EP1675932B1 - Compositions based on mineral oil and an additive mixture - 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

The invention relates to compositions of mineral oil as the main component and minor proportions of an additive mixture and to a process for the preparation of compositions of mineral oil containing the additive mixture.

Compositions of mineral oils as the main component and small amounts of additive mixtures of ethylene-vinyl acetate copolymers, hydrocarbon polymers, esterified maleic anhydride-olefin copolymers, polar nitrogen compounds such as amine salts of polybasic carboxylic acids and esterified polyoxyalkylenes are known ( WO 94/10267 A1 . WO 95/33 012 A1 . EP 0 921 183 A1 . WO 93/14178 A1 . EP 0 889 323 A1 ).

Disadvantages are the insufficient flow behavior and the storage stability of these compositions at low temperatures and the limited lubricity of the formulations when the mineral oil component has a sulfur content below 0.005% by mass.

The object of the invention are compositions of mineral oils as the main component and small proportions of an additive mixture, which have improved flow behavior and improved storage stability at low temperatures and improved lubricity. The improved flow behavior is said to save energy be achieved with the pump units through which the transport of these recipes takes place. The development of the additive mixtures should be carried out from the viewpoint of the use of mineral oils with a very low sulfur content in order to achieve fuels of improved environmental compatibility with regard to pollutant emission.

1. a) Ethylen-Vinylester-Copolymere mit Molmassengewichtsmitteln von 3000 bis 50000 und einem Ethylenanteil von 50 bis 90 Masse% und
2. b) Mischester des Glycerins, bei denen 50 bis 80 Mol% der Hydroxygruppen mit ungesättigten C₁₂-C₄₀-Monocarbonsäuren und 20 bis 50 Mol% der Hydroxygruppen mit partiell imidisierten und/oder teilveresterten Maleinsäureanhydrid-Copolymeren verestert sind, und/oder
3. c) partiell und/oder vollständig imidisierte Copolymere aus Maleinsäureanhydrid und α-Methylstyrol mit Molmassen-Zahlenmitteln von 1500 bis 15000 und mindestens einer Endgruppe auf Basis von dimerem α-Methylstyrol, und/oder
4. d) Wachskompositionen auf Basis nativer Ausgangsprodukte vom Typ
   • d1) wachsartiger oligomerer Ester auf Basis von Glycerinmonostearat und Dimersäure, bei dem das Umsetzungsprodukt zu mindestens 90 Masse% der Struktur
     
     entspricht , wobei n = 1 bis 20, die Summe a+b+c+d = 30, z = 12 bis 20
     Y = H oder
     
     X = H oder -CH₂-CH(OH)-CH₂-O-CO-(CH₂)_z-CH₃, und/oder
   • d2) Wachsester mit vaselinähnlicher Konsistenz auf Basis von mindestens zwei verschiedenen geradkettigen und/oder verzweigten C₁₄-C₃₆-Alkoholen und Dimersäuren, bei dem das Umsetzungsprodukt zu mindestens 80 Masse% der Struktur
     
     entspricht,
     wobei i = 13 bis 35; s= 13 bis 35,
     die Summe von k + m + n + p 30 bis 34 beträgt, und (CH₂)_i oder (CH₂)_s geradkettig oder geradkettig und verzweigt ist,
     enthalten,
     wobei der Gehalt der Additivmischung im Mineralöl 0,005 bis 1 Masse% und das Masseverhältnis der Additivkomponenten a/b oder a/c oder a/d jeweils 10 : 90 bis 90 _: 10 beträgt.

The object of the invention was achieved by compositions of mineral oil as the main component and small amounts of an additive mixture, wherein the additive mixture according to the invention, the additive components

1. a) ethylene-vinyl ester copolymers having a molecular weight of from 3,000 to 50,000 and an ethylene content of 50 to 90% by weight and
2. b) mixed esters of glycerol in which 50 to 80 mol% of the hydroxyl groups are esterified with unsaturated C ₁₂ -C ₄₀ monocarboxylic acids and 20 to 50 mol% of the hydroxyl groups with partially imidized and / or partially esterified maleic anhydride copolymers, and / or
3. c) partially and / or completely imidized copolymers of maleic anhydride and .alpha.-methylstyrene having molecular weight numbers of from 1500 to 15000 and at least one end group based on dimeric .alpha.-methylstyrene, and / or
4. d) wax compositions based on native starting materials of the type
   • d1) waxy oligomeric ester based on glycerol monostearate and dimer acid, in which the reaction product to at least 90% by mass of the structure
     
     where n = 1 to 20, the sum a + b + c + d = 30, z = 12 to 20
     Y = H or
     
     X = H or -CH ₂ -CH (OH) -CH ₂ -O-CO- (CH ₂ ) _z -CH ₃ , and / or
   • d2) wax esters with a vaseline-like consistency based on at least two different straight-chain and / or branched C ₁₄ -C ₃₆ -alcohols and dimer acids, in which the reaction product is at least 80% by mass of the structure
     
     corresponds,
     where i = 13 to 35; s = 13 to 35,
     the sum of k + m + n + p is from 30 to 34, and (CH ₂ ) _i or (CH ₂ ) _{s is} straight-chain or straight-chain and branched,
     contain,
     wherein the content of the additive mixture in the mineral oil from 0.005 to 1 mass% and the mass ratio of the additive components a / b or a / c or a / d, respectively 10: 90 to _90: 10th

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

The ethylene-vinyl ester copolymers may contain as further unsaturated ester components from 1 to 30% by weight, based on the vinyl ester, of (meth) acrylic acid esters such as methyl methacrylate, methyl acrylate, ethyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, ethylene glycol dimethacrylate or hydroxyethyl methacrylate and / or vinyl ethers such as Octyl vinyl ether or hexanediol monovinyl ether included.

Preferably, the ethylene-vinyl ester copolymers as additive component a) in the additive mixture ethylene-vinyl acetate copolymers having a vinyl acetate content of 12 to 50% by mass.

A further preferred variant for the ethylene-vinyl ester copolymers contained in the additive mixture as additive component a) is that the ethylene-vinyl ester copolymers comprise mixtures of 10 to 90% by weight of unmodified ethylene-vinyl ester copolymers and 90 to 10% by mass polar groups are modified ethylene-vinyl ester copolymers.

The modification of the ethylene-vinyl ester copolymers by polar groups consists in the incorporation of special end groups such as aldehyde end groups, preferably end groups of acetaldehyde, propionaldehyde, butyraldehyde or isobutyraldehyde, carboxyalkyl mercapto end groups, preferably end groups of mercaptoacetic acid or mercaptopropionic acid, or alkoxy end groups in the copolymer in which Incorporation of hydroxy and / or carboxy groups in the copolymer by partial oxidation, saponification or acetalization and by grafting polar, ethylenically unsaturated monomers to the copolymer.

The modified ethylene-vinyl ester copolymers are preferably oxidized ethylene-vinyl ester copolymers, partially hydrolyzed ethylene-vinyl ester copolymers, hemiacetals of partially hydrolyzed ethylene-vinyl ester copolymers and / or polar unsaturated monomers of the vinyl ester, (meth) acrylic ester and / or vinyl ether type grafted ethylene-vinyl ester copolymers.

The oxidized ethylene-vinyl ester copolymers are preferably oxidized ethylene-vinyl acetate copolymers having number average molecular weights of from 800 to 5,000, acid numbers of from 2 to 40 mg KOH / g, and OH numbers of from 20 to 150 mg KOH / g.

The partially saponified ethylene-vinyl ester copolymers are preferably partially hydrolyzed ethylene-vinyl acetate copolymers having a number average molecular weight of from 800 to 5,000, in which 5 to 30 mol% of the vinyl acetate units are saponified.

Another preferred variant is that the modified ethylene-vinyl ester copolymers include hemiacetals of ethylene-vinyl ester-vinyl alcohol copolymers with butyraldehyde are. Examples of hemiacetals of ethylene-vinyl ester-vinyl alcohol copolymers with butyraldehyde are hemiacetals of ethylene-vinyl acetate-vinyl alcohol copolymers, according to DD 295 507 A7 have been reacted in heterogeneous phase with butyraldehyde.

The preparation of the grafted ethylene-vinyl ester copolymers can be carried out by reaction with the unsaturated monomers in the extruder ( DD 282 462 B5 ) or in the stirred reactor ( DD 293 125 B5 ) in the presence of thermally decomposing radical formers. It is also possible to carry out the modification in the preparation of the copolymer by the high-pressure process by metering the monomers into the polymer melt in the low-pressure separator or in the discharge extruder.

In particular, the grafted ethylene-vinyl ester copolymers as additive component a) are vinyl acetate-grafted ethylene-vinyl acetate copolymers having a number average molecular weight of 800 to 5000 and a total vinyl acetate content of 20 to 60% by weight, the vinyl acetate content of the copolymer backbone being 10 to 40% by weight and the proportion the grafted vinyl acetate side chains is 10 to 20% by weight.

The ethylene-vinyl ester copolymers in the additive compositions may contain up to 35% by weight of poly-C ₆ -C ₃₆ alkyl (meth) acrylates.

Examples of maleic anhydride copolymers which may be partially imidated or partially esterified as the acid component in the mixed esters of glycerol as additive component b) of the additive mixture are copolymers of Maleic anhydride and the comonomer components C ₂ -C ₂₀ olefins, C ₈ -C ₂₀ vinyl aromatics, C ₄ -C ₂₁ acrylic esters, C ₅ -C ₂₂ methacrylic acid esters, C ₅ -C ₁₄ vinyl silanes, C ₆ -C ₁₅ - Acrylate silanes, acrylic acid, methacrylic acid, acrylonitrile, vinylpyridine, vinyloxazoline, isopropenyloxazoline, vinylpyrrolidone, amino C ₁ -C ₈ alkyl (meth) acrylates, C ₃ -C ₂₀ vinyl esters, C ₃ -C ₂₀ vinyl ethers and / or hydroxy C ₁ -C ₈ alkyl (meth) acrylates. Particularly preferred comonomer components are isobutylene, diisobutylene, vinyl acetate, styrene and α-methylstyrene.

The maleic anhydride copolymers preferably have a maleic anhydride / comonomer molar ratio of 1: 1 to 1: 9 and weight average molecular weights of 5,000 to 500,000. The partial imidization may be carried out with ammonia, C ₁ -C ₂₄ monoalkylamines, C ₆ -C ₁₈ aromatic Monoamines, C ₂ -C ₁₈ -monoamino alcohols, monoaminated poly (C ₂ -C ₄ -alkylene) oxides having a molecular weight of from 400 to 3,000, and / or mono-etherified poly (C ₂ -C ₄ -alkylene) oxides having a molecular weight of from 100 to 10000, the molar ratio being anhydride copolymer / ammonia, amino groups C ₁ -C ₂₄ -monoalkylamines, C ₆ -C ₁₈ -aromatic monoamines, C ₂ -C ₁₈ -monoamino alcohols or monoaminated poly (C ₂ -C ₄ -alkylene) oxide is 1: 1 to 20: 1.

