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
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • 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
  • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
  • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
• • 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
  • C10L1/188—Carboxylic acids; metal salts thereof
  • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
  • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
• • 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
  • C10L1/1981—Condensation polymers of aldehydes or ketones
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
  • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/224—Amides; Imides carboxylic acid amides, imides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/236—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
• • 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
  • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium

Definitions

• the present invention relates to an additive for fuel oils containing Ethylene / vinyl ester / olefin terpolymers and amphiphilic, lubricant-improving Additives, as well as their use to improve cold flow and Lubrication properties of the oils thus added.
• Mineral oils and mineral oil distillates used as fuel oils generally 0.5 wt .-% and more sulfur, which the combustion Causes formation of sulfur dioxide. To the resulting To reduce environmental pollution, the sulfur content of fuel oils lowered further and further.
• EP-A-0 764 198 discloses additives which improve the lubricating effect of fuel oils improve, and the polar nitrogen compounds based on alkylamines or Contain alkylammonium salts with alkyl radicals of 8 to 40 carbon atoms.
• EP-A-0 743 974 discloses the use of mixtures of lubricity additives (Esters of polyhydric alcohols and carboxylic acids with 10 to 25 carbon atoms or Dicarboxylic acids) and flow improvers made from ethylene / unsaturated ester copolymers to synergistically improve the lubricating effect of highly desulfurized oils.
• EP-A-0 807 676 discloses the use of a mixture of one Carboxamide and a cold flow improver and / or an ashless one Dispersant to improve the cold flow properties of low sulfur Fuel oil.
• EP-A-0 680 506 discloses the use of esters of mono- or polyvalent Carboxylic acids with mono- or polyhydric alcohols as Lubricity-improving additive to fuel oils.
• EP-A-0 807 642 discloses cold flow improvers based on terpolymers which Contain structural units of ethylene, vinyl acetate and 4-methylpentene-1, EP-A-807 643 based on ethylene, vinyl acetate and norbornene.
• the object of the present invention was to find additive combinations which are in Middle distillates largely freed from sulfur and aromatic compounds lead to an improvement in the lubricating effect.
• these additives are said to also contain a proportion as a cold flow improver, in the oils mentioned is soluble and effective as such, and the effect of the lubricity additive supports, and vice versa.
• additives which are in addition to lubricating amphiphile terpolymers made of ethylene, vinyl esters and contain certain olefins that have the required properties.
• Another object of the invention are fuel oils, the said Contain additives.
• Another object of the invention is the use of additives for simultaneous improvement of the lubrication and cold flow properties of Fuel oils.
• Preferred proportions of A) and B) are between 10 and 90% by weight, in particular 20 to 80 wt .-% and especially 40 to 60 wt .-%.
• the oil-soluble amphiphile (component A) preferably comprises a radical R 1 having 5 to 40, in particular 12 to 35, carbon atoms.
• R 1 is particularly preferably linear or branched and contains 1 to 3 double bonds in the case of linear radicals.
• the radical R 2 preferably has 2 to 8 carbon atoms and can be interrupted by nitrogen and / or oxygen atoms.
• the sum of the carbon atoms of R 1 and R 2 is at least 10, in particular at least 15.
• component A carries 2 to 5 hydroxyl groups, each carbon atom not carrying more than one hydroxyl group.
• X in formula 1 has the Meaning of oxygen.
• they are fatty acids and esters between carboxylic acids and dihydric or polyhydric alcohols.
• Preferred esters contain at least 10, especially at least 12 carbon atoms.
• Prefers is also that the esters contain free hydroxyl groups, the esterification of the Polyol is not complete with the carboxylic acid.
• Suitable polyols are for example ethylene glycol, propylene glycol, diethylene glycol and higher Alkoxylation products, glycerin, trimethylolpropane, pentaerythritol, diglycerin and higher condensation products of glycerin as well as sugar derivatives. Others too Polyols containing heteroatoms, such as triethanolamine, are suitable.
• reaction products of ethanolamine are Diethanolamine, hydroxypropylamine, dihydroxypropylamine, n-methylethanolamine, Diglycolamine and 2-amino-2-methylpropanol are suitable.
• the implementation takes place preferably by amidation, the resulting amides also containing free OH groups wear. Examples include fatty acid monoethanolamides and diethanolamides and called -N-methylethanolamide.
