stolide compositions exhibiting high oxidative stability and method for improving the oxidative stab

专利摘要:
STOLIDE COMPOSITES EXHIBITING HIGH OXIDATIVE STABILITY. The present invention relates to stolide compositions having high oxidative stability, said compositions comprise at least one compound of formula: (I) Formula I wherein n is an integer equal to or greater than 0; m is an integer equal to or greater than 1; R1, independently for each occurrence, is selected from optionally substituted alkyl, which is saturated or unsaturated, and branched or unbranched, R2 is selected from hydrogen and an alkyl which is saturated or unsaturated, and branched or unbranched, and R3 and R4, independently, for each occurrence, are selected from optionally substituted alkyl, which is saturated or unsaturated, and branched or unbranched. Here, too, are the uses for the compositions and the methods of preparing them.
公开号:BR112013032389B1
申请号:R112013032389-2
申请日:2012-05-30
公开日:2020-12-01
发明作者:Jakob BREDSGUARD；Travis Thompson；Jeremy Forest
申请人:Biosynthetic Technologies, Llc；
IPC主号:

专利说明:

CROSS REFERENCE TO RELATED ORDERS
[001] This application claims the benefit under 35 USC § 119 (e) of Provisional Patent Application No. 61/498, 499, filed on June 17, 2011, Provisional Patent Application No. 61/569, 046, filed on December 9, 2011, and Provisional Patent Application No. 61/643, 072, filed on May 4, 2012, which are incorporated herein by reference in their entirety for all purposes. FIELD
[002] The present invention relates to lubricating compositions comprising one or more stolide compounds and exhibiting high oxidizing stability, and methods of producing them. BACKGROUND
[003] A variety of commercial uses for fatty acid esters such as triglycerides have been described. When used as a lubricant, for example, fatty acid esters can provide a biodegradable alternative to base oil lubricants. However, naturally occurring fatty acid esters are generally deficient in one or more domains, including hydrolytic stability and / or oxidative stability. SUMMARY
[004] Described here are stolide compositions that exhibit high oxidative stability and methods for producing and using them.
[005] In certain embodiments, the composition comprises at least one stolide compound of Formula I:

[006] where
[007] x is, independently for each occurrence, an integer selected from 0, 1,2,3,4,5,6,7, 8, 9, 10, 11, 12, 13, 14, 15, 16 , 17, 18, 19, and 20;
[008] y is, independently for each occurrence, an integer selected from 0, 1,2,3,4,5,6,7, 8, 9, 10, 11, 12, 13, 14, 15, 16 , 17, 18, 19, and 20;
[009] n is an integer selected from 0, 1,2,3,4,5,6,7, 8, 9, 10, 11, and 12;
[0010] R1 is an optionally substituted alkyl group, which is saturated or unsaturated, branched or unbranched, and;
[0011] R2 is selected from hydrogen and optionally substituted alkyl which is saturated or unsaturated, and branched or unbranched;
[0012] wherein each fatty acid residue chain of said at least one compound is independently optionally substituted.
[0013] In certain embodiments, the composition comprises at least one stolide compound of Formula II:

[0014] where
[0015] m is an integer equal to or greater than 1;
[0016] n is an integer equal to or greater than 0;
[0017] R1, independently, for each occurrence, is an optionally substituted alkyl group, which is saturated or unsaturated, branched or unbranched, and;
[0018] R2 is selected from hydrogen and optionally substituted alkyl, which is saturated or unsaturated, branched or unbranched, and; and
[0019] R3 and R4, independently, for each occurrence, are selected from optionally substituted alkyl, which is saturated or unsaturated, and branched or unbranched.
[0020] In certain modalities, the composition comprises at least

[0021] where
[0022] x is, independently for each occurrence, an integer selected from 0, 1,2,3,4,5,6,7, I, 9, 10, 11, 12, 13, 14, 15, 16 , 17, 18, 19, and 20;
[0023] y is, independently for each occurrence, an integer selected from 0, 1,2,3,4,5,6,7, I, 9, 10, 11, 12, 13, 14, 15, 16 , 17, 18, 19, and 20;
[0024] n is an integer equal to or greater than 0;
[0025] R1 is an optionally substituted alkyl group, which is saturated or unsaturated, branched or unbranched, and; and
[0026] R2 is selected from hydrogen and optionally substituted alkyl which is saturated or unsaturated, and branched or unbranched;
[0027] wherein each fatty acid chain residue of said at least one compound is independent and optionally substituted. DETAILED DESCRIPTION
[0028] The stolide compositions described herein can exhibit superior oxidative stability when compared to any other lubricant and / or compositions containing stolide.
