EP1500691A2 - Brennstofföladditive und additivierte Brennstofföle mit verbesserten Kälteeigenschaften - Google Patents
Brennstofföladditive und additivierte Brennstofföle mit verbesserten Kälteeigenschaften Download PDFInfo
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- EP1500691A2 EP1500691A2 EP04016063A EP04016063A EP1500691A2 EP 1500691 A2 EP1500691 A2 EP 1500691A2 EP 04016063 A EP04016063 A EP 04016063A EP 04016063 A EP04016063 A EP 04016063A EP 1500691 A2 EP1500691 A2 EP 1500691A2
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
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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
- C10L1/16—Hydrocarbons
- C10L1/1625—Hydrocarbons macromolecular compounds
- C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
- C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/16—Hydrocarbons
- C10L1/1625—Hydrocarbons macromolecular compounds
- C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
- C10L1/1658—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
- C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
- C10L1/1981—Condensation polymers of aldehydes or ketones
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
- C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/224—Amides; Imides carboxylic acid amides, imides
Definitions
- the present invention relates to mineral oils and mineral oil distillates with improved Cold properties and a polymeric additive for improving the Cold properties.
- Crude oils and middle distillates obtained by the distillation of crude oils such as gas oil, Diesel oil or fuel oil contain different amounts depending on the origin of the crude oils on n-paraffins, which when the temperature is lowered as platelet-shaped crystals crystallize out and partially agglomerate with inclusion of oil. Thereby it comes to a deterioration of the flow properties of these oils or Distillates, whereby, for example, in extraction, transport, storage and / or Use of mineral oils and mineral oil distillates may occur.
- at Mineral oils can undergo this phenomenon of crystallization during transport Pipelines, especially in winter to deposits on the pipe walls, in Individual cases, e.g. at standstill of a pipeline, even to its complete blockage to lead.
- the flow and cold behavior of mineral oils and mineral oil distillates is through Specification of the cloud point (determined according to ISO 3015), the pour point (determined according to ISO 3016) and the Cold Filter Plugging Point (CFPP, determined according to EN 116) described. These parameters are measured in ° C.
- Typical flow improvers for crude oils and middle distillates are copolymers of Ethylene with one or more carboxylic acid esters of vinyl alcohol, such as for example, EVA copolymers. Also copolymers of ethylene with olefins such as propene and block copolymers are as cold flow improvers known.
- Block copolymers are in particular as materials or as a component for Materials are known where, because of their properties as thermoplastic Elastomer are estimated. In addition, there are also applications in oils known.
- JP-A-11 106 764 and JP-A-11 148 085 disclose block copolymers of the type Styrene-butadiene / isoprene-styrene for lowering the CFPP and the pour point of low sulfur or heavy middle distillates. These are alternatives to EVA copolymers and other known pour point depressants for Middle distillates.
- the block copolymers are optionally together with Polyoxyalkylenderivaten used.
- JP-A-2000-256684 discloses the same block copolymers as JP-A-111 06 764 / JP-A-11 148 085 for lowering the CFPP and the pour point of Middle distillates, which also used here together with Polyoxyalkylenderivaten can be.
- the block copolymers have one determined by DSC Glass transition temperature from -10 to 80 ° C.
- U.S. 3,807,975 discloses middle distillates such as diesel, jet fuel and gas oil improved pumpability in the cold, to set a pour point of below -18 ° C additives based on copolymers of ethylene with propylene, Vinyl acetate, aminoalkyl esters or acrylic acid esters and in addition to Improvement of filterability in the cold 50-1,000 ppm of certain copolymers of styrene and butadiene.
- the styrene-butadiene copolymers have Molecular weight of up to 5000 and contain 10 to 30 wt .-% of styrene. It will no structure of the copolymers specified.
- DE-A-2 711 218 discloses fuel oils which, in addition to alkyl hydroxycarboxylates et al a hydrogenated styrene-butadiene copolymer (Mw 96,000, 27% styrene, 63% Butadiene) as pour point depressants.
- EP-A-0 815 184 and EP-A-1 302 526 disclose hydrogenated block copolymers Serve as cold flow improver for middle distillates.
- the blocks consist of crystalline blocks of 1,4-linked dienes on the one hand and non-crystalline ones Blocks of 1,2-linked linear dienes and / or branched dienes on the other hand.
- the block copolymers are used in combination with known ones Used flow improvers.
- DD-254 955 discloses block copolymers EVA polystyrene EVA with 0.4-12% by weight Polystyrene as flow improver for middle distillates. The less soluble in mineral oil Polystyrene block forms here but the middle block, so that one for Triblock copolymers typical gel formation via microphase separation not here can occur.
- EP-A-0 082 399 discloses that after conventional radical Polymerization processes produced ethylene copolymers with living, by anionic polymerization polymers converted into block copolymers can be.
- the ethylene blocks contain polar comonomers such as acrylates; the living radicals are based on homopolymers of styrene or dienes or their more or less random copolymers.
- These Block copolymers may i.a. Mineral oils are added.
- paraffin dispersion in middle distillates is in many cases unsatisfactory with the additives of the prior art.
- oils with a low paraffin content especially in the cold-critical chain length range of C 16 -C 22 , the paraffin dispersion is often difficult because the particles can not be held in suspension by mutual repulsion.
- high paraffin contents as they occur, among other things, even at temperatures far below the cloud point, difficult to disperse.
- Oils with a low content of aromatics are particularly problematic because the solubility of the paraffins here below the cloud point decreases particularly strongly. Therefore, additives are sought, which lead in particular in critical oils and at low storage temperatures to an improved paraffin dispersion.
- olefin copolymers already described as cold additives are random copolymers of ethylene and longer-chain olefins which, on co-crystallization with the paraffins precipitated in the cold from middle distillates, reduce their crystal size and thus lead to improved filterability of the oils in the cold. But they do not contribute to the dispersion of paraffin crystals.
- Another object of the invention is a middle distillate, which is an above contains defined additive.
- Another object of the invention is the use of an additive as above defined for improving the cold flow behavior of middle distillates.
