EP1458837A2 - Distillats d'huile minerale a basse teneur en soufre a proprietes a froid ameliorees, contenant un ester d'un polyol alcoxyle et un copolymere d'ethylene et d'esters insatures - Google Patents

Distillats d'huile minerale a basse teneur en soufre a proprietes a froid ameliorees, contenant un ester d'un polyol alcoxyle et un copolymere d'ethylene et d'esters insatures

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Publication number
EP1458837A2
EP1458837A2 EP02791659A EP02791659A EP1458837A2 EP 1458837 A2 EP1458837 A2 EP 1458837A2 EP 02791659 A EP02791659 A EP 02791659A EP 02791659 A EP02791659 A EP 02791659A EP 1458837 A2 EP1458837 A2 EP 1458837A2
Authority
EP
European Patent Office
Prior art keywords
ethylene
middle distillates
carbon atoms
acid
mol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP02791659A
Other languages
German (de)
English (en)
Other versions
EP1458837B1 (fr
Inventor
Matthias Krull
Martina Hess
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Produkte Deutschland GmbH
Original Assignee
Clariant Produkte Deutschland GmbH
Clariant GmbH
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Filing date
Publication date
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Publication of EP1458837A2 publication Critical patent/EP1458837A2/fr
Application granted granted Critical
Publication of EP1458837B1 publication Critical patent/EP1458837B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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, 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
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    • 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
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
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    • 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
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    • C10L1/00—Liquid carbonaceous fuels
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    • 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
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    • 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, 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
    • C10L1/18—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
    • C10L1/1986—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 complex 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, 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
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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
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    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
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    • 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

