Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/30—Organic compounds compounds not mentioned before (complexes)
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
  • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
  • C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
• • 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
  • C10L10/12—Use of additives to fuels or fires for particular purposes for improving the cetane number
• • 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
• • 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
  • C10L10/16—Pour-point depressants
• • 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
  • C10L1/1802—Organic compounds containing oxygen natural products, e.g. waxes, extracts, fatty oils
• • 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
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters

Definitions

• the present invention relates to fuel compositions which comprise renewable raw materials, to the use of ester-comprising polymers in fuel compositions, and to the processes for operating diesel engines with fuel compositions of the present invention.
• biodiesel is in many cases understood to mean a mixture of fatty acid esters, usually fatty acid methyl esters (FAMEs), with chain lengths of the fatty acid fraction of 14 to 24 carbon atoms with 0 to 3 double bonds. The higher the carbon number and the fewer double bonds are present, the higher is the melting point of the FAME.
• Typical raw materials are vegetable oils (i.e. glycerides) such as rapeseed oils, sunflower oils, soya oils, palm oils, coconut oils and, in isolated cases, even used vegetable oils. These are converted to the corresponding FAMEs by transesterification, usually with methanol under basic catalysis.
• palm oil methyl ester In contrast to rapeseed oil methyl ester (RME), which is frequently used in Europe and typically contains approx. 5% C16:0+C18:0-FAME, palm oil methyl ester (PME) contains approx. 50% C16:0+C18.0-FAME. A similar high C16:0+C18:0 FAME content is also possessed by the analogous derivatives of animal tallows, for example beef tallow. Such a high wax content can barely be influenced by polymeric flow improvers, which are typically added with an addition rate of up to 2%. In comparison to rapeseed oil, palm oil can be obtained with more than three times as high a crop yield per hectare. This gives rise to immense economic advantages. However, a disadvantage is the high pour point of PME, which is about +12° C.
• hydroxy-functional PAMAs are known as flow improvers for biodiesel in the literature (EP 1 032 620 to RohMax Additives GmbH).
• EP 1 032 620 mixtures of fossil fuels with biodiesel fuels are described, but no examples which use such a mixture are adduced.
• a biodiesel fuel especially based on RME, which has particularly good low-temperature properties should be provided.
• RME which has particularly good low-temperature properties
• EP 1 541 662 to 664 details mixtures comprising 75% by volume of diesel fuel of mineral origin and 25% by volume of biodiesel, which comprise 150 ppm of poly(dodecyl methacrylate) and from 100 to 200 ppm of ethylene-vinyl acetate copolymer (EVA).
• EVA ethylene-vinyl acetate copolymer
• the use of EVA is described herein as obligatory. EVA is, however, quite an expensive additive. Accordingly, alternatives in which the use of EVA can be dispensed with are desirable. There is no indication in EP 1 541 663 to the advantageousness of particular ester-comprising polymers.
• a fuel composition containing 20% by weight of diesel fuel of mineral origin and from 0.05 to 5% by weight of at least one ester-comprising polymer which comprises repeat units which are derived from ester monomers having 16 to 40 carbon atoms in the alcohol radical, and repeat units which are derived from ester monomers having 7 to 15 carbon atoms in the alcohol radical, it is surprisingly possible to provide a fuel composition which comprises at least one diesel fuel of mineral origin and at least one biodiesel fuel, which, with a property profile which is very similar to that of mineral diesel fuel, comprises a very high proportion of renewable raw materials.
• inventive fuel compositions can achieve a series of further advantages. These include:
• inventive fuel compositions can be used in conventional diesel engines without the seal materials used customarily being attacked.
• Preferred fuel compositions of the present invention have a particularly high cetane number which can be improved in particular by the use of biodiesel fuels having a high proportion of long-chain saturated fatty acids.
• the present invention is aimed at the use of very oxidation-stable biodiesel fuels. This allows reduction of the formation of deposits in the engine, which can lead to a low overall performance of the engine.
• palm oil alkyl esters can be used in the fuels.
• palm oil is preferred over the customarily used rapeseed oil.
