EP1749873B1 - Additifs et leur utilisation pour améliorer la conductivité électrique et l'écoulement à froid de distillats d'huile minérale - Google Patents

Additifs et leur utilisation pour améliorer la conductivité électrique et l'écoulement à froid de distillats d'huile minérale Download PDF

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EP1749873B1
EP1749873B1 EP06013802.1A EP06013802A EP1749873B1 EP 1749873 B1 EP1749873 B1 EP 1749873B1 EP 06013802 A EP06013802 A EP 06013802A EP 1749873 B1 EP1749873 B1 EP 1749873B1
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alkyl
ppm
nitrogen
alkylphenol
esters
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EP1749873A2 (fr
EP1749873A3 (fr
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Matthias Krull
Werner Reimann
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Clariant Produkte Deutschland GmbH
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Clariant Produkte Deutschland GmbH
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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
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • 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
    • C10L1/18—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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • 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
    • 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
    • C10L1/2366—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amine groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • 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
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/20—Function and purpose of a components of a fuel or the composition as a whole for improving conductivity

Definitions

  • the present invention relates to the use of alkylphenol-aldehyde resins and nitrogen-containing polymers for improving the conductivity of low-boiling mineral oil distillates.
  • the content of mineral oil distillates in sulfur-containing compounds and aromatic hydrocarbons must be further reduced as environmental legislation becomes more stringent.
  • the refinery processes used to produce specification-compliant mineral oil grades also remove other polar and aromatic compounds. Often it also reduces the capacity of the oils for water. As a side effect, the electrical conductivity of these mineral oil distillates is greatly reduced. As a result, electrostatic charges, as they occur in particular under high flow rates, for example when pumping in lines and filters in the refinery, in the distribution chain as well as the consumer, can not be compensated.
  • alkylphenol resins and their derivatives which can be prepared by condensation of alkyl-containing phenols with aldehydes under acidic or basic conditions.
  • alkylphenol resins are used as cold flow improvers, lubricity improvers, oxidation inhibitors, corrosion inhibitors, as well as asphalt dispersants and alkoxylated alkylphenol resins as demulsifiers in crude oils and middle distillates.
  • alkylphenol resins are used as stabilizers for jet fuel.
  • Resins of benzoic acid esters with aldehydes or ketones are also used as cold additives for fuel oils.
  • mineral oil additives are polymers which contain structural elements derived from nitrogen-containing monomers and for example can be added to fuel oils to improve various properties such as cold flowability, lubricity and also to improve electrical conductivity.
  • EP-A-1 088 045 discloses that alkylphenol resins can be used together with oil soluble polar nitrogen compounds to improve the cold properties of middle distillates and the lubricity of low sulfur fuel oils.
  • EP-A-1 502 938 discloses fuel oils of improved conductivity comprising mixtures of polymeric esters of acrylic acid, methacrylic acid and fumaric acid which may optionally contain nitrogen-containing comonomers with either a polysulfone and a polymeric reaction product of epichlorohydrin and an aliphatic primary monoamine or N-alkyl-alkylenediamine or alternatively with an oil-soluble copolymer of alkyl vinyl monomer and cationic vinyl monomer. According to paragraphs 17 to 19, these oils may additionally contain antioxidants such as BHT.
  • EP-A-1640438 teaches the use of an additive composition to improve the conductivity of a heating oil.
  • the additive composition comprises a polymeric condensation product formed by the reaction of an aliphatic Aldehyde or ketone or a reactive equivalent with at least one ester of p-hydroxybenzoic acid is formed.
  • EP-A-857 776 teaches a process for improving the flowability of paraffinic mineral oils and mineral oil distillates by adding flow improvers based on ethylene-vinyl ester copolymers and terpolymers, alkylphenol-aldehyde resins and optionally further paraffin dispersants, mixtures of these various flow improvers and mineral oils and mineral oil distillates contain these flow improvers.
  • WO-2003/042336 teaches additives for low sulfur mineral oil distillates comprising an ester of an alkoxylated polyol and a polar nitrogen containing paraffin dispersant.
  • the invention relates to additives for middle distillates with a maximum of 0.05 wt .-% sulfur content, containing at least one fatty acid ester of alkoxylated polyols having at least 3 OH groups (A) and at least one polar nitrogen-containing paraffin dispersant (D).
  • compositions comprising (1) acrylic-ester-acrylonitrile copolymers and (2) polymeric polyamines; and such compositions in combination with organic liquids, such as hydrocarbon liquids, in which such compositions are effective as antistatic agents.
  • EP-A-1 274 819 discloses fuel oils with improved conductivity, the blends of an oil-soluble copolymer of alkyl vinyl monomer and cationic vinyl monomer, a polysulfone and optionally a polyamine or its sulfonic acid salt.
  • EP-A-0 964 052 discloses copolymers of ethylene with nitrogen-containing comonomers as lubricity improvers for low sulfur middle distillates.
  • conductivity improvers contain as active ingredient component metal ions and / or polysulfones.
  • the latter are copolymers of SO 2 and olefins.
  • ash-forming and sulfur-containing additives are in principle undesirable for use in low-sulfur fuels.
  • the effectiveness of oil-soluble nitrogen compounds known as further additive components as conductivity improvers alone is inadequate and, as well as the combinations of these polar oil-soluble nitrogen compounds with alkoxylated alkylphenol resins according to US 4,356,002 with decreasing aromatics and water content of the oils to be added increasingly unsatisfactory.
  • a subsequent addition of water leads in such oils but only to the dispersion of undissolved water in the oil, which does not contribute to improving the electrical conductivity but rather leads to increased corrosion problems and in the cold the risk of ice formation and consequent blockages of delivery lines and filters ,
  • the object of the present invention was thus to find a superior over the prior art in its effectiveness additive for improving the electrical conductivity of mineral oil distillates with low water content, especially low-aromatic mineral oil distillates, which also ensures safe handling of these oils even at low temperatures.
  • the additive should burn ashless and in particular contain no metals. In addition, it should contain neither halides nor sulfur-containing compounds.
  • aromatic mineral oils can be significantly improved in their electrical conductivity by adding small amounts of phenolic resins (component I) and nitrogen-containing polymers (component II).
  • component I phenolic resins
  • component II nitrogen-containing polymers
  • the conductivity is significantly increased by the combination of these two additive components than would be expected from the effect of the individual substances.
  • the conductivity remains constant with decreasing temperature and in many cases even increases with decreasing temperature.
  • the oils thus additized show a greatly increased conductivity and are therefore much safer to handle, especially at low temperatures.
