KR100749209B1 - Additive mixture as component of mineral oil compositions - Google Patents

Abstract

An additive mixture as component of compositions of mineral oil as the main component and trace portions of an additive mixture contains the additive components a) ethylene-vinylester copolymers with molecular mass weight averages from 3000 to 50000 and an ethylene proportion of 50 to 90 mass %, and b) mixed esters of glycerine in which 50 to 80 mol % of the hydroxy groups are esterified with unsaturated C<SUB>12</SUB>-C<SUB>40 </SUB>monocarboxylic acids and 20 to 50 mol % of the hydroxy groups are esterified with partially imidated and/or partially esterified maleic anhydride copolymers, and/or c) partially and/or completely imidated copolymers consisting of maleic anhydride and alpha-methylstyrene with molecular mass number averages from 1500 to 15000 and at least one terminal group based on dimeric alpha-methyl styrene, and/or d) wax compositions based on natural starting materials of type d1) wax-like oligomeric esters based on glyceryl monostearate and dimeric acid and/or d2) wax esters with vaseline-like consistency, based on at least two different straight-chain and/or branched C<SUB>14</SUB>-C<SUB>36</SUB>-alcohols and dimeric acid whereby the content of the additive mixture in the mineral oil is 0.005 to 1 mass % and the mass proportion of the additive components a/b or a/c or a/d is in the range from 10:90 to 90:10, respectively. The mineral oil compositions are suitable as flowable media to be transported at low temperatures and as mineral oil fuels with high lubricity and flowability.

Description

Additive mixtures as components of mineral oil compositions {ADDITIVE MIXTURE AS COMPONENT OF MINERAL OIL COMPOSITIONS}

The present invention relates to an additive mixture as a composition component composed of a mineral oil as a main component and an additive mixture as a trace component, and a method for producing a mineral oil composition containing the additive mixture.

Additive mixture of mineral oil as main component and ethylene-vinylacetate copolymer, hydrocarbon polymer, esterified maleic anhydride-olefin copolymer, minor nitrogen compound such as amine salt of polyhydric carboxylic acid and esterified polyoxyalkylene as minor component Compositions consisting of are known (WO 94/10 267 A1, WO 95/33 012 A1, EP 0 921 183 A1, WO 93/14 178 A1, EP 0 889 323 A1).

When the sulfur content of the mineral oil component is less than 0.005% by mass, the composition has disadvantages such as insufficient fluidity and stability when stored at low temperatures, and limited lubricity of the formulation.

It is an object of the present invention to provide an additive mixture as a component for a mineral oil composition composed of a mixture of mineral oil as a main component and an additive as a minor component, with improved flowability and stability at low temperature storage, and lubricity. Improved flow behavior results in energy savings in the pump set that transports the blend. The additive mixture has been developed taking into account that mineral oils with very low sulfur content should be used to produce fuels with improved environmental compatibility with regard to pollutant emissions.

An object of the present invention is an additive mixture as a component of a mineral oil composition composed of a mixture of mineral oil as a main component and an additive mixture as a trace component, and as an additive component.

a) an ethylene-vinyl ester copolymer having a mass average molecular weight of 3000 to 50000 and an ethylene content of 50 to 90 mass%, and

b) 50 to 80 mole% of the hydroxy groups are esterified with unsaturated C ₁₂ -C ₄₀ monocarboxylic acids, and 20 to 50 mole% of the hydroxy groups are partially imidized and / or partially esterified with the maleic anhydride copolymer Mixed esters of esterified glycerin, and / or

c) partial and / or fully imidized copolymers of maleic anhydride and α-methylstyrene, having a mass average molecular weight of 1500 to 15000 and at least one terminal group based on dimeric α-methylstyrene, and / or

d) wax compositions based on natural starting materials of the following d1) and d2) types:

d1) wax-like oligomeric esters based on glyceryl monostearate and dimer acids, wherein the conversion product corresponds to the following structure up to 90 mass%, and / or

(Where n is 1 to 20, the sum of a + b + c + d is 30, Z is 12 to 20,

이고, X는 H 또는 -CH₂-CH(OH)-CH₂-O-CO-(CH₂)_z-CH₃임)

X is H or -CH ₂ -CH (OH) -CH ₂ -O-CO- (CH ₂ ) _z -CH ₃

d2) wax esters having a petrolatum-like hardness based on at least two different straight and / or branched C ₁₄ -C ₃₆ -alcohols and dimer acids whose conversion product corresponds to at least 80 mass%

Wherein i is 13 to 35; s is 13 to 35, the sum of k + m + n + p is 30 to 34, and (CH ₂ ) _i or (CH ₂ ) _s is straight or straight and branched )

It is achieved by the additive mixture comprising a, the content of the additive mixture in the mineral oil is 0.005 to 1 mass%, the mass ratio of the additive component a / b or a / c or a / d is 10: 90 to 90:10, respectively do.

Examples of vinyl ester components that may be contained in the ethylene-vinyl ester copolymer as the additive component a) include vinyl acetate, vinyl propionate, 2-ethylhexyl vinyl ester, vinyl laurate, 2-hydroxyethyl vinyl ester, and 4-hydroxybutyl vinyl esters.

Ethylene-vinyl ester copolymers, for vinyl esters, include other unsaturated ester components such as (meth) acrylic ester-like methyl methacrylate, acrylic methyl ester, methacrylic ethyl ester, butyl acrylate, 2-ethylhexyl acrylate, Dodecyl acrylate, ethylene glycol dimethacrylate or hydroxyethyl methacrylate and / or vinyl ethers such as octylvinyl ether or hexanediol monovinyl ether.

Such ethylene-vinylester copolymers are preferred as additive component a) in ethylene-vinylacetate copolymer additive mixtures having a vinyl acetate content of 12-50 mass%.

Other preferred variants of the ethylene-vinyl ester copolymer contained in the additive mixture as the additive component a) are 10 to 90 mass% of the ethylene-vinyl ester copolymer in which the ethylene-vinyl ester copolymer is not modified and the ethylene-modified in the polar group. It is a mixture of 90-10 mass% of vinyl ester copolymers.

The ethylene-vinylester copolymer has a specific end group, such as an aldehyde end group, preferably an acetaldehyde, propionaldehyde, butyraldehyde, or isobutyraldehyde derived end group, carboxyalkylmercapto end group, preferably mercaptoacetic acid. Or a mercaptopropionic acid-derived end group, or an alkoxy end group, is incorporated into the copolymer, and a hydroxy group and / or carboxyl group is incorporated into the copolymer by partial oxidation, saponification, or acetalization, as well as a polar ethylenically unsaturated monomer. Modified polar groups incorporated by grafting on the copolymer.

Modified ethylene-vinylester copolymers, oxidized ethylene-vinylester copolymers, partially saponified ethylene-vinylester copolymers, hemiacetals of partially saponified ethylene-vinylester copolymers, and / or vinyl esters, (meth Preference is given to ethylene-vinylester copolymers grafted with acrylic esters, and / or polar unsaturated monomers of the vinyl ether type.

The oxidized ethylene-vinyl ester copolymer is preferably an oxidized ethylene-vinylacetate copolymer having a number average molecular weight of 800 to 5000, an acid value of 2 to 40 mg KOH / g, and an OH value of 20 to 150 mg KOH / g. to be.

The partially saponified ethylene-vinyl ester copolymer preferably has a number average molecular weight of 800 to 5000, and 5 to 30% by mass of the vinyl acetate units are saponified ethylene-vinylacetate copolymers.

In another preferred variant, the modified ethylene-vinylester copolymer is hemiacetal of ethylene-vinylester-vinyl alcohol copolymer and butyraldehyde. Examples of hemiacetals of ethylene-vinyl ester-vinyl alcohol copolymers and butyraldehydes are hemi of ethylene-vinylacetate-vinyl alcohol copolymers reacting heterogeneously with butyraldehyde as described in [DD 295 507 A7]. There is acetal.

The grafted ethylene-vinylester copolymer can be prepared by reacting with an unsaturated monomer in the presence of a pyrolytic radical former in an extruder (DD 282 462 B5) or a stirred tank reactor (DD 293 125 B5). In addition, during the preparation of the copolymer according to the high pressure method, it is possible to carry out the modification by adding monomer input to the polymer melt in a low pressure separator or discharge extruder.

In particular, the grafted ethylene-vinyl ester copolymer as the additive component a) is grafted with vinyl acetate, has a number average molecular weight of 800 to 5000, a total vinyl acetate content of 20 to 60 mass%, and vinyl of the copolymer skeleton chain It is an ethylene-vinylacetate copolymer having an acetate content of 10 to 40 mass% and a grafted vinylacetate branching ratio of 10 to 20 mass%.

The ethylene-vinylester copolymer in the additive composition may contain up to 35% by mass of poly-C ₆ -C ₃₆ -alkyl (meth) acrylate.

Examples of maleic anhydride copolymers which may exist partially imidized or partially esterified as acid components in mixed esters of glycerine as additive component b) of the additive mixture are maleic anhydride and comonomer components C ₂ -C _20- Olefin, C ₈ -C ₂₀ -vinyl aromatic, C ₄ -C ₂₁ -acrylic ester, C ₅ -C ₂₂ -methacrylic ester, C ₅ -C ₁₄ -vinyl silane, C ₆ -C ₁₅ acrylate silane, acrylic acid , Methacrylic acid, acrylonitrile, vinyl pyridine, vinyl oxazoline, isopropenyl oxazoline, vinyl pyrrolidone, amino-C ₁ -C ₈ -alkyl- (meth) acrylate, C ₃ -C ₂₀ -vinyl ester , A copolymer of C ₃ -C ₂₀ -vinylether and / or hydroxy-C ₁ -C ₈ -alkyl- (meth) acrylate. Particularly preferred comonomer components are isobutylene, diisobutylene, vinyl acetate, styrene and α-methylstyrene.