  • Low sulfur mineral oil distillates with improved cold properties, comprising an ester of an alkoxylated polyol and a copolymer of ethylene and unsaturated esters
  • the invention relates to low-sulfur mineral oil distillates with improved cold flowability and paraffin dispersion, comprising an ester of an alkoxylated polyol and a copolymer of ethylene and unsaturated esters, paraffin-dispersing additives and their use.
  • 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 C 10 - 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 middle distillates with a maximum of 0.05% by weight sulfur, the fatty acid esters of alkoxylated polyols with at least 3 OH groups (A) and at least one cold flow improver (B), this cold flow improver containing at least one copolymer of ethylene and one or comprises several ethylenically unsaturated carboxylic acid esters with an ethylene content of 60 to 90 mol%.
  • 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 cold flow improver (B), this cold flow improver having at least one copolymer of ethylene and one or more ethylenically unsaturated carboxylic acid esters an ethylene content of 60 to 90 mol%, to improve the cold flow properties and paraffin dispersion of middle distillates with a maximum of 0.05 wt .-% 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
  • Cold flow improver comprises at least one copolymer of ethylene and one or more ethylenically unsaturated carboxylic esters with an ethylene content of 60 to 90 mol%.
  • the esters (A) are derived from polyols with 3 or more OH groups, in particular from glycerol, trimethylolpropane, pentaerythritol and the oligomers with 2 to 10 monomer units, such as polyglycerol, which are accessible by condensation.
  • the polyols are generally 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.
  • Fatty acid mixtures contain more than 50% fatty acids with at least 20 carbon atoms. Preferably less than 50% of 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 using reactive derivatives of fatty acids such as esters with lower alcohols (e.g. methyl or ethyl esters) or anhydrides.
  • Suitable polyvalent carboxylic acids are dimer fatty acids, alkenyl succinic acids and aromatic polycarboxylic acids and their derivatives such as anhydrides and C to C 5 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 action 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 using customary methods.
  • the water of reaction can be removed by distillation 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.
  • 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%.
  • Copolymer (B) is particularly preferably a main chain polymer which is not a graft copolymer.
  • 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 esters of neocarboxylic acids, here in particular of neononane,
  • Neodecanoic and neoundecanoic acid Particularly preferred are an ethylene-vinyl acetate copolymer, an ethylene-vinyl propionate copolymer, an ethylene-vinyl acetate-vinyl octanoate terpolymer, an ethylene-vinyl acetate-vinyl-2-ethylhexanoate terpolymer, an ethylene-vinyl acetate-neononanoic acid vinyl ester terpolymer or an ethylene -Vinylacetat-neodecanoate 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, acrylic acid alkyl esters, methacrylic acid alkyl esters with C to C 20 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 of 140 ° C.
  • 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 peryl peroxide, dicuryl peryl peryl peroxide, dicuryl peryl peroxide , Di- (t-butyl) peroxide, 2,2 , -azo-bis (2-methylpropanonitrile),
  • cumene hydroperoxide t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide carbonate, t-butyl perpivalate, t-butyl permaleinate, t-butyl
  • 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.
  • the high-pressure bulk polymerization is carried out batchwise or continuously in known high-pressure reactors, for example autoclaves or tubular reactors, 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.
  • the monomer streams can have different compositions (EP-A-0 271 738).
  • Suitable copolymers or terpolymers are: ethylene-vinyl acetate copolymers with 10 to 40% by weight of vinyl acetate and 60 to 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 to 35% by weight of vinyl acetate and 1 to 25% by weight of the respective neo compound; the terpolymers described in DE-A-196 20 118 made from ethylene, the vinyl ester of one or more aliphatic C 2 - to C- 20 monocarboxylic acids and 4-methylpentene-1;
  • alkylphenol-aldehyde resins (C), paraffin dispersants (D) and / or comb polymers can also be added to the fuel oils according to the invention which contain the components (A) and (B).
  • Preferred embodiments are consequently also the use according to the invention of additives which additionally contain alkylphenol-aldehyde resins (C), paraffin dispersants (D) and / or comb polymers, and the corresponding process.
  • Alkylphenol-aldehyde resins (C) are known in principle and are described, for example, in the 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 mole percent 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 to 10, preferably 1 to 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.
  • the alkylphenol-aldehyde resins are prepared in a known manner by basic catalysis, with condensation products of the resol type being formed, or by acidic catalysis, producing condensation products of the novolak type.
  • the condensates obtained in both ways are suitable for the compositions according to the invention.
  • 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 are reacted with one another, about 0.5 to 2 mol, preferably 0.7 to 1.3 mol and in particular equimolar amounts of aldehyde being used per mol of alkylphenol compound.
  • Suitable alkylphenols are in particular C 4 - to C 50 -alkylphenols such as, for example, 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.
  • alkylphenols are in particular C 4 - to C 50 -alkylphenols such as, for example, o- or p-cresol, n-, sec- and tert
  • the alkylphenols are preferably para-substituted. They are preferably substituted at most 7 mol%, in particular at most 3 mol%, with more than one alkyl group.
  • 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 to 40% 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 an organic solvent which forms an azeotrope with water, for example toluene, xylene, higher aromatics or mixtures thereof.
  • the reaction mixture is heated to a temperature of 90 to 200 ° C, preferably 100 to 160 ° C, the. water of reaction formed is removed during the reaction by azeotropic distillation.
  • Solvents that do not release protons under the conditions of the condensation can remain in the products after the condensation reaction.
  • 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.
  • 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 polar nitrogen-containing paraffin dispersants (D) are low-molecular or polymeric, oil-soluble nitrogen compounds, e.g. 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.
  • 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.
