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
  • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
  • C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
• • 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
  • C10M129/74—Esters of polyhydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
  • C10M2203/102—Aliphatic fractions
  • C10M2203/1025—Aliphatic fractions 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
  • 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
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/17—Fisher Tropsch reaction products
  • C10M2205/173—Fisher Tropsch reaction products 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
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
  • C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
• • 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
  • C10M2207/283—Esters of polyhydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
  • C10M2215/064—Di- and triaryl amines
• • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/22—Heterocyclic nitrogen compounds
  • C10M2215/223—Five-membered rings containing nitrogen and carbon only
• • 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
  • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
  • C10M2219/066—Thiocarbamic type 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
  • C10N2030/04—Detergent property or dispersant property
• • 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
  • C10N2030/64—Environmental friendly compositions
• • 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
  • C10N2040/12—Gas-turbines
• • 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
  • C10N2040/135—Steam engines or turbines
• • 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
  • C10N2070/00—Specific manufacturing methods for lubricant compositions
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

• This invention relates to turbine oil compositions and their manufacture, and specifically to turbine oils comprised of an ester species having ester links on adjacent carbons.
• the use of such esters can provide biodegradable turbine oils having reduced sludge.
• Esters have been used as lubricating oils for over 50 years. They are used in a variety of applications ranging from jet engines to refrigeration. In fact, esters were the first synthetic crankcase motor oils in automotive applications. However, esters have largely given way to polyalphaolefins (PAOs) due to the lower cost of PAOs and their formulation similarities to mineral oils. In fully synthetic motor oils, however, esters are almost always used in combination with PAOs to balance the effect on seals, additive solubility, volatility reduction, and energy efficiency improvement by enhanced lubricity.
• PAOs polyalphaolefins
• Ester-based lubricants in general, have excellent lubrication properties due to the polarity of the ester molecules of which they are comprised. Due to the polarity of the ester functionality, esters have a stronger affinity for metal surfaces than PAOs and mineral oils. As a result, they are very effective in establishing protective films on metal surfaces, such protective films serving to mitigate the wear of such metals. Such lubricants are less volatile than the traditional lubricants and tend to have much higher flash points and much lower vapor pressures. Ester lubricants are excellent solvents and dispersants, and can readily solvate and disperse the degradation by-products of oils, i.e., they greatly reduce sludge buildup.
• ester lubricants are relatively stable to thermal and oxidative processes, the ester functionalities give microbes a handle with which to do their biodegrading more efficiently and more effectively than their mineral oil-based analogues—thereby rendering them more environmentally-friendly.
• ester lubricants are relatively stable to thermal and oxidative processes, the ester functionalities give microbes a handle with which to do their biodegrading more efficiently and more effectively than their mineral oil-based analogues—thereby rendering them more environmentally-friendly.
• the preparation of esters is more involved and more costly than that of their PAO counterparts.
• a turbine oil formulation comprised of a base oil selected from the group consisting of Group II, III and IV base oils and mixtures thereof, and an ester component comprised of at least one diester or triester species having ester links on adjacent carbons.
• the formulation exhibits less than 6 mg of sludge/100 ml of turbine oil as determined by the Cincinnati Milacron Thermal A test, and is imminently suitable for use as a turbine oil.
• the present turbine oil formulation comprising the present diester and triester species having ester links on adjacent carbons, provides a turbine oil with a good balance of properties while also providing a biodegradable alternative.
• the turbine oil exhibits reduced sludge, and can also exhibit improved copper appearance and improved oxidation stability in RPVOT.
• the starting olefins and carboxylic acids used in preparing the diesters and triesters also provides an economical manufacturing route.
• the present invention is directed to a turbine oil composition having an ester component.
• the ester component is comprised of at least one diester or triester species having ester links on adjacent carbons, which ester component can also be bio-derived.
• bio-derived (i.e., derived from a renewable biomass source) fatty (carboxylic) acid moieties are reacted with Fischer-Tropsch (FT)/gas-to-liquids (GTL) reaction products and/or by-products (i.e., ⁇ -olefins) to yield bio-derived diester and triester species that can then be selectively blended with base stock (oil) and one or more additive species to yield a turbine oil finished lubricant product having a biomass-derived component.