The maleic anhydride copolymer preferably has a molar ratio of maleic anhydride to comonomer of 1: 1 to 1: 9 and a molecular weight of 5000 to 500000. Partial imidization includes ammonia, C ₁ -C ₂₄ -monoalkyl amines, C ₆ -C ₁₈ -aromatic monoamines, C ₂ -C ₁₈ -mono-aminoalcohols, monoaminoated poly (C ₂ -C ₄ -alkylene) oxide and / or anhydride group copolymer / ammonia, C ₁ -C ₂₄ -monoalkylamine, C ₆ -C ₁₈ -aromatic monoamine, C _{2 -} C _{18 -} monomethyl amino-alcohol or mono-aminated poly _- (C ₂ - C ₄ - alkylene), each of the mole ratio of the oxide is from 1: 1 to 20: a mono ether of poly in the range of 1 (C ₂ -C ₄ -alkylene) oxide.

Examples of suitable amines in which the maleic anhydride copolymer is partially imidized are C ₁₂ -C ₂₄ -monoalkyl amines such as oleylamine, dodecylamine, hexadecylamine, octadecylamine, or eicosylamine, monosubstituted Diamines such as N-dodecyl-1,3-diaminopropane, N-octadecyl-1,3-diaminopropane, or N-octadecyl propylene triamine, or aminoalcohols such as aminodecane-10-ol or Aminohexadecane-16-ol.

Examples of suitable alcohols in which the maleic anhydride copolymer is partially esterified as an acid in the mixed ester of glycerine as the additive component b) of the additive mixture are C ₁ -C ₁₈ -alcohols such as methanol, ethanol, ethyl hexanol, or Stearyl alcohol.

Examples of unsaturated C ₁₂ -C ₄₀ -monocarboxylic acids contained as esterification components in the mixed ester of glycerin of the additive mixture include oleic acid, ellidic acid, ricinoleic acid, eleostearic acid, linoleic acid, linolenic acid, and eruka Acids, or dimeric acids based on oleic or linolenic acid.

50 to 80 mole percent of the hydroxy groups are esterified with unsaturated C ₁₂ -C ₄₀ -monocarboxylic acids, and 20 to 50 mole percent of the hydroxy groups are partially imidized and / or partially esterified with the maleic anhydride copolymer Examples of suitable methods for preparing mixed esters of glycerolized glycerin are partial reactions of glycerin with unsaturated C _1r C _{4o -monocarboxylic} acids followed by reaction with partially imidized and / or partially esterified maleic anhydride copolymers. Or partially react the glycerin with a partially imidized and / or partially esterified maleic anhydride copolymer, followed by partial reaction with an unsaturated C ₁₂ -C ₄₀ -monocarboxylic acid. The reaction can be carried out as a solvent process in a melt under vacuum degassing at a temperature of 50 to 135 ° C., preferably in a continuous kneader, or at 85 to 140 ° C., preferably in an aromatic solvent.

In the mixed ester of glycerin of the additive mixture, the C ₁₂ -C ₄₀ -monocarboxylic acid contained as esterification component is preferably between 45 and 52 mass% of C relative to the total mass of C ₁₂ -C ₄₀ -monocarboxylic acid. ₂₂ It consists of a monocarboxylic acid.

The partially imidized maleic anhydride copolymer contained as esterification component in the mixed ester of glycerin as the additive component b) of the additive mixture is preferably a C ₆ -C ₂₄ -mono-bonded in anhydride groups / copolymers in the copolymer. is a mono-alkyl amines partially imidized maleic anhydride -α- methyl styrene copolymer _- the range of C ₆ -C ₂₄ 1: the molar ratio of the alkyl amine 8: 1 to 2.

Examples of partially imidized copolymers of maleic anhydride and α-methylstyrene as additive component c) include partial and / or complete imidization of ammonia, C ₁ -C ₂₄ -monoalkylamine, C ₆ -C ₁₈ -Aromatic monoamines, C ₂ -C ₁₈ -monoaminoalcohols, monoaminoated poly- (C ₂ -C ₄ -alkylene) oxides, and / or monoetherized poly (C ₂ -C ₄ -alkylenes ) Anhydride group copolymer / ammonia, amino group, C ₁ -C ₂₄ monoalkylamine, C ₆ -C ₁₈ -aromatic monoamine, C ₂ -C ₁₈ monoaminoalcohol and monoaminoated poly (C _{2) -} C _{4 -} alkylene) the molar ratio of the oxide is 1: 1 copolymers of the two monomers and having a substantially equimolar ratio: 1 to 20.

The partially imidized copolymer consisting of maleic anhydride and α-methylstyrene as additive component c) is preferably maleic anhydride-α-methylstyrene copolymer partially imidated with C ₆ -C ₂₄ -monoalkylamine And the molar ratio of the anhydride groups in the copolymer to the bound C ₆ -C ₂₄ -monoalkylamine in the copolymer is from 8: 1 to 1.3: 1.

Examples of C ₁₂ -C ₂₄ -monoalkylamines in which the partially imidized maleic anhydride-α-methylstyrene copolymer contained in the additive mixture can be imidized are dodecylamine, tetradecylamine, hexadecylamine, octa Decylamine, oleylamine, or eicosylamine.

Glyceryl monostearate and dimer acid based wax-like oligomer esters as additive component d1) are oligomeric esters described in EP 0 934 921 A1. The glyceryl monostearate component can be prepared by cleaving rapeseed oil with an enzyme, isolating the resulting glycerin monooleate and then hydrating it. A suitable method for preparing the dimeric acid component is to separate the vegetable oil and then dimerize the unsaturated fatty acids formed. Oligomeric esters are prepared by solvent-free oligocondensation with an acid catalyst.

As the additive component d1), a wax-like oligomer ester having an oligomerization degree of 2 to 8 is preferable.

Wax ester d2) with petrolatum-like hardness is the wax ester described in EP 0 970 998 A1.

Wax esters d2) having a petrolatum-like hardness contained in the additive mixtures include guerbet alcohols of the form 2-hexyldecane-1-ol, 2-octyldecane-1-ol or 2-octyldecane-1-ol, And wax esters based on dimer acids obtained by separating vegetable oils having a high oleic acid content and then catalytic dimerization. Wax esters can be prepared by catalytic esterification in a stirred tank reactor in which a vacuum of -0.5 to -1.5 bar is applied in the presence of an acid catalyst at a temperature of from 100 to 160 ° C. from a gerbet alcohol and dimer acid.

Examples of mineral oils that form the main component in the mineral oil composition include crude oils and petroleum distillates having a distillation range of 100 to 500 ° C., such as lubricating oils, kerosine, diesel oils, heating oils, high intermediate fuel oils, petroleum, tractor oils, And cracked gasoline. Mineral oils can also be prepared from the Fischer-Tropsch method up to 30 mass% of synthetic hydrocarbons, sunflower oil, soybean oil, rapeseed oil, or animal oils, biodiesel based modified vegetable oils up to 20 mass%, and Or (10) up to 10 mass% alcohol, such as methanol or ethanol.

Preferred are middle distillate derived mineral oils, crude oils or fuel oils, in particular fuel oils, gas oils or diesel oils with a sulfur content of less than 0.05 mass%.

The mineral oil composition may contain other additive components of the fatty acid mixture type for the total weight of the additive components a + b, a + c, a + d, a + b + c, a + b + c + d, or a + c + d. , Polar nitrogen compounds, preferably polyamines, etheramines, aminoalcohols, amine salts, amides or imides of polyhydric carboxylic acids; Modified copolymers of ethylenically unsaturated C ₄ -C ₂₀ -dicarboxyl anhydrides, non-modified ethylene-vinylester copolymers, C ₇ -C ₃₀ -alcohols, polyalkylene glycols, esters of polyoxyalkylene compounds Or C ₂₂ -monocarboxylic acid relative to the total weight of ether, C ₂ -C ₆ -oxyalkyl-crosslinked C ₁₂ -C ₄₀ -monocarboxylic acid, preferably C ₁₆ -C ₂₄ monocarboxylic acid C ₃ -C ₄ -oxyalkyl-crosslinked unsaturated C ₁₆ -C ₂₄ monocarboxylic acid, hydrocarbon polymer, alkylphenol-aldehyde copolymer, C ₈ -C ₁₀₀ -alkyl substituent having a content of 45 to 52% by mass A total of up to 200% by mass of aromatic compounds, carboxylated polyamines, detergents, corrosion inhibitors, demulsifiers, metal deactivators, cetane number improvers, defoamers and / or cosolvents.

Examples of fatty acid mixtures contained in the mineral oil composition as other additive components include saturated and / or unsaturated C ₆ -C ₄₀ -carboxylic acids such as lauric acid, palmitic acid, oleic acid, linolenic acid, dimer fatty acids, and eggs. There is a mixture of kenyl succinic acid.

Examples of polar nitrogen compounds of the polyamine type contained in the mineral oil composition as other additive components include N-hexadecyl-1,3-diaminopropane, N-octadecyl dipropylenetriamine, N-dodecyl-1,3- Diaminopropane, N, N'-didodecyl-1,3-diamino-propane, and N, N'-dioctadecyl-dipropylenetriamine.

Examples of polar nitrogen compounds of the ether-amine type contained in the mineral oil composition as other additive components include 3-methoxypropylamine, 3-N-octyloxypropyl-1,3-diaminopropane, and 3-N- ( 2.4,6-trimethyldecyloxypropyl) -1,3-diaminopropane.

Examples of amino-alcohol type polar nitrogen compounds contained in the mineral oil composition as other additive components include aminopentan-5-ol, aminoundecane-11-ol, and 2-amino-2-methylpropanol.

Examples of amine salts, amides, or imide types of polar nitrogen compound based amines of polyhydric carboxylic acids include C ₈ -C ₄₀ -amines such as hydrated talcamine, tetradecylamine, eicosylamine, di-octadecylamine, Methyl behenylamine, N-oleyl-1,3-diamino-propane, N-stearyl-1-methyl-1,3-diaminopropane or N-oleyldipropylenetriamine.

Examples of polyvalent carboxylic acids based on polar nitrogen compounds of amine salts or amides of polyhydric carboxylic acid type include phthalic acid, isophthalic acid, terephthalic acid, naphthalin dicarboxylic acid, ethylene diamine tetraacetic acid, and cyclohexane dicarboxylic acid.