  • Other paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds, which may be primary
  • Monoalkylamines and / or aliphatic alcohols can be reacted, the reaction products of alkenylspirobislactones with amines and reaction products of terpolymers based on ⁇ , ⁇ -unsaturated Dicarboxylic anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols.
  • suitable paraffin dispersants (D) are listed below.
  • paraffin dispersants (D) mentioned below are prepared in part by reacting compounds which contain an acyl group with an amine.
  • 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 7 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
  • R 7 can be present.
  • amides or amide ammonium salts or ammonium salts e.g. nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1, 2-diamintetraacetic acid are reacted with 0.5 to
  • reaction temperatures are about 80 to 200 ° C., the water of reaction formed being continuously removed to produce the amides. However, the reaction does not have to be carried out completely to give the amide; on the contrary, 0 to 100 mol% of that used can be used
  • Amine in the form of the ammonium salt can also be prepared under analogous conditions.
  • 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.
  • Dioleylamine, dipalmitinamine, dicoconut fatty amine and dibehenylamine and preferably ditallow fatty amine may be mentioned in particular.
  • R 6, R 7, R 8 have the meaning given above and R 11 is C 1 -C 30 - alkyl, preferably C ⁇ -C 22 -alkyl, -C 30 -alkenyl, preferably C 1 -C 22 alkenyl,
  • Benzyl or a radical of the formula - (CH 2 -CH 2 -0) n -R 12 , where R 12 Is hydrogen or a fatty acid residue of the formula C (0) -R, where R C ⁇ -C o-alkenyl, n is a number from 1 to 30 and X is halogen, preferably chlorine, or a methosulfate.
  • 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 mixtures such as coconut fatty acid, tallow fatty acid, hydrogenated
  • Tallow fatty acid, tall oil fatty acid such as N-methyltriethanolammonium distearyl ester chloride, N-methyltriethanolammonium distearyl ester methosulfate, N, N-dimethyl-diethanolammonium distearyl ester chloride, N-methyltriethanolammonium dioleylester chloride, N-methyltriethanolate, N-methyltriethanolate
  • N-methyltriethanolammonium tristearyl ester methosulfate N-methyltriethanolammonium tristearyl ester methosulfate and mixtures thereof.
  • R 14 stands for CONR 6 R 7 or C0 2 "+ H 2 NR 6 R 7
  • R 15 and R 16 stands 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 has at least 10 carbon atoms.
  • 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.
  • the polymers used are generally copolymers of unsaturated esters such as C 1 -C 8 -alkyl (meth) acrylates, fumaric acid di (C 1 -C 8 -alkyl esters), C 1 -C 40 -alkyl vinyl ethers, C 1 -C 4 -alkyl vinyl esters or C 2 -C 4 o-olefins (linear, branched, aromatic) with unsaturated carboxylic acids or their reactive derivatives, such as carboxylic acid anhydrides (acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, citraconic acid, preferably maleic anhydride). 5
  • unsaturated esters such as C 1 -C 8 -alkyl (meth) acrylates, fumaric acid di (C 1 -C 8 -alkyl esters), C 1 -C 40 -alkyl vinyl ethers, C 1 -C 4 -alkyl
  • 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 , depending on the reaction conditions
  • 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 20th 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, the anhydride groups contains, with a secondary amine of the formula HNR 6 R 7 (optionally also with an alcohol if an ester amide is formed). If 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 that is a straight chain or branched
  • May be alkyl group may be bound via the nitrogen atom of the amide group.
  • the suitable amines can be represented by the formula R 6 R 7 NH and the polyamines 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 a whole Number, preferably between 1 and 30.
  • R 19 is a divalent hydrocarbon group, preferably an alkylene or hydrocarbon-substituted alkylene group, and x is a whole Number, preferably between 1 and 30.
  • one of the two or both radicals R 6 and R 7 contain at least 10 carbon atoms, for example 10 to 20 carbon atoms, for example dodecyl,
  • Tetradecyl Tetradecyl, hexadecyl or octadecyl.
  • Suitable secondary amines are dioctylamine and those containing alkyl groups with at least 10 carbon atoms, e.g. didecylamine, didodecylamine, dicocosamine (i.e. mixed
  • Ci 2 -Ci 4 amines dioctadecylamine, hexadecyloctadecylamine, di (hydrogenated tallow) amine (approximately 4% by weight n -CC 4 alkyl, 30% by weight nC-io-alkyl, 60% by weight) % n-Cis-alkyl, the rest is unsaturated).
  • suitable polyamines are N-octadecylpropane diamine, N.N'-dioctadecyl propane diamine, N-tetradecyl butane diamine and
  • N, N'-Dihexadecylhexandiamin N-Cocospropylenediamine (C ⁇ 2 / C 14 - alkylpropylenediamine), N-tallow propylenediamine (Ci ⁇ / Cis-alkylpropylenediamine).
  • 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. Suitable comonomers are: styrene and alkylstyrenes, straight-chain and branched olefins having 2 to 40 carbon atoms, and mixtures thereof with one another.
  • Examples include: styrene, ⁇ -methylstyrene, dimethylstyrene, ⁇ -ethylstyrene, diethylstyrene, i-propylstyrene, tert-butylstyrene, ethylene, propylene, n-butylene, diisobutylene, decene, dodecene, tetradecene, hexadecene, octadecene. Styrene and
  • Isobutene, styrene is particularly preferred.
  • 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 in amounts of about one mole per mole of polymerized dicarboxylic anhydride, ie about 0.9 to 1.1 moles / mole, applied.
  • the use of larger or smaller amounts is possible, but has no advantage. If larger amounts than one mole are used, ammonium salts are obtained in part, since the formation of a second amide group requires higher temperatures, longer residence times and water separation. 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%
  • 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 use of larger or smaller amounts is possible, but has no advantage. If more than two moles are used, free amine is present. If amounts less than one mole are used, there is no complete conversion to the monoamide and a correspondingly reduced effect is obtained.
  • the amide / ammonium salt structure is built up from two different amines.
  • a copolymer of lauryl acrylate and maleic anhydride can first be reacted with a secondary amine, such as hydrogenated ditaig fatty amine, to give the amide, followed by that from the anhydride originating free carboxyl group is neutralized with another amine, eg 2-ethylhexylamine to form the ammonium salt.
  • a secondary amine such as hydrogenated ditaig fatty amine
  • 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 immaterial whether this amine is present in the structure of the amide structure or as the ammonium salt of dicarboxylic acid.
  • Terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkylene ethers of lower, unsaturated alcohols which are characterized in that they contain 20-80, preferably 40-60 mol% of bivalent structural units of the formulas 1 and / or 3, and optionally 2, the structural units 2 originating 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 , 19-80 mol%, preferably 39-60 mol% % of bivalent
  • R 28 is hydrogen or cyc 4 alkyl
  • R 29 is C 6 -C 60 alkyl or C 6 -C 18 aryl and
  • R 30 is hydrogen or methyl
  • R 3 is hydrogen or C 1 -C 4 alkyl
  • R 33 is C 1 -C 4 alkylene, m is a number from 1 to 100,
  • R 32 CC 24 alkyl, C 5 -C 20 cycloalkyl, C 6 -C 8 aryl or -C (0) -R 34 , wherein
  • R 34 CrC- 40 alkyl, C 5 -C ⁇ 0 cycloalkyl or C 6 -C 18 aryl, contain.
  • alkyl, cycloalkyl and aryl radicals can optionally be substituted.
  • Suitable substituents of the alkyl and aryl radicals are, for example, (-CC 6 ) alkyl, halogens such as fluorine, chlorine, bromine and iodine, preferably chlorine and (-C-C 6 ) 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 , Tallow fatty alkyl 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 compounds of the formula 8.
  • ⁇ , ⁇ -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-butene
  • 3-ol or methylbutenols such as 2-methyl-3-buten-1-ol, 2-methyl-3-buten-2-ol and 3-methyl-3-buten-1-ol.
  • Addition products of ethylene oxide and / or propylene oxide onto allyl alcohol are preferred.
  • R 32 is C 1 -C 2 alkyl, C 5 -C 2 o-cycloalkyl or C 6 -C 8 aryl, is added by known processes and with polymerizable lower, unsaturated halides of the formula 12
  • esterification agents such as carboxylic acids, carboxylic acid halides, carboxylic acid anhydrides or carboxylic acid esters with CrC- 4 alcohols.
  • the halides and anhydrides of C 1 -C 4 o-alkyl, C 5 -C 10 -cycloalkyl or C 6 -C 8 arylcarboxylic acids are preferably used.
  • the esterification is generally at
  • the index m indicates the degree of alkoxylation, ie the number of moles of ⁇ -olefin which are added per mole of the formula 20 or 21.
  • Suitable primary amines suitable for the preparation of the terpolymers are the following: 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, dicocosfatty amine, ditaigfatty 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 approximately 500 and 100,000. Suitable examples are listed in EP 606 055.
  • Reaction products of alkanolamines and / or polyetheramines with polymers containing dicarboxylic anhydride groups characterized in that they contain 20-80, preferably 40-60 mol% of bivalent structural units of the formulas 13 and 15 and optionally 14
  • RR 2222 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, CC 3 o-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 formula 8.
  • the aforementioned alkyl, cycloalkyl and aryl radicals have the same meanings as under 8.
  • radicals R 37 and R 38 in formula 13 and R 39 in formula 15 are derived from polyetheramines or alkanolamines of the formulas 16 a) and b), amines of the formula NR 6 R 7 R 8 and, if appropriate, from alcohols having 1 to 30 carbon atoms from.
  • R 53 is hydrogen, C 6 -C 40 alkyl or
  • R 5 5 0 5 0 is hydrogen, C to C 4 alkyl, C 5 to C 12 cycloalkyl or C 6 to
  • R 5 ° 6 °, r R-, 57 independently of one another hydrogen, C to C- 22 alkyl
  • C 2 - to C 2 -alkenyl or Z - OH ZC 2 - to C 4 -alkylene n is a number between 1 and 1000.
  • the polyetheramines used can be prepared, for example, by reductive amination of polyglycols. Furthermore, it succeeds
  • polyetheramines with a primary amino group by adding polyglycols to acrylonitrile and subsequent catalytic hydrogenation.
  • polyetheramines are accessible by reacting polyethers with phosgene or thionyl chloride and subsequent amination to give the polyetheramine.
  • Polyetheramines are commercially available (for example) 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.
  • Formulas 6 and 7 consist of using an alkanolamine of the formulas 16a) or 16b) instead of the polyetheramines and subsequently subjecting them to an alkoxylation.
  • Alkanolamine used.
  • the reaction temperature is between 50 and 100 ° C (amide formation).
  • the reaction takes place at temperatures above 100 ° C. (imide formation).
  • the oxyalkylation usually takes place at temperatures between 70 and
  • alkylene oxides such as ethylene oxide (EO) and / or propylene oxide (PO).
  • EO ethylene oxide
  • PO propylene oxide
  • alkanolamines examples include: monoethanolamine, diethanolamine, N-methylethanolamine, 3-aminopropanol, isopropanol, diglycolamine, 2-amino-2-methylpropanol and their Mixtures.
  • n-hexylamine for example: n-hexylamine, n-octylamine, n-tetradecylamine, n-hexadecylamine, n-stearylamine or else N, N-dimethylaminopropylenediamine,
  • secondary amines examples include: didecylamine, ditetradecylamine, distearylamine, dicocosfettamine, ditaigfettamine and mixtures thereof.
  • alcohols examples include:
  • Preferred dicarboxylic acid is maleic acid or maleic anhydride.
  • Copolymers of 10 to 90% by weight of C 6 -C 24 - olefins and 90 to 10% by weight of NC 6 -C 22 - are preferred
  • Comb polymers can, for example, by the formula AHH
  • 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 dispersing agents 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 for use in
  • Middle distillates are particularly suitable. 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 containing 350 ppm
  • 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 C atoms, only small amounts 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 be other common
  • Additives such as dewaxing agents, corrosion inhibitors, antioxidants, lubricity additives, sludge inhibitors, cetane number improvers, detergent additives, dehazers, Contain 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-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 ⁇ 4 / Ci 6 - ⁇ -olefin,
  • the boiling data are determined in accordance with ASTM D-86, the CFPP value in accordance with EN 116 and the cloud point in accordance with ISO 3015.
  • Table 4 shows the superior effectiveness of the additives according to the invention together with ethylene copolymers for
  • the paraffin dispersion in middle distillates was determined as follows in the short sediment test: 150 ml of the middle distillates mixed with the additive components given in the table were cooled in 200 ml measuring cylinders in a refrigerator at -2 ° C / hour to -13 ° C and for 16 hours Temperature stored. The volume and appearance of both the sedimented paraffin phase and the oil phase above it were then determined and assessed visually. A small amount of sediment with a homogeneously cloudy oil phase or a large sediment volume with a clear oil phase show good paraffin dispersion. In addition, the lower 20% by volume were isolated and the cloud point determined in accordance with ISO 3015. A slight deviation of the cloud point of the lower phase (CP «s) from the blank value of the oil shows good paraffin dispersion.
  • 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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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

