MX2013014751A - Process for preparing a turbine oil comprising an ester component. - Google Patents

Abstract

Provided is a process for preparing 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 and is imminently suitable for use as a turbine oil.

Description

PROCESS FOR THE PREPARATION OF TURBINE OIL THAT UNDERSTANDS AN ESTER COMPONENT Field of the Invention The present invention relates to processes for the preparation of turbine oil compositions, and specifically to turbine oils formed by an ester species having ester bonds in adjacent carbons. The use of the asters allows the preparation of biodegradable turbine oils that have reduced sedimentation.

Background of the Invention The asters have been used as lubricating oils for more than 50 years. They are used in several applications, from reaction engines to refrigeration. In fact, the asters were the first synthetic motor oils of the crankcase in automotive applications. However, asters have given much room to polyalphaolephins (PAO) due to the lower cost of PAOs and the similarity of their formulation with mineral oils. However, in fully synthetic motor oils, asters are almost always used in combination with PAOs to balance the effect on seals, additive solubility, reduction of volatility and the improvement of energy efficiency through improved lubricity.

Ref. 245087 In general, ester-based lubricants have excellent lubricating properties due to the polarity of the ester molecules they are composed in. Due to the polarity of the ester functionality, the esters have a stronger affinity for the surfaces As a result, they are very effective in the establishment of protective films on metal surfaces, such protective films serve to mitigate the wear of metals.Lubricants are less volatile than traditional lubricants and they tend to have higher flash points and lower vapor pressure.The ester lubricants are excellent solvents and dispersants and can solvate and disperse the degradation of oil by-products with ease, that is, they reduce the accumulation of sedimentation in large quantity. that ester lubricants are relatively stable in relation to thermal processes In addition to oxidative and oxidative properties, the ester functionalities provide micro-organisms with a starting point from which to perform their biodegradation more efficiently and more effectively than their mineral oil-based analogues, thus making them more environmentally safe. However, as alluded to above, the preparation of the esters is more complicated and more expensive than that of their PAO equivalents.

Recently, the. novel diester-based lubricant compositions and their corresponding manufacture have been described in Miller et al. , US Patent Application Publication No. 20080194444 A1, published August 14, 2008; and in Miller et al, US Patent Publication No. 20090198075 Al, published August 6, 2009. The diester synthesis described in these patent applications makes the economics of diester lubricant formulations more favorable.

A greater use of Group II base oil (and higher) in finished lubricants such as turbine oils has coincided with a greater awareness about the insoluble formation in finished lubricants. The increase in the formation of insolubles is particularly detrimental in turbine oils. It would be of great benefit to the industry that a turbine oil be provided with good properties but less accumulation of sediment.

Brief Description of the Invention Processes for the preparation of turbine oil formulations comprising a base oil selected from the group consisting of base oils of Groups II, III and IV and mixtures of these and an ester component comprising at least one diester species are provided. or triester that has ester bonds in adjacent carbons. The prepared formulation can exhibit less than 6 mg of sediment / 100 ml of turbine oil as determined by the Cincinnati Milacron A thermal test and is immediately suitable for use as turbine oil.

Among other factors, the present processes allow to effectively and efficiently prepare the turbine oil formulation comprising the present diester and triester species with ester linkages in adjacent coals. The prepared turbine oils exhibit a good balance of properties while also providing a biodegradable alternative. In particular, the turbine oil exhibits reduced sedimentation, and may also exhibit improved copper appearance and improved oxidation stability in RPVOT. The carboxylic acids and starting olefins used in the preparation of the diesters and triesters provide an inexpensive manufacturing route.

Detailed description of the invention The present invention is directed to processes for the preparation of a turbine oil composition with an ester component. The ester component is composed of at least one diester or triester species having ester bonds in adjacent carbons, this ester component can also be bio-derived.

In some embodiments, the bioderivative fatty acid (carboxylic acid) residues (ie, derived from a renewable biomass source) are reacted with reaction products and / or byproducts (ie, α-olefins) Fischer-Tropsch (FT) / gas-to-liquids (GTL) to provide bioderivated diester and triester species that can be mixed selectively with basic solution (oil) and one or more species of additives to provide a finished lubricant of turbine oil with a component derived from biomass.

Given that biolubricants and biofuels are increasingly attracting public attention and are becoming issues of interest to many in the oil industry, the use of biomass in the realization of turbine oils could be attractive from different points of sight (eg, renewability, regulation, economics). As the biomass is used in the embodiment of the present ester component of the turbine oil described herein, the turbine oil is considered to be biolubricating or at least, it is considered to comprise a bio-derived component.

Definitions "Lubricants", as defined herein, are substances (usually a fluid under operating conditions) introduced between two moving surfaces in order to reduce friction and wear between them. This definition is intended to include fats, the viscosity of which is greatly reduced after application of the shear.

As used herein, "base oil" is understood to mean the largest single component (by weight) of a lubricant composition. The base oils are categorized into five groups (I-V) by the American Petroleum Institute (API). See API publication number 1509. The API category for the base oil, as shown in the following table (Table 1), is used to define the compositional nature and / or origin of the base oil.

Table 1 "Mineral-based oils", as defined herein, are those base oils produced by the refining of a crude oil.

"Centistoke", abbreviated "cSt", is a unit for measuring the kinematic viscosity of a fluid (eg, a lubricant), where 1 centistoke equals 1 square millimeter per second (1 cSt = 1 mm2 / s). See, for example, ASTM Standard Guide and Test Method D 2270-04. In the present, the units cSt and mm2 / s are used interchangeably.