Specific examples of the polar nitrogen compounds of the amine salt type contained in the mineral oil composition as other additive components are N-methyl triethanol ammonium distearyl ester chloride and N-methyl triethanol ammonium distearyl ester methosulfate.

Examples of ethylenically unsaturated C ₄ -C ₂₀ -dicarboxylic anhydrides which may be contained as monomer components in the modified copolymers of ethylenically unsaturated C ₄ -C ₂₀ -dicarboxylic acid anhydrides as other additive components are allylsuccinic anhydride. , Bicycloctene dicarboxylic acid anhydride, bicyclooctene dicarboxylic acid anhydride, carbomethoxymaleic anhydride, citraconic anhydride, cyclohexene dicarboxylic acid anhydride, dodecensyl succinic anhydride, glutaconic anhydride, ita Cholic anhydride, maleic anhydride, mesaconic anhydride, methyl bicycloheptene dicarboxylic anhydride and / or methyl cyclohexene dicarboxylic anhydride, with maleic anhydride and / or itaconic anhydride being preferred.

Examples of suitable comonomers for ethylenically unsaturated C ₄ -C ₂₀ -dicarboxylic acid anhydrides which may be contained as monomer components in the modified copolymers of ethylenically unsaturated C ₄ -C ₂₀ -dicarboxylic anhydrides as other additive components. Are ethylenically unsaturated monomers such as C ₂ -C ₂₀ -olefins, C ₈ -C ₂₀ -vinylaromatics, C ₄ -C ₂₁ -acrylic esters, C ₅ -C ₂₂ methacrylic esters, C ₅ -C ₁₄ vinylsilanes , C ₆ -C ₁₅ -acrylate silane, acrylic acid, methacrylic acid, acrylonitrile, vinyl pyridine, vinyl oxazoline, isopropenyl oxazoline, vinyl pyrrolidone, amino-C ₁ -C ₈ -alkyl- (meth) Acrylates, C ₃ -C ₂₀ -vinyl esters, C ₃ -C ₂₀ -vinylethers and / or hydroxy-C ₁ -C ₈ -alkyl- (meth) acrylates. Particularly preferred ethylenically unsaturated monomers are isobutylene, diisobutylene, vinyl acetate, styrene and α-methylstyrene.

Preferred modified copolymers are copolymers of C ₄ -C ₂₀ -ethylenically unsaturated acid anhydrides and ethylenically unsaturated monomers having a molar ratio of 1: 1 to 1: 9 and a mass average molecular weight of 5000 to 500000. These are ammonia, C ₁ -C ₂₄ -monoalkylamine, C ₆ -C ₁₈ -aromatic monoamine, C ₂ -C ₁₈ -monoaminoalcohol, monoaminoated poly (C ₂ -C ₄ -alkylene with a molar mass of 400 to 3000 ) -Oxide, and / or reacted with monoetherized poly (C ₂ -C ₄ -alkylene) oxide having a molar mass of 100 to 10000, anhydride group copolymer / ammonia, C ₁ -C _24- The molar ratio of each monoalkylamine, C ₆ -C ₁₈ -aromatic monoamine, C ₂ -C ₁₈ -monoaminoalcohol or monoaminolated poly- (C ₂ -C ₄ -alkylene) oxide amino group is 1: 1 To 20: 1.

Partial or fully imidized copolymers derived from ethylenically unsaturated C ₄ -C ₂₀ -dicarboxylic anhydrides include C ₁₂ -C ₂₄ -monoalkyl amines such as oleylamine, dodecylamine, hexadecylamine, octadecylamine Or eicosylamine, monosubstituted diamines such as N-dodecyl-1,3-diaminopropane, N-octadecyl-1,3-diaminopropane, or N-octadecyl propylene triamine, or aminoalcohols Particular preference is given to maleic anhydride copolymers which are imidated with, for example, aminodecane-10-ol or aminohexadecane-16-ol.

Examples of C ₇ -C ₃₀ -alcohols which may be contained as mineral additive in the mineral oil composition are dodecanol, stearyl alcohol, and seryl alcohol.

Examples of polyalkylene glycols that may be contained as other additive components in the mineral oil composition are polyethylene glycol, polypropylene glycol, and ethylene oxide-propylene oxide copolymers having a molecular weight of 500 to 5000.

Examples of esters of polyoxyalkylene compounds that may be contained as mineral additives as other additive components include C ₁₀ -C ₂₄ monoalkyl esters or dialkyl esters of polyalkylene glycols such as polyethylene glycol monostearyl esters or polypropylene Glycol dioleate.

Examples of ethers of polyoxyalkylene compounds that may be contained as mineral additives as other additive components include C ₁ -C ₄ -monoalkyl ethers or dialkyl ethers of polyalkylene glycols, such as polyethylene glycol monomethyl ether or polypropylene. Glycol dibutyl ether.

C ₂ -C ₆ -oxyalkyl-crosslinked C ₁₂ -C ₄₀ -monocarboxylic acids which may be contained as mineral additives as other additive components are C ₂ -C ₆ -polyalcohol components and C ₁₂ -C ₄₀ -mono It consists of a carboxylic acid component.

Examples of polyalcohols which may be contained as alcohol components in C ₂ -C ₆ -oxyalkyl-crosslinked C ₁₂ -C ₄₀ -monocarboxylic acids capable of forming other additive components include ethylene glycol, polyalkylene glycol, Glycerin, 1,1,1-tris- (hydroxymethyl) propane, pentaerythreat, and sorbet.

Capable of forming a different additive component C ₂ -C ₆ - oxyalkyl-bridged C ₁₂ -C ₄₀ - monocarboxylic acids of mono carboxylic acid to the carboxylic C ₁₂ -C _40, which may be contained as an acid component Examples are lauric acid, palmitic acid, stearic acid, oleic acid, eladic acid, ricinoleic acid, eleostearic acid, linoleic acid, linolenic acid, and erucic acid, or dioleic acid based on oleic or linolenic acid.

As C ₂ -C ₆ -oxyalkyl-crosslinked C ₁₂ -C ₄₀ -monocarboxylic acids, mixed esters of polyalcohols in which polyalcohols are esterified with a mixture of C ₁₂ -C ₄₀ -monocarboxylic acids are also preferred. . Specific examples of C ₂ -C ₆ -oxyalkyl-crosslinked C ₁₂ -C ₄₀ -monocarboxylic acids include dilinolenic acid, monoesters of C ₃₆ -dimer acid and ethylene glycol, diesters of oleic acid and propylene glycol, and stearic acid Triesters of acids and pentaerythrates.

As a C ₂ -C ₆ -oxyalkyl-crosslinked C ₁₂ -C ₄₀ -monocarboxylic acid, the C ₂₂ -monocarboxylic acid content is 45-52 mass with respect to the total mass of C ₁₆ -C ₂₄ -monocarboxylic acid. Particular preference is given to esters of% C ₃ -C ₄ -polyalcohols and unsaturated C ₁₆ -C ₂₄ monocarboxylic acids.

Examples of unsaturated C ₁₆ -C ₂₄ -monocarboxylic acids that may be contained in the preferred esters of C ₃ -C ₄ -polyalcohols and unsaturated C ₁₆ -C ₂₄ -monocarboxylic acids include oleic acid, linoleic acid, linolenic acid, and There is Mount Ruth.

Examples of hydrocarbon polymers that may be contained as other additive components in the mineral oil composition are copolymers of ethylene and C ₃ -C ₂₀ -α-olefins, such as ethylene-propylene copolymers or ethylene-dodecane copolymers or hydrated diene copolymers. Hydrated polymers of the type polyunsaturated monomers such as hydrated polybutadiene or hydrated polyisoprene having a number average molecular weight of 30000 or less.

Examples of alkyl phenol-aldehyde copolymers that may be contained as mineral additive in the mineral oil composition are copolymers that can be prepared by reacting alkylated phenols such as phenol-propylene oligomer additives with paraformaldehyde.

Examples of aromatic compounds having C ₈ -C ₁₀₀ -alkyl substituents that may be contained as other additive components in the mineral oil composition are Friedel-Crafts of halogenated hydrocarbons such as halogenated polyethylene waxes and aromatic hydrocarbons such as benzene or naphthalin. Krafts) There are compounds that can be prepared by condensation.

Examples of detergents that may be contained as other additive components in the mineral oil composition are aliphatic sulfonic acids, such as C ₈ -C ₃₀ -alkane sulfonates or aromatic-aliphatic alkanes sulfonates, in particular nonylbenzene sulfonic acids, dodecylbenzene sulfonic acids, dododecylbenzene Sulfonic acid, and nonylnaphthalin sulfonic acid.

Examples of demulsifiers that may be contained as other additive components in the mineral oil composition are oxalkylated phenol-formaldehyde condensates, polyalkylene glycol-modified diglysidic ethers, polyesteramines or alkoxylated fatty acids.

Examples of cetane number enhancers that may be included as mineral additives in other mineral components include organic nitrate esters such as ethylhexyl nitrate, cyclohexyl nitrate, or ethoxyethyl nitrate, or soluble organic peroxides, hydroperoxides, or There is a perester.

Preferred antifoams which may be included as mineral additives in other additive components include polyalkylene oxide-siloxane block copolymers and carboxylated polyamines.

Examples of polyalkylene oxide-siloxane block copolymers include combinations of trifunctional siloxane blocks such as monomethyl siloxane groups, difunctional siloxane groups such as dimethyl siloxane groups, and monofunctional siloxane groups such as trimethyl siloxane groups Block copolymers; The preferred length of the siloxane block is 5 to 20 monomer units. Preferred block lengths of the polyalkylene oxide blocks are 2 to 40 monomer units, with polyoxyalkylene blocks comprising ethylene oxide and / or propylene oxide units being preferred.

Examples of carboxylated polyamines as antifoaming agents are the reaction products of C ₈ -C ₂₄ fatty acids and amines such as ethylene diamine, butylene diamine, diethylene triamine and pentaethylene hexamine-1,2-diaminobutanol.

