JP5033422B2 - Additive mixture as a component of mineral oil composition - 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 present invention relates to an additive mixture as a component of a composition having a mineral oil as a main component and a trace amount of additive mixture, and a method for producing a mineral oil composition containing the additive mixture.

  Mineral oil and ethylene-vinyl acetate copolymer, hydrocarbon polymer, esterified maleic anhydride-olefin copolymer, polar nitrogen compound (eg, amine salt of polyvalent carboxylic acid) and minor portion of esterified polyoxyalkylene as main components The composition of the additive mixture is 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).

  Disadvantages include insufficient flow and stability of these compositions when stored at low temperatures, and lubrication of these formulations when the mineral oil component has a sulfur content of less than 0.005% by weight. There are restrictions on performance.

  The object of the present invention is for a composition of mineral oil as the main component and a minor part additive mixture with improved flowability and improved stability during storage at low temperatures and improved lubricity. Providing an additive mixture as a component of Improved flow behavior will result in energy savings in the pump set through which these formulations are transported. These additive mixtures should be developed in view of the use of mineral oils with very low sulfur content to produce fuels with improved environmental compatibility with respect to pollutant emissions.

The object of the present invention is to provide the following additive components according to the present invention:
a) an ethylene-vinyl ester copolymer having a weight average molecular weight of 3000 to 50000 and an ethylene proportion of 50 to 90% by weight,
And
b) 50-80 mol% of hydroxyl groups are esterified with unsaturated C ₁₂ -C ₄₀ monocarboxylic acid and 20-50 mol% of hydroxyl groups are partially imidized maleic anhydride copolymer and / or Or a mixed ester of glycerin that is esterified with a partially esterified maleic anhydride copolymer,
And / or c) partial and / or complete of maleic anhydride and α-methylstyrene having a number average molecular weight of 1500-15000 (Molmassen-Zahlenmitten) and at least one end group based on α-methylstyrene dimer Copolymer imidized into
And / or d) a wax composition comprising:
d1) A wax-like oligomeric ester based on glyceryl monostearate and dimer acid, the conversion product being at least 90% by weight,

(Where n = 1 to 20, total a + b + c + d = 30, Z = 12 to 20, Y = H or

X = H or

Is)
Wax-like oligomeric ester corresponding to the structure,
And / or d2) wax esters having a petrolatum-like consistency, based on at least two different linear and / or branched C ₁₄ -C ₃₆ alcohols and dimer acids, the conversion product being at least 80 mass %But,

[Wherein, i = 13 to 35, s = 13 to 35, the sum of k + m + n + p is 30 to 34, and (CH ₂ ) _i or (CH ₂ ) _s is linear or linear and branched]
Wax ester, corresponding to the structure
Wax compositions based on natural starting products of the type
Containing
The content of the additive mixture in the mineral oil is 0.005 to 1% by mass, and the mass ratio a / b or a / c or a / d of the additive components is 10:90 to 90:10, respectively. is there,
This is achieved by an additive mixture as a component of a composition of mineral oil as the main component and a minor portion of the additive mixture.

  Examples of vinyl ester components that may be included in the ethylene vinyl ester copolymer as additive component a) are vinyl acetate, vinyl propionate, 2-ethylhexyl vinyl ester, vinyl laurate, 2-hydroxyethyl vinyl ester and 4-hydroxy. Butyl vinyl ester.

  The ethylene vinyl ester copolymer is 1 to 30% by mass of other unsaturated ester components based on the vinyl ester, such as methyl methacrylate, methyl acrylate, ethyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate. , (Meth) acrylic acid esters such as dodecyl acrylate, ethylene glycol dimethacrylate or hydroxyethyl methacrylate, and / or vinyl ethers such as octyl vinyl ether or hexanediol monovinyl ether.

  Such ethylene-vinyl ester copolymers are preferred as additive component a) in ethylene-vinyl acetate copolymer additive mixtures having a vinyl acetate content of 12-50% by weight.

  Another preferred variant of the ethylene-vinyl ester copolymer contained as additive component a) in the additive mixture is that the ethylene vinyl ester copolymer is modified with 10 to 90% by weight of unmodified ethylene-vinyl ester copolymer with polar groups Of the resulting ethylene-vinyl ester copolymer 90 to 10% by weight.

  The ethylene-vinyl ester copolymer is modified with polar groups and has specific end groups such as aldehyde end groups, preferably acetaldehyde, propionaldehyde, butyraldehyde or isobutyraldehyde derived end groups, carboxyalkyl mercapto end groups, Preferably, end groups derived from mercaptoacetic acid or mercaptopropionic acid, or those having alkoxy end groups incorporated into the copolymer, by partial oxidation, saponification or acetalization, and polar ethylenically unsaturated monomers into the copolymer By grafting, hydroxy groups and / or carboxy groups are incorporated into the copolymer.

  Oxidized ethylene-vinyl ester copolymers that are modified ethylene-vinyl ester copolymers, partially saponified ethylene-vinyl ester copolymers, hemiacetals of partially saponified ethylene-vinyl ester copolymers and / or Preference is given to ethylene-vinyl ester copolymers grafted with vinyl esters, (meth) acrylic esters and / or vinyl ether type polar unsaturated monomers.

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

  The partially saponified ethylene-vinyl ester copolymer is preferably an ethylene-vinyl acetate copolymer having a number average molecular weight of 800-5000 and saponifying 5-30 mol% of vinyl acetate units. .

  In another preferred variation, the modified ethylene-vinyl ester copolymer is a hemiacetal of ethylene vinyl ester-vinyl alcohol copolymer and butyraldehyde.

  Examples of hemiacetals of ethylene-vinyl ester-vinyl alcohol copolymers and butyraldehyde include hemiacetals of ethylene-vinyl acetate-vinyl alcohol copolymer and butyraldehyde reacted in a heterogeneous phase, as described in DD 295 507 A7. Acetal.

  Grafted ethylene-vinyl ester copolymers are prepared by reacting unsaturated monomers in an extruder (DD 282 462 B5) or in a stirred reaction vessel (DD 293 125 B5) in the presence of a heat-disintegrating radical generator. Can be done. It is also possible to modify during the production of the copolymer according to a high pressure process by adding an input amount of monomer to the polymer melt in a low pressure separator or discharge extruder.

  In particular, the grafted ethylene-vinyl ester copolymer as additive component a) is an ethylene vinyl acetate copolymer having a number average molecular weight of 800-5000 grafted with vinyl acetate and a total vinyl acetate content of 20-60% by weight. Wherein the ethylene-vinyl acetate copolymer has a vinyl acetate content of 10-40% by weight of the copolymer backbone and 10-20% by weight of grafted vinyl acetate branches.

The ethylene-vinyl ester copolymer in the additive composition may comprise up to 35% by weight of poly-C ₆ -C ₃₆ alkyl (meth) acrylate.

Of a partially imidized maleic anhydride copolymer or of a partially esterified maleic anhydride copolymer that may be present as an acid component in a mixed ester of glycerin as additive component b) of the additive mixture examples are maleic anhydride, the comonomer component C ₂ -C ₂₀ olefins, C ₈ -C ₂₀ vinyl aromatics, C ₄ -C ₂₁ acrylic acid ester, C ₅ -C ₂₂ methacrylic acid esters, C ₅ -C ₁₄ vinyl silanes , 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 esters, C ₃ -C ₂₀ vinyl ethers and / or hydroxy -C ₁ -C ₈ alkyl - ( It is a copolymer with (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 comonomer to maleic anhydride of 1: 1 to 1: 9 and a weight average molecular weight of 5,000 to 500,000. Partial imidization, ammonia, C ₁ -C ₂₄ monoalkyl amines, C ₆ -C ₁₈ aromatic monoamines, C ₂ -C ₁₈ monoaminoalcohol, monoamine poly molecular weight 400~3000 (C ₂ ~C ₄ alkylene) oxide, and / or molecular weight obtained was performed using a monoether poly (C ₂ -C ₄ alkylene) oxide 100 to 10,000, the copolymer anhydride groups / ammonia, C ₁ -C ₂₄ monoalkyl amines, The respective molar ratio of C ₆ -C ₁₈ aromatic monoamine, C ₂ -C ₁₈ monoamino alcohol or monoaminated poly (C ₂ -C ₄ alkylene) oxide is from 1: 1 to 20: 1.

Examples of suitable amines from which the maleic anhydride copolymer is partially imidized are C ₁₂ -C ₂₄ monoalkylamines such as oleylamine, dodecylamine, hexadecylamine, octadecylamine or eicosylamine; N-dodecyl-1 , 3-diaminopropane, monosubstituted diamines such as N-octadodecyl-1,3-diaminopropane or N-octadecylpropylenetriamine; or aminoalcohols such as aminodecan-10-ol or aminohexadecan-16-ol.

Examples of suitable alcohols in which the maleic anhydride copolymer as acid component in the mixed ester of glycerin as additive component b) of the additive mixture is partially esterified are C _{1 to} C ₁₈ alcohols such as methanol Ethanol, ethylhexanol or stearyl alcohol.