• FT Fischer-Tropsch
• GTL gas-to-liquids
• biomass is utilized in the making of the present ester component of the turbine oil described herein, such a turbine oil is deemed to be a biolubricant—or at the very least, they are deemed to comprise a bio-derived component.
• “Lubricants,” as defined herein, are substances (usually a fluid under operating conditions) introduced between two moving surfaces so to reduce the friction and wear between them. This definition is intended to include greases, whose viscosity drops dramatically upon application of shear.
• base oil will be understood to mean the single largest component (by weight) of a lubricant composition.
• Base oils are categorized into five groups (I-V) by the American Petroleum Institute (API). See API Publication Number 1509.
• API Base Oil Category as shown in the following table (Table 1), is used to define the compositional nature and/or origin of the base oil.
• Mineral base oils are those base oils produced by the refining of a crude oil.
• the units cSt and mm 2 /s are used interchangeably.
• R n refers to a hydrocarbon group, wherein the molecules and/or molecular fragments can be linear and/or branched.
• C n As defined herein, “C n ,” where “n” is an integer, describes a hydrocarbon molecule or fragment (e.g., an alkyl group) wherein “n” denotes the number of carbon atoms in the fragment or molecule.
• carbon number is used herein in a manner analogous to that of “C n .” A difference, however, is that carbon number refers to the total number of carbon atoms in a molecule (or molecular fragment) regardless of whether or not it is purely hydrocarbon in nature. Linoleic acid, for example, has a carbon number of 18.
• internal olefin refers to an olefin (i.e., an alkene) having a non-terminal carbon-carbon double bond (C ⁇ C). This is in contrast to “ ⁇ -olefins” which do bear a terminal carbon-carbon double bond.
• vicinal refers to the attachment of two functional groups (substituents) to adjacent carbons in a hydrocarbon-based molecule, e.g., vicinal diesters.
• fatty acid moiety refers to any molecular species and/or molecular fragment comprising the acyl component of a fatty (carboxylic) acid.
• bio refers to an association with a renewable resource of biological origin, such as resource generally being exclusive of fossil fuels. Such an association is typically that of derivation, i.e., a bio-ester derived from a biomass precursor material.
• Fischer-Tropsch products refer to molecular species derived from a catalytically-driven reaction between CO and H 2 (i.e., “syngas”). See, e.g., Dry, “The Fischer-Tropsch process: 1950-2000,” vol. 71(3-4), pp. 227-241, 2002; Schulz, “Short history and present trends of Fischer-Tropsch synthesis,” Applied Catalysis A, vol. 186, pp. 3-12, 1999; Claeys and Van Steen, “Fischer-Tropsch Technology,” Chapter 8, pp. 623-665, 2004.
• “Gas-to-liquids,” as used herein, refers to Fischer-Tropsch processes for generating liquid hydrocarbons and hydrocarbon-based species (e.g., oxygenates).
• Copper Appearance refers to the copper corrosion caused by the turbine oil as determined by ASTM D130-10, “Standard Test Method for Corrosiveness to Copper from Petroleum Products by Copper Strip Test.” The lower the number and letter the less corrosion indicated.
• RVOT refers to the oxidation stability of the turbine oil itself, as determined by ASTM D2272-11, “Standard Test Method for Oxidation Stability of Steam Turbine Oils by Rotating Pressure Vessel.”
• test method for determining the relative changes that occur in an oil during use under oxidizing conditions is measured using ASTM D974-08, “Standard Test Method for Acid and Base Number by Color-Indicator Titration.”
• the thermal stability of hydrocarbon based oils is determined by ASTM D2070-91, “Standard Test Method for Thermal Stability of Hydraulic Oils.”
• the present turbine oils comprise a base oil selected from the group consisting of Group II, III, IV base oils and mixtures thereof.
• the Group II, III and IV base oils are as understood and shown in Table 1, which include Gas-to-Liquid (GTL) derived based oils.
• the base oils contain less than 10 wt %, and more likely less than 5 wt % aromatics.
• the base oil is then combined with a quantity of an ester component, which is either a diester or triester species, or a mixture thereof, which ester component species has ester links on adjacent carbons.
• the quantity of ester component is generally in the range of from 0.5 to 15 wt % based on the turbine oil formulation.
• the quantity of ester component will range from 5 to 10 wt %.
• an additive is also combined with the base oil and ester component.
• the additive can be added to the base oil first, the ester first, or upon combining all individual components.
