EP0931824B1 - Process to improve the cold flow properties of fuel oils - Google Patents

Process to improve the cold flow properties of fuel oils Download PDF

Info

Publication number
EP0931824B1
EP0931824B1 EP98124678A EP98124678A EP0931824B1 EP 0931824 B1 EP0931824 B1 EP 0931824B1 EP 98124678 A EP98124678 A EP 98124678A EP 98124678 A EP98124678 A EP 98124678A EP 0931824 B1 EP0931824 B1 EP 0931824B1
Authority
EP
European Patent Office
Prior art keywords
mol
weight
copolymer
vinyl esters
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP98124678A
Other languages
German (de)
French (fr)
Other versions
EP0931824A2 (en
EP0931824A3 (en
Inventor
Matthias Dr. Krull
Werner Dr. Reimann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
clariant Produkte Deutschland GmbH
Original Assignee
Clariant GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clariant GmbH filed Critical Clariant GmbH
Publication of EP0931824A2 publication Critical patent/EP0931824A2/en
Publication of EP0931824A3 publication Critical patent/EP0931824A3/en
Application granted granted Critical
Publication of EP0931824B1 publication Critical patent/EP0931824B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—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

Definitions

  • the present invention relates to a method for improving the Cold flow properties of mineral oils and mineral oil distillates, while simultaneously the filterability of the oils is maintained, an additive for improving the Cold flow properties and fuel oils containing the additives.
  • Crude oils and middle distillates obtained by the distillation of crude oils such as gas oil, Diesel oil or fuel oil
  • Crude oils and middle distillates obtained by the distillation of crude oils contain different depending on the origin of the crude oils
  • Amounts of n-paraffins the platelet-shaped when the temperature is lowered Crystals crystallize and partially agglomerate with the inclusion of oil. This leads to a deterioration of the flow properties of these oils Distillates, whereby, for example, in extraction, transport, storage and / or use of mineral oils and mineral oil distillates may occur.
  • this crystallization phenomenon can occur 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 Ethylenes with carboxylic acid esters of vinyl alcohol. How to set after the DE-A-11 4 799 petroleum distillate fuels having a boiling point between about 120 and 400 ° C oil-soluble copolymers of ethylene and Vinyl acetate having a molecular weight of between about 1,000 and 3,000. Preference is given to copolymers which contain about 60 to 99 wt .-% of ethylene and about 1 to 40 wt .-% vinyl acetate. They are especially effective when they pass through radical polymerization in an inert solvent at temperatures of about 70 to 130 ° C and pressures of 35 to 2100 atm were made (DE-A-19 14 756).
  • EP-A-0 493 769 discloses terpolymers consisting of ethylene, vinyl acetate and neononane or vinyl neodecanoate, and their use as Additives for mineral oil distillates.
  • DE-A-22 06 719 discloses mixtures of ethylene-vinyl acetate copolymers with different Comonomerwitz to improve the cold flow behavior of middle distillates.
  • DE-A-20 37 673 discloses synergistic mixtures of ethylene-vinyl ester copolymers different molecular weights as flow improvers.
  • EP-A-0 254 284 discloses blends of ethylene / vinyl acetate copolymers with Ethylene / vinyl acetate / diisobutylene terpolymers as flow improvers for mineral oils and mineral oil distillates.
  • EP-A-0 648 257 discloses blends of at least 2 ethylene / vinyl ester copolymers, where the vinyl esters of carboxylic acids with 2 to 7 Derive carbon atoms.
  • EP-B-0 648 258 discloses ternary mixtures of ethylene / vinyl ester copolymers, wherein one of the blend components is between 7.5 and 35 and% of the vinyl ester comonomer and another of the mixture components below 10 mol% of Contains vinyl ester comonomers.
  • EP-A-0 113 581 discloses blends of two ethylene / vinyl ester copolymers, in the vinyl esters derived from carboxylic acids of 1 to 4 carbon atoms is.
  • One of the copolymers is a paraffin crystal nucleating agent, while the other Copolymer is a growth inhibitor.
  • EP-A-0 741 181 discloses blends of two copolymers, one of which at least one vinyl ester having alkyl or alkenyl radicals with more than 4 Contains carbon atoms as comonomers.
  • EP-A-0 648 256 discloses ethylene-vinyl ester copolymers as cold flow improvers for mineral oils.
  • the vinyl esters carry acid residues of C 1 to C 28 , and their molar content of the copolymer is less than 11%.
  • WO-96/34073 discloses an additive as a cold flow improver for mineral oils, 10 ° C under Cloud Point have a wax content of less than 2 wt .-%.
  • the Additive comprises a copolymer of ethylene and an unsaturated vinyl ester except Vinyl acetate, wherein the molar ratio of the vinyl ester is greater than 10%.
  • EP-A-0 649 456 discloses copolymers of ethylene and esters of unsaturated Alcohols with which the cold flow behavior of oils with a wax content of more than 2.5 wt .-% can be improved.
  • EP-A-0 706 306 discloses additives for stabilizing CFPP in middle distillates. These additives contain mixtures of copolymers and terpolymers of ethylene and Vinylestern. A disadvantage of the mixtures proposed there is the proportion of highly crystalline polymer fractions, especially at low oil and / or Additive temperatures during additivation The filterability of the additized oils above the cloud point.
  • the data in% by weight relate to the total weight of the mixture of A) and B).
  • Another object of the invention is a fuel oil, which defined above Composition of A and B contains.
  • the mixture of the copolymers from 20 to 40 wt .-% of Components A) and 60 to 80 wt .-% of component B).
  • Preferred vinyl esters for component B) are vinyl acetate, vinyl propionate, Vinylhexanoate, vinyl laurate and vinyl esters of neocarboxylic acids, here in particular of neononan, neodecane and neoundecanoic acid.
  • Preferred acrylic acid esters are acrylic acid alkyl esters with alcohol radicals from 1 to 20, in particular from 2 to 12 and especially from 4 to 8 carbon atoms, such as methyl acrylate, Ethyl acrylate and 2-ethylhexyl acrylate.
  • R 1 and R 2 are preferably hydrogen.
  • R 3 preferably denotes a neoalkyl radical having 7 to 11 carbon atoms, in particular a neoalkyl radical having 8, 9 or 10 carbon atoms.
  • the neoalkyl acids from which the abovementioned neoalkyl radicals can be derived are described by the formula 4:
  • the vinyl ester used for the copolymerization therefore has the formula 5:
  • Copolymer A) preferably contains 5 to 10 mol%, in particular 7 to 10 mol% of the structural units of the formula 2.
  • Copolymer B) is preferably an ethylene copolymer with a Comonomer content of 10 to 20 mol%, preferably 13 to 18 mol%.
  • suitable Comonomers are vinyl esters of aliphatic carboxylic acids having 2 to 15 carbon atoms, see above in that B) in particular an ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer, Ethylene-vinyl acetate-neononanoic acid vinyl ester copolymer or a Ethylene-vinyl acetate-neodecanoic acid vinyl ester terpolymer.
  • Comonomers are olefins such as propene, hexene, butene, isobutene, diisobutylene, 4-methylpentene-1 and norbornene. Particularly preferred are ethylene-vinyl acetate-diisobutylene and ethylene-vinyl acetate-4-methylpentene-1 terpolymers.
  • the copolymers used in the invention are by the usual Copolymerization processes such as suspension polymerization, Solution polymerization, gas phase polymerization or High pressure mass polymerization can be produced.
  • Preferred is the High-pressure bulk polymerization at pressures of preferably 50 to 400, in particular 100 to 300 MPa and temperatures of preferably 50 to 350 ° C, in particular 100 to 250 ° C.
  • the reaction of the monomers is by radicals forming initiators (radical chain starter) initiated.
  • radicals forming initiators radical chain starter
  • Oxygen, hydroperoxides, peroxides and azo compounds such as Cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide carbonate, t-butyl perpivalate, t-butyl per-maleate, t-butyl perbenzoate, Dicumyl peroxide, t-butyl cumyl peroxide, di (t-butyl) peroxide, 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-methylbutyronitrile).
  • the initiators are individually or as a mixture of two or more substances in amounts of from 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Monomer mixture used.
  • components A and B have melt viscosities at 140 ° C of 20 to 10,000 mPas, in particular from 30 to 5000 mPas, especially from 50 to 2000 mPas.
  • component A has a higher by at least 100 mPas Melt viscosity as component B.
  • the desired melt viscosity of Blends are made by selecting the individual components and varying the Blend ratio of the copolymers set.
  • copolymers mentioned under A) and B) may contain up to 5% by weight of further comonomers.
  • Such comonomers may be, for example, vinyl esters, vinyl ethers, alkyl acrylates, alkyl methacrylates having C 1 to C 20 alkyl radicals, isobutylene and higher olefins having at least 5 carbon atoms.
  • Preferred higher olefins are hexene, isobutylene, 4-methylpentene, octene and / or diisobutylene.
  • High pressure bulk polymerization is used in known high pressure reactors, e.g. Autoclaves or tube reactors, discontinuous or continuous, Tube reactors have proven particularly useful.
  • Solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, Benzene or toluene may be included in the reaction mixture.
  • the solvent-free operation is the mixture of the monomers, the initiator and, if used, the moderator, a tubular reactor via the reactor inlet and above supplied to one or more side branches.
  • the monomer streams be composed differently (EP-A-0 271 738).
  • the mixtures of components A and B are mineral oils or Mineral oil distillates added in the form of solutions or dispersions. These Solutions or dispersions preferably contain 1 to 90, in particular 5 to 80% by weight of the mixtures.
  • Suitable solvents or dispersants are aliphatic and / or aromatic hydrocarbons or Hydrocarbon mixtures, e.g. Gasoline 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 types.
  • the specified solvent mixtures contain different amounts of aliphatic and / or aromatic Hydrocarbons.
  • the aliphatics can be straight chain (n-paraffins) or branched his (iso-paraffins).
  • Aromatic hydrocarbons can mono-, di- or be polycyclic and optionally carry one or more substituents.
  • the Mixtures also together with one or more oil-soluble co-additives already used by itself the cold flow properties of crude oils, Improve lubricating oils or fuel oils.
  • oil-soluble co-additives are polar Compounds which cause a paraffin dispersion (paraffin dispersants), as well as comb polymers.
  • Paraffin dispersants reduce the size of the paraffin crystals and cause The paraffin particles do not settle, but colloidly with significantly reduced Sedimentation tendency, remain dispersed.
  • paraffin dispersants have become oil-soluble polar compounds having ionic or polar groups, e.g. amine salts and / or amides 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 are obtained (U.S. 4,211,534).
  • paraffin dispersants are copolymers of the Maleic anhydride and ⁇ , ⁇ -unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols are reacted can (EP-A-0 154 177), the reaction products of Alkenylspirobislactonen with Amines (EP-A-0 413 279) and according to EP-A-0 606 055 reaction products of Terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic acid anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkenyl ether of lower unsaturated Alcohols.
  • Alkylphenol-formaldehyde resins are also known as paraffin dispersants suitable.
  • 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. A-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. A-0 320 766
  • further esterified olefin / maleic anhydride copolymers polymers and cop
  • the mixing ratio (in parts by weight) of the mixtures according to the invention with paraffin dispersants and / or comb polymers is in each case from 1:10 to 20: 1, preferably 1: 1 to 10: 1.
  • middle distillates are particularly well suited.
  • Middle distillates are referred to in particular those mineral oils by Crude oil distillation and boiling in the range of 120 to 400 ° C, such as kerosene, jet fuel, diesel and heating oil.
  • the invention Fuels preferably contain less than 350 ppm and especially less than 200 ppm sulfur.
  • Their content of n-paraffins, the chain lengths, determined with GC of 18 carbon atoms or more, is at least 8 area%, preferably at more than 10 area%.
  • EP-A-0 796 306 Compared to the nearest state of the Technology, in particular to EP-A-0 796 306, has the advantage of inventive method in an improved solubility of the additives, so that the filterability of the oils additivated with them even at low Blending temperatures of oil and / or additive is maintained. Furthermore the mixtures of the invention show pronounced synergistic effects compared to the individual components in CFPP subsidence.
  • the mixtures according to the invention can be used alone or together with other additives are used, for example with Dewaxing aids, corrosion inhibitors, antioxidants, lubricity additives, Dehazem, conductivity improver, cetane improver or Sludge inhibitors.
  • the determination of the boiling characteristics is carried out in accordance with ASTM D-86, the determination of the CFPP value according to EN 116 and the determination of the cloud point according to ISO 3015.
  • the paraffin content is determined by gas chromatographic separation of the oil (detection by FiD) and calculation of the integral of the n paraffins ⁇ C 18 in relation to the total integral. As an approximation, this area integral of n-paraffins ⁇ C 18 is equated with wt% n-paraffins ⁇ C 18 in relation to the total integral.
  • Test oil 1 Test oil 2 Test oil 3 Test oil 4 Test oil 5 Test oil 6 Initial boiling point 180 ° C 169 ° C 183 ° C 183 ° C 184 ° C 182 ° C 20% 267 ° C 255 ° C 226 ° C 232 ° C 258 ° C 243 ° C 90% 350 ° C 350 ° C 330 ° C 358 ° C 329 ° C 351 ° C 95% 365 ° C 364 ° C 347 ° C 378 ° C 344 ° C 366 ° C Cloud point -0.4 ° C -1 ° C -9 ° C + 4 ° C -5 ° C -3 ° C CFPP -3 ° C -3 ° C -12 -4 ° C -9 ° C -6 ° C (90-20)% 83 ° C 95 ° C 104 ° C 126 ° C 71 ° C 108 ° C n-paraffins ⁇ C 18 /
  • the CFPP value of the oil additized with the specified amount of flow improver was measured immediately after the additization and the remainder of the sample at -3 ° C, So stored below the cloud point. At weekly intervals, the Samples heated to 12 ° C, 50 ml taken for a new CFPP measurement and the remainder stored at -3 ° C on.
  • the dosage rate in test oil 1 was 800 ppm additive, 50% in kerosene CFPP (immediately) 1 week 2 weeks 3 weeks 4 weeks A1 + B1 (1: 5) -12 -12 -10 -10 -11 A1 + B2 (1: 3) -13 -16 -12 -15 -14 A2 + B2 (1: 3) -10 -12 -10 -13 -13 A3 + B2 (1: 3) -9 -11 -12 -12 -12 A4 + B1 (1: 4) -12 -13 -11 -12 -10 A5 + B3 (1: 4) -12 -13 -13 -10 -11 B1 (comparison) -10 -4 -5 -3 -4 B2 (comparison) -11 -7 -5 -4 -5 B3 (comparison) -10 -9 -7 -7 -5
  • Test Oil 2 The dosage rate in Test Oil 2 is 800 ppm additive, 50% in kerosene CFPP (immediately) 1 week 2 weeks 3 weeks 4 weeks A5 + B3 (1: 4) -13 -14 -15 -11 -12 A1 + B2 (1: 5) -11 -13 -13 -12 -12 B2 (comparison) -10 -9 -7 -8th -5 B3 (comparison) -10 -9 -6 -6 -5
  • An ADT value ⁇ 15 is considered as an indication that the gas oil is satisfactorily usable in "normal" cold weather. Products with ADT values> 25 are referred to as non-filterable. Solubility of the additives ADT Blank value (without additive) 3.0 A5 + B3 (1: 4) 9.4 A1 + B2 (1: 5) 4.8 A1 + B1 (1: 1) 13.3 A2 + B2 (1: 3) 5.2 B2 (comparison) 5.4 B2 + 4% EVA copolymer with 13.5% by weight of vinyl acetate (according to WO 97/17905) 60 B2 + 10% EVA copolymer with 13.5% by weight of vinyl acetate (according to WO 97/17905) not filterable (115 ml in 20 minutes)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Lubrication Of Internal Combustion Engines (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

