Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
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  • 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
  • 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
• • 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
  • 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
  • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
  • C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
  • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/224—Amides; Imides carboxylic acid amides, imides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
  • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
• • 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
  • 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
• • 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
  • 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
• • 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
  • 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/067—Unsaturated Compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • 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 oils with improved oxidation stability Fatty acid esters and alkylphenol resins, and their use as fuel oils and to improve the lubricating effect of desulfurized middle distillates.
• Oils obtained from animal or vegetable material are mainly metabolites which include triglycerides of monocarboxylic acids, e.g. B. acids with 10 to 25 carbon atoms, and the formula correspond in which R is an aliphatic radical having 10 to 25 carbon atoms, which may be saturated or unsaturated.
• oils contain glycerides from a number of acids, the Number and variety varies with the source of the oil and they can be added Contain phosphoglycerides.
• Such oils can be found in the prior art known methods can be obtained.
• Triglyceride Due to the partially unsatisfactory physical properties of the Triglyceride has become the technique of naturally occurring Triglycerides in fatty acid esters of lower alcohols such as methanol or ethanol convict.
• fatty acid alkyl esters are also used as Additives used for example for mineral oils and mineral oil distillates:
• fuel oils with a reduced to less than 500 ppm Sulfur content has such poor friction and wear-reducing properties Properties that so-called lubricity additives must be added to them.
• lubricity additives are based among other things on esters of unsaturated fatty acids with lower ones Alcohols (biodiesel).
• oily liquids used technically as fuel oils and additives are mainly based on oils from natural sources such as rapeseed, sunflowers, Soya and similar oil seeds. These have a high proportion of unsaturated Fatty acids of more than 50% and preferably of more than 80% on what gives them gives acceptable rheological properties, especially in the cold.
• EP-A-0635558 discloses the use of biodiesel based on C 1 -C 5 alkyl esters of saturated and unsaturated, straight-chain C 12 -C 22 fatty acids as lubrication improvers for gas oils with a low sulfur and aromatic content.
• EP-A-0935645 discloses the use of C 1 -C 30 alkylphenol resins as lubricity additives for low-sulfur diesel.
• the examples show C 18 and C 24 alkylphenol resins.
• WO-99/61562 discloses mixtures of alkylphenol resins, nitrogenous ones Compounds and ethylene copolymers as refrigeration and lubricity additives for low sulfur diesel.
• DE-A-10111857 discloses esters of predominantly saturated unbranched mono-fatty acids with mixtures of C 1 -C 4 monoalcohols with methylated monound / or dihydroxybenzenes as an additive to sulfur-free mineral diesel fuel.
• the hydroxybenzenes improve, among other things, the oxidation stability of the additives.
• the object of the present invention was therefore to base fuel oils and additives to find unsaturated vegetable and animal oils that are one versus the other State of the art improved oxidation stability and at the same time improved Efficacy as a lubricity additive for sulfur-reduced mineral oils and Have mineral oil distillates.
• oily liquids defined above are also used in the following as additives designated.
• Another object of the invention is the use of those defined above oily liquids as fuel oil.
• Another object of the invention are fuel oils with maximum 0.035 wt .-% sulfur content, which contain the additives according to the invention.
• Another object of the invention is the use of the invention Additives to improve the lubricating effect of fuel oils with at most 0.035% by weight sulfur content.
• Another object of the invention is a method for improving the Lubricating effect of fuel oils with a maximum sulfur content 0.035% by weight by adding the additive according to the invention to the fuel oils added.
• Preferred fatty acids which are part of the ester A) are those with 10 to 26 C atoms, in particular 12 to 22 C atoms.
• the alkyl residues or alkenyl residues of Fatty acids consist essentially of carbon and hydrogen. You can however other substituents such as e.g. Hydroxy, halogen, amino or Nitro groups have the predominant hydrocarbon character do not interfere.