  • the invention thus relates to the use of compositions containing at least one alkylphenol-aldehyde resin, which is a structural element of the formula wherein R 5 is C 1 -C 200 alkyl or C 2 -C 200 alkenyl, OR 6 or OC (O) -R 6 , R 6 is C 1 -C 200 alkyl or C 2 -C 200 alkenyl and n is a number from 2 to 100, containing, based on the alkylphenol-aldehyde resin or the alkylphenol-aldehyde resins 0.1 to 10 parts by weight of at least one nitrogen-containing polymer, to improve the electrical conductivity of mineral oil distillates having a water content of less than 150 ppm, so that the mineral oil distillates have a measured according to DIN 51412-TO2-79 conductivity of at least 50 pS / m.
  • alkylphenol-aldehyde resin which is a structural element of the formula wherein R 5 is C 1 -C 200 alky
  • Another object of the invention is the use of at least one alkylphenol-aldehyde resin (component I), which is a structural element of the formula in which R 5 is C 1 -C 200 -alkyl or C 2 -C 200 -alkenyl, OR 6 or OC (O) -R 6 , R 6 is C 1 -C 200 -alkyl or C 2 -C 200 - Alkenyl and n is a number from 2 to 100, for improving the electrical conductivity of mineral oil distillates having a water content of less than 150 ppm, containing 0.1 to 200 ppm of at least one nitrogen-containing polymer (component II) in an amount such that the mineral oil distillates have a conductivity of at least 50 pS / m measured according to DIN 51412-TO2-79.
  • component I alkylphenol-aldehyde resin
  • alkylphenol-aldehyde resins are understood as meaning all polymers which are accessible by condensation of an alkyl radical-carrying phenol with aldehydes or ketones.
  • the alkyl radical can be bonded directly to the aryl radical of the phenol via a C-C bond or via functional groups such as esters or ethers.
  • the mineral oil distillates contain 0.2 to 100 ppm and especially 0.25 to 25 ppm such as 0.3 to 10 ppm of at least one alkylphenol-aldehyde resin and 0.2 to 50 ppm and especially 0.25 to 25 ppm such as 0, 3 to 20 ppm of at least one nitrogen-containing polymer.
  • the mineral oil distillates particularly preferably contain a total of up to 100 ppm, preferably 0.2 to 70 ppm and especially 0.3 to 50 ppm of the combination of alkylphenol-aldehyde resin or alkylphenol-aldehyde resins and nitrogen-containing polymer or nitrogen-containing polymers.
  • 0.2 to 100 ppm and especially 0.25 to 25 ppm such as 0.3 to 10 ppm of at least one alkylphenol-aldehyde resin to improve the electrical conductivity of mineral oil distillates, 0.2 to 50 ppm and especially 0.25 to 25 ppm, such as 0.3 to 20 ppm of at least one nitrogen-containing polymer.
  • the mass ratio between constituent I and constituent II in the inventive additive for mineral oil distillates is preferably between 50: 1 and 1:50, particularly preferably between 10: 1 and 1:10, for example between 4: 1 and 1: 4.
  • the improved in their electrical conductivity mineral oil distillates have an electrical conductivity of preferably at least 60, in particular at least 75 pS / m.
  • Alkylphenol-aldehyde resins as constituent I are known in principle and, for example in the Rompp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, Volume 4, p 3351 et seq , described.
  • Particularly suitable according to the invention are those alkylphenol-aldehyde resins which are derived from alkylphenols having one or two alkyl radicals in the ortho and / or para position to the OH group.
  • Particularly preferred as starting materials are alkylphenols which carry at least two hydrogen atoms capable of condensation with aldehydes on the aromatic and in particular monoalkylated phenols.
  • the alkyl radical is in the para position to the phenolic OH group.
  • alkyl radicals may be identical or different in the alkylphenol-aldehyde resins that can be used in the process, they may be saturated or unsaturated and have up to 200, preferably 1 to 20, in particular 4-16 such as, for example, 6 to 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, tetradecyl, hexadecyl, octadecyl, tripropenyl, tetrapropenyl, poly (propenyl) - and poly (isobutenyl) radicals.
  • these radicals are saturated.
  • mixtures of alkylphenols having different alkyl radicals are used for the preparation of the alkylphenol resins.
  • resins based on butylphenol on the one hand and octyl-, nonyl- and / or dodecylphenol on the other hand in a molar ratio of 1:10 to 10: 1 have proven particularly useful.
  • Suitable alkylphenol resins may also contain or consist of structural units of other phenol analogs such as salicylic acid, hydroxybenzoic acid and derivatives thereof such as esters, amides and salts.
  • Suitable aldehydes for the alkylphenol-aldehyde resins are those having 1 to 12 carbon atoms and preferably those having 1 to 4 carbon atoms such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2-ethylhexanal, benzaldehyde, glyoxylic acid and their reactive equivalents such as paraformaldehyde and trioxane.
  • the molecular weight of the alkylphenol-aldehyde resins as determined by gel permeation chromatography in THF against poly (ethylene glycol) standards is preferably 400-20,000, in particular 800-10,000 g / mol and especially 2,000-5,000 g / mol.
  • the prerequisite here is that the alkylphenol-aldehyde resins, at least in application-relevant concentrations of 0.001 to 1 wt .-% are oil-soluble.
  • these are alkylphenol-formaldehyde resins, the oligo- or polymers having a repetitive structural unit of the formula wherein R 5 is C 1 -C 200 alkyl or C 2 -C 200 alkenyl, OR 6 or OC (O) -R 6 , R 6 is C 1 -C 200 alkyl or C 2 -C 200 alkenyl and n is a number from 2 to 100.
  • R 6 is preferably C 1 -C 20 -alkyl or C 2 -C 20 -alkenyl and in particular C 4 -C 16 -alkyl or C 2 -C 20 -alkenyl, for example C 6 -C 12 -alkyl or alkenyl.
  • R 5 particularly preferably represents C 1 -C 20 -alkyl or -alkenyl and in particular C 4 -C 16 -alkyl or -alkenyl, for example C 6 -C 12 -alkyl or -alkenyl.
  • n is a number from 2 to 50 and especially a number from 3 to 25, such as a number from 5 to 15.
  • alkylphenol-aldehyde resins having C 2 -C 40 -alkyl radicals of the alkylphenol, preferably having C 4 -C 20 -alkyl radicals such as, for example, C 6 -C 12 -alkyl radicals.
  • the alkyl radicals can be linear or branched, preferably they are linear.
  • Particularly suitable alkylphenol-aldehyde resins are derived from alkylphenols with linear alkyl radicals having 8 and 9 carbon atoms.
  • the average molecular weight determined by GPC is preferably between 700 and 20,000 g / mol, in particular between 1,000 and 10,000 g / mol, for example between 2,000 and 3,500 g / mol.
  • alkylphenol-aldehyde resins whose alkyl radicals carry 4 to 200 carbon atoms, preferably 10 to 180 carbon atoms, and oligomers or polymers of olefins having 2 to 6 carbon atoms, such as .alpha for example, derived from poly (isobutylene). They are thus preferably branched.
  • the degree of polymerization (n) here is preferably between 2 and 20, more preferably between 3 and 10 alkylphenol units.