[0029] Examples of compositions include, but are not limited to, refrigerants, fire-resistant and / or non-flammable fluids, dielectric fluids such as transformer fluids, greases, drilling fluids, crankcase oils, hydraulic fluids, engine oils passenger cars, 2 and 4-stroke lubricants, machining fluids, food grade lubricants, cooling fluids, compressor fluids, and plasticized compositions.
[0030] The use of lubricants and lubricating fluid compositions may result in the dispersion of fluids, such compounds and / or compositions in the environment. Petroleum-based oils used in common lubricant compositions, as well as additives, are typically non-biodegradable and can be toxic. The present disclosure provides for the preparation and use of compositions that partially or totally comprise biodegradable base oils, including base oils that comprise one or more stolids.
[0031] In certain embodiments, lubricants and / or compositions that comprise one or more stolides are partially or totally biodegradable and, thus, present a reduced risk to the environment. In certain modalities, lubricants and / or compositions meet the guidelines established by the Organization for Economic Cooperation and Development (OECD) for degradation and accumulation tests. The OECD has indicated that several tests can be used to determine the "biodegradability" of organic chemicals. Aerobic biodegradability by OECD 301D measures the mineralization of the test sample to CO2 in closed aerobic microcosms that simulate an aerobic aquatic environment, with microorganisms seeded from a wastewater treatment plant. OECD 301D is considered representative of most aerobic environments that are susceptible to receiving waste.
[0032] "Ultimate aerobic biodegradability" can be determined by OECD 302D. Under OECD 302D, microorganisms are pre-acclimated for biodegradation of the test material during a pre-incubation period, then incubated in closed tubes with relatively high concentrations of microorganisms and medium enriched with mineral salts. OECD 302D ultimately determines whether test materials are completely biodegradable, albeit under less stringent conditions than "ready" biodegradability tests.
[0033] As used in this specification, the following words, phrases and symbols are generally intended to have the meanings described below, except to the extent that the context in which they are used indicates otherwise. The following abbreviations and terms have the meanings indicated throughout:
[0034] A dash ("-"), which is not between two letters or symbols is used to indicate a point of attachment to a substituent. For example, -C (0) NH2 is linked via the carbon atom.
[0035] "Alkoxy", alone or as part of another substituent, refers to a radical -OR31 where R31 is alkyl, cycloalkyl, cycloalkylalkyl, aryl, or arylalkyl, which can be substituted as defined herein. In some embodiments, the alkoxy groups have 1 to 8 carbon atoms. In some embodiments, alkoxy groups have 1,2,3,4,5,6,7 or 8 carbon atoms. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, cyclohexyloxy, and the like.
[0036] The term "alkyl" alone or as part of another substituent, refers to a saturated or unsaturated, branched, or monovalent straight chain hydrocarbon radical derived by the removal of a hydrogen atom from a single carbon atom of a parent, alkene or alkane alkane. Examples of alkyl groups include, but are not limited to, methyl; ethyls, such as ethanyl, ethenyl, and ethynyl; propyls such as propan-1-yl, propan-2-yl, prop-1-en-1-yl, prop -1-en-2-yl, prop-2-en-1-yl (allyl), prop- 1-in-1-yl, prop-2-in-1-yl, etc .; butyls, such as butan-1-yl, butan-2-yl, 2-methyl-propan-1-yl, 2-methyl-propan-2-yl, but-1-en-1-yl, but-1- en-2-yl, 2-methyl-prop-1-en-1-yl, but-2-en-1-yl, but-2-en-2-yl, buta-1,3-diene-1- ila, buta-1,3-dien-2-yl, but-1-ino-1-yl, but-1-in-3-yl, but-3-in-1-yl, etc., and the like.
[0037] Unless otherwise indicated, the term "alkyl" is specifically intended to include groups having any degree or level of saturation, that is, groups having exclusively individual carbon-carbon bonds, groups having one or more bonds carbon-carbon double bonds, groups having one or more carbon-carbon triple bonds, and groups with mixtures of carbon-carbon, single, double and triple bonds. Whenever a certain level of saturation is desired, the terms "alkanyl", "alkenyl" and "alkynyl" are used. In certain embodiments, an alkyl group comprises from 1 to 40 carbon atoms, in certain embodiments, from 1 to 22 or 1 to 18 carbon atoms, in certain embodiments, from 1 to 16 or 1 to 8 carbon atoms, and in certain modalities of 1 to 6 or 1 to 3 carbon atoms. In certain embodiments, an alkyl group comprises between 8 and 22 carbon atoms, in certain embodiments, from 8 to 18 or 8 to 16. In some embodiments, the alkyl group comprises from 3 to 20 or 7 to 17 carbon atoms. In some embodiments, the alkyl group comprises 1,2,3,4,5,6,7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22 carbon atoms.