L'invention concerne des distillats moyens présentant une teneur en soufre maximale de 0,05 % en poids. Ces distillats contiennent des esters d'acide gras de polyols alcoxylés présentant au moins 3 groupes OH (A) ainsi qu'au moins un additif améliorant la fluidité à froid (B). Selon la présente invention, cet additif améliorant la fluidité à froid contient au moins un copolymère d'éthylène et d'un ou de plusieurs esters d'acide carboxylique éthyléniquement insaturés, lequel copolymère présente une proportion d'éthylène de 60 à 90 % en moles.
EP02791659A 2001-11-14 2002-11-02 Distillats d'huile minerale a basse teneur en soufre a proprietes a froid ameliorees, contenant un ester d'un polyol alcoxyle et un copolymere d'ethylene et d'esters insatures Expired - Lifetime EP1458837B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10155748A DE10155748B4 (de) 2001-11-14 2001-11-14 Schwefelarme Mineralöldestillate mit verbesserten Kälteeigenschaften, umfassend einen Ester eines alkoxylierten Polyols und ein Copolymer aus Ethylen und ungesättigten Estern
DE10155748 2001-11-14
PCT/EP2002/012233 WO2003042337A2 (fr) 2001-11-14 2002-11-02 Distillats d'huile minerale a basse teneur en soufre a proprietes a froid ameliorees