  • alkylphenol-aldehyde resins are accessible by known methods, for example by condensation of the corresponding alkylphenols with formaldehyde, ie with 0.5 to 1.5 moles, preferably 0.8 to 1.2 moles of formaldehyde per mole of alkylphenol.
  • the condensation can be carried out solvent-free, but preferably it is carried out in the presence of an inert or only partially water-miscible inert organic solvent such as mineral oils, alcohols, ethers and the like. Particularly preferred are solvents which can form azeotropes with water.
  • solvents in particular aromatics such as toluene, xylene diethylbenzene and higher-boiling commercial solvent mixtures such as ®Shellsol AB, and solvent naphtha are used.
  • the condensation is preferably carried out between 70 and 200 ° C such as between 90 and 160 ° C. It is usually catalysed by 0.05 to 5 wt .-% bases or preferably by 0.05 to 5 wt .-% acids.
  • acidic catalysts in addition to carboxylic acids such as acetic acid and oxalic acid in particular strong mineral acids such as hydrochloric acid, phosphoric acid and sulfuric acid and sulfonic acids are common catalysts.
  • Particularly suitable catalysts are sulfonic acids which contain at least one sulfonic acid group and at least one saturated or unsaturated, linear, branched and / or cyclic hydrocarbon radical having 1 to 40 C atoms and preferably having 3 to 24 C atoms.
  • Particularly preferred are aromatic sulfonic acids, especially alkylaromatic mono-sulfonic acids having one or more C 1 -C 28 -alkyl radicals and in particular those having C 3 -C 22 -alkyl radicals.
  • Suitable examples are methanesulfonic acid, butanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, Xylenesulfonic acid, 2-mesitylenesulfonic acid, 4-ethylbenzenesulfonic acid, isopropylbenzenesulfonic acid, 4-butylbenzenesulfonic acid, 4-octylbenzenesulfonic acid; Dodecylbenzenesulfonic acid, didodecylbenzenesulfonic acid, naphthalenesulfonic acid. Mixtures of these sulfonic acids are suitable. Usually, these remain after completion of the reaction as such or in neutralized form in the product; Metal ions containing and thus ash-forming salts are usually separated.
  • suitable comb polymers are derived in particular from oil-soluble esters of ethylenically unsaturated carboxylic acids, oil-soluble vinyl esters and / or oil-soluble vinyl ethers, which carry a C 4 - to C 40 -alkyl radical.
  • Particularly suitable polymers are poly (acrylates), poly (methacrylates), poly (maleate) and poly (fumarates), which are esters of acrylic, methacrylic, maleic and / or fumaric acid with C 4 -C 40 alcohols and in particular with C 6 - to derive C 22 alcohols.
  • the alkyl radicals are preferably linear or branched, they are preferably saturated.
  • n-butyl acrylate 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate and the like.
  • Suitable comb polymers IIa is derived from olefins having 6 to 42 carbon atoms.
  • the olefins are linear.
  • the double bond is preferably terminal such as, for example, 1-decane, 1-dodecane, 1-tetradecane, 1-hexadecane.
  • mixtures of different olefins in the chain length range C 20 -C 24 , C 22 -C 28 and C 24 -C 30 are also preferred.
  • the comb polymers IIa) contain at least one nitrogen-containing comonomer whose nitrogen is preferably present in the form of an amino, amido, imido or ammonium group and is bonded to the polymer backbone via a hydrocarbon radical. They are preferably amino or ammonium groups which are bonded to the polymer backbone via a C 2 -C 12 -alkylene radical, which may optionally be interrupted by ester or amide groups. Ammonium groups preferably include salts of primary, secondary and tertiary amines with mineral acids, organic sulfonic acids and preferably with carboxylic acids. Also comonomers carrying quaternary ammonium groups are suitable.
  • Suitable comonomers are polymerizable unsaturated basic amines such as allylamine and diallylamine, amino-bearing olefins such as p- (2-diethylaminoethyl) styrene, nitrogen-containing heterocycles having exocyclic double bond such as vinylpyridine and vinylpyrrolidone, esters of ethylenically unsaturated carboxylic acids with amino alcohols such as N, N- (dimethylamino ) ethyl acrylate, N, N- (dimethylamino) ethyl methacrylate or N, N- (dimethylamino) propyl methacrylate, amides of diamines with ethylenically unsaturated carboxylic acids such as N, N- (dimethylamino) propylmethacrylamide, N- (aminopropyl) morpholine and their quaternized derivatives such as N , N, N
  • nitrile-bearing monomers such as acrylonitrile and methacrylonitrile.
  • the molar ratio between the esters of ethylenically unsaturated carboxylic acids, vinyl esters, vinyl ethers and / or olefins on the one hand and the nitrogen-containing comonomers on the other hand is preferably between 20: 1 and 1: 1, for example between 10: 1 and 3: 1.
  • these copolymers have a nitrogen content of 0.3 to 5 wt .-%, such as 0.5 to 3 wt .-%.
  • the comb polymers IIa can also be up to 20 mol% such as 1 to 10 mol% of other comonomers such as ⁇ -olefins having 4 to 40 carbon atoms, acrylamide, methacrylamide, C 1 -C 20 alkylacrylamide and / or C 1 - C 20 alkyl methacrylamide included.
  • other comonomers such as ⁇ -olefins having 4 to 40 carbon atoms, acrylamide, methacrylamide, C 1 -C 20 alkylacrylamide and / or C 1 - C 20 alkyl methacrylamide included.
  • the comb polymers preferably have molecular weights (Mn) of from 1,000 to 100,000 g / mol, preferably from 5,000 to 50,000 g / mol, by means of gel permeation chromatography in THF against poly (styrene) standards.
  • the comb polymers IIa) are preferably prepared by direct copolymerization of the comonomers. Alternatively, however, they can also be obtained by polymer-analogous reaction of copolymers of esters of ethylenically unsaturated carboxylic acids, vinyl esters, vinyl ethers and / or olefins carrying a C 1 - to C 40 -alkyl radical and ethylenically unsaturated carboxylic acids or reactive derivatives thereof such as anhydrides, acid halides or esters lower alcohols having 1 to 4 carbon atoms with hydroxyamines or polyamines.
  • Suitable hydroxyamines are, for example, N, N-dimethylaminoethanol and N-coconut fatty alkylaminoethanol.
  • Suitable polyamines are, for example, N, N-dimethylaminopropylamine N-coconut fatty alkylpropylenediamine and N-tallow fatty alkylpropylenediamine.
  • a further preparation variant is the grafting of the nitrogen-containing comonomers onto polymers of esters of ethylenically unsaturated carboxylic acids, vinyl esters, vinyl ethers and / or olefins which carry a C 1 - to C 40 -alkyl radical.
  • Quaternary ammonium group-bearing polymers can be prepared by copolymerization of the polymerizable quaternary ammonium compound or by polymer-analogous reaction of an amino group-bearing polymer with alkylating agents such as alkyl halides or sulfuric acid esters. Particularly preferred are halogen-free alkylating agents such as dimethyl sulfate.
