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  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
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  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/04—Mixtures of base-materials and additives
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  • C10L1/14—Organic compounds
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  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
  • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
  • C10L1/1835—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom having at least two hydroxy substituted non condensed benzene rings
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/14—Organic compounds
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/14—Organic compounds
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  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
  • C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/14—Organic compounds
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  • 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
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  • 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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  • C10L1/00—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
  • C10L1/197—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
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  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
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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
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/14—Organic compounds
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  • C10L1/00—Liquid carbonaceous fuels
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  • 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
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  • C10L1/234—Macromolecular compounds
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
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  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
  • C10M2205/022—Ethene
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  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
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  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
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  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/013—Iodine value
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  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
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  • C10N2020/067—Unsaturated Compounds
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  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/40—Low content or no content compositions
  • C10N2030/43—Sulfur free or low sulfur content compositions

Definitions

• the present invention relates to additives which are composed of esters between polyols and fatty acid mixtures and alkylphenol resins having improved oxidation stability, and also to their use for improving the lubricity of highly desulfurized fuel oils.
• Mineral oils and mineral oil distillates which are used as fuel oils generally contain 0.5% by weight or more of sulfur which causes the formation of sulfur dioxide on combustion.
• sulfur content of fuel oils is being ever further reduced.
• the standard EN 590 relating to diesel fuels has prescribed a maximum sulfur content of 350 ppm in Europe since November 1999. Further reductions of the sulfur content are in the pipeline.
• fuel oils having fewer than 50 ppm, and in exceptional cases having fewer than 10 ppm, of sulfur are already being used.
• These fuel oils are generally produced by refining, under hydrogenating conditions, the fractions obtained from crude oil by distillation.
• the desulfurization also removes other substances which confer a natural lubricity on the fuel oils.
• these substances include polyaromatic and polar compounds.
• EP-A-0 680 506 discloses that esters of fatty acids confer improved lubricity to highly desulfurized fuel oils. Particular mention is made of glycerol monooleate and diisodecyl adipate.
• EP-A-0 739 970 discloses the suitability of glycerol ester mixtures for improving the lubricity of low-sulfur fuel oils. Compositions having different degrees of esterification of the polyol and different degrees of saturation of the fatty acids are disclosed.
• EP-A-0 839 174 discloses fuel oils with improved lubricity which are low in sulfur and comprise a mixture of polyolesters with unsaturated fatty acids.
• DE 19614722 discloses mixtures of partial esters of highly unsaturated fatty acids with different polyols which have improved cold stability. Among other uses, these may be added to low-sulfur diesel oils as lubricant additives.
• EP 0743972 discloses fuel oils having improved lubricity which comprise a lubricity improver and a nitrogen compound.
• EP 0935645 discloses the use of C 1 -C 30 -alkylphenol resins as lubricity additives for low-sulfur diesel.
• the examples relate to C 18 — and C 2-4 -alkylphenol resins.
• WO-99/61562 discloses mixtures of alkylphenol resins, nitrogen compounds and ethylene copolymers as cold and lubricity additives for low-sulfur diesel.
• WO 01/19941 discloses partial esters of polyhydric alcohols with unsaturated fatty acids (pentaerythritol esterified with tall oil fatty acid) as lubricity additives having improved cold stability.
• the lubricity additives based on unsaturated fatty acids and their derivatives can resinify on prolonged storage of the additive, and of the additized oils, in particular at elevated temperature, to give products which only have limited oil solubility. This can lead to the formation of separate viscous layers and deposits in the storage container of the additive, in the fuel oil and also in the engine.
• the combustion and condensation products of glycerol, for example, are suspected of being responsible for coke residues and deposits on the injection nozzles of highly supercharged diesel engines.
• the fatty acid esters based on commercial fatty acid mixtures of the prior art additionally show a marked tendency to emulsify in the fuel oils additized by them. This means that emulsification of the water in the fuel oil takes place on contact of such a fuel oil with water. These emulsions to be found in particular on the oil/water phase boundary can only be removed with great difficulty, if at all. Since these emulsions as such cannot be used directly as fuel oils, they reduce the value of the products. This problem occurs to a particularly high degree when esters based on natural fatty acid mixtures are used.
• the invention therefore provides an additive for improving the lubricity of fuel oils having a maximum sulfur content of 0.035% by weight, comprising
• the invention further provides fuel oils having a maximum sulfur content of 0.035% by weight which comprise the additives according to the invention.
• the invention further provides the use of the additives according to the invention for improving the lubricity of fuel oils having a maximum sulfur content of 0.035% by weight.
• the invention further provides a process for improving the lubricity of fuel oils having a maximum sulfur content of 0.035% by weight by adding the additive according to the invention to the fuel oils.
• Preferred fatty acids which are a constituent of the esters A) are those having from 10 to 26 carbon atoms, in particular from 12 to 22 carbon atoms.
• the alkyl radicals or alkenyl radicals of the fatty acids consist substantially of carbon and hydrogen. However, they can also bear further substituents, for example hydroxyl, halogen, amino or nitro groups, as long as these do not impair the predominant hydrocarbon character.
• the fatty acids preferably contain at least one double bond. They can contain a plurality of double bonds, for example 2 or 3 double bonds, and be of natural or synthetic origin. In the case of polyunsaturated carboxylic acids, their double bonds can be isolated or else conjugated.
• at least 50% by weight, in particular at least 75% by weight, especially at least 90% by weight, of the fatty acids contain one or more double bonds.