Examples of cosolvents that may be contained as other additive components in mineral oil compositions include gasoline fractions, toluene, xylene, ethyl benzene, isononanol, ethyl hexanol, dodecyl phenol, epoxidized rapeseed oil, and epoxidized There is soybean oil.

The mineral oil composition composed of a mixture of mineral oil as a main component and an additive mixture as a trace component, according to the present invention, the additive mixture as an additive component

a) an ethylene-vinyl ester copolymer having a mass average molecular weight of 3000 to 50000 and an ethylene content of 50 to 90 mass%, and

b) 50 to 80 mole% of the hydroxy groups are esterified with unsaturated C ₁₂ -C ₄₀ monocarboxylic acids, and 20 to 50 mole% of the hydroxy groups are partially imidized and / or partially esterified with the maleic anhydride copolymer Mixed esters of esterified glycerin, and / or

c) partial and / or fully imidized copolymers of maleic anhydride and α-methylstyrene, having a mass average molecular weight of 1500 to 15000 and at least one terminal group based on dimeric α-methylstyrene, and / or

d) wax compositions based on natural starting materials of the following d1) and d2) types:

d1) wax-like oligomeric esters based on glyceryl monostearate and dimer acids, wherein the conversion product corresponds to the following structure up to 90 mass%, and / or

(Where n is 1 to 20, the sum of a + b + c + d is 30, Z is 12 to 20,

이고, X는 H 또는 -CH₂-CH(OH)-CH₂-O-CO-(CH₂)_z-CH₃임)

X is H or -CH ₂ -CH (OH) -CH ₂ -O-CO- (CH ₂ ) _z -CH ₃

d2) wax esters having a petrolatum-like hardness based on at least two different straight and / or branched C ₁₄ -C ₃₆ -alcohols and dimer acids whose conversion product corresponds to at least 80 mass%

Wherein i is 13 to 35; s is 13 to 35, the sum of k + m + n + p is 30 to 34 and (CH ₂ ) _i or (CH ₂ ) _s is straight or straight and branched )

And a mineral oil composition having a content of the additive mixture in the mineral oil of 0.005 to 1% by mass and a mass ratio of the additive component a / b or a / c or a / d of 10:90 to 90:10, respectively.

A first process step of preparing a solution containing from 1 to 60% by mass of an additive component in a mineral oil intermediate distillate at 20 to 90 ° C,

A second process step of homogenizing the solution containing the additive component with the main component mineral oil

A total of 0 to 200 mass% of other additive components based on the additive component a + b, a + c, a + d, a + b + c, a + b + c + d, or a + c + d; It is prepared using a method prepared by the pre-homogenization process added in the first process step and / or the second process step.

Compositions consisting of a mixture of mineral oil as a main component and an additive as a trace component are particularly suitable as flowable media transported at low temperatures and as mineral oils with high lubricity and flowability.

Examples of flowable media transported at low temperatures are crude oil blends transported from the extraction point of the crude oil through the pipeline to the loading and storage, and diesel or heating oil blends transported in the pipeline.

The invention is illustrated in more detail by the following examples.

Characteristic values were determined by the following test method:

Cloud point (CP): DIN EN 23 015

Cold filter plugging point (CFPP): EN 116

Distillation Analysis: EN ISO 3405, ASTM D 86

Acid number: DIN 53402

Saponification number: DIN 53401

Kinematic Viscosity: DIN 51562

Solidification Point: DIN ISO 2207

Penetration: DIN 51580

Vinyl Acetate Content: Method Modified According to ISO 8995, DIN 16778 Part 2

2 g of sample were weighed to 0.001 g precision and dissolved in a 300 ml Erlenmeyer flask containing 70 ml of xylene distilled under reflux and two boiling beads for about 15 minutes. Approximately 30 ml of ethanol were then slowly added through a reflux condenser and the Erlenmeyer flask was removed from the heating plate to add 30 ml of ethanol, 0.5 N KOH and two boiling beads into the burette, and the sample was refluxed for 1 hour. . The reflux of the sample was stopped again, mixed with 30 ml of methanolic-aqueous 0.5 N HCl and two boiling beads and further refluxed for 15 minutes. After addition of 2-3 drops of phenolphthalein solution (1 mass% in ethanol), the sample was titrated by dropwise addition of ethanol 0.5 N KOH while shaking until the color of the sample turned red. Blank values should be measured simultaneously.

Vinyl acetate content (mass%) =

E = initial sample weight (g)

F = titer of ethanol 0.5 N KOH

V = consumption of 0.5 n ethanolic KOH for the sample (ml)

B = consumption of 0.5 n ethanolic KOH relative to the blank value (ml)

Lubricity: Lubricity test according to ISO 12156-1 (adjust the "wear mark diameter" at 60 ° C)

Short time sedimentation test:

To test the sedimentation tendency of recrystallized paraffin in mineral oil, 500 ml of the sample was stored in a graduated cylinder for 16 hours and then the upper 80% by volume of the sample was drained away. The remaining 20% by volume (100 ml) of the sample was homogenized at 40 ° C. and then the cloud point (CP) was measured according to DIN EN 23 015.

SEDAB Filtration Test:

500 ml of mineral oil sample was shaken vertically 20 times, held at 10 ° C. for 16 hours, shaken vertically 10 times, and placed on a suction cap under vacuum of about 200 hPa (50 mm in diameter, pore size 0.8). The entire sample was filtered all at once. The time for the sample to pass through the filter was measured. The SEDAB filtration test was considered successful if the sample passed the filter in less than 120 seconds.

Example 1

1.1 parent product

1.1.1 Diesel without additives

Placement: 16080601 Test DF 1

Feature Analysis:

Cloud Point (CP): + 6 ℃

Cold filter plugging point (CFPP): + 2 ° C

Lubricity Test: 563 μm

Distillation Analysis:

 1.1.2 Additive Components a)

Ethylene-vinylacetate copolymer wax (made by LEUNA Polymer GmbH, vinyl acetate content 28.3 mass%, mass average molecular weight 3150 g / mol).

1.1.3 Additive Components b)

Mixed esters of glycerin were prepared by melt esterification.

Werner & Pfleiderer ZSK 30 twin screw extruder with maleic anhydride-octadecane copolymer (molar ratio 1: 2.2, acid value 40, number average molecular weight 2400) partially esterified with dodecyl alcohol at 3.8 kg / h A side flow dose unit for liquid medium and two vacuum degassing zones in a feed screw (L / D ratio 48) and a dosing belt weighing continuous scale and were melted at 90 ° C. Glycerin dietyronic acid ester is added at 2.0 kg / h via a side flow dosing unit from a storage tank heated to 90 ° C., reacted at 110 ° C. in a first reaction zone (4.5 min residence time), degassed, and a second Reaction at 130 ° C. in the reaction zone (3.5 min residence time), degassing, self-cleaning melt filter at 85 ° C. using a melt gear pump (extrex SP, Maag pump systems) Transferred into and molded into pastels in a forming press fitted with a cooling conveyor.

The acid value of the resulting mixed ester of glycerin was 8.5 and the melting point range was 52 to 59 ° C.

1.2 Preparation of Solutions Containing Additives in Mineral Oil Intermediate Distillates

20 kg of additive component b) were mixed with 60 kg of a 50% solution of additive component a) in an aromatic hydrocarbon mixture (Solvesso) for 120 minutes at 65 ° C. in a stirred tank reactor and the mixture was transferred to a storage tank.

1.3 Preparation and Testing of Mineral Oil Compositions

The product flow of the additive-free diesel flowing at 800 kg / min (batch 16080601) was injected with 0.48 kg / min of the additive solution according to 1.2 and the mixture was transferred to a storage tank.

As a result of testing the mineral oil formulation for low temperature resistance, the CFPP value was -10 ° C. Lubricity test indicates that the "wear trace diameter" is 405 μm.

The CP value of the short time settling test was + 7 ° C. The SEDAB filtration test was considered passed (84 seconds in 500 ml).

When a mineral oil blend containing only copolymer wax as an additive was prepared under the same conditions, the CFPP value was -3 ° C and the "wear trace diameter" was 520 μm. The CP value of the short time settling test was +10 ° C. The SEDAB filtration test was considered failed (greater than 120 seconds in 468 ml).

Example 2

2.1 Parent Product

2.1.1 Diesel without additives

Placement: 030210 Exam DF 2

Feature Analysis:

Cloud Point (CP): + 7 ℃

Cold filter plugging point (CFPP): + 2 ° C

Lubricity Test: 556 μm

Distillation Analysis:

2.1.2 Additive Components a)

10 mass% of partially saponified ethylene-vinylacetate copolymer wax (mass average molecular weight 1850 g / mol, vinyl acetate content of unsaponified ethylene-vinylacetate copolymer wax, 32.5 mass% saponification degree) and unsaponified Ethylene-vinyl acetate copolymer wax (manufactured by Rona Polymer GmbH, 31% by mass of vinyl acetate, mass average molecular weight 2800 g / mol) 90 mass% was mixed.

2.1.3 Additive Components b)

Mixed esters of glycerin were prepared by melt esterification.

WSKINER & FLYDERERZSK at 3.6 kg / h of α-methylstyrene maleic anhydride-octadecane copolymer (molar ratio 1.3: 1.0, acid value 42, melting point 70 ° C.) partially imidized with C ₁₆ -C ₁₈ -fatty amine The feed screw of a 30 twin screw extruder (L / D ratio 48) was administered in a side flow dosing unit for liquid medium and two vacuum degassing zones, and a belt weighing continuous scale for dosing and dissolved at 110 ° C. with heat. Glycerin dioleyl ester is added to the melt at 1.14 kg / h from a storage tank heated to 90 ° C. via a side flow dosing unit and the melt is reacted at 115 ° C. in a first reaction zone (retention time 4.5 min) and degassed. , React in a second reaction zone (retention time 3.5 minutes) at 130 ° C., degas, transfer into a self-cleaning melt filter using a melt gear pump (Extrex SP, Marg Pump Systems) at 85 ° C., and cool It was molded into pastels in a molding press fitted with a conveyor.