With respect to the molecules and / or molecular fragments described herein, "Rn," where "n" is an index, refers to a hydrocarbon group, where the molecules and / or molecular fragments can be linear and / or branched.

As defined herein, "Cn", where "n" is an integer, describes a molecule or hydrocarbon fragment (eg, an alkyl group) where "n" indicates the amount of carbon atoms in the fragment or molecule.

In the present the term "carbon amount" is used analogously to "Cn". One difference, however, is that the amount of carbon refers to the total amount of carbon atoms in a molecule (or molecular fragment) regardless of whether it is purely hydrocarbon in nature or not. Linoleic acid, for example, has an amount of 18 carbons.

The term "internal olefin", as used herein, refers to an olefin (ie, an alkene) having a non-terminal carbon-carbon double bond (C = C). This differs from "-olefins", which do present a carbon-carbon terminal double bond.

As used herein, the term "vicinal" refers to the joining of two functional groups (substituents) to adjacent carbons in a molecule based on hydrocarbons, for example, vicinal diesters.

As used herein, the term "fatty acid moiety" refers to any molecular species and / or molecular fragment comprising the acyl component of a fatty (carboxylic) acid.

The prefix "bio", as used herein, refers to an association with a renewable resource of biological origin, such as a resource generally exclusive of fossil fuels. The association is usually that of a derivation, that is, a bio-ester derived from a precursor material of the biomass.

As defined herein, "Fischer-Tropsch products" refers to molecular species derived from a catalytically driven reaction between CO and H2 (ie, "synthesis gas"). See, for ex. , Dry, "The Fischer-Tropsch process: 1950-2000," volume 71 (3-4), pp. 227-241, 2002; Schulz, "Short history and present trends of Fischer-Tropsch synthesis," Applied Catalysis A, volume 186, pp. 3-12, 1999; Claeys and Van Steen, "Fischer-Tropsch Technology," Chapter 8, pp. 623-665, 2004.

As used herein, "from gas to liquids" refers to Fischer-Tropsch processes to generate liquid hydrocarbons and hydrocarbon-based species (for example, oxygenates).

The term "comprising" means that it includes the elements or steps that are identified after that term, but none of these elements or steps are exhaustive and one embodiment may include other elements or steps.

The "appearance of copper" refers to copper corrosion caused by turbine oil as determined by the ASTM D130-10 standard, "Standard Test Method for Corrosiveness to Copper from Petroleum Products by Copper Strip Test." ("Standard test method for detecting corrosion of copper by petroleum products by testing the copper strip.") The lower the number and the letter, the less corrosion is indicated.

"RPVOT" refers to the oxidation stability of the turbine oil itself, as determined in the ASTM D2272-11 standard, "Standard Test Method for Oxidation Stability of Steam Turbine Oils by Rotatihg Pressure Vessel." Standard test for the oxidation stability of steam turbine oils by rotating the pressure vessel. ") The ability of the turbine oil to prevent oxidation of the ferrous parts if the water reaches Mixing with the oil is determined in the ASTM D665-06 standard, "Standard Test Method for Rust-Preventing Characteristics of Inhibited Mineral Oil in the Presence of Water." ("Standard test method to detect characteristics that prevent the oxidation of inhibited mineral oil in the presence of water.") The test method to determine the relative changes that occur in an oil during its use under oxidation conditions is measured using the ASTM standard D974-08, "Standard Test Method for Acid and Base Number by Color-Indicator Titration." ("Standard test method for determining the number of acid and base by titration with color indicator.") The thermal stability of hydrocarbon-based oils is determined according to the ASTM standard D2070-91, "Standard Test Method for Thermal Stability of Hydraulic Oils." ("Standard test method for determining the thermal stability of hydraulic oils".) Base oils used in turbine oils The present turbine oils comprise a base oil which is selected from the group consisting of Group II, III, IV base oils and mixtures thereof. The base oils of Group II, III and IV are as understood and shown in Table 1, which includes gas to liquids (GTL) derived from base oils. In some modalities, the base oils contain less than 10% by weight, and more likely less than 5% by weight of aromatics. Then the base oil is combined with an amount of an ester component, which is either a diester or triester species or a mixture thereof, the ester component species having ester linkages in the adjacent carbons. The amount of the ester component in general is in the range of 0.5 to 15% by weight according to the turbine oil formulation. In some embodiments, the amount of the ester component will range from 5 to 10% by weight. In one embodiment, an additive is also combined with the base oil and the ester component. The additive can be added first to the base oil, first the ester, or after the combination of all the individual components. In some embodiments, the additive comprises an antioxidant composition comprised of at least one antioxidant other than a phenolic antioxidant.

Diester component In some embodiments, the ester components combined with the base oil comprise a kind of diester having the following chemical structure: where Rlf R2, R3 and R4 are the same or are selected independently of a carbon fragment C2 to C17.

With respect to the diester species mentioned above, the selection of Ri, R2, R3 and R4 may follow any or all of the different criteria. For example, in some embodiments, Rlt R2, R3 and are selected so that the kinematic viscosity of the composition at a temperature of 100 ° C is normally 3mm / sec or greater. In some or in other embodiments, Rlf R2, R3 and R4 are selected such that the pour point of the resulting electrical insulating oil is at -10 ° C or less, -25 ° C or less; or even -40 ° C or less. In some embodiments, Rx and R2 are selected to have a combined carbon number (ie, a total number of carbon atoms) of from 6 to 14. In these or other embodiments, R3 and R4 are selected to have a carbon number combined from 10 to 34. Depending on the mode, the resulting diester species can have a molecular mass between 340 atomic mass units (amu) and 780 amu In some embodiments, the ester component is substantially homogeneous in relation to its diester component. In some or other embodiments, the diester component comprises a variety (ie, a mixture) of diester species.

