 1-Eicosen, 1-Docosen und 1-Tetracosen, sowie deren Gemische bevorzugt werden.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.
Weitere Beispiele für α -Olefin (B) sind solche Olefine, bei denen es sich um Oligomere oder Polymere von C2- bis C12-Olefinen handelt, bevorzugt von C3- bis C10-Olefinen, besonders bevorzugt von C4- bis C6-Olefinen. Beispiele dafür sind Ethen, Propen, 1-Buten, 2-Buten, iso-Buten, Penten-Isomere sowie Hexen-Isomere, bevorzugt sind Ethen, Propen, 1-Buten, 2-Buten und iso-Buten.Further examples of α- olefins (B) 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.
Namentlich als α -Olefine (B) genannt seien Oligomere und Polymere von Propen, 1-Buten, 2-Buten, iso-Buten, sowie deren Mischungen, besonders Oligomere und Polymere von Propen oder iso-Buten oder von Mischungen aus 1-Buten und 2-Buten. Unter den Oligomeren sind die Trimere, Tetramere, Pentamere und Hexamere sowie deren Gemische bevorzugt.Namely as α- 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. Among the oligomers, the trimers, tetramers, pentamers and hexamers and mixtures thereof are preferred.
Zusätzlich zu dem Olefin (B) kann optional mindestens ein, bevorzugt ein bis vier, besonders bevorzugt ein bis drei, ganz besonders bevorzugt ein oder zwei und insbesondere genau ein weiteres, mindestens 4 Kohlenstoffatome aufweisendes, aliphatisches oder cycloaliphatisches Olefin (C), das ein anderes als (B) ist, in das erfindungsgemäße Copolymer einpolymerisiert werden.In addition to the olefin (B), 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.
Bei den Olefinen (C) kann es sich um Olefine mit endständiger (α-) Doppelbindung handeln oder solche mit nicht-endständiger Doppelbindung, bevorzugt mit α-Doppelbindung. Bevorzugt handelt es sich bei dem Olefin (C) um Olefine mit 4 bis weniger als 12 oder mehr als 30 Kohlenstoffatomen. Sofern es sich bei dem Olefin (C) um ein Olefin mit 12 bis 30 Kohlenstoffatomen handelt, so weist dieses Olefin (C) keine α -ständige Doppelbindung auf.The olefins (C) can be olefins with a terminal ( α -) double bond or those with a non-terminal double bond, preferably with an α 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 α position.
Beispiele für aliphatische Olefine (C) sind 1-Buten, 2-Buten, iso-Buten, Penten-Isomere, Hexen-Isomere, Hepten-Isomere, Octen-Isomere, Nonen-Isomere, Decen-Isomere, Undecen-Isomere sowie deren Gemische.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 .
Beispiele für cycloaliphatische Olefine (C) sind Cyclopenten, Cyclohexen, Cycloocten, Cyclodecen, Cyclododecen, α - oder β -Pinen und deren Gemische, Limonen und Norbornen.Examples of cycloaliphatic olefins (C) are cyclopentene, cyclohexene, cyclooctene, cyclodecene, cyclododecene, α- or β- pinene and mixtures thereof, limonene and norbornene.
Weitere Beispiele für Olefine (C) sind mehr als 30 Kohlenstoffatome aufweisende Polymere von Propen, 1-Buten, 2-Buten oder iso-Buten oder solche enthaltende Olefingemische, bevorzugt von iso-Buten oder solches enthaltende Olefingemische, besonders bevorzugt mit einem mittleren Molekulargewicht Mw im Bereich von 500 bis 5000 g/mol, bevorzugt 650 bis 3000, besonders bevorzugt 800 bis 1500 g/mol.Further examples of 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.
Bevorzugt weisen die iso-Buten in einpolymerisierter Form enthaltenden Oligomere oder Polymere einen hohen Gehalt an terminal angeordneten ethylenischen Doppelbindungen ( α -Doppelbindungen) auf, beispielsweise wenigstens 50 Mol-%, bevorzugt wenigstens 60 Mol-%, besonders bevorzugt wenigstens 70 Mol-% und ganz besonders bevorzugt wenigstens 80 Mol-%.The oligomers or polymers containing isobutene in copolymerized form preferably have a high content of terminally arranged ethylenic double bonds ( α 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%.
Für die Herstellung solcher iso-Buten in einpolymerisierter Form enthaltender Oligomere oder Polymere eignen sich als Isobuten-Quelle sowohl Rein-Isobuten als auch Isobuten-haltige C4-Kohlenwasserstoffströme, beispielsweise C4-Raffinate, insbesondere "Raffinat 1", C4-Schnitte aus der Isobutan-Dehydrierung, C4-Schnitte aus Steamcrackern und aus FCC-Crackern (fluid catalysed cracking), sofern sie weitgehend von darin enthaltenem 1,3-Butadien befreit sind. Ein C4-Kohlenwasserstoffstrom aus einer FCC-Raffinerieeinheit ist auch als "b/b"-Strom bekannt. Weitere geeignete Isobuten-haltige C4-Kohlenwasserstoffströme sind beispielsweise der Produktstrom einer Propylen-Isobutan-Cooxidation oder der Produktstrom aus einer Metathese-Einheit, welche in der Regel nach üblicher Aufreinigung und/oder Aufkonzentrierung eingesetzt werden. Geeignete C4-Kohlenwasserstoffströme enthalten in der Regel weniger als 500 ppm, vorzugsweise weniger als 200 ppm, Butadien. Die Anwesenheit von 1-Buten sowie von cis- und trans-2-Buten ist weitgehend unkritisch. Typischerweise liegt die Isobutenkonzentration in den genannten C4-Kohlenwasserstoffströmen im Bereich von 40 bis 60 Gew.-%. So besteht Raffinat 1 in der Regel im wesentlichen aus 30 bis 50 Gew.-% Isobuten, 10 bis 50 Gew.-% 1-Buten, 10 bis 40 Gew.-% cis- und trans-2-Buten sowie 2 bis 35 Gew.-% Butanen; beim erfindungsgemäßen Polymerisationsverfahren verhalten sich die unverzeigten Butene im Raffinat 1 in der Regel praktisch inert und nur das Isobuten wird polymerisierteiner bevorzugten Ausführungsform setzt man als Monomerquelle für die Polymerisation einen technischen C4-Kohlenwasserstoffstrom mit einem Isobuten-Gehalt von 1 bis 100 Gew.-%, insbesondere von 1 bis 99 Gew.-%, vor allem von 1 bis 90 Gew.-%, besonders bevorzugt von 30 bis 60 Gew.-%, insbesondere einen Raffinat 1-Strom, einen b/b-Strom aus einer FCC-Raffinerieeinheit, einen Produktstrom einer Propylen-Isobutan-Cooxidation oder einen Produktstrom aus einer Metathese-Einheit ein.Both pure isobutene and isobutene-containing C4 hydrocarbon streams, for example C4 raffinates, in particular “
Insbesondere bei Verwendung eines Raffinat 1-Stromes als Isobutenquelle hat sich die Verwendung von Wasser als alleinigem oder als weiterem Initiator bewährt, vor allem wenn man bei Temperaturen von -20° C bis +30° C, insbesondere von 0° C bis +20° C, polymerisiert. Bei Temperaturen von -20° C bis +30° C, insbesondere von 0° C bis +20° C, kann man bei Verwendung eines Raffinat 1-Stromes als Isobutenquelle jedoch auch auf den Einsatz eines Initiators verzichten.In particular when using a
Das genannte Isobuten-haltige Monomerengemisch kann geringe Mengen an Kontaminanten wie Wasser, Carbonsäuren oder Mineralsäuren enthalten, ohne dass es zu kritischen Ausbeute- oder Selektivitätseinbußen kommt. Es ist zweckdienlich, eine Anreicherung dieser Verunreinigungen zu vermeiden, indem man solche Schadstoffe beispielsweise durch Adsorption an feste Adsorbentien wie Aktivkohle, Molekularsiebe oder Ionenaustauscher, aus dem Isobuten-haltigen Monomerengemisch entfernt.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.
Es können, wenn auch weniger bevorzugt, auch Monomermischungen von Isobuten beziehungsweise des Isobuten-haltigen Kohlenwasserstoffgemischs mit olefinisch ungesättigten Monomeren, welche mit Isobuten copolymerisierbar sind, umgesetzt werden. Sofern Monomermischungen des Isobutens mit geeigneten Comonomeren copolymerisiert werden sollen, enthält die Monomermischung vorzugsweise wenigstens 5 Gew.-%, besonders bevorzugt wenigstens 10 Gew.-% und insbesondere wenigstens 20 Gew.-% Isobuten, und vorzugsweise höchstens 95 Gew.-%, besonders bevorzugt höchstens 90 Gew.-% und insbesondere höchstens 80 Gew.-% Comonomere.Even if less preferred, it is also possible to react monomer mixtures of isobutene or the isobutene-containing hydrocarbon mixture with olefinically unsaturated monomers which are copolymerizable with isobutene. If monomer mixtures of isobutene are to be copolymerized with suitable comonomers, 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.
In einer bevorzugten Ausführungsform weist das Stoffgemisch der Olefine (B) und optional (C) gemittelt auf ihre Stoffmengen mindestens 12 Kohlenstoffatome auf, bevorzugt mindestens 14, besonders bevorzugt mindestens 16 und ganz besonders bevorzugt mindestens 17 Kohlenstoffatome auf.In a preferred embodiment, 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.
So weist beispielsweise ein 2:3-Gemisch aus Docosen und Tetradecen einen gemittelten Wert für die Kohlenstoffatome von 0,4 x 22 + 0,6 x 14 = 17,2 auf.For example, a 2: 3 mixture of docoses and tetradecene has an average value for the carbon atoms of 0.4 x 22 + 0.6 x 14 = 17.2.
Die Obergrenze ist weniger relevant und beträgt in der Regel nicht mehr als 60 Kohlenstoffatome, bevorzugt nicht mehr als 55, besonders bevorzugt nicht mehr als 50, ganz besonders bevorzugt nicht mehr als 45 und insbesondere nicht mehr als 40 Kohlenstoffatome.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.
Das optionale Monomer (D) ist mindestens ein Monomer, bevorzugt ein bis drei, besonders bevorzugt ein oder zwei und ganz besonders bevorzugt genau ein Monomer ausgewählt aus der Gruppe bestehend aus
- (Da) Vinylestern,
- (Db) Vinylethern,
- (Dc) (Meth)acrylsäureestern von Alkoholen, die
mindestens 5 Kohlenstoffatome aufweisen, - (Dd) Allylalkoholen oder deren Ether,
- (De) N-Vinylverbindungen, ausgewählt aus der Gruppe bestehend aus Vinylverbindungen von mindestens ein Stickstoffatom enthaltenden Heterocyclen, N-Vinylamide oder N-Vinyllactame,
- (Df) ethylenisch ungesättigte Aromaten und
- (Dg) α,β -ethylenisch ungesättigte Nitrilen
- (Dh) (Meth)acrylsäureamiden und
- (Di) Allylaminen.
- (There) vinyl esters,
- (Db) vinyl ethers,
- (Dc) (meth) acrylic acid esters of alcohols which have at least 5 carbon atoms,
- (Dd) allyl alcohols or their ethers,
- (De) N-vinyl compounds selected from the group consisting of vinyl compounds of heterocycles containing at least one nitrogen atom, N-vinyl amides or N-vinyl lactams,
- (Df) ethylenically unsaturated aromatics and
- (Dg) α , β- ethylenically unsaturated nitriles
- (Dh) (meth) acrylic acid amides and
- (Di) allylamines.
