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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
  • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
  • C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
  • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups

Definitions

• the present invention relates to mixtures of copolymers, on the one hand containing structural units of derivatives of dibasic carboxylic acids and unsaturated esters, on the other hand containing structural units from ethylene and Vinyl esters of tertiary carboxylic acids, and their use as an additive Fuel oils to improve their cold flow properties.
• Crude oils and middle distillates obtained by distilling crude oils such as gas oil, Diesel oil or heating oil contain different ones depending on the origin of the crude oils Amounts of n-paraffins which, when the temperature is lowered, are platelet-shaped Crystallize crystals and partially agglomerate with the inclusion of oil. This leads to a deterioration in the flow properties of these oils or distillates, which means, for example, during extraction, transport, storage and / or use of mineral oils and mineral oil distillates can occur. With mineral oils, this crystallization phenomenon can occur during transport Pipelines, especially in winter, to build up deposits on the pipe walls Individual cases, e.g. if a pipeline is at a standstill, even to completely block it to lead.
• the flow and cold behavior of mineral oils and mineral oil distillates is under other by specifying 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). These parameters are measured in ° C.
• Typical flow improvers for crude oils and middle distillates are copolymers of Ethylene with carboxylic acid esters of vinyl alcohol. So you bet after the DE-A-11 47 799 petroleum distillate fuels with a boiling point between about 120 and 400 ° C oil-soluble copolymers of ethylene and Vinyl acetate with a molecular weight between about 1,000 and 3,000. Copolymers which contain about 60 to 99% by weight of ethylene and about are preferred Contain 1 to 40 wt .-% vinyl acetate. They are particularly effective when passed through radical polymerization in an inert solvent at temperatures of about 70 to 130 ° C and pressures of 35 to 2,100 atm (DE-A-19 14 756).
• comb polymers which are derived from ethylenically unsaturated monomers with longer (for example C 8 -C 30 ), preferably linear, alkyl radicals. These are mainly used in higher-boiling, paraffin-rich mineral oils, optionally in combination with ethylene copolymers to improve the cold flow properties (e.g.
• GB-A-1 469 016 and EP-A-0 214 786 According to EP-A-0 153 176, comb polymers with C 12 -C 14 -alkyl radicals are also used in narrow-cut distillates with, for example (90-20%) distillation ranges from ⁇ 100 ° C. and boiling ends from approximately 340 to 370 ° C. According to US Pat. No. 2,542,542 and GB-A-1,468,588, copolymers of maleic anhydride (MA) and ⁇ -olefins esterified with long-chain fatty alcohols are used for the treatment of crude oils.
• MA maleic anhydride
• ⁇ -olefins esterified with long-chain fatty alcohols are used for the treatment of crude oils.
• GB-A-14 69 016 describes the use of mixtures of ethylene copolymers with comb polymers which are derived from C 6 -C 18 esters of ethylenically unsaturated dicarboxylic acids and olefins or vinyl esters to improve the cold flow properties of middle distillates.
• DE-A-35 14 878 describes esterification products from copolymers of Maleic anhydride with olefinically unsaturated monomers (olefins, especially ethylene and acrylic acid) and primary or secondary alcohols with 16-30 C atoms as pour point depressant for mineral oils containing paraffin.
• This Products have an acid number less than 20 mg KOH / g.
• EP-A-0 214 786 describes middle distillate additives from maleic anhydride and straight-chain 1-olefins, which are esterified polymer-analogously with fatty alcohols, for Improvement of the cold flow properties of middle distillates.
• EP-A-0 320 766 describes polymer mixtures made from a copolymer (A1) made of 10-60% by weight vinyl acetate or a copolymer (A2) made from 15-50% by weight vinyl acetate, 0.5-20% by weight C. 6 -C 24 -alpha-olefin and 15.5-70% by weight of ethylene and a copolymer (B) of 10-90% by weight of C 6 -C 24 -alpha-olefin and 10-90% by weight NC 6 -C 22 alkylmaleimide, the mixing ratio of the copolymers (A1) or (A2) to (B) being 100: 1 to 1: 1.
• These polymer mixtures are used as flow improvers in middle distillates.
• EP-A-0 890 589 describes the use of ethylene-neocarboxylic acid vinyl ester copolymers to improve the Cold flow properties of middle distillates with extremely low cloud point and narrow boiling range, which may also contain comb polymers.
• EP-A-0 931 824 describes mixtures of ethylene-neocarboxylic acid vinyl ester copolymers with further ethylene copolymers with a comonomer content of 10-20 mol%. These can also contain comb polymers.