In some embodiments, the diester component comprises at least one diester species derived from a olefin of C8 to C16 and a carboxylic acid of C2 to Ci8. Commonly, the diester species are produced by reacting each -OH group (in the intermediate) with a different acid, but the diester species can also be produced by reacting each -OH group with the same acid.

In some of the embodiments mentioned above, the diester component combined with the base oil for preparing the turbine oil comprises a diester species selected from the group consisting of decanoic acid ester 2-decanoyloxy-l-hexyl-octyl and its isomers, esters of tetradecanoic acid 1-hexyl-2-tetradecanoyloxy-octyl and its isomers, dodecanoic acid ester 2-dodecanoyloxy-l-hexyl-octyl and its isomers, hexanoic acid 2-hexanoyloxy-l-hexy-octyl ester and its isomers, octanoic acid 2-octanoyloxy-l-hexyl-octyl ester and its isomers, hexanoic acid 2-hexanoyloxy-l-pentyl-heptyl ester and its isomers, octanoic acid 2-octanoyloxy-l-pentyl-heptyl ester and its isomers, decanoic acid ester 2-cecanoyloxy-l-pentyl-heptyl and its isomers, decanoic acid-2-decanoyloxy-l-pentyl-heptyl ester and its isomers, dodecanoic acid-2-dodecanoyloxy-l-pentyl-heptyl ester and its isomers, tetradecanoic l-pentyl-2-tetradecanoyloxy-heptyl ester and its isomers, tetradecanoic acid ester 1- butyl-2-tetradecanoyloxy-hexy and its isomers, dodecanoic acid-l-butyl-2-dodecanoyloxy-hexyl ester and its isomers, decanoic acid ester l-butyl-2-decanoyloxy-hexyl and its isomers, octanoic acid ester l-butyl-2-octanoyloxyhexyl and its isomers, hexanoic acid l-butyl-2-hexanoyloxy-hexyl ester and its isomers, tetradecanoic l-propyl-2-tetradecanoyloxy-pentyl ester and its isomers, acid ester dodecanoic 2 -dedecanoyloxy-1-propyl -pentyl and its isomers, decanoic acid ester 2-decanoyloxy-1-propyl pentyl and its isomers, octanoic acid ester 1-2-octanoyloxy-1-propyl pentyl and its isomers, Hexanoic acid ester 2-hexanoyloxy-1-propyl pentyl and its isomers, and mixtures thereof.

Methods for making the diester components The methods that can be employed in the diester manufacture are further described in US Patent Application Publications 2009/0159837 and 2009/0198075, the publications of which are hereby incorporated by reference in their entirety.

More specifically, in some embodiments, the processes for making the diester species mentioned above, comprise the following steps: epoxidation of an olefin (or amount of olefins) having a carbon number of 8 to 16 to form an epoxide comprising a epoxy ring; ring opening epoxide to form a diol; and esterification (i.e., esterification) of the diol with an esterifying species to form a diester species, wherein the esterifying species are selected from the group consisting of carboxylic acids, acyl acids, acyl halides, acyl anhydrides and combinations of these; where the esterifying species have a carbon number of 2 to 18; and where the diester species have a viscosity of 3 mm2 / sec or more at a temperature of 100 ° C.

In addition, the diester species can be prepared by epoxidation of 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, where the esterifying species is selected from the group consisting of carboxylic acids, acyl halide, acyl anhydride and combinations thereof, where the esterifying species have a carbon number from 2 to 18, and where the diester species has a viscosity and a pour point suitable for use as an electrical insulating oil.

In some embodiments, where an amount of the diester species is formed, it may be substantially homogeneous or it may be a mixture of two or more of these different species of diesters.

In some of the embodiments of the processes mentioned above, the olefin used is a product of the reaction of a Fischer-Tropsch process. In these or other embodiments, the carboxylic acid may be derived from alcohols generated by a Fischer-Tropsch process and / or may be a bio-derived fatty acid.

In some embodiments, the olefin is an α-olefin (ie, an olefin having a double bond in a terminal chain). In the embodiments, it is often necessary to isomerize the olefin in order to internalize the double bond. Isomerization is normally carried out catalytically using a catalyst such as, but not limited to, crystalline aluminosilicate and similar materials and aluminophosphates. See, for example, US patents n. 2,537,283; 3,211,801; 3,270,085; 3,327,014; 3,304,343; 3,448,164; 4,593,146; 3,723,564 and 6,281,404; where the latter claims a catalyst based on crystalline aluminophosphate with one-dimensional pores between 3.8 Á and 5 Á in size.