Examples of suitable amines with which the maleic anhydride copolymers are partially imidized are C ₁₂ -C ₂₄ -monoalkylamines such as oleylamine, dodecylamine, hexadecylamine, octadecylamine or eicosylamine, monosubstituted diamines of the N-dodecyl-1,3-diaminopropane, N- Octadecyl-1,3-diaminopropane or N-octadecyl-propylenetriamine or amino alcohols such as aminodecan-10-ol or amino-hexadecan-16-ol.

Examples of suitable alcohols with which the maleic anhydride copolymers are partially esterified as the acid component in the mixed esters of glycerol as additive component b) of the additive mixture are C ₁ -C ₁₈ -alcohols such as methanol, ethanol, ethylhexanol or stearyl alcohol.

Examples of the unsaturated C ₁₂ -C ₄₀ -monocarboxylic acids contained as esterification component in the mixed esters of glycerol of the additive mixture are oleic acid, elaidic acid, ricinoleic acid, eleostearic acid, linoleic acid, linolenic acid and erucic acid or dimer acids based on oleic acid or linolenic acid.

Examples of suitable processes for preparing the mixed esters of glycerol in which 50 to 80 mol% of the hydroxyl groups are esterified with unsaturated C ₁₂ -C ₄₀ monocarboxylic acids and 20 to 50 mol% of the hydroxyl groups with partially imidized and / or partially esterified maleic anhydride copolymers, are the partial reaction of glycerol with unsaturated C ₁₂ -C ₄₀ monocarboxylic acids and subsequently with partially imidized and / or partially esterified maleic anhydride copolymers or the partial reaction of glycerol with partially imidized and / or partially esterified maleic anhydride copolymers and subsequently with unsaturated C ₁₂ -C ₄₀ monocarboxylic acids. The reaction in the melt, preferably in continuous kneaders at temperatures of 50 to 135 ° C under vacuum degassing, or as a solution process, preferably in aromatic solvents at 85 to 140 ° C, performed.

The mixed esters of glycerol of the additive mixture preferably contain the esterification component C ₁₂ -C ₄₀ monocarboxylic acids from 45 to 52% by weight C ₂₂ monocarboxylic acids, based on the total mass of C ₁₂ -C ₄₀ monocarboxylic acids.

In the mixed esters of glycerol as additive component b) of the additive mixture, the partially imidized maleic anhydride copolymers present as esterification components are preferably partially maleic anhydride-α-methylstyrene copolymers imidized with C ₆ -C ₂₄ -monoalkylamines, in which the molar ratio of anhydride groups in the copolymer / bound C ₆ -C ₂₄ monoalkylamine in the copolymer 8: 1 to 2: 1.

Examples of partially imidized copolymers of maleic anhydride and α-methylstyrene as additive component c) are copolymers having an approximately equimolar ratio of both monomers, in which the partial and / or complete imidization with ammonia, C ₁ -C ₂₄ -mono-alkylamines, C ₆ - C ₁₈ -aromatic monoamines, C ₂ -C ₁₈ -mono-aminoalcohols, monoaminated poly (C ₂ -C ₄ -alkylene) -oxides, and / or mono-etherified poly (C ₂ -C ₄ -alkylene) -oxides, wherein the molar ratio of anhydride copolymer / ammonia, amino groups C ₁ -C ₂₄ monoalkylamines, C ₆ -C ₁₈ aromatic monoamines, C ₂ -C ₁₈ monoamino alcohols or monoaminated poly (C ₂ -C ₄ alkylene) oxide 1 : 1 to 20: 1.

The partially imidized copolymers of maleic anhydride and α-methylstyrene as additive component c) are preferably partially imidized with C ₆ -C ₂₄ monoalkylamines maleic anhydride-α-methylstyrene copolymers in which the molar ratio of anhydride groups in the copolymer / bound C ₆ -C ₂₄ -monoalkylamine in the copolymer is 8: 1 to 1.3: 1.

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

The waxy oligomeric esters based on glycerol monostearate and dimer acid as additive component d1) are those in EP 0 934 921 A1 described oligomeric esters.
The component glycerol monostearate can be prepared by cleavage of rapeseed oil by means of enzymes, isolation of the glycerol monooleate formed and subsequent hydrogenation. A suitable method of preparation of the dimer acid component is the splitting of vegetable oils and the subsequent dimerization of the unsaturated fatty acids formed. The oligomeric esters are prepared by solvent-free oligocondensation with acid catalysis.

Preferred additive components d1) are waxy oligomeric esters which have a degree of oligomerization of from 2 to 8.

The wax esters with a vase-like consistency d2) are those in EP 0 970 998 A1 described wax esters. The wax esters with vaseline-like consistency d2) contained in the additive mixture are preferably wax esters based on Guerbet alcohols of the 2-hexyldecan-1-ol, 2-octyldecan-1-ol or 2-octyldecan-1-ol type and dimer acids obtained by cleavage of Vegetable oils with high oleic acid content and subsequent catalytic dimerization. The production of wax esters from the Guerbet alcohols and dimer acid can be carried out by catalytic esterification in the presence of acidic catalysts at temperatures of 100 to 160 ° C in stirred reactors under application of a vacuum of - 0.5 to -1.5 bar.

Examples of mineral oils which form the major component in the mineral oil compositions are crude oils and petroleum distillates having a boiling range of 100 to 500 ° C, such as lubricating oils, kerosene, diesel, fuel oil, heavy fuel oils, petroleum, tractor fuel and cracked gasoline. The mineral oils may also contain up to 30% by weight of synthesis hydrocarbons from the Fischer-Tropsch synthesis, up to 20% by weight modified vegetable oils based on sunflower oil, soybean oil, rapeseed oil or oils of animal origin, biodiesel and / or up to 10% by weight of alcohols such as methanol or ethanol contain.

The mineral oils are preferably crude oils or fuel oils from a middle distillate with a sulfur content of less than 0.05% by mass, in particular heating oils, gas oils or diesel oils.

The compositions of mineral oil can total up to 200% by weight, based on the additive components a + b, a + c, a + d, a + b + c, a + b + c + d or a + c + d, further additive components from Type of fatty acid mixtures, polar nitrogen compounds, preferably polyamines, ether amines, amino alcohols, amine salts, amides or imides of polybasic carboxylic acids; modified copolymers of ethylenically unsaturated C ₄ -C ₂₀ -dicarboxylic acid anhydrides, unmodified ethylene-vinyl ester copolymers, C ₇ -C ₃₀ -alcohols, polyalkylene glycols, esters or ethers of polyoxyalkylene compounds, C ₂ -C ₆ -oxyalkyl-bridged C ₁₂ -C ₄₀ -monocarboxylic acids, preferably C ₃ -C ₄ -oxyalkyl-bridged unsaturated C ₁₆ -C ₂₄ -monocarboxylic acids with a proportion of C ₂₂ -monocarboxylic acids, based on the total mass of C ₁₆ -C ₂₄ Monocarboxylic acids, from 45 to 52% by weight, hydrocarbon polymers, alkylphenol-aldehyde copolymers, aromatic compounds having C ₈ -C ₁₀₀ -alkyl substituents, carboxylated polyamines, detergents, corrosion inhibitors, demulsifiers, metal deactivators, cetane improvers, defoamers and / or cosolvents.

Examples of the fatty acid mixtures contained in the compositions of mineral oil as further additive components are mixtures of saturated and / or unsaturated C ₆ -C ₄₀ -carboxylic acids such as lauric acid, palmitic acid, oleic acid, linolenic acid, dimer fatty acids and alkenylsuccinic acids.

Examples of the polyamine type polar nitrogen compounds contained in the compositions of mineral oil as further additive components are N-hexadecyl-1,3-diaminopropane, N-octadecyldipropylenetriamine, N-dodecyl-1,3-diaminopropane, N, N'-didodecyl-1 , 3-diaminopropane and N, N'-dioctadecyl-dipropylenetriamine.

Examples of the ethereal polar nitrogen compounds contained in the compositions of mineral oil as further additive components are 3-methoxypropylamine, 3-N-octyloxypropyl-1,3-diaminopropane and 3-N- (2,4,6-trimethyldecyloxypropyl) -1, 3-diaminopropane.

Examples of the polar nitrogen compounds contained in the compositions of mineral oil as further additive components Amino-alcohols are aminopentan-5-ol, aminoundecan-11-ol and 2-amino-2-methylpropanol.

Examples of the amines used in polar nitrogen compounds of the amine salt type, amides or imides of polybasic carboxylic acids are C ₈ -C ₄₀ -amines such as hydrogenated tallamine, tetradecylamine, eicosylamine, dioctadecylamine, methylbehenylamine, N-oleyl-1,3-diaminopropane, N Stearyl-1-methyl-1,3-diaminopropane or N-Oleyldipropylentriamin.

Examples of the polybasic carboxylic acids which are the basis of polar nitrogen compounds of the amine salt or amide type of polybasic carboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, ethylenediaminetetraacetic acid and cyclohexanedicarboxylic acid.

Specific examples of the amine salt type polar nitrogen compounds contained in the mineral oil compositions as further additive components are N-methyltriethanolammonium distearyl ester chloride and N-methyltriethanolammonium distearyl ester methosulfate.

Examples of ethylenically unsaturated C ₄ -C ₂₀ -dicarboxylic acid anhydrides which may be contained as monomer component in the modified copolymers of ethylenically unsaturated C ₄ -C ₂₀ dicarboxylic anhydrides as further additive component are allylsuccinic anhydride, bicycloheptendicarboxylic anhydride, bicyclooctene dicarboxylic acid anhydride, carbomethoxymaleic anhydride, citraconic anhydride, cyclohexene dicarboxylic anhydride, dodecenylsuccinic anhydride , Glutaconic anhydride, itaconic anhydride, Maleic anhydride, mesaconic anhydride, methylbicycloheptheneicarboxylic anhydride and / or methylcyclohexene dicarboxylic anhydride, preferably maleic anhydride and / or itaconic anhydride.

Examples of suitable comonomers for ethylenically unsaturated C ₄ -C ₂₀ -dicarboxylic anhydrides which may be contained as monomer component in the modified copolymers of ethylenically unsaturated C ₄ -C ₂₀ -dicarboxylic anhydrides as further additive component are ethylenically unsaturated monomers of the type C ₂ -C ₂₀ Olefins, C ₈ -C ₂₀ vinyl aromatics, C ₄ -C ₂₁ acrylic acid esters, C ₅ -C ₂₂ methacrylic acid esters, C ₅ -C ₁₄ vinyl silanes, C ₆ -C ₁₅ acrylatesilanes, acrylic acid, methacrylic acid, acrylonitrile, vinylpyridine , Vinyloxazoline, isopropenyloxazoline, vinylpyrrolidone, amino-C ₁ -C ₈ -alkyl- (meth) acrylates, C ₃ -C ₂₀ -vinyl esters, C ₃ -C ₂₀ -vinyl ethers and / or hydroxy-C ₁ -C ₈ -alkyl- (meth) acrylates. Particularly preferred ethylenically unsaturated monomers are isobutylene, diisobutylene, vinyl acetate, styrene and α-methylstyrene.