The acid value of the mixed ester of produced glycerin was 4.5, and the melting point range was 55-66 degreeC.

2.1.4 Other Additives

Dodecylacrylate-ethylacrylate copolymer (molar ratio 2: 1, number average molecular weight 13500)

2.2 Preparation of Solutions Containing Additives in Mineral Oil Intermediate Distillates

Additive component b) 20 kg, 40 kg of 60% solution of additive component a) in C ₈ -C ₉ -diesel aromatic fraction, 20 kg of 10% solution of other additive components, dodecylacrylate-ethylacrylate air in toluene The coalescence was stirred for 120 min at 65 ° C. in a stirred tank reactor and the mixture was transferred to a storage tank.

2.3 Preparation and Testing of Mineral Oil Compositions

The product flow of the additive-free diesel flowing at 800 kg / min (batch 030210 DGO) was injected with an additive solution according to 2.2 at 0.12 kg / min and the mixture was transferred to a storage tank.

As a result of testing the mineral oil blend for low temperature resistance, the CFPP value was -11 ° C. Lubricity test indicates that the "wear trace diameter" is 402 μm.

The CP value of the short time settling test was + 9 ° C. The SEDAB filtration test was considered passed (96 seconds in 500 ml).

When a mineral oil formulation containing only non-saponified copolymer wax as an additive was prepared under the same conditions, the CFPP value was -5 ° C and the "wear trace diameter" was 528 μm. The CP value of the short time settling test was + 12 ° C. The SEDAB filtration test was considered failed (greater than 120 seconds in 468 ml).

Example 3

3.1 Starting Material

3.1.1 Heating oil without additives

Placement: 030225 Test HEL Type 1

Feature Analysis:

Cloud point (CP): + 1 ° C;

Cold filter plugging point (CFPP): -1 ° C

Distillation Analysis:

 3.1.2 Additive Components a)

Oxidized ethylene-vinyl acetate copolymer wax (mass average molecular weight 950 g / mol, acid value 18 mg KOH / g, OH value 70 mg KOH / g) 15 mass% and unoxidized ethylene-vinylacetate copolymer wax (loin 85 mass% of vinyl acetate content 32 mass%, mass mean molecular weight 2300 g / mol) were mixed.

3.1.3 Additive Components b)

Mixed esters of glycerin were prepared by melt esterification.

Werner & Flyderer ZSK 30 with 4.2 kg / h of octadecane maleic anhydride-octadecane copolymer (molar ratio 1.4: 1.0, acid value 57, melting point 55 ° C.) partially imidated with C ₁₆ -C ₁₈ -fatty amine The feed screw of a twin screw extruder (L / D ratio 48) was administered in a side flow dosing unit for liquid medium and two vacuum degassing zones, and a belt weighing continuous scale for dosing and dissolved at heat at 115 ° C. An acid mixture of glycerin and erucic acid and oleic acid is added to the melt at 2.72 kg / h from a storage tank heated to 90 ° C. via a side flow dosage unit and the melt is added at 120 ° C. in a first reaction zone (retention time 4.5 Min), degassing, reacting at 130 ° C. in the second reaction zone (retention time 3.5 min), degassing, and self-cleaning using a melt gear pump (Extrex SP, Maag Pump Systems) at 95 ° C. Transferred into the wash melt filter and molded into pastels in a molding press fitted with a cooling conveyor,

The acid value of the mixed ester of produced glycerin was 3.5, and the melting point range was 55-64 degreeC.

3.2 Preparation of solutions containing additive components in mineral oil intermediate distillates

25 kg of additive component b) were mixed with 50 kg of a 60% solution of additive component a) in a C ₈ -C ₉ -diesel aromatic fraction for 120 minutes at 65 ° C. in a stirred tank reactor and the mixture was transferred to a storage tank.

3.3 Preparation and Testing of Mineral Oil Compositions

The product flow of the additive-free heating oil flowing at 800 kg / min (batch 030225) was injected with 0.24 kg / min of the additive solution according to 3.2 and the mixture was transferred to a storage tank.

As a result of testing the mineral oil blend for low temperature resistance, the CFPP value was -15 ° C.

When a mineral oil formulation containing only copolymer wax as an additive was prepared under the same conditions, the CFPP value was -12 ° C.

Example 4

4.1 Starting Material

4.1.1 Heating oil without additives

Placement: 030218 Exam HEL 2

Feature Analysis:

Cloud point (CP): + 2 ° C;

Cold filter plugging point (CFPP): -1 ° C

Distillation Analysis:

4.1.2 Additive Components a)

Ethylene-vinylacetate copolymer grafted with vinyl acetate (made according to DD 293 125 A5, total vinyl acetate content 38 mass%, mass average molecular weight 3400 g / mol, vinyl acetate content of grafted ethylene-vinylacetate copolymer wax 10 mass% of 32.5 mass%, saponification degree 32 mol%) and 90 mass% of ungrafted ethylene-vinylacetate copolymer wax (Rona Polymer GmbH, Inc., vinyl acetate content 32.5 mass average molecular weight 2400 g / mol) Mixed.

4.1.3 Additive Components b)

Mixed esters of glycerin were prepared by melt esterification.

Α-methylstyrene maleic anhydride copolymer (mol ratio 1.1: 1.0, acid value 55, melting point 64 ° C.) partially esterified with octadecyl alcohol at 4.0 kg / h Werner & Flyderer ZSK 30 twin screw extruder (L / D ratio Side flow dosage units for the liquid medium and two vacuum degassing zones in the feed screw of 48) and dosing belt weighing continuous scale and were thermally dissolved at 90 ° C. An acid mixture of glycerine ester and erucic acid / oleic acid / linolenic acid (molar ratio 6: 1: 1: 1) is added to the melt at 2.4 kg / h from a storage tank heated at 110 ° C. via a side flow dosage unit, and The melt is reacted at 125 ° C. in the first reaction zone (retention time 4.5 minutes), degassed, at 135 ° C. in the second reaction zone (retention time 3.5 minutes), degassed and at 95 ° C. melt gear pump (X Trex SP, Marg Pump Systems) was used to transfer into a self-cleaning melt filter and molded into pastels in a molding press fitted with a cooling conveyor.

The acid value of the mixed ester of the produced glycerin was 5.5, and the melting point range was 53-63 degreeC.

4.1.4 Other Additives Ingredients

Polyethylene Glycol Monomethyl Ether _, Number Average Molecular Weight 1500

2-ethylhexylacrylate-ethylacrylate copolymer (molar ratio 2: 1)

4.2 Preparation of Solutions Containing Additives in Mineral Oil Intermediate Distillates

Additive component b) 20 kg, 20 kg 60% solution of additive component a) in the C ₈ -C ₉ -diesel aromatic fraction, and 1 kg of other additive components, polyethylene glycol monomethyl ether (number average molecular weight 1500), and other additives 8 kg of a 10% solution of the components, ethylhexylacrylate-ethylacrylate copolymer in toluene (molar ratio 2: 1) were introduced into a stirred tank reactor, stirred at 65 ° C. for 120 minutes in the stirred tank reactor, and The mixture was transferred to a storage tank.

4.3 Preparation and Testing of Mineral Oil Compositions

The product flow of the additive-free heating oil flowing at 800 kg / min (batch 030225) was injected with 0.28 kg / min of the additive solution according to 4.2 and the mixture was transferred to a storage tank.

As a result of testing the mineral oil blend for low temperature resistance, the CFPP value was -14 ° C.

When the mineral oil blend containing only copolymer wax as an additive was prepared under the same conditions, the CFPP value was -1 ° C.

Example 5

5.1 Starting Material

5.1.1 Diesel without additives

Placement: 16080601 Test DF 1

Feature Analysis:

Cloud Point (CP): + 6 ° C:

Cold filter plugging point (CFPP): + 2 ° C

Distillation Analysis:

5.1.2 Additive Components a)

Ethylene-vinylacetate copolymer wax (manufactured by Rona Polymer GmbH, 32% by mass vinyl acetate, mass average molecular weight 2300 g / mol)

5.1.3 Additive Components c)

Α-methylstyrene-maleic anhydride copolymer partially imidated with C ₁₆ -C ₁₈ -fatty amine (number average molecular weight 12800 g / mol, acid value 35)

Preparation of the additive component c)

81 L of α-methylstyrene, 7 L of α-methylstyrene-dimer, and 20 L of acetone were placed in a 500 L stirred tank reactor, and the stirred tank reactor was heated to 59 ° C. A solution of 52 kg of maleic anhydride and 2.4 kg of azoisobutyric acid dinitrile in 150 L of acetone was administered to a stirred tank reactor over 6 hours and the reaction mixture was stirred at 70-73 ° C. for an additional 6 hours.

The acid value of the copolymer (MCP5) analysis sample is 445 mg KOH per gram of copolymer. NMR test results show 1.3 α-methylstyrene-dimer end groups per mole.

The polymer solution at 54-56 [deg.] C. was subsequently fed to a dual drum vacuum drier and the ground copolymer was separated from volatile components and acetone having a residual content of 1.1 mass%.

382 kg of C ₈ -C ₉ -diesel aromatic fraction boiling above 160 ° C. and 122 kg of C ₁₆ -C ₁₈ -fatty amine were placed in a 500 L stirred tank reactor and heated to 130 ° C. to partially imidize the copolymer. 135.5 kg of the copolymer was continuously added to this solution over 4 hours. The internal temperature of the stirred tank reactor was raised to 180-185 ° C. and approximately equivalent amounts of C ₈ -C ₉ -diesel aromatic fractions were distilled off at azeotropy to form water. After 6 hours, the total reaction time at 160-190 ° C., 8.5 kg of water and 10.2 kg of solvent were distilled off. A 40% solution of partially imidized copolymer having an acid value of 35 and a number average molecular weight of 12800 g / mol was obtained.

