EP1446464A2 - Additifs pour distillats de petrole pauvres en soufre, contenant un ester d'un polyol alkoxyle et une resine aldehyde alkyle phenol - Google Patents

Additifs pour distillats de petrole pauvres en soufre, contenant un ester d'un polyol alkoxyle et une resine aldehyde alkyle phenol

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Publication number
EP1446464A2
EP1446464A2 EP02802985A EP02802985A EP1446464A2 EP 1446464 A2 EP1446464 A2 EP 1446464A2 EP 02802985 A EP02802985 A EP 02802985A EP 02802985 A EP02802985 A EP 02802985A EP 1446464 A2 EP1446464 A2 EP 1446464A2
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Prior art keywords
carbon atoms
acid
additives
mol
alkylphenol
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EP02802985A
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German (de)
English (en)
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EP1446464B1 (fr
Inventor
Matthias Krull
Martina Hess
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clariant Produkte Deutschland GmbH
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Clariant GmbH
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Classifications

    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
    • C10L1/1981—Condensation polymers of aldehydes or ketones
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
    • C10L1/1985—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 polyethers, e.g. di- polygylcols and derivatives; ethers - esters
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/221—Organic compounds containing nitrogen 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/224—Amides; Imides carboxylic acid amides, imides
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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

Definitions

  • the invention relates to additives for low-sulfur mineral oil distillates with improved cold flowability and paraffin dispersion, comprising an ester of an alkoxylated polyol and an alkylphenol-aldehyde resin, additized fuel oils and the use of the additive.
  • Crude oils and middle distillates obtained by distilling crude oils such as gas oil, diesel oil or heating oil contain different amounts of n-paraffins depending on the origin of the crude oils, which crystallize out as platelet-shaped crystals when the temperature is lowered and partly agglomerate with the inclusion of oil.
  • This crystallization and agglomeration leads to a deterioration in the flow properties of the oils or distillates, as a result of which faults can occur during the extraction, transport, storage and / or use of the mineral oils and mineral oil distillates.
  • the crystallization phenomenon can lead to deposits on the pipe walls, especially in winter, in individual cases, for example when a pipeline is at a standstill, even causing it to become completely blocked.
  • Typical flow improvers for crude oils and middle distillates are copolymers and terpolymers of ethylene with carboxylic acid esters of vinyl alcohol.
  • Another task of flow improver additives is to disperse the wax crystals, i.e. the delay or prevention of sedimentation of the paraffin crystals and thus the formation of a paraffin-rich layer on the bottom of storage containers.
  • EP-A-0 061 895 discloses cold flow improvers for mineral oil distillates which Contain esters, ethers or mixtures thereof.
  • the esters / ethers contain two linear saturated do to C 3 o -alkyl groups and a polyoxyalkylene group with 200 to 5000 g / mol.
  • EP-0 973 848 and EP-0 973 850 disclose mixtures of esters of alkoxylated alcohols with more than 10 C atoms and fatty acids with 10 - 40 C atoms in combination with ethylene copolymers as flow improvers.
  • EP-A-0 935 645 discloses alkylphenol aldehyde resins as a lubricant-improving additive in low-sulfur middle distillates.
  • EP-A-0857776 and EP 1088045 disclose methods for improving the flowability of mineral oils and mineral oil distillates containing paraffin by adding ethylene copolymers and alkylphenol-aldehyde resins and optionally further nitrogen-containing paraffin dispersants.
  • the invention thus relates to additives for middle distillates with a maximum sulfur content of 0.05% by weight, containing at least one fatty acid ester of alkoxylated polyols with at least 3 OH groups (A) and at least one alkylphenol-aldehyde resin (C).
  • Another object of the invention are middle distillates with a maximum
  • sulfur content which contain an additive which contains at least one fatty acid ester of alkoxylated polyols with at least 3 OH groups (A) and at least one alkylphenol-aldehyde resin (C).
  • Another object of the invention is the use of an additive containing at least one fatty acid ester of alkoxylated polyols with at least 3 OH groups (A) and at least one alkylphenol-aldehyde resin (C) to improve the cold flow properties and paraffin dispersion of middle distillates with a maximum of 0.05% by weight .-% sulfur content.
  • the invention further relates to a process for improving the cold flow properties of middle distillates with a maximum sulfur content of 0.05% by weight by adding an additive containing at least one fatty acid ester of alkoxylated polyols with at least 3 OH groups (A) and at least one to the middle distillates Alkylphenol-aldehyde resin (C) added.
  • the esters (A) are derived from polyols with 3 or more OH groups, in particular from glycerol, trimethylolpropane, pentaerythritol and the oligomers containing 2 to 10 monomer units, such as polyglycerol, which are accessible by condensation.
  • the polyols are generally reacted with 1 to 100 mol of alkylene oxide, preferably 3 to 70, in particular 5 to 50 mol, of alkylene oxide per mol of polyol.
  • Preferred alkylene oxides are ethylene oxide, propylene oxide and butylene oxide.
  • the alkoxylation takes place according to known processes.
  • the fatty acids suitable for the esterification of the alkoxylated polyols preferably have 8 to 50, in particular 12 to 30, especially 16 to 26, carbon atoms.
  • Suitable fatty acids are, for example, lauric, tridecanoic, myristic, pentadecane, palmitic, margarine, stearic, isostearic, arachic and behenic acid, oleic and erucic acid, palmitoleic, myristoleic, ricinoleic acid, and from natural fats and Fatty acid mixtures obtained from oils.
  • Preferred fatty acid mixtures contain more than 50% fatty acids with at least 20 carbon atoms.