Beispiele für Vinylester (Da) sind Vinylester von C2- bis C12-Carbonsäuren, bevorzugt Vinylacetat, Vinylpropionat, Vinylbutyrat, Vinylpentanoat, Vinylhexanoat, Vinyloctanoat, Vinyl-2-ethylhexanoat, Vinyldecanoat, sowie Vinylester der Versatic-Säuren 5 bis 10, bevorzugt Vinylester von 2,2-Dimethylpropionsäure (Pivalinsäure, Versatic-Säure 5), 2,2-Dimethylbuttersäure (Neohexansäure, Versatic-Säure 6), 2,2-Dimethylpentansäure (Neoheptansäure, Versatic-Säure 7), 2,2-Dimethylhexansäure (Neooctansäure, Versatic-Säure 8), 2,2-Dimethylheptansäure (Neononansäure, Versatic-Säure 9) oder 2,2-Dimethyloctansäure (Neodecansäure, Versatic-Säure 10).Examples of 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
Beispiele für Vinylether (Db) sind Vinylether von C1- bis C12-Alkanolen, bevorzugt Vinylether von Methanol, Ethanol, iso-Propanol, n-Propanol, n-Butanol, iso-Butanol, sek-Butanol, tert-Butanol, n-Hexanol, n-Heptanol, n-Octanol, n-Decanol, n-Dodecanol (Laurylalkohol) oder 2-Ethylhexanol.Examples of 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.
Bevorzugte (Meth)acrylsäureester (Dc) sind (Meth)acrylsäureester von C5- bis C12-Alkanolen, bevorzugt von n-Pentanol, n-Hexanol, n-Heptanol, n-Octanol, n-Decanol, n-Dodecanol (Laurylalkohol), 2-Ethylhexanol oder 2-Propylheptanol. Besonders bevorzugt sind Acrylsäurepentylester, Acrylsäure-2-ethylhexylester, Acrylsäure-2-propylheptylester.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.
Beispiele für Monomere (Dd) sind Allylalkohole und Allylether von C2- bis C12-Alkanolen, bevorzugt Allylether von Methanol, Ethanol, iso-Propanol, n-Propanol, n-Butanol, iso-Butanol, sek-Butanol, tert-Butanol, n-Hexanol, n-Heptanol, n-Octanol, n-Decanol, n-Dodecanol (Laurylalkohol) oder 2-Ethylhexanol.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.
Beispiele für Vinylverbindungen (De) von mindestens ein Stickstoffatom enthaltenden Heterocyclen sind N-Vinylpyridin, N-Vinylimidazol und N-Vinylmorpholin.Examples of vinyl compounds (De) of heterocycles containing at least one nitrogen atom are N-vinylpyridine, N-vinylimidazole and N-vinylmorpholine.
Bevorzugte Verbindungen (De) sind N-Vinylamide oder N-Vinyllactame:Preferred compounds (De) are N-vinylamides or N-vinyllactams:
Beispiele für N-Vinylamide oder N-Vinyllactame (De) sind N-Vinylformamid, N-Vinylacetamid, N-Vinylpyrrolidon und N-Vinylcaprolactam.Examples of N-vinylamides or N-vinyllactams (De) are N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone and N-vinylcaprolactam.
Beispiele für ethylenisch ungesättigte Aromaten (Df) sind Styrol und α -Methylstyrol.Examples of ethylenically unsaturated aromatics (Df) are styrene and α- methylstyrene.
Beispiele für α,β -ethylenisch ungesättigte Nitrile (Dg) sind Acrylnitril und Methacrylnitril.Examples of α , β- ethylenically unsaturated nitriles (Dg) are acrylonitrile and methacrylonitrile.
Beispiele für (Meth)acrylsäureamide (Dh) sind Acrylamid und Methacrylamid.Examples of (meth) acrylic acid amides (Dh) are acrylamide and methacrylamide.
Beispiele für Allylamine (Di) sind Allylamin, Dialkylallylamin und Trialkyl allylammonium halogenide.Examples of allylamines (Di) are allylamine, dialkylallylamine and trialkyl allylammonium halides.
Bevorzugte Monomere (D) sind (Da), (Db), (Dc), (De) und/oder (Df), besonders bevorzugt (Da), (Db) und/oder (Dc), ganz besonders bevorzugt (Da) und/oder (Dc) und insbesondere (Dc).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).
Das Einbauverhältnis der Monomere (A) und (B) sowie optional (C) sowie optional (D) im aus dem Reaktionsschritt (I) erhaltenen Copolymer ist in der Regel wie folgt:
Das molare Verhältnis von (A) / ((B) und (C)) (in Summe) beträgt in der Regel von 10:1 bis 1:10, bevorzugt 8:1 bis 1:8, besonders bevorzugt 5:1 bis 1:5, ganz besonders bevorzugt 3:1 bis 1:3, insbesondere 2:1 bis 1:2 und speziell 1,5:1 bis 1:1,5. Für den besonderen Fall von Maleinsäureanhydrid als Monomer (A) beträgt das molare Einbauverhältnis von Maleinsäureanhydrid zu Monomeren ((B) und (C)) (in Summe) etwa 1:1. Um einen vollständigen Umsatz des α-Olefins (B) zu erzielen kann es dennoch sinnvoll sein, Maleinsäureanhydrid in einem leichten Überschuß gegenüber dem α-Olefin einzusetzen, beispielsweise 1,01 - 1,5:1, bevorzugt 1,02 - 1,4:1, besonders bevorzugt 1,05 - 1,3:1, ganz besonders bevorzugt 1,07 - 1,2:1 und insbesondere 1,1 - 1,15:1.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. In the special case of maleic anhydride as monomer (A), the molar incorporation ratio of maleic anhydride to monomers ((B) and (C)) (in total) is about 1: 1. In order to achieve complete conversion of the α- olefin (B) it can nevertheless be useful to use maleic anhydride in a slight excess over the α- 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 in particular 1.1-1.15: 1.
Das molare Verhältnis vom obligaten Monomer (B) zum Monomer (C), soweit es anwesend ist, beträgt in der Regel von 1 : 0,05 bis 10, bevorzugt von 1 : 0,1 bis 6, besonders bevorzugt von 1 : 0,2 bis 4, ganz besonders bevorzugt von 1 : 0,3 bis 2,5 und speziell 1 : 0,5 bis 1,5.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.
In einer bevorzugten Ausführungsform ist zusätzlich zu Monomer (B) kein optionales Monomer (C) anwesend.In a preferred embodiment, no optional monomer (C) is present in addition to monomer (B).
Der Anteil an einem oder mehreren der Monomere (D), soweit vorhanden, bezogen auf die Menge der Monomere (A), (B) sowie optional (C) (in Summe) beträgt in der Regel 5 bis 200 mol%, bevorzugt 10 bis 150 mol%, besonders bevorzugt 15 bis 100 mol%, ganz besonders bevorzugt 20 bis 50 mol% und insbesondere 0 bis 25 mol%.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%.
In einer bevorzugten Ausführungsform ist kein optionales Monomer (D) anwesend.In a preferred embodiment, no optional monomer (D) is present.
In einer besonders bevorzugten Ausführungsform besteht das Copolymer aus den Monomeren (A) und (B).In a particularly preferred embodiment, the copolymer consists of monomers (A) and (B).
In einem zweiten optionalen Reaktionsschritt (II) können die im aus (I) erhaltenen Copolymer enthaltenen Anhydridfunktionalitäten teilweise hydrolysiert werden. Bevorzugt werden im Reaktionsschritt (II) Anhydridfunktionalitäten hydrolysiert und Carbonsäureesterfunktionalitäten im wesentlichen intakt gelassen.In a second optional reaction step (II), the anhydride functionalities contained in the copolymer obtained from (I) can be partially hydrolyzed. Preferably, in reaction step (II), anhydride functionalities are hydrolyzed and carboxylic acid ester functionalities are left essentially intact.
Erfindungsgemäß bleiben mehr als 90% der enthaltenen Anhydridfunktionalitäten nach dem Reaktionsschritt (II) intakt, bevorzugt mindestens 92%, besonders bevorzugt mindestens 94%, ganz besonders bevorzugt mindestens 95%, insbesondere mindestens 97% und speziell mindestens 98%.According to the invention, 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%.
Es ist möglich, daß bis zu 99,9% der enthaltenen Anhydridfunktionalitäten nach dem Reaktionsschritt (II) intakt bleiben, bevorzugt bis zu 99,8%, besonders bevorzugt bis zu 99,7%, ganz besonders bevorzugt bis zu 99,5% und insbesondere bis zu 99%.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%.
In einer bevorzugten Ausführungsform wird der Reaktionsschritt (II) nicht durchlaufen, so daß 100% der im aus Reaktionsschritt (I) erhaltenen Copolymer enthaltenen Anhydridfunktionalitäten intakt bleiben.In a preferred embodiment, 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.
Für eine Hydrolyse wird bezogen auf die enthaltenen Anhydridfunktionalitäten die Menge Wasser hinzugegeben, die dem gewünschten Hydrolysegrad entspricht und das aus (I) erhaltene Copolymer in Gegenwart des zugegebenen Wassers erwärmt. In der Regel ist dafür eine Temperatur von vorzugsweise 20 bis 150° C ausreichend, bevorzugt 60 bis 100° C. Falls erforderlich kann die Reaktion unter Druck durchgeführt werden, um das Entweichen von Wasser zu verhindern. Unter diesen Reaktionsbedingungen werden in der Regel selektiv die Anhydridfunktionalitäten im Copolymer umgesetzt, wohingegen etwaige im Copolymer enthaltene Carbonsäureesterfunktionalitäten nicht oder zumindest nur untergeordnet reagieren.For a hydrolysis, based on the anhydride functionalities present, 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. As a rule, a temperature of preferably 20 to 150 ° C., preferably 60 to 100 ° C., is sufficient for this. If necessary, 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.
Sollten die aus Schritt (II) erhaltenen Copolymere noch Reste von Säureanionen enthalten, so kann es bevorzugt sein, diese Säureanionen mit Hilfe eines lonentauschers aus dem Copolymer zu entfernen und bevorzugt gegen Hydroxidionen oder Carboxylationen, besonders bevorzugt Hydroxidionen auszutauschen. Dies ist insbesondere dann der Fall, wenn die im Copolymer enthaltenen Säureanionen Halogenide, schwefelhaltig oder stickstoffhaltig sind. Das aus Reaktionsschritt (II) erhaltene Copolymer weist in der Regel ein gewichtsmittleres Molekulargewicht Mw von 0,5 bis 20 kDa auf, bevorzugt 0,6 bis 15, besonders bevorzugt 0,7 bis 7, ganz besonders bevorzugt 1 bis 7 und insbesondere 1,5 bis 54 kDa auf (bestimmt durch Gelpermeationschromatographie mit Tetrahydrofuran und Polystyrol als Standard).If 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).
Das zahlenmittlere Molekulargewicht Mn beträgt zumeist von 0,5 bis 10 kDa, bevorzugt 0,6 bis 5, besonders bevorzugt 0,7 bis 4, ganz besonders bevorzugt 0,8 bis 3 und insbesondere 1 bis 2 kDa auf (bestimmt durch Gelpermeationschromatographie mit Tetrahydrofuran und Polystyrol als Standard).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).
Die Polydispersität beträgt in der Regel von 1 bis 10, bevorzugt von 1,1 bis 8, besonders bevorzugt von 1,2 bis 7, ganz besonders bevorzugt von 1,3 bis 5 und insbesondere von 1,5 bis 3.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.
Der Gehalt an freien Säuregruppen im Copolymer nach Durchlaufen des Reaktionsschrittes (II) beträgt bevorzugt weniger als 5 mmol/g Copolymer, besonders bevorzugt weniger als 3, ganz besonders bevorzugt weniger als 2 mmol/g Copolymer und insbesondere weniger als 1 mmol/g.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.
In einer bevorzugten Ausführungsform enthalten die Copolymere einen hohen Anteil an benachbarten Carbonsäuregruppen, was durch eine Messung der Adjazenz (engl. Adjacency) bestimmt wird. Dazu wird eine Probe des Copolymers für eine Dauer von 30 Minuten bei einer Temperatur von 290° C zwischen zwei Teflonfolien getempert und an einer blasenfreien Stelle ein FTIR Spektrum aufgenommen. Von den erhaltenen Spektren wird das IR-Spektrum von Teflon subtrahiert, die Schichtdicke bestimmt und der Gehalt an cyclischem Anhydrid bestimmt.In a preferred embodiment, 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.