• R 3 preferably represents a hydroxyl-bearing alkyl radical having 3 to 8 carbon atoms, or preferably C 2 to C 18 alkyl, in particular C 4 to C 12 alkyl.
• R 43 preferably represents a C 2 - to C 8 -, in particular a C 2 - to C 4 -rest.
• the polyamine from which the structural unit formed from R 41 , R 42 and the nitrogen atom connecting them is derived is preferably ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine or a higher homologue of aziridine such as polyethyleneimine, and mixtures thereof. Parts of the amino group can be alkylated. Sternamines and dendrimers are also suitable. This is understood to mean polyamines with generally 2-10 nitrogen atoms which are connected to one another via —CH 2 —CH 2 groups and which are saturated in the marginal position with acyl or alkyl radicals.
• R 44 preferably represents hydrogen, an acyl radical or an alkoxy group of the formula - (OCH 2 CH 2 ) n -, where n is an integer between 1 and 10, and mixtures thereof.
• the amides are generally by condensation of the polyamines with the Carboxylic acids or their derivatives such as esters or anhydrides. It are preferably 0.2 to 1.5 mol, in particular 0.3 to 1.2 mol, especially 1 mol Acid used per base equivalent. The condensation is preferably carried out at Temperatures between 20 and 300 ° C, especially between 50 and 200 ° C below Distilling off the water of reaction. Solvents may be preferred aromatic solvents such as benzene, toluene, xylene, trimethylbenzene and / or commercial solvent mixtures such as B. Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200 are added to the reaction mixture.
• the Products according to the invention generally have a titratable Base nitrogen of 0.01 - 5% and an acid number of less than 20 mg KOH / g, preferably less than 10 mg KOH / g.
• y preferably takes the values 1 or 2.
• Preferred polyols have 2 to 8 carbon atoms. They preferably wear 2, 3, 4 or 5 hydroxyl groups, but no more than they contain carbon atoms.
• the carbon chain of the polyols can be straight-chain, branched, saturated or unsaturated be and optionally contain heteroatoms. It is preferably saturated.
• Preferred carboxylic acids from which the compounds of formula 1 are derived let, or represent the compounds of formula 1, have 5 to 40, especially 12 to 30 carbon atoms.
• the carboxylic acid preferably has one or two carboxyl groups.
• the carbon chain of the carboxylic acids can straight chain, branched, saturated or unsaturated.
• carboxylic acids examples include caprylic acid, Capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, Elaidic acid, linoleic acid, linolenic acid and behenic acid, and carboxylic acids with Heteroatoms such as ricinoleic acid.
• dimer and trimer fatty acids such as they e.g. are accessible by oligomerization of unsaturated fatty acids, as well Alkenyl succinic acids are used.
• component A uses ethers and amines of the formula 2.
• ethers and amines of the formula 2 are partial ethers of polyols, such as, for example, glycerol monooctadecyl ether or hydroxyl-bearing amines, as are obtainable, for example, by alkoxylation of amines of the formula R 1 NH 2 or R 1 R 3 NH with alkylene oxides, preferably ethylene oxide and / or propylene oxide. 1-10, in particular 1-5, mol of alkylene oxide are preferably used per H atom of nitrogen.
• the vinyl esters contained in the terpolymer of component B) are preferred of monocarboxylic acids having 2 to 16, in particular 2 to 12, carbon atoms derived.
• One or more vinyl esters can be contained at the same time.
• the vinyl esters are vinyl acetate, Vinyl propionate, 2-ethylhexanoic acid vinyl ester, neodecanoic acid vinyl ester, Vinyl neononanoate, vinyl neoundecanoate, vinyl pivalate or vinyl laurate, in particular vinyl acetate and / or vinyl propionate.
• the olefin contained in the terpolymer contains 5, 6 or 7 carbon atoms. It is, for example, penten-1, hexen-1 or hepten-1. Especially preferred embodiments of the invention are 4-methylpentene-1 or norbornene.
• the terpolymers preferably contain 10 to 16 mol% of vinyl ester and 1 to 3 mol% of olefin. Their degree of branching, determined by means of NMR spectroscopy, is between 3 and 15, in particular between 3.5 and 10 CH 3 / 100CH 2 groups, which do not originate from the vinyl ester.