  • nitrogen-containing polymers IIa are copolymers of N, N, N, - (trimethylammonium) ethyl methacrylate methosulfate and 2-ethylhexyl acrylate, copolymers of dodecyl methacrylate and dimethylaminopropylmethacrylamide and alternating copolymers of tetradecene and acrylonitrile.
  • Preferred copolymers IIb) contain, in addition to ethylene, from 0.1 to 15, in particular from 1 to 10, mol% of one or more of the nitrogen-containing comonomers. In addition, they may contain further, for example, one, two or three further ethylenically unsaturated comonomers. Suitable further comonomers are, for example Vinyl esters, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, vinyl ethers and olefins.
  • Particularly preferred vinyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl octanoate, vinyl 2-ethylhexanoate, vinyl laurate and vinyl esters of neocarboxylic acids having 8, 9, 10, 11 or 12 C atoms.
  • Particularly preferred acrylic and methacrylic acid esters are derived from alcohols having 1 to 20 C atoms, in particular having 1 to 4 C atoms, such as methanol, ethanol and propanol.
  • Particularly preferred olefins are those having 3 to 10 C atoms, especially propene, butene, isobutylene, diisobutylene, 4-methylpentene, hexene and norbornene. If the copolymers IIb) contain a further comonomer, its molar fraction is preferably up to 15 mol%, in particular from 1 to 12 mol%, for example from 2 to 10 mol%.
  • the melt viscosity of these copolymers is preferably below 10,000 mPas, in particular between 10 and 1,000 mPas, for example between 20 and 500 mPas.
  • the copolymerization of the comonomers takes place by known processes (cf. Ullmanns Encyclopadie der Technischen Chemie, 4th Edition, Vol. 19, pages 169 to 178 ).
  • the polymerization in solution, in suspension, in the gas phase and the high-pressure mass polymerization are suitable.
  • Preference is given to the high-pressure mass polymerization which at pressures of 50 to 400 MPa, preferably 100 to 300 MPa and temperatures of 50 to 350 ° C, preferably 100 to 300 ° C, is performed.
  • the reaction of the comonomers is initiated by free radical initiators (free radical 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) peroxydicarbonate, t-butyl permalate, t-butyl perbenzoate, dicumyl peroxide, t-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 wt .-%, preferably 0.05 to 10 wt .-%, based on the comonomer mixture.
  • the desired melt viscosity and thus the molecular weight of the copolymers is adjusted for a given composition of the comonomer mixture by varying the reaction parameters pressure and temperature and optionally by adding moderators.
  • moderators have hydrogen, saturated or unsaturated hydrocarbons, e.g. Propane, propene, aldehydes, e.g. Propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones, e.g. Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or alcohols, e.g. Butanol, proven.
  • the moderators are used in amounts of up to 20% by weight, preferably 0.05 to 10% by weight, based on the comonomer mixture.
  • the high-pressure mass polymerization is carried out batchwise or continuously in known high-pressure reactors, for example autoclaves or tubular reactors, tube reactors have proven particularly useful. Solvents such as aliphatic hydrocarbons or hydrocarbon mixtures, benzene or toluene may be included in the reaction mixture, although the solvent-free procedure has proven particularly useful.
  • the comonomer streams can be composed differently ( EP-B-0 271 738 and EP-A-0 922 716 ).
  • Copolymers IIb) which are likewise suitable according to the invention can be prepared by reacting ethylene copolymers which contain acid groups with compounds carrying amino groups.
  • Ethylene copolymers and ethylene terpolymers suitable for this purpose are, for example, those which comprise acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid or maleic anhydride.
  • these acid group-containing copolymers are present via the acid groups with alkanolamines such as ethanolamine, propanolamine, diethanolamine, N-ethylethanolamine, N, N-dimethylethanolamine, diglycolamine, 2-amino-2-methylpropanolamine and / or polyamines such as ethylenediamine and dimethylaminopropylamine and / or N-alkylalkylenepolyamines such as N-coconut fatty alkylpropylenediamine or the like Implemented ammonium-carrying compounds or mixtures thereof. From 0.1 to 1.2 moles, preferably equimolar amounts, of amine per mole of acid are used.
  • Both nitrogen-containing ethylene copolymers prepared by direct polymerization and by polymer-analogous reaction can be converted into quaternary ammonium salts by reaction with alkylating agents such as alkyl halides or sulfuric acid esters. Particularly preferred are halogen-free alkylating agents such as dimethyl sulfate.
  • the polymeric polyamines suitable as component IIc) according to the invention are in particular polyamines having 4 or more, preferably 6 or more, for example 8 or more nitrogen atoms in the molecule.
  • the nitrogen atoms are part of the main chain.
  • the polymer backbone preferably carries alkyl side chains of 8 or more carbon atoms.
  • the polymeric polyamines are preferably condensation products of amines and epichlorohydrin or glycidol in a molar ratio of 1: 1 to 1: 1.5. Preference is given to polymers based on primary monoamines, in particular alkylamines, and on the basis of N-alkyl-alkylenediamines whose alkyl radicals have 8 to 24 and in particular 8 to 12 C atoms and whose alkylene radical has 2 to 6 C atoms, for example N-alkyl -1,3-propylenediamine.
  • the alkyl radicals are preferably linear.
  • the condensation products IIc) preferably have degrees of polymerization of 2 to 20.
  • the nitrogen-containing polymers IIa), IIb) as well as IIc), in which the nitrogen is present as a basic amino group, are preferably used as salts and in particular as sulfonic acid salts.
  • Preferred sulfonic acids for salt formation are oil-soluble sulfonic acids such as alkanesulfonic acids, arylsulfonic acids and alkylarylsulfonic acids such as dodecylbenzenesulfonic acid.
  • compositions according to the invention are preferably used as concentrates which contain from 10 to 90% by weight and preferably from 20 to 60% by weight of solvent.
  • Preferred solvents are higher-boiling aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, esters, ethers and mixtures thereof.
  • the mixing ratio between the alkylphenol-aldehyde resins of the invention as component I and nitrogen compounds as component II may vary depending on the application.
  • Such concentrates preferably contain from 0.1 to 10 parts by weight, preferably from 0.2 to 6 parts by weight, of the polar, oil-soluble nitrogen compound per part by weight of alkylphenol-aldehyde resin.
  • the additives according to the invention can also be used in combination with polysulfones.
  • Suitable polysulfones are accessible by copolymerization of sulfur dioxide with 1-olefins having 6 to 20 carbon atoms such as 1-dodecene. They have molecular weights of from 10,000 to 1,500,000, preferably from 50,000 to 900,000 and more preferably from 100,000 to 500,000, measured by GPC against poly (styrene) standards.
  • the preparation of suitable polysulfones is for example US 3,917,466 known.