[0038] The term "aryl", alone or as part of another substituent, refers to a monovalent aromatic hydrocarbon radical derived by the removal of a hydrogen atom from a single carbon atom from an aromatic ring system parent. Aryl includes 5- and 6-membered aromatic carbocyclic rings, for example, benzene; bicyclic ring systems in which at least one ring is carbocyclic and aromatic, for example, naphthalene, indane, and tetralin; and tricyclic ring systems, in which at least one ring is carbocyclic and aromatic, for example, fluorene. Aryl includes several ring systems having at least one carbocyclic aromatic ring fused to at least one aromatic carbocyclic ring, cycloalkyl ring or hetero-cycloalkyl ring. For example, aryl includes 5- and 6-membered aromatic carbocyclic rings fused to a 5- to 7-membered non-aromatic hetero-cycloalkyl ring containing one or more heteroatoms chosen from N, O and S. For such fused bicyclic ring systems, in Since only one of the rings is a carbocyclic aromatic ring, the attachment point may be on the carbocyclic aromatic ring or hetero-cycloalkyl ring. Examples of aryl groups include, but are not limited to, groups derived from aceantrylene, acenaphthene, acephenanthrene, anthracene, azulene, benzene, chrysene, coronene, fluoranthene, fluorene, hexacene, hexafene, hexalene, as-indacene, s-indacene, indane , indene, naphthalene, octacene, octafen, octalene, ovalene, penta-2,4-diene, pentacene, pentalene, pentafene, perylene, phenalene, phenanthrene, picene, pleiadene, pyrene, pyranthrene, rubicene, triphenylene, trinaftalen, and the like. In certain embodiments, an aryl group may contain 5 to 20 carbon atoms, and in certain embodiments, from 5 to 12 carbon atoms. In certain embodiments, an aryl group may contain 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. Arila, however, does not cover or overlap in any form with heteroaryl, separately defined here. Thus, a multiple ring system in which one or more aromatic carbocyclic rings are fused with a hetero-cycloalkyl aromatic ring, is heteroaryl, not aryl, as defined herein.
[0039] "Arylalkyl", alone or as part of another substituent, refers to an acyclic alkyl radical, in which one of the hydrogen atoms attached to a carbon atom, typically, a sp3 terminal or carbon atom, is replaced by an aryl group. Examples of arylalkyl groups include, but are not limited to, benzyl, 2-phenylethan-1-yl, 2-phenylethen-1-yl, naphthylmethyl, 2-naphthylethan-1-yl, 2-naphthylethen-1-yl, naphthobenzyl, 2-naphthophenylethan-1-yl, and the like. When specific alkyl groups are desired, the nomenclature arylalkanyl, arylalkenyl, or arylalkynyl is used. In certain embodiments, an arylalkyl group is C7-30 arylalkyl, for example, the alkanyl, alkenyl or alkynyl portion of the arylalkyl group is C1-10 and the aryl portion is C6-20, and in certain embodiments, an arylalkyl group is C720 arylalkyl, for example, alkanyl, alkenyl or alkynyl of the arylalkyl group is C1-8 and the aryl fraction is C6-12
[0040] "Base oil" and stolide "base material", unless otherwise indicated, refer to any composition comprising one or more stolide compounds. It is to be understood that a stolide "base oil" or "base material" is not limited to compositions for a particular use, and can, in general, refer to compositions comprising one or more stolides, including mixtures of stolids. Base oils and stolide base materials may also include compounds other than stolids.
[0041] "Antioxidant" refers to a substance that is capable of inhibiting, preventing, reducing or ameliorating oxidative reactions in another substance (for example, base oil, such as a stolide compound) when the antioxidant is used in a composition (e.g., lubricating formulation) that includes such substances. An example of an "antioxidant" is an oxygen scavenger.
[0042] "Compounds" refer to compounds covered by structural formula I, II, and III, here and include any specific compounds within the formula, the structure of which is disclosed herein. The compounds can be identified either by their chemical structure and / or chemical name. When the chemical structure and the chemical name conflict, the chemical structure determines the identity of the compound. The compounds described herein can contain one or more chiral centers and / or double bonds and, therefore, can exist as stereoisomers, such as double bonded isomers (i.e., geometric isomers), enanciomers or diastereomers. Accordingly, any chemical structures within the scope of the described specification, in whole or in part, with a relative configuration encompass all possible enanciomers and stereoisomers of the illustrated compounds including the stereoisomerically pure form (for example, geometrically pure, enanciomerically pure or diastereomerically pure ) and enanciomeric and stereoisomeric mixtures. Enanciomeric and stereoisomeric mixtures can be resolved into their enanciomers or stereoisomers, using separation techniques or chiral synthesis techniques well known to those skilled in the art.