• the iodine numbers of the parent fatty acids or fatty acid mixtures of the esters according to the invention are preferably above 100 g of I/100 g, more preferably between 105 and 190 g of I/100 g, in particular between 110 and 180 g of I/100 g and especially between 120 and 180 g of I/100 g, of fatty acid or fatty acid mixture.
• Suitable unsaturated fatty acids include oleic acid, erucic acid, palmitoleic acid, myristoleic acid, linoleic acid, linolenic acid, elaeosteric acid, arachidonic acid and/or ricinoleic acid.
• fatty acid mixtures and fractions obtained from natural fats and oils for example peanut oil fatty acid, fish oil fatty acid, linseed oil fatty acid, palm oil fatty acid, rapeseed oil fatty acid, ricinoleic oil fatty acid, castor oil fatty acid, colza oil fatty acid, soya oil fatty acid, sunflower oil fatty acid, safflower oil fatty acid and tall oil fatty acid, which have appropriate iodine numbers.
• fatty acids are dicarboxylic acids such as dimerized fatty acids and alkyl- and also alkenylsuccinic acids having C 8 -C 50 -alk(en)yl radicals, preferably having C 8 -C 40 -, in particular having C 12 -C 22 -alkyl radicals.
• the alkyl radicals can be linear or branched (oligomerized alkenes, polyisobutylene) and saturated or unsaturated.
• the dicarboxylic acids can be used as such or in mixtures with monocarboxylic acids, and preference is given to proportions of the dicarboxylic acids in mixtures of up to 10% by weight, in particular less than 5% by weight.
• the fatty acid mixtures can contain minor amounts, i.e. up to 20% by weight, preferably less than 10% by weight, in particular less than 5% by weight and especially less than 2% by weight, of saturated fatty acids, for example lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, isostearic acid, arachidic acid and behenic acid.
• saturated fatty acids for example lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, isostearic acid, arachidic acid and behenic acid.
• the fatty acids can also contain 1-40% by weight, especially 1-25% by weight, in particular 1-5% by weight, of resin acids.
• Suitable alcohols contain preferably from 2 to 6, in particular from 3 to 4, carbon atoms, and from 2 to 5, in particular from 3 to 4, hydroxyl groups, but a maximum of one hydroxyl group per carbon atom.
• Particularly suitable alcohols are ethylene glycol, diethylene glycol, propylene glycol, glycerol, trimethylolpropane, neopentyl glycol and pentaerythritol, and also the oligomers obtainable therefrom by condensation and having from 2 to 10 monomer units, for example polyglycerol.
• the partial esters can be prepared from alcohols and fatty acids by esterification in a known manner. As an alternative, it is also possible to partially hydrolyze naturally occurring fats and oils.
• Esters according to the invention are those which can be prepared from a di- or polyhydric alcohol and a fatty acid or a mixture of fatty acids. These include mixtures, for example, of mono-, di- and/or triesters, or optionally higher esters, of an alcohol with different fatty acids, of mono-, di- and/or triesters, or optionally higher esters, different alcohols with different fatty acids, or else mixtures of mono-, di- and/or triesters, or optionally higher esters, of one or more alcohols with different fatty acids. Preference is given to those esters which can be prepared from a fatty acid mixture.
• the esters according to the invention preferably have iodine numbers of more than 50 g of I/100 g of ester, more preferably between 90 and 200 g of I/100 g of ester, in particular between 100 and 180 g of I/100 g of ester and especially between 110 and 150 g of I/100 g of ester.
• the iodine numbers correspond to the iodine number of the parent fatty acid mixture and the alcohol used for esterification in a stoichiometric manner.
• the partial esters having OH numbers of between 110 and 200 mg of KOH/g of ester are notable for a very low tendency to emulsify, in particular in combination with the alkylphenol resins B).
• the HLB range of the additives which is limited by the OH number presumably effects a reduced affinity of the amphiphilic active ingredients for water; at the same time, the formation of surface-active and micellar structures is disrupted by the number of double bonds in the alkyl radicals characterized by means of the iodine number.
• alkylphenol-aldehyde resins (B) present in the additive according to the invention are known in principle and described, for example, in Rompp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, Volume 4, p. 3351ff.
• the alkyl or alkenyl radicals of the alkylphenol have 6-24, preferably 8-22, in particular 9-18, carbon atoms. They may be linear or branched, and the branch may contain secondary and also tertiary structures.
• n- and isohexyl n- and isooctyl, n- and isononyl, n- and isodecyl, n- and isododecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and also tripropenyl, tetrapropenyl, pentapropenyl and polyisobutenyl up to C 24 .
• the prefix iso means that the alkyl chain has one or more secondary branches.
• the alkylphenol-aldehyde resin may also contain up to 20 mol % of phenol units and/or alkylphenols having short alkyl chains, for example butylphenol.
• alkylphenol-aldehyde resin the same or different alkylphenols may be used.
• the aldehyde in the alkylphenol-aldehyde resin has from 1 to 10, preferably from 1 to 4, carbon atoms, and may bear further functional groups. It is preferably an aliphatic aldehyde, more preferably formaldehyde.
• the molecular weight of the alkylphenol-aldehyde resins is preferably 350-10,000, in particular 400-5000 g/mol. This preferably corresponds to a degree of condensation n of from 3 to 40, in particular from 4 to 20. A prerequisite is that the resins are oil-soluble.
• these alkylphenol-formaldehyde resins are those which are oligomers or polymers having a repeating structural unit of the formula
• R A is C 6 -C 24 -alkyl or -alkenyl and n is a number from 2 to 50.