• the crop yield in the production of palm oil is significantly higher than that of rapeseed oil.
• very large amounts of ecologically controversial chemicals, especially fertilizers and crop protection compositions are used.
• rape is not self-compatible in production and has to be cultivated in a crop rotation system, in which case cultivation of rape in the same field is possible only every 3 to 5 years. For this reason, a further increase in rape production is difficult.
• palm oil alkyl esters have a significantly higher cloud point (approx. +13° C. in the case of the methyl ester) in comparison to rapeseed oil alkyl esters; the cloud point of rapeseed oil alkyl ester is significantly lower (approx. ⁇ 7° C. in the case of the methyl ester).
• the present invention thus enables the use of particularly high proportions of palm oil alkyl esters for producing fuel compositions without the low-temperature properties assuming impermissible values.
• the fuel composition of the present invention comprises diesel fuel of mineral origin, i.e. diesel, gas oil or diesel oil.
• Mineral diesel fuel is widely known per se and is commercially available. This is understood to mean a mixture of different hydrocarbons which is suitable as a fuel for a diesel engine. Diesel can be obtained as a middle distillate, in particular by distillation of crude oil.
• the main constituents of the diesel fuel preferably include alkanes, cycloalkanes and aromatic hydrocarbons having about 10 to 22 carbon atoms per molecule.
• Preferred diesel fuels of mineral origin boil in the range of 120 to 450° C., more preferably 170 and 390° C.
• They are preferably those middle distillates which have been subjected to refining under hydrogenating conditions, and which therefore contain only small proportions of polyaromatic and polar compounds.
• Synthetic fuels as obtainable, for example, by the Fischer-Tropsch process, are also suitable as diesel fuels of mineral origin.
• the kinematic viscosity of diesel fuels of mineral origin to be used with preference is in the range of 0.5 to 8 mm 2 /s, more preferably 1 to 5 mm 2 /s and especially preferably 1.5 to 3 mm 2 /s, measured at 40° C. to ASTM D 445.
• the fuel compositions of the present invention comprise at least 20% by weight, in particular at least 30% by weight, preferably at least 50% by weight, more preferably at least 70% by weight and most preferably at least 80% by weight of diesel fuels of mineral origin.
• the present fuel composition comprises at least one biodiesel fuel component.
• Biodiesel fuel is a substance, especially an oil, which is obtained from vegetable or animal material or both, or a derivative thereof which can be used in principle as a replacement for mineral diesel fuel.
• the biodiesel fuel which is frequently also referred to as “biodiesel” or “biofuel” comprises fatty acid alkyl esters formed from fatty acids having preferably 6 to 30, more preferably 12 to 24 carbon atoms, and monohydric alcohols having 1 to 4 carbon atoms. In many cases, some of the fatty acids may contain one, two or three double bonds.
• the monohydric alcohols include in particular methanol, ethanol, propanol and butanol, methanol being preferred.
• oils which derive from animal or vegetable material and which can be used in accordance with the invention are palm oil, rapeseed oil, coriander oil, soya oil, cottonseed oil, sunflower oil, castor oil, olive oil, groundnut oil, corn oil, almond oil, palm kernel oil, coconut oil, mustardseed oil, oils which are derived from animal tallow, especially beef tallow, bone oil, fish oils and used cooking oils.
• oils which derive from cereal, wheat, jute, sesame, rice husks, jatropha, arachis oil and linseed oil may be obtained from these oils by processes known in the prior art.
• Palm oil also: palm fat
• the oil may contain up to 80% C18:0-glyceride.
• biodiesel fuels are lower alkyl esters of fatty acids.
• Useful examples here are commercial mixtures of the ethyl, propyl, butyl and especially methyl esters of fatty acids having 6 to 30, preferably 12 to 24, more preferably 14 to 22 carbon atoms, for example of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselic acid, ricinoleic acid, elaeostearic acid, linoleic acid, linolenic acid, eicosanoic acid, gadoleic acid, docosanoic acid or erucic acid.
• a biodiesel fuel which comprises preferably at least 30% by weight, more preferably at least 35% by weight and most preferably at least 40% by weight of saturated fatty acid esters which have at least 16 carbon atoms in the fatty acid radical.