• Terpolymers according to the invention with an ISO 3219 (B) at 140 ° C. measured melt viscosity of 50 to 5000 mPas, preferably 30 to 1,000 mPas and in particular 50 to 500 mPas.
• the starting materials are copolymerized by known processes (cf. for this e.g. Ullmann's Encyclopedia of Technical Chemistry, 5th edition, Vol. A21, Pages 305 to 413). Polymerization in solution, in suspension, in the gas phase and high pressure bulk polymerization.
• the reaction of the monomers is caused by radicals initiators (radical chain initiators) initiated.
• radicals initiators radiation chain initiators
• Oxygen, hydroperoxides, peroxides and azo compounds such as Cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxidicarbonate, t-butyl perpivalate, t-butyl permaleinate, t-butyl perbenzoate, Dicumyl peroxide, t-butylcumyl peroxide, di- (t-butyl) peroxide, 2,2'-azo-bis (2-methylpropanonitrile), 2,2'-azo-bis (2-methylbutyronitrile).
• the initiators are individual or as a mixture of two or more substances in amounts from 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Monomer mixture used.
• the desired melt viscosity of the terpolymers 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.
• terpolymers To be suitable for use in the additives of the invention, monomer mixtures are used which, in addition to ethylene and optionally a moderator 5 to 40% by weight, preferably 10 to 40% by weight Vinyl ester and 1 to 40 wt .-% olefin contain. With that of the composition of the terpolymer differing composition of the monomer mixture you bear the different polymerization rate of the monomers Bill.
• the polymers are obtained as colorless melts which Solidify at room temperature to waxy solids.
• additives according to the invention also together with one or more oil-soluble Co-additives are used, which alone have the cold flow properties and / or lubricating effect of crude oils, lubricating oils or fuel oils improve.
• oil-soluble Co-additives are paraffin dispersants, alkylphenol-aldehyde resins and comb polymers.
• Paraffin dispersants reduce the size of the wax crystals and cause the paraffin particles do not settle, but colloidally with significantly reduced Sedimentation efforts, remain dispersed.
• paraffin dispersants oil-soluble polar compounds with ionic or polar groups, e.g. Amine salts and / or amides proven by the reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic Mono-, di-, tri- or tetracarboxylic acids or their anhydrides can be obtained.
• paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols can be implemented Reaction products of alkenyl spirobis lactones with amines and Reaction products of terpolymers based on ⁇ , ⁇ -unsaturated Dicarboxylic anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkylene ethers lower unsaturated alcohols.
• Alkylphenol-formaldehyde resins are also available Paraffin dispersants suitable. The following are some suitable ones Paraffin dispersants listed.
• the additives according to the invention can also be used in a mixture with alkylphenol-formaldehyde resins.
• these alkylphenol-formaldehyde resins are those of the formula wherein R 51 is C 4 -C 50 alkyl or alkenyl, [OR 52 ] for ethoxy and / or propoxy, n for a number from 5 to 100 and p for a number from 0 to 50.
• the invention Additives used together with comb polymers.
• Suitable comb polymers are fumarate / vinyl acetate copolymers (cf. EP 0 153 176 A1), copolymers of a C 6 - to C 24 - ⁇ -olefin and an NC 6 - to C 22 -alkylmaleimide (cf. EP-A- 0 320 766), also esterified olefin / maleic anhydride copolymers, polymers and copolymers of ⁇ -olefins and esterified copolymers of styrene and maleic anhydride.
• fumarate / vinyl acetate copolymers cf. EP 0 153 176 A1
• copolymers of a C 6 - to C 24 - ⁇ -olefin and an NC 6 - to C 22 -alkylmaleimide cf. EP-A- 0 320 766
• esterified olefin / maleic anhydride copolymers polymers and
• the mixing ratio (in parts by weight) of the additives according to the invention with paraffin dispersants or comb polymers 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 and lubricating properties of animal, vegetable or mineral oils, alcoholic fuels such as methanol and ethanol, as well as mixtures of alcoholic fuels and mineral oils. They are particularly well suited for use in middle distillates. Middle distillates are mineral oils that are obtained by distilling crude oil and boil in the range of 120 to 450 ° C, such as kerosene, jet fuel, diesel and heating oil.
• the additives according to the invention are preferably used in middle distillates which contain at most 500 ppm, in particular less than 200 ppm, and in special cases less than 50 ppm of sulfur. These are generally middle distillates which have been subjected to hydrogenation refining and which therefore contain only small amounts of polyaromatic and polar compounds which give them a natural lubricating effect.