In einer bevorzugten Ausführungsform beträgt die Adjazenz mindestens 10 %, bevorzugt mindestens 15%, besonders bevorzugt mindestens 20%, ganz besonders bevorzugt mindestens 25% und insbesondere mindestens 30%.In a preferred embodiment, 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%.
Der mit dem erfindungsgemäßen Copolymer additivierte Kraftstoff ist ein Ottokraftstoff oder insbesondere ein Mitteldestillat-Kraftstoff, vor allem ein Dieselkraftstoff.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.
Der Kraftstoff kann weitere übliche Additive zur Wirksamkeitsverbesserung und/oder Verschleißunterdrückung enthalten.The fuel can contain other customary additives to improve effectiveness and / or suppress wear.
Häufig werden die beschriebenen Copolymere in Form von Kraftstoffadditivgemischen eingesetzt, zusammen mit üblichen Additiven:
Im Falle von Dieselkraftstoffen sind dies in erster Linie übliche Detergenz-Additive, Trägeröle, Kaltfließverbesserer, Schmierfähigkeitsverbesserer (Lubricity Improver), andere Korrosionsinhibitoren als die beschriebenen Copolymere, Demulgatoren, Dehazer, Antischaummittel, Cetanzahlverbesserer, Verbrennungsverbesserer, Antioxidantien oder Stabilisatoren, Antistatika, Metallocene, Metalldeaktivatoren, Farbstoffe und/oder Lösungsmittel.The 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.
Demgemäß ist ein weiterer Gegenstand der Erfindung die Verwendung von Copolymeren, erhältlich durch
- in einem ersten Reaktionsschritt (I) Copolymerisation von
- (A) mindestens einem Anhydrid einer ethylenisch ungesättigten Dicarbonsäure,
- (B) mindestens einem α-Olefin
mit von mindestens 12bis zu einschließlich 30 Kohlenstoffatomen, - (C) optional mindestens einem weiteren,
mindestens 4 Kohlenstoffatome aufweisenden, aliphatischen oder cycloaliphatischen Olefin, das ein anderes als (B) ist und - (D) optional eines oder mehrerer weiterer copolymerisierbarer Monomere, die verschieden von den Monomeren (A), (B) und (C) sind, ausgewählt aus der Gruppe bestehend aus (Da) Vinylestern,
- (Db) Vinylethern,
- (Dc) (Meth)acrylsäureestern von Alkoholen, die
mindestens 5 Kohlenstoffatome aufweisen, - (Dd) Allylalkoholen oder deren Ether,
- (De) N-Vinylverbindungen, ausgewählt aus der Gruppe bestehend aus Vinylverbindungen von mindestens ein Stickstoffatom enthaltenden Heterocyclen, N-Vinylamide oder N-Vinyllactame,
- (Df) ethylenisch ungesättigte Aromaten
- (Dg) α,β -ethylenisch ungesättigte Nitrilen,
- (Dh) (Meth)acrylsäureamiden und
- (Di) Allylaminen,
- in einem zweiten optionalen Reaktionsschritt (II) teilweise Hydrolyse der im aus (I) erhaltenen Copolymer enthaltenen Anhydridfunktionalitäten, mit der Maßgabe, daß mehr als 90% der enthaltenen Anhydridfunktionalitäten nach dem Reaktionsschritt (II) intakt bleiben, in Additivpaketen, enthaltend mindestens ein Additiv ausgewählt aus der Gruppe bestehend aus Detergenz-Additiven, Trägerölen, Kaltfließverbesserern, Schmierfähigkeitsverbesserern (Lubricity Improver), andere Korrosionsinhibitoren als die beschriebenen Copolymere, Demulgatoren, Dehazern, Antischaummitteln, Cetanzahlverbesserern, Verbrennungsverbesserern, Antioxidantien, Stabilisatoren, Antistatika, Metallocenen, Metalldeaktivatoren, Farbstoffen und Lösungsmitteln, zur Verringerung des Kraftstoffverbrauches von direkteinspritzenden Dieselmotoren, insbesondere von Dieselmotoren mit Common-Rail-Einspritzsystemen und/oder zur Minimierung des Leistungsverlustes (powerloss) in direkteinspritzenden Dieselmotoren, insbesondere in Dieselmotoren mit Common-Rail-Einspritzsystemen.
- in a first reaction step (I) copolymerization of
- (A) at least one anhydride of an ethylenically unsaturated dicarboxylic acid,
- (B) at least one α- olefin having from at least 12 up to and including 30 carbon atoms,
- (C) optionally at least one further aliphatic or cycloaliphatic olefin which has at least 4 carbon atoms and which is other than (B) and
- (D) optionally one or more further copolymerizable monomers, which are different from the monomers (A), (B) and (C), selected from the group consisting of (Da) vinyl esters,
- (Db) vinyl ethers,
- (Dc) (meth) acrylic acid esters of alcohols which have at least 5 carbon atoms,
- (Dd) allyl alcohols or their ethers,
- (De) N-vinyl compounds selected from the group consisting of vinyl compounds of heterocycles containing at least one nitrogen atom, N-vinyl amides or N-vinyl lactams,
- (Df) ethylenically unsaturated aromatics
- (Dg) α , β -ethylenically unsaturated nitriles,
- (Dh) (meth) acrylic acid amides and
- (Di) allylamines,
- in a second optional reaction step (II) partial hydrolysis of the anhydride functionalities contained in the copolymer obtained from (I), with the proviso that more than 90% of the anhydride functionalities contained remain intact after reaction step (II), selected in additive packages containing at least one additive from the group consisting of detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors other than the copolymers described, demulsifiers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants, stabilizers, antistatic agents, metallocenes, to reduce the fuel consumption of direct injection diesel engines, in particular of diesel engines with common rail injection systems and / or to minimize the power loss in direct injection diesel engines, in particular in die selmotoren with common rail injection systems.
Im Falle von Ottokraftstoffen sind dies vor allem Schmierfähigkeitsverbesserer (Friction Modifier), andere Korrosionsinhibitoren als die beschriebenen Copolymere, Demulgatoren, Dehazer, Antischaummittel, Verbrennungsverbesserer, Antioxidantien oder Stabilisatoren, Antistatika, Metallocene, Metalldeaktivatoren, Farbstoffe und/oder Lösungsmittel.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.
Demgemäß ist ein weiterer Gegenstand der Erfindung die Verwendung von Copolymeren, erhältlich durch
- in einem ersten Reaktionsschritt (I) Copolymerisation von
- (A) mindestens einem Anhydrid einer ethylenisch ungesättigten Dicarbonsäure,
- (B) mindestens einem α-Olefin
mit von mindestens 12bis zu einschließlich 30 Kohlenstoffatomen, - (C) optional mindestens einem weiteren,
mindestens 4 Kohlenstoffatome aufweisenden, aliphatischen oder cycloaliphatischen Olefin, das ein anderes als (B) ist und - (D) optional eines oder mehrerer weiterer copolymerisierbarer Monomere, die verschieden von den Monomeren (A), (B) und (C) sind, ausgewählt aus der Gruppe bestehend aus
- (Da) Vinylestern,
- (Db) Vinylethern,
- (Dc) (Meth)acrylsäureestern von Alkoholen, die
mindestens 5 Kohlenstoffatome aufweisen, - (Dd) Allylalkoholen oder deren Ether,
- (De) N-Vinylverbindungen, ausgewählt aus der Gruppe bestehend aus Vinylverbindungen von mindestens ein Stickstoffatom enthaltenden Heterocyclen, N-Vinylamide oder N-Vinyllactame,
- (Df) ethylenisch ungesättigte Aromaten
- (Dg) α,β -ethylenisch ungesättigte Nitrilen,
- (Dh) (Meth)acrylsäureamiden und
- (Di) Allylaminen,
- in einem zweiten optionalen Reaktionsschritt (II) teilweise Hydrolyse der im aus (I) erhaltenen Copolymer enthaltenen Anhydridfunktionalitäten, mit der Maßgabe, daß mehr als 90% der enthaltenen Anhydridfunktionalitäten nach dem Reaktionsschritt (II) intakt bleiben, in Additivpaketen, enthaltend mindestens ein Additiv ausgewählt aus der Gruppe bestehend aus Schmierfähigkeitsverbesserern (Friction Modifier), andere Korrosionsinhibitoren als die beschriebenen Copolymere, Demulgatoren, Dehazern, Antischaummitteln, Verbrennungsverbesserern, Antioxidantien, Stabilisatoren, Antistatika, Metallocenen, Metalldeaktivatoren, Farbstoffen und Lösungsmitteln, zur Verringerung von Ablagerungen im Einlasssystem eines Ottomotors, wie insbesondere DISI und PFI (Port Fuel Injector) -Motoren.
- in a first reaction step (I) copolymerization of
- (A) at least one anhydride of an ethylenically unsaturated dicarboxylic acid,
- (B) at least one α- olefin having from at least 12 up to and including 30 carbon atoms,
- (C) optionally at least one further aliphatic or cycloaliphatic olefin which has at least 4 carbon atoms and which is other than (B) and
- (D) optionally one or more further copolymerizable monomers, which are different from the monomers (A), (B) and (C), selected from the group consisting of
- (There) vinyl esters,
- (Db) vinyl ethers,
- (Dc) (meth) acrylic acid esters of alcohols which have at least 5 carbon atoms,
- (Dd) allyl alcohols or their ethers,
- (De) N-vinyl compounds selected from the group consisting of vinyl compounds of heterocycles containing at least one nitrogen atom, N-vinyl amides or N-vinyl lactams,
- (Df) ethylenically unsaturated aromatics
- (Dg) α , β -ethylenically unsaturated nitriles,
- (Dh) (meth) acrylic acid amides and
- (Di) allylamines,
- in a second optional reaction step (II) partial hydrolysis of the anhydride functionalities contained in the copolymer obtained from (I), with the proviso that more than 90% of the anhydride functionalities contained remain intact after reaction step (II), selected in additive packages containing at least one additive from the group consisting of lubricity improvers (friction modifiers), corrosion inhibitors other than the copolymers described, demulsifiers, dehazers, antifoam agents, combustion improvers, antioxidants, stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and solvents, to reduce deposits in the intake system of a gasoline engine, such as especially DISI and PFI (Port Fuel Injector) engines.
Typische Beispiele geeigneter Co-Additive sind im folgenden Abschnitt aufgeführt:
B1) Detergenz-AdditiveTypical examples of suitable co-additives are listed in the following section:
B1) detergent additives
Vorzugsweise handelt es sich bei den üblichen Detergenz-Additiven um amphiphile Substanzen, die mindestens einen hydrophoben Kohlenwasserstoffrest mit einem zahlengemittelten Molekulargewicht (Mn) von 85 bis 20.000 und mindestens eine polare Gruppierung besitzen, die ausgewählt ist unter:
- (Da) Mono- oder Polyaminogruppen
mit bis zu 6 Stickstoffatomen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat; - (Db) Nitrogruppen, gegebenenfalls in Kombination mit Hydroxylgruppen;
- (Dc) Hydroxylgruppen in Kombination mit Mono- oder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat;
- (Dd) Carboxylgruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen;
- (De) Sulfonsäuregruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen;
- (Df) Polyoxy-C2- bis C4-alkylengruppierungen, die durch Hydroxylgruppen, Monooder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat, oder durch Carbamatgruppen terminiert sind;
- (Dg) Carbonsäureestergruppen;
- (Dh) aus Bernsteinsäureanhydrid abgeleiteten Gruppierungen mit Hydroxy-und/oder Amino- und/oder Amido- und/oder Imidogruppen; und/oder
- (Di) durch Mannich-Umsetzung von substituierten Phenolen mit Aldehyden und Mono- oder Polyaminen erzeugten Gruppierungen.