Particularly 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 molecular weights of 5000 to 500,000, with ammonia, C ₁ -C ₂₄ monoalkylamines , C ₆ -C ₁₈ -aromatic monoamines, C ₂ -C ₁₈ -monoamino alcohols, monoaminated poly (C ₂ -C ₄ -alkylene) oxides having a molecular weight of from 400 to 3000, and / or monoetherified poly (C ₂ -C ₄ -) alkylene) oxides having a molecular weight of from 100 to 10,000, the molar ratio being anhydride copolymer / ammonia, amino groups C ₁ -C ₂₄ -monoalkylamines, C ₆ -C ₁₈ -aromatic monoamines, C ₂ -C ₁₈ -monoamino alcohols or monoaminated poly (C ₂ -C ₄ -alkylene) oxide 1 _: 1 to 20 _: 1.

Particularly suitable as partially or completely imidized copolymers of ethylenically unsaturated C ₄ -C ₂₀ -dicarboxylic anhydrides with C ₁₂ -C ₂₄ -monoalkylamines such as oleylamine, dodecylamine, hexadecylamine, octadecylamine or eicosylamine, monosubstituted diamines of the N-dodecyl-1,3- type diaminopropane, N-octadecyl-1,3-diaminopropane or N-octadecylpropylene triamine or aminoalcohols such as aminodecan-10-ol or aminohexadecan-16-ol imidated maleic anhydride copolymers.

Examples of C ₇ -C ₃₀ alcohols which may be included as further additive components in the mineral oil compositions are dodecanol, stearyl alcohol and ceryl alcohol.

Examples of polyalkylene glycols which may be contained as further additive components in the mineral oil compositions are polyethylene glycols, polypropylene glycols and ethylene oxide-propylene oxide copolymers having molecular weights of 500 to 5,000.
Examples of esters of polyoxyalkylene compounds which may be included as further additive components in the mineral oil compositions are C ₁₀ -C ₂₄ monoalkyl ester or dialkyl esters of polyalkylene glycols such as polyethylene glycol monostearyl ester or polypropylene glycol dioleate.

Examples of ethers of polyoxyalkylene compounds which may be present as further additive components in the compositions of mineral oil are C ₁ -C ₄ -monoalkylether- or dialkyl ethers of polyalkylene glycols such as polyethylene glycol monomethyl ether or polypropylene glycol dibutyl ether.

The C ₂ -C ₆ -oxyalkyl-bridged C ₁₂ -C ₄₀ monocarboxylic acids, which may be included as further additive component in the mineral oil compositions, consist of a C ₂ -C ₆ polyalcohol component and a C ₁₂ -C ₄₀ -conocarboxylic acid component ,

Examples of polyalcohols which may be contained as the alcohol component in the C ₂ -C ₆ -oxyalkyl-bridged C ₁₂ -C ₄₀ monocarboxylic acids as further additive component are ethylene glycol, polyalkylene glycols, glycerol, 1,1,1-tris- (hydroxymethyl) propane, pentaerythritol and sorbitol.

Examples of C ₁₂ -C ₄₀ monocarboxylic acids which may be contained as the carboxylic acid component in the C ₂ -C ₆ -oxyalkyl-bridged C ₁₂ -C ₄₀ monocarboxylic acids as further additive component are lauric acid, palmitic acid, stearic acid, oleic acid, elaidic acid, ricinoleic acid, eleostearic acid , Linoleic acid, linolenic acid and erucic acid or dimer acids based on oleic acid or linolenic acid.

Also preferred as C ₂ -C ₆ -oxyalkyl-bridged C ₁₂ -C ₄₀ monocarboxylic acids are mixed esters of polyalcohols in which the polyalcohols are esterified by mixtures of C ₁₂ -C ₄₀ monocarboxylic acids. Specific examples of C ₂ -C ₆ -oxyalkyl-bridged C ₁₂ -C ₄₀ monocarboxylic acids are the monoesters of ethylene glycol with dilinolenic acid, a C ₃₆ -dimeric acid, the diester of propylene glycol with oleic acid and the triester of pentaerythritol with stearic acid.

Particularly preferred as C ₂ -C ₆ -oxyalkylverbrückte C ₁₂ -C ₄₀ monocarboxylic acids are esters of unsaturated C ₁₆ -C ₂₄ monocarboxylic acids with C ₃ -C ₄ polyalcohols, wherein the proportion of C ₂₂ monocarboxylic acids, based on the total mass of C ₁₆ -C ₂₄ monocarboxylic acids, 45 to 52% by mass.

Examples of unsaturated C ₁₆ -C ₂₄ -monocarboxylic acids which may be present in the preferred esters of unsaturated C ₁₆ -C ₂₄ -monocarboxylic acids with C ₃ -C ₄ -polyalcohols are oleic acid, linoleic acid, linolenic acid and erucic acid.

Examples of hydrocarbon polymers which may be included as further additive components in the mineral oil compositions are copolymers of ethylene and C ₃ -C ₂₀ alpha-olefins such as ethylene-propylene copolymers or ethylene-dodecene copolymers or hydrogenated polyunsaturated monomer polymers of the hydrogenated diene copolymer type such as hydrogenated polybutadiene or hydrogenated polyisoprene having number average molecular weights of up to 30,000.

Examples of alkylphenol-aldehyde copolymers that may be included as additional additive components in the mineral oil compositions are copolymers that can be prepared by reacting alkylated phenols, such as phenol-propylene oligomer adducts, with paraformaldehyde.

Examples of aromatic compounds having C ₈ -C ₁₀₀ -alkyl substituents, which may be contained as further additive components in the compositions of mineral oil, are compounds obtained by Friedel-Krafts condensation halogenated hydrocarbons such as halogenated polyethylene wax can be prepared with aromatic hydrocarbons such as benzene or naphthalene.

Examples of detergents which may be included as further additive components in the compositions of mineral oil are aliphatic sulfonic acids such as C ₈ -C ₃₀ alkanesulfonates or aromatic-aliphatic alkanesulfonates, in particular nonylbenzenesulfonic acid, dodecylbenzenesulfonic acid, didodecylbenzenesulfonic acid and nonylnaphthalenesulfonic acid.

Examples of demulsifiers which may be included as further additive components in the mineral oil compositions are oxalkylated phenol-formaldehyde condensates, polyalkylene glycol-modified diglycidyl ethers, polyesteramines or alkoxylated fatty acids.

Examples of cetane improvers which may be included as further additive components in the mineral oil compositions are organic nitric acid esters such as ethylhexyl nitrate, cyclohexyl nitrate or ethoxyethyl nitrate, or soluble organic peroxides, hydroperoxides or peresters.

Preferred defoamers which may be included as further additive components in the mineral oil compositions are polyalkylene oxide-siloxane block copolymers and carboxylated polyamines.

Examples of polyalkylene oxide-siloxane block copolymers are block copolymers which are a combination of trifunctional Siloxane blocks such as monomethylsiloxane groups, difunctional siloxane groups such as dimethylsiloxane groups and monofunctional siloxane groups such as trimethylsiloxane groups, a preferred length of the siloxane blocks is 5 to 20 monomer units. For the polyalkylene oxide blocks, the preferred length is 2 to 40 monomer units, preferably polyoxyalkylene blocks of ethylene oxide and / or propylene oxide units.

Examples of carboxylated polyamines as defoamers are reaction products of C ₈ -C ₂₄ -fatty acids and amines such as ethylenediamine, butylenediamine, diethylenetriamine and pentaethylenehexamine-1,2-diaminobutanol.

Examples of cosolvents which may be included as additional additive components in the mineral oil compositions are gasoline fractions, toluene, xylene, ethylbenzene, isononanol, ethylhexanol, dodecylphenol, epoxidized rapeseed oil and epoxidized soybean oil.

1. a) Ethylen-Vinylester-Copolymere mit Molmassengewichtsmitteln von 3000 bis 50000 und einem Ethylenanteil von 50 bis 90 Masse% und
2. b) Mischester des Glycerins, bei denen 50 bis 80 Mol% der Hydroxygruppen mit ungesättigten C₁₂-C₄₀-Monocarbonsäuren und 20 bis 50 Mol% der Hydroxygruppen mit partiell imidisierten und/oder teilveresterten Maleinsäureanhydrid-Copolymeren verestert sind, und/oder
3. c) partiell und/oder vollständig imidisierte Copolymere aus Maleinsäureanhydrid und α-Methylstyrol mit Molmassen-Zahlenmitteln von 1500 bis 15000 und mindestens einer Endgruppe auf Basis von dimerem α-Methylstyrol, und/oder
4. d) Wachskompositionen auf Basis nativer Ausgangsprodukte vom Typ
   • d1) wachsartige oligomerer Ester auf Basis von Glycerinmonostearat und Dimersäure, bei dem das Umsetzungsprodukt zu mindestens 90 Masse% der Struktur
     
     entspricht ,
     wobei n = 1 bis 20, die Summe a+b+c+d = 30, z = 12 bis 20
     Y = H oder
     
     
     X = H oder -CH₂-CH(OH)-CH₂-O-CO-(CH₂)_z-CH₃, und/oder
   • d2) Wachsester mit vaselinähnlicher Konsistenz auf Basis von mindestens zwei verschiedenen geradkettigen und/oder verzweigten C₁₄-C₃₆-Alkoholen und Dimersäuren, bei dem das Umsetzungsprodukt zu mindestens 80 Masse% der Struktur
     
     entspricht,
     wobei i = 13 bis 35; s= 13 bis 35,
     die Summe von k + m + n + p 30 bis 34 beträgt, und (CH₂)_i oder (CH₂)_s geradkettig oder geradkettig und verzweigt ist, enthalten,
     wobei der Gehalt der Additivmischung im Mineralöl 0,005 bis 1 Masse% und das Masseverhältnis der Additivkomponenten a/b oder a/c oder a/d jeweils 10 : 90 bis 90 : 10 beträgt,
   nach einem Vorhomogenisierungsverfahren hergestellt werden, bei dem
   • in der ersten Verfahrensstufe 1 bis 60 Masse% Additivkomponenten enthaltende Lösungen in Mineralöl-Mitteldestillaten bei 20 bis 90°C hergestellt werden, und
   • in der zweiten Verfahrensstufe die Additivkomponenten enthaltenden Lösungen mit dem Mineralöl als Hauptkomponente homogenisiert werden,
   wobei dem Mineralöl insgesamt 0 bis 200 Masse%, bezogen auf die Additivkomponenten a+b, a+c, a+d, a+b+c, a+b+c+d oder a+c+d, weitere Additivkomponenten in der ersten und/oder zweiten Verfahrensstufe zugesetzt werden.