As an example of these Fischer-Tropsch alpha-olefins (-olefins) for isomerization can be isomerized to the corresponding internal olefins followed by epoxidation. Then the epoxies can be transformed into the corresponding diols by opening the ring epoxide followed by diacylation (i.e., diesterification) with the appropriate carboxylic acids or their acylating derivatives. It is usually necessary to convert alpha olefins to internal olefins since the diesters of alpha olefins, especially the short chain alpha olefins, tend to be solids or waxes. The "internalization" of alpha olefins followed by the transformation in the functionalities of the diester introduces the branching along the chain, which reduces the turbidity point of the products that are intended to be obtained. The ester groups, due to their polar nature, would further improve the viscosity of the final product. The addition of ester branches will increase the amount of carbon and, therefore, the viscosity. You can also decrease the associated runoff and turbidity points. It is usually preferable to have few branches longer than many short branches, since the increased branching tends to decrease the viscosity index (VI).

With respect to the epoxidation step (i.e., the epoxidation step), in some embodiments, the aforementioned olefin (in an internal olefin form) can be reacted with a peroxide (e.g., H202) or a peroxide acid (for example, peroxyacetic acid) to generate an epoxide. See, for example, D. Swern, in Organic Peroxides Volume II, Wiley-Interscience, New York, 1971, p. 355-533, · and B. Plesnicar, in Oxidation in Organic Chemistry, Part C, W. Trahanovsky (ed.), Academic Press, New York 1978, p. 221-253. The defines can be efficiently converted into the corresponding diols by a highly selective reagent such as osmium tetroxide (M. Schroder, Chem. Rev. tomo 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).

With respect to the step of the epoxide ring opening to the corresponding diol, this step can be an acid-catalyzed or base-catalyzed hydrolysis. Examples of acid catalysts include, but are not limited to, Brónsted acids based on minerals (eg, HCl, H 2 S0, H 3 PO 4, perhalogenates, etc.), Lewis acids (eg, TiCl and AlCl 3), solid acids such as aluminas. acids and silicas or their mixtures and the like. See, for example, Chem. Rev. tome 59, p. 737, 1959 and Angew. Chem. Int. Ed., Volume 31, p. 1179, 1992. Basal catalyzed hydrolysis typically involves the use of bases, such as aqueous solutions of sodium or potassium hydroxide.

With respect to the step of esterifying (esterification), an acid is normally used to catalyze the reaction between the -OH groups of the diol and the carboxylic acid (s). Suitable acids include, non-exhaustive mode, sulfuric acid (Munch-Peterson, Org Synth., V, pp. 762, 1973), sulfonic acid (Alien and Sprangler, Org Synth., III, p.203, 1955), hydrochloric acid (Eliel et al., Org Synth., IV, p.169, 1963), and phosphoric acid (among others). In some embodiments, the carboxylic acid used in this step is first converted to an acyl chloride (through, for example, thionyl chloride or PC13). Alternatively, an acyl chloride could be used directly. When an acyl chloride is used, an acid catalyst is not needed and a base such as pyridine, 4-dimethylaminopyridine (DMAP) or triethylamine (TEA) is usually added to react with a HC1 produced. When pyridine or DMAP is used, it is believed that these amines also act as a catalyst by forming a more reactive acylating intermediate. See, for ex. , Fersh et al. , J. Am. Chem. Soc., Volume 92, pp. 5432-5442, 1970 and Hofle et al. Angew Chem. Int. Ed. Engl. , volume 17, p. 569, 1978.

Regardless of the source of the olefin, in some embodiments the carboxylic acid used in the method described above derives from the biomass. In some embodiments, this involves the extraction of some oil component (eg, triglyceride) from the biomass and hydrolysis of triglycerides of which the oil component is formed to form free carboxylic acids.

Triester component In some embodiments, the ester component combined with the base oil comprises a species of triester having the following chemical structure: where Rl7 R2, R3, and R are the same or independently selected from hydrocarbon groups of C2 to C2o (groups with a carbon amount of 2 to 20), and where "n" is an integer from 2 to 20.

With respect to the aforementioned triester species, the selection of RX 1 R2, R 3 and R 4, and n can follow any or all of the different criteria. For example, in some embodiments, Rx, R2, R3 and R4 and n are selected so that the kinematic viscosity of the composition at a temperature of 100 ° C is usually 3mm2 / sec or greater. In some or in other embodiments, Ri, R2, R3 and R4 and n are selected such that the pour point of the resulting electrical insulating oil is at -10 ° C or less, for example, -25 ° C or less or even - 40 ° C or less. In some embodiments, Ri is selected to have a total carbon amount of 6 to 12. In these or other modalities, R2 is selected to have a total amount of carbon. carbon from 1 to 20. In these or other embodiments, R3 and R4 are selected to have a combined carbon number of 4 to 36. In these or other embodiments, n is selected to be an integer from 5 to 10. Depending on of the modality, the resulting triester species can commonly have a molecular mass of between 400 atomic mass units (amu) and 1100 amu, and most commonly between 450 amu and 1000 amu In some embodiments, the ester component is substantially homogeneous in relation to its triester component. In some other embodiments, the triester component comprises a variety (i.e., a mixture) of the triester species. In this or other embodiments, the triester components described above further comprise one or more triester species.

In some of the embodiments described above, the triester component combined with the base oil for preparing the turbine oil comprises one or more triesters of the alkyl ester type of 9,10-bis-alkanoyloxy-octadecanoic acid and isomers and mixtures thereof. these wherein 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 wherein the alkanoyloxy is selected from the group consisting of ethanoyloxy, propanoyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy, nonaoyloxy, decanoyloxy, undacanoyloxy, dodecanoyloxy, tridecanoyloxy, tetradecanoyloxy, pentadecanoyloxy, hexadecanoyloxy and octadecanoyloxy, hexyl ester of 9,10-bis-hexanoyloxy-octadecanoic acid and decyl ester of acid 9,10-bis-decanoyloxy-octadecanoic are examples of the triesters.