• the additive comprises an antioxidant composition comprised of at least one antioxidant other than a phenolic antioxidant.
• ester component combined with the base oil comprises a diester species having the following chemical structure:
• R 1 , R 2 , R 3 , and R 4 are the same or independently selected from a C 2 to C 17 carbon fragment.
• R 1 , R 2 , R 3 , and R 4 can follow any or all of several criteria.
• R 1 , R 2 , R 3 , and R 4 are selected such that the kinematic viscosity of the composition at a temperature of 100° C. is typically 3 mm 2 /sec or greater.
• R 1 , R 2 , R 3 , and R 4 are selected such that the pour point of the resulting electrical insulating oil is ⁇ 10° C. or lower, ⁇ 25° C. or lower; or even ⁇ 40° C. or lower.
• R 1 and R 2 are selected to have a combined carbon number (i.e., total number of carbon atoms) of from 6 to 14.
• R 3 and R 4 are selected to have a combined carbon number of from 10 to 34.
• such resulting diester species can have a molecular mass between 340 atomic mass units (a.m.u.) and 780 a.m.u.
• the ester component is substantially homogeneous in terms of its diester component.
• the diester component comprises a variety (i.e., a mixture) of diester species.
• the diester component comprises at least one diester species derived from a C 8 to C 16 olefin and a C 2 to C 18 carboxylic acid.
• the diester species are made by reacting each —OH group (on the intermediate) with a different acid, but such diester species can also be made by reacting each —OH group with the same acid.
• the diester component combined with the base oil to prepare the turbine oil comprises a diester species selected from the group consisting of decanoic acid 2-decanoyloxy-1-hexyl-octyl ester and its isomers, tetradecanoic acid-1-hexyl-2-tetradecanoyloxy-octyl esters and its isomers, dodecanoic acid 2-dodecanoyloxy-1-hexyl-octyl ester and its isomers, hexanoic acid 2-hexanoyloxy-1-hexy-octyl ester and its isomers, octanoic acid 2-octanoyloxy-1-hexyl-octyl ester and its isomers, hexanoic acid 2-hexanoyloxy-1-pentyl-heptyl ester and isomers, octanoic acid
• the processes for making the above-mentioned diester species comprise the following steps: epoxidizing an olefin (or quantity of olefins) having a carbon number of from 8 to 16 to form an epoxide comprising an epoxide ring; opening the epoxide ring to form a diol; and esterifying (i.e., subjecting to esterification) the diol with an esterifying species to form a diester species, wherein such esterifying species are selected from the group consisting of carboxylic acids, acyl acids, acyl halides, acyl anhydrides, and combinations thereof; wherein such esterifying species have a carbon number from 2 to 18; and wherein the diester species have a viscosity of 3 mm 2 /sec or more at a temperature of 100° C.
• the diester species can be prepared by epoxidizing an olefin having from about 8 to about 16 carbon atoms to form an epoxide comprising an epoxide ring.
• the epoxidized olefin is reacted directly with an esterifying species to form a diester species, wherein the esterifying species is selected from the group consisting of carboxylic acids, acyl halides, acyl anhydrides, and combinations thereof, wherein the esterifying species has a carbon number of from 2 to 18, and wherein the diester species has a viscosity and a pour point suitable for use as an electrical insulating oil.
• the quantity of diester species can be substantially homogeneous, or it can be a mixture of two or more different such diester species.
• the olefin used is a reaction product of a Fischer-Tropsch process.
• the carboxylic acid can be derived from alcohols generated by a Fischer-Tropsch process and/or it can be a bio-derived fatty acid.
• the olefin is an ⁇ -olefin (i.e., an olefin having a double bond at a chain terminus).
• a catalyst such as, but not limited to, crystalline aluminosilicate and like materials and aluminophosphates. See, e.g., U.S. Pat. Nos.
• Fischer-Tropsch alpha olefins can be isomerized to the corresponding internal olefins followed by epoxidation.
• the epoxides can then be transformed to the corresponding diols via epoxide ring opening followed by di-acylation (i.e., di-esterification) with the appropriate carboxylic acids or their acylating derivatives.
