EA011632B1 - Mineral oil compositions comprising additive mixture, method for producing thereof and use - Google Patents

Abstract

The invention relates to an additive mixture as component of mineral oil compositions, comprising as main component and trace proportions of the additive mixture the following additive components: a) ethylene vinyl ester copolymers with molecular mass weight averages of 3,000 to 50,000 and an ethylene proportion of 50 to 90 mass %; b) mixed esters of glycerine, in which 50 to 80 mol % of the hydroxy groups are esterified with unsaturated C-Cmonocarboxylic acids and 20 to 50 mol % of the hydroxy groups are esterified with partially imidated and/or partially esterified maleic acid anhydride copolymers; and/or c) partially and/or completely imidated copolymers of maleic acid anhydride and alpha -methylstyrol with molecular mass number averages of 1,500 to 15,000 and at least one terminal group based on dimeric alpha –methylstyrol; and/or d) wax compositions based on natural starting materials of type d1) wax-like oligomeric esters based on glyceryl monostearate and dimeric acids and/or d2) waxy esters with the consistency of vaseline, based on at least two different straight chain and/or branched C-Calcohols and dimeric acids, whereby the content of the additive mixture in the mineral oil is 0.005 to 1 mass % and the mass proportions of the additive components a/b, or a/c, or a/d is 10:90 to 90:10 respectively. The mineral oil compositions are suitable as low temperature flow transportable media and as mineral oil fuels with high ease of flow.

Description

This invention relates to a mixture of additives as a component of compositions containing mineral oil as a component and trace amounts of an additive mixture, as well as to a method for producing compositions containing mineral oil, which contains a mixture of additives.

Compositions containing mineral oil as a main component and trace amounts of additive mixtures include ethylene vinyl acetate copolymers, hydrocarbon polymers, esterified copolymers of maleic anhydride and olefins, polar nitrogen compounds such as amine salts of polyvalent carboxylic acids, and esterified polyoxyalkylene known from No. 0 94/102 67A1, No. 0 95 / 33012A1, EP 0921183A1, No. 0 93 / 14178A1, EP 0889323A1.

Disadvantages include insufficient fluidity and storage stability of these compositions at low temperatures, as well as the limited lubricity of these compositions when the mineral oil component has a sulfur content of less than 0.005 wt.%.

The aim of the present invention is to provide a mixture of additives as a component of mineral oil compositions as their main component and trace amounts of an additive mixture that have improved fluidity and improved storage stability at low temperatures and improved lubricity. Improved fluidity results in energy savings in the pump system through which these formulations are pumped. These additive mixtures are developed taking into account the fact that in order to obtain mineral oil with improved environmental compatibility from the point of view of polluting emissions, oil with a very low sulfur content should be used.

The purpose of the present invention is achieved by a mixture of additives as a component of mineral oil compositions as a main component and trace amounts of an additive mixture containing the following additives according to the invention:

a) copolymers of ethylene and vinyl ester with a weight average molecular weight of from 3,000 to 50,000 and an ethylene portion of 50-90 wt.%;

b) mixed glycerol esters, where 50-80 mol% of the hydroxyl groups are esterified with unsaturated C1 ₂ -C ₄₀ monocarboxylic acids and 20-50 mol% of the hydroxyl groups are esterified with partially imidated and / or partially esterified maleic anhydride copolymers; and / or

c) partially and / or fully imidated copolymers of maleic anhydride and α-methylstyrene with a weight average molecular weight of from 1,500 to 15,000 and at least one end group based on dimeric α-methylstyrene; and / or

g) wax compositions based on natural starting materials such as

J1) wax-like oligomeric esters based on glyceryl monostearate and dimeric acid, where the conversion product corresponds to at least 90 wt.% Structure

where η is 1-20;

the sum (a + b + d) is 30;

ζ is 12-20;

Υ represents H or

- CO - (CH ₂ ) ₀ - OH - (CH _g ) c - CH ₃

I

Н ₃ С - (СН _₽ ) „- СН - (СНг) а - СО - ОН

X represents H or —CH ₂ —CH (0H) —CH ₂ —0 — C0- (CH ₂ ) ;; —CH ₃ and / or 2) wax esters with a vaseline-like consistency based on at least two different linear and / or branched C14-C36 alcohols and dimeric acids, where the conversion product corresponds to at least 80 wt.% structure

H ₃ C - (SND - O - CO - (CH _g ) _to - CH - CH - (CH ₂ ) _ha - CH ₃

I I

НзС- (СНг) _p (СН ₂ ) p-СО-О- (СН ₂ ) ₅ -CH ₃ where 1 is 13-35;

equal to 13-35;

the sum (k + t + η + ρ) is 30-34 and (CH ₂ ) ₁ or (CH ₂ ) ₈ are linear or branched, whereby the content of additives in the mineral oil is 0.005-1 wt.%, and the mass pro

- 1 011632 portion of the components of additives a / b, a / c or a / ά is in the range from 10:90 to 90:10, respectively.

Examples of vinyl ester components that can be included as a component of additives a) in ethylene-vinyl ester copolymers are vinyl acetate, vinyl propionate, 2-ethylhexyl vinyl ester, vinyl laurate, 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ester.

The copolymers of ethylene and vinyl ester may contain 1-30 wt.% With respect to the vinyl ester of other unsaturated ester components such as (meth) acrylic esters, for example methyl methacrylate, methyl acrylic acid ester, methacrylic acid ethyl ester, 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.

Copolymers of ethylene and vinyl ester are preferred as a component of additives a) in a mixture of additives, a copolymer of ethylene and vinyl acetate, which contains vinyl acetate in an amount of 12-50 wt.%.

Another preferred embodiment of the copolymers of ethylene and vinyl ester contained as an additive component a) in a mixture of additives is when the copolymers of ethylene and vinyl ester are mixtures of 10-90 wt.% Of unmodified copolymers of ethylene and vinyl ester and 90- 10 wt.% Copolymers of ethylene and vinyl ester modified with polar groups.

The copolymers of ethylene and vinyl ester are modified by polar groups where certain end groups are introduced into the copolymer, such as aldehyde, preferably end groups of acetaldehyde, propionic aldehyde, butyric or isobutyric aldehydes; terminal carboxyalkyl mercapto groups, preferably terminal groups of mercaptoacetic acid or mercaptopropionic acid; or terminal alkoxy groups or hydroxyl groups or carboxyl groups are introduced into the copolymer by partial oxidation, saponification or acetylation, as well as by grafting polar ethylene unsaturated monomers onto the copolymer.

Modified ethylene-vinyl ester copolymers, oxidized ethylene-vinyl ester copolymers, partially saponified ethylene-vinyl ester copolymers, hemiacetals of partially saponified ethylene-vinyl ester copolymers, and / or ethylene-vinyl ester copolymers grafted with polar nenas are preferred. such as a vinyl ester, a (meth) acrylic ester and / or a vinyl ether.

The oxidized copolymers of ethylene and vinyl ester are preferably oxidized copolymers of ethylene and vinyl acetate with a number average molecular weight of 800 to 5000, an acid number of 2 to 40 mg KOH / g and a hydroxyl number of 20 to 150 mg KOH / g.

Partially saponified ethylene vinyl ester copolymers are ethylene vinyl acetate copolymers with a number average molecular weight of 800 to 5000, in which 5-30 wt.% Vinyl acetate units are saponified.

In another preferred embodiment, the modified copolymers of ethylene and vinyl ester are the hemiacetals of copolymers of ethylene, vinyl ester and vinyl alcohol with butyric aldehyde. Examples of hemiacetals of copolymers of ethylene, vinyl ester and vinyl alcohol with oil aldehyde are hemiacetals of copolymers of ethylene vinyl acetate-vinyl alcohol, which react in a heterogeneous phase with oil aldehyde, as described in ΌΌ 295507A7.

Grafted copolymers of ethylene and vinyl ester can be prepared by reacting unsaturated monomers in an extruder (ΌΌ 282462B5) or in a stirred tank reactor (ΌΌ 293125B5) in the presence of thermally decomposed free radical initiators. It is also possible to carry out a modification in the process of producing a copolymer at high pressure by introducing a dose of monomer into the polymer melt in a low pressure separator or in a discharge extruder.

In particular, grafted copolymers of ethylene and vinyl ester as a component of additives 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 20-600 wt.%, The vinyl acetate content of the main chain of the copolymer is from 10 to 40 wt.% and part of the grafted vinyl acetate branches is up to 10-20 wt.%.

The copolymers of ethylene and vinyl ester in the additive compositions may contain up to 35 wt.% PolyC1 ₂ -C ₄₀ alkyl (meth) acrylate.

Examples of copolymers of maleic anhydride, which may be partially imidated or partially esterified as an acid component in mixed glycerol esters as a component of additives b) of an additive mixture, are copolymers of maleic anhydride and comonomer components of C ₂ -C ₂₀ olefins, C ₈ -C ₂₀ vinyl aromatic compounds, C4-C21 acrylic esters, C5-C22 methacrylic esters, C5-C14 vinyl silane,

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Sa-C ^ akrilatsilanov, acrylic acid, methacrylic acid, acrylonitrile, vinylpyridine, vinyloxazoline, izopropeniloksazolina, vinyl pyrrolidone, amino-C 1 C ₈ alkyl (meth) acrylate compound C ₂ -C ₈ ovinilovogo ether, C ₃ -C ₂₀ vinyl ester and / or hydroxyC ₁ -C ₈ alkyl (meth) acrylate. Particularly preferred comonomer components are isobutylene, diisobutylene, vinyl acetate, styrene and α-methyl styrene.

Maleic anhydride copolymers preferably have a molar ratio of maleic anhydride to comonomer of 1: 1 to 1: 9 and a weight average molecular weight of 5000 to 500000. Partial imidation can be carried out using ammonia, C ₁ -C ₂₄ monoalkylamine, aromatic C _b -C ₁₈ monoamines, C ₂ -C ₁₈ monoalcohols, monoaminated poly (C ₂ -C ₄ alkylene) oxides with a molecular weight of 400-3000 and / or mono-esterified poly (C ₂ -C ₄ alkylene) oxides with a molecular weight of 100-10000, and the molar ratio copolymer with anhydride group and ammonia, C ₂ -C ₂₄ monoalkylamino, C _b aromatic monoamines -C _18, C ₂ -C ₁₈ monoaminospirtam or monoamidated poly (C ₂ -C ₄ alkylene) oxide, respectively, is in the range from 1: 1 to 20: one.