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

50 to 80 mole% of the hydroxyl groups are esterified with unsaturated C ₁₂ -C ₄₀ monocarboxylic acids, 20-50 mol% of the hydroxyl groups, the partially imidized maleic anhydride copolymers, and A suitable method for the preparation of mixed esters of glycerol esterified with a partially esterified maleic anhydride copolymer is glycerin and an unsaturated C ₁₂ -C ₄₀ monocarboxylic acid followed by a partial imide Partial reaction with a conjugated maleic anhydride copolymer and / or a partially esterified maleic anhydride copolymer, or glycerin and a partially imidized maleic anhydride copolymer and / or a partially esterified maleic anhydride copolymers, followed by a partial reaction of an unsaturated C ₁₂ -C ₄₀ monocarboxylic acid That. The reaction is carried out in the molten state, preferably under vacuum degassing at a temperature of 50-135 ° C. in a continuous kneader, or preferably as a solvent process at 85-140 ° C. in an aromatic solvent. sell.

In the mixed ester of glycerin of the additive mixture, the C ₁₂ -C ₄₀ monocarboxylic acid contained as the esterification component is preferably 45 to 52% by mass of C _{22 based on} the total weight of the C ₁₂ -C ₄₀ monocarboxylic acid. It consists of monocarboxylic acid.

Partially imidized maleic anhydride copolymers contained as esterification component in the mixed esters of glycerol of the additive as component b) of the additive mixture, preferably partially in C ₆ -C ₂₄ monoalkylamine Maleic anhydride-α-methylstyrene copolymer imidized in a molar ratio of anhydride groups in the copolymer / bound C ₆ -C ₂₄ monoalkylamine in the copolymer of 8: 1 to 2: 1. One maleic anhydride-α-methylstyrene copolymer.

Examples of partially imidized copolymers of maleic anhydride and α-methylstyrene as additive component c) are copolymers in which both monomers are in an approximately equimolar ratio, with partial and / or complete imidization but ammonia, C ₁ -C ₂₄ monoalkyl amines, C ₆ -C ₁₈ aromatic monoamines, C ₂ -C ₁₈ monoaminoalcohol, monoamine poly (C ₂ -C ₄ alkylene) oxide and / or mono-etherified, Conducted with poly (C ₂ -C ₄ alkylene) oxide, copolymer anhydride group / ammonia, C ₁ -C ₂₄ monoalkylamine, C ₆ -C ₁₈ aromatic monoamine, C ₂ -C ₁₈ monoamino alcohol and monoamine A copolymer in which the molar ratio of the respective amino groups of the modified poly (C ₂ -C ₄ alkylene) oxide is 1: 1 to 20: 1, respectively.

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

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

  Wax-like oligomeric esters based on glyceryl monostearate and dimer acid as additive component d1) are oligomeric esters as described in EP 0 934 921 A1. The glyceryl monostearate component can be produced by enzymatic cleavage of rapeseed oil, isolation of the glyceryl monooleate formed, and subsequent hydrogenation. A suitable method for producing the dimer acid component is dimerization of unsaturated fatty acids that are formed after cutting of the vegetable oil. The oligomeric ester is produced by solventless oligocondensation with an acid catalyst.

  The additive component d1) is preferably a wax-like oligomeric ester having a degree of oligomerization of 2-8.

  The wax ester d2) having a petroleum jelly-like consistency is a wax ester described in EP 0 970 998 A1.

  The wax ester d2) having a petrolatum-like consistency contained in the additive mixture is a 2-hexyldecan-1-ol, 2-octyldecan-1-ol or 2-octyldecan-1-ol type gel (Guerbet). Preference is given to wax esters based on alcohols and dimer acids obtained by cleaving vegetable oils having a high oleic acid content and then catalytic dimerization. The presence of an acidic catalyst at a temperature of 100 to 160 ° C. in a stirred reaction vessel by applying a vacuum of −0.5 to −1.5 bar from Gerve alcohol and dimer acid. It can be prepared by catalytic esterification below.

  Examples of mineral oils that form the main component in mineral oil compositions include crude oil and petroleum fractions in the distillation range of 100-500 ° C, such as lubricating oil, kerosene, diesel oil, heating oil, heavy oil fuel, petroleum, Such as tractor fuel and cracked gasoline. Mineral oil may be up to 30% by weight of a Fischer-Tropsch synthetic hydrocarbon, up to 20% by weight of sunflower oil, soybean oil, rapeseed oil modified vegetable oil, animal oil, biodiesel and / or 10%. % Of alcohols such as methanol or ethanol.

  The mineral oil is preferably crude oil or a fuel oil derived from a middle distillate having a sulfur content of less than 0.05% by mass, particularly fuel oil, light oil or diesel oil.

The composition of mineral oil comprises a mixture of fatty acids, polar nitrogen compounds, preferably polyamines, ether amines, amino alcohols, polyalcohols, up to a total of 200% by weight with respect to the additive components a + b, a + c, a + d, a + b + c, a + b + c + d Amine salts, amides or imides of divalent 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, polyoxyalkylenes The ester or ether of the compound, the C ₂ -C ₆ oxyalkyl bridged C ₁₂ -C ₄₀ monocarboxylic acid, preferably the content of C ₂₂ monocarboxylic acid relative to the total weight of the C ₁₆ -C ₂₄ monocarboxylic acid is 45-52 C ₃ -C ₄ oxyalkyl bridged unsaturated C ₁₆ -C ₂₄ Nokarubon acid, hydrocarbon polymers, alkylphenol - aldehyde copolymers, aromatic compounds having C ₈ -C ₁₀₀ alkyl substituents, carboxylated polyamines, detergents, corrosion inhibitors, demulsifiers, metal deactivators, cetane number Other additive components such as enhancers, antifoams and / or cosolvents may be included.

Examples of fatty acid mixtures contained as other additive components in the mineral oil composition is saturated and / or unsaturated C ₆ -C ₄₀ carboxylic acids, such as lauric acid, palmitic acid, oleic acid, linoleic acid, dimer fatty acid , Alkenyl succinic acid and the like.

  Examples of polyamine type polar nitrogen compounds contained as other additive components in the mineral oil composition include 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 ether amine type polar nitrogen compounds contained as other additive components in the mineral oil composition include 3-methoxypropylamine, 3-N-octyloxypropyl-1,3-diaminopropane and 3-N- (2,4,6-trimethyldecyloxypropyl) -1,3-diaminopropane.

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

Examples of amines used as raw materials for polynitrocarboxylic acid amine salts, amide or imide type polar nitrogen compounds are hydrated tolamine, tetradecylamine, eicosylamine, dioctadecylamine, methylbehenylamine, N-oleyl- 1,3-diaminopropane, a C ₈ -C ₄₀ amine, such as N- stearyl-1-methyl-1,3-diaminopropane or N- oleyl dipropylenetriamine.

  Examples of the polyvalent carboxylic acid used as the raw material of the polyvalent carboxylic acid amine salt or amide type polar nitrogen compound are phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, ethylenediaminetetraacetic acid and cyclohexanedicarboxylic acid.

  Specific examples of amine salt type polar nitrogen compounds included as other additive components in mineral oil compositions include N-methyltriethanolammonium distearyl ester chloride and N-methyltriethanolammonium distearyl ester methosulfate It is.

Examples of other ethylenically unsaturated C ₄ -C ₂₀ optionally ethylenically be included as a monomer component in the modified copolymer of dicarboxylic anhydride-unsaturated C ₄ -C ₂₀ dicarboxylic acid anhydride as an additive component, Allyl succinic anhydride, bicycloheptene dicarboxylic acid anhydride, bicyclooctene dicarboxylic acid anhydride, carbomethoxymaleic anhydride, citraconic anhydride, cyclohexenedicarboxylic anhydride, dodecenyl succinic anhydride, glutaconic anhydride, itaconic anhydride, maleic anhydride Mesaconic anhydride, methylbicycloheptene dicarboxylic acid anhydride and / or methylcyclohexene dicarboxylic acid anhydride, preferably maleic anhydride and / or itaconic anhydride.

Comonomers suitable for ethylenically unsaturated C ₄ -C ₂₀ dicarboxylic acid anhydrides which may be included as monomer components in modified copolymers of ethylenically unsaturated C ₄ -C ₂₀ dicarboxylic acid anhydrides as other additive components Examples of C _{2 to} C ₂₀ olefins, C _{8 to} C ₂₀ vinyl aromatics, C _{4 to} C ₂₁ acrylic esters, C _{5 to} C ₂₂ methacrylates, C _{5 to} C ₁₄ vinyl silanes, C _{6 to} C ₁₅ acrylate silanes, 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 vinyl ethers and / or hydroxy -C ₁ -C ₈ alkyl - (meth) ethylenically unsaturated mono- such acrylate Ma. The ethylenically unsaturated monomers are particularly preferably isobutylene, diisobutylene, vinyl acetate, styrene and α-methylstyrene.