  • the additives according to the invention may also be added to mineral oil distillates for improving cold flowability in combination with other additives such as, for example, ethylene copolymers, paraffin dispersants, comb polymers, polyoxyalkylene compounds and / or olefin copolymers.
  • the additives according to the invention for mineral oil distillates contain in a preferred embodiment, in addition to the constituents I and II, one or more of the constituents III to VII.
  • ethylene copolymers are, in particular, those which, in addition to ethylene, contain 6 to 21 mol%, in particular 10 to 18 mol%, of comonomers.
  • the olefinically unsaturated compounds are preferably vinyl esters, acrylic esters, methacrylic esters, alkyl vinyl ethers and / or alkenes, where the mentioned compounds may be substituted with hydroxyl groups.
  • One or more comonomers may be included in the polymer.
  • said alkyl groups may be substituted with one or more hydroxyl groups.
  • R 1 is a branched alkyl radical or a neoalkyl radical having 7 to 11 carbon atoms, in particular having 8, 9 or 10 carbon atoms.
  • Particularly preferred vinyl esters are derived from secondary and especially tertiary carboxylic acids whose branching is in the alpha position to the carbonyl group.
  • Suitable vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl hexanoate, vinyl heptanoate, vinyl octanoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate and versatic acid esters such as vinyl neononanoate, vinyl neodecanoate, vinyl neoundecanoate.
  • these ethylene copolymers contain vinyl acetate and at least one further vinyl ester of the formula 1 in which R 1 is C 4 to C 30 -alkyl, preferably C 4 to C 16 -alkyl, especially C 6 - to C 12 -alkyl ,
  • Suitable acrylic esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n- and isobutyl (meth) acrylate, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl , Hexadecyl, octadecyl (meth) acrylate and mixtures of these comonomers.
  • An example of such an acrylic ester is hydroxyethyl methacrylate.
  • the alkenes are preferably simple unsaturated hydrocarbons having 3 to 30 carbon atoms, especially 4 to 16 carbon atoms and especially 5 to 12 carbon atoms.
  • Suitable alkenes include propene, butene, isobutylene, pentene, hexene, 4-methylpentene, octene, diisobutylene and norbornene and its derivatives such as methylnorbornene and vinylnorbornene.
  • said alkyl groups may be substituted with one or more hydroxyl groups.
  • terpolymers which, apart from ethylene, have from 3.5 to 20 mol%, in particular from 8 to 15 mol% of vinyl acetate and from 0.1 to 12 mol%, in particular from 0.2 to 5 mol%, of at least one longer-chain and preferably branched one Vinyl esters such as vinyl 2-ethylhexanoate, vinyl neononanoate or vinyl neodecanoate, the total comonomer content being between 8 and 21 mol%, preferably between 12 and 18 mol%.
  • copolymers contain, in addition to ethylene and 8 to 18 mol% of vinyl esters, 0.5 to 10 mol% of olefins such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene and / or norbornene.
  • olefins such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene and / or norbornene.
  • These ethylene copolymers and terpolymers preferably have melt viscosities at 140 ° C. of from 20 to 10,000 mPas, in particular from 30 to 5,000 mPas, especially from 50 to 2,000 mPas.
  • the means of 1 H-NMR spectroscopy, certain degrees of branching are preferably between 1 and 9 CH 3/100 CH 2 groups, especially between 2 and 6 CH 3/100 CH 2 groups, which do not stem from the comonomers.
  • the polymers underlying the mixtures differ in at least one characteristic.
  • they may contain different comonomers, have different comonomer contents, molecular weights and / or degrees of branching.
  • the mixing ratio between the additives according to the invention and ethylene copolymers as constituent III can vary within wide limits depending on the application, with the ethylene copolymers III often representing the greater proportion.
  • Such additive mixtures preferably contain from 2 to 70% by weight, preferably from 5 to 50% by weight, of the inventive additive combination of I and II and from 30 to 98% by weight, preferably from 50 to 95% by weight, of ethylene copolymers.
  • paraffin dispersants which are suitable as further component according to the invention are preferably reaction products of fatty amines with compounds which contain at least one acyl group.
  • the preferred amines are compounds of the formula NR 6 R 7 R 8 , in which R 6 , R 7 and R 8 may be identical or different, and at least one of these groups is C 8 -C 36 -alkyl, C 6 - C 36 -cycloalkyl, C 8 -C 36 -alkenyl, in particular C 12 -C 24 -alkyl, C 12 -C 24 -alkenyl or cyclohexyl, and the other groups are either hydrogen, C 1 -C 36 -alkyl, C 2 -C 36 alkenyl, cyclohexyl, or a group of the formulas - (AO) x -E or - (CH 2 ) n -NYZ, where A is an ethyl or propyl group, x is
  • the alkyl and alkenyl radicals can be linear or branched and contain up to two double bonds. They are preferably linear and substantially saturated, ie they have iodine numbers of less than 75 gl 2 / g, preferably less than 60 gl 2 / g and in particular between 1 and 10 gl 2 / g. Particularly preferred are secondary fatty amines in which two of the groups R 6 , R 7 and R 8 are C 8 -C 36 -alkyl, C 6 -C 36 -cycloalkyl, C 8 -C 36 -alkenyl, in particular C 12 -C 24 alkyl, C 12 -C 24 alkenyl or cyclohexyl.
  • Suitable fatty amines are, for example, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, behenylamine, didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine, dioctadecylamine, dieicosylamine, dibehenylamine as well as their mixtures.
  • the amines contain chain cuts based on natural raw materials such as coco fatty amine, tallow fatty amine, hydrogenated tallow fatty amine, dicocosfettamine, ditallow fatty amine and di (hydrogenated tallow fatty amine).
  • Particularly preferred amine derivatives are amine salts, imides and / or amides such as, for example, amide ammonium salts of secondary fatty amines, in particular dicocosfettamine, ditallow fatty amine and distearylamine.
  • Particularly preferred paraffin dispersants as constituent II comprise at least one acyl group converted to an ammonium salt. Specifically, they contain at least two, for example at least three or at least four and in the case of polymeric paraffin dispersants also five or more ammonium groups.
  • Suitable carbonyl compounds for the reaction with amines are both monomeric and polymeric compounds having one or more carboxyl groups. In the case of the monomeric carbonyl compounds, preference is given to those having 2, 3 or 4 carbonyl groups. They can also contain heteroatoms such as oxygen, sulfur and nitrogen.
  • carboxylic acids examples include maleic, fumaric, crotonic, itaconic, succinic, C 1 -C 40 -alkenylsuccinic, adipic, glutaric, sebacic, and malonic acids and benzoic, phthalic, trimellitic and pyromellitic acid, nitrilotriacetic acid , Ethylenediaminetetraacetic acid and their reactive derivatives such as esters, anhydrides and acid halides.
