Classifications

• • 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
  • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
  • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
  • C10M129/68—Esters
  • C10M129/72—Esters of polycarboxylic acids
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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
  • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
  • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
  • C10M105/32—Esters
  • C10M105/36—Esters of polycarboxylic acids
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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
  • 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
  • C10M2205/026—Butene
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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
  • 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
  • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
• • 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
  • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
  • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
• • 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
  • C10M2207/285—Esters of aromatic polycarboxylic 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/285—Esters of aromatic polycarboxylic acids
  • C10M2207/2855—Esters of aromatic polycarboxylic acids used as base material
• • 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
  • C10N2020/011—Cloud point
• • 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
  • C10N2020/02—Viscosity; Viscosity index
• • 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
  • C10N2020/069—Linear chain 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
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/071—Branched chain compounds
• • C—CHEMISTRY; METALLURGY
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  • 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
  • C10N2020/085—Non-volatile 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
  • C10N2030/02—Pour-point; Viscosity index
• • 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
  • C10N2030/74—Noack Volatility
• • 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
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
• • 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
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
  • C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
• • 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
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
  • C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
• • 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
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
• • 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
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/20—Metal working
• • 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
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
• • 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
  • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
  • C10N2050/10—Semi-solids; greasy

Definitions

• the commercially available lubricant compositions are produced from a multitude of different natural or synthetic components. To improve the required properties, according to the field of use, further additives are usually added.
• the various lubricants must satisfy extremely high criteria such as high viscosity index, good rheological performance, particularly at extreme temperatures, high oxidation stability, good thermal and hydrolytic stability and comparable properties.
• the present invention is directed to the use of a 2,5-furandicarboxylic acid ester obtainable by reacting a mixture comprising
• the plant in which the 2,5-furandicarboxylic acid or the material to be processed into 2,5-furandicarboxylic acid is formed can be a genetically modified (genetically engineered by recombinant DNA or RNA technology) plant.
• the 2,5-furandicarboxylic acid is obtained starting from material obtained from a natural, wild-type plant which has not been modified by recombinant technology.
• the radical R denotes a moiety selected from the group consisting of hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl, isopentadecyl, isohexadecyl, isoheptadecyl,
• the radical R denotes a branched or linear, substituted or unsubstituted aliphatic hydrocarbon moiety having from 8 to 18 carbon atoms, or even more preferably, 8 to 16 carbon atoms.
• the 2,5-furandicarboxylic acid esters are preferably used in an amount of 3.5 to 45 percent by weight, more preferably in an amount of from 5.0 to 35.0 percent by weight, and most preferably in an amount of 10.0 to 30.0 percent by weight, based on the total amount of the lubricant composition.
• Preferred base oils contemplated for optional use in the lubricating oil compositions according to the present invention include mineral oils, poly-alpha-olefin synthetic oils and mixtures thereof.
• the mineral oils useful as optional components in the lubricant compositions according to the present invention include all common mineral oil base stocks. This includes oils that are naphthenic, paraffinic or aromatic in chemical structure.
• the GTL base oils may be mixed with more conventional base oils such as Groups I to V as specified by API.
• the base oil component of the lubricant compositions of the present invention may include 1 to 100 percent by weight of GTL base oil.
• Oils may be refined by conventional methodology using acid, alkali, and clay or other agents such as aluminum chloride, or they may be extracted oils produced, for example, by solvent extraction with solvents such as phenol, sulfur dioxide, furfural, dichlordiethyl ether, etc.
• the monocarboxylic and dicarboxylic acid esters that can be optionally used in addition are present in the lubricant compositions either individually, or in the form of mixtures comprising at least one monocarboxylic acid ester and at least one dicarboxylic acid ester.
• the alcohol mixture comprises 80 to 95 percent by weight of 2-n-propyl-heptanol, 1.0 to 10 percent by weight of 2-propyl-4-methyl-hexanol, 1.0 to 10 percent by weight of 2-propyl-5-methyl-hexanol and 0.1 to 2.0 percent by weight of 2-isopropyl-heptanol, whereby the weight of each component is related to the total weight of the monoalcohols.
