WO2013000997A1 - Quaternisierte stickstoffverbindungen und deren verwendung als additive in kraft- und schmierstoffen - Google Patents
Quaternisierte stickstoffverbindungen und deren verwendung als additive in kraft- und schmierstoffen Download PDFInfo
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
- C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C)
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
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- C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
- C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
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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
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/224—Amides; Imides carboxylic acid amides, imides
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- 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
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
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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
- C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
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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
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
Definitions
- Quaternized nitrogen compounds and their use as additives in fuels and lubricants are used as additives in fuels and lubricants.
- the present invention relates to novel quaternized nitrogen compounds, their preparation and use as a fuel and lubricant additive, in particular as a detergent additive additive packages containing these compounds; as well as with it additized fuels and lubricants. Furthermore, the present invention relates to the use of these quaternized nitrogen compounds as a fuel additive for reducing or preventing deposits in the injection systems of direct injection diesel engines, especially in common rail injection systems, to reduce the fuel consumption of direct injection diesel engines, especially common rail diesel engines Injection systems, and to minimize the power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems.
- direct-injection diesel engines the fuel is injected through a multi-hole injection nozzle directly into the combustion chamber of the engine and finely distributed (atomized) instead of being introduced into a vortex 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 engines achieve a very high torque even at low speeds.
- the diesel fuel is pumped from a pump with pressures up to 2000 bar into a high-pressure line, the common rail.
- spur lines run to the various injectors, which inject the fuel directly into the combustion chamber.
- the full pressure is always applied to the common rail, which allows a multiple injection or a special injection form. In the other injection systems, however, only a smaller variation of the injection is possible.
- Injection in the common rail is essentially subdivided into three groups: (1) pre-injection, which essentially achieves softer combustion, so that hard combustion noises ("nails") are reduced and engine running appears quiet; (2.) main injection, which is responsible in particular for a good torque curve; and (3.) post-injection, which provides in particular for a low NO x value.
- pre-injection which essentially achieves softer combustion, so that hard combustion noises ("nails") are reduced and engine running appears quiet
- main injection which is responsible in particular for a good torque curve
- post-injection which provides in particular for a low NO x value.
- the fuel is not burned in the rule, but evaporated by residual heat in the cylinder.
- the exhaust gas / fuel mixture formed during this process is transported to the exhaust gas system, where the fuel acts as a reducing agent for the nitrogen oxides NO x in the presence of suitable catalysts.
- the pollutant emissions of the engine eg the emission of nitrogen oxides (NO x ), carbon monoxide (CO) and particulate matter (soot) can be positively influenced in the common-rail injection system.
- NO x nitrogen oxides
- CO carbon monoxide
- particulate matter particulate matter
- deposits is further enhanced by structural developments of the injectors, in particular by the change in the geometry of the nozzles (narrower, conical openings with rounded outlet). For a permanently optimal functioning of engine and injectors such deposits must be prevented or reduced in the nozzle openings by suitable fuel additives
- 4,171,959 describes quaternized ammonium salts of hydrocarbyl-substituted succinimides which are suitable as detergent additives for gasoline fuel compositions.
- alkyl halides are preferably used.
- the quaternized ammonium salts provided by the teachings have as counterion either a halide or a C 2 -C 8 hydrocarbyl carboxylate or a C 2 -C 8 hydrocarbyl sulfonate group.
- PI BSA with low bismaleination levels ⁇ 20% is also not described therein.
- cold flow improvers which are prepared by quaternization of special tertiary monoamines which carry at least one C8-C4o-alkyl radical with a Ci-C4-alkyl ester of special carboxylic acids.
- carboxylic acid esters are dimethyloxalate, dimethyl maleate, dimethyl phthalate and dimethyl fumarate.
- WO 2006/135881 describes quaternized ammonium salts prepared by condensation of a hydrocarbyl-substituted acylating agent and an oxygen- or nitrogen-containing tertiary-amino-containing compound followed by quaternization by means of hydrocarbyl epoxide in combination with stoichiometric amounts of an acid such as in particular acetic acid.
- Further quaternizing agents claimed in WO 2006/135881 are dialkyl sulfates, benzyl halides and hydrocarbyl-substituted carbonates, dimethyl sulfate, benzyl chloride and dimethyl carbonate being investigated experimentally.
- the quaternizing agents preferably used in WO 2006/135881 have serious disadvantages, such as: toxicity or carcinogenicity (eg dimethyl sulfate and alkylene oxides and benzyl halides), no residue-free combustion (eg dimethyl sulfate and alkyl halides), as well as insufficient reactivity, which is too incomplete Quaternization or non-economic reaction conditions (long reaction times, high reaction temperatures, excess of quaternizing agent, eg dimethyl carbonate).
- toxicity or carcinogenicity eg dimethyl sulfate and alkylene oxides and benzyl halides
- no residue-free combustion eg dimethyl sulfate and alkyl halides
- insufficient reactivity which is too incomplete Quaternization or non-economic reaction conditions (long reaction times, high reaction temperatures, excess of quaternizing agent, eg dimethyl carbonate).
- the additives according to the invention produced in this way are superior to the conventionally prepared additives according to the prior art in a number of respects: they have low toxicity (owing to the targeted choice of the quaternizing agent, burn off ashless), show a high content of quaternized product, and allow an economic reaction during their production and surprisingly have improved handling properties, such as in particular improved solubility, such as in particular in diesel performance additive packages, at the same time show the additives of the invention an improved effect on the prevention of deposits in diesel engines, as illustrated in particular by the enclosed application examples.
- a fuel or lubricant composition in particular a fuel composition, containing in a major amount of a conventional fuel or lubricant a proportion (in particular an effective amount) of at least one reaction product comprising a quaternized nitrogen compound (or a partial fraction containing a quaternized nitrogen compound obtained by purification from the reaction product thereof), wherein the reaction product is obtainable by
- quaternizing agent which converts the at least one quaternizable, such as tertiary, amino group into a quaternary ammonium group
- the quaternizing agent being the alkyl esters of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid (especially a mono- or dicarboxylic acid) or an aliphatic polycarboxylic acid (especially dicarboxylic acid).
- a fuel or lubricant composition in particular a fuel composition, containing in a main amount of a conventional fuel or lubricant a proportion (in particular an effective amount) of at least one reaction product comprising a quaternized nitrogen compound (or a reaction product obtained by purification containing a quaternized nitrogen compound). partial fraction thereof), wherein the reaction product is obtainable by Reacting a quaternizable high molecular weight hydrocarbyl-substituted polycarboxylic acid compound containing at least one quaternizable amino group with a quaternizing agent which converts the at least one quaternizable, such as tertiary, amino group into a quaternary ammonium group,
- the quaternizing agent is the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid (especially a mono- or dicarboxylic acid) or an aliphatic polycarboxylic acid (especially dicarboxylic acid).
- a fuel composition according to any one of the preceding claims wherein from about 1.1 to about 2.0 or about 1.25 to about 2.0 equivalents per equivalent of quaternizable tertiary nitrogen atom, e.g. 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, or 1.9 equivalents of quaternizing agent.
- hydrocarbyl-substituted polycarboxylic acid compound is a polyisobutenylic acid or an anhydride thereof, which has a bis-maleic degree equal to or less than about 20% or equal to or less than about 15%, such as e.g. 15, 14, 13, 12, 1, 1, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, or 0.1%.
- Low levels of bismaleination can contribute to a significant improvement in the solubility of the additive and / or compatibility of the ingredients in the formulation of additive packages.
- a fuel or lubricant composition in particular fuel composition, according to one of the preceding embodiments, wherein the quaternizing agent is a compound of general formula 1
- Ri is a low molecular weight hydrocarbyl radical, such as alkyl or alkenyl radical, in particular a lower alkyl radical, in particular methyl or ethyl
- R 2 is an optionally substituted mononuclear cyclic hydrocarbyl radical, in particular an aryl or cycloalkyl or cycloalkenyl radical, in particular aryl, such as phenyl, where the substituent is selected from OH, NH 2, NO 2, C (O) OR 3, and R iOC (0) -, wherein R1 has the meanings given above and R3 is H or R1, where the substituent is in particular OH.