- Another object of the invention is a method for improving the Cold flow behavior and / or the paraffin dispersion of middle distillates, by you add him an additive as defined above.
- the paraffin dispersants which are suitable according to the invention are preferably reaction products of fatty amines with compounds which contain an acyl group.
- the alkyl and alkenyl radicals can be linear or branched and contain up to two double bonds. They are preferably linear and substantially saturated, ie they have iodine numbers of less than 75 gl 2 / g, preferably less than 60 gl 2 / g and in particular between 1 and 10 gl 2 / g. Particularly preferred are secondary fatty amines in which two of the groups R 6 , R 7 and R 8 are C 8 -C 36 -alkyl, C 6 -C 36 -cycloalkyl, C 8 -C 36 -alkenyl, in particular C 12 -C 24 alkyl, C 12 -C 24 alkenyl or cyclohexyl.
- Suitable fatty amines are, for example, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, behenylamine, didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine, dioctadecylamine, dieicosylamine, dibehenylamine and mixtures thereof.
- the amines contain chain cuts based on natural raw materials such as coconut fatty amine, tallow fatty amine, hydrogenated tallow fatty amine, dicocosfettamine, di-tallow fatty amine and di (hydrogenated tallow fatty amine).
- Particularly preferred amine derivatives are amine salts, imides and / or amides such as amide ammonium salts of secondary fatty amines, in particular of dicocosfettamine, di-tallow fatty amine and distearylamine.
- Suitable carbonyl compounds for the reaction with amines are both low molecular weight and polymeric compounds having one or more carboxyl groups.
- carboxylic acids examples include maleic, fumaric, crotonic, itaconic, succinic, C 1 -C 40 -alkenylsuccinic, adipic, glutaric, sebacic, and malonic acids and benzoic, phthalic, trimellitic and pyromellitic acid, nitrilotriacetic acid , Ethylenediaminetetraacetic acid and their reactive derivatives such as esters, anhydrides and acid halides.
- Copolymers of ethylenically unsaturated acids such as, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, have proven particularly suitable as polymeric carbonyl compounds, particular preference is given to copolymers of maleic anhydride.
- Suitable comonomers are those which impart oil solubility to the copolymer. Oil-soluble is understood here to mean that the copolymer dissolves without residue in the middle distillate to be additized after reaction with the fatty amine in practice-relevant metering rates.
- Suitable comonomers are, for example, olefins, alkyl esters of acrylic acid and methacrylic acid, alkyl vinyl esters, alkyl vinyl ethers having 2 to 75, preferably 4 to 40 and in particular 8 to 20 carbon atoms in the alkyl radical.
- the alkyl radical bound to the double bond is equivalent here.
- the molecular weights of the polymeric carbonyl compounds are preferably between 400 and 20,000, more preferably between 500 and 10,000, for example between 1,000 and 5,000.
- Paraffin dispersants which have proved particularly suitable by reaction aliphatic or aromatic amines, preferably long-chain aliphatic Amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides are obtained (see US 4 211 534).
- Amides and ammonium salts of aminoalkylene polycarboxylic acids such as Nitrilotriacetic acid or ethylenediaminetetraacetic acid with secondary amines as Paraffin dispersants are suitable (compare EP 0 398 101).
- paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols can be implemented (see EP-A-0 154 177, EP 07777712), which Reaction products of alkenyl spiro-bis-lactones with amines (see EP-A-0 413 279 B1) and, according to EP-A-0 606 055 A2, reaction products of terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic anhydrides, ⁇ , ⁇ -unsaturated compounds and Polyoxyalkylenethern lower unsaturated alcohols.
- the type A blocks have low solubility in Middle distillates and aggregate by microphase separation to form micelle-like structures, while the B blocks have oil-soluble structures and at least partially co-crystallize with the paraffins. requirement is that they are in the application-relevant concentration at least at elevated temperatures (e.g., 50 ° C) clear in the middle distillate.
- Suitable block copolymers are known per se and partly commercial available, e.g. under the brand name Kraton TM.
- the blocks A and B may be homopolymers, random or tapered copolymers As long as the solution properties for the respective blocks characteristic stay.
- the A blocks may be copolymer blocks of styrene-co-methylstyrene or styrene-co-butadiene as long as the individual blocks the Properties of a poly (vinyl aromatic) show.
- the A blocks exist more than 80%, in particular 90 to 100%, of monoalkenylaryl units.
- Suitable as A blocks are monoalkenylaryl polymers derived from styrene and its Homologues such as o-methylstyrene, p-methylstyrene, p-propylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, alpha-methylstyrene, vinylnaphthalene, vinylanthracene and derive similar compounds.
- Preferred monomers are monocyclic Monovinylaromatics such as styrene and alpha-methylstryol. Especially preferred is styrene.
- the blocks preferably have a molecular weight of from 1,000 to 50,000, preferably 2,000 to 20,000.
- the A blocks are preferably monoalkenylaryl homopolymers, in particular poly (styrene).
- Suitable B blocks include, for example, poly (olefins), which are derived from dienes for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 3-butyl-1,3-octadiene, 1,3-pentadiene (piperylene), 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4-ethyl-1,3-hexadiene and the like Derive connections.
- 1,3-butadiene and isoprene are the preferred ones Monomer units of the blocks B.
- butadiene it can be homopolymers as well Be copolymers of different olefins.
- the solubility of the additives and their ability to co-crystallize with Paraffins are influenced by the proportion of 1,4- and 1,2-polymers.
- the poly (butadiene) units preferably between 10 and 60%, in particular 20 to 50% 1,2-configuration;
- Butadiene copolymers preferably contain 20 to 45 mol% branched Monomer units such.
- block copolymers are, for example, poly (styrene-b-butadiene-bstyrene), Poly (styrene-b-isoprene-b-styrene) and poly (styrene-b-isoprene-co-butadiene-b-styrene).
- the diene-derived olefin blocks can be used to lower their olefinic Unsaturation hydrogenated by known hydrogenation.
- the content of In this case, olefinic double bonds are in particular around 50%, preferably in order at least 80% and especially by at least 90% such as at least 95% of the original double bonds reduced.
