EP2162515B1 - Huiles minérales contenant des additifs détergents dotées d'une fluidité à froid améliorée - Google Patents

Huiles minérales contenant des additifs détergents dotées d'une fluidité à froid améliorée Download PDF

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EP2162515B1
EP2162515B1 EP08773479.4A EP08773479A EP2162515B1 EP 2162515 B1 EP2162515 B1 EP 2162515B1 EP 08773479 A EP08773479 A EP 08773479A EP 2162515 B1 EP2162515 B1 EP 2162515B1
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alkyl
oil
use according
radical
carbon atoms
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EP2162515A1 (fr
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Matthias Krull
Robert Janssen
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Clariant International Ltd
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Clariant International Ltd
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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
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures 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
    • C10L1/16—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
    • 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
    • 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
    • C10L1/1817—Compounds of uncertain formula; reaction products where mixtures of compounds are obtained
    • 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
    • C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds 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 an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
    • 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
    • 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
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)

Definitions

  • the present invention relates to the use of nucleating agents to improve the cold flowability of mineral oil distillates containing detergent additives, as well as the mineral oil distillates additive.
  • paraffin-rich crude oils are extracted and processed, which consequently also lead to paraffin-rich fuel oils.
  • the paraffins contained in particular in middle distillates can crystallize on lowering the temperature of the oil and partially agglomerate with the inclusion of oil. This crystallization and agglomeration can cause blockages of the filters in engines and firing systems, especially in winter, which prevents safe metering of the fuels and may possibly lead to a complete interruption of the fuel supply.
  • the paraffin problem is also exacerbated by the environmental reasons to reduce the sulfur content increasing hydrodesulfurization of fuel oils, which leads to an increased proportion of cold-critical paraffins in the fuel oil.
  • middle distillates are often added chemical additives, so-called cold flow improvers or flow improvers, modify the crystal structure and Agglomerationsne noticed the precipitated paraffins, so that the so-additive oils still pump or use at temperatures, often more than 20 ° C. lower than non-additized oils.
  • cold flow improver oil-soluble copolymers of ethylene and unsaturated esters, oil-soluble polar nitrogen compounds and / or comb polymers are usually used. In addition, however, other additions have been proposed.
  • detergent additives are being developed with ever increasing effectiveness. In addition, they are often used in very high dosage rates. It is reported that this reduces, for example, in diesel fuels, the specific consumption and the performance of the engines is increased.
  • these additives often have negative effects on the cold flowability of middle distillates and in particular on the efficacy of known cold flow improvers. Especially with middle distillates with low boiling point and simultaneously low aromatic content, it is often difficult or even impossible to adjust in the presence of modern detergent additives using conventional flow improvers a satisfactory cold flow behavior. For example, the addition of detergent additives often results in an antagonistic effect on the effectiveness of the added cold flow improvers.
  • the paraffin dispersion of the middle distillate, set by paraffin dispersants is impaired, without being able to be reconstituted by increased metering of paraffin dispersant.
  • the CFPP measured filterability with cold flow improvers additive oils is significantly reduced in the cold and can be compensated only by greatly increased dosage of the flow improver.
  • detergent additives which are derived from higher polyamines and those which are, for example, conditional have very high molecular weights by multiple alkylation and / or acylation of these polyamines.
  • those detergent additives whose hydrophobic residue is derived from sterically hindered olefins and / or higher molecular weight and / or polyfunctionalized poly (olefins).
  • WO-03/042337 teaches middle distillates with a maximum of 0.05% by weight of sulfur containing fatty acid esters of alkoxylated polyols having at least 3 OH groups (A) and at least one cold flow improver (B), said cold flow improver comprising at least one copolymer of ethylene and one or more ethylenically unsaturated carboxylic acid esters having an ethylene content of 60 to 90 mol%.
  • US 4678479 teaches a diesel fuel composition
  • a hydrocarbonaceous diesel having a cetane number ranging from 25 to 60, a polyolefin and a polyamine wherein at least one hydrocarbon chain has at least 25 carbon atoms and is bonded directly to a nitrogen atom.
  • the invention thus relates to the use of at least one oil-soluble olefin copolymer B) acting as nucleator for the paraffin crystallization of ethylene and from 3 to 40 mol% of olefins having 3 to 30 carbon atoms for improving the response with regard to the reduction of pour point and CFPP.
  • ashless nitrogen-containing detergent additive A which is an oil-soluble, amphiphilic compound comprising at least one alkyl or alkenyl radical is bonded to a polar group, wherein the alkyl or alkenyl radical comprises 10 to 500 carbon atoms and the polar group comprises 2 or more nitrogen atoms, the ashless nitrogen-containing detergent additive A) comprises a polar moiety derived from polyamines of the formula (R 9) 2 N- [AN (R 9)] q- (R9) wherein each R 9 independently of one another represents hydrogen, an alkyl or hydroxyalkyl radical having up to 24 C atoms, a polyoxyalkylene radical - (AO) r - or polyiminoalkylene radical - [AN (R 9 )] s - (R 9 ) but where at least one R 9 is hydrogen, q is an integer from 1 to 19,
  • Another object of the invention are middle distillates having a sulfur content of less than 100 ppm and a 90% distillation point of below 360 ° C, containing the above additive, and wherein 10 to 10,000 ppm of the ashless, nitrogen-containing detergent additive A) and per part by weight of this Constituent A) 0.1 to 10 parts by weight of the oil-soluble compound N) acting as nucleator for the paraffin crystallization are contained.
  • the improvement in the response of cold flow improvers C) is understood according to the invention to improve at least one cold property of middle distillates adjusted by cold flow improver C) and impaired by the addition of a detergent additive A) by addition of an olefin copolymer B) acting as nucleating agent for the paraffin crystallization , Specifically, by adding the nucleating agent B), the cold property set or adjustable without the presence of the detergent additive A) by the cold flow improver C) is achieved.
  • Cold properties are understood here individually or in combination as the pour point, the cold filter plugging point, the low-temperature flow, and the paraffin dispersion of middle distillates.
  • Particularly affected is the response of flow improvers in middle distillates containing more than 10 ppm of a nitrogen-containing detergent additive A), especially more than 20 ppm and especially more than 40 ppm such as 50 to 2000 ppm of nitrogen-containing detergent additive A).
  • the additives according to the invention preferably contain from 0.01 to 10 parts by weight, based on one part by weight of the nitrogen-containing detergent additive A, and in particular from 0.05 to 5 parts by weight, for example from 0.1 to 3 parts by weight of the oil-soluble olefin copolymer B) acting as nucleator for the paraffin crystallization.
  • Ashless means that the additives in question essentially consist only of elements which form gaseous reaction products during combustion.
  • the additives consist essentially only of the elements carbon, hydrogen, oxygen and nitrogen.
  • ashless additives are substantially free of metals and metal salts.