  • Copolymers of ethylenically unsaturated acids such as, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, have proven particularly suitable as polymeric carbonyl compounds, particular preference is given to copolymers of maleic anhydride.
  • Suitable comonomers are those which impart oil solubility to the copolymer. Oil-soluble means here that the copolymer dissolves without residue in the mineral oil distillate to be added after reaction with the fatty amine in practice-relevant metering rates.
  • Suitable comonomers are, for example, olefins, alkyl esters of acrylic acid and methacrylic acid, alkyl vinyl esters and alkyl vinyl ethers having 2 to 75, preferably 4 to 40 and in particular 8 to 20 carbon atoms in the alkyl radical.
  • the carbon number refers to the bonded to the double bond alkyl radical.
  • Particularly suitable comonomers are olefins with a terminal double bond.
  • the molecular weights of the polymeric carbonyl compounds are preferably between 400 and 20,000, more preferably between 500 and 10,000, for example between 1,000 and 5,000.
  • Paraffin dispersants which have been obtained by reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides have proven particularly suitable (cf. US 4 211 534 ).
  • amides and ammonium salts of aminoalkylene polycarboxylic acids such as nitrilotriacetic acid or ethylenediaminetetraacetic acid with secondary amines are suitable as paraffin dispersants (cf. EP 0 398 101 ).
  • paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds, which can optionally be reacted with primary monoalkylamines and / or aliphatic alcohols (cf. EP-A-0 154 177 . EP 0 777 712 ), the reaction products of Alkenylspirobislactonen with amines (see. EP-A-0 413 279 B1) and after EP-A-0 606 055 A2 reaction products of terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic acid anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols.
  • the mixing ratio between the additives according to the invention and paraffin dispersants as constituent IV may vary depending on the application.
  • Such additive mixtures preferably contain from 10 to 90% by weight, preferably from 20 to 80% by weight, of the inventive additive combination of I and II and from 10 to 90% by weight, preferably from 20 to 80% by weight, of paraffin dispersant.
  • Suitable comb polymers are, for example, copolymers of ethylenically unsaturated dicarboxylic acids such as maleic or fumaric acid with other ethylenically unsaturated monomers such as olefins or vinyl esters such as vinyl acetate.
  • Particularly suitable olefins are ⁇ -olefins having 10 to 24 carbon atoms such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and mixtures thereof.
  • olefins based on oligomerized C 2 -C 6 -olefins such as poly (isobutylene) with a high proportion of terminal double bonds are suitable as comonomers.
  • these copolymers are at least 50% esterified with alcohols having 10 to 22 carbon atoms.
  • Suitable alcohols include n-decen-1-ol, n-dodecan-1-ol, n-tetradecan-1-ol, n-hexadecan-1-ol, n-octadecan-1-ol, n-eicosan-1-ol and their mixtures.
  • comb polymers are poly (alkyl acrylates), poly (alkyl methacrylates) and poly (alkyl vinyl ethers) derived from alcohols having 12 to 20 carbon atoms and poly (vinyl esters) derived from fatty acids having 12 to 20 carbon atoms ,
  • Suitable polyoxyalkylene compounds are esters, ethers and ethers / esters of polyols which carry at least one alkyl radical having 12 to 30 carbon atoms.
  • the alkyl groups are derived from an acid, the remainder is derived from a polyhydric alcohol; If the alkyl radicals come from a fatty alcohol, the remainder of the compound derives from a polyacid.
  • Suitable polyols are polyethylene glycols, polypropylene glycols, polybutylene glycols and their copolymers having a molecular weight of about 100 to about 5000, preferably 200 to 2000.
  • alkoxylates of polyols such as glycerol, trimethylolpropane, pentaerythritol, neopentyl glycol, as well as the thereof Condensation accessible oligomers having 2 to 10 monomer units, such as Polyglycerol.
  • Preferred alkoxylates are those having from 1 to 100, in particular from 5 to 50, mol of ethylene oxide, propylene oxide and / or butylene oxide per mole of polyol. Esters are especially preferred.
  • Fatty acids containing 12 to 26 carbon atoms are preferred for reaction with the polyols to form the ester additives, more preferably C 18 to C 24 fatty acids, especially stearic and behenic acid.
  • the esters can also be prepared by esterification of polyoxyalkylated alcohols. Preference is given to completely esterified polyoxyalkylated polyols having molecular weights of from 150 to 2,000, preferably from 200 to 600. Particularly suitable are PEG-600 dibehenate and glycerol-ethylene glycol tribehenate.
  • Suitable olefin copolymers as further constituent of the additive according to the invention can be derived directly from monoethylenically unsaturated monomers or can be prepared indirectly by hydrogenation of polymers derived from polyunsaturated monomers such as isoprene or butadiene.
  • preferred copolymers contain structural units which are derived from ⁇ -olefins having 3 to 24 carbon atoms and have molecular weights of up to 120,000 g / mol.
  • Preferred ⁇ -olefins are propylene, butene, isobutene, n-hexene, isohexene, n-octene, isooctene, n-decene, isodecene.
  • the comonomer content of ⁇ -olefins having 3 to 24 C atoms is preferably between 15 and 50 mol%, more preferably between 20 and 35 mol% and especially between 30 and 45 mol%. These copolymers may also contain minor amounts, eg, up to 10 mol% of other comonomers such as non-terminal olefins or non-conjugated olefins.
  • Preferred are ethylene-propylene copolymers.
  • the olefin copolymers can be prepared by known methods, for example by Ziegler or metallocene catalysts.
  • olefin copolymers are block copolymers containing blocks of olefinically unsaturated aromatic monomers A and blocks of hydrogenated polyolefins B.
  • Particularly suitable are block copolymers of the structure (AB) n A and (AB) m , where n is a number between 1 and 10 and m is a number between 2 and 10.
  • the mixing ratio between the inventive additive combinations of I and II and the further constituents V, VI and VII is generally in each case between 1:10 and 10: 1, preferably between 1: 5 and 5: 1.
  • the additives can be used alone or together with other additives, e.g. with other pour point depressants or dewaxing aids, with antioxidants, cetane number improvers, dehazers, demulsifiers, detergents, dispersants, defoamers, dyes, corrosion inhibitors, lubricity additives, sludge inhibitors, odorants and / or cloud point depressants.
  • other pour point depressants or dewaxing aids with antioxidants, cetane number improvers, dehazers, demulsifiers, detergents, dispersants, defoamers, dyes, corrosion inhibitors, lubricity additives, sludge inhibitors, odorants and / or cloud point depressants.
  • the additives of the invention increase the conductivity of mineral oil distillates such as gasoline, kerosene, jet fuel, diesel and heating oil, in particular in oils with low aromatic content of less than 21 wt .-%, in particular less than 19 wt .-%, especially less than 18 Wt .-% such as less than 17 wt .-% are beneficial. Since they also improve the cold flow properties, especially of mineral oil distillates such as kerosene, jet fuel, diesel and heating oil, their use can be achieved a significant saving in the total additives of the oils, since no additional conductivity improvers must be used.