• di-acylation i.e., di-esterification
• the above-described olefin in one embodiment an internal olefin
• a peroxide e.g., H 2 O 2
• a peroxy acid e.g., peroxyacetic acid
• Olefins can be efficiently transformed to the corresponding diols by highly selective reagent such as osmium tetra-oxide (M. Schroder, Chem. Rev. vol. 80, p. 187, 1980) and potassium permanganate (Sheldon and Kochi, in Metal-Catalyzed Oxidation of Organic Compounds, pp. 162-171 and 294-296, Academic Press, New York, 1981).
• highly selective reagent such as osmium tetra-oxide (M. Schroder, Chem. Rev. vol. 80, p. 187, 1980) and potassium permanganate (Sheldon and Kochi, in Metal-Catalyzed Oxidation of Organic Compounds, pp. 162-171 and 294-296, Academic Press, New York, 1981).
• this step can be acid-catalyzed or based-catalyzed hydrolysis.
• exemplary acid catalysts include, but are not limited to, mineral-based Br ⁇ nsted acids (e.g., HCl, H 2 SO 4 , H 3 PO 4 , perhalogenates, etc.), Lewis acids (e.g., TiCl 4 and AlCl 3 ) solid acids such as acidic aluminas and silicas or their mixtures, and the like. See, e.g., Chem. Rev. vol. 59, p. 737, 1959; and Angew. Chem. Int. Ed., vol. 31, p. 1179, 1992.
• Based-catalyzed hydrolysis typically involves the use of bases such as aqueous solutions of sodium or potassium hydroxide.
• an acid is typically used to catalyze the reaction between the —OH groups of the diol and the carboxylic acid(s).
• Suitable acids include, but are not limited to, sulfuric acid (Munch-Peterson, Org. Synth., V, p. 762, 1973), sulfonic acid (Allen and Sprangler, Org. Synth., III, p. 203, 1955), hydrochloric acid (Eliel et al., Org. Synth., IV, p. 169, 1963), and phosphoric acid (among others).
• the carboxylic acid used in this step is first converted to an acyl chloride (via, e.g., thionyl chloride or PCl 3 ).
• an acyl chloride could be employed directly.
• an acid catalyst is not needed and a base such as pyridine, 4-dimethylaminopyridine (DMAP) or triethylamine (TEA) is typically added to react with an HCl produced.
• DMAP 4-dimethylaminopyridine
• TAA triethylamine
• pyridine or DMAP it is believed that these amines also act as a catalyst by forming a more reactive acylating intermediate. See, e.g., Fersh et al., J. Am. Chem. Soc., vol. 92, pp. 5432-5442, 1970; and Hofle et al., Angew. Chem. Int. Ed. Engl., vol. 17, p. 569, 1978.
• the carboxylic acid used in the above-described method is derived from biomass.
• this involves the extraction of some oil (e.g., triglyceride) component from the biomass and hydrolysis of the triglycerides of which the oil component is comprised so as to form free carboxylic acids.
• oil e.g., triglyceride
• the ester component combined with the base oil comprises a triester species having the following chemical structure:
• R 1 , R 2 , R 3 , and R 4 are the same or independently selected from C 2 to C 20 hydrocarbon groups (groups with a carbon number from 2 to 20), and wherein “n” is an integer from 2 to 20.
• R 1 , R 2 , R 3 , and R 4 , and n can follow any or all of several criteria.
• R 1 , R 2 , R 3 , and R 4 and n are selected such that the kinematic viscosity of the composition at a temperature of 100° C. is typically 3 mm 2 /sec or greater.
• R 1 , R 2 , R 3 , and R 4 and n are selected such that the pour point of the resulting electrical insulating oil is ⁇ 10° C. or lower, e.g., ⁇ 25° C. or even ⁇ 40° C. or lower.
• R 1 is selected to have a total carbon number of from 6 to 12.
• R 2 is selected to have a carbon number of from 1 to 20.
• R 3 and R 4 are selected to have a combined carbon number of from 4 to 36.
• n is selected to be an integer from 5 to 10.
• such resulting triester species can typically have a molecular mass between 400 atomic mass units (a.m.u.) and 1100 a.m.u., and more typically between 450 a.m.u. and 1000 a.m.u.
• the ester component is substantially homogeneous in terms of its triester component.
• the triester component comprises a variety (i.e., a mixture) of such triester species.
• such above-described triester components further comprise one or more triester species.