- the quaternizing agent is a phthalate or a salicylate, such as dimethyl phthalate, or methyl salicylate.
- Fuel or lubricant composition in particular fuel composition, according to one of the preceding embodiments, wherein the quaternization agent is a compound of the general formula 2
- R1 and Ria independently of one another represent a low molecular weight hydrocarbyl radical, such as an alkyl or alkenyl radical, in particular a lower alkyl radical, and
- A represents hydrocarbylene (in particular C 1 -C 6 -alkylene or C 2 -C 7 -alkenylene).
- Fuel or lubricant composition in particular fuel composition, according to one of the preceding embodiments, wherein the quaternized nitrogen compound has a number average molecular weight in the range of 400 to 5000, in particular 800 to 3000 or 900 to 1500.
- a fuel or lubricant composition in particular a fuel composition, according to one of the preceding embodiments, wherein the quaternizing agent is selected from alkyl salicylates, dialkyl phthalates and dialkyl oxalates; wherein alkylsalicylates, especially Niedrigalkylsalicylate, such as methyl, ethyl and n-propyl salicylates are particularly mentioned.
- the reactive with the polycarboxylic acid (addable or condensable), an oxygen or nitrogen group and at least one quaternizable amino group-containing compound is selected from
- a Hydroxyalkyl-substituted mono- or polyamines having at least one quaternizable, primary, secondary or tertiary amino group
- b straight-chain or branched, cyclic, heterocyclic, aromatic or nonaromatic polyamines having at least one primary or secondary amino group and having at least one quaternizable, primary, secondary or tertiary amino group;
- a Hydroxyalkyl-substituted primary, secondary or tertiary monoamines and hydroxyalkyl-substituted primary, secondary or tertiary diamines.
- b straight-chain or branched aliphatic diamines having two primary amino groups; Di- or polyamines having at least one primary and at least one secondary amino group; Di- or polyamines having at least one primary and at least one tertiary amino group; aromatic carbo-cyclic diamines having two primary amino groups; aromatic heterocyclic polyamines having two primary amino groups; aromatic or non-aromatic heterocycles having a primary and a tertiary amino group;
- Fuel composition according to one of the preceding embodiments selected from diesel fuels, biodiesel fuels, gasoline fuels, and alkanol-containing gasolines.
- a fuel or lubricant composition in particular a fuel composition, according to any one of the preceding embodiments, wherein the hydrocarbyl-substituted polycarboxylic acid compound is a polyisobutenyl succinic acid or anhydride (PIBSA) thereof, which has a low bismaleination degree, in particular 10% or less than 10%, such as 2 to 9, or 3 to 7%.
- PIBSAs are derived from HR-PIB having an Mn in the range of about 400 to 3,000.
- compositions are fuel compositions, especially diesel fuels. 13.
- Reaction product obtainable by a process according to the definition in one of the preceding embodiments, in particular according to embodiment 3, 4, 5, 6 and especially embodiment 8, 9 or 10, or from the reaction product obtained by partial or complete purification quaternized nitrogen compound.
- quaternized reaction products which are prepared from polyisobutenyl succinic acid or an anhydride thereof, said compound having a bis-maleination degree equal to or less than about 20% or equal to or less than about 15%, e.g. 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, or 0.1%.
- This polyisobutenyl succinic acid compound is reacted (by addition or condensation) with a compound comprising at least one oxygen or nitrogen group which is reactive (in particular can be added or condensed) with the polyisobutenyl succinic acid compound and then quaternized.
- quaternized reaction products are obtained, which are obtained by quaternization using an excess of quaternizing agent.
- quaternizing agent for each equivalent of quaternizable tertiary nitrogen, about 1.1 to about 2.0, or about 1.25 to about 2.0 equivalents, e.g. 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8 or 1, 9 equivalents of quaternizing used.
- Particularly useful quaternizing agents are those of formula (1), in particular the lower alkyl esters of salicylic acid such as methyl salicylate, ethyl salicylate, n- and i-propyl salicylate, and n-, i- or tert-butyl salicylate.
- embodiments (A) and (B) are combined, i. the quaternizable compounds prepared from the above polyisobutenylsuccinic acid compounds according to embodiment (A) are quaternized according to embodiment (B).
- the quaternizing agent is the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid (especially a mono- or dicarboxylic acid) or an aliphatic polycarboxylic acid (especially dicarboxylic acid).
- reaction product or a quaternized nitrogen compound according to embodiment 13 or a compound prepared according to embodiment 14 as a fuel additive or lubricant additive, in particular Kraftstoffaddi- tiv, in particular diesel fuel additive.
- a “condensation” or “condensation reaction” in the context of the present invention describes the reaction of two molecules with elimination of a smaller molecule, in particular a water molecule. If such cleavage is not detectable analytically, especially in stoichiometric amounts undetectable, and the two molecules nevertheless react, e.g. under addition, the respective conversion of the two molecules takes place "without condensation.” Unless otherwise indicated, the following general meanings apply:
- Hydrocarbon radicals which may optionally additionally contain heteroatoms, such as, for example, O, N, NH, S, in their chain.
- “Long-chain” or “high molecular weight” hydrocarbyl radicals have a number-average molecular weight (M n ) of 85 to 20,000, such as 13 to 10,000, or 200 to 10,000 or 350 to 5,000, such as 350 to 3,000, 500 to 2,500, 700 to 2,500, or 800 to 1, 500.
- M n number-average molecular weight
- They are composed essentially of C 2-6, in particular C 2-4, monomer units, such as ethylene, propylene, n- or isobutylene or mixtures thereof, it being possible for the various monomers to be randomly distributed or incorporated in polymerized form as blocks.
- Such long-chain hydrocarbyl radicals are also referred to as polyalkylene radicals or P0IV-C2-6 or poly-C2-4-alkylene radicals. Suitable long-chain hydrocarbyl radicals and their preparation are also described, for example, in WO2006 / 135881 and the literature cited therein.
- polystyrene radicals examples include polyisobutenyl radicals derived from so-called “highly reactive” polyisobutenes (HR-PI B), which are distinguished by a high content of terminal double bonds (cf., for example, also Rath et al, Lubrication Science (1999 ), 1-2, 175-185). Terminal arranged double bonds are alpha-olefinic double bonds of the type
- Suitable highly reactive polyisobutenes are, for example, polyisobutenes which have a proportion of vinylidene double bonds of greater than 70 mol%, in particular greater than 80 mol% or greater than 85 mol%. Particular preference is given to polyisobutenes which have uniform polymer skeletons. Uniform polymer skeletons have, in particular, those polyisobutenes which are composed of at least 85% by weight, preferably at least 90% by weight and more preferably at least 95% by weight, of isobutene units. Preferably, such highly reactive polyisobutenes have a number average molecular weight in the range mentioned above.
- the highly reactive polyisobutenes may have a polydispersity in the range from 1:05 to 7, in particular from about 1, 1 to 2.5, for example of less than 1, 9 or less than 1.5.
- polydispersity is meant the quotient of weight average molecular weight Mw divided by the number average molecular weight Mn.
- Other number average molecular weights can be adjusted in a manner known in principle by mixing polyisobutenes of different number average molecular weights or by extractive enrichment of polyisobutenes of specific molecular weight ranges.
- PIBSA is prepared in a manner known in principle by reacting PI B with maleic anhydride (MSA), which in principle produces a mixture of PIBSA and bismaleized PIBSA (BM PIBSA, see Scheme 1, below), which is generally not separated, but instead is used as such in subsequent reactions.
- MSA maleic anhydride
- BM PIBSA bismaleized PIBSA
- the ratio of the two components to one another can be indicated by the "degree of bismeralization" (BMG)
- BMG degree of bismeralization
- the BMG is known per se (see also US 5,883,196)
- the BMG can also be determined according to the following formula:
- Hydrocarbyl-substituted polycarboxylic acid compounds having a "low degree of bismalization”, in particular corresponding polyisobutenylsuccinic acids or anhydrides thereof (altogether also referred to as PIBSA), are known from the prior art, in particular bis-maleation grades of 20% or less, or 15% or less, such as 14, 13, 12, or 10%, or 10% or less, such as 2-9, 3-8, 4-7, 5, or 6%, their targeted preparation is described, for example, in US 5,883,196.