The modified copolymer is a copolymer having a molar ratio of C _{4 to} C ₂₀ ethylenically unsaturated acid anhydride to ethylenically unsaturated monomer of 1: 1 to 1: 9 and a weight average molecular weight of 5,000 to 500,000. there are, ammonia, C ₁ -C ₂₄ monoalkyl amines, C ₆ -C ₁₈ aromatic monoamines, C ₂ -C ₁₈ monoaminoalcohol, monoamine poly (C ₂ -C ₄ alkylene) having a molecular weight of 400 to 3000 oxide , and / or molecular weight was reacted with monomethyl ether poly (C ₂ -C ₄ alkylene) oxide 100 to 10,000, anhydride groups / ammonia copolymer, C ₁ -C ₂₄ monoalkyl amines, C ₆ -C ₁₈ aromatic monoamines, for each of the amino groups of C ₂ -C ₁₈ mono amino alcohol or monoamine poly (C ₂ -C ₄ alkylene) oxide Le ratio of 1: 1 to 20: a copolymer is particularly preferably 1.

Particularly suitable as partially or fully imidized copolymers derived from ethylenically unsaturated C ₄ -C ₂₀ dicarboxylic acid anhydrides are such as oleylamine, dodecylamine, hexadecylamine, octadecylamine or eicosylamine C ₁₂ -C ₂₄ monoalkyl amine; N- dodecyl-1,3-diaminopropane, monosubstituted diamines such as N- octadodecyl 1,3-diaminopropane or N- octadecyl propylene triamine; or aminodecane-10-ol, Or a maleic anhydride copolymer imidized with an amino alcohol such as aminohexadecan-16-ol.

Examples of C ₇ -C ₃₀ alcohols that can be included as other additive components in the mineral oil composition are dodecanol, stearyl alcohol and ceryl alcohol.

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

Examples of esters of the polyoxyalkylene compound may be included as other additive components in the mineral oil composition, C ₁₀ -C ₂₄ monoalkyl esters or dialkyl esters of polyalkylene glycols, such as polyethylene glycol monostearyl ester or dioleate Acid polypropylene glycol.

Examples of ethers of polyoxyalkylene compounds in the mineral oil composition can be included as other additive components, C ₁ -C ₄ monoalkyl ethers or dialkyl ethers of polyalkylene glycols such as polyethylene glycol monostearyl ether or polypropylene Glycol dibutyl ether.

C ₂ -C ₆ oxyalkyl crosslinked C ₁₂ -C ₄₀ monocarboxylic acids that may be included as other additive components in the mineral oil composition, C ₂ -C ₆ polyhydric alcohol component and C ₁₂ -C ₄₀ monocarboxylic It consists of an acid component.

Examples of polyhydric alcohols other may be included as the alcohol component in MAY formed additive component C ₂ -C ₆ oxyalkyl crosslinked C ₁₂ -C ₄₀ monocarboxylic acids, ethylene glycol, polyalkylene glycol, glycerine, 1,1,1-tris- (hydroxymethyl) -propane, pentaerythritol and sorbite.

Examples of C ₁₂ -C ₄₀ monocarboxylic acids that may be included as carboxylic acid components in C ₂ -C ₆ oxyalkyl bridged C ₁₂ -C ₄₀ monocarboxylic acids that may form other additive components include lauric acid, Dimer acids based on palmitic acid, stearic acid, oleic acid, elaidic acid, ricinoleic acid, eleostearic acid, linoleic acid, linolenic acid and erucic acid, or oleic acid or linolenic acid.

Further, as the C ₂ -C ₆ oxyalkyl crosslinked C ₁₂ -C ₄₀ monocarboxylic acid, a polyhydric alcohol is esterified with a mixture of C ₁₂ -C ₄₀ monocarboxylic acids, mixed esters of polyhydric alcohols are preferred. Specific examples of C ₂ -C ₆ oxyalkyl bridged C ₁₂ -C ₄₀ monocarboxylic acids include monoesters of ethylene glycol and dilinolenic acid, a C ₃₆ dimer acid, diesters of propylene glycol and oleic acid, pentaerythritol and Triester with stearic acid.

C ₂ -C ₆ oxyalkyl cross-linked C ₁₂ -C ₄₀ monocarboxylic acid as an ester of unsaturated C ₁₆ -C ₂₄ monocarboxylic acid with C ₃ -C ₄ polyhydric alcohol, unsaturated C ₁₆ -C ₂₄ C ₂₂ monocarboxylic acid content to the total weight of the monocarboxylic acids are particularly preferred ester is 45 to 52 mass%.

Examples of preferred C ₃ -C ₄ polyhydric alcohol may be included in the esters of unsaturated C ₁₆ -C ₂₄ monocarboxylic acids with unsaturated C ₁₆ -C ₂₄ monocarboxylic acids, oleic acid, linoleic acid, linolenic acid, and Erucic acid.

Examples of included may be a hydrocarbon polymer as the other additive components in the mineral oil composition, of ethylene and C ₃ -C _{20-.alpha.-olefin} copolymer, ethylene - propylene copolymer, or ethylene - de decene polymer such as Or a hydrated polymer of a number of unsaturated monomers of the hydrated diene copolymer type, such as hydrated polybutadiene or hydrated polyisoprene, having a number average molecular weight up to 30,000.

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

Examples of aromatic compounds having a good C ₈ -C ₁₀₀ alkyl substituents may be included as other additive components in the mineral oil composition, and halogenated hydrocarbons such as halogenated polyethylene wax, benzene or naphthalene such as It can be produced by Friedel-Craft condensation with aromatic hydrocarbons.

Examples of good surfactants are also included as another additive components in the mineral oil compositions are aliphatic sulfonic acids, e.g., C ₈ -C ₃₀ alkane sulfonate or aromatic aliphatic alkane sulfonates, In particular, nonylbenzenesulfonate, dodecylbenzenesulfonate, didodecylbenzenesulfonate and nonylnaphthalenesulfonate.

  Examples of demulsifiers that may be included as other additive components in the mineral oil composition are oxyalkylated phenol formaldehyde condensates, polyalkylene glycol-modified diglycid ethers, polyester amines, or alkoxylated fatty acids.

  Examples of cetane improvers that may be included as other additive components in mineral oil compositions are organic nitrates such as ethyl hexyl nitrate, cyclohexyl nitrate or ethoxyethyl nitrate, or soluble organics such as hydroperoxides or peresters. Peroxide.

  Examples of antifoaming agents that can be included as other additive components in the mineral oil composition are polyalkylene oxide-siloxane block copolymers and carboxylated polyamines.

  Examples of polyalkylene oxide-siloxane block copolymers are block copolymers comprising a combination of trifunctional siloxane blocks such as monomethylsiloxane groups, bifunctional siloxane groups such as dimethylsiloxane groups, and monofunctional siloxane groups such as trimethylsiloxane groups. The preferred length of the siloxane block is 5 to 20 monomer units. A preferred length of the polyalkylene-oxide block is 2 to 40 monomer units, and a polyoxyalkylene block composed of ethylene oxide and / or propylene oxide is preferred.

Examples of carboxylated polyamines as defoaming agent is a reaction product of a C ₈ -C ₂₄ fatty acids and amines (e.g., ethylenediamine, butylene diamine, diethylenetriamine and pentaethylene hexamine-1,2-aminobutanol).

  Examples of co-solvents that may be included as other additive components in mineral oil compositions are gasoline fractions, toluene, xylene, ethylbenzene, isononanol, ethylhexanol, dodecylphenol, epoxidized rapeseed oil and epoxidized soybean oil. is there.

The composition of the mineral oil as the main component and the minor part additive mixture is according to the present invention,
Additive components:
a) an ethylene-vinyl ester copolymer having an average molecular weight of 3000-50000 (Molmassengwichschmitteln) and an ethylene proportion of 50-90% by weight,
And
b) 50-80 mol% of the hydroxyl groups are esterified with unsaturated C12-C40 monocarboxylic acid, and 20-50 mol% of the hydroxyl groups are partially imidized maleic anhydride copolymer and / or partially A mixed ester of glycerin which is esterified with a maleic anhydride copolymer esterified to
And / or c) partial and / or complete of maleic anhydride and α-methylstyrene having a number average molecular weight of 1500-15000 (Molmassen-Zahlenmitten) and at least one end group based on α-methylstyrene dimer A copolymer imidized on and / or d) a wax composition comprising:
d1) A wax-like oligomeric ester based on glyceryl monostearate and dimer acid, the conversion product being at least 90% by weight,

Where n = 1-20, total a + b + c + d = 30, Z = 12-20 and Y = H or

X = H or

Is)
Wax-like oligomeric ester corresponding to the structure,
And / or d2) wax esters having a petrolatum-like consistency based on at least two different linear and / or branched C ₁₄ -C ₃₆ alcohols and dimer acids, the conversion product being at least 80% by weight But,

[Wherein, i = 13 to 35; s = 13 to 35, the sum of k + m + n + p is 30 to 34, and (CH ₂ ) _i or (CH ₂ ) _s is linear or linear and branched]
Wax ester, corresponding to the structure
Wax compositions based on natural starting products of the type
Containing
The content of the additive mixture in the mineral oil is 0.005 to 1% by mass, and the mass ratio a / b or a / c or a / d of the additive components is 10:90 to 90:10, respectively. is there,
Mineral oil composition
-In the first process step, a solution containing 1 to 60% by weight of the additive component in middle distillate mineral oil is produced at 20-90 ° C; and-in the second process step, the solution containing the additive component In a pre-homogeneous process that homogenizes with mineral oil as the main component,
Further, in the first and / or second process step, a method of adding other additive components in total 0 to 200% by mass to the mineral oil based on the additive components a + b, a + c, a + d, a + b + c, a + b + c + d or a + c + d. Use to manufacture.