  • Nucleators are understood to be compounds which initiate the crystallization of paraffins on cooling a paraffin-containing oil. They thus shift the beginning of the paraffin crystallization of the oil additized with them, which can be determined, for example, by measuring the cloud point or the Wax Appearance Temperature (WAT), to higher temperatures. These are compounds that are soluble in the oil above the cloud point and begin to crystallize just above the temperature of the paraffin saturation and then serve as seed for the crystallization of the paraffins. Thus, they prevent over-saturation of the oil with paraffins and lead to crystallization near the saturation concentration. This leads to the formation of a multiplicity of equally small paraffin crystals.
  • WAT Wax Appearance Temperature
  • paraffin crystallization thus begins at a higher temperature than in non-additized oil. This can be determined, for example, by measuring the WAT by means of differential scanning calorimetry (DSC) with a slow cooling of the oil at, for example, -2 K / min.
  • DSC differential scanning calorimetry
  • the alkyl or alkenyl group imparts oil-solubility to the detergent additives.
  • alkyl radical has 15 to 500 carbon atoms and in particular 20 to 350 carbon atoms, for example 50 to 200 carbon atoms.
  • This alkyl radical can be linear or branched, in particular it is branched.
  • the alkyl radical is derived from Oligomeric lower olefins having 3 to 6 carbon atoms such as propene, butene, pentene or hexene and mixtures thereof.
  • Preferred isomers of these olefins are isobutene, 2-butene, 1-butene, 2-methyl-2-butene, 2,3-dimethyl-2-butene, 1-pentene, 2-pentene and iso-pentene and mixtures thereof.
  • olefin mixtures containing more than 70 mol%, especially more than 80 mol%, for example more than 90 mol% or more than 95 mol% of 2-methyl-2-butene, 2,3-dimethyl 2-butene and / or isobutene.
  • Particularly suitable for the preparation of such detergent additives are highly reactive low molecular weight polyolefins having a proportion of terminal double bonds of at least 75%, especially at least 85% and in particular at least 90% such as at least 95%.
  • Particularly preferred low molecular weight polyolefins are poly (isobutylene), poly (2-butene), poly (2-methyl-2-butene), poly (2,3-dimethyl-2-butene), poly (ethylene-co-isobutylene) and atactic poly (propylene).
  • the molecular weight of particularly preferred polyolefins is between 500 and 3000 g / mol.
  • Such oligomers of lower olefins are accessible for example by polymerization by means of Lewis acids such as BF 3 and AlCl 3 , by means of Ziegler catalysts and in particular by means of metallocene catalysts.
  • the polar component of the detergent additives which are particularly problematic for the response of known cold additives is derived from polyamines having 2 to 20 N atoms.
  • polyamines correspond to the formula (R 9) 2 N- [AN (R 9)] q- (R 9) wherein each R 9 is independently hydrogen, an alkyl or hydroxyalkyl radical of up to 24 carbon atoms, a polyoxyalkylene radical - (AO) r - or polyiminoalkylene radical - [AN (R 9 )] s - (R 9 ) but wherein at least one R 9 is hydrogen, q is an integer from 1 to 19, A is an alkylene radical having 1 to 6 C atoms, r and s independently of one another are from 1 to 50.
  • these are mixtures of polyamines and in particular mixtures of poly (ethylene amines) and / or poly (propyleneamines).
  • Heavy polyamines are generally understood as meaning mixtures of polyalkylenepolyamines which, in addition to small amounts of TEPA and PEHA, mainly contain oligomers having 7 or more nitrogen atoms, of which two or more are in the form of primary amino groups. These polyamines often also contain branched structural elements via tertiary amino groups.
  • Suitable amines include those which comprise cyclic structural units derived from piperazine.
  • the piperazine units may preferably carry hydrogen at one or both nitrogen atoms, an alkyl or hydroxyalkyl radical having up to 24 carbon atoms or a polyiminoalkylene radical - [AN (R 9 )] s - (R 9 ), where A, R 9 and s have the meanings given above.
  • Suitable amines include alicyclic diamines such as 1,4-di (aminomethyl) cyclohexane and heterocyclic nitrogen compounds such as imidazolines and N-aminoalkylpiperazines such as N- (2-aminoethyl) piperazine.
  • detergent additives whose polar portion is derived from hydroxyl-bearing polyamines, heterocycle-substituted polyamines, and aromatic polyamines are problematic. Examples which may be mentioned are: N- (2-hydroxyethyl) ethylenediamine, N, N 1 -bis- (2-hydroxyethyl) ethylene diamine, N- (3-hydroxybutyl) tetra (methylene) diamine, N-2-aminoethylpiperazine, N-2- and N-3-aminopropylmorpholine, N-3- (dimethylamino) propylpiperazine, 2-heptyl-3- (2-aminopropyl) imidazoline, 1,4-bis (2-aminoethyl) piperazine, 1- (2-hydroxyethyl) piperazine, various isomers of phenylenediamine and naphthalenediamine and mixtures of these amines.
  • Detergent additives based on heavy polyamines in which R 9 is hydrogen in the above formula and q has values of at least 3, in particular at least 4, such as 5, 6 or 7, are particularly critical for the cold additization of middle distillates.
  • R 9 is hydrogen in the above formula and q has values of at least 3, in particular at least 4, such as 5, 6 or 7, are particularly critical for the cold additization of middle distillates.
  • a proportion of more than 10 wt .-%, in particular more than 20 wt .-% and especially of more than 50 wt .-% of amines having q-values of 4 or higher and especially with q Values of 5 or higher and in particular with q values of 6 or higher on the total amount of amines used have proven particularly critical.
  • oil-soluble alkyl moiety and the polar head group of the detergent additives may be linked together either directly via a C-N or through an ester, amide or imide bond.
  • preferred detergent additives are alkylpolyamines, Mannich reaction products, hydrocarbyl-substituted succinic acid amides and imides, and mixtures of these classes of substances.
  • the detergent additives linked via C-N bonds are preferably alkylpoly (amines) which are obtainable, for example, by reacting polyisobutylenes with polyamines, for example by hydroformylation and subsequent reductive amination with the abovementioned polyamines.
  • alkylpoly amines
  • one or more alkyl radicals may be bound to the polyamine.
  • Detergent additives based on higher polyamines having more than 4 N atoms, for example those having 5, 6 or 7 N atoms, are particularly critical for the cold addition.
  • Detergent additives containing amide or imide bonds are obtainable, for example, by reaction of alkenylsuccinic anhydrides with polyamines.
  • Alkenylsuccinic anhydride and polyamine are preferably reacted in a molar ratio of about 1: 0.5 to about 1: 1.
  • the preparation of the underlying Alkenylbernsteinklaanhydride is usually carried out by addition of ethylenically unsaturated polyolefins or chlorinated polyolefins to ethylenically unsaturated dicarboxylic acids.
  • alkenyl succinic anhydrides can be prepared by reaction of chlorinated polyolefins with maleic anhydride.
  • the preparation also succeeds by thermal addition of polyolefins to maleic anhydride in an "ene reaction".
  • highly reactive olefins with a high content of, for example, more than 75% and especially more than 85 mol%, based on the total number of polyolefin molecules, of isomers having a terminal double bond are particularly suitable.
  • the molar ratio of the two reactants in the reaction between maleic anhydride and polyolefin can vary within wide limits. Preferably, it may be between 10: 1 and 1: 5, with molar ratios of 6: 1 to 1: 1 being particularly preferred.
  • Maleic anhydride is preferably used in stoichiometric excess, for example 1.1 to 3 moles of maleic anhydride per mole of polyolefin. Excess maleic anhydride can be removed from the reaction by, for example, distillation.
  • the accessible reaction products have, based on the reacted with unsaturated carboxylic acids fractions of the poly (olefins) on average a Malein istsgrad of more than 1, preferably about 1.01 to 2.0 and in particular 1.1 to 1.8 dicarboxylic acid per alkyl radical. Reaction with the abovementioned amines results in products with markedly increased effectiveness as detergent additives. On the other hand, as the degree of maleation increases, so does the impairment of the efficacy of cold flow improvers.
  • alkenyl succinic anhydrides with polyamines leads to products which can carry one or more amide and / or imide bonds per polyamine and depending on the Maleinleitersgrad one or two polyamines per alkyl radical.
