WO2005040316A2 - Melange additif utilise comme composant de compositions a base d'huile minerale - Google Patents

Melange additif utilise comme composant de compositions a base d'huile minerale Download PDF

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Publication number
WO2005040316A2
WO2005040316A2 PCT/DE2004/002316 DE2004002316W WO2005040316A2 WO 2005040316 A2 WO2005040316 A2 WO 2005040316A2 DE 2004002316 W DE2004002316 W DE 2004002316W WO 2005040316 A2 WO2005040316 A2 WO 2005040316A2
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Prior art keywords
mass
additive
copolymers
mineral oil
ethylene
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PCT/DE2004/002316
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German (de)
English (en)
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WO2005040316A3 (fr
Inventor
Hiltrud TÄUBERT
Wolfgang Haubold
Torsten Meyer
Erhard Brauer
Irene Klimek
Dietrich Von Der Wense
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Leuna Polymer GmbH
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Leuna Polymer GmbH
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Priority claimed from DE2003149861 external-priority patent/DE10349861B4/de
Priority claimed from DE2003149860 external-priority patent/DE10349860B4/de
Priority claimed from DE2003149859 external-priority patent/DE10349859B4/de
Priority to CA2542812A priority Critical patent/CA2542812C/fr
Priority to DE502004008662T priority patent/DE502004008662D1/de
Priority to KR1020067007786A priority patent/KR100749209B1/ko
Application filed by Leuna Polymer GmbH filed Critical Leuna Polymer GmbH
Priority to EA200600809A priority patent/EA011632B1/ru
Priority to US10/576,897 priority patent/US20070130821A1/en
Priority to JP2006535938A priority patent/JP5033422B2/ja
Priority to EP04817260A priority patent/EP1675932B1/fr
Publication of WO2005040316A2 publication Critical patent/WO2005040316A2/fr
Publication of WO2005040316A3 publication Critical patent/WO2005040316A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/1915—Esters ester radical containing compounds; ester ethers; carbonic acid esters complex esters (at least 3 ester bonds)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1983—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyesters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/1817—Compounds of uncertain formula; reaction products where mixtures of compounds are obtained
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2300/00—Mixture of two or more additives covered by the same group of C10L1/00 - C10L1/308
    • C10L2300/40—Mixture of four or more components

Definitions

  • the invention relates to an additive mixture as a constituent of compositions of mineral oil as the main component and small proportions of an additive mixture, and to a method for producing compositions from mineral oil which contain the additive mixture.
  • compositions of mineral oils as the main component and small proportions of additive mixtures of ethylene-vinyl acetate copolymers, hydrocarbon polymers, esterified maleic anhydride-olefin copolymers, polar nitrogen compounds such as amine salts of polyvalent carboxylic acids and esterified polyoxyalkylenes are known (WO 94/10 267 Al, WO 95 / 33 012 AI, EP 0 921 183 AI, WO 93/14 178 AI, EP 0 889 323 AI).
  • the disadvantages are the inadequate flow behavior and the storage stability of these compositions at low temperatures and the limited lubricity of the recipes if the mineral oil component has a sulfur content of less than 0.005% by mass.
  • the object of the invention is an additive mixture as a constituent of compositions of mineral oils as the main component and small proportions of an additive mixture which have improved flow behavior and improved storage stability at low temperatures and improved lubricity.
  • the improved flow behavior is said to save energy can be achieved with the pump units through which these formulations are transported.
  • the development of the additive mixtures should take place from the point of view of using mineral oils with a very low sulfur content in order to achieve fuels with improved environmental compatibility with regard to pollutant emissions.
  • the object of the invention was achieved by an additive mixture as a constituent of compositions composed of mineral oil as the main component and small proportions of an additive mixture, the additive mixture according to the invention comprising the additive components a) ethylene-vinyl ester copolymers with weight-average weights of 3000 to 50,000 and an ethylene content of 50 to 90% by mass and b) mixed esters of glycerol in which 50 to 80 mol% of the hydroxyl groups with unsaturated Ci 2 -C 4 o-monocarboxylic acids and 20 to 50 mol% of the hydroxyl groups with partially imidized and / or partially esterified maleic anhydride copolymers are esterified, and / or c) partially and / or completely imidized copolymers of maleic anhydride and ⁇ -methylstyrene with number average molecular weights from 1500 to 15000 and at least one end group based on dimeric ⁇ -methylstyrene, and / or d) wax compositions based
  • Y H or - CO - (CH 2 ) d - CH - (CH 2 ) b - CH 3 IH 3 C - (CH 2 ) C - CH - (CH 2 ) a - CO - OH
  • X H or -CH 2 -CH (OH) -CH 2 -0-CO- (CH 2 ) Z -CH 3 , and / or d2) wax esters with a vaseline-like consistency based on at least two different straight-chain and / or branched C; -C 36 alcohols and dimer acids, in which the reaction product contains at least 80% by mass of the structure H 3 C - (CH 2 ) i - O - CO - (CH 2 ) k - CH - CH - (CH 2 ) m - CH 3
  • vinyl ester components which can be contained in the ethylene-vinyl ester copolymers as additive component a) are vinyl acetate, vinyl propionate, 2-ethylhexyl vinyl ester, vinyl laurate, 2-hydroxyethyl vinyl ester and 4-hydroxybutyl vinyl ester.
  • the ethylene-vinyl ester copolymers can contain, as further unsaturated ester components, 1 to 30% by mass, based on the vinyl ester, of (meth) acrylic acid esters such as methyl methacrylate, methyl acrylate, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, or ethyl methacrylate and / or contain vinyl ethers such as octyl vinyl ether or hexanediol monovinyl ether.
  • (meth) acrylic acid esters such as methyl methacrylate, methyl acrylate, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, or ethyl methacrylate
  • vinyl ethers such as octyl vinyl ether or hexanediol monovinyl ether.
  • the ethylene-vinyl ester copolymers are preferred as additive component a) in the additive mixture of ethylene-vinyl acetate copolymers with a vinyl acetate content of 12 to 50% by mass.
  • ethylene-vinyl ester copolymers contained in the additive mixture as additive component a) are mixtures of 10 to 90% by weight of unmodified ethylene-vinyl ester copolymers and 90 to 10% by weight % are ethylene-vinyl ester copolymers modified by polar groups.