  Compositions of mineral oil as the main component and a minor part additive mixture are particularly suitable as a fluid medium to be transported at low temperatures and as a mineral oil fuel having high lubricity and fluidity.

  Examples of fluid media to be transported at low temperatures are transportation of crude oil blends from crude oil mine sites to loading and storage through pipelines, as well as transportation of diesel or heating oil blends in pipelines .

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

Examples Characteristic values are as follows:
Cloud point (CP): DIN EN 23 015
Cryogenic filter clogging point (CFPP): EN 116
Distillation analysis: EN ISO 3405, ASTM D 86
Acid value: DIN 53402
Saponification value: DIN 53401
Kinematic viscosity: DIN 51562
Freezing point: DIN ISO 2207
Permeability: DIN 51580
Vinyl acetate content: measured according to a modified method according to ISO 8995, DIN 16778 part 2.

  A 2 g sample is accurately weighed with 0.001 g accuracy and dissolved in a 300 ml Erlenmeyer flask containing 70 ml of distilled xylene and two zeolites under reflux for about 15 minutes. Then about 30 ml of ethanol is slowly added through the reflux condenser, the Erlenmeyer flask is removed from the heating plate, 30 ml of ethanol, 0.5 N (n) KOH from the burette, and two zeolites are added. And reflux the sample for 1 hour. Again, the sample is removed from reflux, mixed with 30 ml of aqueous methanolic 0.5N (n) HCl and two zeolites and refluxed for an additional 15 minutes. After adding 2-3 drops of phenolphthalein solution (1% by weight in ethanol), the sample was titrated drop by drop with ethanolic 0.5N (n) KOH until the color changed to red. To do. The blank value should be measured simultaneously.

E = weight of original sample (unit: g)
F = Coefficient of ethanolic 0.5N (n) KOH V = 0.5N (n) ethanolic KOH consumption for the sample (unit: ml)
B = 0.5N (n) ethanolic KOH consumption for blank value (unit: ml)

  Lubricity: Lubricity test according to ISO 12156-1 (adjustment at 60 ° C. “wear scar diameter”)

Short-time sedimentation test:
To test the sedimentation tendency of recrystallized paraffin in mineral oil, a 500 ml sample is stored in a stage cylinder for 16 hours, and then the top 80% by volume of the sample is withdrawn and discarded. The remaining 20% by volume (100 ml) of the sample is homogenized at 40 ° C. and the cloud point (CP) is then measured according to DIN EN 23 015.

SEDAB filtration test:
A 500 ml mineral oil sample was shaken up and down 20 times, maintained at 10 ° C. for 16 hours, shaken up and down 10 times, and a cellulose nitrate filter (diameter 50 mm, pore diameter 0.8 μm) placed on a suction cap, about 200 hPa Filter all samples at once with a vacuum. Measure the time for the sample to pass through the filter. The SEDAB filtration test passes when the sample passes through the filter in a time of <120 seconds.

Example 1
1.1 Starting product (Ausgangsprodukte)
1.1.1 Diesel without additives Batch: 16080801 Test DK 1
Characteristic:
Cloud point (CP): + 6 ° C;
Low temperature filter clogging point (CFPP): + 2 ° C
Lubrication test: 563 μm
Distillation analysis:

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

1.1.3 Additive component b)
A mixed ester of glycerin was prepared in a melt esterification process.

  Maleic anhydride-octadecene copolymer partially esterified with dodecyl alcohol (molar ratio 1: 2.2, acid number 40, number average molecular weight 2400), L / D ratio 48, side flow for liquid medium Charge at 3.8 kg / h into a feed screw of a Werner & Pfleiderer ZSK 30 twin screw extruder equipped with a unit, two vacuum degassing zones and a belt-type weighing continuous scale for charging and melt at 90 ° C. Add glycerin dierucate from a storage tank heated to 90 ° C. to the melt at 2.0 kg / h via a side flow input unit and within the first reaction zone (residence time 4.5 minutes) Reaction at 110 ° C., degassing, reaction at 130 ° C. in the second reaction zone (residence time 3.5 minutes), degassing, and melt gear pump (extrex SP in self-cleaning melt filter at 85 ° C. , Magag pump systems) and molded into an aromatic tablet using a briquette press equipped with a cooling conveyor.

  The resulting mixed ester of glycerin has an acid value of 8.5 and a melting range of 52-59 ° C.

1.2 Manufacture of a solution containing additive components in middle distillate mineral oil 20 kg of additive component b) is added to 50 parts of additive component a) in an aromatic hydrocarbon mixture (Solvesso) in a stirred reaction vessel. Mix with 60 kg of% solution at 65 ° C. for 120 minutes and transfer the mixture to a storage tank.

1.3 Preparation and testing of mineral oil composition The additive solution according to 1.2 is injected at 0.48 kg / min into the additive-free diesel, batch 16080801, product stream flowing at 800 kg / min, Transfer the mixture to a storage tank.

  Testing the mineral oil formulation for low temperature resistance indicated a CFPP value of -10 ° C. The lubricity test shows a “wear scar diameter” of 405 μm.

  The CP value of the short-time sedimentation test is + 7 ° C. The SEDAB filtration test is accepted (500 ml in 84 seconds).

  When a mineral oil formulation containing only 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-time sedimentation test is + 10 ° C. The SEDAB filtration test is rejected (468 ml in> 120 seconds).

Example 2
2.1 Starting product 2.1.1 Diesel batch without additives: 030210 Test DF 2
Characteristic:
Cloud point (CP): + 7 ° C;
Low temperature filter clogging point (CFPP): + 2 ° C
Lubricity test: 556 μm
Distillation analysis:

2.1.2 Additive component a)
10% by weight of partially saponified ethylene-vinyl acetate copolymer wax (weight average molecular weight 1850 g / mol, vinyl acetate content of non-saponified ethylene-vinyl acetate copolymer wax 32.5% by weight, degree of saponification 15 mol%) and 90% by mass of unsaponified ethylene-vinyl acetate copolymer wax (manufactured by LEUNA Polymer GmbH, vinyl acetate content 31% by mass, weight average molecular weight 2800 g / mol) is mixed.

2.1.3 Additive component b)
A mixed ester of glycerin was prepared in a melt esterification process.

Α-Methylstyrene maleic anhydride-octadecene copolymer (molar ratio 1.3: 1.0, acid value 42, melting point 70 ° C.) partially imidized with C ₁₆ -C ₁₈ aliphatic amine Via a continuous weighing scale, 3.6 kg / h in the feed screw of a Werner & Pfleiderer ZSK 30 twin screw extruder with L / D ratio 48, side-flow unit for liquid medium and two vacuum degassing zones And dissolved by heating at 110 ° C. Glycerol dioleol ester is added to the melt at 1.14 kg / h via a side flow input unit from a storage tank heated to 90 ° C., and the melt is added to the first reaction zone (retention time 4.5 minutes). ) At 115 ° C., degassed, reacted at 130 ° C. in the second reaction zone (residence time 3.5 minutes), degassed, and melt gear pump into self-cleaning melt filter at 85 ° C. (Extrex SP, Maag pump systems), and formed into an aromatic tablet using a briquette press equipped with a cooling conveyor. The resulting mixed ester of glycerin has an acid number of 4.5 and a melting range of 55-66 ° C.

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

2.2 Production of a solution containing additive components in middle distillate mineral oil 20 kg of additive component b), 40 kg of a 60% solution of additive component a) in a C _{8 to} C ₉ diesel aromatic fraction, and 20 kg of a 10% solution of dodecyl acrylate-ethyl acrylate copolymer of another additive component in toluene is stirred for 120 minutes at 65 ° C. in a stirred reaction vessel and the mixture is transferred to a storage vessel.

2.3 Production and testing of mineral oil composition The additive solution according to 2.2 is injected at 0.12 kg / min into a product stream flowing at 800 kg / min of diesel without additives, batch 030210 DGO. Transfer the mixture to a storage tank.