  • the additives of the invention can be set in areas or at times, in which due to the climatic conditions so far no cold additives were used by admixing paraffin-rich, cheaper mineral oil fractions such as cloud point and / or CFPP of the oils to be upgraded to higher, which the economy of the refinery improved.
  • the additives of the invention also contain no metals that could lead to ash during combustion and thus deposits in the combustion chamber or exhaust system and particle pollution of the environment.
  • the conductivity of the oils according to the invention does not drop when the temperature drops, and in many cases even a rise in conductivity not known from additives of the prior art has been observed with decreasing temperature, so that safe handling is ensured even at low ambient temperatures.
  • Another advantage of the additives of the invention is the preservation of the electrical conductivity even during prolonged, that is several weeks storage of the additized oils.
  • the additives according to the invention are particularly advantageous in mineral oil distillates which contain less than 350 ppm of sulfur, more preferably less than 100 ppm of sulfur, in particular less than 50 ppm of sulfur and in special cases less than 10 ppm of sulfur.
  • the water content of such oils is below 150 ppm, sometimes below 100 ppm, such as below 80 ppm.
  • the electrical conductivity of such oils is usually below 10 pS / m and often even below 5 pS / m.
  • Particularly preferred mineral oil distillates are middle distillates.
  • the middle distillate is in particular those mineral oils which are obtained by distillation of crude oil and boil in the range of 120 to 450 ° C, for example kerosene, jet fuel, diesel and fuel oil.
  • Their preferred sulfur, aromatics and water contents are as already stated above.
  • the compositions according to the invention are particularly advantageous in middle distillates which have 90% distillation points below 360 ° C., in particular 350 ° C. and in special cases below 340 ° C.
  • aromatic compounds is meant the sum of mono-, di- and polycyclic aromatic compounds as determinable by HPLC according to DIN EN 12916 (2001 edition).
  • the middle distillates may also contain minor amounts, such as up to 40% by volume, preferably 1 to 20 vol .-%, especially 2 to 15 such as 3 to 10 vol .-% of the oils of animal and / or vegetable origin described in more detail below, such as fatty acid methyl esters.
  • the additives of the invention are also useful for improving the electrostatic properties of turbine fuels. These are fuels boiling in the temperature range of about 65 ° C to about 330 ° C and marketed, for example, under the designations JP-4, JP-5, JP-7, JP-8, Jet A and Jet A-1. JP-4 and JP-5 are specified in US Military Specification MIL-T-5624-N and JP-8 in US Military Specification MIL-T-83133-D; Jet A, Jet A-1 and Jet B are specified in the ASTM D1655.
  • Table 1 Characterization of the test oils: Oils from European refineries were used as test oils. The CFPP value is determined in accordance with EN 116 and the determination of the cloud point in accordance with ISO 3015. The determination of the aromatic hydrocarbon groups is carried out in accordance with DIN EN 12916 (November 2001 edition) Test oil 1 Test oil 2 Test Oil 3 (Cf.) distillation IBP [° C] 212 188 160 20% [° C] 244 249 229 90% [° C] 322 336 339 FBP [° C] 342 361 371 Cloud Point [° C] -8.8 -12.5 4.6 Density @ 15 ° C [g / cm 3 ] .8302 .8264 .8410 Water content @ 20 ° C [Ppm] 25 35 185 sulfur content [Ppm] 4 6 173 elec.
  • Dosing rate additive A Dosing rate additive B Conductivity [pS / m] @ 25 ° C @ 10 ° C 32 (Cf.) 25 ppm A1 - - 1 0 33 (Cf.) 10 ppm A2 - - 2 0 34 (Cf.) 25 ppm A2 - - 4 2 35 25 ppm A4 - - 5 3 36 (See) 25 ppm A6 - - 2 1 37 (Cf.) - - 10 ppm B1 5 3 38 (Cf.) - - 20 ppm B1 12 10 39 (Cf.) - - 10 ppm B2 4 2 40 (Cf.) - - 20 ppm B2 8th 7 41 (Cf.) - - 20 ppm B3 14 12 42 (Cf.) - - 20 ppm B4 16 13 43 8 ppm A1 8 ppm B1 94 106 44 8 ppm A1 8 ppm
  • compositions according to the invention have a pronounced synergistic effect on the individual components. Moreover, they show that the compositions according to the invention increase the electrical conductivity, in particular of aromatics-poor fuel oils with a low water content, more than the known additives of the prior art.
  • the conductivity of the inventive mineral oil distillates increases with decreasing temperature.
  • the additives used also improve other properties of middle distillates, such as, for example, paraffin dispersion and lubricity, a comparable conductivity can be achieved with lower additive dosing with conventional additives.
  • Another advantage of the invention is that with the additives of the invention in addition to the improvement of the conductivity at the same time the cold properties are improved, which allows the manufacturer of the fuel oil to process a higher proportion of paraffin-rich, cold problematic distillation cuts.

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Claims (15)

  1. Utilisation de compositions, qui contiennent au moins une résine d'alkylphénol-aldéhyde, la résine d'alkylphénol-aldéhyde comprenant une unité structurale de répétition de formule
    Figure imgb0014
     dans laquelle R5 représente alkyle en C1-C200 ou alcényle en C2-C200, O-R6 ou O-C(O)-R6, R6 représente alkyle en C1-C200 ou alcényle en C2-C200, et n représente un nombre de 2 à 100, et, par rapport à la résine d'alkylphénol-aldéhyde, 0,1 à 10 parties en poids d'au moins un polymère contenant de l'azote, pour améliorer la conductivité de distillats d'huiles minérales ayant une teneur en eau inférieure à 150 ppm, de sorte que les distillats d'huiles minérales présentent une conductivité mesurée selon DIN 51412-TO2-79 d'au moins 50 pS/m.
  2. Utilisation d'au moins une résine d'alkylphénol-aldéhyde, la résine d'alkylphénol-aldéhyde comprenant une unité structurale de répétition de formule
    Figure imgb0015
     dans laquelle R5 représente alkyle en C1-C200 ou alcényle en C2-C200, O-R6 ou C)-C(O)-R6, R6 représente alkyle en C1-C200 ou alcényle en C2-C200, et n représente un nombre de 2 à 100, pour améliorer la conductivité électrique de distillats d'huiles minérales ayant une teneur en eau inférieure à 150 ppm, qui contiennent 0,1 à 200 ppm d'au moins un polymère contenant de l'azote, en une quantité telle que les distillats d'huiles minérales présentent une conductivité mesurée selon DIN 51412-TO2-79 d'au moins 50 pS/m.
  3. Utilisation selon la revendication 1 et/ou 2, dans laquelle le groupe alkyle de la résine d'alkylphénol-aldéhyde comprend 2 à 40 atomes de carbone.