The compositions of mineral oil as the main component and minor proportions of an additive mixture are prepared by a process comprising, in accordance with the invention, mineral oil compositions containing the additive components

1. a) ethylene-vinyl ester copolymers having a molecular weight of from 3,000 to 50,000 and an ethylene content of 50 to 90% by weight and
2. b) mixed esters of glycerol in which 50 to 80 mol% of the hydroxyl groups with unsaturated C ₁₂ -C ₄₀ monocarboxylic acids and 20 to 50 mol% of the hydroxyl groups with partially imidized and / or partially esterified Maleic anhydride copolymers are esterified, and / or
3. c) partially and / or completely imidized copolymers of maleic anhydride and .alpha.-methylstyrene having molecular weight numbers of from 1500 to 15000 and at least one end group based on dimeric .alpha.-methylstyrene, and / or
4. d) wax compositions based on native starting materials of the type
   • d1) waxy oligomeric esters based on glycerol monostearate and dimer acid, in which the reaction product to at least 90% by mass of the structure
     
     corresponds
     where n = 1 to 20, the sum a + b + c + d = 30, z = 12 to 20
     Y = H or
     
     
     X = H or -CH ₂ -CH (OH) -CH ₂ -O-CO- (CH ₂ ) _z -CH ₃ , and / or
   • d2) wax esters with a vaseline-like consistency based on at least two different straight-chain and / or branched C ₁₄ -C ₃₆ -alcohols and dimer acids, in which the reaction product is at least 80% by mass of the structure
     
     corresponds,
     where i = 13 to 35; s = 13 to 35,
     the sum of k + m + n + p is from 30 to 34, and (CH ₂ ) _i or (CH ₂ ) _{s is} straight-chain or straight-chain and branched,
     wherein the content of the additive mixture in the mineral oil is 0.005 to 1% by mass and the mass ratio of the additive components a / b or a / c or a / d is in each case from 10:90 to 90:10,
   be prepared by a Vorhomogenisierungsverfahren in which
   • in the first process stage 1 to 60% by weight of additive components containing solutions are prepared in mineral oil middle distillates at 20 to 90 ° C, and
   • in the second process stage, the solutions containing the additive components are homogenized with the mineral oil as main component,
   wherein the mineral oil a total of 0 to 200 mass%, based on the additive components a + b, a + c, a + d, a + b + c, a + b + c + d or a + c + d, further additive components in the be added to the first and / or second stage of the process.

The compositions of mineral oil as a main component and small proportions of an additive mixture are suitable, in particular, as flowable media to be transported at low temperatures and as a mineral oil fuel with high lubricity and flowability.

Examples of the flowable media to be transported at low temperatures are the transport of crude oil formulations from the source of the crude oil through pipelines for loading and storage as well as the transport of diesel or fuel oil formulations in pipelines.

The invention is illustrated by the following examples.

EXAMPLES

• Cloud Point (CP) : DIN EN 23 015
• Cold Filter Plugging Point (CFPP) : EN 116
• Siedeanalyse : EN ISO 3405, ASTM D 86
• Säurezahl: DIN 53402
• Verseifungszahl: DIN 53401
• Kinematische Viscosität : DIN 51562
• Erstarrungspunkt : DIN ISO 2207
• Penetration : DIN 51580
• Vinylacetatgehalt : modifiziertes Verfahren nach ISO 8995, DIN 16778 Teil 2
• 2 g Probe werden auf 0,001 g genau eingewogen und in einem 300 ml Erlenmeyerkolben mit 70 ml destilliertem Xylen und 2 Siedeperlen rd. 15 min unter Erwärmung am Rückflusskühler gelöst. Anschließend werden rd. 30 ml Ethanol langsam durch den Rückflusskühler zugegeben, der Erlenmeyerkolben wird von der Heizplatte genommen, es werden 30 ml Ethanol, 0,5 n KOH aus der Bürette und 2 Siedeperlen hinzugefügt, und die Probe wird 1 h am Rückfluss gekocht. Danach wird die Probe erneut vom Rückfluss genommen, mit 30 ml methanolisch-wässriger 0,5 n HCl und 2 Siedeperlen versetzt und 15 min am Rückfluss weitergekocht. Die Probe wird anschließend nach Zugabe von 2 bis 3 Tropfen Phenolphthalein-Lösung (1 Masse% in Ethanol) mit ethanolischer 0,5 n KOH tropfenweise unter Schütteln bis zum Farbumschlag nach rot titriert. Parallel dazu ist ein Blindwert zu ermitteln. $$\mathrm{Vinylacetatgehalt\; in\; Mass}\mathrm{\%}\mathrm{=}\frac{\mathrm{(}\mathrm{V}\mathrm{-}\mathrm{BW}\mathrm{)}\mathrm{\times }\mathrm{F}\mathrm{\times }\mathrm{43}}{\mathrm{10}\mathrm{\times }\mathrm{E}}$$
  
  • E = Einwaage in g
  • F = Faktor der ethanolischen 0,5 n KOH
  • V = Verbrauch in ml an 0,5 n ethanolischer KOH für die Probe
  • B = Verbrauch in ml an 0,5 n ethanolischer KOH für den Blindwert

Schmierfähigkeit: Lubricity-Test (korrigierter "wear scar diameter" bei 60°C)
nach ISO 12156-1The key figures were determined according to the following test methods:

• Cloud Point (CP): DIN EN 23 015
• Cold Filter Plugging Point (CFPP): EN 116
• Boiling analysis: EN ISO 3405, ASTM D 86
• Acid number: DIN 53402
• Saponification number: DIN 53401
• Kinematic Viscosity: DIN 51562
• Freezing point: DIN ISO 2207
• Penetration: DIN 51580
• Vinyl acetate content: modified process according to ISO 8995, DIN 16778 Part 2
• 2 g sample are weighed to the nearest 0.001 g and rd in a 300 ml Erlenmeyer flask with 70 ml of distilled xylene and 2 Siedeperlen. Dissolved for 15 minutes under reflux at the reflux condenser. Subsequently, approx. Slowly add 30 ml of ethanol through the reflux condenser, remove the Erlenmeyer flask from the hot plate, add 30 ml of ethanol, 0.5 n KOH from the burette and 2 boiling beads, and boil the sample for 1 h at reflux. Thereafter, the sample is again taken from the reflux, mixed with 30 ml of methanolic-aqueous 0.5 N HCl and 2 Siedeperlen and further boiled for 15 min at reflux. The sample is then after addition of 2 to 3 drops of phenolphthalein solution (1% by weight in ethanol) with ethanolic 0.5 N KOH titrated dropwise with shaking until the color changes to red. In parallel, a blank value has to be determined. $$\mathrm{Vinyl\; acetate\; content\; in\; mass}\mathrm{\%}\mathrm{=}\frac{\mathrm{(}\mathrm{V}\mathrm{-}\mathrm{BW}\mathrm{)}\mathrm{\times }\mathrm{F}\mathrm{\times }\mathrm{43}}{\mathrm{10}\mathrm{\times }\mathrm{e}}$$
  
  • E = weight in g
  • F = factor of ethanolic 0.5 n KOH
  • V = consumption in ml of 0.5 N ethanolic KOH for the sample
  • B = consumption in ml of 0.5 N ethanolic KOH for the blank value

Lubricity: Lubricity test (corrected "wear scar diameter" at 60 ° C)
according to ISO 12156-1

Short-term sediment test:

To check the sedimentation tendency of crystallized paraffins in mineral oil, a 500 ml sample is stored in a graduated cylinder for 16 h and then the 80% by volume of the sample present above is filtered off with suction and discarded. The remaining 20% by volume of the sample (100 ml) are homogenized at 40 ° C. and the cloud point (CP) according to DIN EN 23 015 is determined therefrom.

SEDAB filtration test:

A 500 ml mineral oil sample is shaken 20 x vertically, tempered for 16 h at 10 ° C, shaken 10 x vertically, and the entire sample is at once through a filter made of cellulose nitrate (diameter 50 mm, pore size 0.8 .mu.m), on a Suction cup with a vacuum of approx. 200 hPa is added, filtered. The time (s) in which the sample passes through the filter is determined. The SEDAB filtration test is passed if the sample passes the filter for a period <120 s.

example 1 1.1 Starting products 1.1.1 Unadditized diesel

Batch: 16080601 Test DK 1
Characterization:
Cloud Point (CP): +6 ° C;
Cold Filter Plugging Point (CFPP): + 2 ° C
Lubricity test: 563 μm
Boiling analysis: Distilled amount (Vol .-%) / Temperature (° C) IBP 10 20 30 40 50 60 70 80 90 FBP 189 243 259 271 281 292 303 317 334 357 385

1.1.2 Additive component a)

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

1.1.3 Additive component b)

The glycerin mixed ester was prepared by the melt esterification process.

The feed funnel of a Werner & Pfleiderer twin-screw extruder ZSK 30, L / D 48, with side-stream metering device for liquid media and two vacuum degassing zones and weighfeeder, contains a maleic anhydride / octadecene copolymer partially esterified with dodecyl alcohol (molar ratio 1: 2.2, acid number 40, molecular weight). number average 2400) at 3.8 kg / h and melted at 90 ° C. By means of the sidestream metering, glycerol dierraic acid ester is metered into the melt at 2.0 kg / h from a storage tank heated at 90 ° C., reacted in the first reaction zone (residence time 4.5 min) at 110 ° C., degassed, in the second reaction zone reacted at 130 ° C (residence time 3.5 min), degassed, conveyed at 85 ° C by means of melt gear pump (type Extrex SP, Maag pump systems) in a self-cleaning melt filter and shaped for shaping in a pastillation with cooling belt in lozenges.

The resulting glycerol mixed ester has an acid number of 8.5 and a melting range of 52 to 59 ° C.

1.2 Preparation of the additive components containing solutions in mineral oil middle distillates

In a stirred tank 20 kg of the additive component b) are mixed with 60 kg of a 50% solution of the additive component a) in an aromatic hydrocarbon mixture (Solvesso) 120 min at 65 ° C, and the mixture is transferred to a storage tank.

1.3 Preparation and testing of the compositions of mineral oil

The additive solution according to 1.2 is injected at 0.48 kg / min into a product stream of diesel fuel additive 16080601 at 800 kg / min and transferred to a storage tank.

The testing of the cold resistance of the mineral oil formulation results in a CFPP value of -10 ° C. The Lubricity test gives a "wear scar diameter" of 405 for. The CP value of the short-term sediment test is + 7 ° C. The SEDAB filtration test is passed (500 ml in 84 s).