- (Da) mono- or polyamino groups with up to 6 nitrogen atoms, at least one nitrogen atom having basic properties;
- (Db) nitro groups, optionally in combination with hydroxyl groups;
- (Dc) hydroxyl groups in combination with mono- or polyamino groups, at least one nitrogen atom having basic properties;
- (Dd) carboxyl groups or their alkali metal or alkaline earth metal salts;
- (De) sulfonic acid groups or their alkali metal or alkaline earth metal salts;
- (Df) polyoxy-C 2 - to C 4 -alkylene groups which are terminated by hydroxyl groups, mono or polyamino groups, at least one nitrogen atom having basic properties, or by carbamate groups;
- (Dg) carboxylic acid ester groups;
- (Ie) groups derived from succinic anhydride and having hydroxyl and / or amino and / or amido and / or imido groups; and or
- (Di) groups produced by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines.
Der hydrophobe Kohlenwasserstoffrest in den obigen Detergenz-Additiven, welcher für die ausreichende Löslichkeit im Kraftstoff sorgt, hat ein zahlengemitteltes Molekulargewicht (Mn) von 85 bis 20.000, vorzugsweise von 113 bis 10.000, besonders bevorzugt von 300 bis 5.000, stärker bevorzugt von 300 bis 3.000, noch stärker bevorzugt von 500 bis 2.500 und insbesondere von 700 bis 2.500, vor allem von 800 bis 1500. Als typischer hydrophober Kohlenwasserstoffrest, insbesondere in Verbindung mit den polaren insbesondere Polypropenyl-, Polybutenyl- und Polyisobutenylreste mit einem zahlenmittleren Molekulargewicht Mn von vorzugsweise jeweils 300 bis 5.000, besonders bevorzugt 300 bis 3.000, stärker bevorzugt 500 bis 2.500 noch stärker bevorzugt 700 bis 2.500 und insbesondere 800 bis 1.500 in Betracht.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. As 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.
Als Beispiele für obige Gruppen von Detergenz-Additiven seien die folgenden genannt:
Mono- oder Polyaminogruppen (Da) enthaltende Additive sind vorzugsweise Polyalkenmono- oder Polyalkenpolyamine auf Basis von Polypropen oder von hochreaktivem (d.h. mit überwiegend endständigen Doppelbindungen) oder konventionellem (d.h. mit überwiegend mittenständigen Doppelbindungen) Polybuten oder Polyisobuten mit Mn = 300 bis 5000, besonders bevorzugt 500 bis 2500 und insbesondere 700 bis 2500. Derartige Additive auf Basis von hochreaktivem Polyisobuten, welche aus dem Polyisobuten, das bis zu 20 Gew.-% n-Buten-Einheiten enthalten kann, durch Hydroformylierung und reduktive Aminierung mit Ammoniak, Monoaminen oder Polyaminen wie Dimethyl-aminopropylamin, Ethylendiamin, Diethylentriamin, Triethylentetramin oder Tetraethylenpentamin hergestellt werden können, sind insbesondere aus der
Additives containing mono- or polyamino groups (Da) are preferably polyalkene mono- or polyalkene polyamines based on polypropene or highly reactive (i.e. with predominantly terminal double bonds) or conventional (i.e. predominantly central double bonds) polybutene or polyisobutene with M n = 300 to 5000, particularly preferably 500 to 2500 and in particular 700 to 2500. Such additives based on highly reactive polyisobutene, which from the polyisobutene, which can contain up to 20 wt .-% n-butene units, by hydroformylation and reductive amination with ammonia, monoamines or Polyamines such as dimethyl aminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine can be prepared in particular from the
Weitere besondere Monoaminogruppen (Da) enthaltende Additive sind die Hydrierungsprodukte der Umsetzungsprodukte aus Polyisobutenen mit einem mittleren Polymerisationsgrad P = 5 bis 100 mit Stickoxiden oder Gemischen aus Stickoxiden und Sauerstoff, wie sie insbesondere in der
Weitere besondere Monoaminogruppen (Da) enthaltende Additive sind die aus Polyisobutenepoxiden durch Umsetzung mit Aminen und nachfolgender Dehydratisierung und Reduktion der Aminoalkohole erhältlichen Verbindungen, wie sie insbesondere in der
Nitrogruppen (Db), gegebenenfalls in Kombination mit Hydroxylgruppen, enthaltende Additive sind vorzugsweise Umsetzungsprodukte aus Polyisobutenen des mittleren Polymerisationsgrades P = 5 bis 100 oder 10 bis 100 mit Stickoxiden oder Gemischen aus Stickoxiden und Sauerstoff, wie sie insbesondere in der
Hydroxylgruppen in Kombination mit Mono- oder Polyaminogruppen (Dc) enthaltende Additive sind insbesondere Umsetzungsprodukte von Polyisobutenepoxiden, erhältlich aus vorzugsweise überwiegend endständige Doppelbindungen aufweisendem Polyisobuten mit Mn = 300 bis 5000 mit Ammoniak, Mono- oder Polyaminen, wie sie insbeson-dere in der
Carboxylgruppen oder deren Alkalimetall- oder Erdalkalimetallsalze (Dd) enthaltende Additive sind vorzugsweise Copolymere von C2- bis C40-Olefinen mit Maleinsäureanhydrid mit einer Gesamt-Molmasse von 500 bis 20.000, deren Carboxylgruppen ganz oder teilweise zu den Alkalimetall- oder Erdalkalimetallsalzen und ein verbleibender Rest der Carboxylgruppen mit Alkoholen oder Aminen umgesetzt sind. Solche Additive sind insbesondere aus der
Sulfonsäuregruppen oder deren Alkalimetall- oder Erdalkalimetallsalze (De) enthaltende Additive sind vorzugsweise Alkalimetall- oder Erdalkalimetallsalze eines Sulfobernsteinsäurealkylesters, wie er insbesondere in der
Polyoxy-C2-C4-alkylengruppierungen (Df) enthaltende Additive sind vorzugsweise Polyether oder Polyetheramine, welche durch Umsetzung von C2- bis C60-Alkanolen, C6- bis C30-Alkandiolen, Mono- oder Di-C2- bis C30-alkylaminen, C1- bis C30-Alkylcyclo-hexanolen oder C1- bis C30-Alkylphenolen mit 1 bis 30 mol Ethylenoxid und/oder Propylenoxid und/oder Butylenoxid pro Hydroxylgruppe oder Aminogruppe und, im Falle der Polyetheramine, durch anschließende reduktive Aminierung mit Ammoniak, Monoaminen oder Polyaminen erhältlich sind. Derartige Produkte werden insbesondere in der
Carbonsäureestergruppen (Dg) enthaltende Additive sind vorzugsweise Ester aus Mo-no-, Di- oder Tricarbonsäuren mit langkettigen Alkanolen oder Polyolen, insbesondere solche mit einer Mindestviskosität von 2 mm2/s bei 100 ° C, wie sie insbesondere in der
Aus Bernsteinsäureanhydrid abgeleitete Gruppierungen mit Hydroxy- und/oder Amino-und/oder Amido- und/oder insbesondere Imidogruppen (Dh) enthaltende Additive sind vorzugsweise entsprechende Derivate von Alkyl- oder Alkenyl-substituiertem Bernsteinsäureanhydrid und insbesondere die entsprechenden Derivate von Polyisobutenylbernsteinsäureanhydrid, welche durch Umsetzung von konventionellem oder hochreaktivem Polyisobuten mit Mn = vorzugsweise 300 bis 5000, besonders bevorzugt 300 bis 3000, stärker bevorzugt 500 bis 2500, noch stärker bevorzugt 700 bis 2500 und insbesondere 800 bis 1500, mit Maleinsäureanhydrid auf thermischem Weg in einer En-Reaktion oder über das chlorierte Polyisobuten erhältlich sind. Bei den Gruppierungen mit Hydroxy- und/oder Amino- und/oder Amido- und/oder Imidogruppen handelt es sich beispielsweise um Carbonsäuregruppen, Säureamide von Monoaminen, Säure-amide von Di- oder Polyaminen, die neben der Amidfunktion noch freie Amingruppen aufweisen, Bernsteinsäurederivate mit einer Säure- und einer Amidfunktion, Carbonsäureimide mit Monoaminen, Carbonsäureimide mit Di- oder Polyaminen, die neben der Imidfunktion noch freie Amingruppen aufweisen, oder Diimide, die durch die Umsetzung von Di- oder Polyaminen mit zwei Bernsteinsäurederivaten gebildet werden. Derartige Kraftstoffadditive sind allgemein bekannt und beispielsweise in den Dokumenten (1) und (2) beschrieben. Bevorzugt handelt es sich um die Umsetzungsprodukte von Alkyl- oder Alkenyl-substituierten Bernsteinsäuren oder Derivaten davon mit Aminen und besonders bevorzugt um die Umsetzungsprodukte von Polyisobutenyl-substituierten Bernsteinsäuren oder Derivaten davon mit Aminen. Von besonderem Interesse sind hierbei Umsetzungsprodukte mit aliphatischen Polyaminen (Polyalkylenimine) wie insbesondere Ethylendiamin, Diethylentriamin, Triethylentetramin, Tetraethylenpentamin, Pentaethylenhexamin und Hexaethylenheptamin, welche eine Imidstruktur aufweisen.Groups derived from succinic anhydride with hydroxyl and / or amino and / or amido and / or in particular imido groups (Dh) containing additives are preferably corresponding derivatives of alkyl- or alkenyl-substituted succinic anhydride and in particular the corresponding derivatives of polyisobutenylsuccinic anhydride, which by reaction of conventional or highly reactive polyisobutene with M n = preferably 300 to 5000, particularly preferably 300 to 3000, more preferably 500 to 2500, even more preferably 700 to 2500 and in particular 800 to 1500, with maleic anhydride by thermal means in an ene reaction or above the chlorinated polyisobutene are available. 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). They are preferably the reaction products of alkyl- or alkenyl-substituted succinic acids or derivatives thereof with amines and particularly preferably the reaction products of polyisobutenyl-substituted succinic acids or derivatives thereof with amines. Of particular interest here are reaction products with aliphatic polyamines (polyalkyleneimines) such as, in particular, ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine and hexaethylene heptamine, which have an imide structure.
In einer bevorzugten Ausführungsform können die erfindungsgemäßen Verbindungen kombiniert werden mit quaternisierten Verbindungen, wie beschrieben in
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In einer weiteren bevorzugten Ausführungsform können die erfindungsgemäßen Verbindungen kombiniert werden mit quaternisierten Verbindungen, wie beschrieben in
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Durch Mannich-Umsetzung von substituierten Phenolen mit Aldehyden und Mono- oder Polyaminen erzeugte Gruppierungen (Di) enthaltende Additive sind vorzugsweise Umsetzungsprodukte von Polyisobuten-substituierten Phenolen mit Formaldehyd und Mono- oder Polyaminen wie Ethylendiamin, Diethylentriamin, Triethylentetramin, Tetra-ethylenpentamin oder Dimethylaminopropylamin. Die Polyisobutenyl-substituierten Phenole können aus konventionellem oder hochreaktivem Polyisobuten mit Mn = 300 bis 5000 stammen. Derartige "Polyisobuten-Mannichbasen" sind insbesondere in der
Dem Kraftstoff können ein oder mehrere der genannten Detergenz-Additive in solch einer Menge zugegeben werden, dass die Dosierrate an diesen Detergenz-Additiven vozugsweise 25 bis 2500 Gew.-ppm, insbesondere 75 bis 1500 Gew.-ppm, vor allem 150 bis 1000 Gew.-ppm, beträgt. B2) TrägeröleOne 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
Mitverwendete Trägeröle können mineralischer oder synthetischer Natur sein. Geeignete mineralische Trägeröle sind bei der Erdölverarbeitung anfallende Fraktionen, wie Brightstock oder Grundöle mit Viskositäten wie beispielsweise aus der Klasse SN 500 bis 2000, aber auch aromatische Kohlenwasserstoffe, paraffinische Kohlenwasserstoffe und Alkoxyalkanole. Brauchbar ist ebenfalls eine als "hydrocrack oil" bekannte und bei der Raffination von Mineralöl anfallende Fraktion (Vakuumdestillatschnitt mit einem Siedebereich von etwa 360 bis 500 ° C, erhältlich aus unter Hochdruck katalytisch hydriertem und isomerisiertem sowie entparaffiniertem natürlichen Mineralöl). Ebenfalls geeignet sind Mischungen oben genannter mineralischer Trägeröle.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.