  • the modification of the ethylene-vinyl ester copolymers by polar groups consists in the incorporation of special end groups such as aldehyde end groups, preferably end groups made of acetaldehyde, propionaldehyde, butyraldehyde or isobutyraldehyde, carboxyalkylmercapto end groups, preferably end groups made of mercaptoacetic acid or mercaptopropionic acid, or alkoxy end groups in the Copoly er, in the incorporation of hydroxyl and / or carboxy groups in the copolymer by partial oxidation, saponification or acetalization and by grafting polar, ethylenically unsaturated monomers onto the copolymer.
  • special end groups such as aldehyde end groups, preferably end groups made of acetaldehyde, propionaldehyde, butyraldehyde or isobutyraldehyde, carboxyalkylmercapto end groups,
  • the modified ethylene-vinyl ester copolymers are preferably oxidized ethylene-vinyl ester copolymers, partially saponified ethylene-vinyl ester copolymers, semi-acetals of partially saponified ethylene-vinyl ester copolymers and / or by polar unsaturated monomers of the vinyl ester type, (meth) acrylic ester and / / or vinyl ether-grafted ethylene-vinyl ester copolymers.
  • the oxidized ethylene-vinyl ester copolymers are preferably oxidized ethylene-vinyl acetate copolymers with number average molecular weights from 800 to 5000, acid numbers from 2 to 40 mg KOH / g and OH numbers from 20 to 150 mg KOH / g.
  • the partially saponified ethylene-vinyl ester copolymers are preferably partially saponified ethylene-vinyl acetate copolymers with number average molecular weights of 800 to 5000, in which 5 to 30 mol% of the vinyl acetate units are saponified.
  • modified ethylene-vinyl ester copolymers have hemiacetals of ethylene-vinyl ester-vinyl alcohol copolymers with butyral- are debyd.
  • hemiacetals of ethylene-vinyl ester-vinyl alcohol copolymers with butyraldehyde are hemiacetals of ethylene-vinyl acetate-vinyl alcohol copolymers which, according to DD 295 507 A7, have been reacted with butyraldehyde in a heterogeneous phase.
  • the grafted ethylene-vinyl ester copolymers can be prepared by reaction with the unsaturated monomers in an extruder (DD 282 462 B5) or in a stirred reactor (DD 293 125 B5) in the presence of thermally decomposing radical formers. It is also possible to carry out the modification in the production of the copolymer by the high-pressure process by metering the monomers into the polymer melt in the low-pressure separator or into the discharge extruder.
  • the grafted ethylene-vinyl ester copolymers as additive component a) are grafted ethylene-vinyl acetate copolymers with vinyl acetate with molar mass numbers of 800 to 5000 and a total vinyl acetate content of 20 to 60 mass%, the vinyl acetate content of the copolymer backbone chain 10 to 40 mass % and the proportion of the grafted vinyl acetate side chains is 10 to 20% by mass.
  • the ethylene-vinyl ester copolymers in the additive compositions can contain up to 35% by mass of poly-C 6 -C 3 6-alkyl (meth) acrylates.
  • maleic anhydride copolymers which can be partially imidized or partially esterified as an acid component in the mixed esters of glycerol as additive component b) of the additive mixture are copolymers
  • Maleic anhydride and the comonomer components C 2 -C 2 o-olefins, C 8 -C 2 o-vinyl aromatics, C 4 -C 2 ⁇ -acrylic acid esters, C 5 - C 2 -methacrylic acid esters, C 5 -C ⁇ 4 -vinylsilanes, C 5 - C ⁇ 5 - acrylate silanes, acrylic acid, methacrylic acid, acrylonitrile, vinyl pyridine, vinyl oxazoline, isopropenyloxazoline, vinyl pyrrolidone, amino-C 8 -C 8 alkyl (meth) acrylates, C 3 -C 2 o- vinyl esters, C 3 -C 2 o -Vinyl ether and
  • the maleic anhydride copolymers preferably have a molar ratio of maleic anhydride / comonomer of 1: 1 to 1: 9 and molar mass weight average of 5000 to 500000.
  • the partial imidization can be carried out with ammonia, C 1 -C 24 monoalkylamines, C 6 -C 18 aromatic monoamines, C 2 -C 8 -monoa monoalcohols, monoaminated poly (CC 4 -alkylene) oxides with a molecular weight of 400 to 3000, and / or mono-retracted poly (C 2 -C 4 -alkylene) oxides with a molecular weight of 100 to 10,000, the molar ratio of anhydride groups copolymer / ammonia, amino groups C 1 -C 24 - monoalkyla ine, C 6 -C ⁇ 8 aromatic monoamines, C 2 -C 18 - mono-ino alcohols or mono-inated poly (C 2 -C 4 -
  • Suitable amines with which the maleic anhydride copolymers are partially imidized are C 2 -C 24 -monoalkylamines such as Oleyla in, dodecylamine, hexadecylamine, octadecylamine or eicosylamine, monosubstituted diamines of the N-dodecyl-1 type , 3-diaminopropane, N-octadecyl-1, 3-diaminopropane or N-octadecylpropylenetri in or amino alcohols such as aminodecan-10-ol or A ino-hexadecan-16-ol.
  • C 2 -C 24 -monoalkylamines such as Oleyla in, dodecylamine, hexadecylamine, octadecylamine or eicosylamine, monosubstituted diamines of the N-dodec
  • suitable alcohols with which the maleic anhydride copolymers as the acid component in the mixed esters of glycerol as additive component b) of the additive mixture are partially esterified are —CC 8 alcohols such as methanol, ethanol, ethylhexanol or stearyl alcohol.
  • Examples of the unsaturated C 12 -C 4 o-monocarboxylic acids contained in the mixed esters of the glycerol of the additive mixture as esterification components are oleic acid, elaidic acid, ricinoleic acid, eleostearic acid, linoleic acid, linolenic acid and erucic acid or dimer acids based on oleic acid or linolenic acid.
  • Examples of suitable processes for the preparation of the mixed esters of glycerol in which 50 to 80 mol% of the hydroxyl groups are esterified with unsaturated C 2 -C 40 monocarboxylic acids and 20 to 50 mol% of the hydroxyl groups are esterified with partially imidized and / or partially esterified maleic anhydride copolymers are the partial reaction of glycerol with unsaturated C 2 -C 4 o-monocarboxylic acids and subsequently with partially imidized and / or partially esterified maleic anhydride copolymers or the partial reaction of glycerol with partially imidized and / or partially esterified maleic anhydride copolymers and subsequently with unsaturated C 1 -C 40 monocarboxylic acids.