If a mineral oil formulation containing only the copolymer wax as an additive is produced under the same conditions, the CFPP value is -3 ° C. and the wear scar diameter is 520 μm. The CP value of the short-term sediment test is + 10 ° C. The SEDAB filtration test is considered failed (468 ml in> 120 s).

Example 2

2.1 Starting products 2.1.1 Unadditized diesel

Batch: 030210 test DK 2
Characterization:
Cloud Point (CP): +7 ° C;
Cold Filter Plugging Point (CFPP): + 2 ° C
Lubricity test: 556 μm
Boiling analysis: Distilled amount (Vol .-%) / Temperature (° C) IBP 10 20 30 40 50 60 70 80 90 FBP 235 266 279 291 301 310 320 337 342 357 374

2.1.2 Additive component a)

Mixture of 10% by weight of a partially hydrolyzed ethylene-vinyl acetate copolymer wax (weight average molecular weight 1850 g / mol, vinyl acetate content of the non-saponified ethylene-vinyl acetate copolymer wax 32.5% by weight, degree of saponification 15% by mole) and 90% by weight of a non-saponified ethylene-vinyl acetate Copolymer wax (manufacturer LEUNA Polymer GmbH, vinyl acetate content 31% by mass, weight average molecular weight 2800 g / mol.

2.1.3 Additive component b)

The glycerin mixed ester was prepared by the melt esterification process.

In the feed funnel of a Werner & Pfleiderer twin-screw extruder ZSK 30, L / D 48, with Seitenstromdosiereinrichtung for liquid media and two Vacuumentgasungszonen, using a feeder belt with a C ₁₆ -C ₁₈ fatty amine teilimidisiertes α-methylstyrene maleic anhydride copolymer (molar ratio 1 , 3: 1.0, acid number 42, melting point 70 ° C) with 3.6 kg / h and melted at 110 ° C. Glycerol dioleyl ester is metered into the melt at a rate of 1.14 kg / h from a storage tank heated at 90 ° C., reacted in the first reaction zone (residence time 4.5 min) at 115 ° C., degassed, in the second reaction zone reacted at 130 ° C (residence time 3.5 min), degassed, conveyed at 85 ° C by means of melt gear pump (type Extrex SP, Maag pump systems) in a self-cleaning melt filter and shaped for shaping in a pastillation with cooling belt in lozenges.

The resulting glycerol mixed ester has an acid number of 4.5 and a melting range of 55 to 66 ° C.

2.1.4 Further additive component

Dodecyl acrylate-ethyl acrylate copolymer (molar ratio 2: 1, number average molecular weight 13500)

2.2 Preparation of the additive components containing solutions in mineral oil middle distillates

In a stirred tank 20 kg of the additive component b), 40 kg of a 60% solution of the additive component a) in C ₈ -C ₉ diesel aromatic fraction and 20 kg of a 10% solution of the further additive component dodecyl acrylate-ethyl acrylate copolymer in toluene Stirred for 120 min at 65 ° C, and the mixture transferred to a storage tank.

2.3 Preparation and Testing of Mineral Oil Compositions

In a product stream of non-additive diesel batch 030210 DGO at 800 kg / min, the additive solution according to 2.2 is injected at 0.12 kg / min and transferred to a storage tank.

The testing of the cold resistance of the mineral oil formulation results in a CFPP value of -11 ° C. The Lubricity test gives a wear scar diameter of 402 μm.
The CP value of the short-term sediment test is + 9 ° C. The SEDAB filtration test is passed (500 ml in 96 s).

If a mineral oil formulation containing only the non-saponified copolymer wax as an additive is prepared under the same conditions, the CFPP value is -5 ° C. and the wear scar diameter is 528 μm. The CP value of the short-term sediment test is + 12 ° C. The SEDAB filtration test is considered failed (468 ml in> 120 s).

Example 3 3.1 Starting products 3.1.1 Unadditized fuel oil

Lot: 030225 test HEL type 1
Characterization:
Cloud Point (CP): +1 ° C;
Cold Filter Plugging Point (CFPP): -1 ° C
Boiling analysis: Distilled amount (Vol .-%) / Temperature (° C) IBP 10 20 30 40 50 60 70 80 90 FBP 165 196 213 230 249 269 290 310 327 344 363

3.1.2 Additive component a)

Mixture of 15% by weight of an oxidized ethylene-vinyl acetate copolymer wax (weight average molecular weight 950 g / mol, acid number 18 mg KOH / g, OH number 70 mg KOH / g) and 85% by weight of a non-oxidized ethylene-vinyl acetate copolymer wax (Manufacturer LEUNA Polymer GmbH, vinyl acetate content 32% by weight, weight average molecular weight 2300 g / mol.

3.1.3 Additive component b)

The glycerin mixed ester was prepared by the melt esterification process.

In the feed funnel of a Werner & Pfleiderer twin-screw extruder ZSK 30, L / D 48, with Seitenstromdosiereinrichtung for liquid media and two Vacuumentgasungszonen, is via a belt weighfeeder with 4.2 kg / h with a C ₁₆ -C ₁₈ fatty amine partially imidated octadecene-maleic anhydride copolymer (Molar ratio 1.4: 1.0, acid number 57, melting point 55 ° C) and metered at 115 ° C melted. By means of the sidestream metering, an ester of glycerol and an acid mixture of erucic acid / oleic acid (molar ratio 1: 1, degree of esterification 82 mol%) is metered into the melt at 2.72 kg / h from a storage tank heated at 90 ° C. (in the first reaction zone). Residence time 4.5 min) reacted at 120 ° C, degassed, in the second reaction zone at 130 ° C (residence time 3.5 min) reacted degassed, at 95 ° C by means of melt gear pump (type Extrex SP, Maag pump systems) in a promoted self-cleaning melt filter and shaped for shaping in a pastillation with cooling belt in lozenges.

The resulting glycerol mixed ester has an acid number of 3.5 and a melting range of 55 to 64 ° C.

3.2 Preparation of the additive components containing solutions in mineral oil middle distillates

In a stirred tank 25 kg of the additive component b) and 50 kg of a 60% solution of the additive component a) mixed in C ₈ -C ₉ -Dieselaromatenfraktion 120 min at 65 ° C, and transferred the mixture into a storage tank.

3.3 Preparation and testing of mineral oil compositions

In a product stream of non-additive fuel oil batch 030225 at 800 kg / min, the additive solution according to 3.2 is injected at 0.24 kg / min and transferred to a storage tank.

The testing of the cold resistance of the mineral oil formulation results in a CFPP value of -15 ° C.

If a mineral oil formulation containing only the copolymer wax as an additive is produced under the same conditions, the CFPP value is -12 ° C.

Example 4 4.1 Starting products 4.1.1 Unadditized fuel oil

Lot: 030218 test HEL 2
Characterization:
Cloud Point (CP): +2 ° C;
Cold Filter Plugging Point (CFPP): -1 ° C
Boiling analysis: Distilled amount (Vol .-%) / Temperature (° C) IBP 10 20 30 40 50 60 70 80 90 FBP 173 194 207 225 247 273 299 320 337 355 379

4.1.2 Additive component a)

Mixture of 10% by weight of a vinyl acetate-grafted ethylene-vinyl acetate copolymer wax (prepared according to DD 293 125 A5 , Total content of vinyl acetate 38% by weight, weight average molecular weight 3400 g / mol, vinyl acetate content of the non-grafted ethylene-vinyl acetate copolymer wax 32% by weight) and 90% by weight of an ungrafted ethylene-vinyl acetate copolymer wax (manufacturer LEUNA Polymer GmbH, vinyl acetate content 32.5% by mass %, Weight average molecular weight 2400 g / mol.

4.1.3 Additive component b)

The glycerin mixed ester was prepared by the melt esterification process.

In the feed funnel of a Werner & Pfleiderer twin-screw extruder ZSK 30, L / D 48, with Seitenstromdosiereinrichtung for liquid media and two Vacuumentgasungszonen, via a weighfeeder with 4.0 kg / h with octadecyl alcohol partially esterified α-methylstyrene-maleic anhydride copolymer (molar ratio of 1 , 1: 1.0, acid number 55, melting point 64 ° C) and melted at 90 ° C. About the side stream dosing is from a heated at 110 ° C storage tank, an ester of glycerol and an acid mixture of erucic acid / oleic acid / linoleic acid / linolenic acid (molar ratio 6: 1: 1: 1), degree of esterification 74 mol%) with 2.4 kg / h in the melt metered, reacted in the first reaction zone (residence time 4.5 min) at 125 ° C, degassed, in the second reaction zone at 135 ° C (residence time 3.5 min) reacted, degassed, at 95 ° C by means of melt gear pump (type Extrex SP , Maag pump systems) into a self-cleaning melt filter and formed into lozenges for shaping in a pastillation plant with cooling belt.

The resulting glycerol mixed ester has an acid number of 5.5 and a melting range of 53 to 63 ° C.

4.1.4 Further additive components

Polyethylene glycol monomethyl ether, number average molecular weight 1500
2-ethylhexyl acrylate-ethyl acrylate copolymer (molar ratio 2: 1)

4.2 Preparation of the additive components containing solutions in mineral oil middle distillates

20 kg of the additive component b), 20 kg of a 60% solution of the additive component a) in C ₈ -C ₉ diesel aromatic fraction, 1 kg of the further additive component polyethylene glycol monomethyl ether, number average molecular weight 1500, and 8 kg of a 10 % solution of the further additive component 2-ethylhexyl acrylate-ethyl acrylate copolymer (molar ratio 2: 1) in toluene, Stirred for 120 min at 65 ° C, and the mixture transferred to a storage tank.

4.3 Preparation and testing of mineral oil compositions

In a product stream of non-additive fuel oil batch 030225 at 800 kg / min, the additive solution according to 4.2 is injected at 0.28 kg / min and transferred to a storage tank.

The testing of the cold resistance of the mineral oil formulation gives a CFPP value of -14 ° C.

If a mineral oil formulation containing only the copolymer wax as an additive is produced under the same conditions, the CFPP value is -1 ° C.

Example 5 5.1 Starting products 5.1.1 Unadditized diesel

Batch: 16080601 Test DK 1
Characterization:
Cloud Point (CP): +6 ° C;
Cold Filter Plugging Point (CFPP): + 2 ° C
Boiling analysis: Distilled amount (Vol .-%) / Temperature (° C) IBP 10% 20% 30% 40% 50% 60% 70% 80% 90% FBP 189 243 259 271 281 292 303 317 334 357 385

5.1.2 Additive component a)

Ethylene-vinyl acetate copolymer wax (manufacturer LEUNA Polymer GmbH, vinyl acetate content 32% by mass, weight average molecular weight 2300 g / mol).