Beispiele für geeignete synthetische Trägeröle sind Polyolefine (Polyalphaolefine oder Polyinternalolefine), (Poly)ester, Poly)alkoxylate, Polyether, aliphatische Polyetheramine, alkylphenolgestartete Polyether, alkylphenolgestartete Polyetheramine und Carbonsäureester langkettiger Alkanole.Examples of 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.
Beispiele für geeignete Polyolefine sind Olefinpolymerisate mit Mn = 400 bis 1800, vor allem auf Polybuten- oder Polyisobuten-Basis (hydriert oder nicht hydriert).Examples of suitable polyolefins are olefin polymers with M n = 400 to 1800, especially based on polybutene or polyisobutene (hydrogenated or non-hydrogenated).
Beispiele für geeignete Polyether oder Polyetheramine sind vorzugsweise Polyoxy-C2- bis C4-alkylengruppierungen enthaltende Verbindungen, welche durch Umsetzung von C2- bis C60-Alkanolen, C6- bis C30-Alkandiolen, Mono- oder Di-C2- bis C30-alkylaminen, C1- bis C30-Alkyl-cyclohexanolen oder C1- bis C30-Alkylphenolen mit 1 bis 30 mol Ethylenoxid und/ oder Propylenoxid und/oder Butylenoxid pro Hydroxylgruppe oder Amino-gruppe und, im Falle der Polyetheramine, durch anschließende reduktive Aminierung mit Ammoniak, Monoaminen oder Polyaminen erhältlich sind. Derartige Produkte werden insbesondere in der
Beispiele für Carbonsäureester langkettiger Alkanole sind insbesondere Ester aus Mono-, Di- oder Tricarbonsäuren mit langkettigen Alkanolen oder Polyolen, wie sie insbesondere in der
Weitere geeignete Trägerölsysteme sind beispielsweise in der
Beispiele für besonders geeignete synthetische Trägeröle sind alkoholgestartete Polyether mit etwa 5 bis 35, vorzugsweise etwa 5 bis 30, besonders bevorzugt 10 bis 30 und insbesondere 15 bis 30 C3- bis C6-Alkylenoxideinheiten, z. B. Propylenoxid-, n-Butylenoxid- und Isobutylenoxid-Einheiten oder Gemischen davon, pro Alkoholmolekül. Nichtlimitierende Beispiele für geeignete Starteralkohole sind langkettige Alkanole oder mit langkettigem Alkylsubstituierte Phenole, wobei der langkettige Alkylrest insbesondere für einen geradkettigen oder verzweigten C6- bis C18-Alkylrest steht. Als besondere Beispiele sind zu nennen Tridecanol und Nonylphenol. Besonders bevorzugte alkoholgestartete Polyether sind die Umsetzungsprodukte (Polyveretherungsprodukte) von einwertigen aliphatischen C6- bis C18-Alkoholen mit C3- bis C6-Alkylenoxiden. Beispiele für einwertige aliphatische C6-C18-Alkohole sind Hexanol, Heptanol, Octanol, 2-Ethyl-hexanol, Nonylalkohol, Decanol, 3-Propylheptanol, Undecanol, Dodecanol, Tridecanol, Tetradecanol, Pentadecanol, Hexadecanol, Octadecanol und deren Konstitutions- und Stellungsisomere. Die Alkohole können sowohl in Form der reinen Isomere als auch in Form technischer Gemische eingesetzt werden. Ein besonders bevorzugter Alkohol ist Tridecanol. Beispiele für C3- bis C6-Alkylenoxide sind Propylenoxid, wie 1,2-Propylen-oxid, Butylenoxid, wie 1,2-Butylenoxid, 2,3-Butylenoxid, Isobutylenoxid oder Tetrahydrofuran, Pentylenoxid und Hexylenoxid. Besonders bevorzugt sind hierunter C3- bis C4-Alkylenoxide, d.h. Propylenoxid wie 1,2-Propylenoxid und Butylenoxid wie 1,2-Buty-lenoxid, 2,3-Butylenoxid und Isobutylenoxid. Speziell verwendet man Butylenoxid.Examples of 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. Non-limiting examples of 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. Examples of 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.
Weitere geeignete synthetische Trägeröle sind alkoxylierte Alkylphenole, wie sie in der
Besondere Trägeröle sind synthetische Trägeröle, wobei die zuvor beschriebenen alkoholgestarteten Polyether besonders bevorzugt sind.Special carrier oils are synthetic carrier oils, the alcohol-initiated polyethers described above being particularly preferred.
Das Trägeröl bzw. das Gemisch verschiedener Trägeröle wird dem Kraftstoff in einer Menge von vorzugsweise 1 bis 1000 Gew.-ppm, besonders bevorzugt von 10 bis 500 Gew.-ppm und insbesondere von 20 bis 100 Gew.-ppm zugesetzt.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.
Geeignete Kaltfließverbesserer sind im Prinzip alle organischen Verbindungen, welche in der Lage sind, das Fließverhalten von Mitteldestillat-Kraftstoffen bzw. Dieselkraftstoffen in der Kälte zu verbessern. Zweckmäßigerweise müssen sie eine ausreichende Öllöslichkeit aufweisen. Insbesondere kommen hierfür die üblicherweise bei Mitteldestillaten aus fossilem Ursprung, also bei üblichen mineralischen Dieselkraftstoffen, eingesetzten Kaltfließverbesserer ("middle distillate flow improvers", "MDFI") in Betracht. Jedoch können auch organische Verbindungen verwendet werden, die beim Einsatz in üblichen Dieselkraftstoffen zum Teil oder überwiegend die Eigenschaften eines Wax Anti-Settling Additivs ("WASA") aufweisen. Auch können sie zum Teil oder überwiegend als Nukleatoren wirken. Es können aber auch Mischungen aus als MDFI wirksamen und/oder als WASA wirksamen und/oder als Nukleatoren wirksamen organischen Verbindungen eingesetzt werden.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. In particular, 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. However, 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. However, it is also possible to use mixtures of organic compounds that are effective as MDFI and / or that are effective as WASA and / or that are effective as nucleators.
Typischerweise wird der Kaltfließverbesserer ausgewählt aus:
- (K1) Copolymeren eines C2- bis C40-Olefins mit wenigstens einem weiteren ethylenisch ungesättigten Monomer;
- (K2) Kammpolymeren;
- (K3) Polyoxyalkylenen;
- (K4) polaren Stickstoffverbindungen;
- (K5) Sulfocarbonsäuren oder Sulfonsäuren oder deren Derivaten; und
- (K6) Poly(meth)acrylsäureestern.
- (K1) copolymers of a C 2 to C 40 olefin with at least one further ethylenically unsaturated monomer;
- (K2) comb polymers;
- (K3) polyoxyalkylenes;
- (K4) polar nitrogen compounds;
- (K5) sulfocarboxylic acids or sulfonic acids or their derivatives; and
- (K6) poly (meth) acrylic acid esters.
Es können sowohl Mischungen verschiedener Vertreter aus einer der jeweiligen Klassen (K1) bis (K6) als auch Mischungen von Vertretern aus verschiedenen Klassen (K1) bis (K6) eingesetzt werden.Both mixtures of different representatives from one of the respective classes (K1) to (K6) and mixtures of representatives from different classes (K1) to (K6) can be used.
Geeignete C2- bis C40-Olefin-Monomere für die Copolymeren der Klasse (K1) sind beispielsweise solche mit 2 bis 20, insbesondere 2 bis10 Kohlenstoffatomen sowie mit 1 bis 3, vorzugsweise mit 1 oder 2, insbesondere mit einer Kohlenstoff-Kohlenstoff-Doppelbindung. Im zuletzt genannten Fall kann die Kohlenstoff-Kohlenstoff-Doppelbindung sowohl terminal (α-Olefine) als auch intern angeordnet sein kann. Bevorzugt sind jedoch α -Olefine, besonders bevorzugt α-Olefine mit 2 bis 6 Kohlenstoffatomen, beispielsweise Propen, 1-Buten, 1-Penten, 1-Hexen und vor allem Ethylen.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. In the last-mentioned case, the carbon-carbon double bond can be arranged both terminally (α- olefins) and internally. However, preference is given to α- olefins, particularly preferably α- olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene and, above all, ethylene.
Bei den Copolymeren der Klasse (K1) ist das wenigstens eine weitere ethylenisch ungesättigte Monomer vorzugsweise ausgewählt unter Carbonsäurealkenylestern, (Meth)Acrylsäureestern und weiteren Olefinen.In the copolymers of class (K1), the at least one further ethylenically unsaturated monomer is preferably selected from alkenyl carboxylates, (meth) acrylic acid esters and further olefins.
Werden weitere Olefine mit einpolymerisiert, sind dies vorzugsweise höhermolekulare als das oben genannte C2- bis C40-Olefin-Basismonomere. Setzt man beispielsweise als Olefin-Basismonomer Ethylen oder Propen ein, eignen sich als weitere Olefine insbesondere C10-bis C40- α-Olefine. Weitere Olefine werden in den meisten Fällen nur dann mit einpolymerisiert, wenn auch Monomere mit Carbonsäureester-Funktionen eingesetzt werden.If 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 α- olefins. In most cases, other olefins are only also incorporated into the polymerization when monomers with carboxylic acid ester functions are also used.
Geeignete (Meth)Acrylsäureester sind beispielsweise Ester der (Meth)Acrylsäure mit C1-bis C20-Alkanolen, insbesondere C1- bis C10-Alkanolen, vor allem mit Methanol, Ethanol, Propanol, Isopropanol, n-Butanol, sec.-Butanol, Isobutanol, tert.-Butanol, Pentanol, Hexanol, Heptanol, Octanol, 2-Ethylhexanol, Nonanol und Decanol sowie Strukturisomeren hiervon.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.
Geeignete Carbonsäurealkenylester sind beispielsweise C2- bis C14-Alkenylester, z.B. die Vinyl- und Propenylester, von Carbonsäuren mit 2 bis 21 Kohlenstoffatomen, deren Kohlenwasserstoffrest linear oder verzweigt sein kann. Bevorzugt sind hierunter die Vinylester. Unter den Carbonsäuren mit verzweigtem Kohlenwasserstoffrest sind solche bevorzugt, deren Verzweigung sich in der α-Position zur Carboxylgruppe befindet, wobei das α-Kohlenstoffatom besonders bevorzugt tertiär ist, d. h. die Carbonsäure eine sogenannte Neocarbonsäure ist. Vorzugsweise ist der Kohlenwasserstoffrest der Carbonsäure jedoch linear.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. Among the carboxylic acids with a branched hydrocarbon radical, preference is given to those whose branches are in the α-position to the carboxyl group, the α-carbon atom being particularly preferably tertiary, ie the carboxylic acid being what is known as a neocarboxylic acid. However, the hydrocarbon radical of the carboxylic acid is preferably linear.
Beispiele für geeignete Carbonsäurealkenylester sind Vinylacetat, Vinylpropionat, Vinylbutyrat, Vinyl-2-ethylhexanoat, Neopentansäurevinylester, Hexansäurevinylester, Neononansäurevinylester, Neodecansäurevinylester und die entsprechenden Propenylester, wobei die Vinylester bevorzugt sind. Ein besonders bevorzugter Carbonsäurealkenylester ist Vinylacetat; typische hieraus resultierende Copolymere der Gruppe (K1) sind die mit am häufigsten eingesetzten Ethylen-Vinylacetat-Copolymere ("EVA").Examples of suitable alkenyl carboxylates are 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.
Besonders vorteilhaft einsetzbare Ethylen-Vinylacetat-Copolymere und ihre Herstellung sind in der
Als Copolymere der Klasse (K1) sind auch solche geeignet, die zwei oder mehrere voneinander verschiedene Carbonsäurealkenylester einpolymerisiert enthalten, wobei diese sich in der Alkenylfunktion und/oder in der Carbonsäuregruppe unterscheiden. Ebenfalls geeignet sind Copolymere, die neben dem/den Carbonsäurealkenylester(n) wenigstens ein Olefin und/oder wenigstens ein (Meth)Acrylsäureester einpolymerisiert enthalten.Also suitable as 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.