- Preferred blocks B thus have a poly (ethylene), poly (ethylene-co-propylene) or poly (ethylene-co-butylene), comparable structure.
- Branches of midblock B can be prepared by branched monomers such as e.g. Isoprene can be produced or by 1,2-polymerization of butadiene. Of the Proportion of 1,2-polymerization of butadiene becomes more polar by addition Compounds such as ethers, amines and other Lewis bases and especially of Glykoldialkylethern set. This results in statistical polymers 1,4- and 1,2-polymers.
- branched monomers such as e.g. Isoprene can be produced or by 1,2-polymerization of butadiene.
- Compounds such as ethers, amines and other Lewis bases and especially of Glykoldialkylethern set. This results in statistical polymers 1,4- and 1,2-polymers.
- the polyolefin blocks B preferably have a molecular weight of from 1,000 to 100,000, preferably from 2,000 to 50,000 and especially 5,000 to 20,000.
- On the Proportion of B blocks in the polymer and their degree of branching can be the Crystallinity of the B block and thus its solubility in the middle distillate and its Ability to co-crystallize with the paraffins of the diesel to be added to adjust.
- the block copolymers have at least two A blocks through a B block are separated. They are thus tri-, tetra- and higher block copolymers. Particularly preferred are triblock copolymers containing two monoalkenylaryl blocks and specifically containing two polystyrene blocks.
- the preferred block copolymers have a linear structure, although branched and star-shaped polymers are suitable are.
- the A blocks can be used with respect to the underlying monomers, the Molecular weights and polydispersity are the same or different; prefers derive from styrene.
- Preferred block copolymers contain from 5 to 50% by weight of A blocks, preferably 10 to 45, especially 20 to 40 wt .-%.
- the content of B blocks is Accordingly, between 50 and 95 wt .-%, preferably between 55 and 90 wt .-% and in particular between 60 and 80 wt .-%.
- Blocks are present, provided that the character of the polymers is not fundamental change.
- the molecular weight of the block copolymers of the invention is preferably between 3,000 and 200,000, especially between 6,000 and 150,000 and especially between 10,000 and 110,000 such as between 10,000 and 50,000.
- n is a number between 1 and 5 such as 2 or 3 and m is one Number between 2 and 5.
- Particularly preferred are triblock copolymers with n 1.
- the preparation of the block copolymers can be carried out by customary polymerization processes by initiation with free radicals, cationic or anionic Polymerization initiators or by grafting of A blocks on the finished Polymer B take place. There are both methods of mass, the solution as well the emulsion polymerization suitable.
- Preferred initiators for the anionic polymerization are organometallic compounds and in particular organolithium compounds of the general formula RLi n , wherein R is an aliphatic, cycloaliphatic, aromatic or alkyl-substituted aromatic hydrocarbon radical having 1 to 20 C atoms and n is a number from 1 to 4.
- n-butyllithium, sec-butyllithium and naphthyllithium are particularly preferred.
- Suitable solvents for the polymerization include paraffins, cycloparaffins, aromatics and alkylaromatics having 1 to 19 carbon atoms such as benzene, toluene, cyclohexane, methylcyclohexane, n-butene, n-hexane, n-heptane and the like.
- polar solvents such as Tetrahydrofuran be added.
- tetrablock and higher repeat units can also be reactive via anionic polymerization Block copolymers via low molecular weight crosslinking reagents such.
- organic Halogen compounds dibromoethane
- halogenated alkylsilanes alkyoxysilanes
- difunctional esters such as dialkyl adipates and dimethacrylates
- polyepoxides such as epoxidized linseed oil
- polyanhydrides or polyfunctional reagents such as for example, divinylbenzene, polyvinylbenzene, polyvinyltoluene and oligomers of Divinylbenzene be linked.
- the same or different Diblockcopolymere A-B to symmetric or asymmetric Linked triblock copolymers.
- the resulting polymer can be a linear triblock copolymer or have a branched, circular or star-shaped structure.
- Preferred triblock copolymers are linear.
- the one at the link residual diblock copolymer content does not contribute to paraffin dispersion and should therefore be as low as possible, that is below 25% by weight, preferred between 5 and 20 wt .-% are.
- the additives according to the invention are used as such or as concentrates in used organic solvents. They will be easier to handle advantageously dissolved in organic solvents. These concentrates contain 10 to 90 wt .-%, preferably 20 to 80 wt .-% solvent in addition to the active ingredient.
- Suitable solvents or dispersants are aliphatic and / or aromatic Hydrocarbons or hydrocarbon mixtures, e.g. Petroleum fractions, Kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or commercial Solvent mixtures such as Solvent Naphtha, ®Shellsoll AB, ® Solvesso 150, ® Solvesso 200, ®Exxsol, ®ISOPAR and ®Shellsol D grades.
- the specified Solvent mixtures contain varying amounts of aliphatic and / or aromatic hydrocarbons.
- the aliphatics can be straight-chain (n-paraffins) or branched (iso-paraffins).
- Aromatic hydrocarbons may be mono-, di- or polycyclic and optionally one or more Wear substituents.
- polar solubilizers such as e.g. Butanol, 2-ethylhexanol, decanol, iso-decanol or iso-tridecanol or higher Ether and / or esters are added.
- Solvents are also solvents based on renewable raw materials, such as e.g. Biodiesel based on vegetable oils and the derived methyl esters, in particular rapeseed oil methyl ester, as well as synthetic hydrocarbons which For example, from the Fischer-Tropsch process are available suitable.
- the additives according to the invention can be used individually or as oils to be added be added as a mixture. Preferably, they are diluted with solvents.
- the block copolymers of the invention are oils in amounts of 1 to 2,000 ppm, preferably 5 to 1,000 ppm and in particular 10 to 100 ppm (active substance) added.
- the metering rates for the components and II are usually in the Range between 1 and 10,000 ppm, and preferably between 10 and 1,500 ppm, in particular between 10 and 500 ppm.
- the ratio of components I and II in the additive or in the additized middle distillate is between 1:10 and 1: 0.1.