• saturated fatty acid esters which have at least 16 carbon atoms in the fatty acid radical.
• Biodiesel fuels usable in accordance with the invention preferably have an iodine number of at most 150, in particular at most 125, more preferably at most 70 and most preferably at most 60.
• the iodine number is a measure known per se for the content in a fat or oil of unsaturated compounds, which can be determined to DIN 53241-1.
• the fuel compositions of the present invention form a particularly low level of deposits in the diesel engines.
• these fuel compositions have particularly high cetane numbers.
• the fuel compositions of the present invention may comprise at least 0.5% by weight, in particular at least 3% by weight, preferably at least 5% by weight and more preferably at least 15% by weight of biodiesel fuel.
• the fuel composition of the present invention comprises 0.05 to 5% by weight, preferably 0.08 to 3% by weight and more preferably 0.1 to 1.0% by weight of at least one ester-comprising polymer.
• ester-comprising polymers are understood to mean polymers which are obtainable by polymerizing monomer compositions which comprise ethylenically unsaturated compounds having at least one ester group, which are referred to hereinafter as ester monomers. Accordingly, these polymers contain ester groups as part of the side chain.
• These polymers include in particular polyalkyl (meth)acrylates (PAMAs), polyalkyl fumarates and/or polyalkyl maleates.
• Ester monomers are known per se. These include in particular (meth)acrylates, maleates and fumarates which may have different alcohol radicals.
• the term (meth)acrylates encompasses methacrylates and acrylates, and also mixtures of the two. These monomers are widely known.
• the alkyl radical may be linear, cyclic or branched. Moreover, the alkyl radical may have known substituents.
• the ester-comprising polymers contain repeat units which are derived from ester monomers having 16 to 40 carbon atoms in the alcohol radical, and repeat units which are derived from ester monomers having 7 to 15 carbon atoms in the alcohol radical.
• ester unit is widely known in the technical field.
• the present ester-comprising polymers may preferably be obtained via free-radical polymerization of monomers, the ATRP, RAFT and NMP processes which will be detailed later being included in the free-radical processes in the context of the invention, without any intention that this should impose a restriction.
• double bonds are opened up to form covalent bonds. Accordingly, the repeat unit is formed from the monomers used.
• the ester-comprising polymer may contain 5 to 99.9% by weight, in particular 20 to 98% by weight, preferably 30 to 95% by weight and most preferably 70 to 92% by weight of repeat units which are derived from ester monomers having 7 to 15 carbon atoms in the alcohol radical.
• the ester-comprising polymer may contain 0.1 to 80% by weight, preferably 0.5 to 60% by weight, more preferably 2 to 50% by weight and most preferably 5 to 20% by weight of repeat units which are derived from ester monomers having 16 to 40 carbon atoms in the alcohol radical.
• ester-comprising polymer may contain 0.1 to 30% by weight, preferably 0.5 to 20% by weight, of repeat units which are derived from ester monomers having 1 to 6 carbon atoms in the alcohol radical.
• the ester-comprising polymer comprises preferably at least 40% by weight, more preferably at least 60% by weight, especially preferably at least 80% by weight and most preferably at least 95% by weight of repeat units which are derived from ester monomers.
• Mixtures from which the inventive ester-comprising polymers are obtainable may contain 0 to 40% by weight, preferably 0.1 to 30% by weight, in particular 0.5 to 20% by weight, of one or more ethylenically unsaturated ester compounds of the formula (I)
• R is hydrogen or methyl
• R 1 is a linear or branched alkyl radical having 1 to 6 carbon atoms
• R 2 and R 3 are each independently hydrogen or a group of the formula —COOR′ in which R′ is hydrogen or an alkyl group having 1 to 6 carbon atoms.
• component (I) examples include
• (meth)acrylates fumarates and maleates which derive from saturated alcohols, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate and pentyl (meth)acrylate, hexyl (meth)acrylate; cycloalkyl (meth)acrylates such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate; (meth)acrylates which derive from unsaturated alcohols, such as 2-propynyl (meth)acrylate, allyl (meth)acrylate and vinyl (meth)acrylate.