5.1.4 Other Additives Ingredients

Mixture of C ₃ -oxyalkyl-crosslinked unsaturated C ₁₈ -C ₂₄ -carboxylic acid (92 mol% esterification, 32 mass% of C ₁₈ -unsaturated fatty acid, 48 mass% of C ₂₂ -unsaturated fatty acid, iodine 96)

Ethylacrylate-ethylhexylacrylate copolymer (molar ratio 3: 2, number average molecular weight 13500)

5.2 Preparation of solutions containing additive components in mineral oil intermediate distillates

25 kg of a 40% solution of the additive component c) in the C ₈ -C ₉ -diesel aromatic fraction, 50 kg of a 50% solution of the additive component a) in the aromatic hydrocarbon mixture (Solvesso), another additive component C ₃ -oxyalkyl- 20 kg of a mixture of cross-linked unsaturated C ₁₈ -C ₂₄ -carboxylic acid, and 19 kg of a 20% solution of other additive components, ethyl acrylate-ethylhexyl acrylate copolymer in toluene were added at 90 ° C. in a stirred tank reactor. Mix for minutes and transfer the mixture to a storage tank.

5.3 Preparation and Testing of Mineral Oil Formulations

The product flow of the additive-free diesel flowing at 800 kg / min (batch 16080601) was injected with an additive solution according to 5.2 at 0.48 kg / min and the mixture was transferred to a storage tank.

As a result of testing the mineral oil formulation for low temperature resistance, the CFPP value was -16 ° C. The CP value of the short time sedimentation test was + 5 ° C. The SEDAB filtration test was considered passed (76 seconds in 500 ml).

When a mineral oil blend containing only copolymer wax as an additive was prepared under the same conditions, the CFPP value was -3 ° C and the CP value of the short settling test was + 10 ° C. The SEDAB filtration test was considered failed (greater than 120 seconds in 468 ml).

Example 6

6.1 Starting Material

6.1.1 Diesel without additives

Placement: 030210 Exam DF 2

Feature Analysis:

Cloud point (CP): + 7 ° C;

Cold filter plugging point (CFPP): + 2 ° C

Distillation Analysis:

6.1.2 Additive Components a)

10 mass% of partially saponified ethylene-vinylacetate copolymer wax (mass average molecular weight 1600 g / mol, vinyl acetate content of unsaponified ethylene-vinylacetate copolymer wax, 32 mass% saponification degree) and ethylene-vinyl 90 mass% of acetate copolymer wax (Rona Polymer GmbH, 32 mass% of vinyl acetate content, mass average molecular weight 2300 g / mol) was mixed.

6.1.3 Additives Components c)

Α-methylstyrene-maleic anhydride copolymer partially imidized with dodecylamine (number average molecular weight 14200 g / mol, acid value 56)

Preparation of additive components c)

83 L of α-methylstyrene, 5 L of α-methylstyrene-dimer, and 62 kg of maleic anhydride, and 110 L of 2-butanone were placed in a 500 L stirred tank reactor, and the stirred tank reactor was heated to 70 ° C. A solution of 1.9 kg of dibenzoyl peroxide and 52 L of 2-butanone was administered to a stirred tank reactor over 2 hours and the reaction mixture was stirred at 72-73 ° C. for an additional 10 hours.

The acid value of the copolymer analysis sample was 452 mg KOH per gram of copolymer. NMR test results showed 1.1 alpha -methylstyrene-dimer end groups per mole. The polymer solution at 70 ° C. was continuously administered to a 500 L stirred tank reactor containing 280 L of 2-ethyl hexanol and heated to 150 ° C. to remove 2-butanone-2 by distillation. 104 kg of C ₁₆ -C ₁₈ -fatty amine was added over 4 hours while the temperature was raised to 165-185 ° C. and a small amount of 2-ethyl hexanol was distilled off with water.

A 40% solution of partially imidized copolymer c) with an acid value of 56 and a number average molecular weight of 14200 g / mol was obtained.

6.1.4 Other Additives Ingredients

Triesters of pentaerythrates with oleic acid diethylene glycol monolauroyl ester

6.2 Preparation of Solutions Containing Additives in Mineral Oil Intermediate Distillates

25 kg of 40% solution of additive component c) in 2-ethyl hexanol, 50 kg of 60% solution of additive component a) in C ₈ -C ₉ -diesel aromatic fraction, tree of pentaerythrates with other additive component oleic acid 20 kg of ester, and 1 kg of other additive components, diethylene glycol monolaurol ester, were introduced into a stirred tank reactor, stirred at 65 ° C. for 90 minutes, and the mixture was transferred to a storage tank.

6.3 Preparation and Testing of Mineral Oil Formulations

The product flow of the additive-free diesel flowing at 800 kg / min (batch 030210) was injected with 0.24 kg / min of the additive solution according to 6.2 and the mixture was transferred to a storage tank.

As a result of testing the mineral oil formulation for low temperature resistance, the CFPP value was -7 ° C. The CP value of the short time settling test was +7 ° C. The SEDAB filtration test was considered to have passed (82 seconds in 500 ml).

When the mineral oil formulation containing only copolymer wax as an additive was prepared under the same conditions, the CFPP value was -5 ° C. The CP value of the short time settling test was + 12 ° C. The SEDAB filtration test was considered failed (greater than 120 seconds in 468 ml).

Example 7

7.1 Starting Material

7.1.1 Heating oil without additives

Placement: 030225 Exam HEL 1

Feature Analysis:

Cloud Point (CP): + l ℃:

Cold filter plugging point (CFPP): -1 ° C

Distillation Analysis:

7.1.2 Additive Components a)

15 mass% oxidized ethylene-vinylacetate copolymer wax (mass average molecular weight 950 g / mol, acid value 18 mg KOH / g, OH value 70 mg KOH / g) and unoxidized ethylene-vinyl acetate copolymer wax (loin 85 mass% of vinyl acetate content 32 mass%, mass mean molecular weight 2300 g / mol) were mixed.

7.1.3 Additive Components c)

Α-methylstyrene-maleic anhydride copolymer partially imidated with C ₁₂ -C ₁₄ fatty amine (number average molecular weight 7000 g / mol, acid value 25)

Preparation of additive components c)

83 L of α-methylstyrene, 12 L of α-methylstyrene-dimer, and 62 kg of maleic anhydride and 140 L of 1,2-dichloroethane were placed in a 500 L stirred autoclave and the stirred autoclave was heated to 90 ° C. A solution of 2.5 kg of tert-butylperoxy-2-ethyl hexanoate and 55 L of 1,2-dichloroethane was administered to the stirring autoclave over 2 hours and the reaction mixture was stirred at 90-93 ° C. for an additional 10 hours. .

The acid value of the copolymer analysis sample was 430 mg KOH per gram of copolymer, and as a result of the NMR test, it was 1,4 α-methylstyrene-dimer end group per mole.

The polymer solution at about 90 ° C. was fed to a 500 L stirred tank reactor containing 280 L of C ₈ -C ₉ -diesel aromatic fraction and 122 kg of C ₁₂ -C ₁₄ -fatty amine mixture, and heated to 160 ° C. or lower, 1,2 -Dichloroethane and reaction water were removed by distillation from imidization.

A 40% solution of partially imidized copolymer c) in a C ₈ -C ₉ -diesel aromatic fraction having an acid value of 25 and a number average molecular weight of 7000 g / mol was obtained.

7.1.4 Other Additives

Diester of Ethylene Glycol with Erucic Acid N- (2-hydroxyethyl) oleylamine

7.2 Preparation of Solutions Containing Additives in Mineral Oil Intermediate Distillates

50 kg of a 60% solution of the additive component a) in the C ₈ -C ₉ -diesel aromatic fraction, 20 kg diester of ethylene glycol with erucic acid as another additive component, and 3 kg of other additive components, N- (2- Hydroxyethyl) oleylamine is added to a stirred tank reactor containing 25 kg of a 40% solution of additive component c) in a C ₈ -C ₉ -diesel aromatic fraction at 65 ° C., stirred at 65 ° C. for 90 minutes, The mixture was transferred to a storage tank.

7.3 Preparation and Testing of Mineral Oil Formulations

The product flow of the additive-free heating oil flowing at 800 kg / min (batch 030225) was injected with 0.24 kg / min of the additive solution according to 7.2 and the mixture was transferred to a storage tank.

As a result of the mineral oil blend test for low temperature resistance, the CFPP value was -15 ° C.

When a mineral oil formulation containing only copolymer wax as an additive was prepared under the same conditions, the CFPP value was -13 ° C.

Example 8

8.1 Starting Material

8.1.1 Diesel without additives

Placement: 16080601 Test DF 1

Feature Analysis:

Cloud point (CP): + 6 ° C .;

Cold filter plugging point (CFPP): + 2 ° C

Distillation Analysis:

8.1.2 Additive Components a)

Ethylene-vinylacetate copolymer wax (manufactured by Rona Polymer GmbH, 32% by mass of vinyl acetate, mass average molecular weight 2300 g / mol).

8.1.3 Additive Components c)

Α-methylstyrene-maleic anhydride copolymer partially imidated with stearyl amine (mass average molecular weight 13750 g / mol, acid value 51)

Preparation of additive components c)

81 L of α-methylstyrene, 7 L of α-methylstyrene-dimer, and 20 L of acetone were placed in a 500 L stirred tank reactor, and the stirred tank reactor was heated to 59 ° C. A solution of 52 kg of maleic anhydride and 2.4 kg of azoisobutyric acid dinitrile in 150 L of acetone was administered to a stirred tank reactor over 6 hours and the reaction mixture was stirred at 70-73 ° C. for an additional 6 hours.

The acid value of the copolymer analysis sample is 445 mg KOH per gram of copolymer. NMR test results show 1.3 α-methylstyrene-dimer end groups per mole.

The polymer solution at 54-56 [deg.] C. was continuously fed to a dual drum vacuum drier and the milled copolymer was separated from acetone and volatile components having a residual content of 1.1 mass%.

The copolymer was partially imidized by placing 382 kg of a C ₈ -C ₉ -diesel aromatic fraction boiling above 160 ° C. and 135 kg of stearyl amine in a 500 L stirred tank reactor and heating to 130 ° C. 135.5 kg of copolymer was added continuously to this solution over 4 hours. The temperature inside the stirred tank reactor was raised to 180-185 ° C., and approximately the same amount of C ₈ -C ₉ -diesel aromatic fraction was distilled off at azeotropy to form water. After 6 hours, the total reaction time at 160-190 ° C., 8.5 kg of water and 10.2 kg of solvent were distilled off.