An additive containing copolymers of lower olefins and vinyl esters, and copolymers and terpolymers of ethylene and vinyl esters or acrylic acid esters is used to improve the cold flow properties of fuels. Process for improving the cold flow properties of fuels containing less than 500 ppm sulfur and at least 8 wt.% n-paraffins having a chain length of 8 C or longer comprises adding an additive comprising a mixture of either (A1) 15-50 wt.% copolymer of lower olefins and vinyl esters containing (a) up to 96 mol.% bivalent structure of formula (I): CH2CR1R2 (where R1 and R2 = hydrogen or methyl, and (b) 1-10 mol.% bivalent structure of formula (II): CH2CHOCOR3 (where R3 = 6-16 C alkyl having a tertiary carbon atom); or (A2) 15-50 wt.% copolymer of lower olefins and vinyl esters containing (a) up to 96 mol.% bivalent structure of formula (I), (b) 1-10 mol.% bivalent structure of formula (II), and (c) up to 10 mol.% of bivalent structure of formula (III): CH2CHOCOCH3, in which the sum of the structural units of formula (II) and (III) is 4-12 mol.%; and (B) 85-50 wt.% of a further copolymer or terpolymer of ethylene and vinyl esters or acrylic acid esters.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Verbesserung der Kaltfließeigenschaften von Mineralölen und Mineralöldestillaten, wobei gleichzeitig die Filtrierbarkeit der Öle erhalten bleibt, ein Additiv zur Verbesserung der Kaltfließeigenschaften und Brennstofföle, die die Additive enthalten.The present invention relates to a method for improving the Cold flow properties of mineral oils and mineral oil distillates, while simultaneously the filterability of the oils is maintained, an additive for improving the Cold flow properties and fuel oils containing the additives.

Rohöle und durch Destillation von Rohölen gewonnene Mitteldestillate wie Gasöl, Dieselöl oder Heizöl, enthalten je nach Herkunft der Rohöle unterschiedliche Mengen an n-Paraffinen, die bei Erniedrigung der Temperatur als plättchenförmige Kristalle auskristallisieren und teilweise unter Einschluß von Öl agglomerieren. Dadurch kommt es zu einer Verschlechterung der Fließeigenschaften dieser Öle bzw. Destillate, wodurch beispielsweise bei Gewinnung, Transport, Lagerung und/oder Einsatz der Mineralöle und Mineralöldestillate Störungen auftreten können. Bei Mineralölen kann dieses Kristallisationsphänomen beim Transport durch Rohrleitungen vor allem im Winter zu Ablagerungen an den Rohrwänden, in Einzelfällen, z.B. bei Stillstand einer Pipeline, sogar zu deren völliger Verstopfung führen. Auch bei der Lagerung und Weiterverarbeitung der Mineralöle kann die Ausfällung von Paraffinen Schwierigkeiten verursachen. So kann es im Winter unter Umständen erforderlich sein, die Mineralöle in beheizten Tanks zu lagern. Bei Mineralöldestillaten können als Folge der Kristallisation Verstopfung der Filter in Dieselmotoren und Feuerungsanlagen auftreten, wodurch eine sichere Dosierung der Brennstoffe verhindert wird und gegebenenfalls eine völlige Unterbrechung der Kraftstoff- bzw. Heizmittelzufuhr eintritt.Crude oils and middle distillates obtained by the distillation of crude oils, such as gas oil, Diesel oil or fuel oil, contain different depending on the origin of the crude oils Amounts of n-paraffins, the platelet-shaped when the temperature is lowered Crystals crystallize and partially agglomerate with the inclusion of oil. This leads to a deterioration of the flow properties of these oils Distillates, whereby, for example, in extraction, transport, storage and / or use of mineral oils and mineral oil distillates may occur. For mineral oils, this crystallization phenomenon can occur 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. Also in the storage and processing of mineral oils, the Precipitation of paraffins cause difficulties. This is how it can be during the winter Circumstances may be necessary to store the mineral oils in heated tanks. at As a result of crystallization, mineral oil distillates may become clogged in the filter Diesel engines and firing systems occur, creating a safe dosage the fuel is prevented and possibly a complete interruption of Fuel or Heizmittelzufuhr occurs.

Neben den klassischen Methoden zur Beseitigung der auskristallisierten Paraffine (thermisch, mechanisch oder mit Lösungsmitteln), die sich lediglich auf die Entfernung der bereits gebildeten Ausfällungen beziehen, wurden in den letzten Jahren chemische Additive (sogenannten Fließverbesserer oder Paraffin-Inhibitoren) entwickelt, die durch physikalisches Zusammenwirken mit den ausfallenden Paraffinkristallen dazu führen, daß deren Form, Größe und Adhäsionseigenschaften modifiziert werden. Die Additive wirken dabei als zusätzliche Kristallkeime und kristallisieren teilweise mit den Paraffinen aus, wodurch eine größere Anzahl von kleineren Paraffinkristallen mit veränderter Kristallform resultiert. Ein Teil der Wirkung der Additive wird auch durch eine Dispergierung der Paraffinkristalle erklärt. Die modifizierten Paraffinkristalle neigen weniger zur Agglomeration, so daß sich die mit diesen Additiven versetzten Öle noch bei Temperaturen pumpen bzw. verarbeiten lassen, die oft mehr als 20°C tiefer liegen als bei nichtadditivierten Ölen.In addition to the classic methods for removing the crystallized paraffins (thermally, mechanically or with solvents), which are limited to the Removal of already formed precipitates have been in the last few years Years of chemical additives (so-called flow improvers or paraffin inhibitors) developed by physical interaction with the failing Paraffin crystals cause their shape, size and adhesion properties be modified. The additives act as additional nuclei and crystallize partially with the paraffins, creating a larger number of smaller paraffin crystals with altered crystal form results. A part of Effect of the additives is also explained by a dispersion of paraffin crystals. The modified paraffin crystals are less prone to agglomeration, so that the Pumped with these additives offset oils at temperatures or which are often more than 20 ° C lower than with non-additive oils.

Das Fließ- und Kälteverhalten von Mineralölen und Mineralöldestillaten wird durch Angabe des Cloud Point (bestimmt nach ISO 3015), des Pour-Points (bestimmt nach ISO 3016) und des Cold-Filter-Plugging-Points (CFPP; bestimmt nach EN 116) beschrieben. Diese Kenngrößen werden in °C gemessen.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.