• the mixture comprises 91.0 to 95.0 percent by weight of 2-n-propyl-heptanol, 2.0 to 5.0 percent by weight of 2-propyl-4-methyl-hexanol, 3.0 to 5.0 percent by weight of 2-propyl-5-methyl-hexanol and 0.1 to 0.8 percent by weight of 2-isopropyl-heptanol, whereby the weight of each component is related to the total weight of the monoalcohols.
• an additional optional carboxylic acid ester is obtained by reacting a mixture comprising adipic acid, 2-propyl-heptanol, 2-propyl-4-methyl-hexanol and 2-propyl-5-methyl-hexanol.
• the addition of at least one additive, like an additional customary oil additive, to the lubricating oil compositions of the present invention is possible but not mandatory in every case.
• the mentioned lubricant compositions e.g. greases, gear fluids, metal-working fluids and hydraulic fluids, may additionally comprise further additives that are added in order to improve their basic properties still further.
• Such additives include: further antioxidants or oxidation inhibitors, corrosion inhibitors, friction modifiers, metal passivators, rust inhibitors, anti-foamants, viscosity index enhancers, additional pour-point depressants, dispersants, detergents, further extreme-pressure agents and/or anti-wear agents.
• Such additives are present in the amounts customary for each of them, which range in each case from 0.01 to 30.0 percent by weight, preferably from 0.05 to 20.0 percent by weight, more preferably from 0.1 to 10.0 percent by weight, and even more preferably 0.2 to 5.0 percent by weight, based on the total weight of the lubricating oil composition.
• 0.01 to 30.0 percent by weight preferably from 0.05 to 20.0 percent by weight, more preferably from 0.1 to 10.0 percent by weight, and even more preferably 0.2 to 5.0 percent by weight, based on the total weight of the lubricating oil composition.
• further additives are given below:
• additives such as anti-misting agents may be also optionally added in an amount ranging from 0.05 to 5.0% by vol. in one embodiment, and less than 1 wt. %, in other embodiments.
• a small amount of foam inhibitors in the prior art can also be added to the composition in an amount ranging from 0.02 to 15.0 wt. %.
• the 2,5-furandicarboxylic acid esters to be used as lubricants in the present invention can be obtained by initially providing 2,5-furandicarboxylic acid and/or the at least one branched or linear, substituted or unsubstituted aliphatic C6 to C20 alcohol from a non-renewable and/or renewable source as defined above. It is especially preferred that all components from which the ester is formed, i.e. acid and alcohol is of renewable origin.
• the 2,5-furandicarboxylic acid or a suitable derivative thereof is provided.
• the 2,5-furandicarboxylic acid can be esterified with the at least one branched or linear, substituted or unsubstituted aliphatic C6 to C20 alcohol of the general formula R-OH by use of the corresponding acyl halogenide, preferably the acyl chloride or acyl bromide, or the respective anhydride of 2,5-furandicarboxylic acid.
• the radical R denotes a branched or linear, substituted or unsubstituted aliphatic hydrocarbon moiety having from 10 to 18 carbon atoms.
• the mixture of the at least one alcohol of the general formula R-OH is preferably the mixture of so-called Guerbet alcohols obtainable from the Guerbet reaction, wherein the preferred radical R is a mixture of different radicals in which at least 50 mole % or 65 mole percent, more preferably at least 70 mole percent, even more preferably at least 80 mole %, and most preferably at least 90 mole %, of the total amount of radicals used in this preparation process, have the general formula I, wherein p is 0, 1, 2, 3, or 4; while p is preferably 0,1 or 2, or more preferably p is 2;.
• esterification of the 2,5-furandicarboxylic acid is carried out with the mixture of the at least one branched or linear, substituted or unsubstituted aliphatic C6 to C20 alcohol of the general formula R-OH as defined above.
• This esterification reaction of the 2,5-furandicarboxylic acid preferably includes the following optional or preferred process features.
• Esterification is typically carried out at a temperature range from 50 to 250°C.
• the mixture obtained in the previous step(s) is heated to a temperature in the range of 80°C to 160°C, followed by optionally adding a basic aqueous solution, and optionally followed in a third step by removing the remaining alcohol.
• the esterification catalyst will be preferably used in an effective amount, typically in the range of from 0.05 to 10 wt%, more preferably 0.1 to 5.0 wt% based on the combined amount of acid component (or anhydride) and the alcohol component.