Examples of suitable amines that partially imidate maleic anhydride copolymers are C1 ₂ -C ₂₄ monoalkylamines such as oleylamine, dodecylamine, hexadecylamine, octadecylamine or eicosylamine, monosubstituted diamines such as Y-dodecyl-1,3-di-aminopane 1,3-diaminopropane or Ν-octadecylpropylene triamine, or amino alcohols such as aminodecan-10-ol or aminohexadecan-1b-ol.

Examples of suitable alcohols by which maleic anhydride copolymers are partially esterified as acidic components in mixed glycerol esters as an additive component b) of an additive mixture are C | -C | ₈ alcohols. such as methanol, ethanol, ethylhexanol or stearyl alcohol.

Examples of unsaturated C ₃₂ -C ₄₀ monocarboxylic acids contained as an esterifying component in mixed glycerol esters of an additive mixture are oleic, elaidic, ricinoleic, eleostearic, linoleic, linolenic and erucic acids or dimeric acids based on oleic acid or linolenic acid.

Examples of suitable methods for the preparation of mixed glycerol esters, where 50-80 mol% of hydroxyl groups are esterified with unsaturated C, ₂ -C ₄₀ monocarboxylic acids and 20-50 mol% of hydroxyl groups are esterified with partially imidated and / or partially esterified maleic anhydride copolymers partial reaction of glycerol with unsaturated C ₃₂ -C ₄₀ monocarboxylic acids and subsequently with partially imidated and / or partially esterified maleic anhydride copolymers or partial reaction glycero to partially imidated and / or partially esterified copolymers of maleic anhydride and then with unsaturated C ₃₂ -C ₄₀ monocarboxylic acids. The reaction can be carried out in a melt, preferably in continuous mixers at temperatures from 50 to 135 ° C under vacuum degassing or in a solvent, preferably in aromatic solvents at 85-140 ° C.

In mixed glycerol esters, the mixture of additives C ₃₂ -C ₄₀ monocarboxylic acids contained as an esterifying component preferably consist of 45-52 wt.% C22 monocarboxylic acids with respect to the total weight of C12-C40 monocarboxylic acids.

Partially imidated maleic anhydride copolymers contained as esterification components in the mixed esters of glycerol, as b) additive component mixture of additives preferably are copolymers of maleic anhydride and α-methylstyrene, partially imidated C _b -C ₂₄ monoalkylamines, wherein the molar ratio of anhydride groups in the copolymer to the bound C _b -C ₂₄ monoalkylamine in the copolymer is in the range from 8: 1 to 2: 1.

Examples of partially imidated copolymers of maleic anhydride and α-methylstyrene as additive component c) are the copolymers with an approximately equimolar ratio of both monomers, wherein the partial and / or complete imidation is carried out with ammonia, a C1-C ₂₄ monoalkylamino, C _b aromatic monoamines -C1 _8, C ₂ -C1 ₈ monoaminospirtami, monoamidated poly (C2 -C4 alkylene) oxides and / monoesterified or poly (C2 -C4 alkylene) oxides, while the molar ratio of anhydride groups of the copolymer to ammonia, amino C1 ₂₄ monoalkylamino, aromatic monoamines _b -C1 _8, C ₂ -C ₃₈ monoaminospirtov monoamidated and poly (C2 -C4 alkylene) oxides is respectively from 1: 1 to 20: 1.

Partially imidated copolymers consisting of maleic anhydride and α-methylstyrene, as an additive component c) the additive mixture is preferably copolymers of maleic anhydride and α-methylstyrene partially imidated with _b- C ₂₄ monoalkylamines, where the molar ratio of the anhydride groups in the copolymer to the bound Sb-C24 monoalkylamine in the copolymer is in the range from 8: 1 to 1.3: 1.

Examples of C1 ₂ -C ₂₄ monoalkylamines that can partially imitate the copolymers of maleic anhydride and α-methylstyrene contained in the additive mixture are dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, oleylamine or eicosylamine.

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Voskopodobny oligomeric esters based on glyceryl monostearate and dimeric acids as a component of additives 61) are oligomeric esters described in EP 0934921A1. The glyceryl monostearate component can be obtained by enzymatic cleavage of rape oil, isolation of the glycerol monooleate formed and subsequent hydrogenation. Suitable methods for preparing the dimeric acid component are the breakdown of vegetable oils and the subsequent dimerization of the resulting unsaturated fatty acids. Solvent-free oligomeric esters are prepared by oligocondensation under acid catalysis.

Preferred as components of additives 61) are wax-like oligomeric esters which have an oligomerization degree of 2 to 8.

Wax esters with a vaseline-like consistency 62) are the wax esters described in EP 0970998A1.

Preferred as wax esters with a vaseline-like consistency 62) contained in the additive mixture are wax esters based on Cisbc! type alcohols

2-hexyldecane-1-ol, 2-octyldecane-1-ol or 2-octyldecane-1-ol and dimeric acids obtained by splitting vegetable oils with a high content of oleic acid and subsequent catalytic dimerization. Wax esters can be obtained from Cisb! alcohols and dimeric acid by catalytic esterification in the presence of acid catalysts at temperatures from 100 to 160 ° C in a vessel reactor with stirring using vacuum from -0.5 to -1.5 bar.

Examples of mineral oil, which forms the main component in compositions based on mineral oil, are crude oil and oil distillates with boiling ranges from 100 to 500 ° C, such as lubricating oils, kerosene, diesel fuel, heating oil, heavy oil fuel, oil, tractor fuel and cracked gasoline. Mineral oil may also contain up to 30 wt.% Hydrocarbons synthesized by the Fischer-Tropsch method, up to 20 wt.% Modified vegetable oils based on sunflower oil, soybean oil, rapeseed oil or animal oils, biodiesel mixture and / or up to 10 wt. % alcohols such as methanol or ethanol.

A preferred mineral oil is crude oil or petroleum fuel from a middle distillate with a sulfur content of up to 0.05 wt.%, In particular petroleum fuel, gas oil or diesel fuel.

Compositions of mineral oil can contain a total of up to 200 wt.% With respect to the components of additives (a + b), (a + b), (a + 6), (a + b + e), (a + b + e + 6 ) or (a + c + 6) other components of additives such as mixtures of fatty acids, polar nitrogen compounds, preferably polyamines, ethers of amine, amino alcohols, salts of amines, amides or imides of polyvalent carboxylic acids; modified copolymers of ethylenically unsaturated C ₄ -C ₂₁₀ dicarboxylic anhydrides, unmodified copolymers of ethylene and vinyl ester, C ₇ -C ₃₀ alcohols, polyalkylene glycols, esters or ethers of polyoxyalkylene compounds, C12-C40 monocarboxylic acids with C ₂ -C ₆ hydroxyalkyl preferably unsaturated C ₃₆ -C ₂₄ monocarboxylic acids with a C ₃ -C ₄ oxyalkyl bridge containing 45-52 wt.% C ₂₂ monocarboxylic acids with respect to the total weight of C ₁₆ -C ₂₄ monocarboxylic acids, hydrocarbon polymers er, copolymers of alkyl phenol and aldehyde, aromatic compounds with C ₈ -C 1 ₀₀ alkyl substituents, carboxylated polyamines, detergents, corrosion inhibitors, demulsifiers, metal deactivators, cetane number improvers, antifoams and / or cosolvents.

Examples of mixtures of fatty acids contained as other additive components in mineral oil compositions are mixtures of saturated and / or unsaturated C6-C40 carboxylic acids, such as lauric, palmitic, oleic and linolenic acids, dimeric fatty acids and alkenyl succinic acids.

Examples of polyamine-type polar nitrogen compounds contained as other additive components in mineral oil compositions are Y-hexadecyl-1,3-diaminopropane, Ν-octadecyldipropylenetriamine, Y-dodecyl-1,3-diaminopropane, Y, M'-didodecyl-1, 3-diaminopropane and Ν, Ν'-dioctadecyldipropylenetriamine.

Examples of polar nitrogen compounds such as the amine ether type contained as other additive components in mineral oil compositions are

3-methoxypropylamine, 3-Y-octyloxypropyl-1,3-diaminopropane and 3-Y- (2,4,6-trimethylodecyloxypropyl) -1,3-diaminopropane.

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

Examples of amines on which polar nitrogen compounds such as amine salt, amide or imide of polyvalent carboxylic acids are based are C ₈ -C ₄₀ amines, such as hydrated tallamine, tetradecylamine, eicosylamine, dioctadecylamine, methylbegenylamine, No. oleyl-1,3 diaminopropane, No. stearyl -1-methyl-1, 3-diaminopropane or Ν-oleyl dipropylene triamine.

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Examples of polyvalent carboxylic acids on which polar nitric compounds such as amine salt or amide of polyvalent carboxylic acids are based are phthalic, isophthalic, terephthalic, naphthalenedicarboxylic, ethylenediaminetetraacetic and cyclohexanedicarboxylic acids.

Прим-Methyltriethanolammonium distearyl ester chloride and Ν-methyltriethanolammonium dystearyl ester methosulfate are some examples of polar nitrogen compounds of the amine salt type, which are contained as other additive components in mineral oil compositions.

Examples of ethylenically unsaturated C ₄ -C ₂₀ dicarboxylic acid anhydrides which may be contained as a monomer component in modified copolymers of ethylenically unsaturated C ₄ -C ₂₀ dicarboxylic acids as another additive component are allyl succinic anhydride, bicycloheptoxy dicarboxydicarboxylic dicarboxylic acid dicarboxylic acid anhydride, , citraconic anhydride, cyclohexendicarboxylic anhydride, dodecenyl succinic anhydride, glutaconic anhydride, itaconic anhydride, maleic anhydride, mesaconic anhydride, methylbicycloheptendicarboxylic acid anhydride and / or methylbicyclohexendicarboxylic acid anhydride, of which maleic anhydride and / or itaconic anhydride are preferred.

Examples of suitable comonomers for ethylenically unsaturated C ₄ -C ₂₀ dicarboxylic acid anhydrides which may be contained as a monomer component in modified copolymers of ethylenically unsaturated C ₄ -C ₂₀ dicarboxylic acids as another additive component are ethylenically unsaturated monomers such as C ₂ -C ₂₀ olefins, C ₈ -C ₂₀ vinyl aromatic compounds, C ₄ -C ₂₁ acrylic esters, C5-C ₂₂ methacrylic esters, C ₅ -C ₁₄ vinylsilanes, C ₆ -C ₁₅ acrylatesilanes, acrylic acid, methacrylic acid, acre ilonitrile, vinylpyridine, vinyloxazoline, isopropenyloxazoline, vinylpyrrolidone, aminoC ₁ -C ₈ alkyl (meth) acrylate, C ₃ -C ₂₀ vinyl ether, C ₃ -C ₂₀ vinyl ether and / or hydroxyC ₁ -C ₈ alkyl (meth) acrylate. Particularly preferred ethylenically unsaturated monomers are isobutylene, diisobutylene, vinyl acetate, styrene and α-methyl styrene.