  • Alkenylsuccinic anhydride per mole of polyamine is preferably used for the reaction of 1.0 to 1.7 and in particular 1.1 to 1.5, so that free primary amino groups remain in the product.
  • alkenyl succinic anhydride and polyamine are reacted equimolarly.
  • Typical and particularly preferred acylated nitrogen compounds are obtained by reacting poly (isobutylene), poly (2-butenyl), poly (2-methyl-2-butenyl) -, poly (2,3-dimethyl-2-butenyl) - or Poly (propenyl) succinic anhydrides having an average of about 1.2 to 1.5 anhydride groups per alkyl radical whose alkylene radicals carry between 50 and 400 carbon atoms, with a mixture of poly (ethylene amines) having about 3 to 7 nitrogen atoms and about 1 to 6 ethylene units available.
  • Mannich bases of this kind are prepared by known processes, for example by alkylating phenol and / or salicylic acid with the polyolefins described above, such as, for example, poly (isobutylene), poly (2-butene), poly (2-methyl-2-butene), poly ( 2,3-dimethyl-2-butene) or atactic poly (propylene) and subsequent condensation of the alkylphenol with aldehydes having 1 to 6 carbon atoms such as formaldehyde or its reactive equivalents such as formalin or paraformaldehyde and the above-described polyamines such as TEPA, PEHA or heavy polyamines produced.
  • the average molecular weight determined by means of vapor pressure osmometry is particularly efficient, but at the same time also for the cold additization of middle distillates of particularly critical detergent additives is above 800 g / mol and in particular above 2,000 g / mol such as above 3,000 g / mol.
  • the average molecular weight of the above-described detergent additives can also be increased via crosslinking reagents and adapted to the intended use.
  • Suitable crosslinking reagents are, for example, dialdehydes such as glutaric dialdehyde, bisepoxides derived, for example, from bisphenol A, dicarboxylic acids and their reactive derivatives such as maleic anhydride and alkenylsuccinic anhydrides, and higher polybasic carboxylic acids and their derivatives such as trimellitic acid, trimellitic anhydride and pyromellitic dianhydride.
  • dialdehydes such as glutaric dialdehyde
  • bisepoxides derived, for example, from bisphenol A
  • dicarboxylic acids and their reactive derivatives such as maleic anhydride and alkenylsuccinic anhydrides
  • higher polybasic carboxylic acids and their derivatives such as trimellitic acid, trimellitic anhydride and pyromellitic dianhydride.
  • Olefin copolymers which are suitable as nucleator for paraffin crystallization contain, on the one hand, substantially linear and thus crystallizable segments and, on the other hand, non-crystallizing structural elements with branching polymer main chains.
  • Such copolymers can be derived directly from monoethylenically unsaturated monomers or indirectly by hydrogenation of polymers derived from polyunsaturated monomers such as isoprene or butadiene.
  • they do not contain any structural elements derived from polar comonomers such as vinyl esters, alkyl acrylates, alkyl methacrylates or alkyl vinyl ethers.
  • Olefin copolymers B) used as nucleator for the paraffin crystallization are copolymers of ethylene and 3 to 40 mol% of at least one olefin having 3 to 30 C atoms. These are preferably random copolymers. Particularly preferred copolymers contain, in addition to ethylene, structural units which are derived from olefins having 3 to 24 C atoms, for example 4 to 12 C atoms and in particular 4 to 10 C atoms. The olefins may be linear or branched. Preferably, their double bond is terminal.
  • Preferred olefins are propylene, butene, isobutene, pentene, isopentene, n-hexene, isohexene, n-octene, Isooctene, n-decene, isodecene and longer-chain ⁇ -olefins having 12 to 24 carbon atoms and mixtures thereof.
  • ⁇ -olefins are meant linear alkenes with terminal double bond. Particular preference is given to propene, isobutene, hexene and octene.
  • the comonomer content of olefins having 3 to 30 carbon atoms is preferably between 5 and 30 mol%, particularly preferably between 6 and 25 mol%. These copolymers can also be small amounts, for. B. up to 5 mol% and in particular up to 3 mol% of further comonomers such. Non-terminal olefins, longer chain olefins or polyolefins, with the proviso that the total comonomer content is between 3 and 40 mol%, preferably between 5 and 30 mol% and in particular between 6 and 25 mol%.
  • the comonomer content can be determined by 13 C NMR spectroscopy. Particularly preferred are ethylene-propylene copolymers, ethylene-octene copolymers and ethylene-propene-octene terpolymers.
  • the olefin copolymers B) used as nucleators for the paraffin crystallization are oil-soluble, hydrogenated block copolymers which contain at least one essentially linear and thus crystallizable block and at least one highly branched, non-crystallizable block and thus giving oil solubility.
  • highly branched blocks are understood as meaning, in particular, polymer structures which carry a large number of side chains and, in particular, C 1 -C 6 - such as, for example, C 2 -C 4 -side chains.
  • C atoms of the polymer main chain carries at least one side chain.
  • the crystallizable block is derived from the tail-tail polymerization of a diene, resulting in a post-hydrogenation substantially linear block having a paraffin-like structure.
  • Such crystallizable blocks are obtainable, for example, by 1,4-polymerization of the butadiene and subsequent hydrogenation.
  • the non-crystallizable block is, for example, by homo- or copolymerization of a branched Olefins or by 1,2-polymerization of a linear diene such as butadiene and subsequent hydrogenation produced.
  • Preferred branched olefins are dienes 4 to 8 carbon atoms, such as, for example, isoprene and / or 2,3-dimethylbutadiene.
  • the block copolymers may be, for example, diblock copolymers of the PE-PEP structure of a crystalline (PE) and a non-crystalline block (PEP), triblock copolymers of a non-crystallizable block with two crystallizable blocks at its ends of the structure PE-PEP-PE or multiblock copolymers.
  • the PE content of the polymers is preferably between 8 and 60% by weight, preferably between 10 and 50% by weight, for example between 12 and 45% by weight.
  • the molecular weight of the individual blocks is preferably between 500 and 20,000 g / mol, preferably between 750 and 5,000 g / mol.
  • 90% and especially at least 95% of the original double bonds of the polymer are hydrogenated.
  • Nucleatoren olefin copolymers B can be prepared by known methods, for. Example by means of anionic, or coordinative catalysis and in particular by Ziegler and metallocene catalysts.
  • the average molecular weight Mn of preferred olefin copolymers determined by gel permeation chromatography is between 500 and 50,000 g / mol, more preferably between 800 and 25,000 g / mol and especially between 1,500 and 15,000 g / mol, for example between 2,000 and 10,000 g / mol.
  • the polydispersity of preferred copolymers is between 1.5 and 5.0, such as between 2.0 and 4.0.
  • the quantitative ratio between detergent additive A) and nucleators B) in the additized oil can vary within wide limits. It has proven particularly useful to use from 0.01 to 10 parts by weight, in particular from 0.05 to 5 parts by weight, for example from 0.1 to 3 parts by weight of nucleator per part by weight of detergent additive, in each case based on the active ingredient.
  • Cold flow improvers used are the substances referred to below as oil-soluble polar nitrogen compounds (constituent IV).
  • Ethylene copolymers are preferably used in mixtures with constituent IV. Mixtures of ethylene copolymers (constituent III) with constituents IV and V or constituents IV and VI have proven particularly suitable for the paraffin dispersion.
  • Preferred cold flow improvers as constituent III are copolymers of ethylene and olefinically unsaturated compounds.
  • Suitable ethylene copolymers are, in particular, those which contain, in addition to ethylene, from 8 to 21 mol%, in particular from 10 to 18 mol%, of olefinically unsaturated comonomer compounds.
  • the comonomer content is in this case the case of combination with nucleators of group B) by at least 1 mol% and preferably by at least 2 mol% higher than the nucleators of group B).
  • the olefinically unsaturated compounds are preferably vinyl esters, acrylic esters, methacrylic esters, alkyl vinyl ethers and / or alkenes, it being possible for the abovementioned compounds to be substituted by hydroxyl groups.
  • 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.