  • the fatty acids used for the esterification contain double bonds, in particular less than 10%; in particular, they are largely saturated.
  • Usually saturated means an iodine number of the fatty acid used of up to 5 g I per 100 g fatty acid.
  • the esterification can also be carried out on the basis of reactive derivatives of the fatty acids such as esters with lower alcohols (for example methyl or ethyl esters) or anhydrides.
  • polyvalent carboxylic acids can also be used to esterify the alkoxylated polyols.
  • suitable polyvalent carboxylic acids are dimer fatty acids, alkenyl succinic acids and aromatic polycarboxylic acids and their derivatives such as anhydrides and C to Cs esters.
  • Alkenyl succinic acid and its derivatives with alkyl radicals having 8 to 200, in particular 10 to 50, carbon atoms are preferred.
  • Examples are dodecenyl, octadecenyl and poly (isobutenyl) succinic anhydride.
  • the polyvalent carboxylic acids are preferably used in minor proportions of up to 30 mol%, preferably 1 to 20 mol%, in particular 2 to 10 mol%.
  • Esters and fatty acids are used for the esterification based on the content of hydroxyl groups on the one hand and carboxyl groups on the other hand in a ratio of 1.5: 1 to 1: 1.5, preferably 1.1: 1 to 1: 1.1, in particular equimolar.
  • the paraffin-dispersing effect is particularly pronounced when working with an excess of acid of up to 20 mol%, especially up to 10 mol%, in particular up to 5 mol%.
  • the esterification is carried out according to customary procedures.
  • the reaction of polyol alkoxylate with fatty acid if appropriate in the presence of catalysts such as, for example, para-toluenesulfonic acid, C 2 -C 5 -alkylbenzenesulfonic acids, methanesulfonic acid or acidic ion exchangers, has proven particularly useful.
  • the water of reaction can be separated off by direct condensation or preferably by azeotropic distillation in the presence of organic solvents, in particular aromatic solvents such as toluene, xylene or else higher-boiling mixtures such as ® Shellsol A, Shellsol B, Shellsol AB or Solvent Naphtha.
  • the esterification is preferably carried out completely, ie 1.0 to 1.5 mol of fatty acid per mol of hydroxyl groups are used for the esterification.
  • the acid number of the esters is generally below 15 mg KOH / g, preferably below 10 mg KOH / g, especially below 5 mg KOH / g.
  • alkylphenol-aldehyde resins (C) contained in the additive according to the invention are known in principle and are described, for example, in Römpp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, Volume 4, pp. 3351 ff.
  • the alkyl radicals of the o- or p-alkylphenol have 1-50, preferably 4-20, in particular 6-12 carbon atoms; it is preferably n-, iso- and tert-butyl, n- and iso-pentyl, n- and iso-hexyl, n- and iso-octyl, n- and iso-nonyl, n- and iso-decyl , n- and iso-dodecyl as well as tetrapropenyl, pentapropenyl and polyisobutenyl.
  • the alkylphenol-aldehyde resin can also contain up to 50 mol% of phenol units.
  • the same or different alkylphenols can be used for the alkylphenol-aldehyde resin.
  • the aliphatic aldehyde in the alkylphenol-aldehyde resin has 1-10, preferably 1-4 carbon atoms and can carry further functional groups such as aldehyde or carboxyl groups. It is preferably formaldehyde.
  • the molecular weight of the alkylphenol-aldehyde resins is 400-10,000, preferably 400-5000 g / mol. The prerequisite here is that the resins are oil-soluble.
  • alkylphenol-aldehyde resins are prepared in a known manner by basic catalysis, in which case condensation products of the resol type are formed, or by acidic catalysis, in which condensation products of the novolak type are formed.
  • the condensates obtained in both ways are for the inventive ones Suitable compositions.
  • the condensation in the presence of acidic catalysts is preferred.
  • a bifunctional o- or p-alkylphenol with 1 to 50 carbon atoms, preferably 4 to 20, in particular 6 to 12 carbon atoms per alkyl group, or mixtures thereof and an aliphatic aldehyde with 1 to 10 carbon atoms reacted with each other, about 0.5-2 mol, preferably 0.7-1.3 mol and in particular equimolar amounts of aldehyde being used per mol of alkylphenol compound.
  • Suitable alkylphenols are in particular C - to Cso-alkylphenols such as o- or p-cresol, n-, sec- and tert-butylphenol, n- and i-pentylphenol, n- and iso-hexylphenol, n- and iso- Octylphenol, n- and iso-nonylphenol, n- and iso-decylphenol, n- and iso-dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, tripropenylphenol, tetrapropenylphenol and polyi (isobutenyl) phenol.
  • Cso-alkylphenols such as o- or p-cresol, n-, sec- and tert-butylphenol, n- and i-pentylphenol, n- and is
  • the alkylphenols are preferably para-substituted. They are preferably substituted with more than one alkyl group to a maximum of 7 mol%, in particular to a maximum of 3 mol%.
  • aldehydes are formaldehyde, acetaldehyde, butyraldehyde and glutaraldehyde, formaldehyde is preferred.
  • the formaldehyde can be used in the form of paraformaldehyde or in the form of a preferably 20-40% strength by weight aqueous formalin solution. Appropriate amounts of trioxane can also be used.
  • alkylphenol and aldehyde is usually carried out in the presence of alkaline catalysts, for example alkali hydroxides or alkylamines, or of acidic catalysts, for example inorganic or organic acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acid, sulfamido acids or haloacetic acids, and in the presence of with water an azeotrope-forming organic solvent, for example toluene, xylene, higher aromatics or mixtures thereof.