Typische Fließverbesserer für Rohöle und Mitteldestillate sind Copolymerisate des Ethylens mit Carbonsäureestern des Vinylalkohols. So setzt man nach der DE-A-11 4 799 Erdöldestillat-Treib- bzw. -Brennstoffen mit einem Siedepunkt zwischen etwa 120 und 400°C öllösliche Mischpolymerisate aus Ethylen und Vinylacetat mit einem Molekulargewicht zwischen etwa 1.000 und 3.000 zu. Bevorzugt werden Mischpolymerisate, die etwa 60 bis 99 Gew.-% Ethylen und etwa 1 bis 40 Gew.-% Vinylacetat enthalten. Sie sind besonders wirksam, wenn sie durch radikalische Polymerisation in einem inerten Lösungsmittel bei Temperaturen von etwa 70 bis 130°C und Drücken von 35 bis 2.100 atü hergestellt wurden (DE-A-19 14 756).Typical flow improvers for crude oils and middle distillates are copolymers of Ethylenes with carboxylic acid esters of vinyl alcohol. How to set after the DE-A-11 4 799 petroleum distillate fuels having a boiling point between about 120 and 400 ° C oil-soluble copolymers of ethylene and Vinyl acetate having a molecular weight of between about 1,000 and 3,000. Preference is given to copolymers which contain about 60 to 99 wt .-% of ethylene and about 1 to 40 wt .-% vinyl acetate. They are especially effective when they pass through radical polymerization in an inert solvent at temperatures of about 70 to 130 ° C and pressures of 35 to 2100 atm were made (DE-A-19 14 756).

EP-A-0 493 769 offenbart Terpolymere, die aus Ethylen, Vinylacetat und Neononan- bzw. Neodecansäurevinylester hergestellt werden, sowie ihre Verwendung als Additive für Mineralöldestillate.EP-A-0 493 769 discloses terpolymers consisting of ethylene, vinyl acetate and neononane or vinyl neodecanoate, and their use as Additives for mineral oil distillates.

Im Stand der Technik sind auch Mischungen von Copolymeren als Fließverbesserer beschrieben. Also known in the art are blends of copolymers as flow improvers described.

DE-A-22 06 719 offenbart Mischungen von EthylenNinylacetat-Copolymeren mit unterschiedlichen Comonomergehalten zur Verbesserung des Kaltfließverhaltens von Mitteldestillaten.DE-A-22 06 719 discloses mixtures of ethylene-vinyl acetate copolymers with different Comonomergehalten to improve the cold flow behavior of middle distillates.

DE-A-20 37 673 offenbart synergistische Mischungen von Ethylen-Vinylester-Copolymeren verschiedener Molekulargewichte als Fließverbesserer.DE-A-20 37 673 discloses synergistic mixtures of ethylene-vinyl ester copolymers different molecular weights as flow improvers.

EP-A-0 254 284 offenbart Mischungen aus Ethylen/Vinylacetat-Copolymeren mit Ethylen/Vinylacetat/Diisobutylen-Terpolymeren als Fließverbesserer für Mineralöle und Mineralöldestillate.EP-A-0 254 284 discloses blends of ethylene / vinyl acetate copolymers with Ethylene / vinyl acetate / diisobutylene terpolymers as flow improvers for mineral oils and mineral oil distillates.

EP-A-0 648 257 offenbart Mischungen aus mindestens 2 Ethylen/Vinylester-Copolymeren, wobei die Vinylester sich von Carbonsäuren mit 2 bis 7 Kohlenstoffatomen ableiten.EP-A-0 648 257 discloses blends of at least 2 ethylene / vinyl ester copolymers, where the vinyl esters of carboxylic acids with 2 to 7 Derive carbon atoms.

EP-B-0 648 258 offenbart ternäre Mischungen aus Ethylen/Vinylester-Copolymeren, wobei eine der Mischungskomponenten zwischen 7,5 und 35 und % des Vinylester-Comonomeren und eine weitere der Mischungskomponenten unter 10 mol -% der Vinylester-Comonomeren enthält.EP-B-0 648 258 discloses ternary mixtures of ethylene / vinyl ester copolymers, wherein one of the blend components is between 7.5 and 35 and% of the vinyl ester comonomer and another of the mixture components below 10 mol% of Contains vinyl ester comonomers.

EP-A-0 113 581 offenbart Mischungen aus zwei Ethylen/Vinylester-Copolymeren, in denen der Vinylester aus Carbonsäuren von 1 bis 4 Kohlenstoffatomen abgeleitet ist. Eines der Copolymere ist ein Paraffinkristallkeimbildner, während das andere Copolymer ein Wachstumshemmer ist.EP-A-0 113 581 discloses blends of two ethylene / vinyl ester copolymers, in the vinyl esters derived from carboxylic acids of 1 to 4 carbon atoms is. One of the copolymers is a paraffin crystal nucleating agent, while the other Copolymer is a growth inhibitor.

EP-A-0 741 181 offenbart Mischungen aus zwei Copolymeren, von denen mindestens eines Vinylester mit Alkyl- oder Alkenylresten mit mehr als 4 Kohlenstoffatomen als Comonomere enthält.EP-A-0 741 181 discloses blends of two copolymers, one of which at least one vinyl ester having alkyl or alkenyl radicals with more than 4 Contains carbon atoms as comonomers.

EP-A-0 648 256 offenbart Ethylen-Vinylester-Copolymere als Kaltfließverbesserer für Mineralöle. Die Vinylester tragen Säurereste von C1 bis C28, und ihr molarer Anteil am Copolymeren beträgt unter 11 %.EP-A-0 648 256 discloses ethylene-vinyl ester copolymers as cold flow improvers for mineral oils. The vinyl esters carry acid residues of C 1 to C 28 , and their molar content of the copolymer is less than 11%.

WO-96/34073 offenbart ein Additiv als Kaltfließverbesserer für Mineralöle, die 10°C unter Cloud Point einen Wachsgehalt von weniger als 2 Gew.-% aufweisen. Das Additiv umfaßt ein Copolymer aus Ethylen und einem ungesättigten Vinylester außer Vinylacetat, wobei der molare Anteil des Vinylesters über 10 % liegt.WO-96/34073 discloses an additive as a cold flow improver for mineral oils, 10 ° C under Cloud Point have a wax content of less than 2 wt .-%. The Additive comprises a copolymer of ethylene and an unsaturated vinyl ester except Vinyl acetate, wherein the molar ratio of the vinyl ester is greater than 10%.

EP-A-0 649 456 offenbart Copolymere aus Ethylen und Estern ungesättigter Alkohole, mit denen das Kaltfließverhalten von Ölen mit einem Wachsgehalt von mehr als 2,5 Gew.-% verbessert werden kann.EP-A-0 649 456 discloses copolymers of ethylene and esters of unsaturated Alcohols with which the cold flow behavior of oils with a wax content of more than 2.5 wt .-% can be improved.

EP-A-0 706 306 offenbart Additive zur Stabilisierung des CFPP in Mitteldestillaten. Diese Additive enthalten Mischungen aus Co- und Terpolymeren von Ethylen und Vinylestern. Nachteilig an den dort vorgeschlagenen Mischungen ist der Anteil an hochkristallinen Polymeranteilen, die insbesondere bei niedrigen Öl- und/oder Additivtemperaturen bei der Additivierung die Filtrierbarkeit der additivierten Öle oberhalb des Cloud Points beeinträchtigen.EP-A-0 706 306 discloses additives for stabilizing CFPP in middle distillates. These additives contain mixtures of copolymers and terpolymers of ethylene and Vinylestern. A disadvantage of the mixtures proposed there is the proportion of highly crystalline polymer fractions, especially at low oil and / or Additive temperatures during additivation The filterability of the additized oils above the cloud point.

Insbesondere in Mitteldestillaten mit geringer Destillationsbreite bei gleichzeitig hohem Siedeende bereiten herkömmliche Fließverbesserer Probleme. Man beobachtet, daß der mit solchen Fließverbesserem in diesen Ölen eingestellte CFPP nicht stabil ist, sondern im Verlauf einiger Tage bis Wochen auf den CFPP des nicht additivierten Öls zurückgeht (CFPP-Reversion). Die Ursache dafür ist nicht bekannt. Es wird vermutet, daß sie in einer unvollständigen Rücklösung der Polymeranteile mit niedrigem Comonomergehalt aus dem einmal eingetrübten Öl zu suchen ist. Ein besonderes Problem stellt die Verhinderung der CFPP-Reversion bei Ölen mit niedrigem Schwefelgehalt dar, da diese aufgrund der Entschwefelungschritte besonders hohe Anteile langkettiger n-Paraffine mit Kettenlängen größer als C18 aufweisen.Conventional flow improvers pose problems, in particular in middle distillates with a small distillation range and at the same time a high boiling point. It is observed that the CFPP adjusted with such flow improver in these oils is not stable but due to CFPP of the non-additized oil over several days to weeks (CFPP reversion). The cause is unknown. It is believed that it is to be sought in an incomplete redissolution of the polymer components with low comonomer content from the once cloudy oil. A particular problem is the prevention of CFPP reversion in oils with low sulfur content, since these have particularly high levels of long-chain n-paraffins with chain lengths greater than C 18 due to the desulfurization.

Es bestand daher die Aufgabe, Additive für die genannten Mineralöle und Mineralöldestillate zu finden, die zu einer sehr guten CFPP-Emiedrigung führen, und bei denen keine CFPP-Reversion auftritt und die die Filtrierbarkeit der additivierten Öle oberhalb des Cloud Points nicht beeinträchtigen.It was therefore the task of additives for said mineral oils and To find mineral oil distillates, which lead to a very good CFPP-lowering, and where no CFPP reversion occurs and the filterability of the additized Do not interfere with oils above the cloud point.

Überraschenderweise wurde gefunden, daß Mischungen, die ein Copolymer aus Ethylen und einem Neocarbonsäurevinylester und ein Copolymer aus Ethylen und Vinylestem oder Acrylestem enthalten, eine Lösung dieser Aufgabe darstellen.Surprisingly, it has been found that mixtures comprising a copolymer Ethylene and a vinyl neocarboxylate and a copolymer of ethylene and Vinyl esters or acrylic esters contain a solution to this problem.

Gegenstand der Erfindung ist ein Verfahren zur Verbesserung der Kaltfließeigenschaften von Brennstoffölen mit einem Schwefelgehalt von weniger als 500 ppm und einem Gehalt an n-Paraffinen der Kettenlänge C18 und länger von mindestens 8 Gew.-%, gekennzeichnet durch die Zugabe eines Additivs, enthaltend eine Mischung aus

  • A) 15 bis 50 Gew.-% eines Copolymers aus niederen Olefinen und Vinylestern, bestehend aus
  • a) bis zu 96 mol-% bivalente Struktureinheiten der Formel 1 -CH2-CR1R2-    worin R1 und R2 unabhängig voneinander Wasserstoff oder Methyl bedeuten, und
  • b) 4 bis 10 mol-% bivalente Struktureinheiten der Formel 2
    Figure 00050001
    • worin R3 gesättigtes, verzweigtes C6-C16-Alkyl bedeutet, das ein tertiäres Kohlenstoffatom aufweist, mit der Maßgabe, dass das unter A) genannte Copolymer bis zu 5 Gew.-% weiterer Comonomere ausgewählt aus Vinylestem, Vinylethern, Acrylsäurealkylestern, Methacrylsäurealkylestem mit C1- bis C20-Alkylresten, Isobutylen und höheren Olefinen mit mindestens 5 Kohlenstoffatomen enthalten kann,
    und
  • B) 85 bis 50 Gew-% mindestens eines weiteren Copolymers oder Terpolymers aus Ethylen und Vinylestem oder Acrylsäureestem, das für sich allein ein Kaltfließverbesserer ist.
    • The invention relates to a method for improving the cold flow properties of fuel oils having a sulfur content of less than 500 ppm and a content of n-paraffins of chain length C 18 and longer of at least 8 wt .-%, characterized by the addition of an additive containing a Mix off
  • A) 15 to 50 wt .-% of a copolymer of lower olefins and vinyl esters, consisting of
  • a) up to 96 mol% of bivalent structural units of the formula 1 -CH 2 -CR 1 R 2 - wherein R 1 and R 2 are independently hydrogen or methyl, and
  • b) 4 to 10 mol% of bivalent structural units of the formula 2
    Figure 00050001
    •  wherein R 3 is saturated, branched C 6 -C 16 -alkyl having a tertiary carbon atom, with the proviso that the copolymer mentioned under A) up to 5 wt .-% of other comonomers selected from vinyl esters, vinyl ethers, acrylic acid alkyl esters, Methacrylsäurealkylestem with C 1 - to C 20 -alkyl radicals, isobutylene and higher olefins having at least 5 carbon atoms,
    and
  • B) 85 to 50% by weight of at least one further copolymer or terpolymer of ethylene and vinyl esters or acrylic acid esters, which alone is a cold flow improver.