  • Particularly preferred vinyl esters are derived from secondary and especially tertiary carboxylic acids whose branching is in the alpha position to the carbonyl group.
  • Suitable vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl hexanoate, vinyl heptanoate, vinyl octanoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate and versatic acid esters such as vinyl neononanoate, vinyl neodecanoate, vinyl neoundecanoate.
  • these ethylene copolymers contain vinyl acetate and at least one further vinyl ester of the formula 1 in which R 1 is C 4 to C 30 -alkyl, preferably C 4 to C 16 -alkyl, especially C 6 - to C 12 -alkyl ,
  • Suitable acrylic esters include, for.
  • said alkyl groups may be substituted with one or more hydroxyl groups.
  • An example of such an acrylic ester is hydroxyethyl methacrylate.
  • the alkenes are preferably simple unsaturated hydrocarbons having 3 to 30 carbon atoms, especially 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 vinylnorbornene.
  • said alkyl groups may be substituted with one or more hydroxyl groups.
  • terpolymers which, apart from ethylene, have from 3.5 to 20 mol%, in particular from 8 to 15 mol% of vinyl acetate and from 0.1 to 12 mol%, in particular from 0.2 to 5 mol%, of at least one longer-chain and preferably branched one Vinyl esters such as vinyl 2-ethylhexanoate, vinyl neononanoate or vinyl neodecanoate, wherein the total comonomer content of the terpolymers is preferably between 8 and 21 mol%, in particular between 12 and 18 mol%.
  • copolymers contain, in addition to ethylene and 8 to 18 mol% of vinyl esters of C 2 to C 12 carboxylic acids, from 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.
  • These ethylene copolymers and terpolymers preferably have melt viscosities at 140 ° C. of from 20 to 10,000 mPas, in particular from 30 to 5,000 mPas, especially from 50 to 2,000 mPas.
  • the means of 1 H-NMR spectroscopy, certain degrees of branching are preferably between 1 and 9 CH 3/100 CH 2 groups,
  • the polymers underlying the mixtures differ in at least one characteristic.
  • they may contain different comonomers, have different comonomer contents, molecular weights and / or degrees of branching.
  • the mixing ratio between the additives according to the invention and ethylene copolymers as constituent III can vary within wide limits depending on the application, with the ethylene copolymers III often representing the greater proportion.
  • Such additive and oil mixtures preferably contain 0.1 to 25, preferably 0.5 to 10 parts by weight of ethylene copolymers per part by weight of the additive combination according to the invention.
  • cold flow improvers which are suitable are oil-soluble polar nitrogen compounds (constituent IV). These are preferably reaction products of fatty amines with compounds containing an acyl group.
  • the preferred amines are compounds of the formula NR 6 R 7 R 8 , in which R 6 , R 7 and R 8 may be identical or different, and at least one of these groups is 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, and the other groups are either hydrogen, C 1 -C 36 -alkyl, C 2 -C 36 alkenyl, cyclohexyl, or a group of the formulas - (AO) x -E or - (CH 2 ) n -NYZ, where A is an ethyl or propyl group,
  • polyamines of the formula - [N- (CH 2 ) n ] m -NR 6 R 7 , in which m is a number between 1 and 20 and n, R 6 and R 7 have the meanings given above, are suitable as fatty amines .
  • 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.
  • 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 coco fatty amine, tallow fatty amine, hydrogenated tallow fatty amine, dicocosfettamine, ditallow fatty amine and di (hydrogenated tallow fatty amine).
  • Particularly preferred amine derivatives are amine salts, imides and / or amides such as, for example, amide ammonium salts of secondary fatty amines, in particular dicocosfettamine, ditallow fatty amine and distearylamine.
  • Suitable carbonyl compounds for the reaction with amines are both monomeric and polymeric compounds having one or more carboxyl groups. In the case of the monomeric carbonyl compounds, preference is given to those having 2, 3 or 4 carbonyl groups. They can also contain heteroatoms such as oxygen, sulfur and nitrogen.
  • 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 means here that the copolymer dissolves without residue in the middle distillate to be additive 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 and alkyl vinyl ethers having 2 to 75, preferably 4 to 40 and in particular 8 to 20 carbon atoms in the alkyl radical.
  • the carbon number refers to the alkyl radical attached to the double bond.
  • 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.
  • Oil-soluble polar nitrogen compounds which have been obtained by reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides have proven particularly suitable (cf. US 4 211 534 ).
  • amides and ammonium salts of aminoalkylene polycarboxylic acids such as nitrilotriacetic acid or ethylenediaminetetraacetic acid with secondary amines are suitable as oil-soluble polar nitrogen compounds (cf. EP 0 398 101 ).
  • oil-soluble polar nitrogen compounds are copolymers of maleic anhydride with ⁇ , ⁇ -unsaturated compounds, which can optionally be reacted with primary monoalkylamines and / or aliphatic alcohols (cf. EP-A-0 154 177 . EP-0 777 712 ), the reaction products of Alkenylspirobislactonen with amines (see. EP-A-0 413 279 B1 ) and after EP-A-0 606 055 A2 Reaction products of terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic acid anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols.
  • the mixing ratio between the inventive ethylene copolymers III and oil-soluble polar nitrogen compounds as constituent IV may vary depending on the application.
  • Such additive mixtures preferably contain 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, based on the active compounds, of at least one oil-soluble polar nitrogen compound per part by weight of the additive combination according to the invention.
  • alkylphenol-aldehyde resins as constituent V. These are, in particular, those alkylphenol-aldehyde resins which are derived from alkylphenols having one or two alkyl radicals in ortho and / or para position to the OH group. Particularly preferred as starting materials are alkylphenols which carry at least two hydrogen atoms capable of condensation with aldehydes on the aromatic and in particular monoalkylated phenols. Particularly preferably, the alkyl radical is in the para position to the phenolic OH group.
  • alkyl radicals (which are generally understood to mean hydrocarbon radicals as defined below for constituent V) may be identical or different in the alkylphenol-aldehyde resins which can be used in the process according to the invention, they may be saturated or unsaturated and have preferably 1-20, in particular 4-16 such as 6 to 12 carbon atoms; it is preferably 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, tetradecyl, hexadecyl, octadecyl, tripropenyl, tetrapropenyl, poly (propenyl) - and poly (isobutenyl) radicals.
  • mixtures of alkylphenols having different alkyl radicals are used for the preparation of the alkylphenol resins.
  • resins based on butyphenol on the one hand and octyl, nonyl and / or dodecylphenol in a molar ratio of 1:10 to 10: 1 on the other hand have proven particularly useful.
  • Suitable alkylphenol resins may also contain or consist of structural units of other phenol analogs such as salicylic acid, hydroxybenzoic acid and derivatives thereof such as esters, amides and salts.
  • Suitable aldehydes for the alkylphenol-aldehyde resins are those having 1 to 12 carbon atoms and preferably those having 1 to 4 carbon atoms such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2-ethylhexanal, benzaldehyde, glyoxalic acid and their reactive equivalents such as paraformaldehyde and trioxane.
  • Particularly preferred is formaldehyde in the form of paraformaldehyde and especially formalin.
  • the molecular weight of the alkylphenol-aldehyde resins measured by gel permeation chromatography against poly (styrene) standards in THF is preferably 500-25,000 g / mol, more preferably 800-10,000 g / mol and especially 1,000-5,000 g / mol such as 1500-3,000 g / mol.
  • the prerequisite here is that the alkylphenol-aldehyde resins, at least in application-relevant concentrations of 0.001 to 1 wt .-% are oil-soluble.
  • these are alkylphenol-formaldehyde resins, the oligo- or polymers having a repetitive structural unit of the formula wherein R 11 is C 1 -C 20 alkyl or alkenyl, OR 10 or OC (O) -R 10 , R 10 is C 1 -C 200 alkyl or alkenyl and n is a number from 2 to 100, contain.
  • R 10 is preferably C 1 -C 20 -alkyl or -alkenyl and in particular C 4 -C 16 -alkyl or -alkenyl, for example C 6 -C 12 -alkyl or -alkenyl.