  • the reaction can be carried out in the melt, preferably in continuous kneaders at temperatures from 50 to 135 ° C. under vacuum degassing, or as a solution process, preferably in aromatic solvents at 85
  • the mixed esters of glycerol in the additive mixture preferably contain those contained as the esterification component Ci 2 -C 40 monocarboxylic acids from 45 to 52 mass% C 22 "Mo ocarboxylic acids, based on the total mass of the C 12 -C 4 o monocarboxylic acid.
  • the partially imidized maleic anhydride copolymers contained as esterification components are preferably maleic anhydride- ⁇ -methylstyrene copolymers partially imidized with C 6 -C 24 -monoalkylamines, in which the molar ratio Anhydride groups in the copolymer / bonded C 6 -C 24 monoalkylamine in the copolymer is 8: 1 to 2: 1.
  • Examples of partially imidized copolymers of maleic anhydride and ⁇ -methylstyrene as additive component c) are copolymers with an approximately equimolar ratio of the two monomers, in which the partial and / or complete imidization with ammonia, C 1 -C 24 -monoalkylamines, Ce -Cie aromatic monoamines, C 2 -C 18 monoamino alcohols, monoaminated poly (C 2 -C 4 alkylene) oxides, and / or monoetherified poly (C 2 -C 4 alkylene) oxides, where the molar ratio of anhydride groups copolymer / ammonia, A ino groups -C ⁇ C 24 monoalkylamines, C 6 -C 8 aromatic monoamines, C 2 -C 8 monoamino alcohols or monoaminated poly (C 2 -C 4 alkylene) oxide is 1: 1 to 20: 1.
  • the partially imidized copolymers of maleic anhydride and ⁇ -methylstyrene as additive component c) are preferably maleic anhydride- ⁇ -methylstyrene copolymers partially imidized with C 6 -C 24 ⁇ monoalkylamines, in which the molar ratio of anhydride groups in the copolymer / bound nes C 6 -C 24 monoalkylamine in the copolymer is 8: 1 to 1.3: 1.
  • C 12 -C 24 monoalkylamines with which the partially imidized maleic anhydride- ⁇ -methylstyrene copolymers contained in the additive mixture can be identified are dodecylamine, tetradecyla in, hexadecylamine, octadecyla in, Oleyla in or eicosyla in.
  • the waxy oligomeric esters based on glycerol monostearate and dimer acid as additive component dl) are the oligomeric esters described in EP 0 934 921 A1.
  • the component glycerol monostearate can be prepared by cleaving rapeseed oil using enzymes, isolating the glycerol monooleate formed and subsequent hydrogenation.
  • a suitable production process for the dimer acid component is the splitting of vegetable oils and the subsequent dimerization of the unsaturated fatty acids formed.
  • the oligomeric esters are prepared by solvent-free oligocondensation with acid catalysis.
  • Preferred additive components dl) are waxy oligomeric esters which have a degree of oligomerization of 2 to 8.
  • the wax esters with a vaseline-like consistency d2) are the wax esters described in EP 0 970 988 A1.
  • Preferred are the wax esters contained in the additive mixture with a vaseline-like consistency d2) wax esters based on Guerbet alcohols of the type 2-hexyldecan-l-ol, 2-octyldecan-l-ol or 2-octyldecan-l-ol and dimer acids, which are obtained by cleaving Vegetable oils with high oleic acid part and subsequent catalytic dimerization can be obtained.
  • the wax esters can be prepared from Guerbet alcohols and dimer acid by catalytic esterification in the presence of acidic catalysts at temperatures from 100 to 160 ° C in stirred reactors with a vacuum of - 0.5 to -1.5 bar.
  • mineral oils which form the main component in the mineral oil compositions are crude oils and petroleum distillates with a boiling range of 100 to 500 ° C such as lubricating oils, kerosene, diesel, heating oil, heavy heating oils, petroleum, tractor fuel and cracked gasoline.
  • the mineral oils can also contain up to 30% by mass of synthetic hydrocarbons from the Fischer-Tropsch synthesis, up to 20% by weight of modified vegetable oils based on sunflower oil, soybean oil, rapeseed oil, or oils of animal origin, biodiesel and / or up to 10% by mass of alcohols such as methanol or E. - contain thano1.
  • the mineral oils are preferably crude oils or fuel oils from a middle distillate with a sulfur content below 0.05% by mass, in particular heating oils, gas oils or diesel oils.
  • compositions of mineral oil can contain a total of up to 200% by mass, based on the additive components a + b, a + c, a + d, a + b + c, a + b + c + d or a + c + d, further additive components from Type fatty acid mixtures, polar nitrogen compounds, preferably polyamines, ether amines, amino alcohols, amine salts, amides or imides of polyvalent carboxylic acids; modified copolymers of ethylenically unsaturated C 4 -C 2 o-dicarboxylic acid anhydrides, unmodified ethylene-vinyl ester copolymers, C 7 -C 3 o-alcohols, polyalkylene glycols, esters or ethers of polyoxyalkylene Compounds, c 2 -C 6 -oxyalkyl-bridged C 2 -C 4 o-monocarboxylic acids, preferably C 3 -C 4
  • fatty acid mixtures contained in the compositions from mineral oil as further additive components are mixtures of saturated and / or unsaturated C 6 -C 40 carboxylic acids such as lauric acid, palmitic acid, oleic acid, linolenic acid, di-fatty acids and alkenyl succinic acid.
  • Examples of the polar nitrogen compounds of the polyamine type contained in the compositions of mineral oil as further additive components are N-hexadecyl-1,3-diaminopropane, N-octadecyldipropylenetriamine, N-dodecyl-1,3-diaminopropane, N, N'-didodecyl -l, 3-diaminopropane and N, N '-dioctadecyl-dipropylenetriamine.
  • Examples of the polar nitrogen compounds of the etherene type contained in the compositions from mineral oil as further additive components are 3-methoxypropylamine, 3-N-octyloxypropyl-1, 3-diaminopropane and 3-N- (2,4,6- trimethyldecyloxypropyl) -1, 3-diaminopropane.