• alkylphenol-aldehyde resins are prepared in a known manner by basic catalysis to give condensation products of the resol type, or by acidic catalysis to give condensation products of the novolak type.
• an alkylphenol having 6-24, preferably 8-22, in particular 9-18, carbon atoms per alkyl group, or mixtures thereof are reacted with at least one aldehyde, using about 0.5-2 mol, preferably 0.7-1.3 mol and in particular equimolar amounts of aldehyde, per mole of alkylphenol compound.
• Suitable alkylphenols are in particular n- and isohexylphenol, n- and isooctylphenol, n- and isononylphenol, n- and isodecylphenol, n- and isododecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, tripropenylphenol, tetrapropenylphenol and poly(isobutenyl)phenol up to C 24 .
• the alkylphenols are preferably para-substituted.
• the alkylphenols may bear one or more alkyl radicals.
• the proportion substituted by more than one alkyl group is preferably at most 5 mol %, in particular at most 20 mol % and especially at most 40 mol %.
• At most 40 mol %, in particular at most 20 mol %, of the alkylphenols used preferably bear an alkyl radical in the ortho-position.
• the alkylphenols are unsubstituted by tertiary alkyl groups in the ortho-position to the hydroxyl group.
• the aldehyde may be a mono- or dialdehyde and bear further functional groups such as —COOH.
• Particularly suitable aldehydes are formaldehyde, acetaldehyde, butyraldehyde, glutardialdehyde and glyoxalic acid, preferably formaldehyde.
• the formaldehyde may be used in the form of paraformaldehyde or in the form of a preferably 20-40% by weight aqueous formalin solution. It is also possible to use corresponding amounts of trioxane.
• Alkylphenol is customarily reacted with aldehyde in the presence of alkaline catalysts, for example alkali metal 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.
• alkaline catalysts for example alkali metal hydroxides or alkylamines
• acidic catalysts for example inorganic or organic acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acid, sulfamido acids or haloacetic acids.
• the condensation is preferably carried out without solvent at from 90 to 200° C., preferably at from 100 to 160° C.
• the reaction is effected 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 from 90 to 200° C., preferably 100-160° C., and the water of reaction formed is removed during the reaction by azeotropic distillation. Solvents which release no protons under the conditions of the condensation can remain in the products after the condensation reaction.
• the resins may be used directly or after neutralization of the catalyst, optionally after further dilution of the solution with aliphatic and/or aromatic hydrocarbons or hydrocarbon mixtures, for example petroleum fractions, kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or solvents such as ®Solvent Naphtha, ®Shellsol AB, ®Solvesso 150, ®Solvesso 200, ®Exxsol, ®ISOPAR and ®Shellsol D types.
• aliphatic and/or aromatic hydrocarbons or hydrocarbon mixtures for example petroleum fractions, kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or solvents such as ®Solvent Naphtha, ®Shellsol AB, ®Solvesso 150, ®Solvesso 200, ®Exxsol, ®
• the proportions by weight of the constituents A) and B) in the additives according to the invention may vary within wide limits depending on the application. They are preferably between 10 and 99.999% by weight of A) to from 90 to 0.001% by weight of B), in particular between 20 and 99.995% by weight of A) to from 80 to 0.005% by weight of B). To stabilize the fatty acids, preference is given to using smaller proportions of component B of from 0.001 to 10% by weight, preferably from 0.005 to 5% by weight, of B), but in contrast, to optimize the lubricity, larger proportions of B of, for example, from 5 to 90% by weight, preferably from 10 to 80% by weight and in particular from 25 to 75% by weight, are used.
• Paraffin dispersants are additives which reduce the size of the precipitating paraffin crystals on cooling of the oil and in addition prevent the paraffin particles from depositing, but instead keep them dispersed colloidally with distinctly reduced tendency to sediment.
• the nitrogen-containing paraffin dispersants are preferably low molecular weight or polymeric, oil-soluble nitrogen compounds, for example amine salts, imides and/or amides which are obtained by reacting aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri-, tetra- and/or polycarboxylic acids or their anhydrides.
• Particularly preferred paraffin dispersants contain reaction products of secondary fatty amines having from 8 to 36 carbon atoms, in particular dicoconut fatty amine, ditallow fatty amine and distearylamine.
• paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds which can optionally be reacted with primary monoalkylamines and/or aliphatic alcohols, the reaction products of alkenyl-spiro-bislactones with amines and the reaction products of terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkyl ethers of lower unsaturated alcohols with amines and/or alcohols.
• Some suitable paraffin dispersants are listed hereinbelow.
• paraffin dispersants mentioned below are prepared by reaction of compounds containing an acyl group with an amine.
• each R is C 8 -C 200 -alkenyl, with amines of the formula NR 6 R 7 R 8 .
• Suitable reaction products are mentioned in EP-A-0 413 279.
• the reaction of compounds of the formula with the amines gives amides or amide ammonium salts.
• R 10 is a straight-chain or branched alkylene radical having from 2 to 6 carbon atoms or the radical of the formula
• R 6 and R 7 are, in particular, alkyl radicals having from 10 to 30, preferably from 14 to 24, carbon atoms, and all or some of the amide structures may also be in the form of the ammonium salt structure of the formula
• the amides or amide ammonium salts or ammonium salts are obtained by reaction of the acids with from 0.5 to 1.5 mol of amine, preferably from 0.8 to 1.2 mol of amine, per carboxyl group.
• the reaction temperatures are from about 80 to 200° C., and continuous removal of the water of reaction formed is required to prepare the amides.