Auch Terpolymere aus einem C2- bis C40- α-Olefin, einem C1- bis C20-Alkylester einer ethylenisch ungesättigten Monocarbonsäure mit 3 bis 15 Kohlenstoffatomen und einem C2- bis C14-Alkenylester einer gesättigten Monocarbonsäure mit 2 bis 21 Kohlenstoffatomen sind als Copolymere der Klasse (K1) geeignet. Derartige Terpolymere sind in der
Das wenigstens eine oder die weiteren ethylenisch ungesättigten Monomeren sind in den Copolymeren der Klasse (K1) in einer Menge von vorzugsweise 1 bis 50 Gew.-%, insbeson-dere von 10 bis 45 Gew.-% und vor allem von 20 bis 40 Gew.-%, bezogen auf das Gesamtcopolymer, einpolymerisiert. Der gewichtsmäßige Hauptanteil der Monomereinheiten in den Copolymeren der Klasse (K1) stammt somit in der Regel aus den C2- bis C40-Basis-Olefinen.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.
Die Copolymere der Klasse (K1) weisen vorzugsweise ein zahlenmittleres Molekulargewicht Mn von 1000 bis 20.000, besonders bevorzugt von 1000 bis 10.000 und insbesondere von 1000 bis 8000 auf.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.
Typische Kammpolymere der Komponente (K2) sind beispielsweise durch die Copolymerisation von Maleinsäureanhydrid oder Fumarsäure mit einem anderen ethylenisch ungesättigten Monomer, beispielsweise mit einem α-Olefin oder einem ungesättigten Ester wie Vinylacetat, und anschließende Veresterung der Anhydrid- bzw. Säurefunktion mit einem Alkohol mit wenigstens 10 Kohlenstoffatomen erhältlich. Weitere geeignete Kammpolymere sind Copolymere von α-Olefinen und veresterten Comonomeren, beispielsweise veresterte Copolymere von Styrol und Maleinsäureanhydrid oder veresterte Copolymere von Styrol und Fumarsäure. Geeignete Kammpolymere können auch Polyfumarate oder Polymaleinate sein. Außerdem sind Homo- und Copolymere von Vinylethern geeignete Kammpolymere. Als Komponente der Klasse (K2) geeignete Kammpolymere sind beispielsweise auch solche, die in der
Als Komponente der Klasse (K3) geeignete Polyoxyalkylene sind beispielsweise Polyoxyalkylenester, Polyoxyalkylenether, gemischte Polyoxyalkylenesterether und Gemische davon. Bevorzugt enthalten diese Polyoxyalkylenverbindungen wenigstens eine, vorzugsweise wenigstens zwei lineare Alkylgruppen mit jeweils 10 bis 30 Kohlenstoffatomen und eine Polyoxyalkylengruppe mit einem zahlenmittleren Molekulargewicht von bis zu 5000. Derartige Polyoxyalkylenverbindungen sind beispielsweise in der
Als Komponente der Klasse (K4) geeignete polare Stickstoffverbindungen können sowohl ionischer als auch nicht ionischer Natur sein und besitzen vorzugsweise wenigstens einen, insbesondere wenigstens zwei Substituenten in Form eines tertiären Stickstoffatoms der allgemeinen Formel >NR7, worin R7 für einen C8- bis C40-Kohlenwas-serstoffrest steht. Die Stickstoffsubstituenten können auch quaternisiert, das heißt in kationischer Form, vorliegen. Beispiele für solche Stickstoffverbindungen sind Ammoniumsalze und/oder Amide, die durch die Umsetzung wenigstens eines mit wenigstens einem Kohlenwasserstoffrest substituierten Amins mit einer Carbonsäure mit 1 bis 4 Carboxylgruppen bzw. mit einem geeignetem Derivat davon erhältlich sind. Vorzugsweise enthalten die Amine wenigstens einen linearen C8- bis C40-Alkylrest. Zur Herstellung der genannten polaren Stickstoffverbindungen geeignete primäre Amine sind beispielsweise Octylamin, Nonylamin, Decylamin, Undecylamin, Dodecylamin, Tetradecylamin und die höheren linearen Homologen, hierzu geeignete sekundäre Amine sind beispielsweise Dioctadecylamin und Methylbehenylamin. Geeignet sind hierzu auch Amingemische, insbesondere großtechnisch zugängliche Amingemische wie Fettamine oder hydrierte Tallamine, wie sie beispielsweise in Ullmanns Encyclopedia of Industrial Chemistry, 6. Auflage, im Kapitel "Amines, aliphatic" beschrieben werden. Für die Umsetzung geeignete Säuren sind beispielsweise Cyclohexan-1,2-dicarbonsäure, Cyclohexen-1,2-dicarbonsäure, Cyclopentan-1,2-dicarbonsäure, Naphthalindicarbonsäure, Phthalsäure, Isophthalsäure, Terephthalsäure und mit langkettigen Kohlenwasserstoffresten substituierte Bernsteinsäuren.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.
Insbesondere ist die Komponente der Klasse (K4) ein öllösliches Umsetzungsprodukt aus mindestens eine tertiäre Aminogruppe aufweisenden Poly(C2- bis C20-Carbonsäuren) mit primären oder sekundären Aminen. Die diesem Umsetzungsprodukt zugrundeliegenden mindestens eine tertiäre Aminogruppe aufweisenden Poly(C2- bis C20-Carbonsäuren) enthalten vorzugsweise mindestens 3 Carboxylgruppen, insbesondere 3 bis 12, vor allem 3 bis 5 Carboxylgruppen. Die Carbonsäure-Einheiten in den Polycarbonsäuren weisen vorzugsweise 2 bis 10 Kohlenstoffatome auf, insbesondere sind es Essigsäure-Einheiten. Die Carbonsäure-Einheiten sind in geeigneter Weise zu den Polycarbonsäuren verknüpft, meist über ein oder mehrere Kohlenstoff- und/oder Stickstoffatome. Vorzugsweise sind sie an tertiäre Stickstoffatome angebunden, die im Falle mehrerer Stickstoffatome über Kohlenwasserstoffketten verbunden sind.In particular, 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.
Vorzugsweise ist die Komponente der Klasse (K4) ein öllösliches Umsetzungsprodukt auf Basis von mindestens eine tertiäre Aminogruppe aufweisenden Poly(C2- bis C20-Carbonsäuren) der allgemeinen Formel IIa oder IIb
Weiterhin ist das bevorzugte öllösliche Umsetzungsprodukt der Komponente (K4), insbesondere das der allgemeinen Formel IIa oder IIb, ein Amid, ein Amidammoniumsalz oder ein Ammoniumsalz, in dem keine, eine oder mehrere Carbonsäuregruppen in Amidgruppen übergeführt sind.Furthermore, 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.
Geradkettige oder verzweigte C2- bis C6-Alkylengruppen der Variablen A sind beispielsweise 1,1-Ethylen, 1,2-Propylen, 1,3-Propylen, 1,2-Butylen, 1,3-Butylen, 1,4-Butylen, 2-Methyl-1,3-propylen, 1,5-Pentylen, 2-Methyl-1,4-butylen, 2,2-Dimethyl-1,3-pro-pylen, 1,6-Hexylen (Hexamethylen) und insbesondere 1,2-Ethylen. Vorzugsweise umfasst die Variable A 2 bis 4, insbesondere 2 oder 3 Kohlenstoffatome.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.
C1- bis C19-Alkylengruppen der Variablen B sind vor beispielsweise 1,2-Ethylen, 1,3-Propylen, 1,4-Butylen, Hexamethylen, Octamethylen, Decamethylen, Dodecamethylen, Tetradecamethylen, Hexadecamethylen, Octadecamethylen, Nonadecamethylen und insbeson-dere Methylen. Vorzugsweise umfasst die Variable B 1 bis 10, insbesondere 1 bis 4 Kohlenstoffatome.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.
Die primären und sekundären Amine als Umsetzungspartner für die Polycarbonsäuren zur Bildung der Komponente (K4) sind üblicherweise Monoamine, insbesondere aliphatische Monoamine. Diese primären und sekundären Amine können aus einer Vielzahl von Aminen ausgewählt sein, die - gegebenenfalls miteinander verbundene - Kohlenwasserstoffreste tragen.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.
Meist sind diese den öllöslichen Umsetzungsprodukten der Komponente (K4) zugrundeliegenden Amine sekundären Amine und weisen die allgemeine Formel HN(R8)2 auf, in der die beiden Variablen R8 unabhängig voneinander jeweils geradkettige oder verzweigte C10- bis C30-Alkylreste, insbesondere C14- bis C24-Alkylreste bedeuten. Diese längerkettigen Alkylreste sind vorzugsweise geradkettig oder nur in geringem Grade verzweigt. In der Regel leiten sich die genannten sekundären Amine hinsichtlich ihrer längerkettigen Alkylreste von natürlich vorkommenden Fettsäuren bzw. von deren Derivaten ab. Vorzugsweise sind die beiden Reste R8 gleich.In most cases, 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. As a rule, 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.
Die genannten sekundären Amine können mittels Amidstrukturen oder in Form der Ammoniumsalze an die Polycarbonsäuren gebunden sein, auch kann nur ein Teil als Amidstrukturen und ein anderer Teil als Ammoniumsalze vorliegen. Vorzugsweise liegen nur wenige oder keine freien Säuregruppen vor. Vorzugsweise liegen die öllöslichen Umsetzungsprodukte der Komponente (K4) vollständig in Form der Amidstrukturen vor.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.
Typische Beispiele für derartige Komponenten (K4) sind Umsetzungsprodukte der Nitrilotriessigsäure, der Ethylendiamintetraessigsäure oder der Propylen-1,2-diamintetraessigsäure mit jeweils 0,5 bis 1,5 Mol pro Carboxylgruppe, insbesondere 0,8 bis 1,2 Mol pro Carboxylgruppe, Dioleylamin, Dipalmitinamin, Dikokosfettamin, Distearylamin, Dibehenylamin oder insbesondere Ditalgfettamin. Eine besonders bevorzugte Komponente (K4) ist das Umsetzungsprodukt aus 1 Mol Ethylendiamintetraessigsäure und 4 Mol hydriertem Ditalgfettamin.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.
Als weitere typische Beispiele für die Komponente (K4) seien die N,N-Dialkylammoni-umsalze von 2-N',N'-Dialkylamidobenzoaten, beispielsweise das Reaktionsprodukt aus 1 Mol Phthalsäureanhydrid und 2 Mol Ditalgfettamin, wobei letzteres hydriert oder nicht hydriert sein kann, und das Reaktionsprodukt von 1 Mol eines Alkenylspirobislactons mit 2 Mol eines Dialkylamins, beispielsweise Ditalgfettamin und/oder Talgfettamin, wobei die beiden letzteren hydriert oder nicht hydriert sein können, genannt.Further typical examples of 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.
Weitere typische Strukturtypen für die Komponente der Klasse (K4) sind cyclische Verbindungen mit tertiären Aminogruppen oder Kondensate langkettiger primärer oder sekundärer Amine mit carbonsäurehaltigen Polymeren, wie sie in der
Als Kaltfließverbesserer der Komponente der Klasse (K6) geeignete Poly(meth)acrylsäureester sind sowohl Homo- als auch Copolymere von Acryl- und Methacrylsäure-estern. Bevorzugt sind Copolymere von wenigstens zwei voneinander verschiedenen (Meth)Acrylsäureestern, die sich bezüglich des einkondensierten Alkohols unterscheiden. Gegebenenfalls enthält das Copolymer noch ein weiteres, davon verschiedenes olefinisch ungesättigtes Monomer einpolymerisiert. Das gewichtsmittlere Molekulargewicht des Polymers beträgt vorzugsweise 50.000 bis 500.000. Ein besonders bevorzugtes Polymer ist ein Copolymer von Methacrylsäure und Methacrylsäureestern von gesättigten C14- und C15-Alkoholen, wobei die Säuregruppen mit hydriertem Tallamin neutralisiert sind. Geeignete Poly(meth)acrylsäureester sind beispielsweise in der
Dem Mitteldestillat-Kraftstoff bzw. Dieselkraftstoff wird der Kaltfließverbesserer bzw. das Gemisch verschiedener Kaltfließverbesserer in einer Gesamtmenge von vorzugsweise 10 bis 5000 Gew.-ppm, besonders bevorzugt von 20 bis 2000 Gew.-ppm, stärker bevorzugt von 50 bis 1000 Gew.-ppm und insbesondere von 100 bis 700 Gew.-ppm, z.B. von 200 bis 500 Gew.-ppm, zugegeben.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.