• the fatty acids preferably contain at least one Double bond. You can have several double bonds, for example 2 or 3 Double bonds, contained and be of natural or synthetic origin. at polyunsaturated carboxylic acids can isolate their double bonds or also be conjugated. Mixtures of two or more unsaturated are preferred Fatty acids with 10 to 26 carbon atoms.
• Fatty acid mixtures contain at least 75% by weight, especially at least 90 % By weight of the fatty acids one or more double bonds.
• the iodine numbers of the Fatty acids or fatty acid mixtures on which the esters according to the invention are based are preferably above 50 g J / 100 g, particularly preferably between 100 and 190 g J / 100 g, in particular between 110 and 180 g J / 100 g and especially between 120 and 180 g I / 100 g fatty acid or fatty acid mixture.
• Suitable unsaturated fatty acids are, for example, oleic, eruca, palmitoleic, Myristoleic, linoleic, linolenic, elaeosteric, arachidonic and / or ricinoleic acid.
• those obtained from natural fats and oils are preferred Fatty acid mixtures or fractions, e.g. Peanut oil, fish, linseed oil, palm oil, Rapeseed oil, ricin oil, castor oil, rapeseed oil, soybean oil, sunflower oil, safflower and Tall oil fatty acid used, which have corresponding iodine numbers.
• dicarboxylic acids such as dimer fatty acids and alkyl and alkenyl succinic acids with C 8 -C 50 alk (en) yl radicals, preferably with C 8 -C 40 -, in particular with C 12 -C 22 alk (en) ylresten.
• the alkyl radicals can be linear or branched (oligomerized alkenes, polyisobutylene) and saturated or unsaturated. Contents of up to 10% by weight, in particular less than 5% by weight, based on component A) are preferred.
• the fatty acid mixtures can have minor amounts, i.e. up to 20% by weight, preferably less than 10%, in particular less than 5% and especially less than 2% saturated fatty acids such as lauric, tridecane, Myristin, pentadecane, palmitin, margarine, stearin, isostearin, arachine and Contain beenic acid.
• minor amounts i.e. up to 20% by weight, preferably less than 10%, in particular less than 5% and especially less than 2% saturated fatty acids such as lauric, tridecane, Myristin, pentadecane, palmitin, margarine, stearin, isostearin, arachine and Contain beenic acid.
• the fatty acids can further contain 1-40% by weight, especially 1-25% by weight, in particular 1-5% by weight, of resin acids.
• Suitable alcohols contain 1 to 5 carbon atoms.
• Particularly suitable alcohols are methanol and ethanol, especially methanol.
• esters are made from alcohols and fatty acids in a known manner by esterification produced.
• the transesterification of naturally occurring fats and oils is preferred lower alcohols and especially with methanol, being a by-product Glycerin is created.
• Preferred esters are those which consist of a fatty acid mixture are producible.
• alkylphenol-aldehyde resins (B) contained in the additive according to the invention are known in principle and are described, for example, in the Römpp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, Volume 4, pp. 3351ff. described.
• the alkyl or alkenyl radicals of the alkylphenol have 6-24, preferably 8-22, in particular 9-18, carbon atoms. They can be linear or preferably branched, the branching being able to contain secondary as well as tertiary structural elements.
• the alkylphenol-aldehyde resin can also contain up to 20 mol% phenol units and / or alkylphenols with short alkyl chains such as e.g. B. contain butylphenol. The same or different alkylphenols can be used for the alkylphenol-aldehyde resin.
• the aldehyde in the alkylphenol-aldehyde resin has 1 to 10, preferably 1 to 4 Carbon atoms and can carry other functional groups. It is preferably a aliphatic aldehyde, particularly preferably it is formaldehyde.
• the molecular weight of the alkylphenol-aldehyde resins is preferably 350- 10,000, in particular 400 - 5000 g / mol. This preferably corresponds to one Degree of condensation n from 3 to 40, in particular from 4 to 20. Prerequisite here that the resins are oil-soluble.
• these alkylphenol-formaldehyde resins are those which contain oligomers or polymers with a repetitive structural unit of the formula are where R A is C 6 -C 24 alkyl or alkenyl and n is a number from 2 to 50.