• the conversion to the amide does not have to be completed, but instead from 0 to 100 mol % of the amine used may be in the form of the ammonium salt.
• the compounds mentioned under B1) can also be prepared.
• dialkylamines in which R 6 and R 7 are a straight-chain alkyl radical having from 10 to 30 carbon atoms, preferably from 14 to 24 carbon atoms.
• R 6 and R 7 are a straight-chain alkyl radical having from 10 to 30 carbon atoms, preferably from 14 to 24 carbon atoms.
• dioleylamine dipalmitylamine, dicoconut fatty amine and dibehenylamine and preferably ditallow fatty amine.
• Examples of quaternary ammonium salts of this type include the following: dihexadecyldimethylammonium chloride, distearyldimethylammonium chloride, products of the quaternization 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 and tall oil fatty acid), such as N-methyltriethanolammonium distearyl ester chloride, N-methyltriethanolammonium distearyl ester methosulfate, N,N-dimethyldiethanolammonium distearyl ester chloride, N-methyltriethanolammonium dioleyl ester chloride, N-methyltriethanolammonium trilauryl ester methosulfate, N-methyltriethanolammonium tristearyl
• R 14 is CONR 6 R 7 or CO 2 ⁇ + H 2 NR 6 R 7
• R 15 and R 16 are each H, CONR 17 2 , CO 2 R 17 or OCOR 17 , —OR 17 , —R 17 or —NCOR 17
• R 17 is alkyl, alkoxyalkyl or polyalkoxyalkyl and has at least 10 carbon atoms.
• Preferred carboxylic acids or acid derivatives are phthalic acid (anhydride), trimellitic and pyromellitic acid (dianhydride), isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid (anhydride), maleic acid (anhydride) and alkenylsuccinic acid (anhydride).
• the formulation (anhydride) means that the anhydrides of said acids are also preferred acid derivatives. If the compounds of the above formula are amides or amine salts, they are preferably obtained from a secondary amine which contains a hydrogen- and carbon-containing group having at least 10 carbon atoms.
• R 17 preferably contains from 10 to 30, in particular from 10 to 22, for example from 14 to 20, carbon atoms, and is preferably straight-chain or branched in the 1- or 2-position.
• the other hydrogen- and carbon-containing groups may be shorter, for example contain fewer than 6 carbon atoms, or may, if desired, have at least 10 carbon atoms.
• Suitable alkyl groups include methyl, ethyl, propyl, hexyl, decyl, dodecyl, tetradecyl, eicosyl and docosyl (behenyl).
• polymers containing at least one amide or ammonium group bonded directly to the polymer skeleton, the amide or ammonium group bearing at least one alkyl group having at least 8 carbon atoms on the nitrogen atom are also suitable.
• Polymers of this type can be prepared in various ways. One method is to use a polymer which contains a plurality of carboxyl or carboxylic anhydride groups and to react this polymer with an amine of the formula NHR 6 R 7 in order to obtain the desired polymer.
• Suitable polymers for this purpose are generally copolymers of unsaturated esters, such as C 1 -C 40 -alkyl (meth)acrylates, di(C 1 -C 40 -alkyl) fumarates, C 1 -C 40 -alkyl vinyl ethers, C 1 -C 40 -alkyl vinyl esters or C 2 -C 40 -olefins (linear, branched or aromatic) with unsaturated carboxylic acids or reactive derivatives thereof, such as, for example, carboxylic anhydrides (acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, citraconic acid, preferably maleic anhydride).
• unsaturated esters such as C 1 -C 40 -alkyl (meth)acrylates, di(C 1 -C 40 -alkyl) fumarates, C 1 -C 40 -alkyl vinyl ethers, C 1 -C 40 -alky
• Carboxylic acids are preferably reacted with from 0.1 to 1.5 mol, in particular from 0.5 to 1.2 mol, of amine per acid group, while carboxylic anhydrides are preferably reacted with from 0.1 to 2.5 mol, in particular from 0.5 to 2.2 mol, of amine per acid anhydride group, with amides, ammonium salts, amide ammonium salts or imides being formed, depending on the reaction conditions.
• amides, ammonium salts, amide ammonium salts or imides being formed, depending on the reaction conditions.
• amide group-containing polymers for use in accordance with the invention are the following:
• Copolymers (a) of a dialkyl fumarate, maleate, citraconate or itaconate with maleic anhydride, or (b) of vinyl esters, for example vinyl acetate, vinyl propionate, vinyl 2-ethylhexanoate or vinyl stearate, with maleic anhydride, or (c) of a dialkyl fumarate, maleate, citraconate or itaconate with maleic anhydride and vinyl acetate.
• Particularly suitable examples of these polymers are copolymers of didodecyl fumarate, vinyl acetate and maleic anhydride; ditetradecyl fumarate, vinyl acetate and maleic anhydride; dihexadecyl fumarate, vinyl acetate and maleic anhydride; or the corresponding copolymers in which the itaconate is used instead of the fumarate.
• the desired amide is obtained by reaction of the polymer containing anhydride groups with a secondary amine of the formula HNR1R 7 (optionally also with an alcohol if an ester amide is formed). If polymers containing an anhydride group are reacted, the resultant amino groups will be ammonium salts and amides. Polymers of this type can be used with the proviso that they contain at least two amide groups.
• the polymer containing at least two amide groups contains at least one alkyl group having at least 10 carbon atoms.
• This long-chain group which may be a straight-chain or branched alkyl group, may be bonded via the nitrogen atom of the amide group.
• the amines which are suitable for this purpose may 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 an integer, preferably between 1 and 30.