• the esterification catalyst when the esterification catalyst is selected from organic acids or mineral acids, the esterification is preferably carried out at a temperature range from 50 to 160°C. If the esterification catalyst is selected from amphoteric catalysts, the esterification is preferably carried out at a temperature range from 100 to 250°C, more preferably from 150°C to 200°C.
• WO 02/038531 A1 discloses processes for the preparation of esters, comprising
• the esterification of 2,5-furandicarboxylic acid is carried out in the presence of the above-described alcohol component by use of an organic acid or a mineral acid, particularly sulfuric acid.
• the alcohol component is used in at least two-fold stochiometric amount relative to the 2,5-furandicarboxylic acid or the derivative thereof, based on the reactive OH- and CO 2 H-groups respectively.
• Other optional stochiometric ratios of reactive OH-groups to CO 2 H-groups include 1.0 to 4.0, preferably 1.2 to 3.5, even more preferably 1.4 to 3.0, or 1.6 to 2.5.
• the esterification of the present invention can be preferably carried out at ambient pressure or decreased or increased pressure. Preferably, the esterification is carried out at ambient pressure or decreased pressure.
• the esterification of the present invention can be carried out in the absence of an additional solvent or in the presence of an organic solvent, preferably an organic solvent which is chemically inert under the esterification conditions.
• organic solvents include aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, aromatic and substituted aromatic hydrocarbons or ethers.
• Very preferred solvents are selected from pentane, hexane, heptane, ligroin, petroleum ether (benzene), cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, dibutylether, tetrahydrofuran, dioxane and mixtures thereof.
• Esterification can be carried out in the absence or presence of an inert gas.
• inert gas refers to gas which does not react with the educts, reagents, solvents or the products formed in the reaction under the given process conditions.
• esterification is carried out without the addition of an inert gas.
• the 2,5-furandicarboxylic acid ester which was thus obtained can be further purified by drying and filtering.
• reaction between the 2,5-furandicarboxylic acid and the mixture of the at least one branched or linear, substituted or unsubstituted aliphatic C6 to C20 alcohol of the general formula R-OH can be preferably carried out using stochiometric amounts of 2,5-furandicarboxylic acid and alcohol based on the number of reactive OH- and CO 2 H-groups, particularly when entrainers are used.
• a stochiometric excess (based on the number of reactive OH- and CO 2 H-groups) of the alcohol component of from 0.05 to 1.0 mole per mole of 2,5-furandicarboxylic acid component in order to achieve complete conversion of 2,5-furandicarboxylic acid.
• the esterification reaction between 2,5-furandicarboxylic acid and the at least one alcohol is carried out in two stages, wherein already in the first stage substantial amounts of the desired 2,5-furandicarboxylic acid ester are formed without the addition of a catalyst, preferably at least one of the catalysts as described above.
• the temperatures to be employed in this first stage depend largely on the starting materials. Satisfactory reaction rates are achieved above 100°C, and preferably above 120°C. It is possible to already complete the carboxylic ester formation at these temperatures.
• the temperature continuously up to 160 °C is more advantageous to increase the temperature continuously up to 160 °C.
• 2,5-furandicarboxylic acid rather than the corresponding carboxylic anhydride thereof
• the water formed is removed from the reaction system as an azeotrope with the alcohol, as long as the reaction temperature is above the boiling point of the azeotrope (i.e. in a range from 90°C to 100°C under atmospheric pressure).
• the course and completion of the esterification can in this case be observed via the formation of water.
• the use of subatmospheric or superatmospheric pressure is not ruled out, but is rather restricted to special cases.
• the esterification of the 2,5-furandicarboxylic acid is completed.
• the second stage is carried out in the presence of catalysts at temperatures which are above those employed in the first stage and go up to 250°C. Water formed during the reaction is removed as an azeotrope, with the alcohol acting as an entrainer.
• the reaction mixture comprises not only the desired reaction product, but it may still contain 2,5-furandicarboxylic acid together with excess alcohol and the catalyst.
• the product from the reactor is first neutralized with alkali metal hydroxide or alkaline earth metal hydroxide.