[0043] For the purposes of the present description, "chiral compounds" are compounds that have at least one chirality center (for example, at least one asymmetric atom, in particular at least one asymmetric C atom), having a chirality axis, a chirality plane or a screw structure. "Aquiral compounds" are compounds that are not chiral.
[0044] The compounds of Formula I, II, and III include, but are not limited to, the optical isomers of the compounds of Formula I, II, and III, their racemates, and other mixtures thereof. In such modalities, the individual enanciomers or diastereomers, that is, the optically active forms can be obtained by asymmetric synthesis or by resolution of the racemates.
[0045] The resolution of the racemates can be achieved, for example, by chromatography, using, for example, a chiral high pressure liquid chromatography (HPLC) column. However, unless otherwise indicated, Formula I, II, and III should be considered to cover all asymmetric variants of the compounds described herein, including isomers, racemates, enanciomers, diastereomers, and other mixtures thereof. In addition, compounds of Formula I, II and III include forms E and Z (e.g., cis and trans) of double bonded compounds. The compounds of Formula I, II, and III can also exist in various tautomeric forms, including the enol form, the keto form and mixtures thereof. Therefore, the chemical structures described here encompass all possible tautomeric forms of the compounds illustrated.
[0046] "Cycloalkyl", alone or as part of another substituent, refers to a cyclic, saturated or unsaturated alkyl group. Whenever a certain level of saturation is desired, the nomenclature "cycloalkanyl" or "cycloalkenyl" is used. Examples of cycloalkyl groups include, but are not limited to, groups derived from cyclopropane, cyclobutane, cyclopentane, cyclohexane, and the like. In certain embodiments, it is a C3-15 cycloalkyl cycloalkyl group, and in certain embodiments, C3-12 cycloalkyl or C5-12 cycloalkyl group. In certain embodiments, a cycloalkyl group is a C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, or C15 cycloalkyl.
[0047] "Cycloalkylalkyl", alone or as part of another substituent, refers to an acyclic alkyl radical, in which one of the hydrogen atoms attached to a carbon atom, typically, a sp3 terminal or carbon atom, is substituted by a cycloalkyl group. Where specific alkyl groups are desired, the cycloalkylalkanyl, cycloalkylalkenyl, or cycloalkylalkynyl nomenclature is used. In certain embodiments, a cycloalkylalkyl group is C7-30 cycloalkylalkyl, for example, the alkanyl, alkenyl or alkynyl portion of the cycloalkylalkyl group is C1-10 and the cycloalkyl portion is C6-20, and in certain embodiments, a cycloalkylalkyl group is C7 -20 cycloalkylalkyl, for example, the alkanyl, alkenyl or alkynyl portion of the cycloalkylalkyl group is C1-8 and the cycloalkyl portion is C4-20 or C6-12.
[0048] "Halogen" refers to an atom of fluorine, chlorine, bromine, or iodine.
[0049] The term "heteroaryl" alone or as part of another substituent, refers to a monovalent heteroaromatic radical derived by the removal of a single atom hydrogen atom from a parent heteroaromatic ring system. Heteroaryl encompasses several ring systems having at least one aromatic ring fused to at least one other ring, which can be aromatic or non-aromatic in which at least one atom of the ring is a heteroatom. Heteroaryl encompasses aromatic monocyclic rings of 5 to 12 members, such as monocyclic rings of 5 to 7 members containing one or more, for example, from 1 to 4, or, in certain embodiments, from 1 to 3 hetero atoms chosen from N, O, and S, with the remaining ring atoms being carbon, and the bicyclic hetero-cycloalkyl rings containing one or more, for example, from 1 to 4, or, in certain embodiments, from 1 to 3 hetero atoms chosen from N, O and S, with the remaining ring atoms being carbon, and in which at least one heteroatom is present in an aromatic ring. For example, heteroaryl includes a 5- to 7-membered hetero-cycloalkyl, aromatic ring fused to a 5- to 7-membered cycloalkyl ring. For such fused bicyclic heteroaryl ring systems, where only one of the rings contains one or more heteroatoms, the attachment point may be on the heteroaromatic ring or the cycloalkyl ring. In certain embodiments, when the total number of N, S and S atoms in which the heteroaryl group is greater than one, the heteroatoms are not adjacent to each other. In certain embodiments, the total number of N, S and S atoms in which the heteroaryl group is not more than two. In certain embodiments, the total number of N, S and S atoms in the aromatic heterocycle is not more than one. Heteroaryl does not encompass or overlap the aryl, as defined herein.