  • R 11 is C 1 -C 20 -alkyl or -alkenyl and in particular C 4 -C 16 -alkyl or -alkenyl, for example C 6 -C 12 -alkyl or -alkenyl.
  • n is a number from 2 to 50 and especially a number from 3 to 25, such as a number from 5 to 15.
  • Suitable comb polymers are, for example, copolymers of ethylenically unsaturated dicarboxylic acids such as maleic or fumaric acid with other ethylenically unsaturated monomers such as olefins or vinyl esters such as vinyl acetate.
  • Particularly suitable olefins are ⁇ -olefins having 10 to 20 and especially 12 to 18 carbon atoms such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and mixtures thereof.
  • olefins based on oligomerized C 2 -C 6 -olefins such as poly (isobutylene) with a high proportion of terminal double bonds are suitable as comonomers.
  • these copolymers are at least 50% esterified with alcohols having 10 to 20 and especially 12 to 18 carbon atoms.
  • Suitable alcohols include n-decan-1-ol, n-dodecan-1-ol, n-tetradecan-1-ol, n-hexadecan-1-ol, n-octadecan-1-ol and mixtures thereof.
  • comb polymers are poly (alkyl acrylates), poly (alkyl methacrylates) and poly (alkyl vinyl ethers) derived from alcohols containing 10 to 20 and especially 12 to 18 carbon atoms, and poly (vinyl esters) derived from fatty acids containing 10 to Derive 20 and especially 12 to 18 carbon atoms.
  • the mixing ratio between the additives according to the invention and the further constituents V and VI is generally in each case between 1:10 and 10: 1, preferably between 1: 5 and 5: 1.
  • Additives according to the invention contain 15-80% by weight, preferably 20-70% by weight of detergent additive A), 2-40% by weight, preferably 5-25% by weight of nucleator B) and 15-80% by weight. , preferably 20 - 70 wt .-% cold flow improver C).
  • the additives according to the invention are preferably used as concentrates which contain from 10 to 95% by weight and preferably from 20 to 80% by weight, for example from 25 to 60% by weight, of solvent.
  • Preferred solvents are higher-boiling aliphatic, aromatic hydrocarbons, alcohols, esters, ethers and mixtures thereof.
  • Such concentrates preferably contain from 0.01 to 10 parts by weight, preferably from 0.05 to 5 parts by weight, for example from 0.1 to 3 parts by weight of the nucleator compound B) per part by weight of detergent additive A).
  • novel nucleators B improve the response of detergent-containing middle distillates such as kerosene, jet fuel, diesel and heating oil for conventional flow improvers with regard to the reduction of pour point and CFPP value and the improvement of paraffin dispersion.
  • Particularly preferred mineral oil distillates are middle distillates.
  • the middle distillate is in particular those mineral oils which are obtained by distillation of crude oil, boiling in the range of about 150 to 450 ° C and in particular in the range of about 170 to 390 ° C, for example kerosene, jet fuel, diesel and fuel oil.
  • middle distillates contain about 5 to 50 wt .-%, such as about 10 to 35 wt .-% n-paraffins, of which the longer-chain crystallize on cooling and can affect the flowability of the middle distillate.
  • Particularly advantageous are the compositions of the invention in middle aromatics with low aromatic content of less than 21 wt .-%, such as less than 19 wt .-%.
  • compositions according to the invention are furthermore particularly advantageous in low boiling end middle distillates, ie in middle distillates which have 90% distillation points below 360 ° C., in particular 350 ° C. and in special cases below 340 ° C. and furthermore in such middle distillates, the boiling ranges have between 20 and 90% distillation volume of less than 120 ° C and in particular of less than 110 ° C.
  • aromatic compounds is meant the sum of mono-, di- and polycyclic aromatic compounds as determinable by HPLC according to DIN EN 12916 (2001 edition).
  • the middle distillates may also contain minor amounts, for example up to 40% by volume, preferably 1 to 20% by volume, especially 2 to 15, for example 3 to 10% by volume of the oils of animal and / or vegetable origin described in more detail below such as fatty acid methyl esters.
  • compositions according to the invention are also suitable for improving the cold properties of detergent additives containing fuels based on renewable raw materials (biofuels).
  • biofuels oils obtained from animal and preferably vegetable material or both, and derivatives thereof, which can be used as fuel and especially as diesel or fuel oil.
  • biofuels oils obtained from animal and preferably vegetable material or both, and derivatives thereof, which can be used as fuel and especially as diesel or fuel oil.
  • biofuels examples include rapeseed oil, coriander oil, soybean oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, corn oil, almond oil, palm kernel oil, coconut oil, mustard seed oil, beef tallow, bone oil, fish oils and used edible oils.
  • Other examples include oils derived from wheat, jute, sesame, shea nut, arachis oil and linseed oil.
  • the fatty acid alkyl esters, also referred to as biodiesel can be derived from these oils by methods known in the art.
  • Rapeseed oil which is a mixture of glycerol esterified fatty acids, is preferred because it is available in large quantities and is readily available by squeezing rapeseed.
  • sunflower, palm and soybeans and their mixtures with rapeseed oil are preferred.
  • esters of fatty acids are particularly suitable as biofuels.
  • Preferred esters have an iodine value of from 50 to 150 and in particular from 90 to 125.
  • Mixtures with particularly advantageous properties are those which are principally, i. H. to contain at least 50 wt .-% of methyl esters of fatty acids having 16 to 22 carbon atoms and 1, 2 or 3 double bonds.
  • the preferred lower alkyl esters of fatty acids are the methyl esters of oleic, linoleic, linolenic and erucic acids.
  • the additives can be used alone or together with other additives, for.
  • pour point depressants or dewaxing aids with other detergents, with antioxidants, cetane number improvers, dehazers, Demulsifiers, dispersants, defoamers, dyes, corrosion inhibitors, lubricity additives, sludge inhibitors, odorants and / or additives for lowering the cloud point.
  • detergent additives (A) with different nucleators (B) and further flow improvers (C) with the characteristics given below were used.
  • paraffin dispersion in middle distillates is determined in the short sediment test as follows: 150 ml of the middle distillates mixed with the additive components indicated in the table were cooled to -13 ° C. in a cold cabinet at -2 ° C./hour in 200 ml graduated cylinders and stored at this temperature for 16 hours. Subsequently, the volume and appearance of both the sedimented paraffin phase and the oil phase above are visually determined and assessed. A small amount of sediment and a cloudy oil phase show a good paraffin dispersion.
  • detergent additives A various reaction products of alkenylsuccinic anhydrides (ASA) based on highly reactive polyolefins (proportion of terminal double bonds> 90%, degree of maleation about 1.2 to 1.3) listed in Table 2 with polyamines were used. Alkenyl succinic anhydride and polyamine were reacted thereto in a molar ratio of 1.0 to 1.5 moles of alkenyl succinic anhydride per mole of polyamine (see Table 2). For better meterability, the detergent additives were used as 33% solutions in higher boiling aromatic solvent. The dosage rates given in Tables 2 to 4 for the detergent additives A) and nucleators B) relate to the active ingredients used.
  • ASA alkenylsuccinic anhydrides
  • test oil 1 The determination of the CFPP values in test oil 1 was carried out after adding the oil with 200 ppm C2 and 150 ppm C3.
  • detergent additive A1 the reaction product of poly (isobutenyl) -succinic anhydride and pentaethylene-hexamine according to Table 2
  • detergent additive A2 the reaction product of poly (isobutenyl) succinic anhydride and pentaethylenehexamine according to Table 2, Example 13 used.
  • Table 2 Effect of nucleators on detergent-induced antagonism in test oil 1 example Detergent additive (DA) Dosing rate DA / ppm CFPP in test oil 1 [° C] polyolefin Mw polyolefin polyamine mol of ASA / mol of polyamine without DA with DA with DA + Nucleator 1 PIB 700 TEPA 1.0 150 -29 -25 40 ppm B2 -28 2 PIB 700 TEPA 1.4 150 -29 -26 40 ppm B2 -29 3 PIB 1000 PEHA 1.0 150 -29 -22 80 ppm B3 -29 4 PIB 1000 PEHA 1.5 150 -29 -21 80 ppm B1 -29 5 PIB 1000 PAM 1.0 150 -29 -18 40 ppm B2 -28 6 PIB 1000 PAM 1.3 150 -29 -15 40 ppm B2 -27 7 PIB 1000 PAM 1.3 150 -29 -15 70 ppm B2