- Particularly suitable for their preparation are the above highly reactive polyisobutenes having an Mn in the range from about 500 to 2500, such as 550 to 3000, 1000 to 2000 or 1000 to 1500.
- "Short-chain hydrocarbyl” or “low molecular weight hydrocarbyl” is especially straight-chain or branched alkyl or alkenyl, optionally interrupted by one or more, for example 2, 3 or 4 heteroatom groups, such as -O- or -NH-. or optionally mono- or polysubstituted, such as 2, 3 or 4-times substituted.
- Alkyl or “lower alkyl” in particular represents saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 1 to 6, 1 to 8, or 1 to 10 or 1 to 20 carbon atoms, such as.
- Hydroxyalkyl is in particular the mono- or polysubstituted, in particular simply hydroxylated, analogs of the above-mentioned alkyl radicals, for example the monohydroxylated analogs of the above straight-chain or branched alkyl radicals, for example the linear hydroxyalkyl groups having primary hydroxyl groups, such as hydroxymethyl, 2-hydroxyethyl, 3 Hydroxypropyl, 4-hydroxybutyl.
- Alkenyl is mono- or polysubstituted, in particular monounsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8 2 to 10 or 2 or to 20 carbon atoms and a double bond in any position, for example C 2 -C 6 alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl , 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3 -Methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl,
- Alkylene is straight-chain or mono- or poly-branched hydrocarbon bridging groups having 1 to 10 carbon atoms, such as Ci-Cz-alkylene groups selected from -CH 2 -, - (CH 2 ) 2 -, - (CH 2 ) 3 -, -CH 2 -CH (CH 3 ) -, -CH (CH 3 ) -CH 2 -, - (CH 2 ) 4 -, - (CH 2 ) 2 -CH (CH 3 ) -, -CH 2 -CH (CH 3 ) -CH 2 -, (CH 2 ) 4 -, - (CH 2 ) 5 -, - (CH 2 ) 6 , - (CH 2 ) 7 -, -CH (CH 3 ) - CH 2 -CH 2 -CH (CH 3 ) - or - CH (CH 3 ) -CH 2 -CH 2 -CH (CH 3 ) - or C 1
- Cyclic hydrocarbyl radicals include in particular:
- Cycloalkyl carbocyclic radicals having 3 to 20 carbon atoms, such as C 3 -C 2 - cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctene tyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; Cyclopentyl, cyclohexyl, cycloheptyl and also cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl or C 3 -C 7 -cycloalkyl, such as cyclopropyl, cyclobutyl, are preferred , Cyclopentyl, cyclohex
- Cycloalkenyl monocyclic, monounsaturated hydrocarbon groups having 5 to 8, preferably to 6 carbon ring members, such as cyclopentene-1-yl, cyclopenten-3-yl, cyclohexene-1-yl, cyclohexen-3-yl and cyclohexene-4-yl;
- Aryl mononuclear or polynuclear, preferably mono- or binuclear, optionally substituted aromatic radicals having from 6 to 20, such as, for example, From 6 to 10 ring carbon atoms, e.g. Phenyl, biphenyl, naphthyl, such as 1- or 2-naphthyl, tetrahydronaphthyl, fluorenyl, indenyl and phenanthrenyl. These aryl radicals may optionally carry 1, 2, 3, 4, 5 or 6 identical or different substituents.
- Substituents for radicals specified herein are, in particular, unless otherwise specified, are selected from keto groups, - COOH, -COO-alkyl, - OH, -SH, -CN, amino, -NO 2 , alkyl, or alkenyl groups
- the term "about” in the context of a number or a range of values denotes deviations from the values actually disclosed. This is it usually by usual deviations. These may deviate, for example, by ⁇ 10% to ⁇ 0.1% from the specified values. Typically, such deviations are about ⁇ 8% to ⁇ 1% or ⁇ 5%, ⁇ 4%, ⁇ 3% or ⁇ 2%.
- A3 Polycarboxylic acid compounds, and hydrocarbyl-substituted polycarboxylic acid compounds:
- the polycarboxylic acid compounds used are aliphatic di- or polyvalent (such as 3- or 4-valent), in particular of di-, tri- or tetracarboxylic acids, and analogs thereof, such as anhydrides or lower alkyl esters (partially or completely esterified), and optionally one or more (such as 2 or 3), in particular a long-chain alkyl radical and / or a high molecular weight hydrocarbyl radical, in particular a polyalkylene radical substituted.
- di- or polyvalent such as 3- or 4-valent
- di-, tri- or tetracarboxylic acids and analogs thereof, such as anhydrides or lower alkyl esters (partially or completely esterified), and optionally one or more (such as 2 or 3), in particular a long-chain alkyl radical and / or a high molecular weight hydrocarbyl radical, in particular a polyalkylene radical substituted.
- Examples are C3-C10 polycarboxylic acids, such as the dicarboxylic acids malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and their branched analogues; and the tricarboxylic acid citric acid; and anhydrides or lower alkyl esters thereof.
- the polycarboxylic acid compounds may also be prepared from the corresponding monounsaturated acids and addition of at least one long chain alkyl group and / or high molecular weight hydrocarbyl group. Examples of suitable monounsaturated acids are fumaric acid, maleic acid, itaconic acid.
- the hydrophobic "long chain” or “high molecular weight” hydrocarbyl moiety which provides sufficient solubility of the quaternized product in the fuel has a number average molecular weight (M n ) of from 85 to 20,000, such as 1 to 10,000, or 200 to 10,000 or 350 up to 5,000, such as 350 to 3,000, 500 to 2,500, 700 to 2,500, or 800 to 1,500.
- Typical hydrophobic hydrocarbyl radicals include polypropenyl, polybutenyl and polyisobutenyl radicals, for example having a number average molecular weight M n of 3,500 to 5,000, 350 to 3,000, 500 to 2,500, 700 to 2,500 and 800 to 1,500.
- Suitable hydrocarbyl substituted compounds are e.g. described in DE 43 19 672 and WO2008 / 138836.
- Suitable hydrocarbyl-substituted polycarboxylic acid compounds also include polymeric, especially dimeric, forms of such hydrocarbyl-substituted polycarboxylic acid compounds.
- dimeric forms contain two acid anhydride groups which can be reacted independently of one another in the production process according to the invention with the quaternizable nitrogen compound.
- Suitable quaternizing agents are in principle all suitable as such alkyl esters of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid (especially a mono- or dicarboxylic acid) or an aliphatic polycarboxylic acid (especially dicarboxylic acid) into consideration.
- the quaternization of the at least one quaternizable tertiary nitrogen atom is carried out with at least one quaternizing agent selected from a) compounds of general formula 1 wherein
- Ri is a lower alkyl radical
- R 2 is an optionally substituted mononuclear aryl or cycloalkyl radical, the substituent being selected from OH, NH 2 , NO 2 , C (O) OR 3 ; RiaOC (O) -, wherein Ri a has the meanings given above for R 1, and R 3 is H or R 1; or
- R1 and Ria independently of one another represent a lower alkyl radical
- A represents hydrocarbylene (such as alkylene or alkenylene)
- R 2 is a substituted phenyl radical, where the substituent for HO or an ester radical of the formula R i a OC (O) - which is in the para, meta or in particular ortho position to the radical R i OC (O) - on the aromatic ring ,
- Particularly suitable quaternizing agents are the lower alkyl esters of salicylic acid, such as methyl salicylate, ethyl salicylate, n- and i-propyl salicylate, and n-, i- or tert-butyl salicylate.
- salicylic acid such as methyl salicylate, ethyl salicylate, n- and i-propyl salicylate, and n-, i- or tert-butyl salicylate.
- the quaternizable nitrogen compounds reactive with the polycarboxylic acid compound are selected from
- Hydroxyalkyl-substituted mono- or polyamines having at least one quaternized (for example choline) or quaternizable, primary, secondary or tertiary amino group,
- the quaternizable nitrogen compounds are selected from d. Hydroxyalkyl-substituted primary, secondary, tertiary or quaternary monoamines and hydroxyalkyl-substituted primary, secondary, tertiary or quaternary diamines.