Methods for making the triester component A method for preparing the triester species is described in US Pat. No. 7,544,645, which is incorporated herein by reference in its entirety.

More specifically, in some embodiments, the processes for making the aforementioned triester species comprise the following steps: esterifying (i.e., subjecting to esterification) a monounsaturated fatty acid (or an amount of monounsaturated fatty acids) having a carbon amount of 10 at 22 with an alcohol to form an unsaturated ester (or an amount thereof); epoxidizing the unsaturated ester to form an expoxyester species comprising an epoxide ring; opening the epoxide ring of the epoxy ester species to form a dihydroxyester: and esterifying the dihydroxyester with an esterifying species to form a triester species, wherein the 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 amount of 2 to 19.

In another embodiment, 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 epoxy fatty alcohol ring is opened to create the corresponding triol; and then the triol is esterified with an esterifying species to form a triester species, where the esterifying species is selected from the group consisting of carboxylic acids, acyl halides, acyl anhydrides and combinations thereof, where the esterifying species has an amount of carbon from 2 to 19. The structure of the triester prepared by the above method would be as follows: where R2 / R3 and R are normally the same or are independently selected from the C2 to C2o hydrocarbon groups and are most commonly selected from the C to Ci2 hydrocarbon groups.

In another embodiment, the method may comprise the reduction of a monosaturated fatty acid to alcohol corresponding unsaturated; 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 an amount of carbon from 2 to 19.

In some embodiments, where an amount of the triester species is formed, the amount of triester species may be substantially homogeneous or may be a mixture of two or more of the different triester species. Additionally or alternatively, in some embodiments, such methods additionally comprise a step of mixing the tri-ester compositions with one or more diester species.

In some embodiments, such methods produce compositions comprising at least one type of triester of the alkyl ester type of 9,10-bis-alkanoyloxy-octadecanoic acid and isomers and mixtures thereof where the alkyl is selected from a group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl and octadecyl; and wherein the alkanoyloxy is selected from the group consisting of ethanoyloxy, propanoyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy, nonaoyloxy, decanoyloxy, undacanoyloxy, dodecanoyloxy, tridecanoyloxy tetradecanoyloxy, pentadecanoyloxy hexadeconiloyloxy and octadecanoyloxy. Examples of such triesters include, but are not limited to, hexyl ester of 9,10-bis-hexanoyloxy-octadecanoic acid; hexyl ester of 9,10-bis-octanoyloxy-octadecanoic acid; hexyl ester of 9,10-bis-decanoyloxy-octadecanoic acid; hexyl ester of 9,10-bis-dodecanoyloxy-octadecanoic acid; decyl ester of 9,10-bis-hexanoyloxy-octadecanoic acid; 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-hexanoyloxy-octadecanoic acid octyl ester; 9, 10-bis-octanoyloxy-octadecanoic acid octyl ester: 9,10-bis-decanoyloxy-octadecanoic acid octyl ester; octyl ester of 9, 10-bis-dodecanoyloxy-octadecanoic acid dodecyl ester of 9,10-bis-hexanoyloxy-octadecanoic acid; 9, 10-bis-octanoyloxy-octadecanoic acid dodecyl ester; 9, 10-bis-decanoyloxy-octadecanoic acid dodecyl ester; 9, 10-bis-dodecanoyloxy-octadecanoic acid dodecyl ester and mixtures thereof.

In some of the embodiments of such aforementioned methods, the monounsaturated fatty acid may be an acid fatty bioderivative. In one or another modality of the aforementioned method, the alcohol (s) can be alcohols produced by FT.

In some of the aforementioned method embodiments, the step of esterifying (i.e., esterifying) the unsaturated fatty acid can proceed by an acid catalyzed reaction with an alcohol using, for example, H2SO4 as the catalyst. In some or other embodiments, the esterification can proceed through a conversion of the fatty acid (s) to an acyl halide (chloride, bromide or iodide) or acyl anhydride, followed by a reaction with alcohol.

With respect to the epoxidation step (ie, the epoxidation step), in some embodiments, the aforementioned monounsaturated ester may react with a peroxide (eg, H202) or a peroxide acid (eg, peroxyacetic acid) to generate an epoxy ester species. See, for example, D. Swern, in Organic Peroxides Vol. II, Wiley-Interscience, New York, 1971, p. 355-533; and B. Plesnicar, in Oxidation in Organic Chemistry, Part C, W. Trahanovsky (ed.), Academic Press, New York 1978, p. 221-253. Additionally or alternatively, the olefinic part of the monounsaturated ester can be efficiently transformed into the corresponding dihydroxyester by highly selective reagents such as osmium tetraoxide.

(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).

With respect to the step of opening the epoxide ring to the corresponding hydroxyester, this step is usually an acid-catalyzed hydrolysis. Examples of acidic catalysts include, but are not limited to, Brónsted acids based on minerals (eg, HC1, H2S04, H3P04, perhalogenates, etc.), Lewis acids (eg, TiCl4 and A1C13), solid acids such as silicas. and acid aluminas and their mixtures and the like. See, for example, 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 achieved by base catalyzed hydrolysis using KOH or NaOH solutions.