• the triester component combined with the base oil to prepare the turbine oil comprises one or more triester species of the type 9,10-bis-alkanoyloxy-oetadecanoic acid alkyl ester and isomers and mixtures thereof, where the alkyl is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, and octadecyl; and where the alkanoyloxy is selected from the group consisting of ethanoyloxy, propanoyoxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, oc
• processes for making the above-mentioned triester species comprises the following steps: esterifying (i.e., subjecting to esterification) a mono-unsaturated fatty acid (or quantity of mono-unsaturated fatty acids) having a carbon number of from 10 to 22 with an alcohol to form an unsaturated ester (or a quantity thereof); epoxidizing the unsaturated ester to form an epoxy-ester species comprising an epoxide ring; opening the epoxide ring of the epoxy-ester species to form a dihydroxy-ester: and esterifying the dihydroxy-ester with an esterifying species to form a triester species, wherein such esterifying species are selected from the group consisting of carboxylic acids, acyl halides, acyl anhydrides, and combinations thereof; and wherein such esterifying species have a carbon number of from 2 to 19.
• the method can comprise reducing a monosaturated fatty acid to the corresponding unsaturated alcohol.
• the unsaturated alcohol is then epoxidized to an epoxy fatty alcohol.
• the ring of the epoxy fatty alcohol is opened to make the corresponding triol; and then the triol is esterified with an esterifying species to form a triester species, wherein the esterifying species is selected from the group consisting of carboxylic acids, acyl halides, acyl anhydrides, and combinations thereof, and wherein the esterifying species has a carbon number of from 2 to 19.
• the structure of the triester prepared by the foregoing method would be as follows:
• R 2 , R 3 , and R 4 are typically the same or independently selected from C 2 to C 20 hydrocarbon groups, and are more typically selected from C 4 to C 12 hydrocarbon groups.
• the method can comprise reducing a monosaturated fatty acid to the corresponding unsaturated alcohol; epoxidizing the unsaturated alcohol to an epoxy fatty alcohol; and esterifying the fatty alcohol epoxide with an esterifying species to form a triester species, wherein the esterifying species is selected from the group consisting of carboxylic acids, acyl halides, acyl anhydrides, and combinations thereof, and wherein the esterifying species has a carbon number of from 2 to 19.
• the quantity of triester species can be substantially homogeneous, or it can be a mixture of two or more different such triester species. Additionally or alternatively, in some embodiments, such methods further comprise a step of blending the triester composition(s) with one or more diester species.
• such methods produce compositions comprising at least one triester species of the type 9,10-bis-alkanoyloxy-octadecanoic acid alkyl ester and isomers and mixtures thereof where the alkyl is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, and octadecyl; and where the alkanoyloxy is selected from the group consisting of ethanoyloxy, propanoyoxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy, nonaoyloxy, decan
• Exemplary such triesters include, but not limited to, 9,10-bis-hexanoyloxy-octadecanoic acid hexyl ester; 9,10-bis-octanoyloxy-octadecanoic acid hexyl ester; 9,10-bis-decanoyloxy-octadecanoic acid hexyl ester; 9,10-bis-dodecanoyoxy-octadecanoic acid hexyl ester; 9,10-bis-hexanoyloxy-octadecanoic acid decyl ester; 9,10-bis-decanoyloxy-octadecanoic acid decyl ester; 9,10-bis-octanoyloxy-octadecanoic acid decyl ester; 9,10-bis-dodecanoyloxy-octadecanoic acid decyl ester; 9,10-bis
• the mono-unsaturated fatty acid can be a bio-derived fatty acid.
• the alcohol(s) can be FT-produced alcohols.
• the step of esterifying (i.e., esterification) the mono-unsaturated fatty acid can proceed via an acid-catalyzed reaction with an alcohol using, e.g., H 2 SO 4 as a catalyst.
• the esterifying can proceed through a conversion of the fatty acid(s) to an acyl halide (chloride, bromide, or iodide) or acyl anhydride, followed by reaction with an alcohol.
• the above-described mono-unsaturated ester can be reacted with a peroxide (e.g., H 2 O 2 ) or a peroxy acid (e.g., peroxyacetic acid) to generate an epoxy-ester species.