Geeignete Schmierfähigkeitsverbesserer (Lubricity Improver bzw. Friction Modifier) basieren üblicherweise auf Fettsäuren oder Fettsäureestern. Typische Beispiele sind Tallölfettsäure, wie beispielsweise in der
Geeignete Korrosionsinhibitoren sind z.B. Bernsteinsäureester, vor allem mit Polyolen, Fettsäurederivate, z.B. Ölsäureester, oligomerisierte Fettsäuren, substituierte Ethanol-amine und Produkte, die unter dem Handelsnamen RC 4801 (Rhein Chemie Mannheim, Deutschland), Irgacor® L12 (BASF SE) oder HiTEC 536 (Ethyl Corporation) vertrieben werden.Suitable corrosion inhibitors include Bernsteinsäureester, in particular with polyols, fatty acid derivatives, for example Ölsäureester, 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).
Geeignete Demulgatoren sind z.B. die Alkali- oder Erdalkalisalze von Alkyl-substituier-ten Phenol- und Naphthalinsulfonaten und die Alkali- oder Erdalkalisalze von Fettsäuren, außerdem neutrale Verbindungen wie Alkoholalkoxylate, z.B. Alkoholethoxylate, Phenolalkoxylate, z.B. tert-Butylphenolethoxylat oder tert-Pentylphenolethoxylat, Fettsäuren, Alkylphenole, Kondensationsprodunkte von Ethylenoxid (EO) und Propylenoxid (PO), z.B. auch in Form von EO/PO-Blockcopolymeren, Polyethylenimine oder auch Polysiloxane.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.
Geeignete Dehazer sind z.B. alkoxylierte Phenol-Formaldehyd-Kondensate, wie beispielsweise die unter dem Handelsnamen erhältlichen Produkte NALCO 7D07 (Nalco) und TOLAD 2683 (Petrolite).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).
Geeignete Antischaummittel sind z.B. Polyether-modifizierte Polysiloxane, wie beispielsweise die unter dem Handelsnamen erhältlichen Produkte TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) und RHODOSIL (Rhone Poulenc).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).
Geeignete Cetanzahlverbesserer sind z.B. aliphatische Nitrate wie 2-Ethylhexylnitrat und Cyclohexylnitrat sowie Peroxide wie Di-tert-butylperoxid.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.
Geeignete Antioxidantien sind z.B. substituierte Phenole, wie 2,6-Di-tert.-butylphenol und 6-Di-tert.-butyl-3-methylphenol sowie Phenylendiamine wie N,N'-Di-sec.-butyl-p-phenylendiamin.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.
Geeignete Metalldeaktivatoren sind z.B. Salicylsäurederivate wie N,N'-Disalicyliden-1,2-propandiamin.Suitable metal deactivators are, for example, salicylic acid derivatives such as N, N'-disalicylidene-1,2-propanediamine.
Geeignete sind z.B. unpolare organische Lösungsmittel wie aromatische und aliphatische Kohlenwasserstoffe, beispielsweise Toluol, Xylole, "white spirit" und Produkte, die unter dem Handelsnamen SHELLSOL (Royal Dutch/Shell Group) und EXXSOL (ExxonMobil) vertrieben werden, sowie polare organische Lösungsmittel, bei-spielsweise Alkohole wie 2-Ethylhexanol, Decanol und Isotridecanol. Derartige Lösungsmittel gelangen meist zusammen mit den vorgenannten Additiven und Co-Additiven, die sie zur besseren Handhabung lösen oder verdünnen sollen, in den Dieselkraftstoff.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. Such 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.
Das erfindungsgemäße Additiv eignet sich in hervorragender Weise als Kraftstoffzusatz und kann im Prinzip in jeglichen Kraftstoffen eingesetzt werden. Es bewirkt eine ganze Reihe von vorteilhaften Effekten beim Betrieb von Verbrennungsmotoren mit Kraftstoffen. Bevorzugt wird das erfindungsgemäße quaternisierte Additiv in Mitteldestillat-Kraftstoffen, insbesondere Dieselkraftstoffen, eingesetzt.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.
Gegenstand der vorliegenden Erfindung sind daher auch Kraftstoffe, insbesondere Mitteldestillat-Kraftstoffe, mit einem als Zusatzstoff zur Erzielung von vorteilhaften Effekten beim Betrieb von Verbrennungsmotoren, beispielsweise von Dieselmotoren, insbesondere von direkteinspritzenden Dieselmotoren, vor allem von Dieselmotoren mit Common-Rail-Einspritzsystemen, wirksamen Gehalt an dem erfindungsgemäßen quaternisierten Additiv. Dieser wirksame Gehalt (Dosierrate) liegt in der Regel bei 10 bis 5000 Gew.-ppm, vorzugsweise bei 20 bis 1500 Gew.-ppm, insbesondere bei 25 bis 1000 Gew.-ppm, vor allem bei 30 bis 750 Gew.-ppm, jeweils bezogen auf die Gesamtmenge an Kraftstoff.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.
Die erfindungsgemäße Verwendung betrifft im Prinzip jegliche Kraftstoffe, bevorzugt Diesel- und Ottokraftstoffe.The use according to the invention relates in principle to any fuel, preferably diesel and petrol.
Bei Mitteldestillat-Kraftstoffen wie Dieselkraftstoffen oder Heizölen handelt es sich vorzugsweise um Erdölraffinate, die üblicherweise einen Siedebereich von 100 bis 400° C haben. Dies sind meist Destillate mit einem 95%-Punkt bis zu 360° C oder auch darüber hinaus. Dies können aber auch so genannte "Ultra Low Sulfur Diesel" oder "City Diesel" sein, gekennzeichnet durch einen 95%-Punkt von beispielsweise maximal 345° C und einem Schwefelgehalt von maximal 0,005 Gew.-% oder durch einen 95%-Punkt von beispielsweise 285° C und einem Schwefelgehalt von maximal 0,001 Gew.-%. Neben den durch Raffination erhältlichen mineralischen Mitteldestillat-Kraftstoffen bzw. Dieselkraftstoffen sind auch solche, die durch Kohlevergasung oder Gasverflüssigung ["gas to liquid" (GTL)-Kraftstoffe] oder durch Biomasse-Verflüssigung ["biomass to liquid" (BTL)-Kraftstoffe] erhältlich sind, geeignet. Geeignet sind auch Mischungen der vorstehend genannten Mitteldestillat-Kraftstoffe bzw. Dieselkraftstoffe mit regenerativen Kraftstoffen, wie Biodiesel oder Bioethanol.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. In addition to the mineral middle distillate fuels or diesel fuels obtainable through refining, 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. Mixtures of the aforementioned middle distillate fuels or diesel fuels with regenerative fuels such as biodiesel or bioethanol are also suitable.
Die Qualitäten der Heizöle und Dieselkraftstoffe sind beispielsweise in DIN 51603 und EN 590 näher festgelegt (vgl. auch
Die erfindungsgemäße Verwendung in Mitteldestillat-Kraftstoffen aus fossilem, pflanzlichem oder tierischem Ursprung, die im wesentlichen Kohlenwasserstoffmischungen darstellen, betrifft auch Mischungen aus solchen Mitteldestillaten mit Biobrennstoffölen (Biodiesel). Derartige Mischungen werden von dem Begriff "Mitteldestillat-Kraftstoff" umfasst. Sie sind handelsüblich und enthalten meist die Biobrennstofföle in untergeordneten Mengen, typischerweise in Mengen von 1 bis 30 Gew.-% insbesondere von 3 bis 10 Gew.-%, bezogen auf die Gesamtmenge aus Mitteldestillat fossilen, pflanzlichem oder tierischen Ursprungs und Biobrennstofföl.The use according to the invention in middle distillate fuels of fossil, vegetable or animal origin, which essentially represent hydrocarbon mixtures, also relates to mixtures of such middle distillates with biofuel oils (biodiesel). 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.
Biobrennstofföle basieren in der Regel auf Fettsäureestern, vorzugsweise im wesentlichen auf Alkylester von Fettsäuren, die sich von pflanzlichen und/oder tierischen Ölen und/oder Fetten ableiten. Unter Alkylestern werden üblicherweise Niedrigalkylester, insbesondere C1-bis C4-Alkylester, verstanden, die durch Umesterung der in pflanzlichen und/oder tierischen Ölen und/oder Fetten vorkommenden Glyceride, insbesondere Triglyceride, mittels Niedrigalkoholen, beispielsweise Ethanol oder vor allem Methanol ("FAME"), erhältlich sind. Typische Niedrigalkylester auf Basis von pflanzlichen und/oder tierischen Ölen und/oder Fetten, die als Biobrennstofföl oder Komponenten hierfür Verwendung finden, sind beispielsweise Sonnenblumenmethylester, Palmölmethylester ("PME"), Sojaölmethylester ("SME") und insbesondere Rapsölmethylester ("RME").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") .
Besonders bevorzugt handelt es sich bei den Mitteldestillat-Kraftstoffen bzw. Dieselkraftstoffen um solche mit niedrigem Schwefelgehalt, das heißt mit einem Schwefelgehalt von weniger als 0,05 Gew.-%, vorzugsweise von weniger als 0,02 Gew.-%, insbesondere von weniger als 0,005 Gew.-% und speziell von weniger als 0,001 Gew.-% Schwefel.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.
Als Ottokraftstoffe kommen alle handelsüblichen Ottokraftstoffzusammensetzungen in Betracht. Als typischer Vertreter soll hier der marktübliche Eurosuper Grundkraftstoff gemäß EN 228 genannt werden. Weiterhin sind auch Ottokraftstoffzusammensetzungen der Spezifikation gemäß
Das erfindungsgemäße quaternisierte Additiv eignet sich insbesondere als Kraftstoffzusatz in Kraftstoffzusammensetzungen, insbesondere in Dieselkraftstoffen, zur Überwindung der eingangs geschilderten Probleme bei direkteinspritzenden Dieselmotoren, vor allem bei solchen mit Common-Rail-Einspritzsystemen.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.
Die Erfindung wird nun anhand der folgenden Ausführungsbeispiele näher beschrieben. Insbesondere die im Folgenden genannten Testmethoden sind Teil der allgemeine Offenbarung der Anmeldung und nicht auf die konkreten Ausführungsbeispiele beschränkt.The invention will now be described in more detail with reference to the following exemplary embodiments. In particular, the test methods mentioned below are part of the general disclosure of the application and are not restricted to the specific exemplary embodiments.
Wenn nicht anders angegeben wurde das massenmittlere Mw und zahlenmittlere Molekulargewicht Mn der Copolymere mittels Gel-Permeations-Chromatographie gemessen (GPC). GPC-Trennung erfolgte über zwei PLge Mixed B-Säulen (Agilent) in Tetrahydrofuran bei 35 ° C. Die Kalibrierung erfolgte mittels eines engverteilten Polystyrolstandards (Firma PSS, Deutschland) mit Molekulargewicht 162-50400 Da. Hexylbenzol wurde als Marker für niedriges Molekulargewicht verwendet.Unless stated otherwise, 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.
In einem Reaktor mit Ankerrührer wurde das Olefin oder die Mischung aus Olefinen mit oder ohne Lösungsmittel (als Massepolymerisation) vorgelegt. Die Mischung wurde unter einem Stickstoffstrom und unter Rühren auf die angegebene Temperatur erhitzt. Hierzu gab man den angegebenen Radikalstarter (optional im gleichen Lösungsmittel verdünnt) und geschmolzenes Maleinsäureanhydrid (1 Äquivalent bezogen auf Olefinmonomer). Der Reaktionsansatz wurde bei gleicher Temperatur für die angegebene Reaktionszeit gerührt und dann abgekühlt.The olefin or the mixture of olefins with or without a solvent (as bulk polymerization) 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. To this end, 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.