- the additives according to the invention for middle distillates contain in a preferred Embodiment in addition to the constituents I and II nor one or more Copolymers of ethylene and olefinically unsaturated compounds as an ingredient III.
- ethylene copolymers are those which in addition to ethylene 6 to 21 mol%, in particular 10 to 18 mol% of comonomers.
- these copolymers have melt viscosities at 140 ° C from 20 to 10,000 mPas, in particular from 30 to 5,000 mPas, especially from 50 to 2,000 mPas.
- the olefinically unsaturated compounds are preferably Vinyl esters, acrylic esters, methacrylic esters, alkyl vinyl ethers and / or alkenes, wherein the mentioned compounds may be substituted with hydroxyl groups. It can one or more comonomers may be included in the polymer.
- said alkyl groups may be substituted with one or more hydroxyl groups.
- R 1 is a branched alkyl radical or a neoalkyl radical having 7 to 11 carbon atoms, in particular having 8, 9 or 10 carbon atoms.
- Suitable vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl heptanoate, vinyl octanoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl neononanoate, vinyl neodecanoate, vinyl neo-decanoate, vinyl laurate and vinyl stearate.
- Suitable acrylic esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n- and isobutyl (meth) acrylate, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, Tetradecyl, hexadecyl, octadecyl (meth) acrylate and mixtures of these comonomers.
- said alkyl groups may be substituted with one or more hydroxyl groups.
- An example of such an acrylic ester is hydroxyethyl methacrylate.
- said alkyl groups may be substituted with one or more hydroxyl groups.
- the alkenes are preferably monounsaturated Hydrocarbons having 3 to 30 carbon atoms, in particular 4 to 16 Carbon atoms and especially 5 to 12 carbon atoms.
- Suitable alkenes include propene, butene, isobutylene, pentene, hexene, 4-methylpentene, octene, Diisobutylene and norbornene and its derivatives such as methylnorbornene and Vinyl norbornene.
- the mentioned Alkyl groups substituted with one or more hydroxyl groups.
- Particularly preferred terpolymers contain, apart from ethylene, from 0.1 to 12 mol%, in particular from 0.2 to 5 mol% of vinyl neononanoate or of Neodecanoic acid vinyl ester and 3.5 to 20 mol%, in particular 8 to 15 mol% Vinyl acetate, the total comonomer content being between 8 and 21 mol%, is preferably between 12 and 18 mol%.
- Further particularly preferred Copolymers contain in addition to ethylene and 8 to 18, mol% vinyl esters still 0.5 to 10 mol% of olefins such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, Diisobutylene and / or norbornene.
- additives according to the invention contain ethylene copolymers as constituent III, see above These are in amounts of preferably 1 to 10,000, especially 10 and 1500 ppm used.
- the mixing ratio of the components I, II and III is preferably between 1:10:10 and 1: 0.1: 0.1.
- Alkylphenol-aldehyde resins are described, for example, in Römpp Chemie Lexikon, 9. Edition, Thieme Verlag 1988-92, Volume 4, p 3351 et seq described.
- the alkyl radicals of the o- or p-alkylphenols can in the process according to the invention can be the same or different alkylphenol-aldehyde resins 1-50, preferably 1-20, especially 4-12 carbon atoms; prefers it is n-, iso- and tert-butyl, n- and iso-pentyl, n- and iso-hexyl, n- and iso-octyl, n- and iso-nonyl, n- and iso-decyl, n- and iso-dodecyl, octadecyl and Poly (isobutenyl).
- the aliphatic aldehyde in the alkylphenol-aldehyde resin has preferably 1 to 4 carbon atoms.
- Particularly preferred aldehydes are Formaldehyde, acetaldehyde and butyraldehyde, especially formaldehyde.
- the Molecular weight of the alkylphenol-aldehyde resins is 400-10,000, preferably 400 - 5000 g / mol. The prerequisite here is that the resins are oil-soluble.
- these alkylphenol-formaldehyde resins are those which are oligomers or polymers having a repeating structural unit of the formula wherein R 5 is C 1 -C 50 alkyl or alkenyl and n is a number from 2 to 100.
- R 5 is preferably C 4 -C 20 -alkyl or -alkenyl and in particular C 6 -C 16 -alkyl or -alkenyl.
- n is a number from 4 to 50 and especially from 5 to 25.
- Comb polymers are polymers in which hydrocarbon radicals having at least 8, in particular at least 10, carbon atoms are bonded to a polymer backbone. Preferably, they are homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms. In the case of copolymers, at least 20%, preferably at least 30% of the monomers have side chains (compare Comb-like Polymers - Structure and Properties, NA Platé and VP Shibaev, J. Polym, Sci Macromolecular Revs 1974, 8, 117 ff).
- Suitable comb polymers are, for example, fumarate / vinyl acetate copolymers (cf., EP-A-0 153 176), copolymers of a C 6 -C 24 olefin and an NC 6 - to C 22 -alkylmaleimide (cf. 0 320 766), further esterified olefin / maleic anhydride copolymers, polymers and copolymers of ⁇ -olefins and esterified copolymers of styrene and maleic anhydride.
- fumarate / vinyl acetate copolymers cf., EP-A-0 153 176
- copolymers of a C 6 -C 24 olefin and an NC 6 - to C 22 -alkylmaleimide cf. 0 320 766
- further esterified olefin / maleic anhydride copolymers polymers and copolymers of ⁇ -o
- the mixing ratio (in parts by weight) of the additives according to the invention Comb polymers, alkylphenol resins, olefin copolymers or Polyoxyalkylene derivatives are each 1:10 to 20: 1, preferably 1: 1 to 10: 1 as for example, 1: 1 to 4: 1.
- suitable olefin polymers can derived directly from monoethylenically unsaturated monomers or indirectly by hydrogenation of polymers derived from polyunsaturated monomers how to derive isoprene or butadiene.
- Preferred copolymers contain, in addition to ethylene structural units derived from ⁇ -olefins having 3 to 24 carbon atoms and have molecular weights of up to 120,000.