  • Amino alcohol type compounds are aminopentan- 5-ol, aminoundecan-11-ol and 2-amino-2-methylpropanol.
  • Examples of the amines on which polar amine salts, amides or imides of polyvalent carboxylic acids are based are C 8 -co-amines such as hydrogenated tallamine, tetradecylamine, eicosylamine, dioctadecylamine, methylbehenylamine, N-oleyl-1,3-diaminopropane, N-stearyl-l-methyl-1, 3-diaminopropane or N-oleyldipropylenentriamine.
  • C 8 -co-amines such as hydrogenated tallamine, tetradecylamine, eicosylamine, dioctadecylamine, methylbehenylamine, N-oleyl-1,3-diaminopropane, N-stearyl-l-methyl-1, 3-diaminopropane or N-oleyldipropylenentriamine.
  • polyvalent carboxylic acids on which polar amine salts or amides of polyvalent carboxylic acids are based are phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, ethylenediactetraacetic acid and cyclohexanedicarboxylic acid.
  • polar nitrogen compounds of the amine salt type contained in the compositions from mineral oil as further additive components are N-methyltriethanola monium distearyl ester chloride and N-methyltriethanolammonium distearyl ester methosulfate.
  • Examples of ethylenically unsaturated C 4 -C 2 o-dicarboxylic acid anhydrides which may be present as a monomer component in the modified copolymers of ethylenically unsaturated C 4 -C 2 0 -dicarboxylic acid anhydrides as a further additive component are allylsuccinic anhydride, bicycloheptenedicarboxylic acid anhydride, bicyclo acid anhydride, carbomethoxymaleic anhydride, citraconic anhydride, cyclohexene dicarboxylic acid anhydride, dodecyclic succinic anhydride, glutaconic acid anhydride, ita Conic anhydride, maleic anhydride, mesaconic anhydride, methylbicycloheptenedicarboxylic anhydride and / or methylcyclohexenedicarboxylic anhydride, maleic anhydride and / or itaconic anhydride are preferred.
  • Suitable comonomers for ethylenically unsaturated C 4 -C 2 o-dicarboxylic acid anhydrides which may be present as a monomer component in the modified copolymers of ethylenically unsaturated C 4 -C 2 o-dicarboxylic acid anhydrides as a further additive component are ethylenically unsaturated monomers of the type C 2 -C 2 o-olefins, C 8 - C 2 rj-vinyl aromatic compounds, C 4 -C 2 ⁇ -acrylate, C 5 -C 22 -meth- acrylate, C 5 -C ⁇ -Vinylsilane 4, C 6 -C ⁇ 5 -Acrylatsilane, acrylic acid, methacrylic acid, acrylonitrile, vinyl pyridine, vinyl oxazoline, isopropenyloxazoline, vinyl pyrrolidone, amino-C 8 -C 8 -alkyl- (
  • modified copolymers are copolymers of C 4 -C 2 or unsaturated acid anhydrides and ethylenically unsaturated monomers with a molar ratio of 1: 1 to 1: 9 and molar mass weight average of 5000 to 500000, which with ammonia, C 1 -C 24 - monoalkylamines, C 6 -C 8 -aromatic mono a ines, C 2 -C 8 - monoamino alcohols, monoamine poly (C 2 -C 4 alkylene) - oxides with a molecular weight of 400 to 3000, and / or mono etherten poly (C 2 -C 4 alkylene) oxides with a molecular weight of 100 to 10,000 vice-sets have been wherein the molar ratio of anhydride groups of copolymer / ammonia, amino groups, C 1 -C 24 - monoalkyl, C ö -Cig-aromatic monoamines, C 2 -C 18
  • Particularly suitable as partially or completely i-diseased copolymers of ethylenically unsaturated C4-C20-dicarboxylic acid anhydrides are with C 2 -C 24 -monoalkylamines such as oleylamine, dodecylamine, hexadecylamine, octadecylamine or eicosylamine, monosubstituted diamines of the type N-dodecyl-1 3-diaminopropane, N-octadecyl-1, 3-diaminopropane or N-octadecylpropylenetriamine or amino alcohols such as aminodecan-10-ol or aminohexadecan-16-ol imidized maleic anhydride copolymers.
  • C 2 -C 24 -monoalkylamines such as oleylamine, dodecylamine, hexadecylamine, oc
  • C 7 -C 30 alcohols which may be present as further additive components in the mineral oil compositions are dodecanol, stearyl alcohol and ceryl alcohol.
  • polyalkylene glycols which may be present in the mineral oil compositions as further additive components are polyethylene glycols, polypropylene glycols and ethylene oxide / propylene oxide copolymers with molecular weights of 500 to 5000.
  • esters of polyoxyalkylene compounds which may be contained as other additive components in the mineral oil compositions, are C 1 0-C 24 - Monoalkylester- lenglycoldioleat or dialkyl ethers of polyalkylene glycols such as Polyethylenglycolmonostearylester or polypropylene.
  • ethers of polyoxyalkylene compounds which may be present as further additive components in the mineral oil compositions are C 1 -C 4 - Monoalkyl ether or dialkyl ethers of polyalkylene glycols such as polyethylene glycol monomethyl ether or polypropylene glycol dibutyl ether.
  • the C 2 -C 6 -oxyalkyl-bridged C 12 -C 40 monocarboxylic acids which may be present as a further additive component in the mineral oil compositions, consist of a C 2 -C 6 polyalcohol component and a C 2 -C 4 o-monocarbon acid component.
  • polyalcohols which can be present as an alcohol component in the C 2 -C 5 -oxyalkyl-bridged C 2 -C 40 monocarboxylic acids as a further additive component are ethylene glycol, polyalkylene glycols, glycerol, 1,1,1-tris (hydroxyr ⁇ ethyl) propane, pentaerythritol and sorbitol.
  • Ci 2 _ C 4 o-monocarboxylic acids which may be present as a carboxylic acid component in the C 2 -C 6 -oxyalkyl-bridged C 12 -C 4 0 -monocarboxylic acids as a further additive component are lauric acid, palmitic acid, stearic acid, oleic acid, elaidic acid, ricinoleic acid , Eleostearic acid, linoleic acid, linolenic acid and erucic acid or dimer acids based on oleic acid or linolenic acid.