With respect to the step of esterifying the dihydroxyester to form a triester, an acid is normally 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, pp. 762, 1973), sulfonic acid (Alien and Sprangler, Org Synth., III, pp. 203, 1955). ), hydrochloric acid (Eliel et al., Org Synth., IV, p.169, 1963) and phosphoric acid (among others). In In some embodiments, the carboxylic acid used in this step is first converted to an acyl chloride (or other acyl halide) by, for example, thionyl chloride or PC13. Alternatively, an acyl chloride (or other acyl halide) can be used directly. Where an acyl chloride is used, an acid catalyst is not needed and a base such as pyridine, 4-dimethylaminopyridine (DMAP) or triethylamine (TEA) is usually added to react with a produced HCl. When pyridine or DMAP is used, it is believed that these amines also act as a catalyst by forming a more reactive acylating intermediate. See, for example, Fersh et al. , J. Am. Chem. Soc. , vol. 92, p. 5432-5442, 1970 and Hofle et al. Ange. Chem. Int. Ed. Engl. , vol. 17, p. 569, 1978. Additionally or alternatively, the carboxylic acid can be converted to an acyl anhydrous and / or such a species can be used directly.

Regardless of the source of monounsaturated fatty acids, in some embodiments, the carboxylic acids (or their acyl derivatives) used in the foregoing methods are derived from biomass. In some of the embodiments, this involves the extraction of some oil component (eg, triglyceride) from the biomass and triglyceride hydrolysis of which the oil component is formed to form acids free carboxylic acids In some particular embodiments, where the method described above uses oleic acid for the monounsaturated fatty acids, the resulting triester is of the type: where R2, R3 and R are usually the same or are independently selected from the C2 to C2o hydrocarbon groups and are most commonly selected from the groups C4 to Ci2 hydrocarbon.

With a synthetic strategy according to what was summarized above, the oleic acid can be converted into the triester derivatives (hexyl ester of 9,10-bis-hexanoyloxy-octadecanoic acid ester) and (decyl ester of 9,10-bis-decanoyloxy-octadecanoic acid). First the oleic acid is esterified to provide a monounsaturated ester. The monounsaturated ester is subject to an epoxidation agent to provide an epoxy ester species, which undergoes a ring opening process to provide a dihydroxyester, which can react with an acyl chloride to provide a triester product.

The strategy of the aforementioned synthesis uses the functionality of the double bond in an oleic acid when converting it into a dio through a double bond epoxidation, followed by the opening of an epoxide ring. Accordingly, synthesis begins by converting oleic acid to a suitable alkyl oleate followed by epoxidation and opening of the epoxide ring to the corresponding diol derivative (dihydroxyester).

The variations (ie, alternative embodiments) of the abovementioned processes include, but are not limited to, the use of mixtures of isomeric olefins and / or mixtures of olefins having a different number of carbons. This leads to mixtures of diesters and mixtures of triesters in the aster component.

Variations of the aforementioned processes include, but are not limited to, the use of carboxylic acids derived from FT alcohols by oxidation.

The present turbine oils, comprising the base oil and the ester component, exhibit excellent properties as lubricating oils for turbines. One of the most important characteristics is the low sedimentation. The composition of the turbine oil will generally have less than 6 mg of sediment / 100 ml of turbine oil as determined by the Cincinnati Milacron A thermal test. In some embodiments, the oil of turbine exhibits less than 3 mg of sediment / 100 ml of turbine oil. This overcomes a major problem that has been observed with respect to insolubles in turbine oils. By combining the present synthetic ester component, comprising at least one diester or triester species having adjacent ester or carbon bonds, with a base oil of Groups II, III and / or IV, the present turbine oil exhibits that it can obtain a lower sedimentation.

In another embodiment, the turbine oil also contains an additive component. Antioxidants are additives that can be used successfully, which are known in the industry. In some embodiments, the antioxidant comprises at least one antioxidant other than the phenolic antioxidant, for example, an amino antioxidant. Mixtures of antioxidants may be used, for example, 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, either in the absence of a phenolic antioxidant or in a mixture with a phenolic antioxidant.

Other additive components that can be used in the present turbine oil for their respective functions includes detergents, anti-wear agents, metal deactivators, corrosion inhibitors, oxidation inhibitors, friction modifiers, antifoaming agents, viscosity index improvers, demulsifying agents, emulsifying agents, antioxidants, complexing agents, extreme pressure additives , reducers of the point of runoff and combinations of these.

In addition to minor sedimentation, in some embodiments, the present turbine oil exhibits an improved copper appearance, as measured by ASTM D130-10, and an improved oxidation stability according to PVOT. The appearance of copper indicates a minimum copper corrosion, which is generally better than 3? as determined by ASTM D130-10. The oxidative stability of RPVOT, as measured according to ASTM D22272-11, is at least 250 minutes, and in some embodiments is more than 1000 minutes.

Once the ester component has been prepared, the combination of the base oil, the ester component and any additive can be achieved by any suitable mixing means. Generally, the final turbine oil comprises from 0.5 to 15% by weight of the ester component and has a VI of at least 90.

The following examples are provided to demonstrate and / or illustrate in a more complete manner particular embodiments of the present invention. Those skilled in the art should appreciate that the methods described in the examples below represent merely exemplary embodiments of the present invention. Nevertheless, in view of the present description those skilled in the art should appreciate that various changes can be made to the specific embodiments described and may still obtain a similar or similar result without departing from the spirit and scope of the present invention.