Particularly preferred as modified copolymers are copolymers of anhydrides of ethylenically unsaturated C ₄ -C ₂₀ dicarboxylic acids and ethylenically unsaturated monomers with a molar ratio of from 1: 1 to 1: 9 and a weight average molecular weight of from 5,000 to 500,000, which reacted with ammonia, C ₁ -C ₂₄ monoalkylamines, Sb-C ₁₈ aromatic monoamines, C2-C18 monoalcohols, monoaminated poly (C2-C4 alkylene) oxides with a molecular weight of 400-3000 and / or mono-esterified poly (C2-C4 alkylene) oxides with a molecular weight of 10010000, moreover, the molar ratio of the anhydride groups of the copolymer to the amino groups of ammonia, C ₁ -C ₂₄ monoalkylamine, Cb-C ₁₈ aromatic monoamines, C ₂ -C ₁₈ monoalcohols or monoaminated poly (C2-C4 alkylene) oxides, respectively, is in the range from 1: 1 to 20: 1.

Particularly suitable as partially or fully imidated copolymers of ethylenically unsaturated C4-C20 dicarboxylic acid anhydrides are maleic anhydride copolymers imidated with C ₁₂ -C ₂₄ monoalkylamines such as oleylamine, dodecylamine, hexadecylamine, octadecylamine, eicosamidylamide, 1-diacamelamide 3-diaminopropane, No. octadecyl-1,3-diaminopropane or Ν-octadecylpropylene triamine, or amino alcohols such as aminodecan-10-ol or aminohexadecan-16-ol.

Examples of C ₇ -C ₃₀ alcohols that may be contained as other additive components in mineral oil compositions are dodecanol, stearyl alcohol and ceryl alcohol.

Examples of polyalkylene glycols that may be contained as other additive components in mineral oil compositions are polyethylene glycols, polypropylene glycols and copolymers of ethylene oxide and propylene oxide with a molecular weight of from 500 to 5000.

Examples of esters of polyoxyalkylene compounds which may be contained as other additive components in mineral oil compositions are C ₁₀ -C ₂₄ monoalkyl esters 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 contained as other additive components in mineral oil compositions are C1-C4 monoalkyl ethers or polyalkylene glycol dialkyl ethers such as polyethylene glycol monomethyl ether or polypropylene glycol dibutyl ether.

C ₁₂ -C ₄₀ monocarboxylic acids with a C ₂ -C ₆ oxyalkyl bridge, which may be contained as other additive components in mineral oil compositions, consist of a C2-C6 polyalcohol component and a C12-C40 monocarboxylic acid component.

Examples of polyalcohols which may be contained as an alcohol component in C ₁₂ -C ₄₀ monocarboxylic acids with a C ₂ -C ₆ hydroxyalkyl bridge which may form another component of additives are ethylene glycol, polyalkylene glycols, glycerol, 1,1,1-tris- ( hydroxymethyl) propane, pentaerythritol and sorbitol.

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Examples of C ₁₂ -C ₄₀ monocarboxylic acids which may be contained as a carboxylic acid component in C ₁₂ -C ₄₀ monocarboxylic acids with a C ₂ -C ₆ oxyalkyl bridge which may form another component of additives are lauric, palmitic, stearic, oleic, elaidic, ricinoleic, eleostearic, linoleic, linolenic and erucic acids or dimeric acids based on oleic acid or linolenic acid.

Mixed esters of polyalcohols, where the polyalcohols are esterified with mixtures of C ₁₂ -C ₄₀ monocarboxylic acids, are also preferred as C ₁₂ -C ₄₀ monocarboxylic acids with a C ₂ -Cboxyalkyl bridge. Specific examples of the C ₁₂ -C ₄₀ monocarboxylic acids with C ₂ are bridged -Sboksialkilnym monoester of ethylene glycol with dilinolenovoy acid Szvdimernaya acid diester of propylene glycol with oleic acid triester and pentaerythritol with stearic acid.

Especially preferred as C ₁₂ -C ₄₀ monocarboxylic acids with a C ₂ -Cboxyalkyl bridge are esters of unsaturated C ₁₆ -C ₂₄ monocarboxylic acids with C ₃ -C ₄ polyalcohols, the content of C ₂₂ monocarboxylic acid relative to the total weight of C ₁₆ -C ₂₄ monocarboxylic acids is 45-52 wt.%.

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

Examples of hydrocarbon polymers that may be contained as other additive components in mineral oil compositions are ethylene and C ₃ -C ₂₀ aolefin copolymers, such as ethylene-propylene copolymers or ethylene-dodecene copolymers, or hydrated polymers of many unsaturated monomers such as hydrated copolymers diene, such as hydrated polybutadiene or hydrated polyisoprene with a number average molecular weight of up to 30,000.

Examples of copolymers of alkyl phenol and aldehyde that may be contained as other additive components in mineral oil compositions are copolymers that can be prepared by reacting alkylated phenols, such as the adduct of a phenolpropylene oligomer with paraformaldehyde.

Examples of aromatic compounds with C ₈ -C ₁₀₀ alkyl substituents that may be contained as other additive components in mineral oil compositions are compounds that can be prepared by Friedel-Crafts condensation of halogenated hydrocarbons, such as halogenated polyethylene wax, with aromatic hydrocarbons, like benzene or naphthalene.

Examples of detergents that may be contained as other additive components in mineral oil compositions are aliphatic sulfonic acids, such as C ₈ -C ₃₀ alkanesulfonates or aromatic aliphatic alkanesulfonates, in particular nonylbenzenesulfonic acid, dodecylbenzenesulfonic acid, and dodecyl sulfonic acid and dodecyl sulfonic acid.

Examples of demulsifiers that may be contained as other additive components in mineral oil compositions are oxyalkylated phenol-formaldehyde condensates, polyalkylene glycol modified diglycidyl ethers, polyetheramines or alkoxylated fatty acids.

Examples of cetane number modifiers that may be contained as other additive components in mineral oil compositions are organic nitrogen esters, such as ethyl hexyl nitrate, cyclohexyl nitrate or ethoxy ethyl nitrate, or soluble organic peroxides, hydroperoxides or esters. Preferred antifoams that may be contained as other additive components in mineral oil compositions are polyalkylene oxide siloxane block copolymers and carboxylated polyamines.

Examples of polyalkylene oxide siloxane block copolymers are block copolymers that contain a combination of trifunctional siloxane blocks, such as monomethyl siloxane groups; dysfunctional siloxane groups such as dimethylsiloxane groups; and monofunctional siloxane groups, such as trimethylsiloxane groups; the preferred length of the siloxane blocks is from 5 to 20 monomer units. The preferred length of the polyalkylene oxide blocks is 2-40 monomer units, preferred are polyalkylene oxide blocks consisting of ethylene oxide and / or propylene oxide units.

Examples of carboxylated polyamines as anti-foaming agents are the reaction products of C ₈ -C ₂₄ fatty acids and amines such as ethylenediamine, butylenediamine, diethylene triamine and pentaethylene hexamine-1,2-diaminobutanol.

Examples of cosolvents that may be contained as other additive components in mineral oil compositions are gasoline fractions, toluene, xylene, ethylbenzene, isononanol, ethylhexanol, dodecylphenol, epoxidized sepez oil and epoxidized soybean

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Mineral oil compositions as a main component and trace amounts of the additive mixture are prepared by a process in which the mineral oil compositions of the present invention contain the following additive components:

a) copolymers of ethylene and vinyl ester with a weight average molecular weight of from 3,000 to 50,000 and an ethylene content of 50-90 wt.% and

b) glycerol mixed esters, where 50-80 mol% of the hydroxyl groups are esterified with unsaturated C ₃₂ -C ₄₀ monocarboxylic acids and 20-50 mol% of the hydroxyl groups are esterified with partially imidated and / or partially esterified maleic anhydride copolymers; and / or

c) partially and / or fully imidated copolymers of maleic anhydride and α-methylstyrene with a weight average molecular weight of from 1,500 to 15,000 and at least one end group based on dimeric α-methylstyrene; and / or

b) wax compositions based on natural starting materials of the type

61) wax-like oligomeric esters based on glyceryl monostearate and dimeric acid, where the conversion product is at least 90 wt.% Consistent with the structure

CH ₂ - O - CO - (CH ₂ ) _g - CH _E

I

I

CH ₂ - O - CO - (CH ₂ ) _a - SC, - (CH _g ) b - CH

I (CH _g ) g-

where η is 1-20;

the sum (a + b + 6) is 30;

ζ is 12-20.

Υ represents H or

- CO - (CH ₂ ) _a - CH - (CH ₂ ) _b - CH 3

I

НЗС - (СН _g ) _s - СН - (СН _g ) _а - СО - ОН

X represents H or —CH ₂ —CH (OH) —CH ₂ —O — CO— (CH ₂ ) ;; —CH ₃ , and / or

62) wax esters with a vaseline-like consistency based on at least two different linear and / or branched C1 ₄ -C ₃₆ alcohols and dimeric acids, where the conversion product is at least 80 wt.% Consistent with the structure

НЗС - (СНД, - О - СО - (СН ₂ ) _к - СН - СН - (СН ₂ ) _t - СНз

I I

H ₃ C - (CH _g ) ((CH _g ) p - CO - O - (CH ₂ ) _a - CH 3 where ί is 13-35;

equal to 13-35;

the sum (k + t + η + ρ) is 30-34 and (CH ₂ ) ₁ or (CH ₂ ) ₈ are linear or branched, whereby the content of the additive mixture in mineral oil is 0.005-1 wt.% and the mass ratio of the components additives a / b, a / c or a / 6 are in the range from 10:90 to 90:10, respectively, obtained by the method of preliminary homogenization, in which solutions containing 1-60 wt.% of the components of the additives in the middle distillates of mineral oil, get at 20-90 ° C in the first stage and solutions containing additive components homogenize mineral refined oil as the main component in the second stage, while other components of additives with a total mass of 0-200 wt.% in relation to the components of additives (a + b), (a + c), (a + 6), (a + b + c), (a + b + c + 6) or (a + c + 6) are introduced in the first and / or second stage.

Compositions of mineral oil as a main component and trace amounts of the additive mixture are particularly suitable as fluids transported at low temperatures and as mineral oils with high lubricity and fluidity.

Examples of transporting fluids transported at low temperatures are transportation of crude oil compositions from a production site through pipelines with loading and storage, and transportation of diesel or heating oil compositions through pipelines.