[0050] Examples of heteroaryl groups include, but are not limited to, groups derived from acridine, arsindol, carbazole, β-carboline, chroman, chromene, cinoline, furan, imidazole, indazole, indole, indoline, indolizine, isobenzofuran, isochromene, isoindole, isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole, oxazole, perimidine, phenanthridine, phenanthroline, phenazine, phthalazine, pteridine, purine, pyran, pyrazine, pyrazole, pyridazine, quinidine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine quinolizine, quinoxaline, tetrazole, thiadiazole, thiazole, thiophene, triazole, xanthene, and the like. In certain embodiments, a heteroaryl group is a 5- to 20-membered heteroaryl, and in certain modalities to a 5- to 12-membered heteroaryl or 5- to 10-membered heteroaryl. In certain embodiments, a heteroaryl group is a heteroaryl of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 members. In certain embodiments, heteroaryl groups are those derived from thiophene, pyrrole, benzothiophene, benzofuran, indole, pyridine, quinoline, imidazole, oxazole and pyrazine.
[0051] "Heteroarylalkyl", alone or as part of another substituent, refers to an acyclic alkyl radical, in which one of the hydrogen atoms attached to a carbon atom, typically, a sp3 terminal or carbon atom, is replaced by a heteroaryl group. Where specific alkyl groups are intended, the heteroarylalkanyl, heteroarylalkenyl, or heteroarylalkynyl nomenclature is used. In certain embodiments, a heteroarylalkyl group is a 6 to 30 membered heteroarylalkyl, for example, the alkanyl, alkenyl or alkynyl portion of the heteroarylalkyl is 1 to 10 members, and the heteroaryl portion is a 5 to 20 membered heteroaryl, and in certain embodiments, 6 to 20 membered heteroarylalkyl, such as the alkanyl, alkenyl or alkynyl of the heteroarylalkyl is 1 to 8 members, and the heteroaryl portion is a 5 to 12 membered heteroaryl.
[0052] "Hetero-cycloalkyl", alone or as part of another substituent, refers to a cyclic, partially saturated or unsaturated alkyl group in which one or more carbon atoms (and any associated hydrogen atoms) are substituted , independently, with the same or different heteroatom. Examples of heteroatoms to replace the carbon atom (s) include, but are not limited to, N, P, O, S, Si, etc. In case a certain level of saturation is desired, the nomenclature "hetero-cycloalkanyl" or "hetero-cycloalkenyl" is used. Examples of heterocycloalkyl groups include, but are not limited to, groups derived from epoxides, azirines, thyranes, imidazolidine, morpholine, piperazine, piperidine, pyrazolidine, pyrrolidine, quinuclidine and the like.
[0053] "Hetero-cycloalkylalkyl", alone or as part of another substituent, refers to an acyclic alkyl radical, in which one of the hydrogen atoms attached to a carbon atom, typically, a terminal or carbon atom sp3, is replaced by a heterocycloalkyl group. When specific alkyl groups are desired, the hetero-cycloalkylalkanyl, hetero-cycloalkylalkenyl, or hetero-cycloalkylalkynyl nomenclature is used. In certain embodiments, a hetero-cycloalkylalkyl group is a 6 to 30 membered hetero-cycloalkylalkyl group, for example, the alkanyl, alkenyl or alkynyl portion of the hetero-cycloalkylalkyl is 1 to 10 members, and the hetero-cycloalkyl portion is a hetero -cycloalkyl of 5 to 20 members, and in certain embodiments, hetero-cycloalkylalkyl of 6 to 20 members, for example, the alkanyl, alkenyl or alkynyl of hetero-cycloalkylalkyl is 1 to 8 members, and the hetero-cycloalkyl portion is one 5- to 12-membered hetero-cycloalkyl.
[0054] "Mixture" refers to a collection of molecules or chemicals. Each component of a mixture can be varied independently. The mixture may contain, or consist essentially of, two or more substances mixed with or without a constant percentage composition, in which each component may or may not maintain its essential original properties, and in which the molecular phase mixture may or may not occur. In mixtures, the components that make up the mixture may or may not remain distinguishable from each other due to their chemical structure.
[0055] "Aromatic parent ring system" refers to a saturated cyclic or polycyclic ring system having a conjugated π (pi) electron system. Included in the definition of "parent aromatic ring system" are fused ring systems in which one or more of the rings are aromatic and one or more of the rings are saturated or unsaturated, such as, for example, fluorene, indane, indene, phenalene, etc. Examples of aromatic parent ring systems include, but are not limited to, aceanthylene, acenaphthene, acephenanthrene, anthracene, azulene, benzene, chrysene, coronene, fluoranthene, fluorene, hexacene, hexafene, hexalene, as-indacene, s-indacene, indane, indene, naphthalene, octacene, octafen, octalene, ovalene, penta-2,4-diene, pentacene, pentalene, pentafene, perylene, phenalene, phenanthrene, picena, pleiadene, pyrene, pyranthrene, rubicene, triphenylene, trinafthalen, and the like .