  Testing the mineral oil formulation for low temperature resistance indicated a CFPP value of -11 ° C. The lubricity test shows a “wear scar diameter” of 402 μm. The CP value of the short-time sedimentation test is + 9 ° C. The SEDAB filtration test is accepted (500 ml in 96 seconds).

  When a mineral oil formulation containing only non-saponified copolymer wax as an additive is produced under the same conditions, the CFPP value is −5 ° C. and the “wear scar diameter” is 528 μm. The CP value of the short-time sedimentation test is + 12 ° C. The SEDAB filtration test is rejected (468 ml in> 120 seconds).

Example 3
3.1 Starting product 3.1.1 Heating oil without additives Batch: 030225 Test HEL Type 1 Characteristics:
Cloud point (CP): + 1 ° C;
Low temperature filter clogging point (CFPP): -1 ° C
Distillation analysis:

3.1.2 Additive component a):
15% by weight ethylene oxide-vinyl acetate copolymer wax (weight average molecular weight 950 g / mol, acid value 18 mg KOH / g, OH value 70 mg KOH / g) and 85% by weight non-oxide ethylene-vinyl acetate copolymer wax (LEUNA Polymer GmbH) Manufactured, vinyl acetate content 32 mass%, weight average molecular weight 2300 g / mol).

3.1.3 Additive component b)
A mixed ester of glycerin was produced by the melt esterification method.

An octadecene maleic anhydride-octadecene copolymer partially imidized with a C ₁₆ -C ₁₈ aliphatic amine (molar ratio 1.4: 1.0, acid value 57, melting point 55 ° C.) Through a feed screw of a Werner & Pfleiderer ZSK 30 twin screw extruder equipped with an L / D ratio of 48, a side flow injection unit for liquid media and two vacuum degassing zones, at 4.2 kg / h. And dissolved by heating at 115 ° C. A mixture of glycerin, erucic acid and oleic acid was added to the melt from the storage tank heated to 90 ° C. at a rate of 2.72 kg / h via a side flow input unit, and the melt was added to the first reaction zone (residence). Reaction at 120 ° C. within 4.5 minutes), degassing, reaction at 130 ° C. within the second reaction zone (residence time 3.5 minutes), degassing, self-cleaning melt filter at 95 ° C. It is conveyed inside using a melt gear pump (extrex SP, Maag pump systems) and formed into an aromatic tablet by a briquette press equipped with a cooling conveyor.

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

3.2 Manufacture of a solution containing additive components in middle distillate mineral oil 25 kg of additive component b) and 50 kg of 60% solution of additive component a) in C _{8 to} C ₉ diesel aromatic fraction and Mix for 120 minutes in a stirred reaction vessel at 65 ° C. and transfer the mixture to a storage vessel.

3.3 Production and testing of mineral oil composition The additive solution according to 3.2 is injected at 0.24 kg / min into a product stream flowing at 800 kg / min of heating oil, batch 030225 without additive. And transfer the mixture to a storage tank.

  Testing the mineral oil formulation for low temperature resistance indicated a CFPP value of -15 ° C.

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

Example 4
4.1 Starting product 4.1.1 Heating oil without additives Batch 030218 Test HEL 2
Characteristic:
Cloud point (CP): + 2 ° C;
Low temperature filter clogging point (CFPP): -1 ° C
Distillation analysis:

4.1.2 Additive component a)
Ethylene-vinyl acetate copolymer wax grafted with vinyl acetate (prepared according to DD 293 125 A5, total vinyl acetate content 38% by weight, weight average molecular weight 3400 g / mol, vinyl acetate content of ungrafted ethylene-vinyl acetate copolymer wax 32.5 wt%, saponification degree 32 mol%) 10 wt% and 90 wt% ungrafted ethylene-vinyl acetate copolymer wax (manufactured by LEUNA Polymer GmbH, vinyl acetate content 32.5 wt%, weight average molecular weight 2400 g / mol).

4.1.3 Additive component b)
A mixed ester of glycerin was produced by the melt esterification method.

  Α-Methylstyrene maleic anhydride copolymer partially esterified with octadecyl alcohol (molar ratio 1.1: 1.0, acid number 55, melting point 64 ° C.) is passed through a belt-type metered continuous scale via L / Charged at 4.0 kg / h into the feed screw of a Werner & Pfleiderer ZSK 30 twin screw extruder with D ratio 48, lateral flow inlet unit for liquid medium and two vacuum degassing zones, heated at 90 ° C To dissolve. 1. Establish an ester of glycerin and a mixture of erucic acid / oleic acid / linolenic acid (molar ratio 6: 1: 1: 1) into the melt from a storage tank heated to 110 ° C. via a side flow input unit. Added at 4 kg / h, the melt is reacted at 125 ° C. in the first reaction zone (retention time 4.5 minutes), degassed and in the second reaction zone (retention time 3.5 minutes) React at 135 ° C, deaerate, transport at 95 ° C into self-cleaning melt filter using melt gear pump (extrex SP, Maag pump systems) and form into aromatic tablets with briquette press equipped with cooling conveyor To do.

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

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

4.2 Manufacture of a solution containing additive components in middle distillate mineral oil 20 kg of additive component b), 20 kg of 60% solution of additive component a) in C ₈ -C ₉ diesel aromatic fraction, and 1 kg of other additive component polyethylene glycol monomethyl ether (number average molecular weight 1500) and other additive component ethylhexyl acrylate-ethyl acrylate copolymer (2: 1 molar ratio) in toluene 8 kg 8% Introduce into a stirred reaction vessel, stir for 120 minutes at 65 ° C., and transfer the mixture to a storage vessel.

4.3 Production and testing of mineral oil composition The additive solution according to 4.2 is injected at 0.28 kg / min into a product stream flowing at 800 kg / min of heating oil without additives, batch 030225 And transfer the mixture to a storage tank.

  Testing the mineral oil formulation for low temperature resistance indicated a CFPP value of -14 ° C.

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

Example 5
5.1 Starting product 5.1.1 Diesel batch without additives: 16080601 Test DF 1
Characteristic:
Cloud point (CP): + 6 ° C;
Low temperature filter clogging point (CFPP): + 2 ° C;
Distillation analysis:

5.1.2 Additive component a)
Ethylene-vinyl acetate copolymer wax (manufactured by LEUNA Polymer GmbH, vinyl acetate content 32 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 aliphatic amine, number average molecular weight 12800 g / mol, acid value 35

Preparation of additive component c) 81 l of α-methylstyrene, 7 l of α-methylstyrene dimer and 20 l of acetone are placed in a 500 l stirred reactor and the stirred reactor is heated to 59 ° C. A solution containing 52 kg of maleic anhydride and 2.4 kg of azoisobutyric acid dinitrile in 150 liters of acetone is uniformly charged into a stirred reaction vessel over 6 hours, and the reaction mixture is further stirred at 70-73 ° C. for 6 hours. To do.

  The analytical sample of copolymer (MCP5) has an acid number of 445 mg KOH / g copolymer. NMR test results show 1.3 α-methylstyrene-dimer end groups per mole.

  The polymer solution, still at 54-56 ° C., is now fed continuously into a vacuum double drum dryer and cut into a powder copolymer with 1.1% by weight of volatile components and acetone residue.

Put C ₈ -C ₉ diesel aromatic fraction 382kg and C ₁₆ -C ₁₈ fatty amine 122kg boils at 160 ° C. than in 500l volumes stirred reactor, heated to 130 ° C. for partial imidation of a copolymer To do. 135.5 kg of copolymer are continuously added to this solution over 4 hours. This raises the temperature inside the stirred reaction vessel to 180-185 ° C., forming water, which is distilled off by azeotropy with an approximately equal amount of C ₈ -C ₉ diesel aromatic fraction. After a total reaction time of 6 hours at 160-190 ° C., 8.5 kg of water and 10.2 kg of solvent are distilled off. A 40% solution of a partially imidized copolymer (acid number 35, number average molecular weight 12800 g / mol) is obtained.

5.1.4 Other additive components Mixture of C ₃ oxyalkyl cross-linked unsaturated C ₁₈ -C ₂₄ carboxylic acid (degree of esterification 92 mol%, C ₁₈ unsaturated fatty acid content 32% by mass, C ₂₂ unsaturated fatty acid content 48% by mass, iodine value 96)

  Ethyl acrylate-ethyl hexyl acrylate copolymer, molar ratio 3: 2, number average molecular weight 13500

5.2 Preparation of a solution containing additive components in middle distillate mineral oil 40% solution of additive component c) in C _{8 to} C ₉ diesel aromatic fraction 25 kg in aromatic hydrocarbon mixture (Solvesso) 50 kg of a 50% solution of additive component a), 20 kg of a mixture of C ₃ -oxyalkyl bridged unsaturated C ₁₈ -C ₂₄ carboxylic acids as other additive components, and an acrylic of another other additive component in toluene 19 kg of a 20% solution of ethyl acrylate-ethyl hexyl acrylate copolymer is mixed in a stirred reaction vessel for 90 minutes at 65 ° C. and the mixture is transferred to a storage vessel.