A 40% solution of partially imidized copolymer having an acid value of 51 and a mass average molecular weight of 13750 g / mol was obtained.

8.1.4 Other Additives

A mixture of C ₃ -oxyalkyl-crosslinked unsaturated C ₁₈ -C ₂₄ carboxylic acids (92 mol% esterification, 32 mass% C ₁₈ -unsaturated fatty acid content, 48 mass% C ₂₂ -unsaturated fatty acid content, iodine number 96)

Ethylacrylate-octadecylacrylate copolymer (molar ratio 4: 1, number average molecular weight 8400)

8.2 Preparation of Solutions Containing Additives in Mineral Oil Intermediate Distillates

25 kg of a 40% solution of the additive component c) in the C ₈ -C ₉ -diesel aromatic fraction, 50 kg of a 50% solution of the additive component a) in the aromatic hydrocarbon mixture (Solvesso), another additive component C ₃ -oxyalkyl- Mix 20 kg of cross-linked unsaturated C ₁₈ -C ₂₄ -carboxylic acid and 19 kg of 20% solution of other additive components, ethylacrylate-octadecylacrylate copolymer in toluene at 65 ° C. in a stirred tank reactor for 90 minutes And the mixture was transferred to a storage tank.

8.3 Preparation and Testing of Mineral Oil Formulations

The product flow of the additive-free diesel flowing at 800 kg / min (batch 16080601) was injected with 0.48 kg / min of the additive solution according to 8.2 and the mixture was transferred to a storage tank.

As a result of testing the mineral oil formulation for low temperature resistance, the CFPP value was -17 ° C.

When a mineral oil formulation containing only copolymer wax as an additive was prepared under the same conditions, the CFPP value was -3 ° C.

Example 9

9.1 Starting Material

9.1.1 Diesel without additives

Placement: 16080601 Test DF 1

Feature Analysis:

Cloud Point (CP): + 6 ° C:

Cold filter plugging point (CFPP): + 2 ° C

Lubricity Test: 563 μm

Distillation Analysis:

9.1.2 Additive Components a)

Ethylene-vinylacetate copolymer wax (manufactured by Rona Polymer GmbH, 32% by mass of vinyl acetate, mass average molecular weight 2300 g / mol).

9.1.3 Additive Components d2)

Wax ester (hardness similar to petrolatum, acid value 7.9 mg KOH / g, saponification value 113 mg KOH / g, kinematic viscosity 20.6 mm ² / s, solidification point 34.5 ° C)

Preparation of additive components d2)

A mixture of 25 kg of dimer acid (unsaturated C ₁₈ -fatty acid derived dimerization product, average carbon number 36), 5 kg of stearyl alcohol and 7 kg of cetyl alcohol was dissolved thermally at 120 ° C. while introducing an inert gas in a 70 L stirred tank reactor. 50 g of H ₂ SO ₄ was added and the reaction water was removed until the acid value became 7.9 mg KOH / g. After cooling the melt, the catalyst was neutralized with 0.5 L of 10% NaHCO ₃ , the aqueous phase was separated off and the wax ester was discharged.

9.1.4 Other Additives

Ethylacrylate-ethylhexylacrylate copolymer (molar ratio 3: 2, number average molecular weight 13500)

9.2 Preparation of Solutions Containing Additive Components in Mineral Oil Intermediate Distillates

25 kg of 40% solution of additive component d2) in C ₈ -C ₉ -diesel aromatic fraction, 50 kg of 50% solution of additive component a) in aromatic hydrocarbon mixture (Solvesso), and 15 kg of 20% solution of other additive components The ethylacrylate-ethylhexylacrylate copolymer in toluene was mixed in a stirred tank reactor at 65 ° C. for 90 minutes and the mixture was transferred to a storage tank.

9.3 Preparation of Mineral Oil Compositions

The product flow of the additive-free diesel flowing at 800 kg / min (batch 16080601) was injected with 0.48 kg / min of the additive solution according to 9.2 and the mixture was transferred to a storage tank.

As a result of testing the mineral oil blend for low temperature resistance, the CFPP value was -14 ° C. Lubricity test indicates that the "wear mark diameter" is 412 μm.

When the mineral oil composition containing only the unmodified copolymer wax a) as an additive was prepared under the same conditions, the CFPP value was -3 ° C.

Example 10

10.1 Starting Material

10.1.1 Diesel without Additives

Placement: 030210 Exam DF 2

Feature Analysis:

Cloud Point (CP): + 7 ℃:

Cold filter plugging point (CFPP): + 2 ° C

Lubricity Test: 556 μm

Distillation Analysis:

10.1.2 Additive Components a)

20 mass% of partially saponified ethylene-vinylacetate copolymer wax (mass average molecular weight 1600 g / mol, vinyl acetate content of unsaponified ethylene-vinylacetate copolymer wax, 32 mass% saponification degree) and ethylene-vinyl 80 mass% of acetate copolymer wax (Rona Polymer GmbH, 32 mass% of vinyl acetate content, mass average molecular weight 2300 g / mol) was mixed.

10.1.3 Additive Components d2)

Wax ester (similar hardness to petrolatum, acid value 8.6 mg KOH / g , saponification value 118 mg KOH / g, kinematic viscosity 23.1 mm ² / s, solidification point 35.2 ° C)

Preparation of additive components d2)

A mixture of 25 kg of dimer acid (unsaturated C ₁₈ -fatty acid derived dimerization product, average carbon number 36), 5 kg of stearyl alcohol, and 8 kg of eicosane alcohol was heated at 120 ° C. while introducing an inert gas in a 70 L stirred tank reactor. After dissolving, 50 g of H ₂ SO ₄ was added and reacted with removing the reaction water until the acid value became 8.6 mg KOH / g. After cooling the melt, the catalyst was neutralized with 1.0 L of 10% NaHCO ₃ , the aqueous phase was separated off and the wax ester was discharged.

10.1.4 Other Additives Ingredients

Triesters of pentaerythrates with oleic acid

10.2 Preparation of Solutions Containing Additives in Mineral Oil Intermediate Distillates

22 kg of a 50% solution of the additive component d2) in 2-ethyl hexanol, 50 kg of a 60% solution of the additive component a) in the C ₈ -C ₉ -diesel aromatic fraction, and pentaerythrate with oleic acid as another additive component 20 kg of triester were introduced into a stirred tank reactor, stirred at 65 ° C. for 90 minutes, and the mixture was transferred to a storage tank.

10.3 Preparation of Mineral Oil Compositions

The additive solution according to 10.2 was injected at 0.30 kg / min into the product flow (batch 030210) of the additive-free diesel flowing at 800 kg / min. The mixture was transferred to a storage tank.

As a result of testing the mineral oil composition for low temperature resistance, the CFPP value was -8 ° C. Lubricity test indicates that the "wear mark diameter" is 425 μm.

When the mineral oil composition containing only the unmodified copolymer wax a) as an additive was prepared under the same conditions, the CFPP value was -5 ° C and the "wear trace diameter" was 528 µm .

Example 11

11.1 Starting Material

11.1.1 Heating oil without additives

Placement: 030225 Exam HEL 1

Feature Analysis:

Cloud Point (CP): + 1 ℃

Cold filter plugging point (CFPP): -1 ° C

11.1.2 Additive Components a)

Oxidized ethylene-vinylacetate copolymer wax (mass average molecular weight 950 g / mol, acid value 18 mg KOH / g, OH value 70 mg KOH / g) 25 mass% and unoxidized ethylene-vinylacetate copolymer wax (loin 75 mass% of vinyl acetate content 32 mass% of vinyl acetate content, and a mass average molecular weight 2300 g / mol) were mixed.

11.1.3 Additive Components d1)

Oligomeric esters prepared according to EP 0 934 921 Al by solvent-free oligocondensation from an acid catalyzed reaction from glyceryl monostearate and dimer acid (unsaturated C ₁₈ -fatty acid derived dimerization product, average carbon number 36) (Acid value 12 mg KOH / g, saponification value 175 mg KOH / g, kinematic viscosity (100 ° C) 65 mm ² / s, solidification point 42 ° C)

11.1.4 Other Additives

N- (2-hydroxyethyl) oleylamine

11.2 Preparation of Solutions Containing Additives in Mineral Oil Intermediate Distillates

50 kg of a 60% solution of additive component a) in a C ₈ -C ₉ -diesel aromatic fraction, and 3 kg of other additive components, N- (2-hydroxyethyl oleylamine, C ₈ -C ₉ -diesel at 65 ° C It was added to a stirred tank reactor containing 23 kg of a 40% solution of the additive component d1) in the aromatic fraction, stirred at 65 ° C. for 90 minutes, and the mixture was transferred to a storage tank.

11.3 Preparation of Mineral Oil Compositions

The product solution of the additive-free heating oil flowing at 800 kg / min (batch 030225) was injected with 0.28 kg / min of the additive solution according to 11.2 and the mixture was transferred to a storage tank.

As a result of testing the mineral oil formulation for low temperature resistance, the CFPP value was -16 ° C.

When the mineral oil composition containing only the unmodified copolymer wax a) as an additive was prepared under the same conditions, the CFPP value was -130 ° C.

Example 12

12.1 Starting Material

12.1.1 Diesel without Additives

Placement: 16080601 Test DF 1

Feature Analysis:

Cloud Point (CP): + 6 ℃

Cold filter plugging point (CFPP): + 2 ° C

Distillation Analysis:

12.1.2 Additive Components a)

Ethylene-vinylacetate copolymer wax (manufactured by Rona Polymer GmbH, 32% by mass of vinyl acetate, mass average molecular weight 2300 g / mol).