    • Die Angaben in Gew.-% beziehen sich auf das Gesamtgewicht der Mischung aus A) und B).The data in% by weight relate to the total weight of the mixture of A) and B).

    Ein weiterer Gegenstand der Erfindung ist ein Brennstofföl, das die oben definierte Zusammensetzung aus A und B enthält.Another object of the invention is a fuel oil, which defined above Composition of A and B contains.

    Ein weiterer Gegenstand der Erfindung ist ein Additiv zur Verbesserung der Kaltfließeigenschaften von Mineralölen und Mineralöldestillaten, enthaltend eine Mischung aus

  • A) 15 bis 50 Gew.-% eines Copolymers aus niederen Olefinen und Vinylestem, bestehend aus
  • a) bis zu 96 mol-% bivalente Struktureinheiten der Formel 1 -CH2-CR1R2- worin R1 und R2 unabhängig voneinander Wasserstoff oder Methyl bedeuten, und
  • b) 4 bis 10 mol-% bivalente Struktureinheiten der Formel 2
    Figure 00070001
    • worin R3 gesättigtes, verzweigtes C6-C16-Alkyl bedeutet, das ein tertiäres Kohlenstoffatom aufweist
    und
  • B) 85 bis 50 Gew-% mindestens eines weiteren Copolymers oder Terpolymers aus Ethylen und Vinylestem oder Acrylsäureestem, das für sich allein ein Kaltfließverbesserer ist.
    • Another object of the invention is an additive for improving the cold flow properties of mineral oils and mineral oil distillates containing a mixture of
  • A) 15 to 50 wt .-% of a copolymer of lower olefins and vinyl esters, consisting of
  • a) up to 96 mol% of bivalent structural units of the formula 1 -CH 2 -CR 1 R 2 - wherein R 1 and R 2 are independently hydrogen or methyl, and
  • b) 4 to 10 mol% of bivalent structural units of the formula 2
    Figure 00070001
    •  wherein R 3 is saturated, branched C 6 -C 16 -alkyl having a tertiary carbon atom
    and
  • B) 85 to 50% by weight of at least one further copolymer or terpolymer of ethylene and vinyl esters or acrylic acid esters, which alone is a cold flow improver.

    • Vorzugsweise besteht die Mischung der Copolymeren aus 20 bis 40 Gew.-% der Komponenten A) und 60 bis 80 Gew.-% der Komponente B).Preferably, the mixture of the copolymers from 20 to 40 wt .-% of Components A) and 60 to 80 wt .-% of component B).

    Bevorzugte Vinylester für die Komponente B) sind Vinylacetat, Vinylpropionat, Vinylhexanoat, Vinyllaurat und Vinylester von Neocarbonsäuren, hier insbesondere von Neononan-, Neodecan- und Neoundecansäure. Bevorzugte Acrylsäureester sind Acrylsäurealkylester mit Alkoholresten von 1 bis 20, insbesondere von 2 bis 12 und speziell von 4 bis 8 Kohlenstoffatomen, wie beispielsweise Methylacrylat, Ethylacrylat und 2-Ethylhexylacrylat.Preferred vinyl esters for component B) are vinyl acetate, vinyl propionate, Vinylhexanoate, vinyl laurate and vinyl esters of neocarboxylic acids, here in particular of neononan, neodecane and neoundecanoic acid. Preferred acrylic acid esters are acrylic acid alkyl esters with alcohol radicals from 1 to 20, in particular from 2 to 12 and especially from 4 to 8 carbon atoms, such as methyl acrylate, Ethyl acrylate and 2-ethylhexyl acrylate.

    R1 und R2 bedeuten vorzugsweise Wasserstoff. R3 bedeutet vorzugsweise einen Neoalkylrest mit 7 bis 11 Kohlenstoffatomen, insbesondere einen Neoalkylrest mit 8, 9 oder 10 Kohlenstoffatomen. Die Neoalkylsäuren, von denen sich die oben genannten Neoalkylreste ableiten lassen, werden durch die Formel 4 beschrieben:

    Figure 00070002
    R 1 and R 2 are preferably hydrogen. R 3 preferably denotes a neoalkyl radical having 7 to 11 carbon atoms, in particular a neoalkyl radical having 8, 9 or 10 carbon atoms. The neoalkyl acids from which the abovementioned neoalkyl radicals can be derived are described by the formula 4:
    Figure 00070002

    R' und R'' sind lineare Alkylreste mit zusammen vorzugsweise 5 bis 9, insbesondere 6 bis 8 und speziell 7 oder 8 Kohlenstoffatomen. Der zur Copolymerisation verwendete Vinylester hat demzufolge die Formel 5:

    Figure 00080001
    R 'and R "are linear alkyl radicals together preferably having 5 to 9, in particular 6 to 8 and especially 7 or 8 carbon atoms. The vinyl ester used for the copolymerization therefore has the formula 5:
    Figure 00080001

    Vorzugsweise handelt es sich um die Vinylester der Neononan-, Neodecan- und Neoundecansäure. Copolymer A) enthält vorzugsweise 5 bis 10 mol-%, insbesondere 7 bis 10 mol-% der Struktureinheiten der Formel 2.Preferably, the vinyl esters of neononane, neodecane and Neoundecansäure. Copolymer A) preferably contains 5 to 10 mol%, in particular 7 to 10 mol% of the structural units of the formula 2.

    Copolymer B) ist vorzugsweise ein Ethylen-Copolymerisat mit einem Comonomergehalt von 10 bis 20 mol-%, bevorzugt 13 bis 18 mol-%. Geeignete Comonomere sind Vinylester aliphatischer Carbonsäuren mit 2 bis 15 C-Atomen, so daß B) insbesondere ein Ethylen-Vinylacetat-Copolymer, Ethylen-Vinylpropionat-Copolymer, Ethylen-Vinylacetat-Neononansäurevinylester- Copolymer oder ein Ethylen-Vinylacetat-Neodecansäurevinylester-Terpolymer ist. Weitere geeignete Comonomere sind Olefine wie Propen, Hexen, Buten, Isobuten, Diisobutylen, 4-Methylpenten-1 und Norbornen. Besonders bevorzugt sind Ethylen-Vinylacetat-Diisobutylen und Ethylen-Vinylacetat-4-Methylpenten-1-Terpolymerisate.Copolymer B) is preferably an ethylene copolymer with a Comonomer content of 10 to 20 mol%, preferably 13 to 18 mol%. suitable Comonomers are vinyl esters of aliphatic carboxylic acids having 2 to 15 carbon atoms, see above in that B) in particular an ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer, Ethylene-vinyl acetate-neononanoic acid vinyl ester copolymer or a Ethylene-vinyl acetate-neodecanoic acid vinyl ester terpolymer. Other suitable Comonomers are olefins such as propene, hexene, butene, isobutene, diisobutylene, 4-methylpentene-1 and norbornene. Particularly preferred are ethylene-vinyl acetate-diisobutylene and ethylene-vinyl acetate-4-methylpentene-1 terpolymers.

    Die erfindungsgemäß verwendeten Copolymere sind durch die üblichen Copolymerisationsverfahren wie beispielsweise Suspensionspolymerisation, Lösungspolymerisation, Gasphasenpolymerisation oder Hochdruckmassepolymerisation herstellbar. Bevorzugt ist dabei die Hochdruckmassepolymerisation bei Drucken von vorzugsweise 50 bis 400, insbesondere 100 bis 300 MPa und Temperaturen von vorzugsweise 50 bis 350 °C, insbesondere 100 bis 250°C. Die Reaktion der Monomeren wird durch Radikale bildende Initiatoren (Radikalkettenstarter) eingeleitet. Zu dieser Substanzklasse gehören z.B. Sauerstoff, Hydroperoxide, Peroxide und Azoverbindungen wie Cumolhydroperoxid, t-Butylhydroperoxid, Dilauroylperoxid, Dibenzoylperoxid, Bis(2-ethylhexyl)peroxid-carbonat, t-Butylperpivalat, t-Butylpermaleinat, t-Butylperbenzoat, Dicumylperoxid, t-Butylcumylperoxid, Di-(t-butyl)peroxid, 2,2'-Azo-bis(2-methylpropionitril), 2,2'-Azo-bis(2-methylbutyronitril). Die Initiatoren werden einzeln oder als Gemisch aus zwei oder mehr Substanzen in Mengen von 0,01 bis 20 Gew.-%, vorzugsweise 0,05 bis 10 Gew.-%, bezogen auf das Monomerengemisch, eingesetzt.The copolymers used in the invention are by the usual Copolymerization processes such as suspension polymerization, Solution polymerization, gas phase polymerization or High pressure mass polymerization can be produced. Preferred is the High-pressure bulk polymerization at pressures of preferably 50 to 400, in particular 100 to 300 MPa and temperatures of preferably 50 to 350 ° C, in particular 100 to 250 ° C. The reaction of the monomers is by radicals forming initiators (radical chain starter) initiated. To this substance class include e.g. Oxygen, hydroperoxides, peroxides and azo compounds such as Cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide carbonate, t-butyl perpivalate, t-butyl per-maleate, t-butyl perbenzoate, Dicumyl peroxide, t-butyl cumyl peroxide, di (t-butyl) peroxide, 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-methylbutyronitrile). The initiators are individually or as a mixture of two or more substances in amounts of from 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Monomer mixture used.

    Vorzugsweise haben die Komponenten A und B Schmelzviskositäten bei 140°C von 20 bis 10.000 mPas, insbesondere von 30 bis 5000 mPas, speziell von 50 bis 2000 mPas. Vorzugsweise hat die Komponente A eine um mindestens 100 mPas höhere Schmelzviskosität als Komponente B. Die gewünschte Schmelzviskosität der Mischungen wird durch Auswahl der Einzelkomponenten und Variation des Mischungsverhältnisses der Copolymeren eingestellt.Preferably, components A and B have melt viscosities at 140 ° C of 20 to 10,000 mPas, in particular from 30 to 5000 mPas, especially from 50 to 2000 mPas. Preferably, component A has a higher by at least 100 mPas Melt viscosity as component B. The desired melt viscosity of Blends are made by selecting the individual components and varying the Blend ratio of the copolymers set.

    Die unter A) und B) genannten Copolymere können bis zu 5 Gew.-% weiterer Comonomere enthalten. Solche Comonomere können beispielsweise Vinylester, Vinylether, Acrylsäurealkylester, Methacrylsäurealkylester mit C1- bis C20-Alkylresten, Isobutylen und höhere Olefine mit mindestens 5 Kohlenstoffatomen sein. Bevorzugt als höhere Olefine sind Hexen, Isobutylen, 4-Methylpenten, Octen und/oder Diisobutylen.The copolymers mentioned under A) and B) may contain up to 5% by weight of further comonomers. Such comonomers may be, for example, vinyl esters, vinyl ethers, alkyl acrylates, alkyl methacrylates having C 1 to C 20 alkyl radicals, isobutylene and higher olefins having at least 5 carbon atoms. Preferred higher olefins are hexene, isobutylene, 4-methylpentene, octene and / or diisobutylene.