EXAMPLE 1 Synthesis of diol from tetradecene In a 3-neck, 3-necked reaction flask, equipped with an overhead stirrer and placed in an ice bath, 260 grams of 30% hydrogen peroxide (2.3 mole H202) was added to 650 grams of 88% weight of formic acid (12.4 mol). To this mixture, 392 grams (2 mole) of a mixture of tetradecene isomers (1-tetradecene, 2-tetradecene, 3-tetradececo, 4-tetradecene, 5-tetradecene, 6-tetradecene and 7-tetradecene) were added. drop by means of an addition funnel over a period of 45 minutes keeping the reaction temperature below 45 ° C. Once the addition of olefins was complete, the reaction was stirred while cooling in a Ice bath to prevent the temperature rise above 40-45 ° C for 2 hs. Then the ice bath was removed and the reaction was stirred 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, a 1M solution of 400 ml of ice cold sodium hydroxide was added in small portions and carefully to the remaining reaction concentrate. Once all of 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 of 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 time). The ethyl acetate extracts were combined and dried over anhydrous MgSO 4. Filtration, followed by concentration in a rotary evaporator under reduced pressure in a hot water bath, provided a mixture of tetradecenes-diol as a 96% yield waxy substance (443 grams). The tetradecenes-diols were characterized by infrared spectroscopy (IR) and nuclear magnetic resonance (NMR), as well as gas chromatography / mass spectrometry (GC / MS).

EXAMPLE 2 Diester synthesis Into a 1-L, 3-necked reaction flask equipped with an overhead stirrer, reflux condenser and addition funnel, 440 grams (0.95 mol) of the tetradecene-diol mixture (prepared as described above) were mixed. in Example 1), 1148 grams (5.7 mole) of lauric acid and 17.5 grams of 85% by weight of H3PO4 (0.15 mole). The resulting mixture was heated to 150 ° C and stirred for several hours while the progress of the reaction was monitored by spectral NMR and GC / MS analysis. After stirring for 6 hours, the reaction was completed and the mixture was cooled to room temperature. The reaction mixture was washed with 1000 ml of water and the organic layer was separated using a separatory funnel. The organic layer was further rinsed with 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 a very light yellow oil at 84% yield (1000 grams). The mixture of the diester product was hydrogenated to remove any residual olefin that might have formed by elimination during the reaction of esterification. The final product, a colorless oil, was analyzed by IR and NMR spectroscopy, and by GC / MS.

The sequence of molecular transformation and reactions is for epoxidation of 7-tetradecene, which is typical for all epoxidation and dihydroxylation of all other olefins by this method.

EXAMPLE 3 Comparative series The turbine oils were prepared by combining 5% by weight of the following diester prepared from Example 2 with three commercial Group II turbine oils: Turbine-1 oil; Turbine-2 oil and Turbine-3 oil, which is an amino-free version of Turbine-2 oil. The basic turbine oils already contained all kinds of additives, for example, antioxidants. The characteristics and physical properties of the prepared turbine oils were analyzed. The basic turbine oils were also analyzed, without the ester component. The results are shown in Table 2 below. The amounts of the components of each turbine oil are shown in Table 2, in% by weight of the total turbine formulation.

Table 2 From the foregoing results, it can be seen that the present turbine oils contain an ester component which can exhibit excellent and improved deposits of lesser sediment. Note in particular the results of Turbine Oil 1 and Turbine Oil 2. The appearance of improved copper and oxidative stability can also be noted. In general, improved turbine oil can be achieved by using the ester component, which can also offer a biodegradable turbine oil option that has lower sedimentation.

All patents and publications referred to herein are incorporated herein by reference to the extent not inconsistent therewith. It will be understood that some of the particular structures, functions and operations described above of the modalities described above do not need to exercise present invention and are included in the description simply by way of completeness of the exemplary modality (s). Additionally, it will be understood that the specific structures, functions, and operations set forth in the aforementioned patents and publications may be exercised in conjunction with the present invention, but are not essential for its exercise. Accordingly, it will be understood that the invention may be exercised otherwise than as specifically described without departing from the spirit and scope of the present invention as defined by the appended claims.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (15)

CLAIMS Having described the invention as above, the content of the following claims is claimed as property:

1. A process for the production of a turbine oil, characterized in that it comprises the following stages: a) epoxidizing an olefin having from about 8 to about 16 carbon atoms to form an epoxide comprising an epoxide ring; b) opening the epoxide ring of step a) and forming a diol; c) esterifying the diol of step b) 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 amount of 2 to 18; Y d) combining an amount of a diester species with a quantity of base oils of Group II, III and / or IV and an antioxidant composition composed of at least one antioxidant other than a phenolic antioxidant.

2. A process for the production of a turbine oil, characterized in that it comprises the following stages: a) epoxidize an olefin that has about 8 to about 16 carbon atoms to form an epoxide comprising an epoxide ring; Y b) reacting the epoxide comprising the epoxide ring 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, where the species esterifier has a carbon amount of 2 to 18, and c) combining an amount of the diester species with a quantity of base oils of Group II, III and / or IV and an antioxidant composition composed of at least one antioxidant other than a phenolic antioxidant.

3. A process for the production of a turbine oil, characterized by comprising the following steps: a) esterifying a monounsaturated fatty acid having from 10 to 22 carbon atoms with an alcohol, which thus forms an unsaturated ester; b) epoxidizing the unsaturated ester of step a), which thereby forms a kind of epoxy ester comprising an epoxide ring; c) opening the ring of the epoxy ester species from step b), which thus forms a hydroxy ester; d) esterifying the dihydroxy ester of step c) with an esterifying species to form a triester species, wherein the esterifying species is selected from the group consisting of of carboxylic acids, acyl halides, acyl anhydrides and combinations thereof and where the esterifying species has a carbon amount of 2 to 19; Y e) combining an amount of the diester species with a quantity of base oils of Group II, III and / or IV and an antioxidant composition composed of at least one antioxidant other than a phenolic antioxidant.