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Claims (21)

  1. Utilisation d'au moins un copolymère oléfinique B) soluble dans les huiles, agissant en tant qu'agent de nucléation pour la cristallisation de paraffines, constitué d'éthylène et de 3 à 40% en moles d'oléfines avec 3 à 30 atomes C, pour améliorer la réponse au regard de la réduction du point d'écoulement et de la valeur CFPP, ainsi que pour améliorer la dispersion des paraffines d'agents d'amélioration de l'écoulement à froid d'huiles minérales C), qui sont différentes de B) dans des distillats moyens, qui contiennent au moins un additif détergent azoté sans cendres A), qui est un composé amphiphile soluble dans les huiles, qui comprend au moins un radical alkyle ou alcényle, qui est relié à un groupe polaire, le radical alkyle ou alcényle comprenant 10 à 500 atomes C et le groupe polaire comprenant 2 atomes d'azote ou plus, l'additif détergent azoté sans cendres A) comprenant une fraction polaire, qui est dérivée de polyamines de formule

            (R9)2N-[A-N(R9)]q-(R9)

    dans laquelle les R9 représentent chacun indépendamment les uns des autres l'hydrogène, un radical alkyle ou hydroxyalkyle contenant jusqu'à 24 atomes C, un radical polyoxyalkylène -(A-O)r- ou un radical polyiminoalkylène -[A-N(R9)]s-(R9), au moins un R9 représentant toutefois l'hydrogène, q représente un nombre entier de 1 à 19, A représente un radical alkylène de 1 à 6 atomes C, et r et s représentent indépendamment l'un de l'autre des nombres entiers de 1 à 50, des composés azotés polaires solubles dans les huiles étant utilisés en tant qu'agents d'amélioration de l'écoulement à froid C), qui sont des produits de réaction de composés de formule NR6R7R8, dans laquelle R6, R7 et R8 peuvent être identiques ou différents, et au moins un de ces groupes représente alkyle en C8-C36, cycloalkyle en C6-C36, alcényle en C8-C36, notamment alkyle en C12-C24, alcényle en C12-C24 ou cyclohexyle, et les autres groupes signifient soit hydrogène, alkyle en C1-C36, alcényle en C2-C36, cyclohexyle, soit un groupe de formule -(A-O)x-E ou - (CH2)n-NYZ, A représentant un groupe éthyle ou propyle, x signifiant un nombre de 1 à 50, E = H, alkyle en C1-C30, cycloalkyle en C5-C12 ou aryle en C6-C30, et n = 2, 3 ou 4, et Y et Z signifiant indépendamment l'un de l'autre H, alkyle en C1-C30 ou -(A-O)x, avec des composés qui contiennent au moins un groupe acyle.
  2. Utilisation selon la revendication 1, dans laquelle, par rapport à une partie en poids de l'additif détergent azoté A), 0,01 à 10 parties en poids du copolymère oléfinique B) soluble dans les huiles, agissant en tant qu'agent de nucléation pour la cristallisation de paraffines, sont utilisées.
  3. Utilisation selon la revendication 1 et/ou 2, dans laquelle le distillat moyen contient 10 à 10 000 ppm d'un additif détergent azoté sans cendres A).
  4. Utilisation selon une ou plusieurs des revendications 1 à 3, dans laquelle l'additif détergent azoté sans cendres A) contient un radical alkyle de 15 à 500 atomes C.
  5. Utilisation selon la revendication 4, dans laquelle le radical alkyle est dérivé d'oligomères d'oléfines inférieures contenant 3 à 6 atomes C ou leurs mélanges.
  6. Utilisation selon la revendication 5, dans laquelle un mélange d'oligomères d'oléfines inférieures contenant 3 à 6 atomes C est utilisé, qui contient plus de 70 % en moles de 2-méthyl-2-butène, de 2,3-diméthyl-2-butène et/ou d'isobutène.
  7. Utilisation selon une ou plusieurs des revendications 1 à 6, dans laquelle l'additif détergent azoté sans cendres A) est fabriqué en utilisant des polyoléfines de faible poids moléculaire hautement réactives, lesquelles présentent des poids moléculaires de 500 à 3 000 g/mol, ayant une proportion de doubles liaisons terminales d'au moins 75 % en moles.
  8. Utilisation selon la revendication 7, dans laquelle R9 représente l'hydrogène et q prend des valeurs d'au moins 3.
  9. Utilisation selon une ou plusieurs des revendications 1 à 8, dans laquelle l'additif détergent azoté sans cendres A) comprend un radical alkyle soluble dans les huiles et un groupe de tête polaire, et le radical alkyle soluble dans les huiles et le groupe de tête polaire sont reliés l'un avec l'autre par une liaison C-N ou par une liaison ester, amide ou imide.
  10. Utilisation selon une ou plusieurs des revendications 1 à 9, dans laquelle l'additif détergent azoté sans cendres A) présente un poids moléculaire moyen déterminé par osmométrie sous pression de vapeur supérieur à 800 g/mol.
  11. Utilisation selon une ou plusieurs des revendications 1 à 10, dans laquelle les copolymères oléfiniques B) agissant en tant qu'agent de nucléation pour la cristallisation de paraffines sont des copolymers en bloc saturés solubles dans les huiles qui comprennent au moins un bloc, lequel peut être obtenu par le biais d'une polymérisation 1, 4 du butadiène et d'une hydrogénation subséquente, et au moins un bloc ramifié, non cristallisable.