  • the reaction mixture is heated to a temperature of 90 to 200 ° C., preferably 100-160 ° C., the water of reaction formed being removed during the reaction by azeotropic distillation.
  • Solvents that are under the conditions of
  • the resins can be used directly or after neutralization of the catalyst, if appropriate after further dilution of the solution with aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, for example gasoline fractions, kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or solvents such as ® Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol, ® ISOPAR and ® Shellsol D types.
  • aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures for example gasoline fractions, kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or solvents such as ® Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol, ® ISOP
  • the alkylphenol resins can then optionally be alkoxylated by reaction with 1 to 10, especially 1 to 5, mol of alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide per phenolic OH group.
  • the additives or fuel oils according to the invention which contain the constituents (A) and (C) can also have ethylene copolymers (B), paraffin dispersants (D) and / or comb polymers added to them.
  • Preferred embodiments are consequently also fuel oils according to the invention which contain ethylene copolymers (B), paraffin dispersants (D) and / or comb polymers, and the use according to the invention of additives which contain ethylene copolymers (B), paraffin dispersants (D) and / or comb polymers, and the corresponding Method.
  • Copolymer B) is preferably an ethylene copolymer with an ethylene content of 60 to 90 mol% and a comonomer content of 10 to 40 mol%, preferably 12 to 18 mol%.
  • Suitable comonomers are vinyl esters of aliphatic carboxylic acids with 2 to 15 carbon atoms.
  • Preferred vinyl esters for copolymer B) are vinyl acetate, vinyl propionate, vinyl hexanoate, vinyl octanoate, Vinyl 2-ethylhexanoate, vinyl laurate and vinyl ester of neocarboxylic acids, here in particular of neononanoic acid, neodecanoic acid and neoundecanoic acid.
  • an ethylene-vinyl acetate copolymer an ethylene-vinyl propionate copolymer, an ethylene-vinyl acetate-vinyl octanoate terpolymer, an ethylene-vinyl acetate-vinyl-2-ethylhexyl terpolymer, an ethylene-vinyl acetate-neononanoic acid vinyl ester terpolymer or an ethylene Vinyl acetate neodecanoic acid vinyl ester terpolymer.
  • Preferred acrylic acid esters are acrylic acid esters with alcohol residues from 1 to 20, in particular from 2 to 12 and especially from 4 to 8 carbon atoms, such as, for example, methyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • the copolymers can contain up to 5% by weight of further comonomers.
  • Such comonomers can be, for example, vinyl esters, vinyl ethers, alkyl acrylates, alkyl methacrylates with C 1 -C 2 -alkyl radicals, isobutylene and olefins. Hexene, isobutylene, octene and / or diisobutylene are preferred as higher olefins.
  • Suitable comonomers are olefins such as propene, hexene, butene, isobutene, diisobutylene, 4-methylpentene-1 and norbornene.
  • Ethylene-vinyl acetate-diisobutylene and ethylene-vinyl acetate-4-methylpentene-1 terpolymers are particularly preferred.
  • the copolymers preferably have melt viscosities at 140 ° C. of 20 to 10,000 mPas, in particular 30 to 5000 mPas, especially 50 to 2000 mPas.
  • the copolymers (B) can be prepared by the customary copolymerization processes, such as, for example, suspension polymerization, solvent polymerization, gas phase polymerization or high-pressure bulk polymerization.
  • High-pressure bulk polymerization is preferred at pressures of preferably 50 to 400, in particular 100 to 300 MPa and temperatures of preferably 50 to 350, in particular 100 to 250 ° C.
  • the reaction of the monomers is initiated by radical initiators (radical chain initiators).
  • This class of substances includes, for example, oxygen, hydroperoxides, peroxides and azo compounds such as cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide carbonate, t-butyl perpivalate, t-butyl permaleinate, t-butyl peryl peroxide, dicumyl perbenzoate, Butylcumyl peroxide, di (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile).
  • the initiators are used individually or as a mixture of two or more substances in amounts of 0.01 to 20% by weight, preferably 0.05 to 10% by weight, based on the monomer mixture.
  • High pressure bulk polymerization is carried out in known high pressure reactors, e.g. Autoclaves or tubular reactors, carried out batchwise or continuously, tubular reactors have proven particularly useful.
  • Solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures,
  • Benzene or toluene can be contained in the reaction mixture.
  • the solvent-free mode of operation is preferred.
  • the mixture of the monomers, the initiator and, if used, the moderator is fed to a tubular reactor via the reactor inlet and via one or more side branches.
  • Suitable copolymers or terpolymers are:
  • Ethylene-vinyl acetate copolymers with 10-40% by weight of vinyl acetate and 60-90% by weight of ethylene;
  • ethylene / vinyl acetate / neononanoic acid vinyl ester or neodecanoic acid vinyl ester terpolymers known from EP-B-0 493 769, which, in addition to ethylene, contain 10-35% by weight of vinyl acetate and 1-25% by weight of the respective neo compound; the terpolymers described in DE-A-196 20 118 made of ethylene, the vinyl ester of one or more aliphatic C 2 - to C 2 o-monocarboxylic acids and 4-methylpentene-1;
  • the polar nitrogen-containing paraffin dispersants (D) are low-molecular or polymeric, oil-soluble nitrogen compounds, for example amine salts, imides and / or amides, which are obtained by reacting aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di- , Tri- or tetracarboxylic acids or their anhydrides are obtained.
  • Particularly preferred paraffin dispersants contain reaction products of secondary fatty amines with 8 to 36 carbon atoms, in particular dicocos fatty amine, ditallow fatty amine and distearyl amine.
  • paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds which can optionally be reacted with primary monoalkylamines and / or aliphatic alcohols, the reaction products of alkenyl spirobislactones with amines and reaction products of terpolymers based on ⁇ , ⁇ -unsaturated dride, dicarboxylic acids Unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols.
  • paraffin dispersants (D) are listed below.
  • the paraffin dispersants (D) mentioned below are prepared in part by reacting compounds which contain an acyl group with an amine.
  • R is in each case C 8 -C 2 oo-alkenyl, with amines of the formula
  • R 10 is a straight-chain or branched alkylene radical having 2 to 6 carbon atoms or the radical of the formula
  • R 6 and R are in particular alkyl radicals having 10 to 30, preferably 14 to 24, carbon atoms
  • the amide structures also partially or completely in the form of the ammonium salt structure of the formula
  • the amides or amide-ammonium salts or ammonium salts for example of nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diamine tetraacetic acid, are reacted with 0.5 to 1.5 mol of amine, preferably 0.8 to 1.2 mol, by reaction of the acids Amine obtained per carboxyl group.
  • the reaction temperatures are about 80 to 200 ° C, with
  • Dialkylamines are particularly suitable in which R 6 , R 7 is a straight-chain alkyl radical having 10 to 30 carbon atoms, preferably 14 to 24 carbon atoms.
  • R 6 , R 7 is a straight-chain alkyl radical having 10 to 30 carbon atoms, preferably 14 to 24 carbon atoms.
  • dioleylamine, dipalmitinamine, dicoconut fatty amine and dibehenylamine are preferred
  • n is a number from 1 to 30 and X is halogen, preferably chlorine, or a methosulfate.
  • dihexadecyldimethylammonium chloride distearyldimethylammonium chloride
  • quaternization products of esters of di- and triethanolamine with long-chain fatty acids lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid and fatty acid fatty acids, such as coco fatty acid fatty acids, such as coco fatty acid fatty acids, such as coco fatty acid fatty acids, , such as N-methyltriethanolammonium distearyl ester chloride, N-methyltriethanolammonium distearyl ester methosulfate, N, N-dimethyl-diethanolammonium distearyl ester chloride, N-methyltriethanolammonium dioleylester chloride, N-methyltriethanolammonium triethyl sulfonate, methyl-triethanolate, n-methylium trisulfon
  • R 14 stands for CONR 6 R 7 or C0 2 "+ H 2 NR 6 R 7 ,
  • R 15 and R 16 for H, CONR 17 2 , C0 2 R 17 or OCOR 17 , -OR 17 , -R 17 or -
  • R 17 is alkyl, alkoxyalkyl or polyalkoxyalkyl and at least
  • Preferred carboxylic acids or acid derivatives are phthalic acid (anhydride), trimellite, pyromellitic acid (dianhydride), isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid (anhydride), maleic acid (anhydride), alkenylsuccinic acid (anhydride).
  • the formulation (anhydride) means that the anhydrides of the acids mentioned are preferred acid derivatives.
  • the compounds of the above formula are amides or amine salts, they are preferably obtained from a secondary amine containing a group containing hydrogen and carbon having at least 10 carbon atoms.
  • R 17 contains 10 to 30, in particular 10 to 22, for example 14 to 20 carbon atoms and is preferably straight-chain or branched at the 1- or 2-position.
  • the other hydrogen and carbon containing groups can be shorter, eg contain less than 6 carbon atoms, or, if desired, can have at least 10 carbon atoms.
  • Suitable alkyl groups include methyl, ethyl, propyl, hexyl, decyl, dodecyl, tetradecyl, eicosyl and docosyl (behenyl).
  • Polymers are also suitable which contain at least one amide or ammonium group bonded directly to the backbone of the polymer, the amide or ammonium group carrying at least one alkyl group of at least 8 carbon atoms on the nitrogen atom.
  • Such polymers can be produced in various ways. One way is to use a polymer containing multiple carboxylic acid or anhydride groups and react that polymer with an amine of the formula NHR 6 R 7 to obtain the desired polymer.
  • polymers generally copolymers of unsaturated esters such as CrC o-alkyl (meth) acrylates, fumaric acid di (C 1 -C 4 o -alkyl esters), C 1 -C 4 -alkyl vinyl ethers, C 1 -C 4 o-alkyl vinyl esters or C 2 -C 4 o-olefins (linear, branched, aromatic) with unsaturated carboxylic acids or their reactive derivatives, such as carboxylic anhydrides (acrylic acid,
  • unsaturated esters such as CrC o-alkyl (meth) acrylates, fumaric acid di (C 1 -C 4 o -alkyl esters), C 1 -C 4 -alkyl vinyl ethers, C 1 -C 4 o-alkyl vinyl esters or C 2 -C 4 o-olefins (linear, branched, aromatic) with unsaturated carboxylic acids or their reactive derivatives, such
  • Methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, citraconic acid, preferably maleic anhydride) are suitable.
  • Carboxylic acids are preferably reacted with 0.1 to 1.5 mol, in particular 0.5 to 1.2 mol, of amine per acid group, carboxylic anhydrides preferably with 0.1 to 2.5, in particular 0.5 to 2.2 mol, of amine per acid anhydride group , whereby, depending on the reaction conditions, amides, ammonium salts, amide-ammonium salts or imides are formed.
  • copolymers containing unsaturated carboxylic anhydrides give half amide and half amine salts when reacted with a secondary amine due to the reaction with the anhydride group. Water can be split off by heating to form the diamond.