- preferred ⁇ -olefins are propylene, butene, isobutene, n-hexene, isohexene, n-octene, isooctene, n-decene, isodecene.
- the comonomer content of olefins is preferably between 15 and 50 mol%, more preferably between 20 and 45 mol% and especially between 30 and 35 mol%. These copolymers can also be minor amounts, e.g. up to 10 mol% of other comonomers such as e.g. non-terminal olefins or not Contain conjugated olefins. Preferred are ethylene-propylene copolymers.
- the olefin copolymers can be prepared by known methods, e.g. by Ziegler or metallocene catalysts.
- Suitable flow improvers are polyoxyalkylene compounds such as For example, esters, ethers and ethers / esters containing at least one alkyl radical with 12 carry up to 30 carbon atoms.
- esters, ethers and ethers / esters containing at least one alkyl radical with 12 carry up to 30 carbon atoms.
- the alkyl groups are derived from an acid, it is derived the remainder of a polyhydric alcohol; the alkyl radicals come from one Fatty alcohol, the remainder of the compound is derived from a polyacid.
- Suitable polyols are polyethylene glycols, polypropylene glycols, polybutylene glycols and their copolymers having a molecular weight of about 100 to about 5000, preferably 200 to 2000.
- alkoxylates of polyols such as glycerol, trimethylolpropane, pentaerythritol, neopentyl glycol, as well as from them Condensation accessible oligomers having 2 to 10 monomer units, such as polyglycerol.
- Preferred alkoxylates are those having from 1 to 100, in particular from 5 to 50, mol of ethylene oxide, propylene oxide and / or butylene oxide per mole of polyol. Esters are especially preferred.
- Fatty acids containing 12 to 26 carbon atoms are preferred for reaction with the polyols to form the ester additives, preferably using C 18 to C 24 fatty acids, especially stearic and behenic acid.
- the esters can also be prepared by esterification of polyoxyalkylated alcohols. Preference is given to completely esterified polyoxyalkylated polyols having molecular weights of from 150 to 2,000, preferably from 200 to 600. Particularly suitable are PEG-600 dibehenate and glycerol-ethylene glycol tribehenate.
- the stated constituents of the additive according to the invention can furthermore with known additives such as antioxidants, cetane number improvers, dehazers, Demulsifiers, detergents, dispersants, defoamers, Dewaxing aids, dyes, corrosion inhibitors, Conductor and / or lubricity additives are used.
- additives such as antioxidants, cetane number improvers, dehazers, Demulsifiers, detergents, dispersants, defoamers, Dewaxing aids, dyes, corrosion inhibitors, Conductor and / or lubricity additives are used.
- the additives according to the invention are suitable for improving the cold flow properties of animal, vegetable or mineral oils.
- they disperse the paraffins that precipitate below the cloud point. They also lower the cloud point of the additized oils. They are particularly well suited for use in middle distillates.
- the middle distillate is in particular those mineral oils which are obtained by distillation of crude oil and boil in the range of 120 to 450 ° C, for example kerosene, jet fuel, diesel and fuel oil.
- middle distillates are used which contain less than 350 ppm sulfur, more preferably less than 200 ppm sulfur, in particular less than 50 ppm sulfur and in special cases less than 10 ppm sulfur.
- middle distillates which have been subjected to a hydrogenating refining, and therefore contain only small amounts of polyaromatic and polar compounds.
- the additives according to the invention show particular advantages in oils with a low content of aromatic compounds of less than 25%, preferably less than 20% and in particular less than 18%.
- aromatic compounds is meant the sum of mono-, di- and polycyclic aromatic compounds as determinable by HPLC according to prEN 12916 (1997 edition).
- the additives according to the invention are particularly advantageous in oils with a low proportion of n-paraffins in the cold-critical chain length range of C 16 -C 22 of less than 12% by weight, in particular less than 10% by volume and especially less than 8% by weight. %.
- These are preferably middle distillates which have 95% distillation points below 370 ° C., in particular 350 ° C. and in special cases below 340 ° C.
- the additive mixtures according to the invention can also be used in biodiesel become.
- Biodiesel or “biofuel” are fatty acid alkyl esters from fatty acids with 14 to 24 C atoms and alcohols with 1 to 4 C atoms. Usually a major part of the fatty acids contains one, two or three Double bonds. It is particularly preferred to e.g. around Rapsölchuremethylester and mixtures thereof with others convincedölklareestern.
- the additives according to the invention can be used with equal success used in mixtures of fatty acid methyl esters and mineral oil diesel. Such mixtures preferably contain up to 25 wt .-%, in particular up to 10 wt .-%, especially up to 5 wt .-% of fuel oil animal or vegetable Origin.
- improved mineral oils or mineral oil distillates contain from 0.001 to 2% by volume, preferably from 0.005 to 0.5% by volume of the mixtures, based on the distillate.
- the CFPP value is determined in accordance with EN 116 and the determination of the cloud point in accordance with ISO 3015.
- the n-paraffins are determined by means of gas chromatography (with FID detector) and baseline integration of the chromatograms obtained. Characterization of the used test oils oil CP [° C] C 16 -C 22 [%] Aromatics [%] Density [g / cm 3 ] Test oil 1 - 10.0 9.4 22.5 0.835 Test oil 2 -7.1 7.5 17.5 0.826 Test oil 3 - 3.0 10.2 23.9 0.832
- the ABA triblock copolymers used are hydrogenated triblock copolymers based on poly (styrene-b-butadiene-b-styrene). The degree of hydrogenation is more than 90% of the original double bonds.
- the molecular weights were determined in THF by calibration with polystyrene.
- the composition of the polymer was determined by 1 H and 13 C NMR spectroscopy. Characterization of the block copolymers used Poly (styrene) content mw 1,2-polybutadiene in the B block A1) 28.5% by weight 90,300 34% A2) 28.0% by weight 73,600 36% A3) 22.0% by weight 24,000 44%
- the cold flow behavior was determined as follows:
- test oils were used at room temperature with the indicated amounts of optionally preheated additives, 15 minutes with occasional Shake to 40 ° C and then cooled to room temperature. From The middle distillate thus additive was, according to EN 116, the CFPP value (Cold Filter Plugging Point).