• a peroxide e.g., H 2 O 2
• a peroxy acid e.g., peroxyacetic acid
• the olefinic portion of the mono-unsaturated ester can be efficiently transformed to the corresponding dihydroxy ester by highly selective reagents such as osmium tetra-oxide (M. Schroder, Chem. Rev. vol. 80, p. 187, 1980) and potassium permanganate (Sheldon and Kochi, in Metal-Catalyzed Oxidation of Organic Compounds, pp. 162-171 and 294-296, Academic Press, New York, 1981).
• highly selective reagents such as osmium tetra-oxide (M. Schroder, Chem. Rev. vol. 80, p. 187, 1980) and potassium permanganate (Sheldon and Kochi, in Metal-Catalyzed Oxidation of Organic Compounds, pp. 162-171 and 294-296, Academic Press, New York, 1981).
• this step is usually an acid-catalyzed hydrolysis.
• acid catalysts include, but are not limited to, mineral-based Br ⁇ nsted acids (e.g., HCl, H 2 SO 4 , H 3 PO 4 , perhalogenates, etc.), Lewis acids (e.g., TiCl 4 and AlCl 3 ), solid acids such as acidic aluminas and silicas or their mixtures, and the like. See, e.g., Chem. Rev. vol. 59, p. 737, 1959; and Angew. Chem. Int. Ed., vol. 31, p. 1179, 1992.
• the epoxide ring opening to the diol can also be accomplished by base-catalyzed hydrolysis using aqueous solutions of KOH or NaOH.
• an acid is typically used to catalyze the reaction between the —OH groups of the diol and the carboxylic acid(s).
• Suitable acids include, but are not limited to, sulfuric acid (Munch-Peterson, Org. Synth., V, p. 762, 1973), sulfonic acid (Allen and Sprangler, Org. Synth., III, p. 203, 1955), hydrochloric acid (Eliel et al., Org. Synth., IV, p. 169, 1963), and phosphoric acid (among others).
• the carboxylic acid used in this step is first converted to an acyl chloride (or another acyl halide) via, e.g., thionyl chloride or PCl3.
• an acyl chloride or other acyl halide could be employed directly.
• an acid catalyst is not needed and a base such as pyridine, 4-dimethylaminopyridine (DMAP) or triethylamine (TEA) is typically added to react with an HCl produced.
• DMAP 4-dimethylaminopyridine
• TAA triethylamine
• the carboxylic acids (or their acyl derivatives) used in the above-described methods are derived from biomass. In some such embodiments, this involves the extraction of some oil (e.g., triglyceride) component from the biomass and hydrolysis of the triglycerides of which the oil component is comprised so as to form free carboxylic acids.
• oil e.g., triglyceride
• the resulting triester is of the type:
• R 2 , R 3 and R 4 are typically the same or independently selected from C 2 to C 20 hydrocarbon groups, and are more typically selected from C 4 to C 12 hydrocarbon groups.
• oleic acid can be converted to triester derivatives (9,10-bis-hexanoyloxy-octadecanoic acid hexyl ester) and (9,10-bis-decanoyloxy-octadecanoic acid decyl ester).
• Oleic acid is first esterified to yield a mono-unsaturated ester.
• the mono-unsaturated ester is subjected to an epoxidation agent to give an epoxy-ester species, which undergoes ring-opening to yield a dihydroxy ester, which can then be reacted with an acyl chloride to yield a triester product.
• the strategy of the above-described synthesis utilizes the double bond functionality in oleic acid by converting it to the diol via double bond epoxidation followed by epoxide ring opening. Accordingly, the synthesis begins by converting oleic acid to the appropriate alkyl oleate followed by epoxidation and epoxide ring opening to the corresponding diol derivative (dihydroxy ester).
• Variations (i.e., alternate embodiments) on the above-described processes include, but are not limited to, utilizing mixtures of isomeric olefins and or mixtures of olefins having a different number of carbons. This leads to diester mixtures and triester mixtures in the ester component.
• Variations on the above-described processes include, but are not limited to, using carboxylic acids derived from FT alcohols by oxidation.
• the present turbine oils comprised of the base oil and ester component, show excellent properties as a lubricating oil for turbines.
• One of the most important characteristics is reduced sludge.
• the turbine oil composition will generally have less than 6 mg of sludge/100 ml of turbine oil as determined by the Cincinnati Milacron Thermal A Test. In some embodiments, the turbine oil exhibits less than 3 mg of sludge/100 ml of turbine oil. This overcomes a major problem which has been observed with regard to insoluble formation in turbine oils.