5.3 Manufacture and testing of mineral oil blends The additive solution according to 5.2 is injected into the product stream flowing at 800 kg / min of additive-free diesel, batch 1608601, at 0.48 kg / min. Transfer the mixture to a storage tank.

  Testing the mineral oil formulation for low temperature resistance indicated a CFPP value of -16 ° C. The CP value of the short-time sedimentation test is + 5 ° C. The SEDAB filtration test is accepted (500 ml in 76 seconds).

  When a mineral oil formulation containing only copolymer wax as an additive is produced under the same conditions, the CFPP value is -3 ° C. The CP value of the short-time sedimentation test is + 10 ° C. The SEDAB filtration test is rejected (468 ml in> 120 seconds).

Example 6
6.1 Starting product 6.1.1 Diesel without additive Batch: 030210 Test DF 2
Characteristic:
Cloud point (CP): + 7 ° C;
Low temperature filter clogging point (CFPP): + 2 ° C
Distillation analysis:

6.1.2 Additive component a)
10% by weight partially saponified ethylene-vinyl acetate copolymer wax (weight average molecular weight 1600 g / mol, vinyl acetate content 32% by weight of non-saponified ethylene-vinyl acetate copolymer wax, saponification degree 15% by mole) and 90% by weight Ethylene-vinyl acetate copolymer wax (manufactured by LEUNA Polymer GmbH, vinyl acetate content 32 mass%, weight average molecular weight 2300 g / mol) is mixed.

6.1.3 Additive component c)
α-methylstyrene-maleic anhydride copolymer, partially imidized with dodecylamine, number average molecular weight 14200 g / mol, acid number 56

Preparation of additive component c) 83 l of α-methylstyrene, 5 l of α-methylstyrene dimer and 62 kg of maleic anhydride and 110 l of 2-butanone are placed in a 500 l stirred reactor and the stirred reactor is 70 Heat to ° C. A solution of 1.9 kg dibenzoyl peroxide and 52 l 2-butanone is charged uniformly into the stirred reaction vessel over 2 hours and the reaction mixture is stirred for an additional 10 hours at 72-73 ° C.

The analytical sample of the copolymer has an acid number of 452 mg KOH / g copolymer. As a result of NMR test, it is 1.1α-methylstyrene-dimer end group per mole. The polymer solution, still at a temperature of 70 ° C., is continuously charged into a 500 liter stirred reactor containing 280 liters of 2-ethylhexanol and heated to 150 ° C. while 2-butanone-2 Is distilled off. While adding 104 kg of C ₁₆ -C ₁₈ aliphatic amine over 4 hours, the temperature is raised to 165-185 ° C. and water is distilled off along with a small amount of 2-ethylhexanol.

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

6.1.4 Other additive components Triester of pentaerythritol and stearic acid Diethylene glycol monolauroyl ester

6.2 Manufacture of solution containing additive component in middle distillate mineral oil 40% solution of additive component c) in 2-ethylhexanol 25 kg, additive component in C ₈ -C ₉ diesel aromatic fraction a) 50% of a 60% solution, 20 kg of a triester of pentaerythritol and stearic acid as other additive components, and 1 kg of diethylene glycol monolauroyl ester as another additive component are introduced into a stirred reaction vessel for 90 minutes, 65 Stir at 0 ° C. and transfer the mixture to a storage tank.

6.3 Manufacture and testing of mineral oil blends The additive solution according to 6.2 is injected at 0.24 kg / min into a product stream flowing at 800 kg / min for diesel without additives, batch 030210, Transfer the mixture to a storage tank.

  Testing the mineral oil formulation for low temperature resistance indicated a CFPP value of -7 ° C. The CP value of the short-time sedimentation test is + 7 ° C. The SEDAB filtration test is accepted (500 ml in 82 seconds).

  When a mineral oil formulation containing only copolymer wax as an additive is produced under the same conditions, the CFPP value is -5 ° C. The CP value of the short-time sedimentation test is + 12 ° C. The SEDAB filtration test is rejected (468 ml in> 120 seconds).

Example 7
7.1 Starting product 7.1.1 Heating oil without additives Batch: 030225 Test HEL 1
Characteristic:
Cloud point (CP): + 1 ° C;
Low temperature filter clogging point (CFPP): -1 ° C
Distillation analysis:

7.1.2 Additive component a)
15% by weight ethylene oxide-vinyl acetate copolymer wax (weight average molecular weight 950 g / mol, acid value 18 mg KOH / g, OH value 70 mg KOH / g) and 85% by weight non-oxide ethylene-vinyl acetate copolymer wax (LEUNA Polymer GmbH) Manufactured, vinyl acetate content 32 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 aliphatic amine, number average molecular weight 7000 g / mol, acid number 25

Preparation of additive component 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 are placed in a 500 l stirred autoclave and Heat to ° C. A solution of 2.5 kg of tert-butylperoxy-2-ethylhexanoate and 55 l of 1,2-dichloroethane was charged uniformly into the stirred autoclave over 2 hours and the reaction mixture was added for another 10 hours, 90-93. Stir at ° C.

  The analytical sample of the copolymer has an acid number of 430 mg KOH / g copolymer. NMR test results show 1.4 α-methylstyrene-dimer end groups per mole.

The polymer solution, still at about 90 ° C., is now placed in a 500 liter stirred reactor containing 280 liters of a C ₈ -C ₉ diesel aromatic fraction and 122 kg of a C ₁₂ -C ₁₄ aliphatic amine mixture. While heating to 160 ° C., 1,2-dichloroethane and reaction water derived from imidization were distilled off.

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

7.1.4 Other additive components Diester of ethylene glycol and erucic acid N- (2-hydroxyethyl) oleylamine

7.2 manufacture C ₈ -C ₉ diesel aromatic fraction in a solution containing the additive component in the middle distillate mineral oils, additives 60% solution 50 kg, ethylene glycol other additives of component a) 40% solution of the diester 20kg of erucic acid, and the other additive components N-(2-hydroxyethyl) oleylamine, of 65 ℃ C ₈ ~C ₉ additive component c diesel aromatic distillate) Add to a 500 liter stirred reactor containing 25 kg and stir for 90 minutes at 65 ° C. and transfer the mixture to a storage tank.

7.3 Manufacture and testing of mineral oil formulations The additive solution according to 7.2 is injected at 0.24 kg / min into a product stream flowing at 800 kg / min of heating oil without additives, batch 030225 And transfer the mixture to a storage tank.

  Testing the mineral oil formulation for low temperature resistance indicated a CFPP value of -15 ° C.

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

Example 8
8.1 Starting product 8.1.1 Diesel without additive Batch: 16080601 Test DF 1
Characteristic:
Cloud point (CP): + 6 ° C;
Low temperature filter clogging point (CFPP): + 2 ° C
Distillation analysis:

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

8.1.3 Additive component c)
α-methylstyrene-maleic anhydride copolymer, partially imidized with stearylamine, weight average molecular weight 13750 g / mol, acid value 51

Preparation of additive component c) 81 l of α-methylstyrene, 7 l of α-methylstyrene dimer and 20 l of acetone are placed in a 500 l stirred reactor and the stirred reactor is heated to 59 ° C. A solution containing 52 kg of maleic anhydride and 2.4 kg of azoisobutyric acid dinitrile in 150 liters of acetone is uniformly charged into a stirred reaction vessel over 6 hours, and the reaction mixture is further stirred at 70-73 ° C. for 6 hours. To do.

  The analytical sample of the copolymer has an acid number of 445 mg KOH per gram of copolymer. NMR test results show 1.3 α-methylstyrene-dimer end groups per mole.

  The polymer solution, still at 54-56 ° C., is now fed continuously into a vacuum double drum dryer and cut into a powder copolymer with 1.1% by weight of volatile components and acetone residue.

382 kg of C ₈ -C ₉ diesel aromatic fraction boiling above 160 ° C. and 135 kg of stearylamine are placed in a 500 l stirred reactor and heated to 130 ° C. for partial imidization of the copolymer. 135.5 kg of copolymer are continuously added to this solution over 4 hours. This raises the temperature inside the stirred reaction vessel to 180-185 ° C., forming water, which is distilled off by azeotropy with an approximately equal amount of C ₈ -C ₉ diesel aromatic fraction. After a total reaction time of 6 hours at 160-190 ° C., 8.5 kg of water and 10.2 kg of solvent are distilled off. A 40% solution of a copolymer having an acid number of 51 and a number average molecular weight of 1370 g / mol, partially imidized with stearylamine, is obtained.