• R 6 and R 7 preferably contain at least 10 carbon atoms, for example from 10 to 20 carbon atoms, for example dodecyl, tetradecyl, hexadecyl or octadecyl.
• suitable secondary amines are dioctylamine and those which contain alkyl groups having at least 10 carbon atoms, for example didecylamine, didodecylamine, dicoconut amine (i.e. mixed C 12 -C 14 -amines), dioctadecylamine, hexadecyloctadecylamine, di(hydrogenated tallow) amine (approximately 4% by weight of n-C 14 -alkyl, 30% by weight of n-C 10 -alkyl, 60% by weight of n-C 18 -alkyl, the remainder is unsaturated).
• doecylamine didodecylamine
• dicoconut amine i.e. mixed C 12 -C 14 -amines
• dioctadecylamine hexadecyloctadecylamine
• di(hydrogenated tallow) amine approximately 4% by weight of n
• polystyrene resin examples include N-octadecylpropanediamine, N,N′-dioctadecylpropanediamine, N-tetradecylbutanediamine and N,N′-dihexadecylhexanediamine, N-(coconut)propylenediamine (C 12 /C 14 -alkylpropylenediamine), N-(tallow)propylenediamine (C 16 /C 18 -alkylpropylenediamine).
• the amide-containing polymers typically have a number average molecular weight of from 1000 to 500,000, for example from 10,000 to 100,000.
• the reaction can be carried out before or after the polymerization.
• the structural units of the copolymers are derived from, for example, maleic acid, fumaric acid, tetrahydrophthalic acid, citraconic acid, preferably maleic anhydride. They can be employed either in the form of their homopolymers or in the form of the copolymers. Suitable comonomers are the following: styrene and alkylstyrenes, straight-chain and branched olefins having from 2 to 40 carbon atoms, and mixtures thereof.
• Examples include the following: styrene, ⁇ -methylstyrene, dimethylstyrene, ⁇ -ethylstyrene, diethylstyrene, isopropylstyrene, tert-butylstyrene, ethylene, propylene, n-butylene, diisobutylene, decene, dodecene, tetradecene, hexadecene and octadecene. Preference is given to styrene and isobutene, particular preference is given to styrene.
• Examples of specific polymers include the following: polymaleic acid, an equimolar styrene-maleic acid copolymer with an alternating structure, styrene-maleic acid copolymers with a random structure in the ratio 10:90 and an alternating copolymer of maleic acid and isobutene.
• the molecular weights of the polymers are generally from 500 g/mol to 20,000 g/mol, preferably from 700 to 2000 g/mol.
• the polymers or copolymers are reacted with the amines at temperatures of from 50 to 200° C. over the course of from 0.3 to 30 hours.
• the amine here is used in amounts of approximately one mole per mole of copolymerized dicarboxylic anhydride, i.e. from about 0.9 to 1.1 mol/mol.
• the use of larger or smaller amounts is possible, but does not bring any advantage. If larger amounts than one mole are used, ammonium salts are partly obtained, since the formation of a second amide group requires higher temperatures, longer residence times and separation of water. If smaller amounts than one mole are used, complete conversion to the monoamide does not take place, and a correspondingly reduced action is obtained.
• Copolymers consisting of from 10 to 95 mol % of one or more alkyl acrylates or alkyl methacrylates having C 1 -C 26 -alkyl chains and from 5 to 90 mol % of one or more ethylenically unsaturated dicarboxylic acids or anhydrides thereof, the copolymers having been substantially reacted with one or more primary or secondary amines to give the monoamide or amide/ammonium salt of the dicarboxylic acid.
• the copolymers consist of from 10 to 95 mol %, preferably from 40 to 95 mol % and particularly preferably from 60 to 90 mol %, of alkyl (meth)acrylates and from 5 to 90 mol %, preferably from 5 to 60 mol % and particularly preferably from 10 to 40 mol %, of the olefinically unsaturated dicarboxylic acid derivatives.
• the alkyl groups of the alkyl (meth)acrylates contain from 1 to 26, preferably from 4 to 22 and particularly preferably from 8 to 18, carbon atoms. They are preferably straight-chain and unbranched. However, it is also possible for up to 20% by weight of cyclic and/or branched components to be present.
• alkyl (meth)acrylates are 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, and anhydrides thereof, and fumaric acid. Preference is given to maleic anhydride.
• Suitable amines are compounds of the formula HNR 6 R 7 .
• the dicarboxylic acids in the form of the anhydrides, if available, in the copolymerization, for example 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 polymers are reacted with the amines at temperatures of from 50 to 200° C. over the course of from 0.3 to 30 hours.
• the amine here is used in amounts of from approximately one to two moles per mole of copolymerized dicarboxylic anhydride, i.e. from about 0.9 to 2.1 mol/mol. The use of larger or smaller amounts is possible, but does not bring any advantage. If larger amounts than 2 mol are used, free amine is present. If smaller amounts than one mole are used, complete conversion to the monoamide does not take place, and a correspondingly reduced action is obtained.
• the amide/ammonium salt structure may be built up from two different amines.
• a copolymer of lauryl acrylate and maleic anhydride can firstly be reacted with a secondary amine, such as hydrogenated ditallow fatty amine, to give the amide, after which the free carboxyl group originating from the anhydride is neutralized using another amine, for example 2-ethylhexylamine, to give the ammonium salt.
• a secondary amine such as hydrogenated ditallow fatty amine
• another amine for example 2-ethylhexylamine
• reaction is firstly carried out with ethylhexylamine to give the monoamide, then with ditallow fatty amine to give the ammonium salt.