• the alkylphenol-aldehyde resins are prepared in a known manner by basic catalysis, whereby condensation products of the resol type arise, or by acidic catalysis, producing condensation products of the novolak type.
• an alkylphenol having 6 to 24, preferably 8 to 22, in particular 9 to 18 carbon atoms per alkyl group, or mixtures thereof and at least one aldehyde are reacted with one another, about 0.5 2 mol, preferably 0.7 - 1.3 mol and in particular equimolar amounts of aldehyde can be used.
• Suitable alkylphenols are, in particular, n- and iso-hexylphenol, n- and iso-octylphenol, n- and iso-nonylphenol, n- and iso-decylphenol, n- and iso-dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, tripropetraphenylphenol, tripropenylphenol (isobutenyl) phenol to C 24 .
• the alkylphenols are preferably para-substituted.
• the alkylphenols can carry one or more alkyl radicals. They are preferably at most 5 mol%, especially at most 20 mol% and especially at most 40 mol% with more than an alkyl group. Preferably carry at most 40 mol%, in particular at most 20 mol% of the alkylphenols used in the ortho position an alkyl radical.
• the alkylphenols ortho to the hydroxyl group are not included tertiary alkyl groups substituted.
• the aldehyde can be a mono- or dialdehyde and other functional groups wear like -COOH.
• Particularly suitable aldehydes are formaldehyde, acetaldehyde, Butyraldehyde, glutardialdehyde and glyoxalic acid, formaldehyde is preferred.
• the Formaldehyde can be in the form of paraformaldehyde or in the form of a preferred 20 - 40 wt .-% aqueous formalin solution can be used. It can too appropriate amounts of trioxane can be used.
• alkylphenol and aldehyde usually takes place in the presence of alkaline catalysts, for example alkali hydroxides or alkylamines, or of acidic catalysts, for example inorganic or organic acids, such as hydrochloric acid, sulfuric acid; Phosphoric acid, sulfonic acid, sulfamido acids or Haloacetic acids.
• alkaline catalysts for example alkali 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 solvent-free at 90 to 200 ° C, preferably carried out at 100 to 160 ° C.
• a water Azeotropic organic solvent for example toluene, xylene, higher aromatics or mixtures thereof.
• the reaction mixture is on a Temperature of 90 to 200 ° C, preferably 100-160 ° C heated, the resulting Water of reaction is removed during the reaction by azeotropic distillation. Solvent that does not have protons under the conditions of condensation split off, can remain in the products after the condensation reaction.
• the Resins can 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, e.g.
• the proportions by weight of components A) and B) in the additives according to the invention can vary widely depending on the application. They lay preferably between 10 and 99.999% by weight A) to 90 to 0.001% by weight B), in particular between 20 and 99.995% by weight A) to 80 to 0.005% by weight B).
• smaller portions of the Components B from 0.001 to 20% by weight, preferably 0.005 to 10% by weight B) used, whereas to optimize the lubricity larger portions B of for example 5 to 90% by weight, preferably 10 to 80% by weight and in particular 15 up to 75% by weight can be used.
• Paraffin dispersants are additives that increase the size when the oil cools reduce the precipitated paraffin crystals and also cause the Paraffin particles do not settle, but colloidally with significantly reduced Sedimentation efforts, remain dispersed.
• paraffin dispersants are preferably low molecular weight or polymeric, oil-soluble compounds with ionic or polar groups such as amine salts, imides and / or amides.
• Particularly preferred paraffin dispersants contain reaction products of secondary fatty amines with 8 to 36 carbon atoms, in particular dicocos fatty amine, ditallow fatty amine and distearyl amine.
• Paraffin dispersants which are 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 (cf. US Pat. No. 4,211,534) have proven particularly useful.
• 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), the reaction products of alkenyl spirobis lactones with amines (cf. 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 polyoxylalkylene ethers of lower unsaturated alcohols.
• paraffin dispersants are prepared by reacting compounds containing an acyl group with an amine.