12.1.3 Additive Components d1)

Oligomeric esters prepared according to EP 0 934 921 Al by solvent-free oligocondensation from an acid catalyzed reaction from glyceryl monostearate and dimer acid (unsaturated C ₁₈ -fatty acid derived dimerization product, average carbon number 36) (Acid value 14 mg KOH / g, saponification value 185 mg KOH / g, kinematic viscosity (100 ° C) 76 mm ² / s, solidification point 42 ° C)

12.1.4 Other Additives

Mixture of C ₃ -oxyalkyl-crosslinked unsaturated C ₁₈ -C ₂₄ -carboxylic acid (92 mol% esterification, 32 mass% of C ₁₈ -unsaturated fatty acid, 48 mass% of C ₂₂ -unsaturated fatty acid, iodine 96)

Ethylacrylate-octadecylacrylate copolymer (molar ratio 4: 1, number average molecular weight 8400)

12.2 Preparation of Solutions Containing Additives Components in Mineral Oil Intermediate Distillates

25 kg of 50% solution of additive component d1) in C ₈ -C ₉ -diesel aromatic fraction, 50 kg of 50% solution of additive component a) in aromatic hydrocarbon mixture (Solvesso), other additive component C ₃ -oxyalkyl- 12 kg of cross-linked unsaturated C _Is- C ₂₄ -carboxylic acid, and 15 kg of 20% solution of other additive components, ethylacrylate-octadecylacrylate copolymer in toluene, were stirred for 90 minutes at 65 ° C. in a stirred tank reactor. Was mixed and the mixture was transferred to a storage tank.

12.3 Preparation and Testing of Mineral Oil Compositions

The product flow of the additive-free diesel flowing at 800 kg / min (batch 16080601) was injected with 0.52 kg / min of the additive solution according to 12.2 and the mixture was transferred to a storage tank.

As a result of testing the mineral oil blend for low temperature resistance, the CFPP value was -18 ° C.

When the mineral oil composition containing only the unmodified copolymer wax a) as an additive was prepared under the same conditions, the CFPP value was -3 ° C.

Claims (12)

A mineral oil composition composed of a mixture of mineral oil as a main component and an additive as a trace component, and the additive mixture is used as an additive component. a) an ethylene-vinyl ester copolymer having a mass average molecular weight of 3000 to 50000 and an ethylene content of 50 to 90 mass%, and b) 50 to 80 mole% of the hydroxy groups are esterified with unsaturated C ₁₂ -C ₄₀ monocarboxylic acids, and 20 to 50 mole% of the hydroxy groups are partially imidized and / or partially esterified with the maleic anhydride copolymer Mixed esters of esterified glycerin, and / or c) partial and / or fully imidized copolymers of maleic anhydride and α-methylstyrene, having a mass average molecular weight of 1500 to 15000 and at least one terminal group based on dimeric α-methylstyrene, and / or d) wax compositions based on natural starting materials of the following d1) and d2) types: d1) wax-like oligomeric esters based on glyceryl monostearate and dimer acids, wherein the conversion product corresponds to the following structure up to 90 mass%, and / or

(Where n is 1 to 20, the sum of a + b + c + d is 30, Z is 12 to 20,

X is H or -CH ₂ -CH (OH) -CH ₂ -O-CO- (CH ₂ ) _z -CH ₃ d2) wax esters having a petrolatum-like hardness based on at least two different straight and / or branched C ₁₄ -C ₃₆ -alcohols and dimer acids whose conversion product corresponds to at least 80 mass%

Wherein i is 13 to 35; s is 13 to 35, the sum of k + m + n + p is 30 to 34, and (CH ₂ ) _i or (CH ₂ ) _s is straight or straight and branched ) Wherein the content of the additive mixture in the mineral oil is from 0.005 to 1 mass%, and the mass ratio of the additive component a / b or a / c or a / d is 10:90 to 90:10, respectively. The composition according to claim 1, wherein the ethylene-vinyl ester copolymer of the additive mixture is an ethylene-vinylacetate copolymer having a content of vinyl acetate of 12 to 50 mass%. The composition of claim 1, wherein the ethylene-vinylester copolymer of the additive mixture is a mixture of 10 to 90 mass% of the unmodified ethylene-vinylester copolymer and 90 to 10 mass% of the ethylene-vinylester copolymer modified with a polar group. . 4. The modified ethylene-vinylester copolymer of the additive mixture according to claim 3, wherein the modified ethylene-vinylester copolymer is oxidized ethylene-vinylester copolymer, partially saponified ethylene-vinylester copolymer, hemiacetal of partially saponified ethylene-vinylester copolymer and (Or) an ethylene-vinylester copolymer grafted with a polar ester of vinyl ester, (meth) acrylic ester, and / or vinyl ether type. Any one of claims 1 to A method according to any one of claim 4, wherein the C ₁₂ -C ₄₀ contained as esterification components of the additive mixture of glycerol mixed ester-shot of a monocarboxylic acid-mono-carboxylic acid is C ₁₂ -C ₄₀ The partially imidized maleic anhydride copolymer comprised of 45 to 52 mass% C ₂₂ -monocarboxylic acid by mass and contained as esterification component was partially imidized with C ₆ -C ₂₄ monoalkyl-amine A maleic anhydride-α-methylstyrene copolymer, wherein the molar ratio of bonded C ₆ -C ₂₄ -monoalkylamine in the anhydride group / copolymer in the copolymer is in the range of 8: 1 to 1.3: 1. 5. The maleic acid according to claim 1, wherein the partially imidized copolymer of maleic anhydride and α-methylstyrene as additive component c) is partially imidized with C ₆ -C ₂₄ monoalkylamines. Anhydride-α-methylstyrene copolymer, wherein the molar ratio of bound C ₆ -C ₂₄ monoalkylamine in the anhydride group / copolymer in the copolymer is from 8: 1 to 1.3: 1. The wax ester according to any one of claims 1 to 4, wherein the wax ester with vaseline-like hardness as the additive component d2) is 2-hexyldecane-1-ol, 2-octyldecan-1-ol or 2-octyldecane 1. A composition which is a wax ester based on dimer acid obtained by separation of a 1-ol type of gerbet alcohol and a vegetable oil having a high oleic acid content and subsequent catalytic dimerization. 5. The mineral oil according to claim 1, wherein the mineral oil is a crude or fuel oil derived from an intermediate distillate having a sulfur content of less than 0.05% by mass, preferably heating oil, gas oil, or diesel oil. 6. Composition. The additive component a + b, a + c, a + d, a + b + c, a + b + c + d, or a + c + d according to any one of claims 1-4. Other additive components such as fatty acid mixtures, polar nitrogen compounds, preferably polyamines, etheramines, aminoalcohols, amine salts, amides or imides of polyhydric carboxylic acids; Of modified copolymers of ethylenically unsaturated C ₄ -C ₂₀ -dicarboxylic acid anhydrides, non-modified ethylene-vinylester copolymers, C ₇ -C ₃₀ -alcohols, polyalkylene glycols, polyoxyalkylene compounds C ₂₂ -monocarboxylic acid relative to the total weight of the ester or ether, C ₂ -C ₆ -oxyalkyl-crosslinked C ₁₂ -C ₄₀ -monocarboxylic acid, preferably C ₁₆ -C ₂₄ monocarboxylic acid C ₃ -C ₄ -oxyalkyl-crosslinked unsaturated C ₁₆ -C ₂₄ monocarboxylic acid, hydrocarbon polymer, alkylphenol-aldehyde copolymer, C ₈ -C ₁₀₀ -alkyl substituent having a content of 45 to 52% by mass A mineral oil composition containing a total of 0 to 200 mass% of an aromatic compound, a carboxylated polyamine, a detergent, a corrosion inhibitor, a demulsifier, a metal deactivator, a cetane number improver, an antifoaming agent, and / or a cosolvent. Consisting of a mixture of mineral oil as a main component and an additive as a trace component, and the additive mixture as an additive a) an ethylene-vinyl ester copolymer having a mass average molecular weight of 3000 to 50000 and an ethylene content of 50 to 90 mass%, and b) 50 to 80 mole% of the hydroxy groups are esterified with unsaturated C ₁₂ -C ₄₀ monocarboxylic acids, and 20 to 50 mole% of the hydroxy groups are partially imidized and / or partially esterified with the maleic anhydride copolymer Mixed esters of esterified glycerin, and / or c) partial and / or fully imidized copolymers of maleic anhydride and α-methylstyrene, having a mass average molecular weight of 1500 to 15000 and at least one terminal group based on dimeric α-methylstyrene, and / or d) wax compositions based on natural starting materials of the following d1) and d2) types: d1) wax-like oligomeric esters based on glyceryl monostearate and dimer acids, wherein the conversion product corresponds to the following structure up to 90 mass%, and / or

(Where n is 1 to 20, the sum of a + b + c + d is 30, Z is 12 to 20,

X is H or -CH ₂ -CH (OH) -CH ₂ -O-CO- (CH ₂ ) _z -CH ₃ d2) wax esters having a petrolatum-like hardness based on at least two different straight and / or branched C ₁₄ -C ₃₆ -alcohols and dimer acids whose conversion product corresponds to at least 80 mass%

Wherein i is 13 to 35; s is 13 to 35, the sum of k + m + n + p is 30 to 34 and (CH ₂ ) _i or (CH ₂ ) _s is straight or straight and branched ) To the mineral oil composition, the content of the additive mixture in the mineral oil is 0.005 to 1% by mass and the mass ratio of the additive component a / b or a / c or a / d is 10:90 to 90:10, respectively. A first process step of preparing a solution containing from 1 to 60% by mass of an additive component in a mineral oil intermediate distillate at 20 to 90 ° C, and A second process step of homogenizing the solution containing the additive component with the main component mineral oil A total of from 0 to 200 mass of other additive components, the additive component a + b, a + c, a + d, a + b + c, a + b + c + d, or a + c + d A process for preparing a composition consisting of a mixture of mineral oil as a main component and an additive as a trace component, prepared by a pre-homogenization process in which% is added to the mineral oil in the first process step and / or the second process step. A flowable medium transported at low temperature, comprising the composition according to any one of claims 1 to 4. A mineral oil fuel having high lubricity and fluidity, comprising the composition according to any one of claims 1 to 4.