4. A process for the production of a turbine oil, characterized in that it comprises the following stages: a) reducing a monosaturated fatty acid to a corresponding unsaturated alcohol; b) epoxidizing the unsaturated alcohol to an epoxy fatty alcohol; c) open the ring of the epoxy fatty alcohol to create a corresponding triol; d) esterifying the triol of step c) 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 where the esterifying species has a carbon amount of 2 to 19; Y e) combining an amount of the diester species with a quantity of base oils of Group II, III and / or IV and an antioxidant composition composed of at least one antioxidant other than a phenolic antioxidant.

5. A process for the production of a turbine oil, characterized in that it comprises the following stages: a) reducing a monosaturated fatty acid to a corresponding unsaturated alcohol; b) epoxidizing the unsaturated alcohol to an epoxide fatty alcohol; c) esterifying the epoxide fatty alcohol with an esterifying species to form a triester species where the esterifying species is selected from the group consisting of carboxylic acids, acyl halides, acyl anhydrides and combinations thereof and where the esterifying species has an amount of carbon from 2 to 19; Y d) combining an amount of the diester species with a quantity of base oils of Group II, III and / or IV and an antioxidant composition composed of at least one antioxidant other than a phenolic antioxidant.

6. A process for the production of a turbine oil, characterized in that it comprises combining an amount of a diester species having the following structure: where Rlf R2, R3 and R4 are identical or are independently selected from hydrocarbon groups having 2 to 17 carbon atoms, with a quantity of base oils of Group II, III and / or IV and an antioxidant composition composed of at least one antioxidant other than a phenolic antioxidant.

7. A process for the production of a turbine oil, characterized in that it comprises combining an amount of a triester species having the following structure: where Ri, R2, R3 and R4 are identical or are independently selected from hydrocarbon groups having from 2 to 20 carbon atoms and where "n" is an integer from 2 to 20, with a quantity of base oils of Group II, III and / or IV and an antioxidant composition composed of at least one antioxidant other than a phenolic antioxidant.

8. A process for the production of a turbine oil, characterized in that it comprises combining an amount of a triester species having the following structure: where R2, R3, and R4 are identical or are independently selected from C2 to C2o hydrocarbon groups / with a quantity of base oils of Group II, III and / or IV and an antioxidant composition composed of at least one antioxidant other than a phenolic antioxidant.

9. The process according to claim 6, characterized in that the diester is selected from the group consisting of decanoic acid ester 2-decanoyloxy-l-hexyl-octyl and its isomers, esters of tetradecanoic acid 1-hexyl-2-tetradecanoyloxy-octyl and its isomers, dodecanoic acid ester 2-dodecanoyloxy-l-hexyl-octyl and its isomers, hexanoic acid ester 2-hexanoyloxy-l-hexy-octyl and its isomers, octanoic acid ester 2-octanoyloxy-l-hexyl- octyl and its isomers, hexanoic acid 2-hexanoyloxy-l-pentyl-heptyl ester and its isomers, octanoic acid 2-octanoyloxy-l-pentyl-heptyl ester and its isomers, decanoic acid 2-cecanoyloxy-l-pentyl ester heptyl and its isomers, decanoic acid ester 2-decanoyloxy-l-pentyl-heptyl and its isomers, dodecanoic acid-2-dodecanoyloxy-l-pentyl-heptyl ester and its isomers, tetradecanoic acid ester l-pentyl 2 -tetradecanoyloxy-heptyl and its isomers, acid ester tetradecanoic 1-butyl-2-tetradecanoyloxy-hexy and its isomers, dodecanoic acid-l-butyl-2-dodecanoyloxy-hexyl ester and its isomers, decanoic acid ester 1-butyl-2-decanoyloxy-hexyl and their isomers, octanoic acid ester l-butyl-2-octanoyloxyhexyl and its isomers, hexanoic acid l-butyl-2-hexanoyloxyhexyl ester and its isomers, tetradecanoic l-propyl-2-tetradecanoyloxy-pentyl ester and its isomers, dodecanoic acid 2-dodecanoyloxy-1-propyl-pentyl ester and its isomers, decanoic acid ester 2-decanoyloxy-l-propyl pentyl and its isomers, octanoic acid ester 1-2-octanoyloxy-l-propyl -pentyl and its isomers, hexanoic acid 2-hexanoyloxy-1-propyl pentyl ester and its isomers, and mixtures thereof.

10. The process according to claim 6, 7 or 8, characterized in that the antioxidant comprises an amino antioxidant.

11. process according to claim 6, 7 or 8, characterized in that the antioxidant comprises a mixture of a phenolic antioxidant and at least one other non-phenolic antioxidant.

12. The process according to claim 6, characterized in that the diester species is prepared using an esterifying species which is a carboxylic acid.

13. The process according to claim 12, characterized in that the carboxylic acid is derived from a bio-derived fatty acid.

14. The process in accordance with the claim 12, characterized in that the carboxylic acid is derived from alcohols generated by a Fisher-Tropsch process.

15. The process according to claim 7 or 8, characterized in that the triester species is prepared using an esterifying species which is a carboxylic acid.