• saturated alcohols such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropy
• compositions to be polymerized preferably contain 10 to 98% by weight, in particular 20 to 95% by weight, of one or more ethylenically unsaturated ester compounds of the formula (II)
• R is hydrogen or methyl
• R 4 is a linear or branched alkyl radical having 7 to 15 carbon atoms
• R 5 and R 6 are each independently hydrogen or a group of the formula —COOR′′ in which R′′ is hydrogen or an alkyl group having 7 to 15 carbon atoms.
• component (II) examples include
• (meth)acrylates fumarates and maleates which derive from saturated alcohols, such as 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, 2-tert-butylheptyl(meth)acrylate, octyl (meth)acrylate, 3-isopropylheptyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (meth)acrylate, 2-methyldodecyl (meth)acrylate, tridecyl (meth)acrylate, 5-methyltridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate; (meth)acrylates which derive from unsaturated alcohols, for example oleyl (meth)acrylate
• preferred monomer compositions contain 0.1 to 80% by weight, preferably 0.5 to 60% by weight, more preferably 2 to 50% by weight and most preferably 5 to 20% by weight of one or more ethylenically unsaturated ester compounds of the formula (III)
• R is hydrogen or methyl
• R 7 is a linear or branched alkyl radical having 16 to 40, preferably 16 to 30, carbon atoms
• R 8 and R 9 are each independently hydrogen or a group of the formula —COOR′′′ in which R′′′ is hydrogen or an alkyl group having 16 to 40, preferably 16 to 30, carbon atoms.
• component (III) examples include (meth)acrylates which derive from saturated alcohols, such as hexadecyl (meth)acrylate, 2-methylhexadecyl (meth)acrylate, heptadecyl (meth)acrylate, 5-isopropylheptadecyl (meth)acrylate, 4-tert-butyloctadecyl (meth)acrylate, 5-ethyloctadecyl (meth)acrylate, 3-isopropyloctadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, cetyleicosyl (meth)acrylate, stearyleicosyl (meth)acrylate, docosyl (meth)acrylate and/or eicosyltetratriacontyl (meth)acrylate;
• saturated alcohols such as hex
• cycloalkyl (meth)acrylates such as 2,4,5-tri-t-butyl-3-vinylcyclohexyl (meth)acrylate, 2,3,4,5-tetra-t-butylcyclohexyl (meth)acrylate; and the corresponding fumarates and maleates.
• ester compounds having a long-chain alcohol radical can be obtained, for example, by reacting (meth)acrylates, fumarates, maleates and/or the corresponding acids with long-chain fatty alcohols, which generally gives a mixture of esters, for example (meth)acrylates with various long-chain alcohol radicals.
• These fatty alcohols include Oxo Alcohol® 7911 and Oxo Alcohol® 7900, Oxo Alcohol® 1100; Alfol® 610, Alfol® 810, Lial® 125 and Nafol® types (Sasol); Alphanol® 79 (ICI); Epal® 610 and Epal® 810 (Afton); Linevol® 79, Linevol® 911 and Neodol® 25E (Shell AG); Dehydad®, Hydrenol® and Lorol® types (Cognis); Acropol® 35 and Exxal® 10 (Exxon Chemicals); Kalcol 2465 (Kao Chemicals).
• R2, R3, R5, R6, R8 and R9 of the formulae (I), (II) and (III) are each hydrogen in particularly preferred embodiments.
• the weight ratio of ester monomers of the formula (II) to the ester monomers of the formula (III) may be within a wide range.
• the ratio of ester compounds of the formula (II) which contain 7 to 15 carbon atoms in the alcohol radical to the ester compounds of the formula (III) which contain 16 to 40 carbon atoms in the alcohol radical is preferably in the range of 50:1 to 1:30, more preferably in the range of 10:1 to 1:3, especially preferably 5:1 to 1:1.
• Component (IV) comprises in particular ethylenically unsaturated monomers which can be copolymerized with the ethylenically unsaturated ester compounds of the formulae (I), (II) and/or (III).