8.1.4 Other additive components Mixture of C ₃ -oxyalkyl cross-linked unsaturated C ₁₈ -C ₂₄ carboxylic acid (degree of esterification 92 mol%, C ₁₈ unsaturated fatty acid content 32 mass%, C ₂₂ unsaturated fatty acid 48% by mass, iodine value 96)
Ethyl acrylate-octadecyl acrylate copolymer (molar ratio 4: 1, number average molecular weight 8400)

8.2 a 40% solution 25 kg, aromatic hydrocarbon mixtures middle distillate additive component c of manufacturing C ₈ -C ₉ diesel aromatic fraction in a solution containing the additive components in mineral oil) (Solvesso) in 50 kg of a 50% solution of additive component a), 20 kg of a mixture of C ₃ oxyalkyl bridged unsaturated C ₁₈ -C ₂₄ carboxylic acids as other additive components, and another additive component ethyl acrylate in toluene 19 kg of a 20% solution of octadecyl acrylate copolymer is mixed in a stirred reaction vessel for 90 minutes at 65 ° C. and the mixture is transferred to a storage vessel.

8.3 Production and Testing of Mineral Oil Formulation The additive solution according to 8.2 is injected into the product stream flowing at 800 kg / min of diesel without additives, batch 16080801 at 0.48 kg / min, Transfer the mixture to a storage tank. Testing the mineral oil formulation for low temperature resistance indicated a CFPP value of -17 ° C. When a mineral oil formulation containing only the copolymer as an additive is produced under the same conditions, the CFPP value is -3 ° C.

Example 9
9.1 Starting product 9.1.1 Diesel without additive Batch: 16080601 Test DF 1
Characteristic:
Cloud point (CP): + 6 ° C;
Low temperature filter clogging point (CFPP): + 2 ° C
Lubricity test: 563 μm
Distillation analysis:

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

9.1.3 Additive component d2)
Vaseline-like viscous wax ester, acid value 7.9 mg KOH / g, saponification degree 113 mg KOH / g, kinematic viscosity 20.6 mm ² / s, freezing point 34.5 ° C.

Preparation of additive component d2) Dimer acid 25 kg of mixture (dimerization product from unsaturated _C18 fatty acid, average carbon number 36), 5 kg of stearyl alcohol and 7 kg of cetyl alcohol at 120 ° C. in 70 l volume of stirring reaction Dissolve by heating in a bath, add 50 g H ₂ SO ₄ and react while removing the water of reaction until an acid number of 7.9 mg KOH / g is achieved. After allowing the melt to cool, the catalyst is neutralized with 0.5 l of 10% NaHCO ₃ , the aqueous phase is separated and the wax ester is removed.

9.1.4 Other additive components Ethyl acrylate-ethyl hexyl acrylate copolymer (molar ratio 3: 2, number average molecular weight 13500)

9.2 a 40% solution 25 kg, aromatic hydrocarbon mixtures of the additive components of the middle distillate mineral producing C ₈ -C ₉ diesel aromatic fraction in a solution containing the additive component in the oil d2) (Solvesso) in 50 kg of a 50% solution of additive component a) and 15 kg of a 20% solution of ethyl acrylate-ethylhexyl acrylate copolymer of other additive components in toluene are mixed in a stirred reaction vessel at 65 ° C. for 90 minutes, Transfer the mixture to a storage tank.

9.3 Manufacture of mineral oil composition The additive solution according to 9.2 is injected into the product stream flowing at 800 kg / min of additive-free diesel, batch 1608601 at 0.48 kg / min, and the mixture is injected Transfer to storage tank.

  Testing the mineral oil formulation for low temperature resistance indicated a CFPP value of -14 ° C. The lubricity test shows a “wear scar diameter” of 412 μm.

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

Example 10
10.1 Starting product 10.1.1 Diesel batch without additives: 030210 Test DF 2
Characteristic:
Cloud point (CP): + 7 ° C;
Low temperature filter clogging point (CFPP): + 2 ° C
Lubricity test: 556 μm
Distillation analysis:

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

10.1.3 Additive component d2)
Vaseline-like viscous wax ester, acid value 8.6 mg KOH / g, saponification degree 118 mg KOH / g, kinematic viscosity 23.1 mm ² / s, freezing point 35.2 ° C.

Preparation of additive component d2) Dimer acid 25 kg of mixture (dimerization product from unsaturated C ₁₈ fatty acids, average carbon number 36), 5 kg of stearyl alcohol and 8 kg of eicosane alcohol at 120 ° C. in 70 l volume Dissolve by heating in the reaction vessel, add 50 g H ₂ SO ₄ and react while removing the water of reaction until an acid number of 8.6 mg KOH / g is achieved. After allowing the melt to cool, the catalyst is neutralized with 1.0 l of 10% NaHCO ₃ , the aqueous phase is separated and the wax ester is removed.

10.1.4 Other additive components Triesters of pentaerythritol and oleic acid

10.2 50% solution of middle distillate additive components produced in 2-ethylhexanol of the solution containing the additive components in mineral oil d2) 22 kg, additive components C ₈ -C ₉ diesel aromatic distillate 50 kg of a 60% solution of a) and 20 kg of a triester of pentaerythritol and oleic acid as other additive components in toluene are introduced into a stirred reaction vessel, stirred for 90 minutes at 65 ° C., and the mixture stored Transfer to tank.

10.3 Production of Mineral Oil Formulation The additive solution according to 10.2 is injected at 0.30 kg / min into the additive-free diesel, batch 030210, product stream flowing at 800 kg / min and the mixture is injected. Transfer to storage tank.

  Testing the mineral oil formulation for low temperature resistance indicated a CFPP value of -8 ° C. The lubricity test shows a “wear scar diameter” of 425 μm.

  When a mineral oil formulation containing only unmodified copolymer wax a) as an additive is produced under the same conditions, the CFPP value is -5 ° C. and the “wear scar diameter” is 528 μm.

Example 11
11.1 Starting product 11.1.1 Heating oil without additives Batch: 030225 Test HEL 1
Characteristic:
Cloud point (CP): + 1 ° C;
Low temperature filter clogging point (CFPP): -1 ° C
Distillation analysis:

11.1.2 Additive component a):
25% by weight ethylene oxide-vinyl acetate copolymer wax (weight average molecular weight 950 g / mol, acid value 18 mg KOH / g, OH value 70 mg KOH / g) and 75% by weight non-oxide ethylene-vinyl acetate copolymer wax (LEUNA Polymer GmbH) Manufactured, vinyl acetate content 32 mass%, weight average molecular weight 2300 g / mol).

11.1.3 Additive component d1)
Oligomer ester, acid value 12 mg KOH / g, saponification degree 175 mg KOH / g, kinematic viscosity (100 ° C.) 65 mm ² / s, freezing point 42 ° C. according to EP 0 934 921 A1, glyceryl monostearate and dimer acid ( Prepared from dimerization products from unsaturated _C18 fatty acids, average carbon number 36) by solventless oligocondensation with acid catalysts.

11.4 Other additive components N- (2-hydroxyethyl) oleylamine

11.2 middle distillate additive components a manufacturing C ₈ -C ₉ diesel aromatic fraction in a solution containing the additive components in mineral oil) 60% solution 50 kg, other additive components N-(2 - hydroxyethyl) oleylamine 3 kg, was added to a stirred reaction vessel containing the 40% solution 23kg of C ₈ -C ₉ additive components for diesel aromatic distillate d1) of 65 ° C., 90 min, stirred at 65 ° C. And transfer the mixture to a storage tank.

11.3 Manufacture and testing of mineral oil compositions The additive solution according to 11.2 is injected at 0.28 kg / min into a product stream flowing at 800 kg / min of heating oil without additives, batch 030225. And transfer the mixture to a storage tank.

  Testing the mineral oil formulation for low temperature resistance indicated a CFPP value of -16 ° C.

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

Example 12
12.1 Starting product 12.1.1 Diesel-free diesel batch: 16080601 Test DF 1
Characteristic:
Cloud point (CP): + 6 ° C;
Low temperature filter clogging point (CFPP): + 2 ° C
Distillation analysis:

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

12.1.3 Other additive components d1)
Oligomer ester, acid value 14 mg KOH / g, saponification degree 185 mg KOH / g, kinematic viscosity (100 ° C.) 76 mm ² / s, freezing point 42 ° C. according to EP 0 934 921 A1, glyceryl monostearate and dimer acid ( Prepared from dimerized products from unsaturated _C18 fatty acids, average carbon number 36) by solventless oligocondensation with acid catalysts.

12.1.4 Additive component C ₃ oxyalkyl cross-linked unsaturated C ₁₈ -C ₂₄ carboxylic acid mixture, degree of esterification 92 mol%, C ₁₈ unsaturated fatty acid content 32% by weight, C ₂₂ unsaturated fatty acid Content 48% by mass, iodine value 96
Ethyl acrylate-octadecyl acrylate copolymer (molar ratio 4: 1, number average molecular weight 8400)

12.2 50% solution 50 kg, aromatic hydrocarbon mixtures of the additive components of the middle distillate mineral producing C ₈ -C ₉ diesel aromatic fraction in a solution containing the additive component in the oil d1) (Solvesso) in 50 kg of a 50% solution of additive component a), 12 kg of a mixture of C ₃ oxyalkyl bridged unsaturated C ₁₈ -C ₂₄ carboxylic acids as other additive components, and another additive component acrylic acid in toluene 15 kg of a 20% solution of ethyl-octadecyl acrylate copolymer is mixed in a stirred reaction vessel for 90 minutes at 65 ° C. and the mixture is transferred to a storage vessel.