5.1.3 Additive component c)

α-Methylstyrene-maleic anhydride copolymer, partially-imidized with C ₁₆ -C ₁₈ -fatty amine, number-average molecular weight 12800 g / mol, acid number 35

Preparation of the additive component c)

81 l of α-methylstyrene, 7 l of α-methylstyrene dimer and 20 l of acetone are introduced into a 500 l stirred reactor and the stirred reactor is heated to 59 ° C. Within 6 h, a solution of 52 kg of maleic anhydride and 2.4 kg Azoisobuttersäuredinitril in 150 1 of acetone is uniformly metered into the stirred reactor and the reaction mixture is stirred for a further 6 h at 70 to 73 ° C.

An analysis pattern of the copolymer (MCP5) has an acid number of 445 mg KOH per gram of copolymer. NMR studies reveal 1.3 α-methylstyrene dimer end groups / mole.

The still 54 to 56 ° C warm polymer solution is then fed continuously to a two-roll vacuum dryer and separated into a powdered copolymer with about 1.1% by mass residual volatile and in acetone.

For partial imidization of the copolymer in a 500 1 stirred reactor above a 160 ° C boiling C ₈ -C ₉ -Dieselaromatenfraktion in an amount of 382 kg and 122 kg C ₁₆ -C ₁₈ fatty amine are introduced and heated to 130 ° C. 135.5 kg of the copolymer are continuously metered into this solution within 4 hours. The internal temperature in the stirred reactor rises to 180 to 185 ° C, and it forms water, which is distilled off azeotropically with an approximately equal amount of C ₈ -C ₉ -Dieselaromatenfrak-tion. After a total of 6 hours of reaction time at 160 to 190 ° C, 8.5 kg of water and 10.2 kg of solvent are distilled off. A 40% strength solution of the partially imidized copolymer having an acid number of 35 and a molar mass number average of 12800 g / mol is obtained.

5.1.4 Further additive components

Mixture of C ₃ -oxyalkyl-bridged unsaturated C ₁₈ -C ₂₄ -carboxylic acids, degree of esterification 92 mol%, content of C ₁₈ -unsaturated fatty acids 32 mass%, content of C ₂₂ -unsaturated fatty acids 48 mass%, iodine number 96 ethyl acrylate-ethylhexyl acrylate copolymer (molar ratio 3: 2, number average molecular weight 13500)

5.2 Preparation of the additive components containing solutions in mineral oil middle distillates

In a stirred vessel, 25 kg of a 40% solution of additive component c) in C ₈ -C ₉ -Dieselaromatenfraktion, 50 kg of a 50% solution of the additive component a) in an aromatic hydrocarbon mixture (Solvesso), 20 kg of a mixture of C ₃ -oxyalkyl bridged unsaturated C ₁₈ -C ₂₄ carboxylic acids as further additive component and 19 kg of a 20% solution of the further additive component ethyl acrylate-ethylhexyl acrylate copolymer in toluene for 90 min at 65 ° C mixed, and transferred the mixture into a storage tank.

5.3 Preparation and testing of the mineral oil formulation

The additive solution according to 5.2 is injected at 0.48 kg / min into a product stream of diesel fuel additive 16080601 at 800 kg / min and transferred to a storage tank.

The testing of the cold resistance of the mineral oil formulation results in a CFPP value of -16 ° C. The CP value of the short-term sediment test is + 5 ° C. The SEDAB filtration test is passed (500 ml in 76 s).

If a mineral oil formulation containing only the copolymer wax as an additive is produced under the same conditions, the CFPP value is -3 ° C. The CP value of the short-term sediment test is + 10 ° C. The SEDAB filtration test is considered failed (468 ml in> 120 s).

Example 6 6.1 Starting products 6.1.1 Unadditized diesel

Batch: 030210 test DK 2
Characterization:
Cloud Point (CP): +7 ° C;
Cold Filter Plugging Point (CFPP): + 2 ° C
Boiling analysis: Distilled amount (Vol .-%) / Temperature (° C) IBP 10% 20% 30% 40% 50% 60% 70% 80% 90% FBP 235 374 266 279 291 301 310 320 337 342 357

6.1.2 Additive component a)

Mixture of 10 wt% of a partially hydrolyzed ethylene-vinyl acetate copolymer wax (weight average molecular weight 1600 g / mol, vinyl acetate content of non-saponified ethylene-vinyl acetate copolymer wax 32 wt%, degree of saponification 15 mol%) and 90 wt% of an ethylene-vinyl acetate copolymer wax (manufacturer LEUNA Polymer GmbH, vinyl acetate content 32% by weight, weight average molecular weight 2300 g / mol).

6.1.3 Additive component c)

α-methylstyrene-maleic anhydride copolymer, partially dimidinated with dodecylamine, number average molecular weight 14200 g / mol, acid number 56

Preparation of the additive component c)

In a 500 1 stirred reactor 83 1 α-methylstyrene, 5 1 α-methylstyrene dimer 62 kg of maleic anhydride and 110 1 2-butanone presented and the stirred reactor heated to 70 ° C. Within 2 h, a solution of 1.9 kg of dibenzoyl peroxide in 52 l of 2-butanone is metered evenly into the stirred reactor and the reaction mixture is stirred at 72 to 73 ° C for a further 10 h.
An analytical pattern of the copolymer has an acid number of 452 mg KOH per gram of copolymer. NMR studies reveal 1.1 α-methylstyrene dimer end groups / mole.
The about 70 ° C warm polymer solution is now continuously metered in a 500 1 stirred reactor containing 280 1 2-ethylhexanol and heated to a temperature of 150 ° C, distilled off of 2-butanone-2. Now within 4 hours 104 kg of a C ₁₆ - C ₁₈ fatty amine are metered, wherein the temperature is raised to 165 to 185 ° C to distill off water together with a small amount of 2-ethylhexanol.
This gives a 40% solution of the partially imidized copolymer c) in 2-ethylhexanol having an acid number of 56 and a molecular weight average of 14,200 g / mol.

6.1.4 Further additive components

Triester of pentaerythritol with oleic acid
Diethylenglycolmonolauroylester

6.2 Preparation of the additive components containing solutions in mineral oil middle distillates

In a stirred vessel 25 kg of a 40% solution of the additive component c) in 2-ethylhexanol, 50 kg of a 60% solution of the additive component a) in C ₈ -C ₉ -Dieselaromatenfraktion, 20 kg triester of pentaerythritol added with oleic acid as a further additive component and 1 kg of the further additive component diethylene glycol monolaurol ester, stirred for 90 min at 65 ° C, and transferred the mixture into a storage tank.

6.3 Preparation and testing of the mineral oil formulation

In a product stream of non-additive diesel batch 030210 at 800 kg / min, the additive solution according to 6.2 is injected at 0.24 kg / min and transferred to a storage tank.

Testing the cold resistance of the mineral oil formulation results in a CFPP value of -7 ° C. The CP value of the short-term sediment test is + 7 ° C. The SEDAB filtration test is passed (500 ml in 82 s).

If a mineral oil formulation containing only the copolymer wax as an additive is produced under the same conditions, the CFPP value is -5 ° C. The CP value of the short-term sediment test is + 12 ° C. The SEDAB filtration test is considered failed (468 ml in> 120 s).

Example 7 7.1 Starting products 7.1.1 Unadditized fuel oil

Lot: 030225 test HEL 1
Characterization:
Cloud Point (CP): +1 ° C;
Cold Filter Plugging Point (CFPP): -1 ° C
Boiling analysis: Distilled amount (Vol .-%) / Temperature (° C) IBP 10% 20% 30% 40% 50% 60% 70% 80% 90% FBP 165 196 213 230 249 269 290 310 327 344 363

7.1.2 Additive component a)

Mixture of 15% by weight of an oxidized ethylene-vinyl acetate copolymer wax (weight average molecular weight 950 g / mol, acid number 18 mg KOH / g, OH number 70 mg KOH / g) and 85% by weight of a non-oxidized ethylene-vinyl acetate copolymer wax (Manufacturer LEUNA Polymer GmbH, vinyl acetate content 32% by mass, weight average molecular weight 2300 g / mol).

7.1.3 Additive component c)

α-methylstyrene-maleic anhydride copolymer, partially imidized with C ₁₂ -C ₁₄ -fatty amine mixture, weight average molecular weight 7000 g / mol, acid number 25

Preparation of the additive component c)

In a 500 1 stirred autoclave 83 1 α-methyl styrene, 12 l of α-methylstyrene dimer, 62 kg of maleic anhydride and 140 1 presented 1,2-dichloroethane and heated to 90 ° C.

Within 2 h, a solution of 2.5 kg of tert-butyl peroxy-2-ethylhexanoate in 55 l of 1,2-dichloroethane is metered evenly into the stirred autoclave and the reaction mixture is stirred at 90 to 93 ° C. for a further 10 h.

An analysis pattern of the copolymer has an acid value of 430 mg KOH per gram of copolymer. NMR studies show 1.4 α-methylstyrene dimer end groups / mole.

The about 90 ° C warm polymer solution is now continuously in a 500 1 stirred reactor containing 280 1 of a C ₈ -C ₉ -Dieselaromatenfraktion and 122 kg of a C ₁₂ - C ₁₄ fatty amine mixture and heated to a temperature of 160 ° C. , Metered with distilling off of 1,2-dichloroethane and the water of reaction of the imidization.

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

7.1.4 Further additive components

Diester of ethylene glycol with erucic acid
N- (2-hydroxyethyl) oleylamine

7.2 Preparation of the additive components containing solutions in mineral oil middle distillates

In a stirred tank containing 25 kg of a 40% solution of the additive component c) in C ₈ -C ₉ -Dieselaromatenfraktion at 65 ° C, 50 kg of a 60% solution of the additive component a) in C ₈ -C ₉ -Dieselaromatenfraktion, 20 kg of diester of ethylene glycol with erucic acid as a further additive component and 3 kg of the further additive component N- (2-hydroxyethyl) oleylamine, stirred for 90 min at 65 ° C, and the mixture into a Storage tank transferred.

7.3 Production and testing of the mineral oil formulation

In a product stream of non-additive fuel oil batch 030225 at 800 kg / min, the additive solution according to 7.2 is injected at 0.24 kg / min and transferred to a storage tank.

The testing of the cold resistance of the mineral oil formulation results in a CFPP value of -15 ° C.

If a mineral oil formulation containing only the copolymer wax as an additive is produced under the same conditions, the CFPP value is -13 ° C.

Example 8 8.1 Starting products 8.1.1 Unadditized diesel

Batch: 16080601 Test DK 1
Characterization:
Cloud Point (CP): +6 ° C;
Cold Filter Plugging Point (CFPP): + 2 ° C
Boiling analysis: Distilled amount (Vol .-%) / Temperature (° C) IBP 10% 20% 30% 40% 50% 60% 70% 80% 90% FBP 189 243 259 271 281 292 303 317 334 357 385

8.1.2 Additive component a)

Ethylene-vinyl acetate copolymer wax (manufacturer LEUNA Polymer GmbH, vinyl acetate content 32% by mass, weight average molecular weight 2300 g / mol).