• R 1 * and R 2 * are each independently selected from the group consisting of hydrogen, halogens, CN, linear or branched alkyl groups having 1 to 20, preferably 1 to 6 and more preferably 1 to 4, carbon atoms which may be substituted by 1 to (2n+1) halogen atoms, where n is the number of carbon atoms of the alkyl group (for example CF 3 ), ⁇ , ⁇ -unsaturated linear or branched alkenyl or alkynyl groups having 2 to 10, preferably 2 to 6 and more preferably 2 to 4, carbon atoms which may be substituted by 1 to (2n ⁇ 1) halogen atoms, preferably chlorine, where n is the number of carbon atoms of the alkyl group, for example CH 2 ⁇ CCl—, cycloalkyl groups having 3 to 8 carbon atoms which may be substituted by 1 to (2n ⁇ 1) halogen atoms, preferably chlorine, where n is the number of carbon atoms of the cycloalkyl groups
• the preferred comonomers (IV) include hydroxyalkyl (meth)acrylates such as 3-hydroxypropyl methacrylate, 3,4-dihydroxybutyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,5-dimethyl-1,6-hexanediol (meth)acrylate, 1,10-decanediol (meth)acrylate; aminoalkyl (meth)acrylates such as N-(3-dimethylaminopropyl)methacrylamide, 3-diethylaminopentyl methacrylate, 3-dibutylaminohexadecyl (meth)acrylate; nitriles of (meth)acrylic acid and other nitrogen-containing methacrylates, such as N-(methacryloyloxyethyl)diisobutyl ketimine, N-(methacryloyloxyethyl)dihexadec
• methacrylates of halogenated alcohols such as 2,3-dibromopropyl methacrylate, 4-bromophenyl methacrylate, 1,3-dichloro-2-propyl methacrylate, 2-bromoethyl methacrylate, 2-iodoethyl methacrylate, chloromethyl methacrylate; oxiranyl methacrylates such as 2,3-epoxybutyl methacrylate, 3,4-epoxybutyl methacrylate, 10,11-epoxyundecyl methacrylate, 10,11-epoxyhexadecyl methacrylate, 2,3-epoxycyclohexyl methacrylate; glycidyl methacrylate; phosphorus-, boron- and/or silicon-containing methacrylates such as 2-(dimethylphosphato)propyl methacrylate, 2-(ethylenephosphito)propyl methacrylate, dimethylphosphinomethyl
• the proportion of comonomers (IV) can be varied depending on the use and property profile of the polymer. In general, this proportion may be in the range from 0 to 60% by weight, preferably from 0.01 to 20% by weight and more preferably from 0.1 to 10% by weight. Owing to the combustion properties and for ecological reasons, the proportion of the monomers which comprise aromatic groups, heteroaromatic groups, nitrogen-containing groups, phosphorus-containing groups and sulphur-containing groups should be minimized. The proportion of these monomers can therefore be restricted to 1% by weight, in particular 0.5% by weight and preferably 0.01% by weight.
• the comonomers (IV) and the ester monomers of the formulae (I), (II) and (III) can each be used individually or as mixtures.
• ester-comprising polymers have a better activity in mixtures of mineral diesel fuel and biodiesel fuel which comprise merely a small proportion, if any, of units which are derived from hydroxyl-containing monomers. This is especially true of biodiesel fuels which have a high proportion of saturated fatty acids which have at least 16 carbon atoms in the acid radical.
• ester-comprising polymers to be used with preference in the inventive fuel mixtures preferably contain at most 5% by weight, preferably at most 3% by weight, more preferably at most 1% by weight and most preferably at most 0.1% by weight of units which are derived from hydroxyl-containing monomers. These include hydroxyalkyl (meth)acrylates and vinyl alcohols. These monomers have been detailed above.