  12. Utilisation selon la revendication 1, dans laquelle les oléfines possèdent 4 à 24 atomes C.
  13. Utilisation selon une ou plusieurs des revendications 1 à 12, dans laquelle le poids moléculaire des copolymères oléfiniques B) est compris entre 500 et 50 000 g/mol.
  14. utilisation selon une ou plusieurs des revendications 1 à 13, dans laquelle les oléfines polymérisées avec de l'éthylène sont sélectionnées parmi le propylène, le butène l'isobutène, le pentène, l'isopentène, le n-hexène, l'isohexène, le n-octène, l'isooctène, le n-décène et l'isodécène.
  15. Utilisation selon une ou plusieurs des revendications 1 à 14, dans laquelle la teneur des copolymères oléfiniques B) en oléfines ayant de trois à 30 atomes C est comprise entre 5 et 30 % en moles.
  16. Utilisation selon une ou plusieurs des revendications 1 à 15, dans laquelle les copolymères oléfiniques B) sont des copolymères d'éthylène-propylène.
  17. Utilisation selon une ou plusieurs des revendications 11 à 16, dans laquelle les blocs ramifiés non cristallisables sont dérivés de butadiène hydrogéné 1,4-polymérisé.
  18. Utilisation selon une ou plusieurs des revendications 11 à 16, dans laquelle les blocs ramifiés non cristallisables dérivent de butadiène hydrogéné 1,2-polymérisé ou de polymères hydrogénés de diènes ramifiés.
  19. Utilisation selon une ou plusieurs des revendications 1 à 18, dans laquelle le rapport de quantités entre l'additif détergent A) et les copolymères oléfiniques B) agissant en tant qu'agent de nucléation pour la cristallisation de paraffines dans l'huile supplémentée est de 0,01 à 10 parties en poids d'agent de nucléation par partie en poids d'additif détergent, à chaque fois par rapport à l'agent actif.
  20. Additifs, contenant :
    a) au moins un additif détergent azoté sans cendres A), qui est un composé amphiphile soluble dans les huiles, qui comprend au moins un radical alkyle ou alcényle, qui est relié à un groupe polaire, le radical alkyle ou alcényle comprenant 10 à 500 atomes C et le groupe polaire comprenant 2 atomes d'azote ou plus, l'additif détergent azoté sans cendres A) comprenant une fraction polaire, qui est dérivée de polyamines de formule

            (R9)2N-[A-N(R9)]q-(R9)

    dans laquelle les R9 représentent chacun indépendamment les uns des autres l'hydrogène, un radical alkyle ou hydroxyalkyle contenant jusqu'à 24 atomes C, un radical polyoxyalkylène -(A-O)r- ou un radical polyiminoalkylène -[A-N(R9)]s-(R9), au moins un R9 représentant toutefois l'hydrogène, q représente un nombre entier de 1 à 19, A représente un radical alkylène de 1 à 6 atomes C, et r et s représentent indépendamment l'un de l'autre des nombres entiers de 1 à 50, et
    b) au moins un copolymère oléfinique B) soluble dans les huiles, agissant en tant qu'agent de nucléation pour la cristallisation de paraffines, constitué d'éthylène et de 3 à 40% en moles d'oléfines avec 3 à 30 atomes C,
    et
    c) un agent d'amélioration de l'écoulement à froid des huiles minérales C) différent de B), des composés azotés polaires solubles dans les huiles étant utilisés en tant qu'agents d'amélioration de l'écoulement à froid C), qui sont des produits de réaction de composés de formule NR6R7R8, dans laquelle R6, R7 et R8 peuvent être identiques ou différents, et au moins un de ces groupes représente alkyle en C8-C36, cycloalkyle en C6-C36, alcényle en C8-C36, notamment alkyle en C12-C24, alcényle en C12-C24 ou cyclohexyle, et les autres groupes signifient soit hydrogène, alkyle en C1-C36, alcényle en C2-C36, cyclohexyle, soit un groupe de formule -(A-O)x-E ou-(CH2)n-NYZ, A représentant un groupe éthyle ou propyle, x signifiant un nombre de 1 à 50, E = H, alkyle en C1-C30, cycloalkyle en C5-C12 ou aryle en C6-C30, et n = 2, 3 ou 4, et Y et Z signifiant indépendamment l'un de l'autre H, alkyle en C1-C30 ou -(A-O)x, avec des composés qui contiennent au moins un groupe acyle, et dans lesquels l'additif contient 15 à 80% en poids du constituant A), 2 à 40% en poids du constituant B), et 15 à 80% en poids du constituant C).
  21. Distillats moyens ayant une teneur en soufre inférieure à 100 ppm et un point de distillation à 90% inférieur à 360°C, contenant un additif selon la revendication 22, et dans lesquels 10 à 10 000 ppm de l'additif détergent azoté sans cendres A), ainsi que, par partie en poids de ce constituant A), 0,1 à 10 parties en poids du composé B) soluble dans les huiles, agissant en tant qu'agent de nucléation pour la cristallisation de paraffines, sont contenus.
EP08773479.4A 2007-06-20 2008-06-17 Huiles minérales contenant des additifs détergents dotées d'une fluidité à froid améliorée Not-in-force EP2162515B1 (fr)

Priority Applications (1)

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PL08773479T PL2162515T3 (pl) 2007-06-20 2008-06-17 Oleje mineralne o polepszonej płynności w niskiej temperaturze, zawierające dodatki detergentowe