• At least one amine is used here which has at least one straight-chain, unbranched alkyl group having more than 16 carbon atoms. It is not important here whether this amine is present in the build-up of the amide structure or as the ammonium salt of the dicarboxylic acid.
• R 22 and R 23 are each independently hydrogen or methyl, a and b are zero or one and a+b is one,
• R 24 and R 25 are identical or different and are each —NHR 6 , N(R 6 ) 2 and/or —OR 27 groups, and R 27 is a cation of the formula H 2 N(R 6 ) 2 or H 3 NR 6 , 19-80 mol %, preferably 39-60 mol %, of divalent structural units of the formula 4
• R 28 is hydrogen or C 1 -C 4 -alkyl
• R 29 is C 6 -C 60 -alkyl or C 6 -C 18 -aryl
• R 30 is hydrogen or methyl
• R 31 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 is C 1 -C 24 -alkyl, C 5 -C 20 -cycloalkyl, C 6 -C 18 -aryl or —C(O)—R 34 where R 34 is C 1 -C 40 -alkyl, C 5 -C 10 -cycloalkyl or C 6 -C 18 -aryl.
• alkyl, cycloalkyl and aryl radicals may be substituted or unsubstituted.
• Suitable substituents of the alkyl and aryl radicals are, for example, (C 1 -C 6 )-alkyl, halogens, such as fluorine, chlorine, bromine and iodine, preferably chlorine, and (C 1 -C 6 )-alkoxy.
• Alkyl here is a straight-chain or branched hydrocarbon radical. Specific examples include: 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 alkyl, tallow fatty alkyl and behenyl.
• Cycloalkyl here is a cyclic aliphatic radical having 5-20 carbon atoms.
• Preferred cycloalkyl radicals are cyclopentyl and cyclohexyl.
• Aryl here is a substituted or unsubstituted aromatic ring system having from 6 to 18 carbon atoms.
• the terpolymers consist of the divalent structural units of the formulae 1 and 3, and 4 and 5, and optionally 2. They additionally only contain, as known per se, the end groups formed in the polymerization by initiation, inhibition and chain termination.
• Examples include the following ⁇ , ⁇ -unsaturated olefins: styrene, ⁇ -methylstyrene, dimethylstyrene, ⁇ -ethylstyrene, diethylstyrene, i-propylstyrene, tert-butylstyrene, diisobutylene and ⁇ -olefins, such as decene, dodecene, tetradecene, pentadecene, hexadecene, octadecene, C 20 - ⁇ -olefin, C 24 - ⁇ -olefin, C 30 - ⁇ -olefin, tripropenyl, tetrapropenyl, pentapropenyl and mixtures thereof.
• ⁇ -olefins having from 10 to 24 carbon atoms and styrene, particularly preference to
• the structural units of the formula 5 are derived from polyoxyalkylene ethers of lower, unsaturated alcohols of the formula 9.
• the monomers of the formula 9 are products of the etherification (R 32 ⁇ —C(O)R 34 ) or esterification (R 32 ⁇ —C(O)R 34 ) of polyoxyalkylene ethers (R 32 ⁇ H).
• the polyoxyalkylene ethers (R 32 ⁇ H) can be prepared by processes known per se, for example by the addition of ⁇ -olefin oxides, such as ethylene oxide, propylene oxide and/or butylene oxide, onto polymerizable, lower, unsaturated alcohols of the formula 10
• Polymerizable, lower, unsaturated alcohols of this type are, for example, allyl alcohol, methallyl alcohol, butenols, such as 3-buten-1-ol and 1-buten-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. Preference is given to the products of the addition of ethylene oxide and/or propylene oxide onto allyl alcohol.
• Examples of primary amines suitable for the preparation of the terpolymers include the following:
• n-stearylamine or also N,N-dimethylaminopropylenediamine, cyclohexylamine, dehydroabietylamine and mixtures thereof.
• Examples of secondary amines which are suitable for the preparation of the terpolymers include the following: didecylamine, ditetradecylamine, distearylamine, dicoconut fafty amine, ditallow fatty amine and mixtures thereof.
• the terpolymers have K values (measured by the Ubbelohde method in 5% by weight solution in toluene at 25° C.) of from 8 to 100, preferably from 8 to 50, corresponding to average molecular weights (M w ) of from about 500 to 100,000. Suitable examples are listed in EP 606 055.
• R 22 and R 23 are each independently hydrogen or methyl
• a and b are zero or 1, and a +b is 1,
• R 37 ⁇ —OH, —O—[C 1 -C 30 -alkyl], —NR 6 R 7 , —O 5 N r R 6 R 7 H 2
• R 39 -(A-O) x -E
• A an ethylene or propylene group
• E H, C 1 -C 30 -alkyl, C 5 -C 12 -cycloalkyl or C 6 -C 30 -aryl,
• the structural units of the formulae 13, 14 and 15 are derived from ⁇ , ⁇ -unsaturated dicarboxylic anhydrides of the formulae 6 and/or 7.
• the structural units of the formula 4 are derived from the ⁇ , ⁇ -unsaturated olefins of the formula 8.
• the abovementioned 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 polyether-amines or alkanolamines of the formulae 16 a) and b), amines of the formula NR 6 R 7 R 8 and optionally alcohols having from 1 to 30 carbon atoms.