• ester-comprising polymers have a better activity in mixtures of mineral diesel fuel and biodiesel fuel which comprise only a small proportion, if any, of repeat units which derive from monomers having oxygen-containing alcohol radicals of the formula (IV)
• R is hydrogen or methyl
• R 10 is an alkyl radical which is substituted by an OH group and has 2 to 20 carbon atoms, or an alkoxylated radical of the formula (V)
• R 13 and R 14 are each independently hydrogen or methyl
• R 15 is hydrogen or an alkyl radical having 1 to 20 carbon atoms
• n is an integer of 1 to 30
• R 11 and R 12 are each independently hydrogen or a group of the formula —COOR′′′′ in which R′′′′ is hydrogen or an alkyl radical which is substituted by an OH group and has 2 to 20 carbon atoms, or an alkoxylated radical of the formula (V)
• R 13 and R 14 are each independently hydrogen or methyl
• R 15 is hydrogen or an alkyl radical having 1 to 20 carbon atoms
• n is an integer of 1 to 30.
• Ester-comprising polymers to be used with preference have a thickening efficiency TE100 in the range of 4.0 to 50 mm 2 /s, preferably 7.5 to 29 mm 2 /s.
• the designations KV100 and KV40 describe the kinematic viscosity of the oil at 100° C. and 40° C. respectively to ASTM D445, the abbreviation VI the viscosity index determined to ASTM D 2270.
• the ester-comprising polymers to be used in accordance with the invention may generally have a molecular weight in the range of 1000 to 1 000 000 g/mol, preferably in the range of 25 000 to 700 000 g/mol and more preferably in the range of 40 000 to 600 000 g/mol and most preferably in the range of 60 000 to 300 000 g/mol, without any intention that this should impose a restriction. These values are based on the weight-average molecular weight M w of the polydisperse polymers in the composition. This parameter can be determined by GPC.
• the preferred copolymers which can be obtained by polymerizing unsaturated ester compounds preferably have a polydispersity M w /M n in the range of 1 to 10, more preferably 1.05 to 6.0 and most preferably 1.2 to 5.0. This parameter can be determined by GPC.
• ester-comprising polymers may be random copolymers, gradient copolymers, block copolymers and/or graft copolymers.
• Block copolymers and gradient copolymers can be obtained, for example, by altering the monomer composition discontinuously during the chain growth.
• the blocks derived from ester compounds of the formulae (I), (II) and/or (III) preferably have at least 30 monomer units.
• polyalkyl esters from the above-described compositions.
• ATRP Atom Transfer Radical Polymerization
• RAFT Reversible Addition Fragmentation Chain Transfer
• the usable initiators include the azo initiators widely known in the technical field, such as AIBN and 1,1-azobiscyclohexanecarbonitrile, and also peroxy compounds such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl per-2-ethylhexanoate, ketone peroxide, tert-butyl peroctoate, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropylcarbonate, 2,5-bis(2-ethylhexanoylperoxy)-2
• Suitable chain transferrers are in particular oil-soluble mercaptans, for example dodecyl mercaptan or 2-mercaptoethanol, or else chain transferrers from the class of the terpenes, for example terpineols.
• the ATRP process is known per se. It is assumed that it is a “living” free-radical polymerization, without any intention that this should restrict the description of the mechanism.
• a transition metal compound is reacted with a compound which has a transferable atom group. This transfers the transferable atom group to the transition metal compound, which oxidizes the metal. This reaction forms a radical which adds onto ethylenic groups.
• the transfer of the atom group to the transition metal compound is reversible, so that the atom group is transferred back to the growing polymer chain, which forms a controlled polymerization system.
• the structure of the polymer, the molecular weight and the molecular weight distribution can be controlled correspondingly. This reaction is described, for example, by J S.
• inventive polymers may be obtained, for example, also via RAFT methods. This process is presented in detail, for example, in WO 98/01478 and WO 2004/083169, to which reference is made explicitly for the purposes of disclosure.
• inventive polymers are also obtainable by NMP processes (nitroxide-mediated polymerization), which is described, inter alia, in U.S. Pat. No. 4,581,429.
• the polymerization may be carried out at standard pressure, reduced pressure or elevated pressure.
• the polymerization temperature too is uncritical. However, it is generally in the range of ⁇ 200-200° C., preferably 0°-130° C. and more preferably 600-120° C.
• the polymerization may be carried out with or without solvent.
• solvent is to be understood here in a broad sense.