  • C 2 -CG-oxyalkylverb Wegte C 1 2-C 40 - monocarboxylic acids also Mischester of polyalcohols, in which the polyalcohols by mixtures of C 1 2-C 40 - are esterified monocarboxylic acids.
  • Specific examples of C 2 -C 6 ⁇ oxyalkyl-bridged Ci2-C 4 o-monocarboxylic acids are the monoester of ethylene glycol with dilinolenic acid, a C 36 dimeric acid, the diester of propylene glycol with oleic acid and the triester of pentaerythritol with stearic acid.
  • C 2 -C 6 ⁇ oxyalkyl-bridged C 12 -C 4 o monocarboxylic acids are esters of unsaturated C 16 -C 2 4 ⁇ monocarboxylic acids with C3-C polyalcohols, the proportion of C 22 monocarboxylic acids, based on the total mass, se of the C 15 -C 24 monocarboxylic acids, is 45 to 52 mass%.
  • Examples of unsaturated C 5 -C 24 monocarboxylic acids which may be contained in the preferred esters of unsaturated C16-C24 monocarboxylic acids with C 3 -C 4 polyalcohols are oleic acid, linoleic acid, linolenic acid and erucic acid.
  • hydrocarbon polymers which can be contained as other additive components in the mineral oil compositions are copolymers of ethylene and C 3 -C 2 oo; -01efinen such as ethylene-propylene copolymers or ethylene-dodecene copolymers or hydrogenated polymers of multi- unsaturated monomers of the type hydrogenated diene copolymers such as hydrogenated polybutadiene or hydrogenated polyisoprene with number average molecular weights up to 30,000.
  • alkylphenol-aldehyde copolymers which can be present as additional additive components in the mineral oil compositions are copolymers which can be prepared by reacting alkylated phenols such as phenol-propylene-oligomer adducts with paraformaldehyde.
  • aromatic compounds having C 8 -C ⁇ 0 o _ alkyl substituents which may be contained as other additive components in the mineral oil compositions are compounds represented by Friedel-Krafts- Condensation of halogenated hydrocarbons such as halogenated polyethylene wax with aromatic hydrocarbons such as benzene or naphthalene can be produced.
  • detergents which may be present as additional additive components in the mineral oil compositions are aliphatic sulfonic acids such as C 8 -C 3 o-alkanesulfonates or aromatic-aliphatic alkanesulfonates, in particular nonylbenzenesulfonic acid, dodecylbenzenesulfonic acid, didodecylbenzenesulfonic acid and nonylnaphthalenesulfonic acid.
  • aliphatic sulfonic acids such as C 8 -C 3 o-alkanesulfonates or aromatic-aliphatic alkanesulfonates
  • nonylbenzenesulfonic acid dodecylbenzenesulfonic acid
  • didodecylbenzenesulfonic acid didodecylbenzenesulfonic acid and nonylnaphthalenesulfonic acid.
  • demulsifiers which may be contained in the mineral oil compositions as further additive components are oxalkylated phenol-formaldehyde condensates, polyalkylene glycol-modified diglycidyl ethers, polyesteramines or alkoxylated fatty acids.
  • cetane improvers which can be contained in the mineral oil compositions as further additive components are organic nitric acid esters such as ethylhexyl nitrate, cyclohexyl nitrate or ethoxyethyl nitrate, or soluble organic peroxides, hydroperoxides or peresters.
  • Preferred defoamers which may be present as additional additive components in the mineral oil compositions, are polyalkylene oxide-siloxane block copolymers and carboxylated polyamines.
  • polyalkylene oxide-siloxane block copolymers are block copolymers which are a combination of trifunctional Containing siloxane blocks such as monomethylsiloxane groups, difunctional siloxane groups such as dimethylsiloxane groups and monofunctional siloxane groups such as trimethylsiloxane groups, a preferred length of the siloxane blocks is 5 to 20 monomer units.
  • the preferred length for the polyalkylene oxide blocks is 2 to 40 monomer units; polyoxyalkylene blocks composed of ethylene oxide and / or propylene oxide units are preferred.
  • carboxylated polyamines as defoamers are reaction products of C 8 -C 24 fatty acids and amines such as ethylenediamine, butylenediamine, diethylenetriamine and pentaethylenehexamine-1,2-diaminobutanol.
  • cosolvents which may be present as additional additive components in the mineral oil compositions are gasoline fractions, toluene, xylene, ethylbenzene, isononanol, ethylhexanol, dodecylphenol, epoxidized rapeseed oil and epoxidized soybean oil.
  • compositions of mineral oil as the main component and small proportions of an additive mixture are produced by a process in which, according to the invention, compositions of mineral oil which comprise the additive components
  • ethylene-vinyl ester copolymers with a molecular weight of 3000 to 50,000 and an ethylene content of 50 to 90% by mass
  • compositions of mineral oil as the main component and small proportions of an additive mixture are particularly suitable as flowable media to be transported at low temperatures and as a mineral oil fuel with high lubrication and fluidity.
  • Examples of the flowable media to be transported at low temperatures are the transport of raw Oil formulations from the crude oil production facility through pipelines for loading and storage as well as the transportation of diesel or heating oil formulations in pipelines.
  • Vinyl acetate content modified method according to ISO 8995, DIN 16778 part 2 2 g sample are weighed to the nearest 0.001 g and in a 300 ml Erlenmeyer flask with 70 ml distilled xylene and 2 boiling beads approx. Solved for 15 min while heating the reflux condenser. Then approx. 30 ml of ethanol are slowly added through the reflux condenser, the Erlenmeyer flask is removed from the hotplate, 30 ml of ethanol, 0.5 N KOH from the burette and 2 boiling pearls are added, and the sample is refluxed for 1 h.
  • V consumption in ml of 0.5 N ethanolic KOH for the sample
  • B consumption in ml of 0.5 N ethanolic KOH for the blank value
  • Lubricity test (corrected "wear scar dia eter” at 60 ° C) according to ISO 12156-1
  • a 500 ml sample is stored in a measuring cylinder for 16 h and then the 80% by volume of the sample above is sucked off and discarded. The remaining 20 vol% of the sample (100 ml) are homogenized at 40 ° C and the cloud point (CP) is determined according to DIN EN 23 015.