Publications (2)

Publication Number Publication Date
EP1458837A2 true EP1458837A2 (fr) 2004-09-22
EP1458837B1 EP1458837B1 (fr) 2006-09-13

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EP02791659A Expired - Lifetime EP1458837B1 (fr) 2001-11-14 2002-11-02 Distillats d'huile minerale a basse teneur en soufre a proprietes a froid ameliorees, contenant un ester d'un polyol alcoxyle et un copolymere d'ethylene et d'esters insatures

Country Status (7)

Country Link
US (1) US7347881B2 (fr)
EP (1) EP1458837B1 (fr)
JP (1) JP2005509085A (fr)
KR (1) KR20050042254A (fr)
DE (2) DE10155748B4 (fr)
ES (1) ES2272801T3 (fr)
WO (1) WO2003042337A2 (fr)

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EP1690919B1 (fr) * 2005-02-11 2016-03-02 Infineum International Limited Compositions d'huile combustible
US9051527B2 (en) 2005-02-11 2015-06-09 Infineum International Limited Fuel oil compositions
DE102005061465B4 (de) * 2005-12-22 2008-07-31 Clariant Produkte (Deutschland) Gmbh Detergenzadditive enthaltende Mineralöle mit verbesserter Kältefließfähigkeit
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
DE102007028304A1 (de) * 2007-06-20 2008-12-24 Clariant International Limited Detergenzadditive enthaltende Mineralöle mit verbesserter Kältefließfähigkeit
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DE102007028305A1 (de) * 2007-06-20 2008-12-24 Clariant International Limited Detergenzadditive enthaltende Mineralöle mit verbesserter Kältefließfähigkeit
DE102007028307A1 (de) * 2007-06-20 2008-12-24 Clariant International Limited Detergenzadditive enthaltende Mineralöle mit verbesserter Kältefließfähigkeit
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CA3038772A1 (fr) 2016-09-29 2018-04-05 Ecolab Usa Inc. Inhibiteurs de paraffine, compositions de suppression de paraffine et procedes
GB202111108D0 (en) * 2021-08-02 2021-09-15 Innospec Ltd Compositions, and methods and uses relating thereto

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Also Published As

Publication number Publication date
KR20050042254A (ko) 2005-05-06
US7347881B2 (en) 2008-03-25
DE10155748A1 (de) 2003-05-28
WO2003042337A3 (fr) 2004-02-19
WO2003042337A2 (fr) 2003-05-22
DE10155748B4 (de) 2009-04-23
ES2272801T3 (es) 2007-05-01
DE50208168D1 (de) 2006-10-26
JP2005509085A (ja) 2005-04-07
US20040255511A1 (en) 2004-12-23
EP1458837B1 (fr) 2006-09-13

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