- the paraffin dispersion was detected as follows in the short sediment test: 100 ml of the above-described additized middle distillates were cooled in measuring cylinders in a cold box at -2 ° C / h from -1 ° C to the storage temperature specified for the respective oils and 16 hours at this temperature stored. Subsequently, the volume and appearance of both the sedimented paraffin phase and the overlying oil phase were determined and assessed visually. A small amount of sediment and a cloudy oil phase show a good paraffin dispersion. A clear oil phase without sediment shows a lowering of the cloud point. In addition, the lower 20% by volume were isolated and the cloud point was determined according to ISO 3015. Only a small deviation of the cloud point of the lower phase (CP KS ) from the blank value of the oil shows a good paraffin dispersion.
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Abstract
Description
Bei den bereits als Kälteadditive beschriebenen Olefincopolymeren handelt es sich um statistische Copolymere aus Ethylen und längerkettigen Olefinen, die über Cokristallisation mit den in der Kälte aus Mitteldestillaten ausfallenden Paraffinen deren Kristallgröße verringern und somit zu einer verbesserten Filtrierbarkeit der Öle in der Kälte führen. Sie leisten aber keinen Beitrag zur Dispergierung der Paraffinkristalle.
und
B für Blöcke steht, die aus Strukturelementen auf Basis von Polyolefinen aufgebaut und zur Kokristallisation mit den aus dem Mitteldestillat bei Abkühlung ausfallenden Paraffinen befähigten sind, und
n eine Zahl zwischen 1 und 10 und m eine Zahl zwischen 2 und 10 ist.
Geeignete Lösemittel für die Polymerisation umfassen Paraffine, Cycloparaffine, Aromaten und Alkylaromaten mit 1 bis 19 C-Atomen wie beispielsweise Benzol, Toluol, Cyclohexan, Methylcyclohexan, n-Buten, n-Hexan, n-Heptan und ähnliche.
- A
- R', COOR', OCOR', R"-COOR', OR';
- D
- H, CH3, A oder R";
- E
- H, A;
- G
- H, R", R"-COOR', einen Arylrest oder einen heterocyclischen Rest;
- M
- H, COOR", OCOR", OR", COOH;
- N
- H, R", COOR", OCOR, einen Arylrest;
- R'
- eine Kohlenwasserstoffkette mit 8 bis 50 Kohlenstoffatomen;
- R"
- eine Kohlenwasserstoffkette mit 1 bis 10 Kohlenstoffatomen;
- m
- eine Zahl zwischen 0,4 und 1,0; und
- n
- eine Zahl zwischen 0 und 0,6.
Fettsäuren mit 12 bis 26 C-Atomen sind bevorzugt zur Umsetzung mit den Polyolen zur Bildung der Esteradditive, wobei bevorzugt C18- bis C24-Fettsäuren verwendet werden, speziell Stearin- und Behensäure. Die Ester können auch durch Veresterung von polyoxyalkylierten Alkoholen hergestellt werden. Bevorzugt sind vollständig veresterte polyoxyalkylierte Poylole mit Molekulargewichten von 150 bis 2000, bevorzugt 200 bis 600. Besonders geeignet sind PEG-600-Dibehenat und Glycerin-Ethylenglykol-Tribehenat.
Charakterisierung der eingesetzten Testöle | ||||
Öl | CP [°C] | C16-C22 [%] | Aromaten [%] | Dichte [g/cm3] |
Testöl 1 | - 10,0 | 9,4 | 22,5 | 0,835 |
Testöl 2 | -7,1 | 7,5 | 17,5 | 0,826 |
Testöl 3 | - 3,0 | 10,2 | 23,9 | 0,832 |
Charakterisierung der eingesetzten Blockcopolymere | |||
Poly(styrol)-Gehalt | Mw | 1,2-Polybutadien im B-Block | |
A1) | 28,5 Gew.-% | 90.300 | 34 % |
A2) | 28,0 Gew.-% | 73.600 | 36 % |
A3) | 22,0 Gew.-% | 24.000 | 44 % |
Charakterisierung der eingesetzten Fließverbesserer | |
B1 | Terpolymer aus Ethylen, 30 Gew.-% Vinylacetat und 8 Gew.-% Neodecansäurevinylester mit einer Schmelzviskosität bei 140°C von 95 mPa·s, 65 %ig in Kerosin |
B2 | Mischung aus 2 Teilen eines Terpolymers aus Ethylen, 31 Gew.-% Vinylacetat und 9 Gew.-% Neodecansäurevinylester mit einer Schmelzviskosität bei 140°C von 220 mPa·s und 1 Teil eines Copolymers aus Ethylen und 31 Gew.-% Vinylacetat mit einer Schmelzviskosität bei 140°C von 140 mPa·s, 60 %ig in Kerosin |
B3 | Mischung gleicher Teile des Copolymers B1 und eines Ethylen-Vinylacetat-Copolymere mit 33% Vinylacetat und einer Schmelzviskosität bei 140°C von 145 mPas, 65 %ig in Kerosin |
C1 | Umsetzungsprodukt eines Dodecenyl-Spirobioslactons mit einer Mischung aus primärem und sekundärem Talgfettamin, 60 %ig in Solvent Naphtha (hergestellt gemäß EP-A-0 413 279) |
C2 | Umsetzungsprodukt eines Terpolymers aus einem C14/C16-α-Olefin, Maleinsäureanhydrid und Allylpolyglykol mit 2 Equivalenten sekundärem Talgfettamin pro Mol Maleinsäureanhydrid, 50 %ig in Solvent Naphtha (hergestellt gemäß EP-A-0 606 055) |