  • polymers containing amide groups for use according to the invention are:
  • Copolymers (a) of a dialkyl fumarate, maleate, citraconate or itaconate with maleic anhydride, or (b) of vinyl esters, e.g.
  • Vinyl acetate or vinyl stearate with maleic anhydride or (c) a dialkyl fumarate, maleate, citraconate or itaconate with maleic anhydride and vinyl acetate.
  • the desired amide is obtained by reacting the polymer containing anhydride groups with a secondary amine of the formula HNR 6 R 7 (optionally also with an alcohol if an ester amide is formed).
  • polymers containing an anhydride group When polymers containing an anhydride group are reacted, the resulting amino groups will be ammonium salts and amides. Such polymers can be used provided that they contain at least two amide groups.
  • the polymer containing at least two amide groups contain at least one alkyl group with at least 10 carbon atoms.
  • This long-chain group which can be a straight-chain or branched alkyl group, can be bound via the nitrogen atom of the amide group.
  • the suitable amines can by the formula R 6 R 7 NH and
  • Polyamines are represented by R 6 NH [R 19 NH] X R 7 , where R 19 is a divalent hydrocarbon group, preferably an alkylene or hydrocarbon-substituted alkylene group, and x is an integer, preferably between 1 and 30.
  • R 19 is a divalent hydrocarbon group, preferably an alkylene or hydrocarbon-substituted alkylene group, and x is an integer, preferably between 1 and 30.
  • one of the two or both R 6 and R 7 contain at least 10 carbon atoms, for example 10 to 20 carbon atoms, for example dodecyl, tetradecyl, hexadecyl or octadecyl.
  • suitable secondary amines are dioctylamine and those which contain alkyl groups with at least 10 carbon atoms, for example didecylamine, didodecylamine, dicocosamine (ie mixed C 2 -Ci 4 -amines), dioctadecylamine, hexadecyloctadecylamine, di- (hydrogenated tallow) amine (approximately 4 % By weight n--C 4 alkyl, 30% by weight n--C 0 alkyl, 60% by weight n-Ci ⁇ -alkyl, the rest is unsaturated).
  • polyamines examples include N-octadecyl propane diamine, N.N'-dioctadecyl propane diamine, N-tetradecyl butane diamine and N.N'-dihexadecyl hexane diamine.
  • N-Cocospropylenediamine C ⁇ 2 / C ⁇ 4 - alkyl propylene diamine
  • N-tallow propylene diamine Ci 6 / C ⁇ 8 alkylpropylene diamine
  • the amide-containing polymers usually have an average number-average molecular weight of 1000 to 500,000, for example 10,000 to 100,000.
  • the reaction can be carried out before or after the polymerization.
  • the structural units of the copolymers derive from e.g. Maleic acid, fumaric acid, tetrahydrophthalic acid, citraconic acid, preferably maleic anhydride. They can be used both in the form of their homopolymers and of the copolymers.
  • Comonomers are suitable: styrene and alkylstyrenes, straight-chain and branched olefins with 2 to 40 carbon atoms, and their mixtures with one another.
  • examples include: styrene, ⁇ -methylstyrene, dimethylstyrene, ⁇ -ethylstyrene, diethylstyrene, i-propylstyrene, tert-butylstyrene, ethylene, propylene, n-butylene, diisobutylene, decene,
  • polymers which may be mentioned in detail are: polymaleic acid, a molar, alternating styrene / maleic acid copolymer, randomly constructed styrene / maleic acid copolymers in a ratio of 10:90 and an alternating copolymer of maleic acid and i-butene.
  • the molar masses of the polymers are generally 500 g / mol to 20,000 g / mol, preferably 700 to 2000 g / mol.
  • the reaction of the polymers or copolymers with the amines takes place at temperatures of 50 to 200 ° C in the course of 0.3 to 30 hours.
  • the amine is used in amounts of about one mole per mole of polymerized dicarboxylic anhydride, ie about 0.9 to 1.1 moles / mole.
  • the use of larger or smaller amounts is possible, but has no advantage. If quantities greater than one mole are used, ammonium salts are partially obtained, since the formation of a second amide group requires higher temperatures, longer residence times and water removal. If amounts less than one mole are used, there is no complete conversion to the monoamide and a correspondingly reduced effect is obtained.
  • Copolymers consisting of 10 to 95 mol% of one or more
  • the copolymers consist of 10 to 95 mol%, preferably 40 to 95 mol% and particularly preferably 60 to 90 mol% of alkyl (meth) acrylates and 5 to 90 mol%, preferably 5 to 60 mol -% and particularly preferably 10 to 40 mol% of the olefinically unsaturated dicarboxylic acid derivatives.
  • the alkyl groups of the alkyl (meth) acrylates contain from 1 to 26, preferably 4 to 22 and particularly preferably 8 to 18 carbon atoms. They are preferably straight-chain and unbranched. However, up to 20% by weight of cyclic and / or branched portions can also be present.
  • alkyl (meth) acrylates examples include n-octyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-hexadecyl (meth) acrylate and n-octadecyl (meth) acrylate and mixtures thereof.
  • ethylenically unsaturated dicarboxylic acids are maleic acid, tetrahydrophthalic acid, citraconic acid and itaconic acid or their anhydrides and fumaric acid.
  • Maleic anhydride is preferred.
  • the dicarboxylic acids in the form of the anhydrides, if available, in the copolymerization, e.g. Maleic anhydride, itaconic anhydride, citraconic anhydride and tetrahydrophthalic anhydride, since the anhydrides generally copolymerize better with the (meth) acrylates.
  • the anhydride groups of the copolymers can then be reacted directly with the amines.