• R 54 is hydrogen or C 1 -C 4 -alkyl
• R 55 is hydrogen, C 1 - to C 4 -alkyl, C 5 - to C 12 -cycloalkyl or C 6 — to C 3-0 -aryl
• R 56 and R 57 are each independently hydrogen, C 1 - to C 22 -alkyl, C 2 - to C 22 -alkenyl or Z-OH
• Z is C 2 - to C 4 -alkylene
• n is a number from 1 to 1000.
• the structural units of the formulae 6 and 7 have preferably been derivatized using mixtures of at least 50% by weight of alkylamines of the formula HNR 6 R 7 R 8 and at most 50% by weight of polyether-amines or alkanolamines of the formulae 16 a) and b).
• Another possibility for the derivatization of the structural units of the formulae 6 and 7 comprises employing an alkanolamine of the formulae 16a) or 16b) instead of the polyether-amines and subsequently subjecting the product to oxyalkylation.
• reaction temperature is from 50 to 100° C. (amide formation). In the case of primary amines, the reaction is carried out at temperatures above 100° C. (imide formation).
• the oxyalkylation is typically carried out at temperatures of from 70 to 170° C. with catalysis by bases, such as NaOH or NaOCH 3 , by introducing gaseous alkylene oxides, such as ethylene oxide (EO) and/or propylene oxide (PO). From 1 to 500 mol, preferably from 1 to 100 mol, of alkylene oxide are usually added per mole of hydroxyl groups.
• bases such as NaOH or NaOCH 3
• gaseous alkylene oxides such as ethylene oxide (EO) and/or propylene oxide (PO).
• EO ethylene oxide
• PO propylene oxide
• alkanolamines include the following: monoethanolamine, diethanolamine, N-methylethanolamine, 3-aminopropanol, isopropanol, diglycol amine, 2-amino-2-methylpropanol and mixtures thereof.
• Examples of primary amines include the following: n-hexylamine, n-octylamine, n-tetradecylamine, n-hexadecylamine, n-stearylamine or else N,N-dimethylaminopropylenediamine, cyclohexylamine, dehydroabietylamine and mixtures thereof.
• secondary amines include the following: didecylamine, ditetradecylamine, distearylamine, dicoconut fatty amine, ditallow fatty amine and mixtures thereof.
• Examples of alcohols include the following:
• These can be obtained either by reaction of a polymer containing anhydride groups with amines of the formula H 2 NR 6 or by imidation of the dicarboxylic acid followed by copolymerization.
• the preferred dicarboxylic acid here is maleic acid or maleic anhydride.
• the polar nitrogen-containing paraffin dispersants may be added to the additives according to the invention or added separately to the additized middle distillate.
• the ratio between paraffin dispersants and the additives according to the invention is between 5:1 and 1:5 and preferably between 3:1 and 1:3.
• the additives according to the invention may also be used together with one or more oil-soluble coadditives which in themselves improve the lubricity and/or cold-flow properties of crude oils, lubricant oils or fuel oils.
• oil-soluble coadditives are vinyl acetate-containing copolymers or terpolymers of ethylene, comb polymers and also oil-soluble amphiphiles.
• additives according to the invention are used in a mixture with ethylene/vinyl acetate/vinyl 2-ethylhexanoate terpolymers, ethylene/vinyl acetate/vinyl neononanoate terpolymers and/or ethylene/vinyl acetate/vinyl neodecanoate terpolymers to simultaneously improve the flowability and lubricity of mineral oils or mineral oil distillates.
• the terpolymers of vinyl 2-ethylhexanoates, vinyl neononanoates or vinyl neodecanoates contain from 10 to 35% by weight of vinyl acetate and from 1 to 25% by weight of the particular long-chain vinyl ester.
• further preferred copolymers also contain from 0.5 to 20% by weight of olefin having from 3 to 10 carbon atoms, for example isobutylene, diisobutylene, 4-methylpentene or norbornene.
• the additives according to the invention are used together with comb polymers.
• This refers to polymers in which hydrocarbon radicals having at least 8, in particular at least 10, carbon atoms are bonded to a polymer backbone. These are preferably homopolymers whose alkyl side chains have at least 8 and in particular at least 10 carbon atoms. In copolymers, at least 20%, preferably at least 30%, of the monomers have side chains (cf. Comb-like Polymers-Structure and Properties; N. A. Platé and V. P. Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff).
• suitable comb polymers are, for example, fumarate/vinyl acetate copolymers (cf. EP 0 153 76 A1), copolymers of a C 6 -C 24 - ⁇ -olefin and an N—C 6 -C 22 -alkylmaleimide (cf. EP 0 320 766), and also esterified olefin/maleic anhydride copolymers, polymers and copolymers of a-olefins and esterified copolymers of styrene and maleic anhydride.
• fumarate/vinyl acetate copolymers cf. EP 0 153 76 A1
• copolymers of a C 6 -C 24 - ⁇ -olefin and an N—C 6 -C 22 -alkylmaleimide cf. EP 0 320 766
• esterified olefin/maleic anhydride copolymers polymers and copo
• Comb polymers can be described, for example, by the formula
• A is R′, COOR′, OCOR′, R′′-COOR′ or OR′;
• D is H, CH 3 , A or R;
• E is H or A
• G is H, R′′, R′′—COOR′, an aryl radical or a heterocyclic radical
• M is H, COOR′′, OCOR′′, OR′′ or COOH;
• N is H, R′′, COOR′′, OCOR, COOH or an aryl radical
• R′ is a hydrocarbon chain having 8-150 carbon atoms
• R′′ is a hydrocarbon chain having from 1 to 10 carbon atoms
• m is a number between 0.4 and 1,0;
• n is a number between 0 and 0.6.