• the present synthetic ester component comprised of at least one diester or triester species having ester links on adjacent carbons, with a Group II, III and/or IV base oil, the present turbine oil exhibiting reduced sludge can be obtained.
• the turbine oil also contains an additive component.
• Antioxidants are additives which can be successfully used, which are known to the industry.
• the antioxidant comprises at least one antioxidant other than a phenolic antioxidant, e.g., an amine antioxidant. Mixtures of antioxidants can be used, e.g., a mixture of aminic and phenolic antioxidants or a mixture of dithiocarbamate, tolutriazole and phenolic antioxidants. It has been found that favorable results are achieved when antioxidants other than phenolic antioxidants are used, whether in the absence of a phenolic antioxidant or in mixture with a phenolic antioxidant.
• additive components which can be used in the present turbine oil for their respective functions include detergents, anti-wear agents, metal deactivators, corrosion inhibitors, rust inhibitors, friction modifiers, anti-foaming agents, viscosity index improvers, demulsifying agents, emulsifying agents, antioxidants, complexing agents, extreme pressure additives, pour point depressants, and combinations thereof.
• the present turbine oils exhibit improved copper appearance, as measured by ASTM D130-10, and improved oxidation stability in RPVOT.
• the copper appearance indicates minimal copper corrosion, generally better than 3 A as determined by ASTM D130-10.
• the RPVOT oxidative stability, as measured by ASTM D22272-11, is at least 250 minutes, and in some embodiments is over 1000 minutes.
• the combination of the base oil, ester component and any additives can be achieved by any suitable mixing means.
• the final turbine oil is comprised of from 0.5 to 15 wt % of the ester component and has a VI of at least 90.
• the reaction was allowed to stir while cooling in an ice bath to prevent a rise in the temperature above 40-45° C., for 2 hrs. The ice bath was then removed and the reaction was allowed to stir at room temperature overnight.
• the reaction mixture was concentrated with a rotary evaporator in a hot water bath at about 30 mmHg to remove most of the water and formic acid. Then, 400 ml of ice-cold 1M solution of sodium hydroxide was added in small portions and carefully to the remaining reaction concentrate. Once all the sodium hydroxide solution was added, the mixture was allowed to stir for an additional 2 hours at about 75-80° C.
• the mixture was then diluted with 500 ml ethyl acetate and transferred to a separatory funnel. The organic layer was separated and the aqueous layer was extracted 3 times with ethyl acetate (300 ml each). The ethyl acetate extracts were all combined and dried over anhydrous MgSO 4 . Filtration, followed by concentration on a rotary evaporator at reduced pressure in a hot water bath yielded a tetradecenes-diol mixture as a waxy substance in 96% yield (443 grams). The tetradecenes-diols were characterized by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopes, as well as gas-chromatography/mass spectrometry (GC/MS).
• IR infrared
• NMR nuclear magnetic resonance
• the organic layer was further rinsed with brine solution (1000 ml of saturated sodium chloride solution).
• brine solution 1000 ml of saturated sodium chloride solution.
• the resulting mixture was then distilled at 220° C. and 100 mmHg (Torr) to remove excess lauric acid.
• the diester product (the remaining residue in the distillation flask) was recovered as faint clear yellow oil in 84% yield (1000 grams).
• the mixture of diesters' product was hydrogenated to remove any residual olefins that could have formed by elimination during the esterification reaction.
• the final product, a colorless oil was analyzed by IR and NMR spectroscopes, and by GC/MS.
• Turbine oils were prepared by combining 5 wt % of the foregoing prepared diester of Example 2 with three different commercial Group II turbine oils: Turbine Oil-1; Turbine Oil-2; and Turbine Oil-3, which is an amine free version of Turbine Oil-2.
• the basic turbine oils already contained any additives, e.g., antioxidants. The physical characteristics and properties of the prepared turbine oils were then tested. The basic turbine oils, without the diester component, were also tested. The results are shown in Table 2 below. The amounts of the components of each Turbine Oil are noted in Table 2 in wt % of the overall turbine formulation.
• the present turbine oils containing the ester component can exhibit excellent and improved reduced sludge deposits.
• an improved turbine oil is achieved by utilizing the ester component, which also offers an option of biodegradable turbine oils having reduced sludge.

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