  • a 500 ml mineral oil sample is shaken 20 times vertically, temperature-controlled at 10 ° C. for 16 h, shaken 10 times vertically, and the entire sample is passed through a filter made of cellulose nitrate (diameter 50 mm, pore size 0.8 ⁇ m) on a suction cup with a vacuum of approx. 200 hPa is applied, filtered. The time (s) during which the sample runs through the filter is determined. The SEDAB filtration test is passed if the sample passes the filter within a period of ⁇ 120 s. example 1
  • IBP 10 20 30 40 50 60 70 80 90 FBP
  • Ethylene-vinyl acetate copolymer wax (manufacturer LEUNA Polymer GmbH, vinyl acetate content 28.3 mass%, molar mass weight average 3150 g / mol).
  • the mixed glycerin ester was prepared by the melt esterification process.
  • a maleic anhydride octadecene copoly er partially esterified with dodecyl alcohol is placed in the feed hopper of a Werner & Pfleiderer ZSK 30, L / D 48 twin screw extruder with side flow metering device for liquid media and two vacuum degassing zones and metering belt weigher (molar ratio 1: 2 , 2, acid number 40, molmas sen number average 2400) dosed at 3.8 kg / h and melted at 90 ° C.
  • glycerine dierucic acid ester is metered into the melt at 2.0 kg / h from a storage tank heated at 90 ° C., reacted in the first reaction zone (residence time 4.5 min) at 110 ° C., degassed in the second reaction zone at 130 ° C (residence time 3.5 min), degassed, conveyed at 85 ° C by means of a melt gear pump (type extrex SP, Maag pump Systems) into a self-cleaning melt filter and shaped into pastilles for shaping in a pastillation system with cooling belt.
  • a melt gear pump type extrex SP, Maag pump Systems
  • the resulting glycerol mixed ester has an acid number of 8.5 and a melting range of 52 to 59 ° C. ⁇ 1.2
  • the additive solution according to 1.2 is injected into a product stream of non-additized diesel batch 16080601 at 800 kg / min at 0.48 kg / min and transferred to a storage tank. Testing the cold resistance of the mineral oil formulation gives a CFPP value of -10 ° C. The lubricity test gives a wear scar diameter of 405 ⁇ m. The CP value of the short-term sediment test is + 7 ° C. The SED7AB filtration test is passed (500 ml in 84 s).
  • the CFPP value is -3 ° C and the "wear scar diameter" is 520 ⁇ m.
  • the CP value of the short-term sediment test is + 10 ° C
  • the SEDAB filtration test is considered failed (468 ml in> 120 s).
  • IBP 10 20 30 40 50 60 70 80 90 FBP
  • the mixed glycerin ester was produced by the melt esterification process.
  • glycerol diol ester is metered from a storage tank heated at 90 ° C into the melt, reacted in the first reaction zone (residence time 4.5 min) at 115 ° C, degassed, in the second reaction zone at 130 ° C (dwell time 3.5 min) converted, degassed, at 85 ° C by means of a melt gear pump (type extrex SP, Maag pump Systems) conveyed into a self-cleaning melt filter and shaped into pastilles for shaping in a pastillation system with cooling belt.
  • the resulting glycerol blend has an acid number of 4.5 and a melting range of 55 to 66 ° C.
  • Dodecyl acrylate-ethyl acrylate copolymer (2: 1 molar ratio, number average molecular weight 13500)
  • the additive solution according to 2.2 is injected into a product stream of non-additized Diesel Charge 030210 DGO at 800 kg / min at 0.12 kg / min and transferred to a storage tank.
  • the CFPP value of the short-term sediment test gives a CFPP value of -11 ° C.
  • the lubricity test results in a "wear scar dia eter" of 402 ⁇ m.
  • the CP value of the short-term sediment test is + 9 ° C.
  • the SEDAB filtration test is considered passed (500 ml in 96 s). If a mineral oil formulation containing only the unsaponified copolymer wax as an additive is produced under the same conditions, the CFPP value is -5 ° C and the "wear scar diameter ' " is 528 ⁇ m.
  • the CP value of the short-term sediment test is + 12 ° C.
  • the SEDAB filtration test is deemed failed (468 ml in> 120 s). ⁇
  • IBP 10 20 30 40 50 60 70 80 90 FBP
  • the mixed glycerin ester was produced by the melt esterification process.
  • an ester of glycerol and an acid mixture of erucic acid / oleic acid (molar ratio 1: 1, degree of esterification 82 mol%) is metered into the melt at 2.72 kg / h from a storage tank heated at 90 ° C. first reaction zone (residence time 4.5 min) at 120 ° C, degassed, in the second reaction zone at 130 ° C (residence time 3.5 min), degassed, at 95 ° C using a melt gear pump (type extrex SP, Maag pump Systems ) conveyed into a self-cleaning melt filter and shaped into pastilles for shaping in a pastillation system with cooling belt.
  • a melt gear pump type extrex SP, Maag pump Systems
  • the resulting glycerol mixed ester has an acid number of 3.5 and a melting range of 55 to 64 ° C.
  • the additive solution according to 3.2 is injected into a product stream of non-additized heating oil batch 030225 at 800 kg / min at 0.24 kg / min and transferred to a storage tank.
  • the CFPP value is -12 ° C.
  • IBP 10 20 30 40 50 60 70 80 90 FBP
  • the mixed glycerin ester was produced by the melt esterification process.
  • the resulting glycerol mixed ester has an acid number of 5.5 and a melting range of 53 to 63 ° C.
  • the additive solution according to 4.2 is injected into a product stream of non-additized heating oil batch 030225 at 800 kg / min at 0.28 kg / min and transferred to a storage tank.
  • the CFPP value is -1 ° C.
  • Ethylene-vinyl acetate copolymer wax manufactured by manufacturer, vinyl acetate content 32% by mass, mol weight weight average 2300 g / mol).
  • stirred reactor 500 1 81 1 ⁇ -methylstyrene, ⁇ -1 7 submitted methylstyrene dimer and 20 liters of acetone and the stirred reactor at 59 ° C heated.
  • a solution of 52 kg of maleic anhydride and 2.4 kg of azoisobutyronitrile in 150 l of acetone is metered uniformly into the stirred reactor within 6 hours and the reaction mixture is stirred at 70 to 73 ° C. for a further 6 hours.