- 7 011632

The present invention is explained in more detail by the examples below.

Examples.

The value of the characteristics is determined in accordance with the following test methods: cloud point (SR): ΌΙΝ ΕΝ 23015;

cold filter clogging point (SERP): ΕΝ 116; distillation analysis: ΕΝ Ι8Θ 3405, L8TM Ό86;

acid number: OGI 53402;

saponification number: ΌΙΝ 53401;

kinematic viscosity: ΌΙΝ 51562;

pour point: ΌΙΝ Ι8Θ 2207;

penetration: ΌΙΝ 51580.

Vinyl acetate content: modified method according to Ι8Θ8995, ΌΙΝ 16778, part 2.

g of the sample is weighed with an accuracy of 0.001 g and dissolved in a 300 ml Erlenmeyer flask with 70 ml of distilled xylene and 2 boiling beads while boiling under reflux for about 15 minutes. Then, approximately 30 ml of ethanol is slowly added through a reflux condenser, the Erlenmeyer flask is removed from the heating plate, 30 ml of ethanol, 0.5N, are added. KOH from a burette and 2 boiling balls and the sample are refluxed for 1 hour. The sample is again removed from boiling, mixed with 30 ml of 0.5N methanol-water. HC1 and 2 with boiling balls and refluxed for another 15 minutes. After adding 2-3 drops of a solution of phenolphthalein (1 wt.% In ethanol), the sample is titrated drop by drop with shaking with 0.5N ethanol. KOH before the color changes to red. At the same time determine the idle value (V - Βν) x P x 43

The content of vinyl acetate (wt.%) = --------------------- 10 x E where E represents the initial weight of the sample, g;

E is an indicator of ethanol 0.5n. KOH;

V represents a flow rate (in ml) of 0.5n. ethanol KOH per sample;

B represents a flow rate (in ml) of 0.5n. ethanol KOH at idle experience.

Lubricity. Lubricity test (adjusted wear spot diameter at 60 ° C) in accordance with KO 12156-1.

Short-term sedimentation test.

When determining the tendency to sedimentation of recrystallized paraffins in mineral oil, 500 ml of the sample is stored in a graduated cylinder for 16 hours, then the upper 80 vol.% Of the sample is removed and drained. The remaining 20 vol.% Of the sample (100 ml) is homogenized at 40 ° C, then the cloud point (CP) is determined according to ΌΙΝ 23015.

ΔΕΌΆΒ filtration test.

A sample of 500 ml of mineral oil is shaken vertically 20 times, kept at 10 ° C for 16 hours, shaken vertically 10 times and the whole sample is filtered through a filter of cellulose nitrate (50 mm in diameter, 0.8 μm pore size), which is suction cup under vacuum approximately 200 GPa. Determine the time during which the sample passes through the filter. The sample is considered to have passed the δΕΌΆΒ filter test if the sample passes through the filter for a period of time <120 s.

Example 1

1.1. Source products.

1.1.1. Diesel fuel without additives.

Lot: 16080601, test ΌΕ 1.

Characteristics:

cloud point (SR): 6 ° C;

cold filter clogging point (SERR): 2 ° C;

lubricity test: 563 microns.

Distillation analysis

Distilled amount (vol.%) / Temperature (° С)

TNK 10 twenty thirty 40 fifty 60 70 80 90 CPC 189 243 259 271 281 292 303 317 334 357 385

TNC - boiling point.

CPC - final boiling point.

- 8 011632

1.1.2. Component of additives a).

Wax of a copolymer of ethylene and vinyl acetate (manufactured by LEIMA Ro1uteg STH, vinyl acetate content of 28.3 wt.%, Weight average molecular weight of 3150 g / mol).

1.1.3. Additive component b).

Mixed glycerol ester is prepared by a melt esterification process.

A copolymer of maleic anhydride and octadecene, partially esterified with dodecyl alcohol (molar ratio 1: 2.2, acid number 40, number average molecular weight 2400), is dosed at a rate of 3.8 kg / h into the feeding screw of the twin-screw extruder \ Vegpeg & RG1e1beg Ζ8Κ 30, I-ratio 48 with a side dispenser for liquid media and two vacuum degassing zones and a continuous tape dispenser for dispensing and melting at 90 ° C. The glycerol dieseric ester from the storage tank heated to 90 ° C is fed into the melt using a side meter at a speed of 2.0 kg / h, where it is reacted in the first reaction zone (holding time 4.5 min) at 110 ° C, degassed, subjected to interaction in the second reaction zone at 130 ° C (exposure time 3.5 min), degassed, fed at 85 ° C to a self-cleaning melt filter using a gear melt pump (exbeh 8P, Maad pumping systems) and formed into a press with a cooling conveyor in tablets.

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

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

kg of the additive component b) is mixed in a vessel reactor with stirring with 60 kg of a 50% solution of the additive component a) in a mixture of aromatic hydrocarbons (8o1ueg5o) for 120 minutes at 65 ° C and the mixture is transferred to a storage tank.

1.3. Obtaining and testing compositions of mineral oil.

The additive solution according to Claim 1.2 is introduced at a rate of 0.48 kg / min into the product stream of diesel fuel without additives, a batch of 16080601, flowing at a speed of 800 kg / min, and the mixture is loaded into a storage container.

Testing the composition of mineral oil for resistance to low temperatures gives a SERR value of -10 ° C. Determination of lubricity shows a wear spot diameter of 405 μm.

The CP value of the short-term sedimentation test is 7 ° C. The 8EIA filter test is considered matured (500 ml in 84 s).

If the composition of mineral oil, which contains only copolymer wax as an additive, is obtained under the same conditions, the SERP value is −3 ° C. and the diameter of the wear spot is 520 μm.

The CP value of short-term sedimentation is 10 ° C. The 8EIAB filtration test is considered inconsistent (468 ml for> 120 s).

Example 2

2.1. Source products.

2.1.1. Diesel fuel without additives.

Lot: 030210, test IE 2

Characteristics:

cloud point (SR): 7 ° С;

cold filter clogging point (SERR): 2 ° C;

lubricity test: 556 microns

Distillation analysis

Distilled amount (vol.%) / Temperature (° С)

Transnational corporation 10 twenty thirty 40 fifty 60 70 80 90 CPC 235 266 279 291 301 310 320 337 342 357 374

2.1.2. Component of additives a).

10 wt.% Of partially saponified wax of ethylene-vinyl acetate copolymer are mixed (weight average molecular weight of 1850 g / mol, vinyl acetate content of unsaponified ethylene-vinyl acetate copolymer wax is 32.5 wt.%, Saponification degree is 15 mol.%) And 90 wt.% Of unsaponified a wax of a copolymer of ethylene and vinyl acetate (manufactured by the company LIIIA Ro1uteg STN, the content of vinyl acetate is 31 wt.%, the weight average molecular weight is 2800 g / mol).

2.1.3. Additive component b).

Mixed glycerol ester is prepared by a melt esterification process.

A copolymer of α-methylstyrene, maleic anhydride and octadecene, partially imidated with C1 ₆ -C1 ₈ fatty amine (molar ratio 1.3: 1.0, acid number 42, melting point

- 9 011632

70 ° C), dosed at a rate of 3.6 kg / h using a continuous tape dispenser into the feed screw of a twin-screw extruder \ Usgpsg & RPS1bssgsg Ζ8Κ 30, L / O ratio 48 with a side dispenser for a liquid medium and two vacuum degassing zones and dissolve when heated at 110 ° C. Glycerol dioleyl ester from a storage tank heated to 90 ° C is fed into the melt using a side meter at a speed of 1.14 kg / h, the melt is reacted in the first reaction zone (exposure time 4.5 min) at 115 ° C degassed, subjected to interaction in the second reaction zone at 130 ° C (holding time 3.5 min), degassed, fed at 85 ° C to a self-cleaning melt filter using a gear melt pump (ex (Ex 8H, Maad pumping systems) and molded in a press with a cooling conveyor in tablets.

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

2.1.4. Other components of additives.

A copolymer of dodecyl acrylate and ethyl acrylate (molar ratio 2: 1, number average molecular weight 13500).

2.2. Preparation of solutions containing additive components in medium mineral oil distillates kg additive component b), 40 kg of a 60% solution of the additive component a) in a C ₈ -C ₉ diesel aromatic fraction and 20 kg of a 10% solution of another additive component, a dodecyl acrylate-ethyl acrylate copolymer, in toluene is mixed for 120 min in a vessel reactor with stirring at 65 ° C and the mixture is transferred to a storage tank.

2.3. Obtaining and testing compositions of mineral oil.

The additive solution according to claim 2.2 is introduced at 0.12 kg / min into the diesel product stream without additives, batch 030210 текущего, flowing at a speed of 800 kg / min, and the mixture is loaded into a storage tank.

Testing the composition of mineral oil for resistance to low temperatures gives a CPPP value of -11 ° C. The determination of lubricity shows a wear spot diameter of 402 μm.

The CP value of the short-term sedimentation test is 9 ° C. The 8 цию filtration test is considered to have passed (500 ml in 96 s).

If the composition of mineral oil, which contains only unsaponifiable copolymer wax as an additive, is obtained under the same conditions, the CPPP value is −5 ° C. and the diameter of the wear spot is 528 μm.

The CP value of short-term sedimentation is 12 ° C. The 8ΕΌΆΒ filtration test is considered inconsistent (468 ml for> 120 s).

Example 3

3.1. Source materials.

3.1.1. Heating oil without additives.

Lot: 030225, test NY, type 1.

Characteristics:

cloud point (SR): 1 ° С;

cold filter clogging point (СРРР): -1 ° С.

Distillation analysis

Distilled amount (vol.%) / Temperature (° С)

TNK 10 twenty thirty 40 fifty 60 70 80 90 CPC 165 196 213 230 249 269 290 310 327 344 363

3.1.2. Component of additives a).

15 wt.% Of oxidized wax of ethylene-vinyl acetate copolymer are mixed (weight average molecular weight 950 g / mol, acid number 18 mg KOH / g, OH number 70 mg KOH / g) and 85 wt.% Unoxidized wax copolymer of ethylene and vinyl acetate (made by the company ΕΕυΝΆ Ро1утег ОшЬН, the content of vinyl acetate is 32 wt.%, the mass-average molecular weight is 2300 g / mol).

3.1.3. Additive component b).

Mixed glycerol ester is prepared by a melt esterification process.