    Die Hochdruckmassepolymerisation wird in bekannten Hochdruckreaktoren, z.B. Autoklaven oder Rohrreaktoren, diskontinuierlich oder kontinuierlich durchgeführt, besonders bewährt haben sich Rohrreaktoren. Lösungsmittel wie aliphatische und/oder aromatische Kohlenwasserstoffe oder Kohlenwasserstoffgemische, Benzol oder Toluol, können im Reaktionsgemisch enthalten sein. Bevorzugt ist die lösungsmittelfreie Arbeitsweise. In einer bevorzugten Ausführungsform der Polymerisation wird das Gemisch aus den Monomeren, dem Initiator und, sofern eingesetzt, dem Moderator, einem Rohrreaktor über den Reaktoreingang sowie über einen oder mehrere Seitenäste zugeführt. Hierbei können die Monomerenströme unterschiedlich zusammengesetzt sein (EP-A-0 271 738).High pressure bulk polymerization is used in known high pressure reactors, e.g. Autoclaves or tube reactors, discontinuous or continuous, Tube reactors have proven particularly useful. Solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, Benzene or toluene may be included in the reaction mixture. Preferably, the solvent-free operation. In a preferred embodiment of Polymerization is the mixture of the monomers, the initiator and, if used, the moderator, a tubular reactor via the reactor inlet and above supplied to one or more side branches. In this case, the monomer streams be composed differently (EP-A-0 271 738).

    Die Mischungen der Komponenten A und B werden Mineralölen oder Mineralöldestillaten in Form von Lösungen oder Dispersionen zugesetzt. Diese Lösungen oder Dispersionen enthalten vorzugsweise 1 bis 90, insbesondere 5 bis 80 Gew.-% der Mischungen. Geeignete Lösungs- oder Dispersionsmittel sind aliphatische und/oder aromatische Kohlenwasserstoffe oder Kohlenwasserstoffgemische, z.B. Benzinfraktionen, Kerosin, Decan, Pentadecan, Toluol, Xylol, Ethylbenzol oder kommerzielle Lösungsmittelgemische wie Solvent Naphtha, ®Shellsoll AB, ®Solvesso 150, ®Solvesso 200, ®Exxsol-, ®ISOPAR- und ®Shellsol D-Typen. Die angegebenen Lösemittelgemische enthalten unterschiedliche Mengen an aliphatischen und/oder aromatischen Kohlenwasserstoffen. Die Aliphaten können geradkettig (n-Paraffine) oder verzweigt sein (iso-Paraffine). Aromatische Kohlenwasserstoffe können mono-, di- oder polyzyklisch sein und gegebenfalls einen oder mehrere Substituenten tragen. Durch die Mischungen der Komponenten A und B in ihren rheologischen Eigenschaften verbesserte Mineralöle oder Mineralöldestillate enthalten 0,001 bis 2, vorzugsweise 0,005 bis 0,5 Gew.-% der Mischungen, bezogen auf das Destillat.The mixtures of components A and B are mineral oils or Mineral oil distillates added in the form of solutions or dispersions. These Solutions or dispersions preferably contain 1 to 90, in particular 5 to 80% by weight of the mixtures. Suitable solvents or dispersants are aliphatic and / or aromatic hydrocarbons or Hydrocarbon mixtures, e.g. Gasoline 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 types. The specified solvent mixtures contain different amounts of aliphatic and / or aromatic Hydrocarbons. The aliphatics can be straight chain (n-paraffins) or branched his (iso-paraffins). Aromatic hydrocarbons can mono-, di- or be polycyclic and optionally carry one or more substituents. By the mixtures of components A and B in their rheological properties improved mineral oils or mineral oil distillates contain from 0.001 to 2, preferably 0.005 to 0.5 wt .-% of the mixtures, based on the distillate.

    Zur Herstellung von Additivpaketen für spezielle Problemlösungen können die Mischungen auch zusammen mit einem oder mehreren öllöslichen Co-Additiven eingesetzt werden, die bereits für sich allein die Kaltfließeigenschaften von Rohölen, Schmierölen oder Brennölen verbessern. Beispiele solcher Co-Additive sind polare Verbindungen, die eine Paraffindispergierung bewirken (Paraffindispergatoren), sowie Kammpolymere.For the production of additive packages for special problem solutions, the Mixtures also together with one or more oil-soluble co-additives already used by itself the cold flow properties of crude oils, Improve lubricating oils or fuel oils. Examples of such co-additives are polar Compounds which cause a paraffin dispersion (paraffin dispersants), as well as comb polymers.

    Paraffindispergatoren reduzieren die Größe der Paraffinkristalle und bewirken, daß die Paraffinpartikel sich nicht absetzen, sondern kolloidal mit deutlich reduziertem Sedimentationsbestreben, dispergiert bleiben. Als Paraffindispergatoren haben sich öllösliche polare Verbindungen mit ionischen oder polaren Gruppen, z.B. Aminsalze und/oder Amide bewährt, die durch Reaktion aliphatischer oder aromatischer Amine, vorzugsweise langkettiger aliphatischer Amine, mit aliphatischen oder aromatischen Mono-, Di-, Tri- oder Tetracarbonsäuren oder deren Anhydriden erhalten werden (US-4 211 534). Andere Paraffindispergatoren sind Copolymere des Maleinsäureanhydrids und α,β-ungesättigten Verbindungen, die gegebenenfalls mit primären Monoalkylaminen und/oder aliphatischen Alkoholen umgesetzt werden können (EP-A-0 154 177), die Umsetzungsprodukte von Alkenylspirobislactonen mit Aminen (EP-A-0 413 279) und nach EP-A-0 606 055 Umsetzungsprodukte von Terpolymerisaten auf Basis α,β-ungesättigter Dicarbonsäureanhydride, α,β-ungesättigter Verbindungen und Polyoxyalkenylether niederer ungesättigter Alkohole. Auch Alkylphenol-Formaldehydharze sind als Paraffindispergatoren geeignet.Paraffin dispersants reduce the size of the paraffin crystals and cause The paraffin particles do not settle, but colloidly with significantly reduced Sedimentation tendency, remain dispersed. As paraffin dispersants have become oil-soluble polar compounds having ionic or polar groups, e.g. amine salts and / or amides 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 are obtained (U.S. 4,211,534). Other paraffin dispersants are copolymers of the Maleic anhydride and α, β-unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols are reacted can (EP-A-0 154 177), the reaction products of Alkenylspirobislactonen with Amines (EP-A-0 413 279) and according to EP-A-0 606 055 reaction products of Terpolymers based on α, β-unsaturated dicarboxylic acid anhydrides, α, β-unsaturated compounds and polyoxyalkenyl ether of lower unsaturated Alcohols. Alkylphenol-formaldehyde resins are also known as paraffin dispersants suitable.

    Unter Kammpolymeren versteht man Polymere, bei denen Kohlenwasserstoffreste mit mindestens 8, insbesondere mindestens 10 Kohlenstoffatomen an einem Polymerrückgrat gebunden sind. Vorzugsweise handelt es sich um Homopolymere, deren Alkylseitenketten mindestens 8 und insbesondere mindestens 10 Kohlenstoffatome enthalten. Bei Copolymeren weisen mindestens 20 %, bevorzugt mindestens 30 % der Monomeren Seitenketten auf (vgl. Comb-like Polymers - Structure and Properties; N.A. Platé and V.P. Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff). Beispiele für geeignete Kammpolymere sind z.B. Fumarat/Vinylacetat-Copolymere (vgl. EP-A- 0 153 176), Copolymere aus einem C6-C24-α-Olefin und einem N-C6- bis C22-Alkylmaleinsäureimid (vgl. EP-A-0 320 766), ferner veresterte Olefin/Maleinsäureanhydrid-Copolymere, Polymere und Copolymere von α-Olefinen und veresterte Copolymere von Styrol und Maleinsäureanhydrid.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). Examples of suitable comb polymers are, for example, fumarate / vinyl acetate copolymers (cf., EP-A-0 153 176), copolymers of a C 6 -C 24 -α-olefin and an NC 6 - to C 22 -alkylmaleimide (cf. A-0 320 766), further esterified olefin / maleic anhydride copolymers, polymers and copolymers of α-olefins and esterified copolymers of styrene and maleic anhydride.

    Beispielsweise können Kammpolymere durch die Formel

    Figure 00110001
    beschrieben werden. Darin bedeuten

    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.
    For example, comb polymers can be represented by the formula
    Figure 00110001
    to be discribed. Mean in it
    A
    R ', COOR', OCOR ', R''-COOR', OR ';
    D
    H, CH 3, A or R '';
    e
    H, A;
    G
    H, R ", R" -COOR ', an aryl radical or a heterocyclic radical;
    M
    H, COOR ", OCOR", OR ", COOH;
    N
    H, R ", COOR", OCOR, an aryl radical;
    R '
    a hydrocarbon chain of 8 to 50 carbon atoms;
    R ''
    a hydrocarbon chain of 1 to 10 carbon atoms;
    m
    a number between 0.4 and 1.0; and
    n
    a number between 0 and 0.6.

    Das Mischungsverhältnis (in Gewichtsteilen) der erfindungsgemäßen Mischungen mit Paraffindispergatoren und/oder Kammpolymeren beträgt jeweils 1:10 bis 20:1, vorzugsweise 1:1 bis 10:1. The mixing ratio (in parts by weight) of the mixtures according to the invention with paraffin dispersants and / or comb polymers is in each case from 1:10 to 20: 1, preferably 1: 1 to 10: 1.

    Als Brennstoffkomponente sind Mitteldestillate besonders gut geeignet. Als Mitteldestillate bezeichnet man insbesondere solche Mineralöle, die durch Destillation von Rohöl gewonnen werden und im Bereich von 120 bis 400°C sieden, wie beispielsweise Kerosin, Jet-Fuel, Diesel und Heizöl. Die erfindungsgemäßen Brennstoffe enthalten vorzugsweise weniger als 350 ppm und speziell weniger als 200 ppm Schwefel. Ihr mit GC bestimmter Gehalt an n-Paraffinen, die Kettenlängen von 18 Kohlenstoffatomen oder mehr aufweisen, liegt bei mindestens 8 Flächen-%, bevorzugt bei mehr als 10 Flächen-%. Im Vergleich zum nächstliegenden Stand der Technik, insbesondere zu EP-A-0 796 306, besteht der Vorteil des erfindungsgemäßen Verfahrens in einer verbesserten Löslichkeit der Additive, so daß die Filtrierbarkeit der mit ihnen additivierten Öle auch bei niedrigen Einmischungstemperaturen von Öl und/oder Additiv erhalten bleibt. Außerdem zeigen die erfindungsgemäßen Mischungen ausgeprägte synergistische Effekte gegenüber den Einzelkomponenten bei der CFPP-Absenkung.As a fuel component middle distillates are particularly well suited. When Middle distillates are referred to in particular those mineral oils by Crude oil distillation and boiling in the range of 120 to 400 ° C, such as kerosene, jet fuel, diesel and heating oil. The invention Fuels preferably contain less than 350 ppm and especially less than 200 ppm sulfur. Their content of n-paraffins, the chain lengths, determined with GC of 18 carbon atoms or more, is at least 8 area%, preferably at more than 10 area%. Compared to the nearest state of the Technology, in particular to EP-A-0 796 306, has the advantage of inventive method in an improved solubility of the additives, so that the filterability of the oils additivated with them even at low Blending temperatures of oil and / or additive is maintained. Furthermore the mixtures of the invention show pronounced synergistic effects compared to the individual components in CFPP subsidence.