- hydroxyalkyl-substituted polyamines and especially “hydroxyalkyl-substituted diamines” may be mentioned: (N-hydroxyalkyl) alkylenediamines, ⁇ , ⁇ -dihydroxyalkylalkylenediamines wherein the hydroxyalkyl groups are the same or different and are also as defined above.
- Hydroxyalkyl stands in particular for 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl
- Alkylene stands in particular for ethylene, propylene or butylene.
- Suitable “diamines” are alkylenediamines and also the N-alkyl-substituted analogs thereof, such as N-monoalkylated alkylenediamines and the N, N or N, N'-dialkylated alkylenediamines.
- Alkylene in particular represents straight-chain or branched C 1-7 or C 1-4 -alkylene.
- Alkylene as defined above, is in particular C 1 -C 4 -alkyl as defined above
- Examples are, in particular, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butylenediamine and isomers thereof, pentanediamine and isomers thereof, Hexanediamine and isomers thereof, heptanediamine and isomers thereof, and mono- or polysubstituted, for example mono- or di-C 1 -C 4 -alkylated, for example methylated, derivatives of the abovementioned diamine compounds, such as 3-dimethylamino-1-propylamine (DMAPA ), ⁇ , ⁇ -diethylaminopropylamine, and N, N-dimethylaminoethylamine.
- DMAPA 3-dimethylamino-1-propylamine
- DMAPA 3-dimethylamino-1-propylamine
- DMAPA 3-di
- Suitable straight-chain “polyamines” are, for example, dialkylenetriamine, triallenetetramine, tetraalkylenepentamine, pentaalkylenehexamine and the N-alkyl-substituted analogs thereof, such as N-monoalkylated and the N, N or N, N'-dialkylated alkylene polyamines branched C1-7 or C1-4-alkylene, as defined above.
- Alkyl is in particular C1-4-alkyl as defined above.
- Examples are in particular diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenhexamine, dibutylenetriamine, tributylenetetramine, tetrabutylenepentamine, pentabutylenhexamine; and the ⁇ , ⁇ -dialkyl derivatives thereof, in particular the N, N-di-Ci-4-alkyl derivatives thereof. Examples which may be mentioned are: N, N-dimethyldimethylenetriamine, ⁇ , ⁇ -diethyldimethylenetriamine, N, N-
- Dipropyldimethylenetriamine N, N-dimethyldiethylene-1,2-triamine, N, N-diethyldiethylene-1,2-triamine, N, N-dipropyldiethylene-1,2-triamine, N, N-dimethyldipropylene-1,3-triamine ( ie DMAPAPA), N, N-diethyl-dipropylene-1,3-triamine, N, N-dipropyl-dipropylene-1,3-triamine, N, N-dimethyl-dibutylene-1,4-triamine, N, N-diethyl-dibutylene-1, 4- triamine, N, N-
- Aromatic carbocyclic diamines having two primary amino groups are the di-amino substituted derivatives of benzene, biphenyl, naphthalene, tetrahydronaphthalene, fluorene, indene, and phenanthrene.
- Aromatic or non-aromatic heterocyclic polyamines having two primary amino groups are the derivatives of the following heterocycles substituted with two amino groups:
- 5- or 6-membered saturated or monounsaturated heterocycles containing one to two nitrogen atoms and / or one oxygen or sulfur atom or one or two oxygen and / or sulfur atoms as ring members eg.
- tetrahydrofuran pyrrolidine, isoxazolidine, isothiazolidine, pyrazolidine, oxazolidine, thiazolidine, imidazolidine, pyrroline, piperidine, piperidinyl, 1, 3-dioxane, tetrahydropyran, hexahydropyridazine, hexahydropyrimidine, piperazine;
- 5-membered aromatic heterocycles containing, in addition to carbon atoms, one, two or three nitrogen atoms or one or two nitrogen atoms and one sulfur or oxygen atom as ring members, e.g. Furan, thian, pyrrole, pyrazole, oxazole, thiazole, imidazole and 1, 3,4-triazole; Isoxazole, isothiazole, thiadiazole, oxadiazole 6-membered heterocycles containing in addition to carbon atoms one or two or one, two or three nitrogen atoms as ring members, for.
- Aromatic or non-aromatic heterocycles containing one primary and one tertiary amino group include the above-mentioned N-heterocycles which are aminoalkylated at least one ring N atom and in particular an amino Ci-4 _ alkyl group carry.
- Aromatic or non-aromatic Heterocycles having a tertiary amino group and a hydroxyalkyl group are, for example, the abovementioned N-heterocycles which are hydroxyalkylated on at least one ring N atom and in particular carry a hydroxy-C 1-4 -alkyl group.
- the following groups of individual classes of quaternizable nitrogen compounds may be mentioned in particular:
- the reaction of the hydrocarbyl-substituted polycarboxylic acid compound with the quaternizable nitrogen compound according to the present invention can be carried out under thermally controlled conditions so that substantially no condensation reaction occurs. In particular, no formation of water of reaction is observed. In particular, such a reaction takes place at a temperature in the range of 10 to 80, in particular 20 to 60 or 30 to 50 ° C.
- the reaction time may be in the range of a few minutes or a few hours, e.g. about 1 minute to about 10 hours.
- the reaction can be carried out at about 0.1 to 2 atm pressure, but especially at about atmospheric pressure.
- an inert gas atmosphere such as e.g. Nitrogen, appropriate
- the reaction can also be carried out under elevated, condensation-promoting temperatures, eg. B. in the range of or 90 to 100 ° C or 100 to 170 ° C.
- the reaction time may be in the range of a few minutes or a few hours, e.g. about 1 minute to about 10 hours.
- the reaction can be carried out at about 0.1 to 2 atm pressure, but especially at about atmospheric pressure.
- the reactants are presented in particular in approximately equimolar amounts, optionally a lower, z. B. 0.05 to 0.5 times, such as 0.1 to 0.3 times, more molar Excess of the polycarboxylic acid compound desirable.
- the reactants may be presented in a suitable inert organic aliphatic or aromatic solvent or a mixture thereof. Typical examples include Solvesso series solvents, toluene or xylene.
- the solvent can also serve, for example, to azeotrope condensation water from the reaction mixture. In particular, however, the reactions are carried out without solvent.
- reaction product thus formed can theoretically be further purified or the solvent removed. Usually, however, this is not absolutely necessary, so that the reaction product can be converted into the next synthesis step, the quaternization, without further purification. b) Quaternization
- the reaction product or reaction mixture from stage a) is mixed with at least one compound of the above formula 1 or 2, in particular in the required stoichiometric amounts, in order to achieve the desired quaternization.
- Per equivalent of quaternizable tertiary nitrogen atom can be e.g. 0.1 to 2.0, 0.2 to 1, 5, or 0.5 to 1, 25 equivalents, to Quater- nhnesstoff use. In particular, however, approximately equimolar proportions of the compound are used to quaternize a tertiary amine group. Correspondingly, higher amounts are required to quaternize a secondary or primary amine group.
- the quaternizing agent is added in excess, such. For example, per equivalent of quaternizable tertiary nitrogen atom 1, 1 to 2.0, 1, 25 to 2 or 1, 25 to 1, 75 equivalents of quaternizing.
- reaction time can be in the range of a few minutes or a few hours, such as about 10 minutes to about 24 hours.
- the reaction can be carried out at about 0.1 to 20 bar, such as 1 to 10 or 1, 5 to 3 bar pressure, but especially at about atmospheric pressure.
- the reactants may be presented in a suitable inert organic aliphatic or aromatic solvent or a mixture thereof for quaternization, or there may still be a sufficient amount of solvent from reaction step a).
- suitable inert organic aliphatic or aromatic solvent or a mixture thereof for quaternization or there may still be a sufficient amount of solvent from reaction step a).
- Typical examples include Solvesso series solvents, toluene or xylene.
- the quaternization can also be carried out in the absence of a solvent
- an acid may be expedient.
- the quaternization can also be carried out in the presence of a Lewis acid.
- the quaternization can also be carried out in the absence of any acid.
- the final reaction product thus formed can theoretically be further purified or the solvent removed.