[0056] "Heteroaromatic parent ring system" refers to an aromatic parent ring system in which one or more carbon atoms (and any associated hydrogen atoms) are independently replaced with the same or different heteroatom. Examples of heteroatoms to replace carbon atoms include, but are not limited to, N, P, O, S, Si, etc. Specifically included within the definition of "parent heteroaromatic ring systems" are fused ring systems in which one or more of the rings are aromatic, and one or more of the rings are saturated or unsaturated, such as, for example, arsindole, benzodioxane, benzofuran, chroman, chromene, indole, indoline, xanthene, etc. Examples of parent heteroaromatic ring systems include, but are not limited to, arsindol, carbazole, β-carboline, chroman, chromene, cinoline, furan, imidazole, indazole, indole, indoline, indolizine, isobenzofuran, isochromene, isoindole, isoindoline , isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole, oxazole, perimidine, phenanthridine, phenanthroline, phenazine, phthalazine, pteridine, purine, pyran, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, quinizoline, pyridine, quinoline, pyridine, quinoline , tetrazole, thiadiazole, thiazole, thiophene, triazole, xanthene, and the like.
[0057] "Substituted" refers to a group in which one or more hydrogen atoms are independently replaced with the same or different substituent (s). Examples of substituents include, but are not limited to, -, -R64, -R60, -O-, -OH, - = O, -OR60, -SR60, - S-, - = S, -NR60R61, - = NR60 , -CN, -CF3, -OCN, -SCN, -NO, -NO2, - = N2, - N3, -S (O) 2O-, -S (O) 2OH, -S (O) 2R60, -OS (O2) O-, -OS (O) 2R60, -P (O) (O-) 2, - P (O) (OR60) (O-), -OP (O) (OR60) (OR61), - C (O) R60, -C (S) R60, -C (O) OR60, - C (O) NR60R61, -C (O) O-, -C (S) OR60, -NR62C (O) NR60R61, - NR62C (S) NR60R61, -NR62C (NR63) NR60R61, -C (NR62) NR60R61, -S (O) 2, - NR60R61, -NR63S (O) 2R60, -NR63C (O) R60, and S (O) R60 ;
[0058] wherein each of -R64 is independently a halogen atom, each of R60 and R61 independently represents alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, hetero-cycloalkyl, hetero-cycloalkyl groups substituted, aryl, substituted aryl, heteroaryl, substituted heteroaryl, arylalkyl, substituted arylalkyl, heteroarylalkyl, or substituted heteroarylalkyl, or R60 and R61 together with the nitrogen atom to which they are attached, form a substituted hetero-cycloalkyl, hetero-cycloalkyl , heteroaryl, or a substituted heteroaryl ring, and R62 and R63 independently represent alkyl, substituted alkyl, aryl, substituted aryl, arylalkyl, substituted arylalkyl, cycloalkyl, substituted cycloalkyl, hetero-cycloalkyl, substituted hetero-cycloalkyl, heteroaryl, substituted heteroaryl, heteroaryl groups heteroarylalkyl, substituted or heteroarylalkyl, or R62 and R63 together with the atom at which there they are linked, form one or more hetero-cycloalkyl, substituted hetero-cycloalkyl, heteroaryl, or substituted heteroaryl rings;
[0059] wherein the "substituted" substituents, as defined above for R60, R61, R62 and R63, are substituted with one or more, such as one, two, or three, groups selected independently from alkyl, -alkyl- OH, -O-haloalkyl, -alkyl-NH2, alkoxy, cycloalkyl, cycloalkylalkyl, -NH2, - = NH, -CN, -CF3, -OCN, -SCN, -NO, -NO2, - = N2, -N3, -S (O) 2O-, -S (O) 2, -S (O) 2OH, -OS (O2) O-, --SO2 (alkyl), -SO2 (phenyl), --SO2 (haloalkyl), --SO2NH2, --SO2NH (alkyl), - -SO2NH (phenyl), -P (O) (O-) 2, -P (O) (O-alkyl) (O-), -OP (O) ( O-alkyl) (O-alkyl), --CO2H, --C (O) O (alkyl), --CON (alkyl) (alkyl), - -CONH (alkyl), --CONH2, --C ( O) (alkyl), --C (O) (phenyl), - -C (O) (haloalkyl), --OC (O) (alkyl), --N (alkyl) (alkyl), --NH ( alkyl), N (alkyl) (alkylphenyl), --NH (alkylphenyl), --NHC (O) (alkyl), - -NHC (O) (phenyl), --N (alkyl) C (O) (alkyl ), and -N (alkyl) C (O) (phenyl).