A copolymer of octadecene, maleic anhydride and octadecene, partially imidated

C1 ₆ -C1 ₈ fatty amine (molar ratio 1.4: 1.0, acid number 57, melting point

55 ° C), dosed at a rate of 4.2 kg / h using a continuous tape dispenser into the feed screw of a twin-screw extruder ^ EGPEG & RDEIegeg Ζ8Κ30, L / O ratio 48 with a side meter for liquid media and two vacuum degassing zones and dissolve when heated at 115 ° C. Glycerin and an acid mixture of erucic and oleic acids from a storage tank heated to 90 ° C are introduced into the melt using a side meter at a speed of 2.72 kg / h, the melt is subjected to interaction in

- 10 011632 the first reaction zone (exposure time 4.5 min) at 120 ° C, degassed, reacted in the second reaction zone at 130 ° C (exposure time 3.5 min), degassed, fed at 95 ° C to a self-cleaning filter melt using a gear melt pump (ex (those 8P, Maad pumping systems) and molded in a press with a cooling conveyor into tablets.

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

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

kg of the additive component b) is mixed with a 50 kg 60% solution of the additive component a) in a C ₈ -C ₉ diesel aromatic fraction for 120 min in a vessel reactor with stirring at 65 ° C and the mixture is transferred to a storage tank.

3.3. Obtaining and testing compositions of mineral oil.

The additive solution according to claim 3.2 is introduced at a rate of 0.24 kg / min into the product stream of heating oil without additives, a batch of 030225 flowing at a speed of 800 kg / min, and the mixture is loaded into a storage tank.

Testing the composition of mineral oil for resistance to low temperatures gives a SERP value of -15 ° C.

If the composition of mineral oil, which contains only copolymer wax as an additive, is obtained under the same conditions, the SERP value is -12 ° C.

Example 4

4.1. Source materials.

4.1.1. Heating oil without additives.

Lot: 030218, test NE 2.

Characteristics:

cloud point (SR): 2 ° C;

cold filter clogging point (SERR): -1 ° C.

Distillation analysis

Distilled amount (vol.%) / Temperature (° С)

Transnational corporation 10 twenty thirty 40 fifty 60 70 80 90 ctk 173 194 207 225 247 273 299 320 337 355 379

4.1.2. Component of additives a).

10 wt.% Of ethylene vinyl acetate copolymer wax are grafted with a graft of vinyl acetate (obtained in accordance with ΌΌ 293125A5, total vinyl acetate content is 38 wt.%, Molecular weight average molecular weight is 3400 g / mol, vinyl acetate content in wax of ungrafted ethylene vinyl acetate copolymer is 32.5 wt. wt.%, saponification degree 32 mol.%) and 90 wt.% wax of the unvaccinated copolymer of ethylene and vinyl acetate (manufactured by Rohuteg CbHN, vinyl acetate content 32.5 wt.%, weight average molecular weight 2400 g / mol).

4.1.3. Additive component b).

Mixed glycerol ester is prepared by a melt esterification process.

A copolymer of α-methylstyrene and maleic anhydride, partially esterified with octadecyl alcohol (molar ratio 1.1: 1.0, acid number 55, melting point 64 ° C), is dosed at a rate of 4.0 kg / h using a continuous tape dispenser in the feed the screw of the twin-screw extruder ХУегпег & РПейегег Ζ8Κ 30, L / O ratio 48 with a side dispenser for a liquid medium and two vacuum degassing zones and dissolve when heated at 90 ° C. Glycerol ester and the erucic acid / oleic acid / linolenic acid mixture (molar ratio 6: 1: 1: 1) from the storage vessel heated to 110 ° C. are introduced into the melt using a side meter at a rate of 2.4 kg / h, the melt is subjected to interaction in the first reaction zone (exposure time 4.5 minutes) at 125 ° C, degassed, subjected to interaction in the second reaction zone at 135 ° C (exposure time 3.5 minutes), served at 95 ° C in self-cleaning melt filter using a melt gear pump and molded in a press with cooling waiting conveyor into tablets.

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

4.1.4. Other components of additives.

Polyethylene glycol monomethyl ether, number average molecular weight 1500.

A copolymer of 2-ethylhexyl acrylate and ethyl acrylate (molar ratio 2: 1).

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

kg of the additive component b), 20 kg of a 60% solution of the additive component a) in a C8-C9 diesel aromatic fraction and 1 kg of another additive component, polyethylene glycol monomethyl ether 11 011632 cal, the number average molecular weight of 1500, and 8 kg of a 10% solution of the other component of an additive, a copolymer of ethyl hexyl acrylate and ethyl acrylate (molar ratio 2: 1), is added to toluene in a stirred reactor with stirring, mixed for 120 min at 65 ° C and the mixture is transferred to a storage tank.

4.3. Obtaining and testing the composition of mineral oil.

The additive solution according to paragraph 4.2 is introduced at a rate of 0.28 kg / min into the product stream of heating oil without additives, batch 030225, flowing at a speed of 800 kg / min, and the mixture is loaded into a storage tank.

Testing the composition of mineral oil for resistance to low temperatures gives a SERP value of -14 ° C.

If the composition of mineral oil, which contains only copolymer wax as an additive, is obtained under the same conditions, the SERP value is -1 ° C.

Example 5

5.1. Source materials.

5.1.1. Diesel fuel without additives.

Lot: 16080601, test ΌΕ 1.

Characteristics:

cloud point (SR): 6 ° C;

Cold Filter Clogging Point (CEPR): 2 ° C.

Distillation analysis

Distilled amount (vol.%) / Temperature (° С)

TNK 10 twenty thirty 40 fifty 60 70 80 90 CPC 189 243 259 271 281 292 303 317 334 357 385

5.1.2. Component of additives a).

Wax of a copolymer of ethylene and vinyl acetate (manufactured by ΕΕυΝΆ Ро1утег СН, vinyl acetate content of 32 wt.%, Weight average molecular weight of 2300 g / mol).

5.1.3. Additive component c).

A copolymer of α-methylstyrene and maleic anhydride, partially imidated with C1 ₆ -C1 ₈ fatty amine, number average molecular weight 12800 g / mol, acid number 35.

Obtaining an additive component c).

l of α-methylstyrene, 7 l of dimer of α-methylstyrene and 20 l of acetone are loaded into a 500 l stirred reactor and the stirred reactor is heated to 59 ° C. A solution of 52 kg of maleic anhydride and 2.4 kg of dinitrile azoisobutyric acid in 150 l of acetone is uniformly dosed into the reactor with stirring for 6 hours and the reaction mixture is stirred for more than 6 hours at 70-73 ° C.

The analyzed copolymer sample (MCP5) has an acid number of 445 mg KOH per 1 g of copolymer. NMR analysis gives 1.3 terminal groups of α-methylstyrene dimer per 1 mol.

The polymer solution, which is still at 54-56 ° C, is now continuously fed into a double-drum vacuum dryer and separated into a powdery copolymer with a residual content of 1.1 wt.% Volatile ingredients and acetone.

382 kg of C ₈ -C ₉ diesel aromatic fraction boiling above 160 ° C and 122 kg of C _{1 6} -C ₈ fatty amine are loaded into a 500 L stirred tank reactor and heated at 130 ° C to partially imitate the copolymer. 135.5 kg of the copolymer is continuously introduced into this solution for 4 hours. This increases the temperature inside the vessel reactor with stirring to 180-185 ° C, and the resulting water is azeotroped with approximately equal amounts of C8-C9 diesel aromatic fraction. After 6 hours of total reaction time at 160-190 ° C, 8.5 kg of water and 10.2 kg of solvent are distilled off. A 40% solution of a partially imidated copolymer with an acid number of 35 and a number average molecular weight of 12800 g / mol is obtained.

5.1.4. Other components of additives.

A mixture of unsaturated C ₃₈ -C ₂₄ carboxylic acids with a C ₃ alkyl bridge, the degree of esterification is 92 mol%, the content of C ₃₈ unsaturated fatty acids 32 wt.%, The content of C ₂₂ unsaturated fatty acids 48 wt.%, The iodine number 96.

A copolymer of ethyl acrylate and ethyl hexyl acrylate (molar ratio 3: 2, number average molecular weight 13500).

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

kg of a 40% solution of the additive component component c) in a C ₈ -C ₉ diesel aromatic fraction, 50 kg of a 50% solution of the component of the additive component a) in an aromatic hydrocarbon mixture (§о1ее§8о), 20 kg of a mixture of unsaturated C1 ₈ -C ₂₄ carboxylic acids with With a ₃ oxyalkyl bridge as another component, a cage and 19 kg of a 20% solution of another component of additives, a copolymer of ethyl acrylate and ethyl hexyl acrylate, are mixed in toluene in a vessel reactor with stirring for 90 min at 65 ° C and the mixture is transferred to a container storage.

5.3. Obtaining and testing the composition of mineral oil.

The additive solution according to paragraph 5.2 is injected at a speed of 0.48 kg / min into the product stream of diesel fuel without additives, a batch of 16080601, flowing at a speed of 800 kg / min, and the mixture is loaded into a storage tank.

Testing the composition of mineral oil for resistance to low temperatures gives a SERP value of -16 ° C.

The CP value of the short-term sedimentation test is 5 ° C. The 8 тра filtration test is considered to have passed (500 ml in 76 s).

If the composition of mineral oil, which contains only unsaponifiable copolymer wax as an additive, is obtained under the same conditions, the SERP value is -3 ° C.

The CP value of short-term sedimentation is 10 ° C. The 8ΕΌΆΒ filtration test is considered inconsistent (468 ml for> 120 s).

Example 6

6.1. Source materials.

6.1.1. Diesel fuel without additives.

Lot: 030210, test ΌΕ 2.

Characteristics:

cloud point (SR): 7 ° С;

Cold Filter Clogging Point (CEPR): 2 ° C.

Distillation analysis

Distilled amount (vol.%) / Temperature (° С)

Transnational corporation 10 twenty thirty 40 fifty 60 70 80 90 CPC 235 266 279 291 301 310 320 337 342 357 374

6.1.2. Component of additives a).

10 wt.% Wax of partially saponified ethylene-vinyl acetate copolymer is mixed (mass-average molecular weight 1600 g / mol, vinyl acetate content of wax of unsaponified ethylene-vinyl acetate copolymer 32 wt.%, Saponification degree 15 mol.%) And 90 wt.% Ethylene copolymer wax and vinyl acetate (manufactured by ΕΕυΝΆ Ро1утег СНН. vinyl acetate content is 32 wt.%, weight average molecular weight is 2300 g / mol).

6.1.3. Additive component c).

A copolymer of α-methylstyrene and maleic anhydride, partially imidated with dodecylamine, number average molecular weight 14,200 g / mol, acid number 56.