• paraffin dispersants can be added to the additives according to the invention or added separately to the middle distillate to be added.
• Quantity ratio between paraffin dispersants and those according to the invention Additives is between 5: 1 and 1: 5 and preferably between 3: 1 and 1: 3.
• additives according to the invention also together with one or more oil-soluble Co-additives are used, which alone have the lubricating effect and / or Improve the cold flow properties of crude oils, lubricating oils or fuel oils.
• oil-soluble Co-additives are copolymers containing vinyl acetate or Terpolymers of ethylene, comb polymers and oil-soluble amphiphiles.
• the additives according to the invention in a mixture with ethylene / vinyl acetate / vinyl 2-ethylhexanoate terpolymers, Ethylene / vinyl acetate / neononanoic acid vinyl ester terpolymers and / or ethylene vinyl acetate / vinyl neodecanoate terpolymers to improve fluidity and Lubricating effect of mineral oils or mineral oil distillates.
• neodecanoic acid vinyl esters contain 10 to 35% by weight of vinyl acetate and 1 to 25 wt .-% of the respective long-chain vinyl ester. More preferred In addition to ethylene and 10 to 35% by weight of vinyl esters, copolymers also contain 0.5 to 20 wt .-% olefin with 3 to 10 carbon atoms such.
• the additives according to the invention are used together with comb polymers.
• comb polymers This is understood to mean polymers in which hydrocarbon radicals having at least 8, in particular at least 10, carbon atoms are bonded to a polymer backbone. They are preferably homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms. In the case of copolymers, at least 20%, preferably at least 30%, of the monomers have side chains (cf. Comb-like Polymers-Structure and Properties; NA Platé and VP Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff).
• Suitable comb polymers are, for example, fumarate / vinyl acetate copolymers (cf. EP 0 153 176 A1), copolymers of a C 6 -C 24 -a olefin and an NC 6 -C 22 alkylmaleimide (cf. EP-A-0 320 766), furthermore esterified olefin / maleic anhydride copolymers, polymers and copolymers of ⁇ -olefins and esterified copolymers of styrene and maleic anhydride.
• fumarate / vinyl acetate copolymers cf. EP 0 153 176 A1
• copolymers of a C 6 -C 24 -a olefin and an NC 6 -C 22 alkylmaleimide cf. EP-A-0 320 766
• esterified olefin / maleic anhydride copolymers polymers and copolymers of
• the mixing ratio (in parts by weight) of the additives according to the invention Ethylene copolymers or comb polymers are each 1:10 to 20: 1, preferably 1: 1 to 10: 1.
• the oily liquids according to the invention are particularly suitable for use as Suitable for fuel oil in diesel engines.
• the oily liquids according to the invention are oils as additives in quantities from 0.001 to 10% by weight, preferably 0.01 to 5% by weight and especially 0.02 to 2 wt .-% added. They can be used as such or dissolved in solvents, such as.
• aliphatic and / or aromatic hydrocarbons or Hydrocarbon mixtures such as Toluene, xylene, ethylbenzene, decane, Pentadecane, gasoline fractions, diesel, kerosene or commercial Solvent mixtures such as Solvent Naphtha, ®Shellsol AB, ®Solvesso 150, ®Solvesso 200, ®Exxsol, ®Isopar and ®Shellsol D types, as well as polar solvents such as Alcohols, glycols and esters can be used.
• Solvent Naphtha ®Shellsol AB, ®Solvesso 150, ®Solvesso 200, ®Exxsol, ®Isopar and ®Shellsol D types, as well as polar solvents such as Alcohols, glycols and esters can be used.
• polar solvents such as Alcohols, glycols and esters
• polar solvents such as Alcohols, glycols and esters
• the oily liquids according to the invention can be stored at elevated temperature for a long time without aging effects, without there being any signs of aging such as resinification and the formation of insoluble structures or deposits in storage containers and / or engine parts. They also improve the oxidation stability of the oils they contain. This is particularly advantageous for oils that contain large amounts of oils from cracking processes. Furthermore, they show an improvement in the lubricity of middle distillates that is superior to the individual components. The dosing rate required for setting the specification can thus be reduced.