    Die erfindungsgemäßen Mischungen können allein oder auch zusammen mit anderen Zusatzstoffen verwendet werden, beispielsweise mit Entwachsungshilfsmitteln, Korrosionsinhibitoren, Antioxidantien, Lubricity-Additiven, Dehazem, Leitfähigkeitsverbesserem, Cetanzahlverbesserem oder Schlamminhibitoren. The mixtures according to the invention can be used alone or together with other additives are used, for example with Dewaxing aids, corrosion inhibitors, antioxidants, lubricity additives, Dehazem, conductivity improver, cetane improver or Sludge inhibitors.

    BeispieleExamples Tabelle 1: Charakterisierung der AdditiveTable 1: Characterization of the additives

    Es werden folgende Co-und Terpolymere des Ethylens, jeweils 50 %ig in Kerosin suspendiert, eingesetzt: Vinylacetat Neodecansäurevinylester V140 A1) -- 35 % (7,1 mol-%) 203 mPas A2) 19,0 % (8,3 mol-%) 15 % (2,9 mol-%) 743 mPas A3) 19,3% (8,5 mol-%) 15 % (2,9 mol-%) 292 mPas A4) 20,0 % (8,4 mol-%) 10 % (1,8 mol-%) 457 mPas A5) 23,0 % (9,8 mol-%) 9,5% (1,8 mol-%) 850 mPas B1) 32,0 % (13,3 mol-%) -- 125 mPs B2) 32,0 % (14,0 mol-%) 6 % (1,6 mol-%) 110 mPas B3) 31,7 % (14,9 mol-%) 11 % (2,2 mol-%) 240 mPas V140 = Schmelzviskosität bei 140°C gemäß EN 3219 The following copolymers and terpolymers of ethylene, each 50% suspended in kerosene, are used: vinyl acetate neodecanoate V 140 A1) - 35% (7.1 mol%) 203 mPas A2) 19.0% (8.3 mol%) 15% (2.9 mol%) 743 mPas A3) 19.3% (8.5 mol%) 15% (2.9 mol%) 292 mPas A4) 20.0% (8.4 mol%) 10% (1.8 mol%) 457 mPas A5) 23.0% (9.8 mol%) 9.5% (1.8 mol%) 850 mPas B1) 32.0% (13.3 mol%) - 125 mPs B2) 32.0% (14.0 mol%) 6% (1.6 mol%) 110 mPas B3) 31.7% (14.9 mol%) 11% (2.2 mol%) 240 mPas V 140 = melt viscosity at 140 ° C according to EN 3219

    Tabelle 2: Charakterisierung der TestöleTable 2: Characterization of the test oils

    Die Bestimmung der Siedekenndaten erfolgt gemäß ASTM D-86, die Bestimmung des CFPP-Werts gemäß EN 116 und die Bestimmung des Cloud Points gemäß ISO 3015. Die Bestimmung des Paraffingehalts erfolgt durch gaschromatographische Trennung des Öls (Detektion mittels FiD) und Berechnung des Integrals der n-Paraffine ≥ C18 im Verhältnis zum Gesamtintegral. Näherungsweise wird dieses Flächenintegral der n-Paraffine ≥ C18 im Verhältnis zum Gesamtintegral mit Gew.-% n-Paraffine ≥ C18 gleichgesetzt. Testöll 1 Testöl 2 Testöl 3 Testöl 4 Testöl 5 Testöl 6 Siedebeginn 180°C 169°C 183°C 183°C 184°C 182°C 20 % 267°C 255°C 226°C 232°C 258°C 243°C 90 % 350°C 350°C 330°C 358°C 329°C 351°C 95% 365°C 364°C 347°C 378°C 344°C 366°C Cloud Point -0,4°C -1°C -9°C +4°C -5°C -3°C CFPP -3°C -3°C -12°C -4°C -9°C -6°C (90-20)% 83°C 95°C 104°C 126°C 71°C 108°C n-Paraffine ≥ C18/Gew.-% 11,8 10,9 9,6 10,5 8,5 11,3 S-Gehalt/ppm 270 540 175 375 295 430 The determination of the boiling characteristics is carried out in accordance with ASTM D-86, the determination of the CFPP value according to EN 116 and the determination of the cloud point according to ISO 3015. The paraffin content is determined by gas chromatographic separation of the oil (detection by FiD) and calculation of the integral of the n paraffins ≥ C 18 in relation to the total integral. As an approximation, this area integral of n-paraffins ≥ C 18 is equated with wt% n-paraffins ≥ C 18 in relation to the total integral. Test oil 1 Test oil 2 Test oil 3 Test oil 4 Test oil 5 Test oil 6 Initial boiling point 180 ° C 169 ° C 183 ° C 183 ° C 184 ° C 182 ° C 20% 267 ° C 255 ° C 226 ° C 232 ° C 258 ° C 243 ° C 90% 350 ° C 350 ° C 330 ° C 358 ° C 329 ° C 351 ° C 95% 365 ° C 364 ° C 347 ° C 378 ° C 344 ° C 366 ° C Cloud point -0.4 ° C -1 ° C -9 ° C + 4 ° C -5 ° C -3 ° C CFPP -3 ° C -3 ° C -12 ° C -4 ° C -9 ° C -6 ° C (90-20)% 83 ° C 95 ° C 104 ° C 126 ° C 71 ° C 108 ° C n-paraffins ≥ C 18 / wt% 11.8 10.9 9.6 10.5 8.5 11.3 S content / ppm 270 540 175 375 295 430

    Bestimmung der CFPP-StabilitätDetermination of CFPP stability

    Der CFPP-Wert des mit der angegebenen Menge Fließverbesserer additivierten Öls wurde direkt nach der Additivierung gemessen und der Rest der Probe bei -3°C, also unterhalb des Cloud Points gelagert. In wöchentlichen Abständen wurden die Proben auf 12°C erwärmt, 50 ml für eine erneute CFPP-Messung entnommen und der Rest bei -3°C weiter gelagert. The CFPP value of the oil additized with the specified amount of flow improver was measured immediately after the additization and the remainder of the sample at -3 ° C, So stored below the cloud point. At weekly intervals, the Samples heated to 12 ° C, 50 ml taken for a new CFPP measurement and the remainder stored at -3 ° C on.

    Tabelle 3: CFPP-Stabilität in Testöl 1Table 3: CFPP stability in test oil 1

    Die Dosierrate in Testöl 1 betrug 800 ppm Additiv, 50 % in Kerosin CFPP (sofort) 1 Woche 2 Wochen 3 Wochen 4 Wochen A1 + B1 (1:5) -12 -12 -10 -10 -11 A1 + B2 (1:3) -13 -16 -12 -15 -14 A2 + B2 (1:3) -10 -12 -10 -13 -13 A3 + B2 (1:3) -9 -11 -12 -12 -12 A4 + B1 (1:4) -12 -13 -11 -12 -10 A5 + B3 (1:4) -12 -13 -13 -10 -11 B1 (Vergleich) -10 -4 -5 -3 -4 B2 (Vergleich) -11 -7 -5 -4 -5 B3 (Vergleich) -10 -9 -7 -7 -5 The dosage rate in test oil 1 was 800 ppm additive, 50% in kerosene CFPP (immediately) 1 week 2 weeks 3 weeks 4 weeks A1 + B1 (1: 5) -12 -12 -10 -10 -11 A1 + B2 (1: 3) -13 -16 -12 -15 -14 A2 + B2 (1: 3) -10 -12 -10 -13 -13 A3 + B2 (1: 3) -9 -11 -12 -12 -12 A4 + B1 (1: 4) -12 -13 -11 -12 -10 A5 + B3 (1: 4) -12 -13 -13 -10 -11 B1 (comparison) -10 -4 -5 -3 -4 B2 (comparison) -11 -7 -5 -4 -5 B3 (comparison) -10 -9 -7 -7 -5

    Tabelle 4: CFPP-Stabilität in Testöl 2Table 4: CFPP stability in test oil 2

    Die Dosierrate in Testöl 2 beträgt 800 ppm Additiv, 50 % in Kerosin CFPP (sofort) 1 Woche 2 Wochen 3 Wochen 4 Wochen A5 + B3 (1:4) -13 -14 -15 -11 -12 A1 + B2 (1:5) -11 -13 -13 -12 -12 B2 (Vergleich) -10 -9 -7 -8 -5 B3 (Vergleich) -10 -9 -6 -6 -5 The dosage rate in Test Oil 2 is 800 ppm additive, 50% in kerosene CFPP (immediately) 1 week 2 weeks 3 weeks 4 weeks A5 + B3 (1: 4) -13 -14 -15 -11 -12 A1 + B2 (1: 5) -11 -13 -13 -12 -12 B2 (comparison) -10 -9 -7 -8th -5 B3 (comparison) -10 -9 -6 -6 -5

    Tabelle 5a): CFPP-Stabilität in Testöl 6Table 5a): CFPP stability in test oil 6 CFPP-Werte sofort nach AdditivierungCFPP values immediately after additization

    Additivadditive CFPP (°C)CFPP (° C) 50 ppm50 ppm 100 ppm100 ppm 150 ppm150 ppm B1B1 -10-10 -15-15 -16-16 B2B2 - 9- 9 -14-14 -15-15 A4 + B1 (1:3)A4 + B1 (1: 3) -11-11 -16-16 -17-17 A4 + B2 (1:5)A4 + B2 (1: 5) -10-10 -14-14 -15-15

    Tabelle 5b): CFPP-Stabilität in Testöl 6Table 5b): CFPP stability in test oil 6 CFPP-Werte nach 4-tägiger Lagerung bei 2 °CCFPP values after 4 days storage at 2 ° C

    Additivadditive CFPP (°C)CFPP (° C) 50 ppm50 ppm 100 pm100 pm 150 ppm150 ppm B1B1 -9-9 -10-10 -9-9 B2B2 -8-8th -10-10 -9-9 A4 + B1 (1:3)A4 + B1 (1: 3) -11-11 -15-15 -17-17 A4 + B2 (1:5)A4 + B2 (1: 5) -17-17 -20-20 -23-23 CFPP-Synergismus in Testöl 3CFPP synergism in test oil 3 50 ppm50 ppm 100 ppm100 ppm 200 ppm200 ppm A1 + B2 (1:1)A1 + B2 (1: 1) -19-19 -22-22 -27-27 A1 + B1 (1:1)A1 + B1 (1: 1) -20-20 -21-21 -24-24 A1 (Vergleich)A1 (comparison) -16-16 -18-18 -18-18 B1 (Vergleich)B1 (comparison) -17-17 -20-20 -23-23 B2 (Vergleich)B2 (comparison) -11-11 -15-15 -22-22 CFPP-Synergismus in Testöl 4CFPP synergism in test oil 4 100 ppm100 ppm 200 ppm200 ppm 300 ppm300 ppm A1 +B2(1:1)A1 + B2 (1: 1) -11-11 -14-14 -15-15 A1+ B1(1:1)A1 + B1 (1: 1) -11-11 -14-14 -15-15 A1 (Vergleich)A1 (comparison) -6-6 -8-8th -10-10 B1 (Vergleich)B1 (comparison) 11 -8-8th -12-12 B2 (Vergleich)B2 (comparison) -3-3 -2-2 -5-5