  • the reaction of the polymers with the amines takes place at temperatures of 50 to 200 ° C in the course of 0.3 to 30 hours.
  • the amine is in amounts of about one to two moles per mole of polymerized dicarboxylic anhydride, i.e. about 0.9 to 2.1 mol / mol applied.
  • the amide / ammonium salt structure is built up from two different amines.
  • a copolymer of lauryl acrylate and maleic anhydride may first be reacted with a secondary amine such as hydrogenated
  • Ditaigfettamin be converted to the amide, after which the free carboxyl group originating from the anhydride is neutralized with another amine, for example 2-ethylhexylamine to the ammonium salt.
  • another amine for example 2-ethylhexylamine to the ammonium salt.
  • the reverse procedure is conceivable: First, with ethylhexylamine to the monoamide, then with ditaig fatty amine to the ammonium salt.
  • At least one amine is preferably used which has at least one straight-chain, unbranched alkyl group with more than 16 carbon atoms. It is irrelevant whether this amine on
  • Amide / ammonium salts it can sometimes be advantageous to prepare the monoamides or amide / ammonium salts of the monomers and then to copolymerize them directly during the polymerization. In most cases, however, this is technically much more complex, since the amines can attach to the double bond of the monomeric dicarboxylic acid and then none
  • Copolymerization is more possible.
  • Contain 80 preferably 40-60 mol% of bivalent structural units of the formulas 1 and / or 3, and optionally 2, where the structural units 2 originate from unreacted anhydride residues,
  • R 22 and R 23 independently of one another are hydrogen or methyl, a, b is zero or one and a + b is one,
  • R 24 and R 25 are identical or different and for the groups -NHR 6 ,
  • R 27 stands for a cation of the formula H 2 N (R 6 ) 2 or H 3 NR 6 ,
  • R> 2 M 8 is hydrogen or CC 4 alkyl
  • R 29 mean Ce-Ceo alkyl or C 6 -C 8 aryl
  • R 30 is hydrogen or methyl
  • R 31 is hydrogen or CC 4 alkyl
  • R 33 -C 4 alkylene, m is a number from 1 to 100
  • R 32 C 1 -C 2 alkyl, C 5 -C 2 o-cycloalkyl, C 6 -C 8 aryl or -C (O) -R 34 , wherein
  • R 34 CC 4 o-alkyl, C 5 -C 0 cycloalkyl or C 6 -C 8 aryl, contain.
  • alkyl, cycloalkyl and aryl radicals can optionally be substituted.
  • Suitable substituents of the alkyl and aryl radicals are, for example, (Ci-C ⁇ J-alkyl, halogens such as fluorine, chlorine, bromine and iodine, preferably chlorine and (CrC ⁇ J-alkoxy.
  • alkyl stands for a straight-chain or branched hydrocarbon radical.
  • alkyl stands for a straight-chain or branched hydrocarbon radical.
  • the following may be mentioned in detail: n-butyl, tert-butyl, n-hexyl, n-octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, dodecenyl, tetrapropenyl, tetradecenyl, pentapropenyl, hexadecenyl, octadecenyl and eicosanyl or mixtures, such as coconut alkyll , Taigfettalkyl and Behenyl.
  • Cycloalkyl here stands for a cyclic aliphatic radical with 5-20 carbon atoms. Preferred cycloalkyl radicals are cyclopentyl and cyclohexyl. Aryl here stands for an optionally substituted aromatic ring system with 6 to 18 carbon atoms.
  • the terpolymers consist of the bivalent structural units of the formulas 1 and 3 and 4 and 5 and, if appropriate, 2. They only contain, in a manner known per se, the end groups formed in the polymerization by initiation, inhibition and chain termination.
  • Structural units of the formulas 1 to 3 are derived in particular from ⁇ , ⁇ -unsaturated dicarboxylic acid anhydrides of the formulas 6 and 7
  • maleic anhydride such as maleic anhydride, itaconic anhydride, citraconic anhydride, preferably maleic anhydride.
  • the structural units of the formula 4 are derived from the ⁇ , ⁇ -unsaturated
  • ⁇ , ⁇ -unsaturated olefins may be mentioned by way of example: styrene, ⁇ -methylstyrene, dimethylstyrene, ⁇ -ethylstyrene, diethylstyrene, i-propylstyrene, tert-butylstyrene, diisobutylene and ⁇ -olefins, such as decene, dodecene, tetradecene, pentadecene, Hexadecene, octadecene, C 2 o- ⁇ -olefin, C 24- ⁇ -olefin, C 3 o- ⁇ -olefin, tripropenyl, tetrapropenyl, pentapropenyl and mixtures thereof.
  • Alpha-olefins having 10 to 24 carbon atoms and styrene are preferred, alpha-olef
  • the structural units of the formula 5 are derived from polyoxyalkylene ethers of lower, unsaturated alcohols of the formula 9.
  • Such polymerizable lower unsaturated alcohols are e.g. Allyl alcohol, methallyl alcohol, butenols such as 3-buten-1-ol and 1-buten-3-ol or methyl butenols such as 2-methyl-3-buten-1-ol, 2-methyl-3-buten-2-ol and
  • R 32 is CC 24 alkyl, C 5 -C 20 cycloalkyl or C 6 -C 8 aryl, attached by known methods and with polymerizable lower, unsaturated halides of the formula 12
  • the esterification is generally carried out at temperatures from 0 to 200 ° C., preferably 10 to 100 ° C.
  • the index m indicates the degree of alkoxylation, i.e. the number of moles of ⁇ -olefin added per mole of formula 20 or 21.