8.1.3 Additive component c)

α-methylstyrene-maleic anhydride copolymer, partially staged with stearylamine, molecular weight average 13750 g / mol, acid number 51

Preparation of the additive component c)

81 l of α-methylstyrene, 7 l of α-methylstyrene dimer and 20 l of acetone are introduced into a 500 l stirred reactor and the stirred reactor is heated to 59.degree. Within 6 h, a solution of 52 kg of maleic anhydride and 2.4 kg Azoisobuttersäuredinitril in 150 1 of acetone is uniformly metered into the stirred reactor and the reaction mixture is stirred for a further 6 h at 70 to 73 ° C.

An analysis pattern of the copolymer has an acid number of 445 mg KOH per gram of copolymer. NMR studies yield 1.3 α-methylstyrene dimer end groups / mole.

The still 54 to 56 ° C warm polymer solution is then fed continuously to a two-roll vacuum dryer and into a powdered copolymer with about 1.1% residual volatiles and acetone separated.

For the partial imidization of the copolymer, a C ₈ -C ₉ -diesel aromatic fraction boiling above 160 ° C. in an amount of 382 kg and 135 kg of stearylamine is introduced into a 500 1 stirred reactor and heated to 130 ° C. 135.5 kg of the copolymer are continuously metered into this solution within 4 hours. The internal temperature in the stirred reactor rises to 180 to 185 ° C, and it forms water, which is distilled off azeotropically with an approximately equal amount of C ₈ -C ₉ -Dieselaromatenfraktion. After a total of 6 hours of reaction time at 160 to 190 ° C, 8.5 kg of water and 10.2 kg of solvent are distilled off.
A 40% strength solution of the stearylamine-partially imidized copolymer having an acid number of 51 and a molar mass average of 13750 g / mol is obtained.

8.1.4 Further additive components

Mixture of C ₃ -oxyalkyl-bridged unsaturated C ₁₈ -C ₂₄ -carboxylic acids, degree of esterification 92 mol%, content of C ₁₈ -unsaturated fatty acids 32 mass%, content of C ₂₂ -unsaturated fatty acids 48 mass%, iodine number 96 ethyl acrylate-octadecyl acrylate copolymer (molar ratio 4: 1, number average molecular weight 8400)

8.2 Preparation of the additive components containing solutions in mineral oil middle distillates

In a stirred tank 25 kg of a 40% solution of the additive component c) in C ₈ -C ₉ -Dieseleromatenfraktion, 50 kg of a 50% solution of the additive component a) in an aromatic hydrocarbon mixture (Solvesso), 20 kg of a mixture of C ₃ -oxyalkylverbrückter unsaturated C ₁₈ -C ₂₄ carboxylic acids as further additive component and 19 kg of a 20% solution of the further additive component ethyl acrylate Octadecyl acrylate copolymer in toluene at 65 ° C for 90 minutes, and the mixture transferred to a storage tank.

8.3 Preparation and testing of the mineral oil formulation

In a product stream of non-additive diesel batch 16080601 at 800 kg / min, the additive solution according to 8.2 is injected at 0.48 kg / min and transferred to a storage tank.
The testing of the cold resistance of the mineral oil formulation results in a CFPP value of -17 ° C.
If a mineral oil formulation containing only the copolymer wax as an additive is produced under the same conditions, the CFPP value is -3 ° C.

Example 9 9.1 Starting products 9.1.1 Unadditized diesel

Batch: 16080601 Test DK 1
Characterization:
Cloud Point (CP): +6 ° C;
Cold Filter Plugging Point (CFPP): + 2 ° C
Lubricity test: 563 μm
Boiling analysis: Distilled amount (Vol .-%) / Temperature (° C) IBP 10% 20% 30% 40% 50% 60% 70% 80% 90% FBP 189 243 259 271 281 292 303 317 334 357 385

9.1.2 Additive component a)

Ethylene-vinyl acetate copolymer wax (manufacturer LEUNA Polymer GmbH, vinyl acetate content 32% by mass, weight average molecular weight 2300 g / mol).

9.1.3 Additive component d2)

Wax ester with Vaseline-like consistency, acid number 7.9 mg KOH / g, saponification number 113 mg KOH / g, kinematic viscosity 20.6 mm ² / s, solidification point 34.5 ° C.

Preparation of additive component d2)

A mixture of 25 kg of dimer acid (dimerization product of unsaturated C ₁₈ -fatty acids, average C number 36), 5 kg of stearyl alcohol and 7 kg of cetyl alcohol are melted at 120 ° C. under inert gas introduction in a 70 l stirred reactor and admixed with 50 g of H ₂ SO ₄ reacted while removing the water of reaction until an acid number of 7.9 mg KOH / g is reached. After cooling the melt, the catalyst is neutralized with 0.5 l of 10% NaHCO ₃ , the aqueous phase is separated off, and the wax ester is stripped off.

9.1.4 Further additive components

Ethyl acrylate-ethylhexyl acrylate copolymer (molar ratio 3: 2, number average molecular weight 13500)

9.2 Preparation of the additive component-containing solutions in mineral oil middle distillates

In a stirred tank 25 kg of a 40% solution of the additive component d2) in C ₈ -C ₉ -Dieselaromatenfrak-tion, 50 kg of a 50% solution of the additive component a) in an aromatic hydrocarbon mixture (Solvesso) and 15 kg of a 20% igen solution of the further additive component ethyl acrylate-ethylhexyl acrylate copolymer in toluene for 90 min at 65 ° C mixed, and the mixture transferred to a storage tank.

9.3 Preparation of the mineral oil composition

The additive solution according to 9.2 is injected at 0.48 kg / min into a product stream of diesel fuel additive 16080601 at 800 kg / min and transferred to a storage tank.

The cold resistance test of the mineral oil composition gives a CFPP of -14 ° C. The Lubricity test gives a wear scar diameter of 412 microns.

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

Example 10 10.1 Starting products 10.1.1 Unadditized diesel

Batch: 030210 test DK 2
Characterization:
Cloud Point (CP): +7 ° C;
Cold Filter Plugging Point (CFPP): +2 ° C Lubricity Test: 556 μm
Boiling analysis: Distilled amount (Vol .-%) / Temperature (° C) IBP 10% 20% 30% 40% 50% 60% 70% 80% 90% FBP 235 374 266 279 291 301 310 320 337 342 357

10.1.2 Additive component a)

Mixture of 20% by weight of a partially hydrolyzed ethylene-vinyl acetate copolymer wax (weight average molecular weight 1600 g / mol, vinyl acetate content of non-saponified ethylene-vinyl acetate copolymer wax 32% by mass, degree of saponification 15% by mole) and 80% by weight of ethylene-vinyl acetate copolymer wax (Manufacturer LEUNA Polymer GmbH, vinyl acetate content 32% by mass, weight average molecular weight 2300 g / mol).

10.1.3 additive component d2)

Wax ester with Vaseline-like consistency, acid number 8.6 mg KOH / g, saponification number 118 mg KOH / g, kinematic viscosity 23.1 mm ² / s, solidification point 35.2 ° C.

Preparation of additive component d2)

A mixture of 25 kg dimer acid (dimerization product of unsaturated C ₁₈ -fatty acids, average C-number 36), 5 kg of isostearyl alcohol and 8 kg of eicosanol are melted at 120 ° C. under inert gas introduction in a 70 l stirred reactor and admixed with 50 g of H ₂ SO ₄ as long as reacted with the reaction water until an acid number of 8.6 mg KOH / g is reached. After cooling the melt, the catalyst is neutralized with 1.0 1 5% NaHCO ₃ , the aqueous phase separated, and the wax ester withdrawn.

10.1.4 Further additive components

Triester of pentaerythritol with oleic acid

10.2 Preparation of the additive components containing solutions in mineral oil middle distillates

In a stirred vessel 22 kg of a 50% solution of the additive component d2) in 2-ethylhexanol, 50 kg of a 60% solution of the additive component a) in C ₈ -C ₉ -Dieselaromatenfraktion and 20 kg of a triester of pentaerythritol with oleic acid as another Added additive component, stirred for 90 min at 65 ° C, and the mixture transferred to a storage tank.

10.3 Preparation of the mineral oil composition

The additive solution according to 10.2 is injected at 0.30 kg / min into a product stream of non-additive diesel batch 030210 at 800 kg / min and transferred to a storage tank.

The cold resistance test of the mineral oil composition gives a CFPP value of -8 ° C. The Lubricity test gives a wear scar diameter of 425 μm.

If a composition of mineral oil is prepared under the same conditions, containing exclusively the unmodified copolymer wax a) as an additive, the CFPP value is -5 ° C. and the wear scar diameter is 528 μm.

Example 11 11.1 Starting products 11.1.1 Unadditized fuel oil

Lot: 030225 test HEL 1
Characterization:
Cloud Point (CP): +1 ° C;
Cold Filter Plugging Point (CFPP): -1 ° C
Boiling analysis: Distilled amount (Vol .-%) / Temperature (° C) IBP 10% 20% 30% 40% 50% 60% 70% 80% 90% FBP 165 196 213 230 249 269 290 310 327 344 363

11.1.2 Additive component a)

Mixture of 25 mass% of an oxidized ethylene-vinyl acetate copolymer wax (weight average molecular weight 950 g / mol, acid number 18 mg KOH / g, OH number 70 mg KOH / g) and 75 mass% of a non-oxidized ethylene-vinyl acetate copolymer wax (Manufacturer LEUNA Polymer GmbH, vinyl acetate content 32% by weight, weight average molecular weight 2300 g / mol).

11.1.3 additive component d1)

Oligomeric esters, acid number 12 mg KOH / g, saponification number 175 mg KOH / g, kinematic viscosity (100 ° C) 65 mm ² / s, solidification point 42 ° C, prepared according to EP 0 934 921 A1 from glycerol monostearate and dimer acid (dimerization product of unsaturated C ₁₈ -fatty acids, average C-number 36) by solvent-free oligocondensation with acid catalysis.

11.1.4 Further additive components

N- (2-hydroxyethyl) oleylamine

11.2 Preparation of the additive component-containing solutions in mineral oil middle distillates

In a stirred tank containing 23 kg of a 50% solution of the additive component d1) in C ₈ -C ₉ -Dieselaromatenfraktion at 65 ° C, 50 kg of a 60% solution of the additive component a) in C ₈ -C ₉ -Dieselaromatenfraktion and 3 kg of the additional additive component N- (2-hydroxyethyloleylamine registered, stirred for 90 min at 65 ° C, and the mixture transferred to a storage tank.

11.3 Preparation of mineral oil composition

In a product stream of non-additive fuel oil batch 030225 at 800 kg / min, the additive solution according to 11.2 is injected at 0.28 kg / min and transferred to a storage tank.