- solvents may also be added after the reaction, e.g. Solvesso series solvent, 2-ethylhexanol, or substantially aliphatic solvents. Usually, however, this is not absolutely necessary, so that the reaction product can be used without further purification as an additive, if appropriate after mixing with further additive components (see below).
- the fuel additized with the quaternized additive according to the invention is a gasoline fuel or, in particular, a middle distillate fuel, especially a diesel fuel.
- the fuel may contain other conventional additives to improve the effectiveness and / or wear suppression.
- these are primarily conventional detergent additives, carrier oils, cold flow improvers, lubricity improvers, Corrosion inhibitors, demulsifiers, dehazers, antifoam agents, cetane number improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and / or solvents.
- these are mainly friction modifiers, corrosion inhibitors, demulsifiers, dehazers, antifoams, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and / or solvents.
- suitable co-additives are listed in the following section:
- the usual detergent additives are preferably amphiphilic substances which have at least one hydrophobic hydrocarbon radical with a number-average molecular weight (M n ) of from 85 to 20 000 and at least one polar group selected from:
- Polyoxy-C 2 to C 4 -alkylene groups terminated by hydroxyl groups, mono or polyamino groups, wherein at least one nitrogen atom has basic properties, or terminated by carbamate groups; (Dg) carboxylic acid ester groups; (Ie) derived from succinic anhydride moieties having hydroxy and / or amino and / or amido and / or imido groups; and or
- the hydrophobic hydrocarbon residue in the above detergent additives which provides sufficient solubility in the fuel, has a number average molecular weight (M n ) of from 85 to 20,000, preferably from 13 to 10,000, more preferably from 300 to 5,000, more preferable from 300 to 3,000, more preferably from 500 to 2,500 and especially from 700 to 2,500, especially from 800 to 1500.
- M n number average molecular weight
- hydrophobic hydrocarbon radical in particular in conjunction with the polar in particular polypropenyl, polybutenyl and polyisobutenyl radicals having a number average molecular weight M n is preferably from 300 to 5,000 in each case, more preferably from 300 to 3,000, more preferably from 500 to 2,500, even more preferably from 700 to 2,500 and in particular from 800 to 1,500.
- Such additives based on highly reactive polyisobutene, which from the polyisobutene, the up to 20 wt .-% n Can be produced by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are known in particular from EP-A 244 616 known.
- monoamino (Da) -containing additives are the compounds obtained from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DE-A 196 20 262.
- these reaction products are mixtures of pure nitropolyisobutenes (for example ⁇ , ⁇ -dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (for example ⁇ -nitro- ⁇ -hydroxypolyisobutene).
- Carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) containing additives are preferably copolymers of C2 to C 4 o-olefins with maleic anhydride having a total molecular weight of 500 to 20,000, the carboxyl groups wholly or partly to the alkali metal or alkaline earth metal salts and a remaining radical of the carboxyl groups are reacted with alcohols or amines.
- Such additives are known in particular from EP-A 307 815.
- Such additives are primarily used to prevent valve seat wear and, as described in WO-A 87/01 126, can be advantageously used in combination with conventional fuel detergents such as poly (iso) buteneamines or polyetheramines.
- Sulfonic acid groups or their alkali metal or alkaline earth metal salts (De) containing additives are preferably alkali metal or alkaline earth metal salts of a Sulfobern- steinklaklalesters, as described in particular in EP-A 639 632.
- Such additives are mainly used to prevent valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly (iso) buteneamines or polyetheramines.
- Polyoxy-C2-C4-alkylene (Df) containing additives are preferably lyether or polyetheramines, which by reaction of C2 to C6o-alkanols, C6 to C3o-alkanediols, mono- or D1-C2 to C3o-alkylamines, C 1 -C 30 -alkylcyclohexanols or C 1 -C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines are available.
- Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416.
- polyethers such products also meet carrier oil properties. Typical examples thereof are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and also polyisobutenol butoxylates and propoxylates and the corresponding reaction products with ammonia.
- Carboxylic ester groups (Dg) containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, especially those having a minimum viscosity of 2 mm 2 / s at 100 ° C, as described in particular in DE-A 38 38 918 are described.
- mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 C atoms.
- esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and of isotridecanol. Such products also fulfill carrier oil properties.
- the groups having 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, also have free amine groups , Succinic acid derivatives having 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 reacting di- or polyamines with two succinic acid derivatives.
- the further detergent additive for the purposes of the present invention is used only up to a maximum of 100% of the amount by weight of compounds having betaine structure.
- Such fuel additives are well known and described, for example, in documents (1) and (2). Preference is given to the reaction products of alkyl- or alkenyl-substituted succinic acids or derivatives thereof with amines and particularly preferably to the reaction products of polyisobutenyl-substituted succinic acids or derivatives thereof with amines.
- reaction products with aliphatic polyamines in particular ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine, which have an imide structure.
- Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated moieties containing (Di) additives are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine.
- Such "polyisobutene-Mannich bases" are described in particular in EP-A 831 141.
- One or more of said detergent additives may be added to the fuel in such an amount that the dosage rate of these detergent additives is preferably from 25 to 2500 ppm by weight, in particular from 75 to 1500 ppm by weight, especially from 150 to 1000% by weight . ppm. B2) carrier oils
- Co-used carrier oils may be mineral or synthetic.
- Suitable mineral carrier oils are fractions obtained in petroleum processing, such as bright stock or base oils with viscosities such as from class SN 500 to 2000, but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. It is also useful as a "hydrocrack oil” known and obtained in the refining of mineral oil fraction (Vakuumdestillatites with a boiling range of about 360 to 500 ° C, available from high pressure catalytically hydrogenated and isomerized and dewaxed natural mineral oil). Also suitable are mixtures of the abovementioned mineral carrier oils.
- suitable synthetic carrier oils are polyolefins (polyalphaolefins or polyinternalolefins), (poly) esters, poly) alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-initiated polyethers, alkylphenol-initiated polyetheramines and carboxylic acid esters of long-chain alkanols.
- suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C 2 - to C 4 -alkylene groups which are prepared by reacting C 2 - to C 6 -alkanols, C 6 - to C 3 -oxanediols, mono- or C 1 - to C 20 -alkylamines, C 1 -C 30 -alkylcyclohexanols or C 1 -C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines are available.
- P0IV-C2 to C6 alkylene oxide amines or functional derivatives thereof may be used as the polyether amines.
- these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.
- carboxylic acid esters of long-chain alkanols are in particular esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as described in particular in DE-A 38 38 918.
- mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 carbon atoms.
- suitable representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and of isotridecanol, eg. B.
- di- (n- or isotridecyl) phthalate di- (n- or isotridecyl) phthalate.
- suitable carrier oil systems are described, for example, in DE-A 38 26 608, DE-A 41 42 241, DE-A 43 09 074, EP-A 452 328 and EP-A 548 617.
- suitable synthetic carrier oils are alcohol-started polyethers with about 5 to 35, preferably about 5 to 30, particularly preferably 10 to 30 and in particular 15 to 30 C3 to C6 alkylene oxide units, for.
- suitable starter alcohols are long-chain alkanols or long-chain alkyl-substituted phenols, where the long-chain alkyl radical is, in particular, a straight-chain or branched C 6 - to C 18 -alkyl radical.
- Specific examples include tridecanol and nonylphenol.
- Particularly preferred alcohol-started polyethers are the reaction products (polyetherification products) of monohydric C6- to Cis-aliphatic alcohols with C3- to C6-alkylene oxides.
- monohydric C6-C18 aliphatic alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol and their constitution and positional isomers.
- the alcohols can be used both in the form of pure isomers and in the form of technical mixtures.
- a particularly preferred alcohol is tridecanol.
- C3 to C6 alkylene oxides are propylene oxide, such as 1, 2-propylene oxide, butylene oxide, such as 1, 2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran, pentylene oxide and hexylene oxide.
- Particularly preferred among these are C3 to C4 alkylene oxides, i.
- Propylene oxide such as 1, 2-propylene oxide and butylene oxide such as 1, 2-Buty- lenoxid, 2,3-butylene oxide and isobutylene oxide.
- butylene oxide is used.
- suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A 10 102 913.
- Particular carrier oils are synthetic carrier oils, the alcohol-initiated polyethers described above being particularly preferred.