  • Suitable primary amines suitable for the preparation of the terpolymers are: n-hexylamine, n-octylamine, n-tetradecylamine, n-hexadecylamine, n-stearylamine or else N, N-dimethylaminopropylenediamine, cyclohexylamine, dehydroabietylamine and mixtures thereof.
  • secondary amines suitable for the preparation of the terpolymers are: didecylamine, ditetradecylamine, distearylamine,
  • Dicocos fatty amine Dicocos fatty amine, dietary fatty amine and mixtures thereof.
  • the terpolymers have K values (measured according to Ubbelohde in a 5% strength by weight solution in toluene at 25 ° C.) of 8 to 100, preferably 8 to 50, corresponding to average molecular weights (M w ) of between about 500 and
  • reaction products of alkanolamines and / or polyetheramines with polymers containing dicarboxylic acid anhydride groups characterized in that they contain 20-80, preferably 40-60 mol% of bivalent
  • R 22 and R 23 independently of one another are hydrogen or methyl, a, b is zero or 1 and a + b is 1,
  • R 38 R 37 or NR 6 R 39
  • E H, CrC 30 alkyl, C 5 -C 12 cycloalkyl or C 6 -C 30 aryl, and 80-20 mol%, preferably 60-40 mol%, of bivalent Structural units of formula 4 contain.
  • the structural units of the formulas 13, 14 and 15 are derived from ⁇ , ⁇ -unsaturated dicarboxylic acid anhydrides of the formulas 6 and / or 7.
  • the structural units of the formula 4 are derived from the ⁇ , ⁇ -unsaturated olefins of the formula 8.
  • the aforementioned alkyl, cycloalkyl and aryl radicals have the same meanings as under 8.
  • R 53 is hydrogen, C 6 -C 4 o-alkyl or
  • R 54 hydrogen, CC 4 alkyl R 55 hydrogen, C to C alkyl, C 5 - to -C 2 cycloalkyl or C 6 - to
  • C 30 aryl R 56 , R 57 independently of one another are hydrogen, C to C 22 alkyl,
  • C 2 - to C 22 -alkenyl or Z - OH ZC 2 - to C -alkylene n is a number between 1 and 1000.
  • Mixtures of at least 50% by weight of alkylamines of the formula HNR 6 R 7 R 8 and at most 50% by weight of polyetheramines, alkanolamines of the formulas 16 a) and b) are preferably used to derivatize the structural units of the formulas 6 and 7.
  • polyetheramines used can be prepared, for example, by reductive amination of polyglycols.
  • polyetheramines with a primary amino group can be prepared by adding polyglycols to acrylonitrile and subsequent catalytic hydrogenation.
  • polyetheramines are produced by the reaction of
  • polyethers with phosgene or thionyl chloride and subsequent amination to polyetheramine accessible are (for example) commercially available under the name ® Jeffamine (Texaco). Their molecular weight is up to 2000 g / mol and the ethylene oxide / propylene oxide ratio is from 1:10 to 6: 1.
  • a further possibility for derivatizing the structural units of the formulas 6 and 7 consists in using an alkanolamine of the formulas 16a) or 16b) instead of the polyetheramines and subsequently subjecting them to an oxyalkylation.
  • reaction temperature is between 50 and 100 ° C (amide formation). In the case of primary amines, the reaction takes place at temperatures above 100 ° C. (imide formation).
  • the oxyalkylation is usually carried out at temperatures between 70 and 170 ° C. with the catalysis of bases such as NaOH or NaOCH 3 Gassing of alkylene oxides, such as ethylene oxide (EO) and / or propylene oxide (PO). Usually 1 to 500, preferably 1 to 100, moles of alkylene oxide are added per mole of hydroxyl groups.
  • bases such as NaOH or NaOCH 3
  • alkylene oxides such as ethylene oxide (EO) and / or propylene oxide (PO).
  • EO ethylene oxide
  • PO propylene oxide
  • alkanolamines examples include:
  • primary amines for example: n-hexylamine, n-octylamine, n-tetradecylamine, n-hexadecylamine, n-stearylamine or else N, N-dimethylaminopropylenediamine, cyclohexylamine, dehydroabietylamine and mixtures thereof.
  • alcohols which may be mentioned are: methanol, ethanol, propanol, isopropanol, n-, sec-, tert-butanol, octanol,
  • These are accessible on the one hand by reacting a polymer containing anhydride groups with amines of the formula H 2 NR 6 or by imidation of the dicarboxylic acid and subsequent copolymerization.
  • Preferred dicarboxylic acid is maleic acid or
  • Copolymers of 10 to 90% by weight of C 6 -C 24 - ⁇ -olefins and 90 to 10% by weight of NC 6 -C 22 alkylmaleimide are preferred.
  • Comb polymers can, for example, by the formula
  • R ' is a hydrocarbon chain of 8-150 carbon atoms
  • R is a hydrocarbon chain of 1 to 10 carbon atoms; m is a number between 0.4 and 1.0; and n is a number between 0 and 0.6.
  • the mixing ratio (in parts by weight) of the additives according to the invention with paraffin dispersants, resins or comb polymers is in each case 1:10 to 20: 1, preferably 1: 1 to 10: 1.
  • the additive components according to the invention can be added to mineral oils or mineral oil distillates separately or in a mixture.
  • the individual additive constituents or else the corresponding mixture are dissolved or dispersed in an organic solvent or dispersant before being added to the middle distillates.
  • the solution or dispersion generally contains 5-90, preferably 5-75,% by weight of the additive or additive mixture.