• the alkaline reagent is employed as an aqueous solution containing from 5 to 20 percent by weight, preferably from 10 to 15 percent by weight, of the hydroxide, based on the overall weight of the solution.
• the amount of neutralizing agent to be used depends on the proportion of acid components, free acid and 2,5-furandicarboxylic acid ester in the crude product.
• the use of the selected hydroxides, among which sodium hydroxide has been found to be particularly useful, as aqueous solution having a particular concentration and in a defined excess ensures that the acidic constituents of the reaction mixture are precipitated in a crystalline, very readily filterable form.
• the catalyst is largely decomposed to form likewise easily filterable products.
• the alkaline treatment of the crude 2,5-furandicarboxylic acid ester is not tied to the maintenance of particular temperatures. It is advantageously carried out immediately after the esterification step without prior cooling of the reaction mixture.
• the removal of the free alcohol is typically followed by the drying of the 2,5-furandicarboxylic acid ester.
• drying is achieved by passing an inert gas through the product.
• the crude 2,5-furandicarboxylic acid ester is then filtered to free it of solids.
• the filtration is carried out in conventional filtration equipment at room temperature or at temperatures up to 150°C.
• the filtration can also be facilitated by customary filter aids such as cellulose or silica gel.
• transesterification can also be applied.
• transesterification e.g. a process that involves the reaction of a di-ester of 2,5-furandicarboxylate, preferably as prepared by the esterification process described above, with at least one branched or linear, substituted or un-substituted aliphatic C6 to C20 alcohol of the general formula R-OH in the presence of at least one suitable transesterification catalyst, like preferably a titanium(IV) alcoholate.
• a suitable transesterification catalyst like preferably a titanium(IV) alcoholate.
• Transesterification catalysts that can be used are the conventional catalysts usually used for transesterification reactions, where these are mostly also used in esterification reactions.
• mineral acids such as sulfuric acid and phosphoric acid
• organic sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid
• specific metal catalysts from the group of the tin(IV) catalysts for example dialkyltin dicarboxylates, such as dibutyltin diacetate, trialkyltin alkoxides, monoalkyltin compounds, such as monobutyltin dioxide, tin salts, such as tin acetate, or tin oxides
• titanium catalysts monomeric and polymeric titanates and titanium chelates, for example tetraethyl orthotitanate, tetrapropyl orthotitanate, tetrabutyl orthotitanate, triethanolamine titan
• the amount of transesterification catalyst used is from 0.001 to 10% by weight, preferably from 0.05 to 5% by weight.
• the reaction mixture is preferably heated to the boiling point of the reaction mixture, the reaction temperature therefore being from 20°C to 200°C, depending on the reactants.
• the transesterification can take place at ambient pressure or at reduced or elevated pressure. It is preferable that the transesterification is carried out at a pressure of from 0.001 to 200 bar, particularly from 0.01 to 5 bar.
• the relatively low-boiling-point alcohol eliminated during the transesterification is preferably continuously removed by distillation in order to shift the equilibrium of the transesterification reaction.
• the distillation column necessary for this purpose generally has direct connection to the transesterification reactor, and it is preferable that said column is a direct attachment thereto.
• each of said reactors can have a distillation column, or the vaporized alcohol mixture can preferably be introduced into a distillation column from the final tanks of the transesterification reactor cascade by way of one or more collection lines.
• the relatively high-boiling-point alcohol reclaimed in said distillation is preferably returned to the transesterification.
• an amphoteric catalyst is used, this is generally removed via hydrolysis and subsequent removal of the resultant metal oxide, e.g. via filtration. It is preferable that, after reaction has been completed, the catalyst is hydrolyzed by means of washing with water, and the precipitated metal oxide is removed by filtration. The filtrate can, if desired, be subjected to further work-up for the isolation and/or purification of the product. It is preferable that the product is isolated by distillation.
• the transesterification of the di-ester of 2,5-furandicarboxylic acid preferably takes place in the presence of the alcohol component and in the presence of at least one titanium(IV) alcoholate.
• Preferred titanium(IV) alcoholates are tetrapropoxytitanium, tetrabutoxytitanium, and mixtures thereof. It is preferable that the amount used of the alcohol component is at least twice the stochiometric amount, based on the di-ester of the 2,5-furandicarboxylic acid used.