• Another object of the invention is the use of the invention Additives to improve the cold flow properties of fuel oils.
• Another object of the invention are fuel oils that the contain additives according to the invention.
• R 1 and R 2 are preferably hydrogen. In particular, they are copolymers of ethylene, where up to 10 mol%, in particular up to 5 mol%, can be replaced by lower olefins such as propene and / or butene.
• R 3 in formula A2) preferably denotes a neoalkyl radical with 7 to 11 carbon atoms, in particular a neoalkyl radical with 8, 9 or 10 carbon atoms.
• the copolymer A) according to the invention preferably consists of at most 15, in particular 5 to 10 mol% of structural units of the formula A2). Especially such copolymers A) with 5 to 9 mol% of neononane or are preferred Vinyl neodecanoate as structural unit A2).
• the copolymers A) according to the invention are by the customary copolymerization processes such as suspension polymerization, Solvent polymerization, gas phase polymerization or high pressure bulk polymerization producible.
• High-pressure bulk polymerization is preferred at pressures of preferably 50 to 400, in particular 100 to 300 MPa and Temperatures of preferably 50 to 300, in particular 100 to 250 ° C.
• the Reaction of the monomers is caused by free radical initiators (Radical chain starter) initiated.
• This class of substances includes e.g.
• Oxygen, Hydroperoxides, peroxides and azo compounds such as cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide dicarbonate, t-butyl perpivalate, t-butyl permaleinate, t-butyl perbenzoate, dicumyl peroxide, t-Butylcumyl peroxide, di- (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile).
• the initiators are used individually or as a mixture of two or more substances in amounts of 0.001 to 20% by weight, preferably 0.01 to 10 wt .-%, based on the monomer mixture, used.
• the copolymers A) according to the invention preferably have melt viscosities at 140 ° C from 20 to 10,000 mPas, especially from 30 to 5000 mPas, especially from 50 to 2000 mPas.
• the desired melt viscosity of the copolymers A) is given Composition of the monomer mixture by varying the Reaction parameters pressure and temperature and optionally by adding Moderators hired.
• Hydrogen, saturated or unsaturated hydrocarbons e.g. Propane, aldehydes, e.g. Propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones, e.g. Acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone or alcohols, e.g. Butanol, proven.
• the moderators become dependent on the desired viscosity in quantities up to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Monomer mixture, applied.
• the comonomers suitable for the preparation of the copolymers A) according to the invention are, in particular, neooctane, neononane, neodecane, neoundecane and neododecanoic acid vinyl esters. These esters can be prepared, for example, by vinylation of the neocarboxylic acids accessible by Koch's carboxylic acid synthesis from olefins, CO and H 2 O (Römpp: Chemie-Lexikon, Thieme-Verlag, 9th edition, pp. 4881 and 4901).
• the copolymers A) according to the invention can contain up to 4% by weight of vinyl acetate or up to 5 mol% of further comonomers.
• Suitable comonomers are, for example, vinyl esters of lower carbon acids such as vinyl propionate and vinyl butyrate, vinyl ethers such as vinyl methyl ether and vinyl ethyl ether, (meth) acrylic acid alkyl esters of C 1 -C 4 alcohols such as methyl acrylate, ethyl acrylate, propyl acrylate, n-, iso-, tert-butyl acrylate and the corresponding Esters of methacrylic acid and higher olefins with at least 5 carbon atoms. Hexene, 4-methylpentene, norbornene, octene and diisobutylene are preferred as higher olefins.
• copolymers of the composition mentioned under A mixtures of monomers other than ethylene and optionally a moderator Contain 1 to 50 wt .-%, preferably 3 to 40 wt .-% vinyl ester.
• a moderator Contain 1 to 50 wt .-%, preferably 3 to 40 wt .-% vinyl ester With that of the composition of the copolymer differing composition of the Monomer mixture one carries the different copolymerization factors the monomer calculation.
• the polymers are obtained as colorless melts solidify to waxy solids at room temperature.
• High pressure bulk polymerization is carried out in known high pressure reactors, e.g. Autoclaves or tubular reactors, carried out batchwise or continuously, Tube reactors have proven particularly useful.
• Solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, Benzene or toluene can be contained in the reaction mixture. The is preferred solvent-free mode of operation.
• the Polymerization is the mixture of the monomers, the initiator and, if provided used, the moderator, a tubular reactor via the reactor inlet and via one or more side branches fed.
• the monomer streams be composed differently (EP-A-0 271 738).