Obtaining an additive component c).

l of α-methylstyrene, 5.1 l of dimer of α-methylstyrene, 62 kg of maleic anhydride and 110 l of 2-butanone are charged into a 500 l stirred reactor and the stirred reactor is heated to 70 ° C. A solution of 1.9 kg of dibenzoyl peroxide and 52 L of 2-butanone is uniformly metered into the vessel reactor with stirring for 2 hours, and the reaction mixture is stirred for more than 10 hours at 72-73 ° C.

The analyzed copolymer sample has an acid number of 452 mg KOH per 1 g of copolymer. NMR analysis gives 1.1 terminal groups of α-methylstyrene dimer per 1 mol.

The polymer solution, which is still at 70 ° C, is now continuously dosed into a 500 L stirred tank reactor containing 280 L of 2-ethylhexanol and heated to 150 ° C, while 2-butanone-2 is removed by distillation. 104 kg of C16-C18 fatty amine is introduced over 4 hours when the temperature rises to 165-185 ° C. to remove water along with a small amount of 2-ethylhexanol by distillation.

A 40% solution of partially imidated copolymer c) is obtained with an acid number of 56 and a number average molecular weight of 14,200 g / mol.

6.1.4. Other components of additives.

Pentaerythritol triesters with oleic acid.

Diethylene glycol monolauroyl ester.

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

kg of a 40% solution of additive component c) in 2-ethylhexanol, 50 kg of a 60% solution of additive component a) in a C8-C9 diesel aromatic fraction, 20 kg of pentaerythritol ester with oleic acid as another additive component and 1 kg of another additive component, complex diethylene glycol monolauroyl ether is introduced into the reactor with stirring, mixed for 90 minutes at 65 ° C and the mixture is transferred to a storage tank.

6.3. Obtaining and testing the composition of mineral oil.

The additive solution according to claim 6.2 is introduced at a rate of 0.24 kg / min into the product stream of diesel fuel without additives, a batch of 030210 flowing at a speed of 800 kg / min, and the mixture is loaded into a storage container.

Testing the composition of mineral oil for resistance to low temperatures gives a SERP value of -7 ° C.

The CP value of the short-term sedimentation test is 7 ° C. The 8 тра filtration test is considered to have passed (500 ml in 82 s).

If the composition of mineral oil, which contains only unsaponifiable copolymer wax as an additive, is obtained under the same conditions, the SERP value is -5 ° C.

The CP value of short-term sedimentation is 12 ° C. The 8ΕΌΑΒ filtration test is considered inconsistent (468 ml for> 120 s).

Example 7

7.1. Source materials.

7.1.1. Heating oil without additives.

Lot: 030225, test HE1.

Characteristics:

cloud point (SR): 1 ° С;

cold filter clogging point (SERR): -1 ° C.

Distillation analysis

Distilled amount (vol.%) / Temperature (° С)

Transnational corporation 10 twenty thirty 40 fifty 60 70 80 90 CPC 165 196 213 230 249 269 290 310 327 344 363

7.1.2. Component of additives a).

15 wt.% Wax of an oxidized ethylene-vinyl acetate copolymer are mixed (weight average molecular weight 950 g / mol, acid number 18 mg K0H / g, OH number 70 mg K0H / g) and 85 wt.% Wax of an unoxidized ethylene vinyl acetate copolymer (manufactured by the company ΝΑυ1 Ро1утег СН, vinyl acetate content of 32 wt.%, weight average molecular weight of 2300 g / mol).

7.1.3. Additive component c).

A copolymer of α-methylstyrene and maleic anhydride, partially imidated with C1 ₂ -C1 ₄ fatty amine, number average molecular weight 7000 g / mol, acid number 25.

Obtaining an additive component c).

l of α-methylstyrene, 12 l of dimer of α-methylstyrene, 62 kg of maleic anhydride and 140 l of 1,2-dichloroethane are charged into a 500 l autoclave with stirring and the autoclave with stirring is heated to 90 ° C. A solution of 2.5 kg of tert-butyl peroxy-2-ethylhexanoate and 55 L of 1,2-dichloroethane is uniformly metered into the autoclave with stirring for 2 hours and the reaction mixture is stirred for more than 10 hours at 90-93 ° C.

The analyzed copolymer sample has an acid number of 430 mg K0H per 1 g of copolymer. NMR analysis gives 1.4 end groups of α-methylstyrene dimer per mole.

The polymer solution, which is still at approximately 90 ° C, is now continuously dosed in a 500 L stirred tank reactor containing a mixture of 280 L of C8-C9 diesel aromatic fraction and 122 kg of C1 ₂ -C1 ₄ fatty amine, heated to 160 ° C, while 1,2-dichloroethane and imidation reaction water are removed by distillation.

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

7.1.4. Other components of additives.

Ethylene glycol diesters with erucic acid.

No. (2-hydroxyethyl) oleylamine.

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

kg of a 60% solution of the additive component a) in a C ₈ -C ₉ diesel aromatic fraction, 20 kg of ethylene glycol diester with erucic acid as another additive component and 3 kg of another additive component, No. (2-hydroxyethyl) oleylamine, are loaded into a shell reactor with stirring, containing 25 kg of a 40% solution of the component of additives c) in the C8-C9 diesel aromatic fraction, at 65 ° C, mixed for 90 minutes at 65 ° C and the mixture was transferred to a storage tank.

- 14 011632

7.3. Obtaining and testing the composition of mineral oil.

The additive solution according to claim 7.2 is introduced at 0.24 kg / min into the product stream of heating oil without additives, batch 030225, flowing at a speed of 800 kg / min, and the mixture is loaded into a storage tank.

Testing the composition of mineral oil for resistance to low temperatures gives

CPPP value is -15 ° C.

If the composition of mineral oil, which contains only unsaponifiable copolymer wax as an additive, is obtained under the same conditions, the SERP value is -13 ° C.

Example 8

8.1. Source materials.

8.1.1. Diesel fuel without additives.

Lot: 16080601, test ΌΡ 1.

Characteristics:

cloud point (SR): 6 ° C;

Cold Filter Clogging Point (CEPR): 2 ° C.

Distillation analysis

Distilled amount (vol.%) / Temperature (° С)

TNK 10 twenty thirty 40 fifty 60 70 80 90 CPC 189 243 259 271 281 292 303 317 334 357 385

8.1.2. Component of additives a).

Wax of a copolymer of ethylene and vinyl acetate (manufactured by ΕΕυΝΆ Ро1утег СН, vinyl acetate content of 32 wt.%, Weight average molecular weight of 2300 g / mol).

8.1.3. Additive component c).

A copolymer of α-methylstyrene and maleic anhydride, partially imidated with stearylamine, weight average molecular weight 13750 g / mol, acid number 51.

Obtaining an additive component c).

l of α-methylstyrene, 7 l of dimer of α-methylstyrene and 20 l of acetone are loaded into a 500 l stirred reactor and the stirred reactor is heated to 59 ° C. A solution of 52 kg of maleic anhydride and 2.4 kg of dinitrile azoisobutyric acid in 150 l of acetone is uniformly dosed into the reactor with stirring for 6 hours and the reaction mixture is stirred for more than 6 hours at 70-73 ° C.

The analyzed sample of the copolymer has an acid number of 445 mg KOH per 1 g of copolymer. NMR analysis gives 1.3 terminal groups of α-methylstyrene dimer per 1 mol.

The polymer solution, which is still at 54-56 ° C, is now continuously fed into a vacuum double-drum dryer and separated into a powdery copolymer with a residual content of 1.1% volatile ingredients and acetone.

382 kg of a C ₈ -C ₉ diesel aromatic fraction boiling above 160 ° C and 135 kg of stearylamine are loaded into a 500 L stirred tank reactor and heated at 130 ° C to partially imitate the copolymer. 135.5 kg of the copolymer is continuously introduced into this solution for 4 hours. This increases the temperature inside the vessel reactor with stirring to 180-185 ° C, and the resulting water is azeotroped with approximately equal amounts of C ₈ -C ₉ diesel aromatic fraction. After 6 hours of total reaction time at 160-190 ° C., 8.5 kg of water and 10.2 kg of solvent are distilled off.

A 40% solution of a copolymer partially imidated with stearylamine is obtained with an acid number of 51 and a weight average molecular weight of 13750 g / mol.

8.1.4. Other components of additives.

A mixture of unsaturated C ₃₈ -C ₂₄ carboxylic acids with a C ₃ alkyl bridge, the degree of esterification is 92 mol%, the content of C ₃₈ unsaturated fatty acids 32 wt.%, The content of C ₂₂ unsaturated fatty acids 48 wt.%, The iodine number 96.

A copolymer of ethyl acrylate and octadecyl acrylate (molar ratio 4: 1, number average molecular weight 8400).

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

kg of a 40% solution of the component of additives c) in a C ₈ -C ₉ diesel aromatic fraction, 50 kg of a 50% solution of the component of additives a) in an aromatic hydrocarbon mixture (8o1ue55o), 20 kg of a mixture of unsaturated C18-C24 carboxylic acids with a C3oxyalkyl bridge as another component additives and 19 kg of a 20% solution of another component of additives, a copolymer of ethyl acrylate and octadecyl acrylate, are mixed in toluene in a vessel reactor with stirring for 90 min at 65 ° C and the mixture is transferred to a storage tank.

- 15 011632

8.3. Obtaining and testing the composition of mineral oil.

The additive solution of claim 8.2 is introduced at a rate of 0.48 kg / min into the diesel product stream without additives, a batch of 16080601, flowing at a speed of 800 kg / min, and the mixture is loaded into a storage tank.

Testing the composition of mineral oil for resistance to low temperatures gives a SERP value of -17 ° C.

If the composition of mineral oil, which contains only unsaponifiable copolymer wax as an additive, is obtained under the same conditions, the SERP value is -3 ° C.

Example 9

9.1. Source materials.

9.1.1. Diesel fuel without additives.

Lot: 16080601, test ΌΕ 1.

Characteristics:

cloud point (SR): 6 ° C;

cold filter clogging point (SERR): 2 ° C;

lubricity test: 563 microns.

Distillation analysis

Distilled amount (vol.%) / Temperature (° С)

Transnational corporation 10 twenty thirty 40 fifty 60 70 80 90 CPC 189 243 259 271 281 292 303 317 334 357 385

9.1.2. Component of additives a).

Wax of a copolymer of ethylene and vinyl acetate (manufactured by ΕΕυΝΆ Ро1утег СНН. Vinyl acetate content 32 wt.%, Weight average molecular weight 2300 g / mol).

9.1.3. Additive Component 62).

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, pour point 34.5 ° C.

Obtaining an additive component 62).