Falls eine Hydrolyse erwünscht ist, wurde anschließend in der angegebenen Menge Wasser zugegeben und entweder bei 95° C, 10-14 h oder unter Druck bei 110° C 3 h gerührt.If hydrolysis is desired, 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.
In einem 2 L Glasreaktor mit Ankerrührer wurden eine Mischung aus C20-C24 Olefinen (363,2 g, Durchschnittmolmasse 296 g/mol) und Solvesso 150 (231,5 g, DHC Solvent Chemie GmbH, Speldorf) vorgelegt. Die Mischung wurde im Stickstoffstrom und unter Rühren auf 160 ° C erhitzt. Hierzu gab man innerhalb 5 h eine Lösung von di-tertButylperoxid (29,6 g, Fa. Akzo Nobel) in Solvesso 150 (260,5 g) und geschmolzenes Maleinsäureanhydrid (120,3 g). Der Reaktionsansatz wurde 1 h bei 160 ° C gerührt und dann abgekühlt. Der Wirkstoffgehalt betrug etwa 40%. A mixture of C 20 -C 24 olefins (363.2 g, average molecular weight 296 g / mol) and Solvesso 150 (231.5 g, DHC Solvent Chemie GmbH, Speldorf) were placed in a 2 L glass reactor with anchor stirrer. The mixture was in a stream of nitrogen and with stirring 160 ° C heated. A solution of di-tert-butyl peroxide (29.6 g, Akzo Nobel) in Solvesso 150 (260.5 g) and molten maleic anhydride (120.3 g) were added to this over the course of 5 hours. The reaction mixture was stirred at 160 ° C. for 1 h and then cooled. The active ingredient content was about 40%.
Das GPC (in THF) ergab für das Copolymer ein Mn = 1210 g/mol, Mw = 2330 g/mol, was einer Dispersität von 1,9 entspricht.The GPC (in THF) gave an Mn = 1210 g / mol, Mw = 2330 g / mol for the copolymer, which corresponds to a dispersity of 1.9.
Dem Produkt aus Synthesebeispiel 1 wurde bei einer Temperatur von 95 ° C Wasser (19,9 g) innerhalb 3 h zugegeben und anschliessend 11 h weiter gerührt. Die Säurezahl betrug 104 mg KOH/ g.Water (19.9 g) was added to the product from Synthesis Example 1 at a temperature of 95 ° C. over the course of 3 hours and the mixture was then stirred for a further 11 hours. The acid number was 104 mg KOH / g.
Zur Untersuchung des Einflusses der Additive auf die Performance von direkteinspritzenden Dieselmotoren wurde als weitere Testmethode der IDID-Motorentest, bei dem die Abgastemperaturen der Zylinder am Zylinderausgang beim Kaltstart des DW10-Motors bestimmt wurden. Verwendet wurde ein direkteinspritzender Dieselmotor mit Common-Rail-System des Herstellers Peugeot gemäß Testmethoden CEC F-098-08. Als Kraftstoff wurde ein handelsüblicher B7 Dieselkraftstoff gemäß EN 590 der Fa. Aral eingesetzt. Diesem wurden zur künstlichen Anregung der Bildung von Ablagerungen jeweils 1 Gew.-ppm Natriumnaphthenat sowie 20 Gew.-ppm Dodecenylbernsteinsäure zugesetzt.To investigate the influence of the additives on the performance of direct-injection diesel engines, 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.
Ähnlich wie das Verfahren CEC F-98 -08 wird die Motorleistung während des Tests gemessen. Der Test bestand aus zwei Teilen:
- I. Dirty-up:
- Der Test wurde ohne Zusatz von Verbindungen gemäß dieser Erfindung durchgeführt. Der Test wurde
auf 8 Stunden verkürzt, das CEC F-98 -08 Verfahren wurde ohne Zusatz von Zn, jedoch unter Zugabe von Natriumnaphthenat und Dodecenylbernsteinsäure durchgeführt. Wenn signifikante Abweichungen von Abgastemperaturen beobachtet wurden, wurde die Prüfung vor Erreichen der 8 Stunden-Marke angehalten, um Motorschäden zu vermeiden. Nach dem dirty up- Lauf, ließ man den Motor abkühlen und danach wurde erneut gestartet undim Leerlauf 10 Minuten betrieben. Während dieser 10 Minuten wurde der Motor aufgewärmt. Die Abgastemperatur von jedem Zylinder wurde aufgezeichnet. Je geringer die Unterschiede zwischen den ermittelten Abgas-Temperaturen sind, um so niedriger ist die Menge an gebildeten IDID. - Es wurden jeweils die
Abgastemperaturen der 4 Zylinder ("Z1" bis "Z4") anden Zylinderausgängen nach 0 Minuten ("ϑ0") und nach 10 Minuten ("ϑ10")gemessen. Die Ergebnisse der Abgastemperatur-Messungen mit Durchschnittswerten ("Δ") und den größten Abweichungen von Δ nach unten ("-") und oben ("+") für die beiden Testläufe sind in der folgenden Übersicht zusammengefasst.
- Der Test wurde ohne Zusatz von Verbindungen gemäß dieser Erfindung durchgeführt. Der Test wurde
- II. Clean-up:
- Der Test wurde
auf 8 Stunden verkürzt, das CEC F-98 -08 Verfahren wurde ohne Zusatz von Zn wurde durchgeführt. Es wurden jedoch jeweils 1 Gew.-ppm Natriumnaphthenat sowie 20 Gew.-ppm Dodecenylbernsteinsäure sowie eine erfindungsgemäße Verbindung zugesetzt, und die Motorenleistung bestimmt.
- Der Test wurde
- I. Dirty-up:
- The test was carried out without the addition of compounds according to this invention. The test was shortened to 8 hours, the CEC F-98-08 method was carried out without the addition of Zn, but with the addition of sodium naphthenate and dodecenyl succinic acid. If significant deviations in exhaust gas temperatures were observed, the test was stopped before the 8 hour mark was reached in order to avoid engine damage. After the dirty up run, the engine was allowed to cool down and then restarted and idled for 10 minutes. During these 10 minutes the engine was warmed up. 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 exhaust gas temperatures of the 4 cylinders ("Z1" to "Z4") were measured at the cylinder exits after 0 minutes ("ϑ0") and after 10 minutes ("ϑ10"). The results of the exhaust gas temperature measurements with average values ("Δ") and the largest Deviations from Δ downwards ("-") and upwards ("+") for the two test runs are summarized in the following overview.
- II. Clean-up:
- The test was shortened to 8 hours, the CEC F-98-08 procedure was carried out without the addition of Zn. However, in each
case 1 ppm by weight of sodium naphthenate and 20 ppm by weight of dodecenylsuccinic acid and a compound according to the invention were added, and the engine output was determined.
- The test was shortened to 8 hours, the CEC F-98-08 procedure was carried out without the addition of Zn. However, in each
Nach dem clean up wurde der Motor abgekühlt und erneut gestartet. Die Abgastemperatur von jedem Zylinder wurde aufgezeichnet. Je geringer die Unterschiede zwischen den ermittelten Abgas-Temperaturen sind, um so niedriger ist die Menge an gebildeten IDID.After the clean up, 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.
Es wurden jeweils die Abgastemperaturen der 4 Zylinder ("Z1" bis "Z4") an den Zylinderausgängen nach 0 Minuten ("ϑ0") und nach 10 Minuten ("ϑ10")gemessen. Die Ergebnisse der Abgastemperatur-Messungen mit Durchschnittswerten ("Δ") und den größten Abweichungen von Δ nach unten ("-") und oben ("+") sind in der folgenden Übersicht zusammengefasst.The exhaust gas temperatures of the 4 cylinders ("Z1" to "Z4") were measured at the cylinder exits after 0 minutes ("ϑ0") and after 10 minutes ("ϑ10"). The results of the exhaust gas temperature measurements with average values ("Δ") and the largest deviations from Δ downwards (“-”) and upwards (“+”) are summarized in the following overview.
Wesentliche Abweichungen von dem Mittelwert und signifikanter Unterschied zwischen den einzelnen Zylindern belegen die Präsenz von IDID.Significant deviations from the mean value and significant differences between the individual cylinders prove the presence of IDID.
Die Abweichung vom Mittelwert der Temperatur der Abgase ist niedrig, was für die Entfernung von IDID spricht.The deviation from the mean value of the temperature of the exhaust gases is low, which speaks in favor of the removal of IDID.
Somit sind die Verbindungen gemäß der vorliegenden Erfindung sehr effizient zur Verhinderung/Entfernung in Motoren mit Direkteinspritzung, wie man am Peugeot DW10 Motor in einem Test ähnlich dem CEC F-98-08 sieht, jedoch mit 1 Gew.-ppm Na in Form von Natriumnaphthenat sowie 20 Gew.-ppm Dodecenylbernsteinsäure.Thus, 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.
Claims (11)
- The use of copolymers obtainable by- in a first reaction step (I) copolymerizing(A) at least one anhydride of an ethylenically unsaturated dicarboxylic acid,(B) at least one α-olefin having from at least 12 up to and including 30 carbon atoms,(C) optionally at least one further aliphatic or cycloaliphatic olefin which has at least 4 carbon atoms and is different than (B) and(D) optionally one or more further copolymerizable monomers other than monomers (A), (B) and (C), selected from the group consisting of(Da) vinyl esters,(Db) vinyl ethers,(Dc) (meth)acrylic esters of alcohols having at least 5 carbon atoms,(Dd) allyl alcohols or ethers thereof,(De) 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,(Dg) α,β-ethylenically unsaturated nitriles,(Dh) (meth)acrylamides and(Di) allylamines,followed by- in a second optional reaction step (II) partly hydrolyzing the anhydride functionalities present in the copolymer obtained from (I), with the proviso that more than 90% of the anhydride functionalities present remain intact after reaction step (II), for removing and/or preventing deposits in the injection system of direct injection diesel and/or gasoline engines.
- The use of the copolymers as described in claim 1 as an additive for reducing the fuel consumption of direct injection diesel engines, especially of diesel engines with common rail injection systems.
- The use of the copolymers as described in claim 1 as an additive for minimizing power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems.
- The use according to claim 3 as an additive for minimizing power loss caused by K, Zn, Ca and/or Na ions (called K, Zn, Ca and Na power loss respectively).
- The use of the copolymers as described in claim 1 as a gasoline fuel additive for reducing the level of deposits in the intake system of a gasoline engine, such as, more particularly, DISI and PFI (port fuel injector) engines.
- The use according to claim 1 as a diesel fuel additive for reducing and/or preventing deposits in the injection systems, such as, more particularly, the internal diesel injector deposits (IDIDs), and/or valve sticking in direct injection diesel engines, especially in common rail injection systems.
- The use according to claim 6 as a diesel fuel additive for reducing and/or preventing the internal diesel injector deposits (IDIDs) caused by Na, Ca and/or K ions (called Na, Ca and K soap IDIDs respectively).
- The use according to claim 6 as a diesel fuel additive for reducing and/or preventing the internal diesel injector deposits (IDIDs) caused by polymeric deposits.
- The use according to claim 1, wherein the fuel is selected from diesel fuels, biodiesel fuels, gasoline fuels, and alkanol-containing gasoline fuels.
- The use according to any of the preceding claims, wherein maleic anhydride is used as component (A) and the optional reaction step (II) is not conducted.
- The use according to any of claims 1 to 9, wherein maleic anhydride is used as component (A) and more than 90% and up to 99.9% of the anhydride functionalities remain intact in reaction step (II).
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-
2016
- 2016-07-12 US US15/744,416 patent/US11085001B2/en active Active
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- 2016-07-12 WO PCT/EP2016/066465 patent/WO2017009305A1/en active Application Filing
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