  4. Utilisation selon une ou plusieurs des revendications 1 à 3, dans laquelle le poids moléculaire de la résine d'alkylphénol-aldéhyde est de 400 à 20 000 g/mol.
  5. Utilisation selon une ou plusieurs des revendications 1 à 4, dans laquelle les polymères contenant de l'azote sont choisis parmi :
    a) les polymères en peigne, contenant des unités dérivées de monomères comprenant un radical alkyle en C4 à C40 et d'au moins un comonomère contenant de l'azote,
    b) les copolymères d'éthylène avec des comonomères éthyléniquement insaturés contenant de l'azote, et
    c) les polyamines polymères, fabriquées par condensation d'une monoamine primaire aliphatique ou d'une N-alkyl-alkylène-diamine avec de l'épichlorhydrine ou du glycidol.
  6. Utilisation selon la revendication 5, dans laquelle les polymères contenant de l'azote sont dérivés d'esters solubles dans les huiles d'acides carboxyliques éthyléniquement insaturés, d'esters de vinyle solubles dans les huiles et/ou d'éthers de vinyle solubles dans les huiles, qui portent un radical alkyle en C1 à C40.
  7. Utilisation selon la revendication 5, dans laquelle les polymères contenant de l'azote contiennent en plus de l'éthylène 0,1 à 15 % en moles de comonomères contenant de l'azote choisis parmi :
    i) les aminoacrylates ou -méthacrylates d'alkyle,
    ii) les alkylacrylamides et -méthacrylamides,
    iii) les vinylamides,
    iv) les éthers d'aminoalkyle et de vinyle,
    v) les amines éthyléniquement insaturées et/ou
    vi) les hétérocycles portant un groupe vinyle.
  8. Utilisation selon la revendication 5, dans laquelle les polymères contenant de l'azote sont des produits de condensation d'alkylamines primaires ou de N-alkyl-alkylène-diamines, dont les radicaux alkyle comprennent 8 à 24 et dont le radical alkylène comprend 2 à 6 atomes C, et d'épichlorhydrine ou de glycidol en un rapport molaire de 1:1 à 1:1,5 avec des degrés de condensation de 2 à 20.
  9. Utilisation selon une ou plusieurs des revendications 1 à 8, dans laquelle des copolymères d'éthylène et de 6 à 21 % en moles d'esters vinyliques, d'esters acryliques, d'esters méthacryliques, d'éthers alkylvinyliques et/ou d'alcènes sont en outre contenus.
  10. Utilisation selon une ou plusieurs des revendications 1 à 9, dans laquelle des polymères en peigne de formule
    Figure imgb0016
     sont en outre contenus,
    A signifiant R', COOR', OCOR', R"-COOR', OR' ;
    D signifiant H, CH3, A ou R" ;
    E signifiant H, A ;
    G signifiant H, R", R"-COOR', un radical aryle ou un radical hétérocyclique ;
    M signifiant H, COOR", OCOR", OR", COOH ;
    N signifiant H, R", COOR", OCOR", un radical aryle ;
    R' signifiant une chaîne hydrocarbonée de 8 à 50 atomes de carbone ;
    R" signifiant une chaîne hydrocarbonée de 1 à 10 atomes de carbone ;
    m signifiant un nombre compris entre 0,4 et 1,0 ; et
    n signifiant un nombre compris entre 0 et 0,6.
  11. Utilisation selon une ou plusieurs des revendications 1 à 10, dans laquelle des composés de polyoxyalkylène sont en outre contenus, qui sont des esters, des éthers et des éthers/esters, qui portent au moins un radical alkyle de 12 à 30 atomes C.
  12. Utilisation selon une ou plusieurs des revendications 1 à 11, dans laquelle des copolymères sont en outre contenus, qui contiennent en plus d'unités structurales d'éthylène des unités structurales qui sont dérivées d'α-oléfines de 3 à 24 atomes C, et qui présentent des poids moléculaires de jusqu'à 120 000 g/mol.
  13. Utilisation selon une ou plusieurs des revendications 1 à 12, dans laquelle des polysulfones sont en outre contenues, qui sont dérivées d'oléfines de 6 à 20 atomes C.
  14. Utilisation selon une ou plusieurs des revendications 1 à 13, dans laquelle des dispersants de paraffines sont en outre contenus, qui sont des produits de réaction d'amines grasses avec des composés qui contiennent au moins un groupe acyle, les amines grasses étant des composés de formule NR6R7R8, R6, R7 et R8 pouvant être identiques ou différents, et au moins un de ces groupes représentant alkyle en C8-C36, cycloalkyle en C6-C36, alcényle en C8-C36, notamment alkyle en C12-C24, alcényle en C12-C24 ou cyclohexyle, et les autres groupes représentant hydrogène, alkyle en C1-C36, alcényle en C2-C36, cyclohexyle ou un groupe de formule -(A-O)x-E ou -(CH2)n-NYZ, A représentant un groupe éthyle ou propyle, x signifiant un nombre de 1 à 50, E = H, alkyle en C1-C30, cycloalkyle en C5-C12 ou aryle en C6-C30, et n = 2, 3 ou 4, et Y et Z signifiant indépendamment l'un de l'autre H, alkyle en C1-C30 ou -(A-O)x-E.
  15. Additifs pour distillats d'huiles minérales ayant une teneur en eau inférieure à 150 ppm, qui contiennent au moins une résine d'alkylphénol-aldéhyde et au moins un polymère contenant de l'azote, choisi parmi :
    a) les polymères en peigne, contenant des unités dérivées d'esters d'acides carboxyliques éthyléniquement insaturés, d'esters de vinyle et/ou d'éthers de vinyle, et d'au moins un comonomère contenant de l'azote,
    b) les copolymères d'éthylène avec des comonomères éthyléniquement insaturés contenant de l'azote, et
    c) les polyamines polymères, fabriquées par condensation d'une monoamine primaire aliphatique ou d'une N-alkyl-alkylène-diamine avec de l'épichlorhydrine ou du glycidol,
    en un rapport en masse de 9:1 à 1:9, la résine d'alkylphénol-aldéhyde contenant une unité structurale de répétition de formule
    Figure imgb0017
     dans laquelle R5 représente alkyle en C1-C200 ou alcényle en C2-C200, O-R6 ou O-C(O)-R6, R6 représente alkyle en C1-C200 ou alcényle en C2-C200, et n représente un nombre de 2 à 100.
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DE102005035277B4 (de) 2007-10-11
JP5199554B2 (ja) 2013-05-15
US7713315B2 (en) 2010-05-11
RU2006127366A (ru) 2008-02-10
KR101469522B1 (ko) 2014-12-05
KR20070015086A (ko) 2007-02-01
CA2554168A1 (fr) 2007-01-28
EP1749873A3 (fr) 2009-09-16
US20070022654A1 (en) 2007-02-01
CN1904006B (zh) 2013-03-27
CN1904006A (zh) 2007-01-31
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