• R 4 is preferably an alkyl radical of preferably 10 to 24, in particular 12 to 20, carbon atoms.
• the use of alcohol mixtures for example of dodecanol and tetradecanol or tetradecanol and hexadecanol in a ratio of 1:10 to 10: 1, in particular 3: 1 to 1: 3, has proven particularly useful.
• the additive can be adapted to the oil to be treated by varying the alcohol component. For example, by adding 15% by weight of behenyl alcohol to the above-mentioned mixtures, the effectiveness in oils with an extremely high boiling point of> 390 ° C., in particular> 410 ° C., can be optimized.
• the R 4 radicals can be linear or branched, and the branching can comprise a secondary or tertiary carbon atom.
• Linear radicals R 4 are preferred. If R 4 is branched, it preferably carries this branch in the 2 position. It is possible to use different R 4 radicals, ie to use mixtures of different alcohols in the preparation of the maleic, itaconic and / or fumaric esters.
• Preferred alcohols R 4 -OH are, for example, 1-decanol, 1-dodecanol, 1-tridecanol, isotridecanol, 1-tetradecanol, 1-hexadecanol, 1-octadecanol, eicosanol, docosanol, tetracosanol, their mixtures, and naturally occurring mixtures such as coconut fatty alcohol , Tallow fatty alcohol and behenyl alcohol.
• the alcohols can be of natural as well as synthetic origin.
• the radicals R 4 in formula B1) are alkoxyalkyl radicals of the formula - (OA) x - R 6 wherein A is a C 2 -C 4 alkylene radical, x is an integer from 1 to 100 and R 6 is a C 1 -C 30 alkyl radical.
• the (OA) unit is preferably an ethoxy or propoxy unit. If alkoxylated units of the formula (3) are used for R 4 , this is preferably done in a mixture with radicals R 4 which are not alkoxylated. The proportion of alkoxylated radicals R 4 preferably does not exceed 20 mol% (based on all radicals R 4 ).
• R 6 can be linear or branched. If R 6 is branched, the branch is preferably in the 2 position. R 6 is preferably linear.
• the structural units of the formula B2) are derived from vinyl, acrylic or Methacrylic acid esters. Structural units B2) which differ from Derive vinyl acetate or vinyl propionate.
• the bivalent structural units mentioned under B3) are of polyolefins derived from monoolefins with 3, 4 or 5 carbon atoms.
• Particularly preferred monoolefins as the base of the polyolefins are propylene and isobutylene, from which polypropylene and polyisobutylene are formed as polyolefins.
• the polyolefins preferably have an alkyl vinylidene content of at least
• Alkyl vinylidene content means the content of structural units in the polyolefins based on compounds of the formula decrease in which R 7 or R 8 are methyl or ethyl and the other group is an oligomer of the C 3 -C 5 olefin.
• the number of carbon atoms of the polyolefin is between 35 and 350. In a preferred embodiment of the invention, the number of carbon atoms is between 45 and 250. In a further preferred embodiment of the invention, the proportion of structural units B3) is 1 to 20 mol%, in particular 2 to 15 mol%.
• the polyolefins on which the structural units B3) are based are ionic Polymerization accessible and available as commercial products (e.g. ® Ultravis, ® Napvis, ® Hyvis, ® Glissopal) (Polyisobutenes from BP, BASF with different Alkyl vinylidene contents and molecular weights).
• the average molecular weight of the copolymers B) according to the invention is in generally between 1,500 and 200,000 g / mol, in particular between 2,000 and 100,000 g / mol (GPC against polystyrene standards in THF).
• the copolymers B) according to the invention are preferably produced at Temperatures between 50 and 220 ° C, especially 100 to 190 ° C, especially 130 to 170 ° C.
• the preferred manufacturing process is solvent-free Bulk polymerization, however, it is also possible to carry out the polymerization in the presence aromatic, aliphatic or isoaliphatic aprotic solvents such as hexane, Cyclohexane, toluene, xylene or solvent mixtures such as kerosene or solvent Perform naphtha.
• the temperature can be the boiling point of the solvent or by working under negative or positive pressure can be set particularly easily.
• radical initiators Radar chain starter
• This class of substances includes 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 permaleinate, t-butyl perbenzoate, dicumyl peroxide, t-Butylcumyl peroxide, di- (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile) or 2,2'-azo-bis (2-methylbutyronitrile).