A mixture of 25 kg of dimeric acid (the product of the dimerization of unsaturated C1 ₈ fatty acids, the average number of carbon atoms is 36), 5 kg of stearyl alcohol and 7 kg of cetyl alcohol are dissolved by heating in a 70 L reactor with stirring at 120 ° C with inert gas and subjected to interaction with the addition of 50 g of H ₂ §O ₄ with the removal of reaction water until the acid number reaches 7.9 mg KOH / g. 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 removed.

9.1.4. Other components of additives.

A copolymer of ethyl acrylate and ethyl hexyl acrylate (molar ratio 3: 2, number average molecular weight 135000).

9.2. Obtaining solutions containing additive components in the middle distillates of mineral oil.

kg of a 40% solution of the component of the additives 62) in a C ₈ -C ₉ diesel aromatic fraction, 50 kg of a 50% solution of the component of the additives a) in an aromatic hydrocarbon mixture (§о1ее88о) and 15 kg of a 20% solution of another component of the additives, a copolymer of ethyl acrylate and ethyl hexyl acrylate, in toluene is mixed in a vessel reactor with stirring for 90 min at 65 ° C and the mixture is transferred to a storage tank.

9.3. Obtaining the composition of mineral oil.

The additive solution according to claim 9.2 is injected at a speed of 0.48 kg / min into the diesel product stream without additives, a batch of 16080601, flowing at a speed of 800 kg / min, and the mixture is loaded into a storage tank.

Testing the composition of mineral oil for resistance to low temperatures gives a SERP value of -14 ° C. The lubricity test shows a wear spot diameter of 412 microns.

If the composition of mineral oil, which contains only unmodified copolymer wax a) as an additive, is obtained under the same conditions, the SERP value is -3 ° C.

Example 10

10.1. Source materials.

10.1.1. Diesel fuel without additives.

Lot: 030210, test ΌΕ 2.

Characteristics:

cloud point (SR): 7 ° С;

cold filter clogging point (SERR): 2 ° C;

lubricity test: 556 microns.

- 16 011632

Distillation analysis

Distilled amount (vol.%) / Temperature (° С)

Transnational corporation 10 twenty thirty 40 fifty 60 70 80 90 CT K 235 266 279 291 301 310 320 337 342 357 374

10.1.2. Component of additives a).

20 wt.% Of partially saponified ethylene-vinyl acetate copolymer wax are mixed (weight average molecular weight 1–00 g / mol, vinyl acetate content in the unsaponified ethylene-vinyl acetate copolymer wax is 32 wt.%, Saponification degree is 15 mol.%) And 80 wt.% Ethylene copolymer wax and vinyl acetate (manufactured by ΕΕυΝΆ Ро1утег СН, vinyl acetate content 32 wt.%, weight average molecular weight 2300 g / mol).

10.1.3. Additive component J2).

Wax ester with vaseline-like consistency, acid number 8, b mg KOH / g, saponification number 118 mg KOH / g, kinematic viscosity 23.1 mm ² / s, pour point 35.2 ° C.

Obtaining a component of additives J2).

A mixture of 25 kg of dimeric acid (the product of the dimerization of unsaturated C, ₈ fatty acids, the average number of carbon atoms is 3b), 5 kg of stearyl alcohol and 8 kg of eicosan alcohol are dissolved by heating in a 70 L reactor with stirring at 120 ° C with the introduction of an inert gas and subjected to interaction with the addition of 50 g of H ₂ 8O ₄ with the removal of reaction water until then, until the acid number reaches a value of 8, b mg KOH / g After cooling the melt, the catalyst was neutralized with 1.0 L of 10% NaHCO 3, the aqueous phase was separated and the wax ester was removed.

10.1.4. Other components of additives.

Pentaerythritol triesters with oleic acid.

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

kg of a 50% solution of the component of the additive component J2) in 2-ethylhexanol, 50 kg of a 0% solution of the component of the additive a) in the C8-C9 diesel aromatic fraction and 20 kg of the pentaerythritol ester with oleic acid as another component of the additives are introduced into the reactor with stirring, mixed for 90 min at b5 ° C and the mixture is loaded into a storage tank.

10.3. Obtaining the composition of mineral oil.

The additive solution according to claim 10.2 is introduced at a speed of 0.30 kg / min into the product stream of diesel fuel without additives, a batch of 030210 flowing at a speed of 800 kg / min, and the mixture is loaded into a storage tank.

Testing the composition of mineral oil for resistance to low temperatures gives a SERP value of -8 ° C. The lubricity test shows a wear spot diameter of 425 microns.

If the composition of mineral oil, which contains only unmodified copolymer wax a) as an additive, is obtained under the same conditions, the SERP value is -5 ° C and the diameter of the wear spot is 528 μm.

Example 11

11.1. Source materials.

10.1.1. Heating oil without additives.

Lot: 030225, test HE1.

Characteristics:

cloud point (SR): 1 ° С;

cold filter clogging point (SERR): -1 ° C.

Distillation analysis

Distilled amount (vol.%) / Temperature (° С)

Transnational corporation 10 twenty thirty 40 fifty 60 70 80 90 CPC 165 196 213 230 249 269 290 310 327 344 363

11.1.2. Component of additives a).

Mix 25 wt.% Wax of the oxidized ethylene vinyl acetate copolymer (mass average molecular weight 950 g / mol, acid number 18 mg KOH / g, OH number 70 mg KOH / g) and 75% unoxidized wax copolymer of ethylene and vinyl acetate (manufactured by ΕΕυΝΆ Рол1утег СН, vinyl acetate content 32 wt.%, Weight average molecular weight 2300 g / mol).

11.1.3. Additive component Y1).

Oligomeric ester (acid number 12 mg KOH / g, saponification number 175 mg KOH / g, kinematic viscosity (100 ° C) b5 mm ² / s, pour point 42 ° C) obtained in accordance with EP 0934921A1 from glyceryl monostearate and dimeric acids (product of dimerization of unsaturated

- 17 011632

C18 fatty acids, average number of carbon atoms 36) oligocondensation without solvent under conditions of acid catalysis.

11.1.4. Other additive components are No. (2-hydroxyethyl) oleylamine.

11.2. Obtaining solutions containing additive components in the middle distillates of mineral oil.

kg of a 60% solution of the additive component a) in a C ₈ -C ₉ diesel aromatic fraction and 3 kg of another additive component, No. (2-hydroxyethyl) oleylamine, are introduced into the stirred vessel containing 23 kg of a 40% solution of the additive component 61) in C ₈ -C ₉ diesel aromatic fraction at 65 ° C, mixed for 90 min at 65 ° C and the mixture is loaded into a storage tank.

11.3. Obtaining the composition of mineral oil.

The additive solution according to claim 11.2 is introduced at 0.28 kg / min into the heating oil product stream without additives, batch 030225, flowing at a speed of 800 kg / min, and the mixture is loaded into a storage tank.

Testing the composition of mineral oil for resistance to low temperatures gives a CPPP value of -16 ° C.

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

Example 12

12.1. Source materials.

12.1.1. Diesel fuel without additives.

Lot: 16080601, test IR 1.

Characteristics:

cloud point (SR): 6 ° C;

cold filter plugging point (СРРР): 2 ° С.

Distillation analysis

Distilled amount (vol.%) / Temperature (° С)

Transnational corporation 10 twenty thirty 40 fifty 60 70 80 90 CPC 189 243 259 271 281 292 303 317 334 357 385

12.1.2. Component of additives a).

Wax of a copolymer of ethylene and vinyl acetate (manufactured by ΕΕυΝΆ Ро1утег СНН. Vinyl acetate content 32 wt.%, Weight average molecular weight 2300 g / mol).

12.1.3. Additive component 61).

Oligomeric ester (acid number 14 mg KOH / g, saponification number 185 mg KOH / g, kinematic viscosity (100 ° C) 76 mm ² / s, pour point 42 ° C) obtained in accordance with EP 0934921A1 from glyceryl monostearate and dimeric acids (the product of the dimerization of unsaturated C18 fatty acids, an average of 36 carbon atoms) by solvent-free oligocondensation under conditions of acid catalysis.

12.1.4. Other components of additives.

A mixture of unsaturated C18-C24 carboxylic acids with a C3oxyalkyl bridge, the degree of esterification is 92 mol.%, The content of C1 is ₈ unsaturated fatty acids 32 wt.%, The content of C ₂₂ unsaturated fatty acids is 48 wt.%, The iodine number is 96.

12.2. Obtaining solutions containing additive components in the middle distillates of mineral oil.

kg of a 50% solution of the component of additives 61) in a C ₈ -C ₉ diesel aromatic fraction, 50 kg of a 60% solution of the component of additives a) in an aromatic hydrocarbon mixture (8O1UE55O), 12 kg of a mixture of unsaturated C1 ₈ -C ₂₄ carboxylic acids with C ₃ hydroxyalkyl with a bridge as another component of additives and 15 kg of a 20% solution of another component of additives, a copolymer of ethyl acrylate and octadecyl acrylate, in toluene is mixed in a vessel reactor with stirring for 90 min at 65 ° C and the mixture is transferred to a storage tank.

12.3. Obtaining and testing the composition of mineral oil.

The additive solution according to item 12.2 is introduced at a rate of 0.52 kg / min into the product stream of diesel fuel without additives, a batch of 16080601, flowing at a speed of 800 kg / min, and the mixture is loaded into a storage tank.

Testing the composition of mineral oil for resistance to low temperatures gives

CPPP value is -18 ° C.

If the composition of mineral oil, which contains only unmodified copolymer wax a) as an additive, is obtained under the same conditions, the CPPP value is -18 ° C.