[0060] As used in this report and the appended claims, the articles "one", "one", and "a" and "o" include plural referents unless expressly and unambiguously limited to one referential.
[0061] All numerical ranges here include all numerical values and ranges of all numerical values within the range of recited numerical values.
[0062] The present invention relates to stolide compounds, compositions and methods for their preparation. In certain embodiments, the present description also relates to stolide compounds, compositions comprising the stolide compounds, the synthesis of such compounds, and the formulation of such compositions. In certain embodiments, the present description relates to biosynthetic stolids having desired viscometric properties, maintaining, or even improving other properties, such as oxidation stability and pour point. In certain embodiments, new methods of preparing stolide compounds that exhibit such properties are provided. The present description also relates to a lubricant comprising certain stolide compounds.
[0063] In certain embodiments, the composition comprises at least one stolide compound of Formula I:

[0064] where
[0065] x is, independently for each occurrence, an integer selected from 0, 1,2,3,4,5,6,7, I, 9, 10, 11, 12, 13, 14, 15, 16 , 17, 18, 19, and 20;
[0066] y is, independently for each occurrence, an integer selected from 0, 1,2,3,4,5,6,7, 8, 9, 10, 11, 12, 13, 14, 15, 16 , 17, 18, 19, and 20;
[0067] n is an integer selected from 0, 1,2,3,4,5,6,7, 8, 9, 10, 11, and 12;
[0068] R1 is an optionally substituted alkyl group, which is saturated or unsaturated, branched or unbranched, and; and
[0069] R2 is selected from hydrogen and optionally substituted alkyl which is saturated or unsaturated, and branched or unbranched;
[0070] in which each chain of fatty acid residue referred to by at least one compound is independently optionally substituted.
[0071] In certain embodiments, the composition comprises at least one stolide compound of Formula II:

[0072] where
[0073] m is an integer greater than or equal to 1;
[0074] n is an integer greater than or equal to 0;
[0075] R1, independently, for each occurrence, is an optionally substituted alkyl group, which is saturated or unsaturated, branched or unbranched, and;
[0076] R2 is selected from hydrogen and optionally substituted alkyl, which is saturated or unsaturated, branched or unbranched, and; and
[0077] R3 and R4, independently, for each occurrence, are selected from optionally substituted alkyl, which is saturated or unsaturated, and branched or unbranched.
[0078] In certain embodiments, the composition comprises at least a stolide compound of Formula III:
where x is, independently for each occurrence, a number
[0079] where
[0080] x is, independently for each occurrence, an integer selected from 0 to 20;
[0081] y is, independently for each occurrence, an integer selected from 0 to 20;
[0082] n is an integer greater than or equal to 0;
[0083] R1 is an optionally substituted alkyl group, which is saturated or unsaturated, branched or unbranched, and; and
[0084] R2 is selected from hydrogen and optionally substituted alkyl which is saturated or unsaturated, and branched or unbranched;
[0085] wherein each fatty acid residue chain of said at least one compound is independently optionally substituted.
[0086] In certain embodiments, the composition comprises at least one stolide compound of Formula I, II or III in which R1 is hydrogen.
[0087] The terms "chain" or "fatty acid chain" or "fatty acid chain residue", as used with respect to the stolide compounds of Formula I, II, and III, refer to one or more of fatty acid residues incorporated in stolide compounds, for example, R3 or R4 with Formula II, or the structures represented by CH3 (CH2) yCH (CH2) xC (O) O- in Formula I and III.
[0088] The R1 in Formula I, II, and III, at the top of each Formula shown is an example of what can be referred to as a "cap" or "cover material", as if it "capped" the top of the stolide.
[0089] Likewise, the protecting group may be an organic acid residue of the general formula -OC (O) -alkyl, that is, a carboxylic acid with a substituted or unsubstituted, saturated or unsaturated alkyl, and / or branched or unbranched, as defined herein, or a formic acid residue. In certain embodiments, the "cap" or "cover group" is a fatty acid. In certain embodiments, the coverage group, regardless of its size, is substituted or unsubstituted, saturated or unsaturated, and / or branched or unbranched. The cap or cover material can also be referred to as the primary or alpha (α) chain.