- the carrier oil or the mixture of different carrier oils is added to the fuel in an amount of preferably from 1 to 1000 ppm by weight, more preferably from 10 to 500 ppm by weight and in particular from 20 to 100 ppm by weight.
- Suitable cold flow improvers are in principle all organic compounds which are able to improve the flow behavior of middle distillate fuels or diesel fuels in the cold. Conveniently, they must have sufficient oil solubility. Particularly suitable for this purpose are the middle distillates of fossil origin, ie conventional mineral diesel fuels, used cold flow improvers ("middle distillate flow improvers", "MDFI"). However, it is also possible to use organic compounds which, when used in conventional diesel fuels, have in part or predominantly the properties of a wax anti-settling additive ("WASA"). Also, they can act partly or predominantly as nucleators. However, it is also possible to use mixtures of organic compounds which are active as MDFI and / or which act as WASA and / or as nucleators.
- WASA wax anti-settling additive
- the cold flow improver is selected from:
- Suitable C2 to C4o-olefin monomers for the copolymers of class (K1) are for example those having 2 to 20, in particular 2 to 10 carbon atoms and having 1 to 3, preferably 1 or 2, in particular having a carbon-carbon double bond. In the latter case, the carbon-carbon double bond can be arranged both terminally (a-olefins) and internally.
- ⁇ -olefins more preferably ⁇ -olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene and especially ethylene.
- the at least one further ethylenically unsaturated monomer is preferably selected from carboxylic alkenyl esters, (meth) acrylic esters and further olefins.
- further olefins are polymerized in, these are preferably higher molecular weight than the abovementioned C 2 - to C 4 -olefin base monomers. If, for example, ethylene or propene is used as the olefin base monomer, suitable further olefins are, in particular, C 10 -C 4 -olefins. Other olefins are polymerized in most cases only when monomers with carboxylic acid ester functions are used.
- Suitable (meth) acrylic esters are, for example, esters of (meth) acrylic acid with Cr to C 2 alkanols, in particular C 1 to C 1 alkanols, especially with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert Butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol and structural isomers thereof.
- Suitable carboxylic alkenyl esters are, for example, C 2 - to C 6 -alkenyl esters, for example the vinyl and propenyl esters, of carboxylic acids having 2 to 21 carbon atoms, whose hydrocarbon radical may be linear or branched. Preferred among these are the vinyl esters.
- carboxylic acids with a branched hydrocarbon radical preference is given to those whose branching is in the ⁇ -position to the carboxyl group, the ⁇ -carbon atom being particularly preferably tertiary, ie the carboxylic acid being a so-called neocarboxylic acid.
- the hydrocarbon radical of the carboxylic acid is linear.
- carboxylic alkenyl esters examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, Vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, the vinyl esters being preferred.
- a particularly preferred carboxylic acid alkenyl ester is vinyl acetate; typical resulting copolymers of group (K1) are the most commonly used ethylene-vinyl acetate copolymers ("EVA").
- copolymers of class (K1) are those which contain two or more mutually different carboxylic acid alkenyl esters in copolymerized form, these differing in the alkenyl function and / or in the carboxylic acid group. Also suitable are copolymers which, in addition to the carboxylic acid alkenyl ester (s), contain at least one olefin and / or at least one (meth) acrylic acid ester in copolymerized form.
- Such terpolymers are described in WO 2005/054314.
- a typical such terpolymer is composed of ethylene, 2-ethylhexyl acrylate and vinyl acetate.
- the at least one or the other ethylenically unsaturated monomers are present in the copolymers of class (K1) in an amount of preferably from 1 to 50% by weight, in particular from 10 to 45% by weight and especially from 20 to 40% by weight. %, based on the total copolymer, copolymerized.
- the majority by weight of the monomer units in the copolymers of class (K1) thus usually comes from the C2 to C 4 o-based olefins.
- the copolymers of class (K1) preferably have a number average molecular weight M n of from 1000 to 20,000, particularly preferably from 1000 to 10,000 and in particular from 1000 to 8000.
- Typical comb polymers of component (K2) are, for example, by the copolymerization of maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an ⁇ -olefin or an unsaturated one Esters such as vinyl acetate, and subsequent esterification of the anhydride or acid function with an alcohol having 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 may also be polyfumarates or polymaleinates.
- homopolymers and copolymers of vinyl ethers are suitable comb polymers.
- Comb polymers suitable as a component of class (K2) are, for example, those described in WO 2004/035715 and in "Comb-Like Polymers, Structure and Properties", NA Plate and VP Shibaev, J. Poly. Be. Macromolecular Revs. 8, pages 1 17 to 253 (1974). "Mixtures of comb polymers are also suitable.
- polyoxyalkylenes examples include polyoxyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester ethers and mixtures thereof.
- These polyoxyalkylene compounds preferably comprise at least one, preferably at least two, linear alkyl groups each having from 10 to 30 carbon atoms and a polyoxyalkylene group having a number average molecular weight of up to 5,000.
- Such polyoxyalkylene compounds are described, for example, in EP-A 061 895 and in US Pat. No. 4,491,455.
- Particular polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a number average molecular weight of from 100 to 5,000.
- Polar nitrogen compounds suitable as a component of class (K4) may be of both ionic and nonionic nature, and preferably have at least one, especially at least two, tertiary nitrogen substituent of the general formula> NR 7 , wherein R 7 is Cs to C 40 Hydrocarbon residue.
- the nitrogen substituents may also be quaternized, that is in cationic form.
- nitrogen compounds are ammonium salts and / or amides obtainable by reacting at least one amine substituted with at least one hydrocarbyl radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof.
- the amines contain at least one linear Cs to C4o-alkyl radical.
- Primary amines suitable for the preparation of said polar nitrogen compounds are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine lamin and the higher linear homologues
- secondary amines suitable for this purpose are, for example, dioctadecylamine and methylbehenylamine.
- amine mixtures in particular industrially available amine mixtures such as fatty amines or hydrogenated tallamines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, in the chapter "Amines, aliphatic".
- Suitable acids for the reaction are, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and succinic acids substituted by long-chain hydrocarbon radicals.
- the component of class (K4) is an oil-soluble reaction product of at least one tertiary amino group-containing poly (C 2 - to C 20 -carboxylic acids) with primary or secondary amines.
- the poly (C 2 - to C 20 -carboxylic acids) which have at least one tertiary amino group and are based on this reaction product preferably contain at least 3 carboxyl groups, in particular 3 to 12, especially 3 to 5, carboxyl groups.
- the carboxylic acid units in the polycarboxylic acids preferably have 2 to 10 carbon atoms, in particular they are acetic acid units.
- the carboxylic acid units are suitably linked to the polycarboxylic acids, usually via one or more carbon and / or nitrogen atoms. Preferably, they are attached to tertiary nitrogen atoms, which are connected in the case of several nitrogen atoms via hydrocarbon chains.
- the component of class (K4) is preferably an oil-soluble reaction product based on poly (C 2 - to C 20 -carboxylic acids) of general formula IIa or IIb having at least one tertiary amino group
- variable A is a straight-chain or branched C 2 - to C 6 -alkylene group or the grouping of the formula III HOOC ' ⁇ N ' 0 " 2'0 " 2 '
- the preferred oil-soluble reaction product of component (K4) in particular that of general formula IIa or IIb, is an amide, an amide ammonium salt or an ammonium salt in which no, one or more carboxylic acid groups are converted into amide groups.
- Straight-chain or branched C 2 - to C 6 -alkylene groups of the variable A are, for example, 1, 1-ethylene, 1, 2-propylene, 1, 3-propylene, 1, 2-butylene, 1, 3-butylene, 1, 4-butylene ethylene, 2-methyl-1, 3-propylene, 1, 5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene (hexamethylene) and especially 1, 2-ethylene.
- the variable A preferably comprises 2 to 4, in particular 2 or 3, carbon atoms.
- Cr to Ci9-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, Nonadecamethylen and especially methylene.
- the variable B comprises 1 to 10, in particular 1 to 4, carbon atoms.
- the primary and secondary amines as reaction partners for the polycarboxylic acids to form the component (K4) are usually monoamines, in particular aliphatic monoamines. These primary and secondary amines may be selected from a variety of amines bearing hydrocarbon radicals, optionally linked together.