• the polymerization is preferably carried out in a nonpolar solvent.
• nonpolar solvent include hydrocarbon solvents, for example aromatic solvents such as toluene, benzene and xylene, saturated hydrocarbons, for example cyclohexane, heptane, octane, nonane, decane, dodecane, which may also be present in branched form.
• hydrocarbon solvents for example aromatic solvents such as toluene, benzene and xylene, saturated hydrocarbons, for example cyclohexane, heptane, octane, nonane, decane, dodecane, which may also be present in branched form.
• solvents may be used individually and as a mixture.
• Particularly preferred solvents are mineral oils, diesel fuels of mineral origin, natural vegetable and animal oils, biodiesel fuels and synthetic oils (e.g. ester oils such as dinonyl adipate), and also mixtures thereof
• the inventive fuel composition may comprise further additives in order to achieve specific solutions to problems.
• additives include dispersants, for example wax dispersants and dispersants for polar substances, demulsifiers, defoamers, lubricity additives, antioxidants, cetane number improvers, detergents, dyes, corrosion inhibitors and/or odourants.
• the inventive fuel composition may comprise ethylene copolymers which are described, for example, in EP-A-1 541 663.
• These ethylene copolymers may contain 8 to 21 mol % of one or more vinyl and/or (meth)acrylic esters and 79 to 92% by weight of ethylene.
• Particular preference is given to ethylene copolymers containing 10 to 18 mol % and especially 12 to 16 mol % of at least one vinyl ester.
• Suitable vinyl esters derive from fatty acids having linear or branched alkyl groups having 1 to 30 carbon atoms.
• Examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl heptanoate, vinyl octanoate, vinyl laurate and vinyl stearate, and also esters of vinyl alcohol based on branched fatty acids, such as vinyl isobutyrate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl isononanoate, vinyl neononanoate, vinyl neodecanoate and vinyl neoundecanoate.
• Comonomers which are likewise suitable are esters of acrylic acid and methacrylic acid having 1 to 20 carbon atoms in the alkyl radical, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n- and isobutyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, and also mixtures of two, three or four or else more of these comonomers.
• Particularly preferred terpolymers of vinyl 2-ethylhexanoate, of vinyl neononanoate and of vinyl neodecanoate contain, apart from ethylene, preferably 3.5 to 20 mol %, in particular 8 to 15 mol %, of vinyl acetate and 0.1 to 12 mol %, in particular 0.2 to 5 mol %, of the particular long-chain vinyl ester, the total comonomer content being between 8 and 21 mol %, preferably between 12 and 18 mol %.
• copolymers contain, in addition to ethylene and 8 to 18 mol % of vinyl esters, also 0.5 to 10 mol % of olefins such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene and/or norbornene.
• olefins such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene and/or norbornene.
• the ethylene copolymers preferably have molecular weights which correspond to melt viscosities at 140° C. of from 20 to 10 000 mPas, in particular 30 to 5000 mPas and especially 50 to 1000 mPas.
• the degrees of branching determined by means of 1 H NMR spectroscopy are preferably between 1 and 9 CH 3 /100 CH 2 groups, in particular between 2 and 6 CH 3 /100 CH 2 groups, for example 2.5 to 5 CH 3 /100 CH 2 groups, which do not stem from the comonomers.
• Such ethylene copolymers are described in detail, inter alia, in DE-A-34 43 475, EP-B-0 203 554, EP-B-0 254 284, EP-B-0 405 270, EP-B-0 463 518, EP-B-0 493 769, EP-0 778 875, DE-A-196 20 118, DE-A-196 20 119 and EP-A-0 926 168.
• ethylene-vinyl acetate copolymers and terpolymers which, in addition to ethylene and vinyl acetate repeat units, also have repeat (meth)acrylic ester units.
• These polymers may be structured, for example, as random copolymers, as block copolymers or as graft copolymers.
• the inventive fuel composition may comprise 0.0005 to 2% by weight, preferably 0.01 to 0.5% by weight, of ethylene copolymers.
• the proportion of ethylene copolymers may preferably be at most 0.05% by weight, more preferably at most 0.001% by weight and most preferably at most 0.0001% by weight.