• the transesterification can be carried out in the absence of, or in the presence of, an added organic solvent. It is preferable that the transesterification is carried out in the presence of an inert organic solvent. Suitable organic solvents are those mentioned above for the esterification. Among these are specifically toluene and THF.
• the transesterification is preferably carried out in the temperature range from 50 to 200°C.
• the transesterification can take place in the absence of or in the presence of an inert gas.
• inert gas generally means a gas which under the prevailing reaction conditions does not enter into any reactions with the starting materials, reagents, or solvents participating in the reaction, or with the resultant products. It is preferable that the transesterification takes place without addition of any inert gas.
• the 2,5-furandicarboxylic acid ester to be used as lubricant in the present invention as well as the lubricant compositions according to the present invention comprising the inventive2,5-furandicarboxylic acid ester can be favourably used for various applications.
• engine oils include all sorts of engine oils, including light, medium and heavy duty engine oils, industrial engine oils, marine engine oils, crankshaft oils, compressor oils, refrigerator oils, hydrocarbon compressor oils, very low-temperature lubricating oils and fats, high temperature lubricating oils and fats, wire rope lubricants, textile machine oils, refrigerator oils, aviation and aerospace lubricants, aviation turbine oils, transmission oils, gas turbine oils, spindle oils, spin oils, traction fluids, transmission oils, plastic transmission oils, passenger car transmission oils, truck transmission oils, industrial transmission oils, industrial gear oils, insulating oils, instrument oils, brake fluids, transmission liquids, shock absorber oils, heat distribution medium oils, transformer oils, fats, chain oils, metalworking operations in general, particularly as minimum quantity lubricants for metalworking operations, oil to the warm and cold working, oil for water-based metalworking liquids, oil for neat oil metalworking fluids, oil for semi-synthetic metalworking fluids, oil for synthetic metalworking fluids, drilling detergents for
• the 2,5-furandicarboxylic acid esters of the present invention are used in lubricant compositions, in particular the 2,5-furandicarboxylic acid esters are used in lubricant compositions in automatic transmission fluids, manual transmission fluids, hydraulic fluids, grease, gear fluids, crankcase engine oils, shock absorber fluids, industrial oils, metal-working fluids, transformer oils, biodegradable lubricants and seal plasticizing agents.
• At least 40 mole percent of the 2,5-furandicarboxylic acid preferably at least 50 mole percent, more preferably at least 65 mole percent, even more preferably at least 75 mole percent, and most preferably at least 85 mole percent of the 2,5-furandicarboxylic acid, and sometimes even at least 90 mole percent, or at least 95 mole percent or even 100 mole percent are hereby derived from a renewable source.
• the 2,5-furandicarboxylic acid ester is obtained by esterification of the 2,5-furandicarboxylic acid, preferably of the 2,5-furandicarboxylic acid of at least partial renewable origin, with a mixture of Guerbet alcohols as defined herein, which is a mixture that was obtained from the Guerbet reaction. In another preferred embodiment of the present invention, this mixture of Guerbet alcohols is also at least partially derived from a renewable source.
• one very preferred use is directed to the use of the 2,5-furandicarboxylic acid of at least partial, preferably full, renewable origin with a mixture of Guerbet alcohols of at least partially, preferably fully, renewable origin for the preparation of 2,5-furandicarboxylic acid ester of at least partially, preferably fully, renewable origin.
• the 2,5-furandicarboxylic acid esters obtained from esterification of 2,5-furandicarboxylic acid and at least one branched or linear, substituted or unsubstituted aliphatic C6 to C20 alcohol, like a mixture of Guerbet alcohols as described herein, allow the preparation of lubricant compositions with attractive rheological performance characteristics, favourable viscosity profiles, good hydrolytic and oxidative stability, good seal compatibility and favourable traction behaviour.
• the lubricant compositions of the present invention due to the presence of the 2,5-furandicarboxylic acid ester have excellent hydrolytic and oxidative stability, good seal performance, and attractive rheological performance characteristics, like kinematic viscosity profile, over a very broad temperature range, and favourable traction behaviour when compared with other lubricants that are based on different carboxylic acid esters.