- amines which are the oil-soluble reaction products of component (K4) are secondary amines and have the general formula HN (R 8 ) 2 in which the two variables R 8 independently of one another each represent straight-chain or branched C 10 - to C 30 -alkyl radicals, in particular C 14 - to C24-alkyl radicals mean.
- These longer-chain alkyl radicals are preferably straight-chain or only slightly branched.
- the abovementioned secondary amines are derived with regard to their longer-chain alkyl radicals from naturally occurring fatty acid or from its derivatives.
- the two radicals R 8 are the same.
- the abovementioned secondary amines can be bound to the polycarboxylic acids by means of amide structures or in the form of the ammonium salts, and only one part can be present as amide structures and another part as ammonium salts. Preferably, only a few or no free acid groups are present.
- 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-diaminetetraacetic acid with in each case 0.5 to 1.5 mol per carboxyl group, in particular 0.8 to 1.2 mol per carboxyl group, dioleylamine, dipalmitinamine, dicoco fatty amine, distearylamine, dibehenylamine or, in particular, Ditaigfettamin.
- a particularly preferred component (K4) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated dithiol fatty amine.
- component (K4) include the N, N-dialkylammonium salts of 2-N ', ⁇ '-dialkylamidobenzoates, for example the reaction product of 1 mole of phthalic anhydride and 2 moles of diethfamine, the latter being hydrogenated or unhydrogenated , and the reaction product of 1 mole of a Alkenylspirobislac- tons with 2 moles of a dialkylamine, for example, Ditaigfettamin and / or tallow fatty amine, the latter two may be hydrogenated or unhydrogenated, called.
- N, N-dialkylammonium salts of 2-N ', ⁇ '-dialkylamidobenzoates for example the reaction product of 1 mole of phthalic anhydride and 2 moles of diethfamine, the latter being hydrogenated or unhydrogenated
- the reaction product of 1 mole of a Alkenylspirobislac- tons with 2 moles of a dialkylamine for example, Dit
- component of the class (K4) are cyclic compounds having tertiary amino groups or condensates of long-chain primary or secondary amines with carboxylic acid-containing polymers, as described in WO 93/181 15.
- Sulfocarboxylic acids, sulfonic acids or their derivatives which are suitable as cold flow improvers of the component of the class (K5) are, for example, the oil-soluble carboxylic acid amides and carboxylic esters of ortho-sulfobenzoic acid in which the sulfonic acid function is present as a sulfonate with alkyl-substituted ammonium cations, as described in EP -A 261 957.
- suitable poly (meth) acrylic acid esters are both homo- and copolymers of acrylic and methacrylic acid esters.
- copolymers of at least two mutually different (meth) acrylic acid esters which differ with respect to the fused alcohol.
- the copolymer contains a further, different of which olefinically unsaturated monomer copolymerized.
- the weight-average molecular weight of the polymer is preferably 50,000 to 500,000.
- a particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated C14 and Cis alcohols wherein the acid groups are neutralized with hydrogenated tallamine. Suitable poly (meth) acrylic esters are described, for example, in WO 00/44857.
- the middle distillate fuel or diesel fuel is the cold flow improver or the mixture of various cold flow improvers in a total amount of preferably 10 to 5000 ppm by weight, more preferably from 20 to 2000 ppm by weight, more preferably from 50 to 1000 ppm by weight and in particular from 100 to 700 ppm by weight, for example from 200 to 500 ppm by weight, added.
- Suitable lubricity improvers are usually based on fatty acids or fatty acid esters. Typical examples are tall oil fatty acid, as described, for example, in WO 98/004656, and glycerol monooleate.
- the reaction products of natural or synthetic oils, for example triglycerides, and alkanolamines described in US Pat. No. 6,743,266 B2 are also suitable as such lubricity improvers.
- Suitable corrosion inhibitors are succinic esters, especially with polyols, fatty acid derivatives, for example oleic esters, oligomerized fatty acids, substituted ethanolamines and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany) or HiTEC 536 (Ethyl Corporation).
- RC 4801 Rhein Chemie Mannheim, Germany
- HiTEC 536 Ethyl Corporation
- Suitable demulsifiers are e.g. the alkali or alkaline earth salts of alkyl-substituted phenol and naphthalenesulfonates and the alkali or alkaline earth salts of fatty acids, as well as neutral compounds such as alcohol alkoxylates, e.g. Alcohol ethoxylates, phenol alkoxylates, e.g. tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate, fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), e.g. also in the form of EO / PO block copolymers, polyethyleneimines or polysiloxanes.
- EO ethylene oxide
- PO propylene oxide
- Suitable dehazers are e.g. alkoxylated phenol-formaldehyde condensates such as the NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite) products available under the tradename.
- Suitable antifoams are e.g. Polyether-modified polysiloxanes, such as, for example, the TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc) products available under the tradename.
- Polyether-modified polysiloxanes such as, for example, the TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc) products available under the tradename.
- Cetane number improvers are e.g. aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate and peroxides such as di-tert-butyl peroxide.
- antioxidants are, for example, substituted phenols, such as 2,6-di-tert-butylphenol and 6-di-tert-butyl-3-methylphenol, and also phenylenediamines, such as N, N'-di-sec-butyl-p - phenylenediamine.
- phenylenediamines such as N, N'-di-sec-butyl-p - phenylenediamine.
- Suitable metal deactivators are e.g. Salicylic acid derivatives such as N, N'-disalicylidene-1, 2-propanediamine.
- Suitable ones are e.g. non-polar organic solvents such as aromatic and aliphatic hydrocarbons, for example toluene, xylenes, "white spirit" and products sold under the trade name SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (ExxonMobil), and polar organic solvents, in particular For example, alcohols such as 2-ethylhexanol, decanol and isotridecanol. Such solvents usually arrive together with the aforementioned additives and co-additives which they are intended to dissolve or dilute for better handling into the diesel fuel.
- non-polar organic solvents such as aromatic and aliphatic hydrocarbons, for example toluene, xylenes, "white spirit” and products sold under the trade name SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (ExxonMobil)
- polar organic solvents in particular For example, alcohols such as 2-ethylhex
- the additive of the invention is outstandingly suitable as a fuel additive and can be used in principle in any fuels. It has a number of beneficial effects on the operation of 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 fuels, especially middle distillate fuels, with an effective as an additive to achieve beneficial effects in the operation of internal combustion engines, such as diesel engines, especially direct injection diesel engines, especially of diesel engines with common rail injection systems, effective content on the quaternized additive according to the invention.
- This effective content is generally from 10 to 5000 ppm by weight, preferably from 20 to 1500 ppm by weight, in particular from 25 to 1000 ppm by weight, especially from 30 to 750 ppm by weight, each based on the total amount of fuel.
- Middle distillate fuels such as diesel fuels or fuel oils
- mineral middle distillate mineral fuels or diesel fuels available through refining
- those produced by coal gasification or gas liquefaction [GTL] or by biomass to liquid (BTL) fuels are also included. are available, suitable. Also suitable are mixtures of the abovementioned middle distillate fuels or diesel fuels with regenerative fuels, such as biodiesel or bioethanol.
- the quaternized additive according to the invention can also be used in mixtures of such middle distillates with biofuel oils (biodiesel).
- biofuel oils biodiesel
- such mixtures are also encompassed by the term "middle distillate fuel”. They are commercially available and usually contain the biofuel oils in minor amounts, typically in amounts of 1 to 30 wt .-%, in particular from 3 to 10 wt .-%, based on the total amount of middle distillate of fossil, vegetable or animal origin and biofuel.
- Biofuel oils are generally based on fatty acid esters, preferably substantially on alkyl esters of fatty acids derived from vegetable and / or animal oils and / or fats.
- Alkyl esters are usually lower alkyl esters, especially C 1 to C 4 alkyl esters, understood by transesterification of occurring in vegetable and / or animal oils and / or fats glycerides, especially triglycerides, by means of lower alcohols, for example ethanol or especially methanol (“ FAME ”) are available.