• Preferred fuel compositions consist of
• the inventive fuel compositions preferably have an iodine number of at most 30, more preferably at most 20 and most preferably at most 10.
• the inventive fuel compositions have outstanding low-temperature properties.
• the pour point (PP) to ASTM D97 preferably has values of less than or equal to 0° C., preferably less than or equal to ⁇ 5° C. and more preferably less than or equal to ⁇ 10° C.
• the limit of filterability (cold filter plugging point, CFPP) measured to DIN EN 116 is preferably at most 0° C., more preferably at most ⁇ 5° C. and more preferably at most ⁇ 10° C.
• the cloud point (CP) to ASTM D2500 of preferred fuel compositions may assume values of less than or equal to 0° C., preferably less than or equal to ⁇ 5° C. and more preferably less than or equal to ⁇ 10° C.
• the cetane number to DIN 51773 of inventive fuel compositions is preferably at least 50, more preferably at least 53, in particular at least 55 and most preferably at least 58.
• the viscosity of the present fuel compositions may be within a wide range, and this can be adjusted to the intended use. This adjustment can be effected, for example, by selecting the biodiesel fuels or the mineral diesel fuels. In addition, the viscosity can be varied by the amount and the molecular weight of the ester-comprising polymers used.
• the kinematic viscosity of preferred fuel compositions of the present invention is in the range of 1 to 10 mm 2 /s, more preferably 2 to 5 mm 2 /s and especially preferably 2.5 to 4 mm 2 /s, measured at 40° C. to ASTM D445.
• ester-comprising polymers which comprise repeat units derived from unsaturated esters having 7 to 15 carbon atoms in the alcohol radical and repeat units derived from unsaturated esters having 16 to 40 carbon atoms in the alcohol radical in a concentration of 0.05 to 5% by weight as a flow improver in fuel compositions which comprise at least one diesel fuel of mineral origin and at least one biodiesel fuel accordingly provides fuel compositions with exceptional properties, as a result of which known diesel engines can be operated in a simple and inexpensive manner.
• the remaining amount of 555.6 g of monomer/regulator mixture is admixed with 1.4 g of tert-butyl peroctoate.
• 0.25 g of tert-butyl peroctoate is added, and the feed of the monomer/regulator/initiator mixture by means of a pump is started simultaneously.
• the addition is effected uniformly over a period of 210 min at 100° C. 2 h after the end of feeding, another 1.2 g of tert-butyl peroctoate are added and the mixture is stirred at 100° C. for a further 2 h.
• a 60% clear concentrate is obtained.
• the mass-average molecular weight M w and the polydispersity index PDI of the polymers were determined by GPC.
• the measurements were effected in tetrahydrofuran at 35° C. against a polymethyl methacrylate calibration curve composed of a set of ⁇ 25 standards (Polymer Standards Service or Polymer Laboratories), whose M peak was distributed in a logarithmically uniform manner over the range of 5 ⁇ 10 6 to 2 ⁇ 10 2 g/mol.
• a combination of six columns (Polymer Standards SDV 100 ⁇ /2xSDV LXL/2xSDV 100 ⁇ /Shodex KF-800D) was used.
• an RI detector Align 1100 Series
• the polymers thus obtained were investigated in an 80/20 mixture of mineral diesel/biodiesel.
• the amount of polymer used is shown in Table 2.
• the mineral diesel used was a summer diesel of Australian origin with a pour point of ⁇ 9° C.
• a palm oil methyl ester (PME) (source of palm oil raw material: Malaysia) having a pour point of +12° C. was used as the biodiesel.
• An 80/20 mixture of mineral diesel/biodiesel exhibited a pour point of 0° C.
• ester-comprising polymers containing repeat units which are derived from ester monomers having 16 to 40 carbon atoms in the alcohol radical lead to significantly better low-temperature properties of mixtures which comprise biodiesel, especially palm oil esters, and mineral diesel.
• preferred mixtures which comprise certain ester-comprising polymers have an improved pour point compared to the pure mineral diesel fuel without additive, this improved pour point also being retained in the case of addition of biodiesel.

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