  • the polymer solution which is still 54 to 56 ° C warm, is then fed continuously to a two-roll vacuum dryer and separated into a powdery copolymer with a residual volatile content of around 1.1% by mass and in acetone.
  • a stirred reactor 500 1 a above 160 ° C boiling 6 -C ⁇ Cs-Cg-Dieselaromatenfr submitted 8 fatty amine and hitzt to 130 ° C ER-. 135.5 kg of the copolymer are metered continuously into this solution within 4 hours.
  • the internal temperature in the stirred reactor rises to 180 to 185 ° C., and water is formed, which is distilled off azeotropically with an approximately equal amount of C 8 -C diesel aromatic fraction.
  • a 40% solution of the partially imidated copolymer having an acid number of 35 and a number average molecular weight was obtained of 12,800 'g / mol.
  • the additive solution according to 5.2 is injected into a product stream of non-additized diesel batch 16080601 at 800 kg / min at 0.48 kg / min and transferred to a storage tank.
  • the CFPP value is -3 ° C.
  • the CP value of the short-term sediment test is + 10 ° C.
  • the SEDAB filtration test is considered failed (468 ml in> 120 s).
  • An analytical sample of the copolymer has an acid number of 452 mg KOH per gram of copolymer.
  • NMR investigations show 1.1 ⁇ -methylstyrene dimer end groups / mol.
  • the approximately 70 ° C warm polymer solution is then metered continuously in a 500 1 stirred reactor which contains 280 1 2-ethylhexanol and was heated to a temperature of 150 ° C while distilling off 2-butanone-2.
  • Now 104 kg of a C 16 -C 8 fatty amine are metered in within 4 hours, the temperature being raised to 165 to 185 ° C. in order to distill off water together with a small amount of 2-ethylhexanol.
  • Diesel aromatic fraction 20 kg of trieste from pentaerythritol with oleic acid as a further additive component and 1 kg of the further additive component diethylene glycol monolaurol ester, stirred for 90 min at 65 ° C., and the mixture was transferred to a storage tank.
  • the additive solution according to 6.2 is injected into a product stream of non-additized Diesel Charge 030210 at 800 kg / min at 0.24 kg / min and transferred to a storage tank.
  • the approximately 90 ° C warm polymer solution is now continuously in a 500 1 stirred reactor containing 280 1 of a C 8 -C 9 - Dieselaro atenfr neglect and 122 kg of a C ⁇ 2 - C 14 - fatty amine mixture and heated to a temperature of 160 ° C. was metered in while distilling off 1,2-dichloroethane and the water of reaction of the imidization.
  • a 40% solution of the partially imidized copolymer c) is obtained in a C 8 -C 9 diesel aromatic fraction with an acid number of 25 and a molar weight average of 7000 g / mol.
  • the additive solution according to 7.2 is injected into a product stream of non-additized heating oil batch 030225 at 800 kg / min at 0.24 kg / min and transferred to a storage tank.
  • the CFPP value is -13 ° C.
  • the polymer solution which is still 54 to 56 ° C warm, is now continuously fed to a two-roll vacuum dryer into a powdery copolymer with a residual volatile content of around 1.1% and separated into acetone.
  • a C 8 -C 9 diesel aromatic fraction boiling above 160 ° C. in an amount of 382 kg and 135 kg of stearylamine is placed in a 500 1 stirred reactor and heated to 130 ° C. 135.5 kg of the copolymer are metered continuously into this solution within 4 hours.
  • the internal temperature in the stirred reactor rises to 180 to 185 ° C., and water is formed, which is distilled off azeotropically with an approximately equal amount of C 8 -Cg diesel aromatic fraction.
  • a 40% strength solution of the copolymer, which has been divided into parts with stearylamine, is obtained with an acid number of 51 and a weight-average molecular weight of 13750 g / mol. 8.1.4
  • Other additive components is obtained with an acid number of 51 and a weight-average molecular weight of 13750 g / mol. 8.1.4
  • the additive solution according to 8.2 is injected into a product stream of non-additized diesel batch 16080601 at 800 kg / min at 0.48 kg / min and transferred to a storage tank.
  • the CFPP value is -3 ° C.
  • Additive component d2) ⁇ Wax ester with a consistency similar to Vaseline, acid number 7.9 mg KOH / g, saponification number 113 mg KOH / g, kinematic viscosity 20.6 mm 2 / s, freezing point 34.5 ° C. Production of additive component d2)
  • a mixture of 25 kg of dimer acid (dimerization product from unsaturated Ci ⁇ fatty acids, average C number 36), 5 kg of stearyl alcohol and 7 kg of cetyl alcohol are melted at 120 ° C. in a 70 1 stirred reactor while introducing inert gas and with the addition of 50 g H 2 S0 4 reacted while subtracting the water of reaction until an acid number of 7.9 mg KOH / g is reached. After the melt has cooled, the catalyst is neutralized with 0.5 1 10% NaHC0 3 , the aqueous phase is separated off, and the wax ester is stripped off. 9.1.4 Other additive components
  • Ethyl acrylate-ethylhexyl acrylate copolymer (molar ratio 3: 2, molar mass number average 13500)
  • Triester of pentaerythritol with oleic acid Triester of pentaerythritol with oleic acid
  • the additive solution according to 10.2 is injected into a product stream of non-additized Diesel Charge 030210 at 800 kg / min at 0.30 kg / min and transferred to a storage tank.
  • the CFPP value is -5 ° C. and the “wear scar diameter” is 528 ⁇ m.
  • Oligomeric ester acid number 12 mg KOH / g, saponification number 175 mg KOH / g, kinematic viscosity (100 ° C) 65 mirfVs, solidification point 42 ° C, produced according to EP 0 934 921 AI * from glycerol monostearate and dimer acid (dimerization product from unsaturated C ⁇ 8 fatty acids, average C number 36) by solvent-free oligocondensation with acid catalysis. 11.1.4 Other additive components
  • the additive solution according to 11.2 is injected into a product stream of non-additized heating oil batch 030225 at 800 kg / min at 0.28 kg / min and transferred to a storage tank.
  • the CFPP value is -13 ° C.
  • Ethylene-vinyl acetate copolymer wax (manufacturer LEUNA Polymer GmbH, vinyl acetate content 32 mass%, molar mass weight average 2300 g / mol).