12.3 Production and Testing of Mineral Oil Composition The additive solution according to 12.2 is injected into the product stream flowing at 800 kg / min of diesel without additives, batch 16080801 at 0.52 kg / min, Transfer the mixture to a storage tank.

  Testing the mineral oil formulation for low temperature resistance indicated a CFPP value of -18 ° C.

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

Claims (13)

Additive component a) an ethylene-vinyl ester copolymer having a weight average molecular weight of 3000 to 50000 and an ethylene proportion of 50 to 90% by weight,
And
b) 50-80 mol% of hydroxyl groups are esterified with unsaturated C ₁₂ -C ₄₀ monocarboxylic acid and 20-50 mol% of hydroxyl groups are partially imidized maleic anhydride copolymer and / or Or a mixed ester of glycerin that is esterified with a partially esterified maleic anhydride copolymer,
And / or c) partially and / or fully imidized of maleic anhydride and α-methylstyrene having a number average molecular weight of 1500-15000 and at least one end group based on α-methylstyrene dimer A copolymer and / or d) a wax composition comprising:
d1) A wax-like oligomeric ester based on glyceryl monostearate and dimer acid, the conversion product being at least 90% by weight,

(Where n = 1 to 20, total a + b + c + d = 30, Z = 12 to 20, Y = H or

X = H or

Is)
Wax-like oligomeric ester corresponding to the structure,
And / or d2) a wax ester of petrolatum-like consistency of at least two different linear and / or branched C ₁₄ -C ₃₆ alcohols and dimer acids, the conversion product being at least 80% by weight But,

(Wherein i = 13 to 35; s = 13 to 35, the sum of k + m + n + p is 30 to 34, and (CH ₂ ) _i or (CH ₂ ) _S is linear or linear and branched)
Wax ester, corresponding to the structure
Wax compositions based on natural starting materials of the type
Containing
The content of the additive mixture in the mineral oil is 0.005 to 1% by mass, and the mass ratio a / b or a / c or a / d of the additive components is 10/90 to 90/10, respectively. ,
A composition of mineral oil as the main component and a minor additive mixture.   The composition according to claim 1, wherein the ethylene-vinyl ester copolymer of the additive mixture is an ethylene-vinyl acetate copolymer having a vinyl acetate content of 12-50% by weight.   The ethylene-vinyl ester copolymer of the additive mixture is a mixture of 10-90 wt% unmodified ethylene-vinyl ester copolymer and 90-10 wt% ethylene-vinyl ester copolymer modified with polar groups, The composition according to claim 1 or 2.   The modified ethylene-vinyl ester copolymer of the additive mixture is converted into an oxidized ethylene-vinyl ester copolymer, partially saponified ethylene-vinyl ester copolymer, partially saponified ethylene-vinyl ester copolymer hemi 4. A composition according to claim 3, which is an ethylene-vinyl ester copolymer grafted with acetals and / or polar unsaturated monomers of the vinyl ester, (meth) acrylic ester and / or vinyl ether type. The C ₁₂ -C ₄₀ monocarboxylic acid contained as an esterification component in the glycerin mixed ester of the additive mixture is 45 to 52 mass% of C ₂₂ monocarboxylic acid based on the total weight of the C ₁₂ -C ₄₀ monocarboxylic acid The partially imidized maleic anhydride copolymer consisting of an acid and included as an esterification component is a maleic anhydride-α-methylstyrene copolymer partially imidized with a C ₆ -C ₂₄ monoalkylamine. A maleic anhydride-α-methylstyrene copolymer having a molar ratio of anhydride groups in the copolymer / bound C ₆ -C ₂₄ monoalkylamine in the copolymer of 8/1 to 1.3 / 1. The composition as described in any one of 1-4. Maleic anhydride-α-, which is a partially imidized copolymer of maleic anhydride and α-methylstyrene as additive component c), partially imidized with C ₆ -C ₂₄ monoalkylamine Maleic anhydride-α-methylstyrene, which is a methylstyrene copolymer, wherein 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 The composition according to any one of claims 1 to 4, which is a copolymer.   The wax ester having a petrolatum-like consistency as additive component d2) is 2-hexyldecan-1-ol, 2-octyldecan-1-ol or 2-octyldecan-1-ol which is Guerbet alcohol. A wax ester based on a mold and a dimer acid obtained by cutting a vegetable oil having a high oleic acid content, followed by catalytic dimerization. The composition as described.   The mineral oil composition according to any one of claims 1 to 7, wherein the mineral oil is a heating oil, light oil or diesel oil each having a sulfur content of less than 0.05% by mass. Fatty acid mixture, polar nitrogen compound, ethylenically unsaturated C ₄ -C ₂₀ dicarboxylic acid anhydride in which the mineral oil composition is 0 to 200% by mass in total with respect to the additive components a + b, a + c, a + d, a + b + c, a + b + c + d or a + c + d modified copolymer, a non-modified ethylene things - vinyl ester copolymers, C ₇ -C ₃₀ alcohols, polyalkylene glycols, esters or ethers of polyoxyalkylene compounds, C ₂ -C ₆ oxyalkyl crosslinked C ₁₂ -C ₄₀ monocarboxylic acids, hydrocarbon polymers, alkylphenol - aldehyde copolymers, aromatic compounds having C ₈ -C ₁₀₀ alkyl substituents, carboxylated polyamines, detergents, corrosion inhibitors, demulsifiers, metal deactivators, cetane improvers, 1 or 2 or more selected from the group consisting of defoamers and cosolvents The composition of mineral oil according to any one of claims 1 to 8, comprising the other additive components above.   The composition of mineral oil according to claim 9, wherein the polar nitrogen compound is polyamine, ether amine, amino alcohol, amine salt of polyvalent carboxylic acid, amide or imide. C ₂ -C ₆ oxyalkyl crosslinked C ₁₂ -C ₄₀ monocarboxylic acids, C ₃ ~ C ₂₂ monocarboxylic acid content relative to the total weight of unsaturated C ₁₆ -C ₂₄ monocarboxylic acid is 45 to 52 wt% a C ₄ oxyalkyl crosslinking unsaturated C ₁₆ -C ₂₄ monocarboxylic acids, the composition of the mineral oil of claim 9. Additive component a) an ethylene-vinyl ester copolymer having a weight average molecular weight of 3000 to 50000 and an ethylene proportion of 50 to 90% by weight,
And
b) 50-80 mol% of hydroxyl groups are esterified with unsaturated C ₁₂ -C ₄₀ monocarboxylic acid and 20-50 mol% of hydroxyl groups are partially imidized maleic anhydride copolymer and / or Or a mixed ester of glycerin that is esterified with a partially esterified maleic anhydride copolymer,
And / or c) partially and / or fully imidized of maleic anhydride and α-methylstyrene having a number average molecular weight of 1500-15000 and at least one end group of the α-methylstyrene dimer system Copolymer,
And / or d) a wax composition comprising:
d1) A wax-like oligomeric ester based on glyceryl monostearate and dimer acid, the conversion product being at least 90% by weight

(Where n = 1 to 20, total a + b + c + d = 30, Z = 12 to 20, Y = H or

X = H or

Is)
Wax-like oligomeric ester corresponding to the structure,
And / or d2) wax esters having a petrolatum-like consistency based on at least two different linear and / or branched C ₁₄ -C ₃₆ alcohols and dimer acids, the conversion product being at least 80% by weight But,

[Wherein, i = 13 to 35; s = 13 to 35, the sum of k + m + n + p is 30 to 34, and (CH ₂ ) i or (CH ₂ ) s is linear or linear and branched]
Wax ester, corresponding to the structure
Wax compositions based on natural starting materials of the type
Containing
The content of the additive mixture in the mineral oil is 0.005 to 1% by mass, and the mass ratio a / b or a / c or a / d of the additive components is 10/90 to 90/10, respectively. An additive mixture,
-In the first process step, a solution containing 1 to 60% by weight additive components in middle distillate mineral oil is produced at 20-90 ° C; and-in the second process step, obtained in the first process step. Homogenize the solution with mineral oil as the main component,
Manufactured by pre-homogeneous process,
Furthermore, in the first process step and / or the second process step, another additive component in total of 0 to 200% by mass with respect to the additive component a + b, a + c, a + d, a + b + c, a + b + c + d or a + c + d is added to the mineral oil. ,
A method for producing a composition comprising a mineral oil as a main component and an additive mixture of a trace amount. Use of a composition according to any one of claims 1 to 11 as a fluid medium to be transported and stored at low temperatures.