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DE102007028307A DE102007028307A1 (de) 2007-06-20 2007-06-20 Detergenzadditive enthaltende Mineralöle mit verbesserter Kältefließfähigkeit
PCT/EP2008/004853 WO2008155091A1 (fr) 2007-06-20 2008-06-17 Huiles minérales contenant des additifs détergents dotées d'une fluidité à froid améliorée

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EP2162515B1 true EP2162515B1 (fr) 2019-05-01

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US (1) US8628590B2 (fr)
EP (1) EP2162515B1 (fr)
JP (1) JP5731823B2 (fr)
KR (1) KR101527401B1 (fr)
CA (1) CA2692045A1 (fr)
DE (1) DE102007028307A1 (fr)
PL (1) PL2162515T3 (fr)
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WO (1) WO2008155091A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7875747B2 (en) * 2006-10-10 2011-01-25 Afton Chemical Corporation Branched succinimide dispersant compounds and methods of making the compounds
DE102007028305A1 (de) * 2007-06-20 2008-12-24 Clariant International Limited Detergenzadditive enthaltende Mineralöle mit verbesserter Kältefließfähigkeit
DE102007028306A1 (de) * 2007-06-20 2008-12-24 Clariant International Limited Detergenzadditive enthaltende Mineralöle mit verbesserter Kältefließfähigkeit
US9932436B2 (en) 2013-10-17 2018-04-03 Si Group, Inc. Modified alkylphenol-aldehyde resins stabilized by a salicylic acid
US9944744B2 (en) 2013-10-17 2018-04-17 Si Group, Inc. In-situ alkylphenol-aldehyde resins
GB201810852D0 (en) 2018-07-02 2018-08-15 Innospec Ltd Compositions, uses and methods
MX2021007702A (es) * 2019-01-29 2021-08-05 Shell Int Research Mejoras relacionadas con la economia de combustible.
WO2021145309A1 (fr) * 2020-01-17 2021-07-22 日油株式会社 Auxiliaire au déparaffinage

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4022589A (en) 1974-10-17 1977-05-10 Phillips Petroleum Company Fuel additive package containing polybutene amine and lubricating oil
US4108613A (en) 1977-09-29 1978-08-22 Chevron Research Company Pour point depressants
US4261703A (en) * 1978-05-25 1981-04-14 Exxon Research & Engineering Co. Additive combinations and fuels containing them
FR2426730A1 (fr) * 1978-05-25 1979-12-21 Exxon Research Engineering Co Compositions d'additifs pour ameliorer l'ecoulement et la filtrabilite des fuel-oils distilles
US4211534A (en) 1978-05-25 1980-07-08 Exxon Research & Engineering Co. Combination of ethylene polymer, polymer having alkyl side chains, and nitrogen containing compound to improve cold flow properties of distillate fuel oils
US4357148A (en) * 1981-04-13 1982-11-02 Shell Oil Company Method and fuel composition for control or reversal of octane requirement increase and for improved fuel economy
DE3405843A1 (de) 1984-02-17 1985-08-29 Bayer Ag, 5090 Leverkusen Copolymere auf basis von maleinsaeureanhydrid und (alpha), (beta)-ungesaettigten verbindungen, ein verfahren zu ihrer herstellung und ihre verwendung als paraffininhibitoren
GB2174102A (en) * 1985-04-24 1986-10-29 Shell Int Research Diesel fuel composition
US4968321A (en) * 1989-02-06 1990-11-06 Texaco Inc. ORI-inhibited motor fuel composition
DE3916366A1 (de) 1989-05-19 1990-11-22 Basf Ag Neue umsetzungsprodukte von aminoalkylenpolycarbonsaeuren mit sekundaeren aminen und erdoelmitteldestillatzusammensetzungen, die diese enthalten
US5006130A (en) * 1989-06-28 1991-04-09 Shell Oil Company Gasoline composition for reducing intake valve deposits in port fuel injected engines
DE3926992A1 (de) 1989-08-16 1991-02-21 Hoechst Ag Verwendung von umsetzungsprodukten von alkenylspirobislactonen und aminen als paraffindispergatoren
GB9002133D0 (en) * 1990-01-31 1990-03-28 Exxon Chemical Patents Inc Fuel oil additives and compositions
GB9222458D0 (en) * 1992-10-26 1992-12-09 Exxon Chemical Patents Inc Oil additives and compositions
US5286264A (en) * 1992-12-21 1994-02-15 Texaco Inc. Gasoline detergent additive composition and motor fuel composition
ES2110124T3 (es) 1993-01-06 1998-02-01 Clariant Gmbh Termopolimeros a base de anhidridos de acidos carboxilicos alfa,beta-insaturados, de compuestos alfa,beta-insaturados y de polioxialquileneteres de alcoholes inferiores insaturados.
GB9315205D0 (en) * 1993-07-22 1993-09-08 Exxon Chemical Patents Inc Additives and fuel compositions
DE4430294A1 (de) 1994-08-26 1996-02-29 Basf Ag Polymermischungen und ihre Verwendung als Zusatz für Erdölmitteldestillate
GB9505103D0 (en) 1995-03-14 1995-05-03 Exxon Chemical Patents Inc "Fuel oil additives and compositions"
ATE223953T1 (de) * 1997-01-07 2002-09-15 Clariant Gmbh Verbesserung der fliessfähigkeit von mineralölen und mineralöldestillaten unter verwendung von alkylphenol-aldehydharzen
US6733550B1 (en) * 1997-03-21 2004-05-11 Shell Oil Company Fuel oil composition
GB9725579D0 (en) 1997-12-03 1998-02-04 Exxon Chemical Patents Inc Additives and oil compositions
DE10155748B4 (de) * 2001-11-14 2009-04-23 Clariant Produkte (Deutschland) Gmbh Schwefelarme Mineralöldestillate mit verbesserten Kälteeigenschaften, umfassend einen Ester eines alkoxylierten Polyols und ein Copolymer aus Ethylen und ungesättigten Estern
ES2554978T3 (es) * 2005-12-22 2015-12-28 Clariant Produkte (Deutschland) Gmbh Aceites minerales que contienen unos aditivos para conferir detergencia con una mejorada capacidad para fluir en frío
DE102007028305A1 (de) 2007-06-20 2008-12-24 Clariant International Limited Detergenzadditive enthaltende Mineralöle mit verbesserter Kältefließfähigkeit
DE102007028306A1 (de) 2007-06-20 2008-12-24 Clariant International Limited Detergenzadditive enthaltende Mineralöle mit verbesserter Kältefließfähigkeit
DE102007028304A1 (de) 2007-06-20 2008-12-24 Clariant International Limited Detergenzadditive enthaltende Mineralöle mit verbesserter Kältefließfähigkeit

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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US8628590B2 (en) 2014-01-14
RU2475519C2 (ru) 2013-02-20
KR101527401B1 (ko) 2015-06-09
DE102007028307A1 (de) 2008-12-24
RU2010101590A (ru) 2011-07-27
JP2010530454A (ja) 2010-09-09
PL2162515T3 (pl) 2019-10-31
CA2692045A1 (fr) 2008-12-24
KR20100049038A (ko) 2010-05-11
EP2162515A1 (fr) 2010-03-17
JP5731823B2 (ja) 2015-06-10
WO2008155091A1 (fr) 2008-12-24
US20100192456A1 (en) 2010-08-05

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