• the initiators are used individually or as a mixture from two or more substances in amounts of 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the
• the copolymers can be obtained by copolymerizing polyolefin (component B3) and unsaturated ester (component B2) with either maleic acid, fumaric acid, Itaconic acid, itaconic or maleic anhydride or maleic, fumaric, Itaconic acid ester or maleic acid, itaconic acid imide (component B1) become. If a copolymerization with acids or anhydrides is carried out, then the resulting copolymer is esterified or imidized after production. This Esterification or imidation takes place, for example, by reaction with 1.5 to 2.5 mol alcohol or 0.8 to 1.2 mol amine per mol anhydride at 50 to 300, especially 120 - 250 ° C.
• the water of reaction can by means of an inert gas stream distilled off or discharged by means of azeotropic distillation.
• Copolymers B) with acid numbers less than 50, especially less than 30, especially less than 20 mg KOH / g are preferred.
• Preferred mixtures contain 20-85% of one or more copolymers A and 15-80% of one or more copolymers B, especially 40 - 80% A and 20 - 60% B.
• the further ethylene copolymers C) preferably contain 8-13 mol% of at least one vinyl ester such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl octanoate, neononane and neodecanoic acid vinyl ester, a C 1 -C 30 -alkyl vinyl ester and / or C 1 -C 30 Alkyl (meth) acrylate.
• they preferably contain 1-6 mol% of at least one olefin with 3-8 C atoms such as propene, butene, isobutene, diisobutylene, pentene, hexene, 4-methylpentene, norbornene or octene.
• mixtures of different flow improvers with different quantitative (eg comonomer content) and / or qualitative composition (type of copolymers / terpolymers, molecular weight, degree of branching) can also be used.
• the polymers C) preferably have melt viscosities at 140 ° C. of 50 to 8000 mPas, especially 70 to 3000 mPas.
• the additives according to the invention in a mixture with ethylene / vinyl acetate / Vinyl neononanoic acid terpolymers or ethylene vinyl acetate / Neodecanoic acid vinyl ester terpolymers.
• the terpolymers of Besides contain neononanoic acid vinyl ester or the neodecanoic acid vinyl ester Ethylene 10 to 35 wt .-% vinyl acetate and 1 to 25 wt .-% of the respective Neo connection.
• the Additives according to the invention with terpolymers used in addition to ethylene 10-35% by weight vinyl ester and 0.5 to 20% by weight olefins such as e.g. Diisobutylene, Contain witches, 4-methylpentene and / or norbornene.
• the mixing ratio of the additives according to the invention with the above described ethylene / vinyl acetate copolymers or the terpolymers Ethylene, vinyl acetate and the vinyl esters of neononanoic or neodecanoic acid or from ethylene, vinyl esters and olefins is (in parts by weight) 20: 1 to 1:20, preferably 10: 1 to 1:10, especially 5: 1 to 1: 5.
• the mixtures of the Additives according to the invention with the copolymers mentioned are in particular suitable for improving the flowability of middle distillates.
• the additives according to the invention are mineral oils or mineral oil distillates Form of solutions or dispersions added. These solutions or Dispersions preferably contain 1 to 90, in particular 5 to 80% by weight, especially 10 to 75% by weight of the mixtures. Suitable solution or Dispersing agents 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 solvents Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol-, ® ISOPAR- and ® Shellsol D types as well as aliphatic or aromatic alcohols, ethers and / or Esters.
• the specified solvent mixtures contain different amounts of aliphatic and / or aromatic hydrocarbons.
• the aliphates can straight-chain (n-paraffins) or branched (iso-paraffins).
• Aromatic Hydrocarbons can be mono-, di- or polycyclic and optionally carry one or more substituents.
• improved mineral oils or mineral oil distillates contain 0.001 to 2% by weight, preferably 0.005 to 0.5% by weight of the additives, based on the distillate.
• Additives also together with one or more oil-soluble co-additives are used, which alone have the cold flow properties of crude oils, Improve lubricating oils or fuel oils.
• oil-soluble co-additives are Alkylphenol-aldehyde resins and polar compounds that have a paraffin dispersion effect (paraffin dispersants).
• the additives according to the invention can be used in a mixture with alkylphenol-formaldehyde resins.
• these alkylphenol-formaldehyde resins are those of the formula wherein R 10 is C 4 -C 50 alkyl or alkenyl, R 9 is ethoxy and / or propoxy, n is a number from 5 to 100 and p is a number from 0 to 50.
• Paraffin dispersants reduce the size of the paraffin crystals and ensure that the paraffin particles do not settle, but remain dispersed colloidally with a clearly reduced tendency to sedimentation.