• the mixing ratio (in parts by weight) of the additives according to the invention with ethylene copolymers or comb polymers is in each case from 1:10 to 20:1, preferably from 1:1 to 10:1.
• the additives according to the invention are added to oils in amounts of from 0.0001 to 1% by weight, preferably from 0.001 to 0.1% by weight and especially from 0.002 to 0.05% by weight. They may be used as such or else dissolved in solvents, for example aliphatic and/or aromatic hydrocarbons or hydrocarbon mixtures, for example toluene, xylene, ethylbenzene, decane, pentadecane, petroleum fractions, diesel, kerosene or commercial solvent mixtures such as Solvent Naphtha, ®Shellsol AB, ®Solvesso 150, ®Solvesso 200 and ®Exxsol, ®Isopar and ®Shellsol D types, and also polar solvents such as alcohols, glycols and esters, for example fatty acid alkyl esters and in particular rapeseed oil methyl ester (RME).
• solvents for example aliphatic and/or aromatic hydrocarbons or hydrocarbon mixtures, for
• the additives according to the invention can be stored without aging effects at elevated temperature over a long period, without any symptoms of aging occurring, such as resinification and the formation of insoluble structures or deposits in storage containers and/or engine parts.
• they improve the oxidation stability of the additized oils with simultaneous reduced tendency to emulsify. This is advantageous in particular in oils which contain relatively large fractions of oils from cracking processes.
• a further advantage of the additives according to the invention is their reduced crystallization temperature compared to the fatty acid esters used as lubricity additives in the prior art. For instance, they can also be used at low temperatures of, for example, from 0° C. to ⁇ 20° C. and sometimes even lower without any problem.
• the additives according to the invention are particularly well suited to use in middle distillates.
• Middle distillates refer in particular to those mineral oils which are obtained by distillation of crude oil and boil in the range from 120 to 450° C., for example kerosene, jet fuel, diesel and heating oil.
• the oils can also contain alcohols such as methanol and/or ethanol or consist of these.
• the additives according to the invention are preferably used in those middle distillates which contain fewer than 350 ppm of sulfur, in particular fewer than 200 ppm of sulfur and in special cases fewer than 50 ppm or fewer than 10 ppm, of sulfur.
• middle distillates which have been subjected to refining under hydrogenating conditions, and therefore only contain small fractions of polyaromatic and polar compounds which confer a natural lubricity on them.
• the additives according to the invention are also preferably used in those middle distillates which have 95% distillation points below 370° C., in particular 350° C. and in special cases below 330° C.
• the additives according to the invention are equally suitable for use in synthetic fuels likewise having low lubricity, for example as produced in the Fischer-Tropsch process.
• the oils having improved lubricity have a Wear Scar Diameter measured in the HFRR test of preferably less than 460 ⁇ m, especially less than 450 ⁇ m.
• the additives according to the invention can also be used as components in lubricant oils.
• the mixtures can be used alone or else together with other additives, for example with pour point depressants, corrosion inhibitors, antioxidants, sludge inhibitors, dehazers, conductivity improvers, lubricity additives, and additives for reducing the cloud point. They are also used successfully together with additive packages which contain, inter alia, known ashless dispersing additives, detergents, antifoams, antioxidants, dehazers, demulsifiers and corrosion inhibitors.
• Test oil 1 Test oil 2
• Test oil 3 Distillation IBP [° C.] 202 182 164 20% [° C.] 237 221 214 90% [° C.] 321 280 342
• FBP [° C.] 348 304 367 Cloud Point [° C.] ⁇ 5.9 ⁇ 29.7 ⁇ 7.7 CFPP [° C.] ⁇ 8 ⁇ 33 ⁇ 13 Density at 15° C. [g/cm 3 ] 0.8348 0.8210 0.8293 Sulfur [ppm] 32 6 195
• the additives used are characterized hereinbelow.
• the OH numbers were determined to DIN 53240 by reacting with a defined amount of excess acetic anhydride and subsequently titrating the acetic acid formed.
• Iodine numbers are determined according to Kaufmann. In this method, the sample is admixed with a defined amount of a methanolic bromine solution, which results in an amount of bromine equivalent to the content of double bonds adding onto them. The excess of bromine is back-titrated using sodium thiosulfate.
• Nonylphenol-formaldehyde resin prepared by condensing a mixture of nonylphenol having 0.5 mol% of dinonylphenol with formaldehyde, Mw 2000 g/mol; 50% in Solvent Naphtha
• Dodecylphenol-formaldehyde resin prepared by condensing a mixture of dodecylphenol having 1.3 mol % of didodecylphenol with formaldehyde, Mw 2200 g/mol: 50% in Solvent Naphtha
• B3 C 20-C 24 -Alkylphenol-formaldehyde resin prepared by condensing a mixture of C 20 -C 24 - alkylphenol having 35 mol % of di-(C 20 -C 24 -alkyl)phenol with formaldehyde, Mw 2500 g/mol; 50% in Solvent Naphtha
• the mixture After the conditioning, the mixture is allowed to cool to room temperature for one hour. Subsequently, the mixture is admixed with 500 ml of diesel fuel (test oil 3) and mixed thoroughly. After standing for a period of two hours, the mixture is visually examined for any deposits, cloudiness, insoluble fractions, etc., which give indications of oxidative changes (visual examination). The mixture is then filtered through a 0.8 ⁇ m filter at a pressure differential of 800 mbar. The entire amount has to be filterable within 2 minutes, otherwise the volume which has been filtered after 2 minutes is noted.
• diesel fuel test oil 3

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