  • Suitable solvents or dispersants are aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, for example gasoline fractions, kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or commercial solvent mixtures such as solvent naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol, ® ISOPAR and ® Shellsol D types.
  • polar solubilizers such as 2-ethylhexanol, decanol, iso-decanol or iso-tridecanol can also be added.
  • Mineral oils or mineral oil distillates improved in their cold properties by the additives according to the invention contain 0.001 to 2, preferably 0.005 to 0.5% by weight of the additives, based on the mineral oil or mineral oil distillate.
  • the additives according to the invention are particularly suitable for improving the cold flow properties of animal, vegetable or mineral oils. At the same time, they improve the dispersion of the failed paraffins below the cloud point. They are particularly well suited for use in middle distillates. Middle distillates are mineral oils that are obtained by distilling crude oil and boil in the range of 120 to 450 ° C, such as kerosene, jet fuel, diesel and heating oil.
  • the additives according to the invention are preferably used in low-sulfur middle distillates which contain 350 ppm sulfur and less, particularly preferably less than 200 ppm sulfur and in particular less than 50 ppm sulfur.
  • the additives according to the invention are furthermore preferably used in middle distillates which have 95% distillation points below 365 ° C., in particular 350 ° C. and in special cases below 330 ° C. and, in addition to high levels of paraffins with 18 to 24 carbon atoms, only small proportions Contain paraffins with chain lengths of 24 and more carbon atoms. They can also be used as components in lubricating oils.
  • the mineral oils or mineral oil distillates can also contain other conventional additives such as dewaxing agents, corrosion inhibitors, antioxidants, lubricity additives, sludge inhibitors, cetane number improvers, Detergent additives, dehazers, conductivity improvers or dyes.
  • esters A were used as a 50% solution in aromatic solvent (EO stands for ethylene oxide; PO stands for propylene oxide):
  • the viscosity is determined in accordance with ISO 3219 / B using a rotary viscometer (Haake RV20) with a plate and cone measuring system at 140 ° C.
  • the additives are used to improve handling as 50% solutions in solvent naphtha or kerosene.
  • reaction product of a dodecenyl spirobislactone with a mixture of primary and secondary tallow fatty amine D 2) reaction product of a terpolymer of C Ci ⁇ - ⁇ -olefin, maleic anhydride and allyl polyglycol with 2 equivalents of ditaig fatty amine.
  • Table 4 describes the effectiveness of the additives according to the invention together with ethylene copolymers for mineral oils and mineral oil distillates, which is superior to the prior art, using the CFPP test (Cold Filter Plugging Test according to EN 116).
  • the paraffin dispersion in middle distillates was determined as follows in the short sediment test:
  • the CFPP activity of the esters A according to the invention was measured in combination with equal amounts of C and D in test oil 1 as follows:
  • the additive components A were mixed with 5 parts B2) and tested for their CFPP activity in test oil 2.

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Abstract

L'invention concerne des additifs pour des distillats moyens à teneur maximale en soufre de 0,05 % en poids. Ces additifs contiennent au moins un ester d'acide gras de polyol alkoxylé comportant au moins 3 groupes OH (A) et au moins une résine aldéhyde alkyle phénol (C).
EP02802985A 2001-11-14 2002-11-02 Additifs pour distillats de petrole pauvres en soufre, contenant un ester d'un polyol alkoxyle et une resine aldehyde alkyle phenol Expired - Lifetime EP1446464B1 (fr)

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DE10155747 2001-11-14
DE10155747A DE10155747B4 (de) 2001-11-14 2001-11-14 Additive für schwefelarme Mineralöldestillate, umfassend einen Ester eines alkoxylierten Polyols und ein Alkylphenol-Aldehydharz
PCT/EP2002/012235 WO2003042338A2 (fr) 2001-11-14 2002-11-02 Additifs pour distillats de petrole pauvres en soufre, contenant un ester d'un polyol alkoxyle et une resine aldehyde alkyle phenol

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DE10155774B4 (de) * 2001-11-14 2020-07-02 Clariant Produkte (Deutschland) Gmbh Additive für schwefelarme Mineralöldestillate, umfassend einen Ester alkoxylierten Glycerins und einen polaren stickstoffhaltigen Paraffindispergator
KR100749220B1 (ko) * 2003-10-22 2007-08-13 로이나 폴리머 게엠베하 미네랄 오일 조성물의 성분으로서의 첨가제 혼합물
PL1675881T3 (pl) * 2003-10-22 2011-05-31 Innospec Leuna Gmbh Dodatek stosowany jako składnik kompozycji mineralnych
KR100749209B1 (ko) * 2003-10-22 2007-08-13 로이나 폴리머 게엠베하 미네랄 오일 조성물의 성분으로서의 첨가제 혼합물
JP4645073B2 (ja) * 2004-06-21 2011-03-09 日油株式会社 燃料油用添加剤及び燃料油組成物
EP1801187B2 (fr) * 2005-12-22 2022-03-23 Clariant Produkte (Deutschland) GmbH Huiles minérales contenant des additifs détergents avec capacité de fluidité au froid améliorée
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DE10155747B4 (de) 2008-09-11
WO2003042338A2 (fr) 2003-05-22
US7377949B2 (en) 2008-05-27
US20050000152A1 (en) 2005-01-06
DE50203784D1 (de) 2005-09-01
KR101072787B1 (ko) 2011-10-14
JP2005509086A (ja) 2005-04-07
EP1446464B1 (fr) 2005-07-27
DE10155747A1 (de) 2003-05-28
KR20050042255A (ko) 2005-05-06
ES2243799T3 (es) 2005-12-01
WO2003042338A3 (fr) 2003-10-09

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