• Oil-soluble polar compounds with ionic or polar groups for example amine salts and / or amides, which have been found to be suitable as paraffin dispersants, can be obtained by reacting aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or the like Anhydrides can be obtained.
• paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds, which can optionally be reacted with primary monoalkylamines and / or aliphatic alcohols, the reaction products of alkenyl spirobislactones with amines and reaction products of terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic acid Unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols. Alkylphenol-formaldehyde resins are also suitable as paraffin dispersants.
• the mixing ratio (in parts by weight) of the additives with paraffin dispersants is in each case 1:10 to 20: 1, preferably 1: 1 to 10: 1.
• the additives according to the invention are suitable for improving the cold flow properties of To improve crude oils, distillate oils or fuel oils as well as lubricating oils.
• the Oils can be of mineral, animal or vegetable origin.
• middle distillates are mineral oils which are obtained by distillation of crude oil and range from 120 to Boil 500 ° C, such as kerosene, jet fuel, diesel and heating oil.
• they are effective in oils whose GC content determines n-paraffins, which have chain lengths of 22 carbon atoms or more, at at least 1.0 area%, especially for more than 1.5 area%, especially for 2.0 and more area%.
• the 90% distillation point of the invention Oils are preferably above 345 ° C, especially above 350 ° C, especially above 355 ° C. These oils have cloud points above 5 ° C, in particular above 8 ° C.
• the additives can be used alone or together with other additives used, for example with dewaxing aids, Improving conductivity, defoaming agents, dispersing agents, Corrosion inhibitors, antioxidants, lubricity additives, dehazers or Sludge inhibitors.
• the additive components can be the oils to be additized together as a concentrate mixture in suitable solvents or separately be added.
• the boiling characteristics are determined in accordance with ASTM D-86 the CFPP value according to EN 116 and the determination of the cloud point according to ISO 3015.
• the distribution of the n-paraffins is determined by gas chromatography using an HP 5890 Series II performed. The separation takes place on a silica gel column with 5% cross-linked phenylmethyl silicone ( ⁇ 0.32 mm, length 50 m, film thickness 0.17 ⁇ m). The Detection is carried out by means of a thermal conductivity detector.
• the detected total area of the injected sample is determined in the first step.
• a "valley-to-valley" integration is used to determine the areas for the individual n-paraffins. This area divided by the previously determined total area gives the area percent of the respective n-paraffin. Thus, the proportion of the area of a peak due to an n-paraffin is separated from that for the matrix (isomers of the n-paraffins, naphthenes and aromatics).
• Test oil 1 Test oil 2
• Test oil 3 Initial boiling point [° C] 144 139 152 20% [° C] 234 222 231 90% [° C] 363 355 363 Cloud Point [° C] +10 +8 +16 CFPP [° C] +6 +3 +9 n-paraffins ⁇ C 22 2.4% 2.0% 2.2%
• CFPP effectiveness in test oil 1 example 100 ppm 150 ppm 200 ppm 250 ppm A1 + B1 (3: 1) +1 -2 -6 -10 A2 + B1 (2: 1) 0 -3 -5 -11 A1 + C1 + B1 (1: 1: 1) 0 -5 -7 -12 A1 + A2 + B1 (1: 2: 1) +1 -3 -6 -9 A2 + C3 + B1 (1: 1: 1) +2 0 -5 -10 C3 + B1 (2: 1) (See) +5 +1 -3 -7 CFPP effectiveness in test oil 2 example 100 ppm 150 ppm 200 ppm 250 ppm A

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• 2000
  • 2000-03-14 DE DE10012269A patent/DE10012269C2/de not_active Expired - Fee Related
• 2001
  • 2001-02-02 BR BRPI0100313-5A patent/BR0100313B1/pt not_active IP Right Cessation
  • 2001-02-28 EP EP01104848A patent/EP1134275B1/fr not_active Expired - Lifetime
  • 2001-02-28 DE DE50110842T patent/DE50110842D1/de not_active Expired - Fee Related
  • 2001-02-28 ES ES01104848T patent/ES2270911T3/es not_active Expired - Lifetime
  • 2001-03-13 NO NO20011255A patent/NO20011255L/no not_active Application Discontinuation
  • 2001-03-13 CA CA002340525A patent/CA2340525A1/fr not_active Abandoned
  • 2001-03-13 JP JP2001070616A patent/JP2001294875A/ja active Pending
  • 2001-03-14 US US09/808,481 patent/US6593426B2/en not_active Expired - Fee Related

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