• the additives according to the invention are furthermore preferably used in middle distillates which have 95% distillation points below 370 ° C., in particular 350 ° C. and in special cases below 330 ° C. The effectiveness of the mixtures is better than would be expected from the individual components and compared to the mixtures according to the prior art.
• the additive combinations according to the invention are distinguished under cold blending conditions if the temperature of the oil during the additive is low, ie below 40 ° C., in particular below 20 ° C. and especially below 10 ° C.
• the additive components according to the invention can be mineral oils or Mineral oil distillates can be added separately or in a mixture.
• Mixtures have solutions or dispersions of 10 to 90% by weight, preferably 20-80 wt .-%, the additive combination contain proven.
• Suitable Solvents or dispersing agents are aliphatic and / or aromatic Hydrocarbons or hydrocarbon mixtures, e.g.
• the additives can be used alone or together with other additives, for example with other pour point depressants, dewaxing aids, corrosion inhibitors, antioxidants, conductivity improvers, sludge inhibitors, dehazers and additives for lowering the cloud point. These additives can be added to the oil together with the additive components according to the invention or separately. The effectiveness of the additives according to the invention as a lubricity enhancer and cold flow improver is explained in more detail by the examples below.
• Test oil 1 Test oil 2 Test oil 3 Test oil 4 Test oil 5 Cloud Point (CP) (° C) + 1 - 9.6 - 3.2 - 4.3 - 26.8 Cold Filter Plugging Point (CFPP) (° C) - 2nd - 14 - 6th - 6th - 27 Pour point (PP) (° C) - 3rd - 12th - 9 - 12th - 27 n-paraffin content (% by weight) 23 21.5 18.9 18.2 16.8 Initial boiling point (IBP) (° C) 163 172 187.9 186.9 185.8 Boiling range 90% - 20% (K) 104 76.9 99.8 102.2 89.9 FBP-90% (K) 27 18th 24.2 19.0 21 End of boiling point (FBP) (° C) 332 336 359.6 358.6 320.7 density 0.828 0.831 0.843 0.842 0.819 S content (ppm) 290 35 54.2 478 6 HFRR
• the boiling characteristics were 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 solubility behavior of the additives is determined according to the British Rail Test as follows: 400 ppm of a dispersion of the additive combination heated to 22 ° C are metered into 200 ml of the test oil heated to 22 ° C (see Table 3) and shaken vigorously for 30 seconds. After 24 hours of storage at + 3 ° C for 15 seconds and then again shaken mm ml at 3 ° C in three portions of 50 through a 1.6 ⁇ m-glass fiber microfilter (i 25; Whatman GFA, Order No. 1,820,025 ) filtered.
• An ADT value ⁇ 15 is considered as an indication that the gas oil is normal cold weather can be used satisfactorily. Products with ADT values> 25 are described as not filterable.
• the lubricating effect of the additives was determined using an HFRR device from PCS Instruments performed.
• the additives tempered at 22 ° C become the dosed at 22 ° C oil and shaken vigorously for 30 seconds.
• To 24 hours storage at + 3 ° C, the oil is tested according to the conditions of the British Rail filtered and the lubricating effect on the filtrate determined in the HFRR test.
• the High Frequency Reciprocating Rig Test (HFRR) is described in D. Wei, H. Spikes, Wear, Vol. 111, No. 2, p. 217, 1986 and is carried out at 60 ° C.
• the Results are as a coefficient of friction (Friction) and Wear Scar (WSD) specified. Show a low coefficient of friction and a lower wear scar a good lubricating effect.
• the polymers were 50% in kerosene set.
• the viscosity was determined using a rotary viscometer (Haake RV 20) with plate-cone measuring system at 140 ° C, in accordance with ISO 3219 (B).
• Additives according to the invention are also used in a mixture with paraffin dispersants become.
• the employed Wachsdispergator (F) is a mixture of 2 parts of a reaction product of a terpolymer of C 14/16 - ⁇ -olefin, maleic anhydride and 2 equivalents of di-tallow Allylpolyglkol with and a part of nonylphenol-formaldehyde resin.
• the cold flow improver polymers mentioned and, if appropriate, additionally the wax dispersant mentioned are mixed with the amphiphiles mentioned.

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