C3 | Umsetzungsprodukt aus Phthalsäureanhydrid und 2 Equivalenten Di(hydriertem Talgfett)amin, 50 %ig in Solvent Naphtha (hergestellt gemäß EP-0 398 101 ) |
C4 | Umsetzungsprodukt aus Ethylendiamintetraessigsäure und 4 Equivalenten Di(hydriertem Talgfett)amin, 50 %ig in Solvent Naphtha (hergestellt gemäß EP-0 061 894) |
D1 | Nonylphenolformaldehydharz, hergestellt durch Kondensation von Nonylphenol mit Formaldehyd, Mw 2000 g/mol; 50 %ig in Solvent Naphtha |
Claims (19)
- Additiv zur Verbesserung des Kaltfließverhaltens von Mitteldestillaten, enthaltendI) mindestens einen Paraffindispergator, welcher ein Derivat eines Fettamins ist,II) mindestens ein Blockcopolymer der Struktur (AB)nA oder (AB)m, worin
A für Blöcke steht, die aus olefinisch ungesättigten, aromatischen Monomeren aufgebaut sind,
und
B für Blöcke steht, die aus Strukturelementen auf Basis von Polyolefinen aufgebaut und zur Kokristallisation mit den aus dem Mitteldestillat bei Abkühlung ausfallenden Paraffinen befähigten sind, und
n eine Zahl zwischen 1 und 10 und m eine Zahl zwischen 2 und 10 ist. - Additiv nach Anspruch 1, worin der Paraffindispergator das Umsetzungsprodukt einer Verbindung der Formel NR6R7R8 mit einer weiteren Verbindung, welche eine Acylgruppe enthält, ist, worin R6, R7und R8 gleich oder verschieden sein können, und wenigstens eine dieser Gruppen für C8-C36-Alkyl, C6-C36-Cycloalkyl oder C8-C36-Alkenyl steht, und die übrigen Gruppen entweder Wasserstoff, C1-C36-Alkyl, C2-C36-Alkenyl, Cyclohexyl, oder eine Gruppe der Formeln -(A-O)x-E oder -(CH2)n-NYZ bedeuten, worin A für eine Ethyl- oder Propylgruppe steht, x eine Zahl von 1 bis 50, E = H, C1-C30-Alkyl, C5-C12-Cycloalkyl oder C6-C30-Aryl, und n 2, 3 oder 4 bedeuten, und Y und Z unabhängig voneinander H, C1-C30-Alkyl oder -(A-O)x bedeuten.
- Additiv nach Anspruch 1 und/oder 2, worin die Verbindung der Formel NR6R7R8 ein sekundäres Fettamin ist, worin 2 der Reste R6, R7und R8 für C8-C36-Alkyl, C6-C36-Cycloalkyl oder C8-C36-Alkenyl stehen.
- Additiv nach einem oder mehreren der Ansprüche 1 bis 3, worin die Verbindung, welche eine Acylgruppe enthält, eine niedermolekulare Carbonylverbindung mit 1, 2, 3 oder 4 Carbonylgruppen ist, welche gegebenenfalls Heteroatome wie Sauerstoff, Schwefel und Stickstoff enthalten kann.
- Additiv nach einem oder mehreren der Ansprüche 1 bis 4, worin die Verbindung, welche eine Acylgruppe enthält, ein Säuregruppen oder Säureanhydride enthaltendes Polymer ist.
- Additiv nach einem oder mehreren der Ansprüche 1 bis 5, worin der A-Block des Blockpolymers ein von Styrol oder einem Styrolhomologen abgeleitetes Monoalkenylarylpolymer ist.
- Additiv nach einem oder mehreren der Ansprüche 1 bis 6, worin der A-Block des Blockpolymers ein Molekulargewicht von 1000 bis 50.000 g/mol hat.
- Additiv nach einem oder mehreren der Ansprüche 1 bis 7, worin der A-Block zu mehr als 80 mol-% aus Monoalkenylaryleinheiten besteht.
- Additiv nach einem oder mehreren der Ansprüche 1 bis 8, worin der B-Block des Blockpolymers ein Polyolefin ist, welches sich von Dienen ableiten läßt.
- Additiv nach einem oder mehreren der Ansprüche 1 bis 9, worin der B-Block des Blockpolymers ein Molekulargewicht von 1000 bis 100.000 g/mol hat.
- Additiv nach einem oder mehreren der Ansprüche 1 bis 10, worin der Anteil der A-Blöcke des Blockpolymers zwischen 5 und 50 Gew.-% und der Anteil der B-Blöcke des Blockpolymers zwischen 50 und 95 Gew.-% liegt.
- Additiv nach einem oder mehreren der Ansprüche 1 bis 11, worin das Molekulargewicht der Blockcopolymere zwischen 3.000 und 200.000 g/mol liegt.
- Additiv nach einem oder mehreren der Ansprüche 1 bis 12, worin n eine Zahl zwischen 1 und 5 ist.
- Additiv nach einem oder mehreren der Ansprüche 1 bis 13, worin m eine Zahl zwischen 2 und 5 ist.
- Additiv nach einem oder mehreren der Ansprüche 1 bis 14, das zusätzlich ein oder mehrere Copolymere aus Ethylen und olefinisch ungesättigten Verbindungen enthält.
- Additiv nach Anspruch 15, in dem die ungesättigten Verbindungn Vinylester mit C1 bis C30-Alkylresten sind.
- Additiv nach einem oder mehreren der Ansprüche 1 bis 16, das zusätzlich eines oder mehrere Additive ausgewählt aus den Gruppen der Kammpolymere, Alkylphenolharze, Olefincopolymere und Polyoxyalkylenderivate enthält.
- Mitteldestillat, enthaltend 1 bis 2000 ppm eines Additivs gemäß einem oder mehreren der Ansprüche 1 bis 17.
- Verwendung von 1 bis 2000 ppm eines Additivs gemäß einem oder mehreren der Ansprüche 1 bis 17 zur Verbesserung der Kaltfließeigenschaften von Mitteldestillaten.