    Löslichkeit der MischungenSolubility of the mixtures

    Das Löslichkeitsverhalten der Terpolymerisate wird im British-Rail Test wie folgt bestimmt: 400 ppm einer auf 22°C temperierten Dispersion des Polymerisats in Kerosin werden in 200 ml des auf 22°C temperierten Testöls 5 dosiert und 30 Sekunden kräftig geschüttelt. Nach 24 Stunden Lagerung bei +3°C wird 15 Sekunden geschüttelt und anschließend bei 3°C in drei Portionen von je 50 ml über einen 1,6 µm-Glasfibermicrofilter (Ø 25 mm; Whatman GFA, Best.-Nr. 1820025) filtriert. Aus den drei Filtrationszeiten T1, T2 und T3, deren Summe 20 Minuten nicht übersteigen darf, wird der ADT-Wert wie folgt berechnet: ADT = (T3-T1)T2 · 50 The solubility behavior of the terpolymers is determined in the British Rail test as follows: 400 ppm of a 22 ° C tempered dispersion of the polymer in kerosene are metered into 200 ml of tempered to 22 ° C test oil 5 and shaken vigorously for 30 seconds. After storage for 24 hours at + 3 ° C., it is shaken for 15 seconds and then filtered at 3 ° C. in three 50 ml portions over a 1.6 μm glass fiber microfilter (Ø 25 mm; Whatman GFA, Order No. 1820025) , From the three filtration times T 1 , T 2 and T 3 , the sum of which must not exceed 20 minutes, the ADT value is calculated as follows: ADT = (T3-T1) T2 · 50

    Ein ADT-Wert <15 wird als Anhaltspunkt dafür angesehen, daß das Gasöl in "normal" kalter Witterung zufriedenstellend verwendbar ist. Produkte mit ADT-Werten > 25 werden als nicht filtrierbar bezeichnet. Löslichkeit der Additive ADT Blindwert (ohne Additiv) 3,0 A5 + B3 (1:4) 9,4 A1 + B2 (1:5) 4,8 A1 + B1 (1:1) 13,3 A2 + B2 (1:3) 5,2 B2 (Vergleich) 5,4 B2 + 4 % EVA-Copolymer mit 13,5 Gew.-% Vinylacetat (gemäß WO 97/17905) 60 B2 + 10 % EVA-Copolymer mit 13,5 Gew.-% Vinylacetat (gemäß WO 97/17905) nicht filtrierbar (115 ml in 20 Minuten) An ADT value <15 is considered as an indication that the gas oil is satisfactorily usable in "normal" cold weather. Products with ADT values> 25 are referred to as non-filterable. Solubility of the additives ADT Blank value (without additive) 3.0 A5 + B3 (1: 4) 9.4 A1 + B2 (1: 5) 4.8 A1 + B1 (1: 1) 13.3 A2 + B2 (1: 3) 5.2 B2 (comparison) 5.4 B2 + 4% EVA copolymer with 13.5% by weight of vinyl acetate (according to WO 97/17905) 60 B2 + 10% EVA copolymer with 13.5% by weight of vinyl acetate (according to WO 97/17905) not filterable (115 ml in 20 minutes)

    Liste der verwendeten HandelsbezeichnungenList of used trade names

    Solvent Naphtha ®Shellsol ABSolvent naphtha ®Shellsol AB
    aromatische Lösemittelgemische mit Siedebereich 180 bis 210°Caromatic solvent mixtures with boiling range 180 up to 210 ° C
    ®Solvesso 150 ®Solvesso 200® Solvesso 150 ® Solvesso 200
    aromatisches Lösemittelgemisch mit Siedebereich 230 bis 287°Caromatic solvent mixture with boiling range 230 to 287 ° C
    ®Exxsol®Exxsol
    Dearomatisierte Lösemittel in verschiedenen Siedebereichen, beispielsweise Exxsol D60: 187 bis 215°CDearomatized solvents in various Boiling ranges, for example Exxsol D60: 187 to 215 ° C
    ®ISOPAR (Exxon)®ISOPAR (Exxon)
    isoparaffinische Lösemittelgemische in verschiedenen Siedebereichen, beispielsweise ISOPAR L: 190 bis 210°Cisoparaffinic solvent mixtures in various Boiling ranges, for example ISOPAR L: 190-210 ° C
    ®Shellsol D®Shellsol D
    hauptsächlich aliphatische Lösemittelgemische in verschiedenen Siedebereichenmainly aliphatic solvent mixtures in different boiling ranges

    Claims (11)

    1. A process for improving the cold-flow properties of fuel oils having a sulfur content of less than 500 ppm and a content of n-paraffins having a chain length of C18 or longer of at least 8% by weight, comprising adding an additive comprising a mixture of
      A1) from 15 to 50% by weight of a copolymer of lower olefins and vinyl esters, consisting of
      a) up to 96 mol% of divalent structural units of the formula 1 -CH2-CR1R2- in which R1 and R2, independently of one another, are hydrogen or methyl, and
      b) from 4 to 10 mol% of divalent structural units of the formula 2
      Figure 00240001
      in which R3 is saturated, branched C6-C16-alkyl which contains a tertiary carbon atom, with the proviso that the copolymer mentioned under A) may contain up to 5% by weight of further comonomers selected from vinyl esters, vinyl ethers, alkyl acrylates, alkyl methacrylates having C1-C20-alkyl radicals, isobutylene and higher olefins having at least 5 carbon atoms,
      and
      B) from 85 to 50% by weight of at least one further copolymer or terpolymer of ethylene and vinyl esters or acrylic esters which is per se a cold-flow improver.
    2. The process as claimed in claim 1, wherein R1 and R2 are hydrogen.
    3. The process as claimed in claim 1 and/or 2, wherein R3 is a neoalkyl radical having 7 to 11 carbon atoms, in particular a neoalkyl radical having 8, 9 or 10 carbon atoms.
    4. The process as claimed in one or more of claims 1 to 3, wherein copolymer A1) preferably contains from 5 to 10 mol%, in particular from 7 to 10 mol%, of structural units of the formula 2.
    5. The process as claimed in one or more of claims 1 to 4, wherein the additive mixture used has a melt viscosity at 140°C of from 20 to 10,000 mPas, in particular from 30 to 5000 mPas, especially from 50 to 2000 mPas.
    6. The process as claimed in one or more of claims 1 to 5, wherein the copolymers mentioned under A) or B) contain up to 5% by weight of further comonomers.
    7. The process as claimed in claim 6, wherein the further comonomers used are vinyl esters, vinyl ethers, alkyl acrylates, alkyl methacrylates, isobutylene or higher olefins having at least 5 carbon atoms, preferably hexene, 4-methylpentene or octene or diisobutylene.
    8. The process as claimed in one or more of claims 1 to 7, wherein paraffin dispersants and/or comb polymers are used as further components of the additive composition.
    9. The process as claimed in one or more of claims 1 to 8, wherein the additive mixtures comprise from 20 to 40% by weight of component A) and from 60 to 80% by weight of component B).
    10. An additive for improving the cold-flow properties of mineral oils and mineral-oil distillates, comprising a mixture of
      A) from 15 to 50% by weight of a copolymer of lower olefins and vinyl esters, consisting of
      a) up to 96 mol% of divalent structural units of the formula 1 -CH2-CR1R2- in which R1 and R2, independently of one another, are hydrogen or methyl, and
      b) from 4 to 10 mol% of divalent structural units of the formula 2
      Figure 00260001
      in which R3 is saturated, branched C6-C16-alkyl which contains a tertiary carbon atom, with the proviso that the copolymer mentioned under A) may contain up to 5% by weight of further comonomers selected from vinyl esters, vinyl ethers, alkyl acrylates, alkyl methacrylates having C1-C20-alkyl radicals, isobutylene and higher olefins having at least 5 carbon atoms,
      and
      B) from 85 to 50% by weight of at least one further copolymer or terpolymer of ethylene and vinyl esters or acrylic esters which is per se a cold-flow improver and which has a comonomer content of 10 to 20 mol%.
    11. A fuel-oil composition comprising a fuel oil having a sulfur content of less than 500 ppm and a content of n-paraffins having a chain length of C18 or longer of at least 8% by weight, and an additive comprising a mixture of
      A) from 15 to 50% by weight of a copolymer of lower olefins and vinyl esters, consisting of
      a) up to 96 mol% of divalent structural units of the formula 1 -CH2-CR1R2- in which R1 and R2, independently of one another, are hydrogen or methyl, and
      b) from 4 to 10 mol% of divalent structural units of the formula 2
      Figure 00270001
      in which R3 is saturated, branched C6-C16-alkyl which contains a tertiary carbon atom, with the proviso that the copolymer mentioned under A) may contain up to 5% by weight of further comonomers selected from vinyl esters, vinyl ethers, alkyl acrylates, alkyl methacrylates having C1-C20-alkyl radicals, isobutylene and higher olefins having at least 5 carbon atoms,
      and
      B) from 85 to 50% by weight of at least one further copolymer or terpolymer of ethylene and vinyl esters or acrylic esters which is per se a cold-flow improver and which has a comonomer content of 10 to 20 mol%.
    EP98124678A 1998-01-24 1998-12-24 Process to improve the cold flow properties of fuel oils Expired - Lifetime EP0931824B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE19802690 1998-01-24
    DE19802690A DE19802690C2 (en) 1998-01-24 1998-01-24 Additive for improving the cold flow properties of fuel oils

    Publications (3)

    Publication Number Publication Date
    EP0931824A2 EP0931824A2 (en) 1999-07-28
    EP0931824A3 EP0931824A3 (en) 1999-09-15
    EP0931824B1 true EP0931824B1 (en) 2005-08-31

    Family

    ID=7855580

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP98124678A Expired - Lifetime EP0931824B1 (en) 1998-01-24 1998-12-24 Process to improve the cold flow properties of fuel oils

    Country Status (8)

    Country Link
    US (1) US6110238A (en)
    EP (1) EP0931824B1 (en)
    JP (1) JP4370011B2 (en)
    AT (1) ATE303426T1 (en)
    CA (1) CA2260169C (en)
    DE (2) DE19802690C2 (en)
    ES (1) ES2248874T3 (en)
    NO (1) NO990293L (en)