• Another advantage of the oily liquids according to the invention is their advantage those used according to the prior art as lubricity additives Fatty acid esters reduced crystallization temperature. So you can also at low temperatures of, for example, 0 ° C to -20 ° C and sometimes also lower can be used easily.
• the oily liquids according to the invention are additives for use in Middle distillates are particularly suitable.
• Middle distillates are called especially those mineral oils that are obtained by distilling crude oil and boil in the range of 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 preferred used in middle distillates containing less than 350 ppm sulfur, in particular less than 200 ppm sulfur and in special cases less than 50 ppm or less than 10 ppm sulfur.
• the additives of the invention are also preferably in such middle distillates used, the 95% distillation points below 370 ° C, in particular 350 ° C and in special cases below 330 ° C.
• the oils with improved lubricity have a wear scar diameter of preferred measured in the HFRR test less than 460 ⁇ m, especially less than 450 ⁇ m.
• the oily according to the invention Liquids can also be used as components in lubricating oils.
• the oily liquids can be used alone or together with other additives be used, e.g. with pour point depressants, corrosion inhibitors, Antioxidants, sludge inhibitors, dehazers, conductivity improvers, lubricity additives, and additives to lower the cloud point.
• additives e.g. with pour point depressants, corrosion inhibitors, Antioxidants, sludge inhibitors, dehazers, conductivity improvers, lubricity additives, and additives to lower the cloud point.
• additive packages that include known ashless dispersion additives, detergents, defoamers, antioxidants, dehazers, Demulsifiers and corrosion inhibitors included.
• Iodine numbers are determined according to Kaufmann. For this purpose, a defined amount of a methanolic bromine solution is added to the sample, an amount of bromine which is equivalent to the content of double bonds being deposited. The excess bromine is back-titrated with sodium thiosulfate.
• the mixture After conditioning, the mixture is allowed to cool for one hour at room temperature. Then 500 ml of diesel fuel (test oil 1) is added and mixed well. After two hours of standing, the mixture is visually assessed for possible excretions, turbidity, insoluble components, etc., which give indications of oxidative changes (visual assessment). Then it is filtered through a 0.8 ⁇ m filter at a pressure difference of 800 mbar. The total amount must be filterable within 2 minutes, otherwise the volume filtered after 2 minutes is noted.
• test oil 1 diesel fuel
• the lubricating effect of the additives was tested using an HFRR device from PCS Instruments on additive oils at 60 ° C.
• the High Frequency Reciprocating Rig Test (HFRR) is described in D. Wei, H. Spikes, Wear, Vol. 111, No. 2, p. 217, 1986.
• the results are given as the coefficient of friction and wear scar (WS 1.4).
• a low wear scar and a low coefficient of friction (friction) show a good lubricating effect.
• Wear scar values of less than 460 ⁇ m is considered an indication of a sufficient lubricating effect, although in practice values of less than 400 ⁇ m are aimed for.
• the dosing rates in Table 6 relate to the amount of active ingredient dosed.
• Test oil 1 Test oil 2 distillation IBP [° C] 171 164 20% [° C] 218 214 90% [° C] 323 342 FBP [° C] 352 367 Cloud Point [° C] -8.2 -7.7 CFPP [° C] -12 -13 Density @ 15 ° C [g / cm 3 ] .8262 0.8293 Sulfur [ppm] 15 195 Characterization of the polar nitrogen-containing compounds used C1 Reaction product of a dodecenyl spirobislactone with a mixture of primary and secondary tallow fatty amine, 60% in solvent naphtha (produced according to EP-A-0413279) C2 Reaction product of a terpolymer from a C14 / 16- ⁇ -olefin, maleic anhydride and allyl polyglycol with 2 equivalents of ditallow fatty amine, 50% in solvent naphtha (produced according to EP-A-0606055) C3 Reaction

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