The cold resistance test of the mineral oil composition gives a CFPP value of -16 ° C.

If, under the same conditions, a composition is prepared from mineral oil containing only the unmodified copolymer wax a) as an additive, the CFPP value is -13 ° C.

Example 12 12.1 Starting products 12.1.1 Unadditized diesel

Batch: 16080601 Test DK 1
Characterization:
Cloud Point (CP): +6 ° C;
Cold Filter Plugging Point (CFPP): + 2 ° C
Boiling analysis: Distilled amount (Vol .-%) / Temperature (° C) IBP 10% 20% 30% 40% 50% 60% 70% 80% 90% FBP 189 243 259 271 281 292 303 317 334 357 385

12.1.2 Additive component a)

Ethylene-vinyl acetate copolymer wax (manufacturer LEUNA Polymer GmbH, vinyl acetate content 32% by mass, weight average molecular weight 2300 g / mol).

12.1.3 additive component d1)

Oligomeric ester, acid number 14 mg KOH / g, saponification number 185 mg KOH / g, kinematic viscosity (100 ° C.) 76 mm ² / s, solidification point 47 ° C., prepared according to EP 0 934 921 A1 from glycerol monostearate and dimer acid (dimerization product of unsaturated C ₁₈ -fatty acids, average C-number 36) by solvent-free oligocondensation with acid catalysis.

12.1.4 Further additive components

Mixture of C ₃ -oxyalkyl-bridged unsaturated C ₁₈ -C ₂₄ -carboxylic acids, degree of esterification 92 mol%, content of C ₁₈ -unsaturated fatty acids 32 mass%, content of C ₂₂ -unsaturated fatty acids 48 mass%, iodine number 96 ethyl acrylate-octadecyl acrylate copolymer (molar ratio 4: 1, number average molecular weight 8400)

12.2 Preparation of the additive component-containing solutions in mineral oil middle distillates

In a stirred tank 25 kg of a 50% solution of the additive component d1) in C ₈ -C ₉ -Dieselaromatenfraktion, 50 kg of a 50% solution of the additive component a) in an aromatic hydrocarbon mixture (Solvesso), 12 kg of a mixture C ₃ - oxyalkylverbrückter unsaturated C ₁₈ -C ₂₄ carboxylic acids as further additive component and 15 kg of a 20% solution of ethyl acrylate-octadecyl acrylate copolymer as a further additive component in toluene for 90 min at 65 ° C, and the mixture transferred to a storage tank.

12.3 Preparation and testing of mineral oil composition

The additive solution according to 12.2 is injected at 0.52 kg / min into a product stream of diesel fuel additive 16080601 at 800 kg / min and transferred to a storage tank.

The cold resistance test of the mineral oil composition gives a CFPP value of -18 ° C.

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

Claims (11)

1. Compositions of mineral oil as main component and minor amounts of an additive mixture, characterized in that said additive mixture contains the additive components

   a) ethylene-vinyl ester copolymers having weight average molar masses of 3000 to 50.000 and an ethylene content of 50 to 90% by mass
   and

   b) mixed esters of glycerol, wherein 50 to 80 mol% of the hydroxy groups are esterified with unsaturated C₁₂-C₄₀ monocarboxylic acids and 20 to 50 mol% of the hydroxy groups are esterified with partially imidized and/or partially esterified maleic anhydride copolymers,
   and/or

   c) partially and/or fully imidized copolymers of maleic anhydride and α-methylstyrene having number average molar masses of 1500 to 15000 and at least one terminal group based on dimeric α-methylstyrene, and/or

   d) wax compositions based on native starting materials of the type

   d1) wax-like oligomeric esters based on glycerol monostearate and dimer acid, the reaction product corresponding to at least 90% by mass to the structure

   

   wherein n = 1 to 20, sum a+b+c+d = 30, z = 12 to 20
   Y = H or

   

   X = H or -CH₂-CH(OH)-CH₂-O-CO-(CH₂)_z-CH₃, and/or

   d2) wax ester having a petroleum jelly-like consistency based on at least two different straight-chain and/or branched C₁₄-C₃₆ alcohols and dimer acids, the reaction product corresponding to at least 80% by mass to the structure

   

   wherein i ₌ 13 to 35; s = 13 to 35,
   sum of k + m + n + p is 30 to 34, and (CH₂)_i or (CH₂)_s is straight-chain or straight-chain and branched,
   the content of said additive mixture in the mineral oil being 0.005 to 1% by mass and each of the mass ratios of the additive components a/b or a/c or a/d being 10 : 90 to 90 : 10.
2. Compositions according to claim 1, characterized in that the ethylene-vinyl ester copolymers of the additive mixture are ethylene/vinyl acetate copolymers having a vinyl acetate content of 12 to 50% by mass.
3. Compositions according to claim 1 or claim 2,
   characterized in that the ethylene-vinylester copolymers of the additive mixture are mixtures of 10 to 90% by mass of unmodified ethylene-vinylester copolymers and 90 to 10% by mass of ethylene-vinylester copolymers modified by polar groups.
4. Compositions according to claim 3, characterized in that the modified ethylene-vinylester copolymers of the additive mixture are oxidized ethylene-vinylester copolymers, partially saponified ethylene-vinylester copolymers, hemiacetals of partially saponified ethylene-vinyl ester copolymers, and/or ethylene-vinylester copolymers grafted by polar unsaturated monomers of the vinylester, (meth)acrylicester, and/or vinylether type.
5. Compositions according to one or more of claims 1 to 4, characterized in that in the mixed esters of glycerol of the additive mixture, the C₁₂-C₄₀ monocarboxylic acids contained as esterification component consist of 45 to 52% by mass of C₂₂ monocarboxylic acids, based on the total mass of C₁₂-C₄₀ monocarboxylic acids, and the partially imidized maleic anhydride copolymers contained as esterification components are maleic anhydride-α-methylstyrene copolymers partially imidized with C₆-C₂₄ monoalkylamines, wherein the molar ratio of anhydride groups in the copolymer / bound C₆-C₂₄ monoalkylamine in the copolymer is 8 : 1 to to 1.3 : 1.
6. Compositions according to one or more of claims 1 to 4, characterized in that the partially imidized copolymers of maleic anhydride and α-methylstyrene as additive component c) are partially with C₆-C₂₄ monoalkylamines imidized maleic anhydride-α-methylstyrene copolymers, wherein the molar ratio of anhydride groups in the copolymer / bound C₆-C₂₄ monoalkylamine in the copolymer is 8 : 1 to 1.3 : 1.
7. Compositions according to one or more of claims 1 to 4, characterized in that the wax esters having a petroleum jelly-like consistency as additive component d2) are wax esters based on guerbet alcohols of the type 2-hexyldecan-1-ol, 2-octyldecan-1-ol, or 2-octyldecan-1-ol and dimer acids, obtained by cleavage of vegetable oils having a high oleic acid content and subsequent catalytic dimerization.
8. Compositions of mineral oil according to one or more of claims 1 to 7, characterized in that the mineral oils are crude oils or fuel oils from a middle distillate having a sulfur content below 0.05% by mass, preferably heating oils, gas oils, or diesel oils.
9. Compositions of mineral oil according to one or more of claims 1 to 8, characterized in that said compositions of mineral oil contain a total of 0 to 200% by mass, based on the additive components of a+b, a+c, a+d, a+b+c, a+b+c+d, or a+c+d, of additional additive components of the type fatty acid mixtures, polar nitrogen compounds, preferably polyamines, ether amines, amino alcohols, amine salts, amides or imides of polyvalent carboxylic acids; modified copolymers of ethylenically unsaturated C₄-C₂₀ dicarboxylic acid anhydrides, unmodified ethylene-vinylester copolymers, C₇-C₃₀ alcohols, polyalkylene glycols, esters or ethers of polyoxyalkylene compounds, C₂-C₆ oxyalkyl-bridged C₁₂-C₄₀ monocarboxylic acids, preferably C₃-C₄ oxyalkyl-bridged unsaturated C₁₆-C₂₄ monocarboxylic acids having a content of C₂₂ monocarboxylic acids, based on the total mass of the C₁₆-C₂₄ monocarboxylic acids, of 45 to 52% by mass, hydrocarbon polymers, alkylphenol-aldehyde copolymers, aromatic compounds having C₈-C₁₀₀ alkyl substituents, carboxylized polyamines, detergents, corrosion inhibitors, demulsifiers, metal deactivators, cetane improvers, antifoaming agents, and/or cosolvents.
10. A process for producing compositions of mineral oil as main component and minor amounts of an additive mixture, characterized in that said compositions containing the additive components

    a) ethylene-vinylester copolymers having weight average molar masses of 3000 to 5000 and an ethylene content of 50 to 90% by mass
    and

    b) mixed esters of glycerol, wherein 50 to 80 mol% of the hydroxy groups are esterified with unsaturated C₁₂-C₄₀ monocarboxylic acids and 20 to 50 mol% of the hydroxy groups are esterified with partially imidized and/or partially esterified maleic anhydride copolymers,
    and/or

    c) partially and/or fully imidized copolymers of maleic anhydride and α-methylstyrene having number average molar masses of 1500 to 15000 and at least one terminal group based on dimeric α-methystyrene,
    and/or

    d) wax compositions based on native starting materials of the type

    d1) wax-like oligomeric ester based on glycerol monostearate and dimer acid, the reaction product corresponding to at least 90% by mass to the structure

    

    wherein n = 1 to 20, sum a+b+c+d = 30, z = 12 to 20
    Y = H or

    

    X = H or -CH₂-CH(OH)-CH₂-O-CO-(CH₂)_z-CH₃,
    and/or

    d2) wax ester having a petroleum jelly-like consistency based on at least two different straight-chain and/or branched C₁₄-C₃₆ alcohols and dimer acids, the reaction product corresponding to at least 80% by mass to the structure

    

    wherein i ₌ 13 to 35; s = 13 to 35,
    sum of k + m + n + p is 30 to 34, and (CH₂)_i or (CH₂)_S is straight-chain or straight-chain and branched,
    the content of said additive mixture in the mineral oil being 0.005 to 1% by mass and each of the mass ratios of the additive components a/b or a/c or a/d being 10 : 90 to 90 : 10,
    are produced by a pre-homogenizing process, wherein

    - in the first process step, solutions containing 1 to 60% by mass of additive components in mineral oil middle distillates are produced at 20 to 90 °C, and

    - in the second process step, the solutions containing additive components are homogenized with the mineral oil as main component,

    a total of 0 to 200% by mass, based on the additive components a+b, a+c, a+d, a+b+c, a+b+c+d, or a+c+d, of additional additive components being added to the mineral oil in the first and/or second process step.
11. The use of compositions according to one or more of claims 1 to 9 as flowable media to be transported at low temperatures and as mineral oil fuel with high lubricating effect and flowability.