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EP1749874A2 (de) * | 2005-07-28 | 2007-02-07 | Clariant Produkte (Deutschland) GmbH | Mineralöle mit verbesserter Leitfähigkeit und Kältefliessfähigkeit |
EP1749873A2 (de) * | 2005-07-28 | 2007-02-07 | Clariant Produkte (Deutschland) GmbH | Mineralöle mit verbesserter Leitfähigkeit und Kältefliessfähigkeit |
US8133852B2 (en) | 2005-07-28 | 2012-03-13 | Clariant Produkte (Deutschland) Gmbh | Mineral oils with improved conductivity and cold flowability |
EP2684940A1 (de) * | 2012-07-09 | 2014-01-15 | Infineum International Limited | Additive für Kraftstoffe und Öle mit funktionalisierten Diblock-Copolymeren |
US9133409B2 (en) | 2005-03-29 | 2015-09-15 | Arizona Chemical Company, Llc | Compositions containing fatty acids and/or derivatives thereof and a low temperature stabilizer |
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DE102006062439A1 (de) * | 2006-12-27 | 2008-07-03 | Byk-Chemie Gmbh | Kamm(block)copolymere |
US8540784B2 (en) | 2010-04-23 | 2013-09-24 | Tellus Renewables Llc | Fuel compositions |
CN104604545B (zh) * | 2015-02-12 | 2017-06-06 | 东莞市嘉航实业有限公司 | 电动修枝剪刀 |
KR102357888B1 (ko) * | 2015-09-16 | 2022-02-03 | 인피늄 인터내셔날 리미티드 | 작용화된 이중블록 공중합체를 포함하는 연료 및 오일용 첨가제 |
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EP0673990A1 (de) * | 1994-03-22 | 1995-09-27 | Shell Internationale Researchmaatschappij B.V. | Kohlenwasserstoffölzusammensetzungen mit verbesserten Kaltfliesseigenschaften |
WO1996028523A1 (en) * | 1995-03-14 | 1996-09-19 | Exxon Chemical Patents Inc. | Fuel oil additives and compositions |
EP0857776A1 (de) * | 1997-01-07 | 1998-08-12 | Clariant GmbH | Verbesserung der Fliessfähigkeit von Mineralölen und Mineralöldestillaten unter Verwendung von Alkylphenol-Aldehydharzen |
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- 2004-07-08 EP EP04016063A patent/EP1500691B1/de not_active Expired - Fee Related
- 2004-07-08 DE DE502004004492T patent/DE502004004492D1/de not_active Expired - Fee Related
- 2004-07-20 KR KR1020040056433A patent/KR20050010718A/ko not_active Application Discontinuation
- 2004-07-20 JP JP2004211564A patent/JP2005042113A/ja not_active Withdrawn
- 2004-07-21 US US10/896,128 patent/US7550019B2/en not_active Expired - Fee Related
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Cited By (16)
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US9133409B2 (en) | 2005-03-29 | 2015-09-15 | Arizona Chemical Company, Llc | Compositions containing fatty acids and/or derivatives thereof and a low temperature stabilizer |
US9212332B2 (en) | 2005-03-29 | 2015-12-15 | Arizona Chemical Company, Llc | Compositions containing fatty acids and/or derivatives thereof and a low temperature stabilizer |
US7713315B2 (en) | 2005-07-28 | 2010-05-11 | Clariant Produkte (Deutschland) Gmbh | Mineral oils with improved conductivity and cold flowability |
EP1749873A2 (de) * | 2005-07-28 | 2007-02-07 | Clariant Produkte (Deutschland) GmbH | Mineralöle mit verbesserter Leitfähigkeit und Kältefliessfähigkeit |
EP1749874A2 (de) * | 2005-07-28 | 2007-02-07 | Clariant Produkte (Deutschland) GmbH | Mineralöle mit verbesserter Leitfähigkeit und Kältefliessfähigkeit |
CN1904007B (zh) * | 2005-07-28 | 2011-08-17 | 科莱恩产品(德国)有限公司 | 具有改进的电导率和冷流动性的矿物油 |
US8133852B2 (en) | 2005-07-28 | 2012-03-13 | Clariant Produkte (Deutschland) Gmbh | Mineral oils with improved conductivity and cold flowability |
US8283298B2 (en) | 2005-07-28 | 2012-10-09 | Clariant Produkte (Deutschland) Gmbh | Mineral oils with improved conductivity and cold flowability |
CN1904006B (zh) * | 2005-07-28 | 2013-03-27 | 科莱恩产品(德国)有限公司 | 具有改进的电导率和冷流动性的矿物油 |
EP1749873A3 (de) * | 2005-07-28 | 2009-09-16 | Clariant Produkte (Deutschland) GmbH | Mineralöle mit verbesserter Leitfähigkeit und Kältefliessfähigkeit |
EP1749874A3 (de) * | 2005-07-28 | 2009-09-16 | Clariant Produkte (Deutschland) GmbH | Mineralöle mit verbesserter Leitfähigkeit und Kältefliessfähigkeit |
CN103540368A (zh) * | 2012-07-09 | 2014-01-29 | 英菲诺姆国际有限公司 | 包含官能化二嵌段共聚物的用于燃料和油的添加剂 |
EP2684940A1 (de) * | 2012-07-09 | 2014-01-15 | Infineum International Limited | Additive für Kraftstoffe und Öle mit funktionalisierten Diblock-Copolymeren |
US9540583B2 (en) | 2012-07-09 | 2017-01-10 | Infineum International Limited | Additives for fuels and oils comprising Functionalised diblock copolmers |
CN103540368B (zh) * | 2012-07-09 | 2017-03-29 | 英菲诺姆国际有限公司 | 包含官能化二嵌段共聚物的用于燃料和油的添加剂 |
US9845375B2 (en) | 2012-07-09 | 2017-12-19 | Infineon International Limited | Additives for fuels and oils comprising functionalised diblock copolymers |
Also Published As
Publication number | Publication date |
---|---|
DE10333043A1 (de) | 2005-03-10 |
US20050016060A1 (en) | 2005-01-27 |
EP1500691B1 (de) | 2007-08-01 |
KR20050010718A (ko) | 2005-01-28 |
JP2005042113A (ja) | 2005-02-17 |
EP1500691A3 (de) | 2005-06-15 |
US7550019B2 (en) | 2009-06-23 |
DE502004004492D1 (de) | 2007-09-13 |
ATE368720T1 (de) | 2007-08-15 |
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