• the latter performance characteristics of known lubricant compositions can be further improved by the addition, or supplementation of the 2,5-furandicarboxylic acid ester of the present invention.
• the lubricant compositions of the present invention comprising the 2,5-furandicarboxylic acid esters have kinematic viscosity at 40°C as determined by ASTM D 445 in the range of from 90.0 to 160.0 mm 2 /s, preferably 100.0 to 150.0 mm 2 /s, and more preferably 110.0 to 140.0 mm 2 /s. Most preferred are values in the range of from 120.0 to 135.0 mm 2 /s.
• the lubricant compositions of the present invention comprising the 2,5-furandicarboxylic acid esters have kinematic viscosity at 100°C as determined by ASTM D 445 in the range of from 5.0 to 30.0 mm 2 /s, preferably 10.0 to 25.0 mm 2 /s, and more preferably 12.0 to 20.0 mm 2 /s. Most preferred are values in the range of from 15.0 to 18.0 mm 2 /s.
• the lubricant compositions of the present invention comprising the 2,5-furandicarboxylic acid esters have viscosity index as determined by ASTM D 2270 in the range of from 125 to 160, preferably 130 to 155, and more preferably from 140 to 150.
• the lubricant compositions of the present invention comprising the 2,5-furandicarboxylic acid esters have pour point as determined by ISO 3016 in the range of from -70°C to -40°C, preferably from -65°C to -45°C and more preferably from -60°C to -50°C.
• the lubricant compositions of the present invention comprising the 2,5-furandicarboxylic acid esters have cloud point as determined by ISO 3015 in the range of from -100 to -65, preferably - 90 to -70, and more preferably from -85 to -75.
• the lubricant compositions of the present invention comprising the 2,5-furandicarboxylic acid esters also have good oxidation stability and hydrolytic stability.
• 2-Propylheptanol is commercially available from BASF SE, Ludwigshafen and represents a mixture of 93.0 wt.-% 2-propyl-heptanol, 2.9 wt.-% 2-propyl-4-methyl-hexanol, 3.9 wt.-% 2-propyl-5-methylhexanol and 0.2 wt.-% 2-isopropylheptanol.
• the stirred mixture was heated to reflux (114-155 °C) and 234 g (1.50 mol, 1.0 eq.) 2,5-furandicarboxylic acid were added followed by 11.5 g (0.12 mol, 8 mol-%) 99.9% sulfuric acid in 3 or 4 equal portions whenever conversion slowed.
• the conversion was monitored by the amount of water deposited in the Dean-Stark apparatus. Upon complete conversion a sample was drawn and submitted to GC analysis.
• the cooled reaction mixture was transferred to a separatory funnel and washed twice with 500 mL saturated NaHCO 3 solution (upon addition of the alkaline NaHCO 3 solution vigorous CO 2 formation may result).
• GC-columns Agilent J&W DB-5, 30 m x 0,32 mm x 1,0 ⁇ m or Ohio Valley OV-1701 60 m x 0,32 mm x 0,25 ⁇ m).
• 2-propylheptyl-2,5-furandicarboxylate was highly viscous while at the same time showing a low pour point. Moreover, 2-propylheptyl-2,5-furandicarboxylate is both hydrolytically and thermally stable.
• Lubricant composition 1 wt.-% Diester of 2-propylheptyl 2,5-furandicarboxylate (>98,5%) 10.0 Base oil (Synfluid, PAO-6) 52.0 Viscosity modifier, PIB (Lubrizol® 8406, from Lubrizol) 13.0 Viscosity modifier, OCP (Lubrizol® 8407, from Lubrizol) 13.0 Additive package (Anglamol 6004, available from Lubrizol) 12.0 Characterization of lubricant composition 1 Kinematic viscosity at 40°C (mm 2 /s) ASTM D 445 130,83 Kinematic viscosity at 100°C (mm 2 /s) ASTM D 445 17,668 Viscosity index ASTM D 2270 149 Water content (%) ASTM E 203 0,15 Cloud Point °C ISO 3015 -80 Pour Point °C ISO
• the lubricant composition showed a favorable viscosity profile over a broad range of temperatures while having a low pour point at the same time.

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• 2015
  • 2015-12-11 EP EP15199531.3A patent/EP3178908A1/fr not_active Withdrawn

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