Claims (13)

CLAIM 1. The composition of mineral oil containing, as a main component, mineral oil and trace amounts of a mixture of additives, where the mixture of additives contains the following components: a) copolymers of ethylene and vinyl ester with a weight average molecular weight of from 3,000 to 50,000 and an ethylene content of 50-90 wt.% and b) mixed glycerol esters, where 50-80 mol% of the hydroxyl groups are esterified with unsaturated C ₁₂ -C ₄₀ monocarboxylic acids and 20-50 mol% of the hydroxyl groups are esterified with partially imidated and / or partially esterified maleic anhydride copolymers, where the partial imaging is carried out with ammonia, With ₁ -C ₂₄ monoalkylamines, aromatic C ₆ -C ₁₈ monoamines, C ₂ -C ₁₈ monoalcohols, monoaminated poly (C ₂ -C ₄ alkylene) oxides with a molecular weight of 400 to 3,000 and / or mono-esterified poly (C ₂ -C ₄ alkylene) oxides with a molecular weight of from 100 to 10,000, the molar ratio of the anhydride groups of the copolymer to ammonia, the amino groups of C1-C24 monoalkylamines, aromatic C ₆ -C ₁₈ monoamines, C ₂ -C ₁₈ monoalcohols or monoaminated poly (C ₂ -C ₄ alkylene ) of oxides is, respectively, from 1: 1 to 20: 1, alcohols with which malein Vågå anhydride partially esterified represent C | -C | ₈ alcohols and comonomer components in partially imidated and / or partially esterified maleic anhydride copolymers are C ₂ -C ₂₀ olefins, C ₈ -C ₂₀ vinyl aromatics, C ₄ -C ₂₁ acrylic esters, C ₅ -C ₂₂ methacrylic esters esters, C ₅ -C ₁₄ vinylsilanes, C ₆ -C ₁₅ acrylatesilanes, acrylic acids, methacrylic acids, acrylonitrile, vinyl pyridine, vinyloxazoline, isopropenyloxazoline, vinylpyrrolidone, aminoC ₁ -C ₈ alkyl (meth) acrylate, complex C ₃ -C ₂₀ vinyl ether, simple C ₃ -C ₂₀ vinyl ether and / or hydro CuCl-C8 alkyl (meth) acrylate; and / or c) partially and / or fully imidated copolymers of maleic anhydride and α-methylstyrene with a number average molecular weight of 1500 to 15000 and at least one end group based on dimeric α-methylstyrene, where partial and / or full imidation is carried out with C ₁ -C ammonia ₂₄ monoalkylamines, aromatic C ₆ -C ₁₈ monoamines, C2-C18 monoamino alcohols, monoaminated with poly (C2-C4 alkylene) oxides and / or mono-esterified with poly (C2-C4 alkylene) oxides, while the molar ratio of the anhydride groups of the copolymer to ammonia, the amino groups C ₁ -C _{24 of} monoalkylamines, aromatic C ₆ -C ₁₈ monoamines, C2-C18 monoamino alcohols and monoaminated poly (C2-C4alkylene) oxides are respectively from 1: 1 to 20: 1; and / or g) wax-like compositions based on natural starting materials of the type Y1) wax-like oligomeric esters based on glyceryl monostearate and dimeric acid corresponding to at least 90 wt.% Structure where η is 1-20; the sum (a + b + c + d) is 30; ζ is 12-20; Υ represents H or - CO - (CH _g ) <g CH - (CH _g ) b - CH _E I H ₃ C ~ (CH _g ) _s - CH - (CH _g ) _a - CO - OH X represents H or —CH 2 —CH (OH) —CH ₂ —O — CO— (CH ₂ to —CH ₃ and / or 2) wax esters with a petrolatum consistency based on at least two different linear and / or branched C ₁₄ -C ₃₆ alcohols and dimeric acids corresponding to at least 80 wt.% Structure Н _Э С- (СН ₂ ), - О - СО - (СНг) * - СН - СН - (СНг) t - СНз I I H ₃ C- (CH _g ) _p (CH ₂ ) _P —CO — O— (CH ₂ ) ₃ —CH ₃ where ί is 13-35; - 19 011632 8 is 13-35; the sum (k + t + η + ρ) is 30-34 and (CH ₂ ) ₁ or (CH ₂ ) ₈ are linear or branched, and the content of the additive mixture in mineral oil is 0.005-1 wt.% and the mass ratio of the components of the additives a / b, a / c or a / 6 is in the range from 10:90 to 90:10, respectively. 2. The composition according to claim 1, where the copolymers of ethylene and vinyl ester are copolymers of ethylene and vinyl acetate with a vinyl acetate content of 12-50 wt.%. 3. The composition according to claim 1 or 2, where the copolymers of ethylene and vinyl ester are a mixture of 10-90 wt.% Unmodified copolymers of ethylene and vinyl ester and 90-10 wt.% Copolymers of ethylene and vinyl ester modified with such polar groups like terminal aldehyde groups, terminal carboxyalkyl mercapto groups, terminal alkoxy groups or hydroxyl groups and / or carboxyl groups by partial oxidation, saponification or acetylation, as well as grafting of polar monomers with ethylene saturation per copolymer. 4. The composition according to claim 3, where the modified copolymers of ethylene and vinyl ester are oxidized copolymers of ethylene and vinyl ester, partially saponified copolymers of ethylene and vinyl ester, hemiacetals of partially saponified ethylene and vinyl ester copolymers and / or ethylene and vinyl ester grafted with polar unsaturated monomers such as vinyl ester, (meth) acrylic ester and / or vinyl ether. 5. The composition according to one or more of claims 1 to ₄ , where C ₃₂ -C ₄₀ monocarboxylic acids contained as esterifying components in mixed glycerol esters of the additive mixture consist of 45-52 wt.% C22 monocarboxylic acids with respect to the total weight C ₁₂ -C ₄₀ monocarboxylic acids, and wherein the partially imidated maleic anhydride copolymers contained as esterification components are copolymers of maleic anhydride and α-methylstyrene, partially imidated C ₆ -C ₂₄ monoalkylamines, wherein the molar ootnoshenie anhydride groups and bound C ₆ -C ₂₄ monoalkylamine in the range from 8: 1 to 1.3: 1. 6. The composition according to one or more of claims 1 to 4, wherein the partially imidated copolymers of maleic anhydride and α-methyl styrene as a component of additives c) are copolymers of maleic anhydride and α-methyl styrene partially imidated with C ₆ -C ₂₄ monoalkylamines, where the molar the ratio of anhydride groups to the bound C6-C24 monoalkylamine in the copolymer is in the range from 8: 1 to 1.3: 1. 7. The composition according to one or more of claims 1 to 4, where the vaseline-like wax esters as a component of additives 62) are esters obtained by the esterification of Herbert alcohols of the type 2-hexyldecan-1-ol or 2-octyldecane-1-ol and dimeric acids obtained by the breakdown of vegetable oils with a high content of oleic acid and subsequent catalytic dimerization. 8. The composition according to claim 7, where the esters are obtained by catalytic esterification in the presence of acid catalysts at temperatures from 100 to 160 ° C in a reactor with stirring using vacuum from -0.5 to -1.5 bar. 9. The composition according to one or more of claims 1 to 8, where the mineral oil is a crude oil or oil from a middle distillate with a sulfur content of up to 0.05 wt.%, Preferably heating oil, gas oil or diesel fuel. 10. The composition according to one or more of claims 1 to 8, containing a total of 0 to 200 wt.% In relation to the components of the additives (a + b), (a + c), (a + 6), (a + b + c), (a + b + c + 6) or (a + c + 6) other additive components, such as mixtures of fatty acids, polyamines, ethers, amino alcohols, amine salts, amides or imides of polyvalent carboxylic acids; modified copolymers of ethylenically unsaturated C ₄ -C ₂₀ dicarboxylic anhydrides, unmodified copolymers of ethylene and vinyl ester, C7-C30 alcohols, polyalkylene glycols, esters or ethers of polyoxyalkylene compounds, C ₃₂ -C ₄₀ monocarboxylic acids with C ₂ -C ₆ hydroxy preferably unsaturated C ₃₆ -C ₂₄ monocarboxylic acids with a C ₃ -C ₄ oxyalkyl bridge containing 45-52 wt.% C ₂₂ monocarboxylic acids with respect to the total weight of C ₁₆ -C ₂₄ monocarboxylic acids, ethylene and C ₃ -C ₂₀ copolymers -but -olefins, hydrated polymers of unsaturated monomers such as a hydrated copolymer of diene with a number average molecular weight of up to 30000, copolymers of alkyl phenol and aldehyde, aromatic compounds with C ₈ -C ₁₀₀ alkyl substituents, obtained by Friedel-Crafts condensation of halogenated hydrocarbons with aromatic hydrocarbons, , corrosion inhibitors, demulsifiers, metal deactivators, cetane number modifiers, antifoams and / or cosolvents. - 20 011632 11. The method of obtaining a composition according to claim 1, containing mineral oil as the main component and trace amounts of the additive mixture, in which the additive mixture contains the following components: a) copolymers of ethylene and vinyl ester with a weight average molecular weight of from 3,000 to 50,000 and an ethylene content of 50-90 wt.%; and b) mixed glycerol esters, where 50-80 mol% of hydroxyl groups are esterified with unsaturated C ₁₂ -C ₄₀ monocarboxylic acids and 20-50 mol% of hydroxyl groups are esterified with partially imidated and / or partially esterified maleic anhydride copolymers; and / or c) partially and / or fully imidated copolymers of maleic anhydride and α-methylstyrene with a number average molecular weight of from 1500 to 15000 and at least one end group based on dimeric α-methylstyrene; and / or 6) wax-like compositions based on natural starting materials such as 61) wax-like oligomeric esters based on glyceryl monostearate and dimeric acid, corresponding to at least 90 wt.% Structure I sleep! - o - co - (sleep, - CH - (CHU - CH, I (SNL-SNNSR, - where η is 1-20; the sum (a + b + c + 6) is 30; ζ is 12-20; Υ represents H or - CO - (CH _g ) <g CH - (CH _g ) _b - CH, I НЗС - (СНг) s - СН - (СН ₂ ) _а - СО - ОН X represents H or —CH ₂ —CH (OH) —CH ₂ —O — CO— (CH ₂ ) ^ CH ₃ , and / or 62) wax esters with a vaseline-like consistency based on at least two different linear and / or branched C ₁₄ -C ₃₆ alcohols and dimeric acids corresponding to at least 90 wt.% Structure H _E C - (CH ₂ ), - O - CO - (CH _g ) k - CH - CH - (CH _g ) _ha - CH I I НзС - (СН ₂ ) ((СН _g ) p - СО - О - (СН ₂ )> - СНз where ί is 13-35; 8 is 13-35; the sum (k + t + η + ρ) is 30-34 and (CH ₂ ) ₁ or (CH ₂ ) ₈ are linear or branched, the content of the additive mixture in mineral oil is 0.005-1 wt.% and the weight ratio of the additive components a / B, a / c or a / 6 is in the range from 10:90 to 90:10, respectively, while the composition is obtained by the method of preliminary homogenization, in which solutions containing 1-60 wt.% Additive components in the middle distillates of mineral oil, obtained at 20-90 ° C in the first stage and solutions containing additive components are homogenized with m non-fuel oil as the main component in the second stage, with other components of additives in a total amount of from 0 to 200 wt.% in relation to the components of the additives (a + b), (a + c), (a + 6), (a + B + c), (a + b + c + 6) or (a + c + 6) are introduced into mineral oil at the first and / or second stage. 12. The use of the composition according to one or more of claims 1 to 10 as a fluid transported at low temperatures. 13. The use of the composition according to one or more of claims 1 to 10 as a mineral oil with high lubricity and fluidity.