  • Oligomeric ester acid number 14 mg KOH / g, saponification number 185 mg KOH / g, kinematic viscosity (100 ° C) 76 mm 2 / s, solidification point 47 ° C, produced according to EP 0 934 921 AI from glycerol monostearate and dimer acid (dimerization product from unsaturated cis fatty acids, average C number 36) by solvent-free oligocondensation with acid " catalysis.
  • Testing the cold resistance of the mineral oil composition gives a CFPP value of -18 ° C.
  • the CFPP value is -3 ° C.

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Abstract

L'invention concerne un mélange additif utilisé comme composant de compositions qui contiennent, comme composant principal, de l'huile minérale, et une faible proportion d'un mélange additif. Ce mélange additif est constitué des composés suivants: a) des copolymères éthylène-ester de vinyle présentant des moyennes en poids des masses moléculaires de 3 000 à 50 000 et une teneur en éthylène de 50 à 90 % en masse; b) et des esters mixtes de glycérine, dans lesquels 50 à 80 % en mole des groupes hydroxy sont estérifiés avec des acides monocarboxyliques C12-C40 non saturés et 20 à 50 % en mole des groupes hydroxy sont estérifiés avec des copolymères d'anhydride d'acide maléïque partiellement imidisés et/ou estérifiés; c) et/ou des copolymères partiellement et/ou complètement imidisés constitués d'anhydride d'acide maléïque et de α-méthylstyrol présentant des moyennes en nombre des masses moléculaires de 1 500 à 15 000 et comprenant au moins un groupe terminal à base d'un α-méthylstyrol dimère; et/ou d) des compositions de cire à base de produit de départ naturel du type: d1) ester oligomère de type cire à base de monostéarate de glycérine et d'acide dimère et/ou d2) ester de cire présentant une consistance semblable à celle de la vaseline, à base d'au moins deux alcools C14-C36 différents à chaîne droite et/ou à chaîne ramifiée et d'acides dimères. La teneur de ce mélange additif en huile minérale est de 0,005 à 1 % en masse et le rapport en masse des composants a/b ou a/c ou a/d est de 10:90 à 90:10. Les compositions à base d'huile minérale selon l'invention constituent des substances coulantes à transporter à basse température et des carburants à base d'huile minérale à fort pouvoir lubrifiant et d'une grande fluidité.
PCT/DE2004/002316 2003-10-22 2004-10-15 Melange additif utilise comme composant de compositions a base d'huile minerale Ceased WO2005040316A2 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP04817260A EP1675932B1 (fr) 2003-10-22 2004-10-15 Compositions à base d'huile minérale et d'un mélange d'additifs
JP2006535938A JP5033422B2 (ja) 2003-10-22 2004-10-15 鉱物油組成物の成分としての添加剤混合物
US10/576,897 US20070130821A1 (en) 2003-10-22 2004-10-15 Additive mixture as component of mineral oil compositions
DE502004008662T DE502004008662D1 (de) 2003-10-22 2004-10-15 Zusammensetzungen aus Mineralöl und einer Additivmischung
KR1020067007786A KR100749209B1 (ko) 2003-10-22 2004-10-15 미네랄 오일 조성물의 성분으로서의 첨가제 혼합물
CA2542812A CA2542812C (fr) 2003-10-22 2004-10-15 Melange additif utilise comme composant de compositions a base d'huile minerale
EA200600809A EA011632B1 (ru) 2003-10-22 2004-10-15 Композиция минерального нефтетоплива, содержащая смесь присадок, способ ее получения и ее применение

Applications Claiming Priority (6)

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DE2003149861 DE10349861B4 (de) 2003-10-22 2003-10-22 Additivmischung als Bestandteil von Zusammensetzungen aus Mineralöl
DE2003149859 DE10349859B4 (de) 2003-10-22 2003-10-22 Additivmischung als Bestandteil von Mineralölzusammensetzungen
DE10349859.1 2003-10-22
DE10349861.3 2003-10-22
DE10349860.5 2003-10-22
DE2003149860 DE10349860B4 (de) 2003-10-22 2003-10-22 Additivmischungen als Bestandteil von Mineralölrezepturen

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WO2005040316A2 true WO2005040316A2 (fr) 2005-05-06
WO2005040316A3 WO2005040316A3 (fr) 2005-06-16

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KR (1) KR100749209B1 (fr)
AT (1) ATE417088T1 (fr)
CA (1) CA2542812C (fr)
DE (1) DE502004008662D1 (fr)
EA (1) EA011632B1 (fr)
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1958932A1 (fr) * 2007-02-16 2008-08-20 Cognis IP Management GmbH Ester et ses mélanges tout comme leur utilisation comme lubrifiant ou dans des huiles hydrauliques
US11999920B2 (en) 2020-09-14 2024-06-04 Ecolab Usa Inc. Cold flow additives for plastic-derived synthetic feedstock
US12031097B2 (en) 2021-10-14 2024-07-09 Ecolab Usa Inc. Antifouling agents for plastic-derived synthetic feedstocks
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US12503663B2 (en) 2020-09-14 2025-12-23 Ecolab Usa Inc. Cold flow additives for plastic-derived synthetic feedstock
US12304888B2 (en) 2021-03-10 2025-05-20 Ecolab Usa Inc. Stabilizer additives for plastic-derived synthetic feedstock
US12031097B2 (en) 2021-10-14 2024-07-09 Ecolab Usa Inc. Antifouling agents for plastic-derived synthetic feedstocks

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ES2317082T3 (es) 2009-04-16
EA011632B1 (ru) 2009-04-28
JP5033422B2 (ja) 2012-09-26
CA2542812C (fr) 2010-02-16
EA200600809A1 (ru) 2006-10-27
KR20060096439A (ko) 2006-09-11
ATE417088T1 (de) 2008-12-15
EP1675932A2 (fr) 2006-07-05
JP2007509212A (ja) 2007-04-12
DE502004008662D1 (de) 2009-01-22
KR100749209B1 (ko) 2007-08-13
WO2005040316A3 (fr) 2005-06-16
EP1675932B1 (fr) 2008-12-10
US20070130821A1 (en) 2007-06-14
CA2542812A1 (fr) 2005-05-06

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