- Typical lower alkyl esters based on vegetable and / or animal oils and / or fats which are used as biofuel oil or components thereof are, for example, sunflower methyl ester, palm oil methyl ester ("PME”), soybean oil methyl ester (“SME”) and especially rapeseed oil methyl ester ("RME ").
- the middle distillate fuels or diesel fuels are 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 of less than 0.005% by weight and especially less than 0.001% by weight of sulfur.
- gasoline fuels are all commercially available gasoline fuel compositions into consideration.
- a typical representative here is the market-standard basic fuel of Eurosuper according to EN 228.
- gasoline compositions of the specification according to WO 00/47698 are also possible fields of use for the present invention.
- the quaternized additive according to the invention is particularly suitable as a fuel additive in fuel compositions, in particular in diesel fuels, to overcome the initially described problems in direct injection diesel engines, especially in those with common rail injection systems.
- test methods described herein are not limited to the specific embodiments but are part of the general disclosure of the description and generally applicable in the context of the present invention.
- the power loss (power loss) based on the official test method CEC F-098-08.
- the power loss is a direct measure of the formation of deposits in the injectors.
- the Keep Clean Test is based on the CEC Test Procedure F-098-08 Issue 5.
- the same test setup and motor type (PEUGEOT DW10) are used as in the CEC procedure.
- the test period was 12h without shutdown periods.
- the one-hour test cycle (see following table) from the CEC F-098-08 was traversed 12 times.
- the initial power (Po, KC [kW]) is calculated from the measured torque at 4,000 rpm full load immediately after the engine starts and warms up.
- the procedure is described in issue 5 of the test procedure CEC F-98-08.
- the same test setup and the PEUGEOT DW10 motor type are used.
- the final power (P en d, KC) is determined in the 12th cycle in step 12, (see table above). Again, the operating point is 4000 / min full load. P en d, KC [kW] is calculated from the measured torque.
- the power loss in the KC is calculated as follows:
- PIBSA Made from maleic anhydride and PIB 1000 in a known manner.
- grades having saponification numbers in the range of 84-95 mg KOH / g were used.
- DMAPA was used with the respective PI BSA quality in a molar ratio of 1: 1 corresponding to the saponification number.
- the PIBSA grades used had a degree of bismeralization (BMG) of less than 15%.
- Polyisobutylene succinic anhydride (1659 g) is dissolved in Solvent Naphta Heavy (SNH, Exxon Mobil, CAS 64742-95-5) (1220 g) and 3-dimethylamino-1-propylamine (DMAPA, 153 g) is added.
- the reaction solution is stirred for 8 h at 170 ° C, with formed condensation water is distilled off continuously.
- the PIBSA-DMAPA succinimide is obtained as a solution in Solvent Naphta Heavy (TBN 0.557 mmol / g).
- Polyisobutylene succinic anhydride (PIBSA, 2198 g) is heated to 110 ° C and 3-dimethylamino-1-propylamine (DMAPA, 182 g) is added within 40 min. added, with the reaction mixture heated to 140 ° C. The reaction mixture is heated to 170 ° C and held for 3 h at this temperature, with 28 g of distillate are collected.
- PI BSA-DMAPA succinimide is obtained as a viscous oil (TBN 0.735 mmol / g).
- Polyisobutylene succinic anhydride (PIBSA, 2198 g) is heated to 110 ° C and 3-dimethylamino-1-propylamine (DMAPA, 182 g) is added within 40 min. added, with the reaction mixture heated to 140 ° C. The reaction mixture is heated to 170 ° C and held for 3 h at this temperature, with 28 g of distillate are collected.
- PIBSA-DMAPA succinimide is obtained as a viscous oil (TBN 0.735 mmol / g).
- the additives are used either as a pure substance (as synthesized in the above preparation examples) or in the form of an additive package.
- M1 additive according to preparation example 2 (invention, quaternized with methyl salicylate)
- M2 additive according to preparation example 4 (comparison, quaternized with dimethyl sulfate)
- M3 additive according to preparation example 5 (comparison, quaternized with dimethycarbonate)
- the power loss was determined on the basis of the official test method CEC -098-08 as described above.
- the power loss is a direct measure of the formation of deposits in the injectors.
- a common direct-injection diesel engine with common-rail system was used.
- the fuel used was a commercial diesel fuel from Garrmann (RF-06-03).
- To this was added 1 wt ppm zinc in the form of a zinc didodecanoate solution to artificially stimulate the formation of deposits on the injectors.
- the table below shows the results of relative power loss (powerloss) at 4000 rpm after 12 hours of continuous operation without interruption.
- the value Po indicates the power after 10 minutes and the value P en d the power at the end of the measurement:
- the test results are shown in Table 2.
- Table 2 Results of the DW10 test
- the additive M1 according to the invention has an improved effect compared with the basic value and has an improved effect at least in comparison with the example M3.
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Abstract
Description
Claims
Priority Applications (10)
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AU2012277805A AU2012277805C1 (en) | 2011-06-28 | 2012-06-28 | Quaternized nitrogen compounds and use thereof as additives in fuels and lubricants |
BR112013033798A BR112013033798A2 (pt) | 2011-06-28 | 2012-06-28 | compostos de nitrogênio quaternizados e o uso dos mesmos como aditivos em combustíveis e lubrificantes |
CN201280041927.9A CN103764806B (zh) | 2011-06-28 | 2012-06-28 | 季铵化氮化合物及其在燃料和润滑剂中作为添加剂的用途 |
KR1020147001241A KR102070364B1 (ko) | 2011-06-28 | 2012-06-28 | 4급화된 질소 화합물, 및 연료 및 윤활제에서의 첨가제로서 그의 용도 |
MX2014000038A MX2014000038A (es) | 2011-06-28 | 2012-06-28 | Compuestos de nitrogeno cuaternizados y uso de los mismos como aditivos en combustibles y lubricantes. |
CA2840524A CA2840524C (en) | 2011-06-28 | 2012-06-28 | Quaternized nitrogen compounds and use thereof as additives in fuels and lubricants |
ES12737233.2T ES2579852T3 (es) | 2011-06-28 | 2012-06-28 | Compuestos de nitrógeno cuaternizados y su uso como aditivos en carburantes y lubricantes |
EP12737233.2A EP2726580B1 (de) | 2011-06-28 | 2012-06-28 | Quaternisierte stickstoffverbindungen und deren verwendung als additive in kraft- und schmierstoffen |
AU2016273853A AU2016273853B2 (en) | 2011-06-28 | 2016-12-12 | Quaternized nitrogen compounds and use thereof as additives in fuels and lubricants |
AU2019201700A AU2019201700B2 (en) | 2011-06-28 | 2019-03-13 | Quaternized nitrogen compounds and use thereof as additives in fuels and lubricants |
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EP11171763A EP2540808A1 (de) | 2011-06-28 | 2011-06-28 | Quaternisierte Stickstoffverbindungen und deren Verwendung als Additive in Kraft- und Schmierstoffen |
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KR (1) | KR102070364B1 (de) |
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AU (3) | AU2012277805C1 (de) |
BR (1) | BR112013033798A2 (de) |
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Also Published As
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CA2840524A1 (en) | 2013-01-03 |
EP2540808A1 (de) | 2013-01-02 |
AU2012277805B2 (en) | 2016-09-15 |
AU2016273853A1 (en) | 2017-01-05 |
EP2726580B1 (de) | 2016-04-27 |
AU2019201700B2 (en) | 2020-05-21 |
BR112013033798A2 (pt) | 2017-02-14 |
PL2726580T3 (pl) | 2016-12-30 |
AU2012277805A1 (en) | 2014-02-20 |
CA2840524C (en) | 2020-09-08 |
CN103764806A (zh) | 2014-04-30 |
AU2019201700A1 (en) | 2019-04-04 |
CN103764806B (zh) | 2016-08-17 |
AU2016273853B2 (en) | 2018-12-20 |
ES2579852T3 (es) | 2016-08-17 |
EP2726580A1 (de) | 2014-05-07 |
AU2012277805C1 (en) | 2020-09-03 |
KR102070364B1 (ko) | 2020-01-29 |
KR20140051253A (ko) | 2014-04-30 |
HUE030070T2 (en) | 2017-04-28 |
MX2014000038A (es) | 2014-02-17 |
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