    Families Citing this family (11)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE19729057A1 (en) * 1997-07-08 1999-01-14 Clariant Gmbh Copolymers based on ethylene and unsaturated carboxylic acid esters and their use as mineral oil additives
    DE19754555A1 (en) * 1997-12-09 1999-06-24 Clariant Gmbh Process for the production of ethylene copolymers and their use as an additive to mineral oil and mineral oil distillates
    DE10012269C2 (en) 2000-03-14 2003-05-15 Clariant Gmbh Use of copolymer mixtures as an additive to improve the cold flow properties of middle distillates
    DE10012267B4 (en) * 2000-03-14 2005-12-15 Clariant Gmbh Copolymer blends and their use as an additive to improve the cold flow properties of middle distillates
    EP1391498B1 (en) * 2001-05-08 2016-09-07 Sanyo Chemical Industries, Ltd. Fluidity improver and fuel oil composition
    DE10208326B4 (en) * 2002-02-27 2008-06-19 Innospec Deutschland Gmbh Additives for liquid fuels
    DE10245737C5 (en) * 2002-10-01 2011-12-08 Clariant Produkte (Deutschland) Gmbh Process for the preparation of additive mixtures for mineral oils and mineral oil distillates
    DE10260714A1 (en) * 2002-12-23 2004-07-08 Clariant Gmbh Fuel oils with improved cold properties
    DE102006022720B4 (en) * 2006-05-16 2008-10-02 Clariant International Limited Cold flow improver for vegetable or animal fuel oils
    FR2947558B1 (en) 2009-07-03 2011-08-19 Total Raffinage Marketing TERPOLYMER AND ETHYLENE / VINYL ACETATE / UNSATURATED ESTERS AS ADDITIVES TO ENHANCE COLD LIQUID HYDROCARBONS LIKE MEDIUM DISTILLATES AND FUELS OR COMBUSTIBLES
    WO2019145664A1 (en) 2018-01-25 2019-08-01 Petróleo Brasileiro S.A. - Petrobras Auxiliary system and method for starting or restarting the flow of gelled fluid

    Family Cites Families (27)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US3048479A (en) * 1959-08-03 1962-08-07 Exxon Research Engineering Co Ethylene-vinyl ester pour depressant for middle distillates
    DE1914756C3 (en) * 1968-04-01 1985-05-15 Exxon Research and Engineering Co., Linden, N.J. Use of ethylene-vinyl acetate copolymers for petroleum distillates
    DE2037673C2 (en) * 1970-07-16 1985-07-04 Exxon Research and Engineering Co., Linden, N.J. Polymer mixtures as pour point improvers for hydrocarbons and their use
    US3961916A (en) * 1972-02-08 1976-06-08 Exxon Research And Engineering Company Middle distillate compositions with improved filterability and process therefor
    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
    GB8300016D0 (en) * 1983-01-04 1983-02-09 Exxon Research Engineering Co Middle distillate compositions
    DE3405843A1 (en) * 1984-02-17 1985-08-29 Bayer Ag, 5090 Leverkusen COPOLYMERS BASED ON MALEINIC ACID ANHYDRIDE AND (ALPHA), (BETA) -UNAUSAUTED COMPOUNDS, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS PARAFFIN INHIBITORS
    EP0153177B1 (en) * 1984-02-21 1991-11-06 Exxon Research And Engineering Company Middle distillate compositions with improved low temperature properties
    DE3625174A1 (en) * 1986-07-25 1988-01-28 Ruhrchemie Ag METHOD FOR IMPROVING THE FLOWABILITY OF MINERAL OILS AND MINERAL OIL DISTILLATES
    DE3640613A1 (en) * 1986-11-27 1988-06-09 Ruhrchemie Ag METHOD FOR THE PRODUCTION OF ETHYLENE MIXED POLYMERISATES AND THE USE THEREOF AS AN ADDITION TO MINERAL OIL AND MINERAL OIL FRACTIONS
    DE3742630A1 (en) * 1987-12-16 1989-06-29 Hoechst Ag POLYMER BLENDS FOR IMPROVING THE FLOWABILITY OF MINERAL OIL DISTILLATES IN THE COLD
    DE3926992A1 (en) * 1989-08-16 1991-02-21 Hoechst Ag USE OF TRANSPARENT PRODUCTS OF ALKENYL SPIROBISLACTONES AND AMINES AS PARAFFINDISPERGATORS
    DE4042206A1 (en) * 1990-12-29 1992-07-02 Hoechst Ag ETHYLENE TERPOLYMERISES, THEIR PREPARATION AND THEIR USE AS ADDITIVES FOR MINERALOLE DISTILLATES
    GB9213909D0 (en) * 1992-06-30 1992-08-12 Exxon Chemical Patents Inc Oil additives and compositions
    US5718734A (en) * 1992-06-30 1998-02-17 Exxon Chemical Patents Inc. Oil additives and compositions
    GB9213870D0 (en) * 1992-06-30 1992-08-12 Exxon Chemical Patents Inc Oil additives and compositions
    GB9213904D0 (en) * 1992-06-30 1992-08-12 Exxon Chemical Patents Inc Oil additives and compositions
    GB9213854D0 (en) * 1992-06-30 1992-08-12 Exxon Chemical Patents Inc Additives and fuel compositions
    DK0606055T3 (en) * 1993-01-06 1998-04-14 Clariant Gmbh Terpolymers on the basis of alpha, beta-unsaturated dicarboxylic acid anhydrides, alpha-beta-unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols
    GB9417670D0 (en) * 1994-09-02 1994-10-19 Exxon Chemical Patents Inc Oil additives, compositions and polymers for use therein
    GB9424565D0 (en) * 1994-12-06 1995-01-25 Exxon Chemical Patents Inc Fuel oil compositions
    KR100420430B1 (en) * 1994-12-13 2004-06-24 엑손 케미칼 패턴츠 인코포레이티드 Fuel oil composition
    GB9508644D0 (en) * 1995-04-28 1995-06-14 Exxon Chemical Patents Inc Fuel compositions
    DE19620118C1 (en) * 1996-05-18 1997-10-23 Hoechst Ag Terpolymers of ethylene, their preparation and their use as additives for mineral oil distillates
    DE19620119C1 (en) * 1996-05-18 1997-10-23 Hoechst Ag Terpolymers of ethylene, their production and their use as additives for mineral oil distillates
    DE19729055C2 (en) * 1997-07-08 2000-07-27 Clariant Gmbh Fuel oils based on middle distillates and copolymers of ethylene and unsaturated carboxylic acid esters
    DE19758887A1 (en) * 1997-07-08 2006-10-19 Clariant Gmbh Flow improver for mineral oils

    Also Published As

    Publication number Publication date
    NO990293L (en) 1999-07-26
    DE19802690C2 (en) 2003-02-20
    NO990293D0 (en) 1999-01-22
    CA2260169A1 (en) 1999-07-24
    JP4370011B2 (en) 2009-11-25
    JPH11256171A (en) 1999-09-21
    DE59813030D1 (en) 2005-10-06
    EP0931824A2 (en) 1999-07-28
    CA2260169C (en) 2008-09-16
    ATE303426T1 (en) 2005-09-15
    US6110238A (en) 2000-08-29
    ES2248874T3 (en) 2006-03-16
    DE19802690A1 (en) 1999-07-29
    EP0931824A3 (en) 1999-09-15

    Similar Documents

    Publication Publication Date Title
    EP0922716B1 (en) Process for the manufacture of terpolymers of ethylene and their use as additives to mineral oil and mineral oil distillates
    EP0807642B1 (en) Ethylene terpolymers, their preparation and their use as additives for mineral oil distillates
    EP0398101B1 (en) Reaction products of aminoalkylene-polycarboxylic acids with secondary amines and crude oil middle distillates containing them
    EP0931825B1 (en) Process and product to improve cold flow properties of fuel oils
    EP1146108B1 (en) Copolymer blends and their use as additive to improve the cold flow properties of middle distillates
    DE10260714A1 (en) Fuel oils with improved cold properties
    EP0931824B1 (en) Process to improve the cold flow properties of fuel oils
    EP1022293B1 (en) Copolymers and their use as additives for improving cold flow properties of middle distillates
    EP0900836A1 (en) Additive for mineral oils and mineral oil distillates flowability improvement
    DE19848621A1 (en) Mixture useful as a wax antisettling and lubricity additive for middle distillates comprises reaction products of a tertiary amine polycarboxylic acid and a secondary amine and of maleic anhydride and a primary alkylamine
    EP0890589B1 (en) Solutions or dispersions based on copolymers of olefins and unsaturated carboxylic esters and their use as additives for mineral oils
    EP1134275B1 (en) Copolymer blends and their use as additive to improve the cold flow properties of middle distillates
    EP0892012B1 (en) Flow improvers for mineral oils
    EP0890633B1 (en) Use of copolymers of ethylene and unsaturated carboxylic esters in middle distillates to improve cold flow properties

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    AK Designated contracting states

    Kind code of ref document: A2

    Designated state(s): AT BE CH DE DK ES FI FR GB GR IT LI NL PT SE

    AX Request for extension of the european patent

    Free format text: AL;LT;LV;MK;RO;SI

    PUAL Search report despatched

    Free format text: ORIGINAL CODE: 0009013

    AK Designated contracting states

    Kind code of ref document: A3

    Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    AX Request for extension of the european patent

    Free format text: AL;LT;LV;MK;RO;SI

    RIC1 Information provided on ipc code assigned before grant

    Free format text: 6C 10L 1/18 A, 6C 10L 1/14 B, 6C 08L 23/08 B

    17P Request for examination filed

    Effective date: 20000315

    AKX Designation fees paid

    Free format text: AT BE CH DE DK ES FI FR GB GR IT LI NL PT SE

    17Q First examination report despatched

    Effective date: 20020625

    GRAP Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOSNIGR1

    RBV Designated contracting states (corrected)

    Designated state(s): AT BE DE ES FR GB NL SE

    GRAS Grant fee paid

    Free format text: ORIGINAL CODE: EPIDOSNIGR3

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): AT BE DE ES FR GB NL SE

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: FG4D

    Free format text: NOT ENGLISH

    REF Corresponds to:

    Ref document number: 59813030

    Country of ref document: DE

    Date of ref document: 20051006

    Kind code of ref document: P

    REG Reference to a national code

    Ref country code: SE

    Ref legal event code: TRGR

    GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

    Effective date: 20051116

    RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

    Owner name: CLARIANT PRODUKTE (DEUTSCHLAND) GMBH

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FG2A

    Ref document number: 2248874

    Country of ref document: ES

    Kind code of ref document: T3

    NLT2 Nl: modifications (of names), taken from the european patent patent bulletin

    Owner name: CLARIANT PRODUKTE (DEUTSCHLAND) GMBH

    Effective date: 20060315

    ET Fr: translation filed
    PLBE No opposition filed within time limit

    Free format text: ORIGINAL CODE: 0009261

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

    26N No opposition filed

    Effective date: 20060601

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: CD

    BECN Be: change of holder's name

    Owner name: *CLARIANT PRODUKTE DEUTSCHLAND G.M.B.H.

    Effective date: 20050831

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: ES

    Payment date: 20081021

    Year of fee payment: 11

    Ref country code: AT

    Payment date: 20081020

    Year of fee payment: 11

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: AT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20091224

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FD2A

    Effective date: 20110404

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: ES

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20110322

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: ES

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20091225

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: PLFP

    Year of fee payment: 18

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: PLFP

    Year of fee payment: 19

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: SE

    Payment date: 20161021

    Year of fee payment: 19

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: PLFP

    Year of fee payment: 20

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: FR

    Payment date: 20171226

    Year of fee payment: 20

    Ref country code: NL

    Payment date: 20171221

    Year of fee payment: 20

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: GB

    Payment date: 20171228

    Year of fee payment: 20

    Ref country code: BE

    Payment date: 20171221

    Year of fee payment: 20

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: DE

    Payment date: 20180228

    Year of fee payment: 20

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: SE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20171225

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R071

    Ref document number: 59813030

    Country of ref document: DE

    REG Reference to a national code

    Ref country code: NL

    Ref legal event code: MK

    Effective date: 20181223

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: PE20

    Expiry date: 20181223

    REG Reference to a national code

    Ref country code: BE

    Ref legal event code: MK

    Effective date: 20181224

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

    Effective date: 20181223