[0090] According to the way in which the stolide is synthesized, the alkyl cap or cover group may be the only alkyl group from an organic acid residue in which the resulting stolide is unsaturated. In certain embodiments, it may be desirable to use an organic buffer or fat-saturated acid to increase the total saturation of the stolide and / or to increase the stability resulting from the stolide. For example, in certain embodiments, it may be desirable to provide a method of providing a saturated buffered stolide by hydrogenation of an unsaturated buffer using any suitable methods available to those skilled in the art. Hydrogenation can be used with a variety of fatty acid stock sources, which may include mono- and / or polyunsaturated fatty acids. Without being linked to any particular theory, in certain modalities, the hydrogenation of stolide can help to improve the overall stability of the molecule. However, a fully hydrogenated stolide, such as a stolide with a larger fatty acid cap, may experience increased pour point temperatures. In certain embodiments, it may be desirable to compensate for any loss of desirable pour point characteristics using shorter saturated leveling materials.
[0091] The Formula II R4C (O) O- or CH3 (CH2) yCH (CH2) xC (O) O- Formula I and III structure serves as the "base" or "base chain residue" of stolide. Depending on the way in which the stolide is synthesized, the fatty acid or organic acid residue may be the only residue that remains in its acid-free form after the first synthesis of the stolide. However, in certain embodiments, in an effort to alter or improve the properties of the stolide, the free acid can be reacted with any number of substituents. For example, it may be desirable to react the free acid stolide with alcohols, glycols, amines, or other suitable reagents to provide the corresponding ester, amide, or other reaction products. The base or base chain residue can also be referred to as tertiary or gamma (Y) chains.
[0092] The R3C (O) O- of Formula II or the CH3 (CH2) yCH (CH2) xC (O) O- of Formula I and III structure are bond residues that bind the cover material and acid residues base fat together. There can be any number of residues attached to the stolide, including when n = 0 and the stolide is in its dimeric form. Depending on the form in which the stolide is prepared, a binding residue may be a fatty acid and may initially be unsaturated during synthesis. In some embodiments, stolide will be formed when a catalyst is used to produce a carbocation at the site of unsaturation fatty acid, which is followed by a nucleophilic attack on the carbocation by the carboxylic group of another fatty acid. In some embodiments, it may be desirable to have a fatty acid binder that is monounsaturated so that when you connect the fatty acids together, all points of unsaturation are eliminated. The binding residue (s) can also be called secondary or beta (β) chains.
[0093] In certain embodiments, the cap is an acetyl group, the binding residue (s) is one or more fatty acid residues, and the base chain residue is a fatty acid residue. In certain embodiments, the bond residues present in a stolide differ from one another. In certain embodiments, one or more of the binding residues are different from the base chain residue.
[0094] As mentioned above, in certain embodiments, unsaturated fatty acids suitable for the preparation of stolides can include any mono- or polyunsaturated fatty acid. For example, monounsaturated fatty acids, together with a suitable catalyst, will form a single carbocation that allows the addition of a second fatty acid, in which a single bond is formed between the two fatty acids. Suitable monounsaturated fatty acids may include, but are not limited to, palmitoleic acid (16: 1), vaccenic acid (18: 1), oleic acid (18: 1), eicosenoic acid (20: 1), erucic acid (22 : 1), and nervous acid (24: 1). In addition, in certain embodiments, polyunsaturated fatty acids can be used to create stolids. Suitable polyunsaturated fatty acids may include, but are not limited to, hexadecatrienoic acid (16:03), alpha-linolenic acid (18: 3), stearidonic acid (18:04), eicosatrienoic acid (20: 3), eicosatetraenoic acid (20:04), eicosapentaenoic acid (20: 5), heneicosapentaenoic acid (21: 5), docosapentaenoic acid (22:05), docosahexaenoic acid (22:06), tetracosapentaenoic acid (24: 5), tetracosahexaenoic acid (24: 6), linoleic acid (18: 2), gamma-linolenic acid (18: 3), eicosadienoic acid (20: 2), dihomo-gamma-linolenic acid (20: 3), arachidonic acid (20: 04), docosadienoic acid (20: 2), adrenic acid (22: 4), docosapentaenoic acid (22:05), tetracosatetraenoic acid (22: 4), tetracosapentaenoic acid (24: 5), pinolenic acid (18: 3) , podocarpic acid (20: 3), rumenic acid (18: 2), alpha-calendic acid (18: 3), beta-calendic acid (18: 3), jacaric acid (18: 3), alpha-eleoesteearic acid ( 18: 3), beta-elewestearic (18: 3), catalytic acid (18: 3), punicic acid (18: 3), rumelenic acid (18: 3), alpha-parinic acid (18:04), beta-parinic acid (18: 4), and bosseopentaenoic acid (20: 5). In certain embodiments, hydroxy fatty acids can be polymerized or homopolymerized by reacting the carboxylic acid functionality of a fatty acid with the hydroxy functionality of a second fatty acid. Exemplary hydroxyl fatty acids include, but are not limited to, ricinoleic acid, 6-hydroxystearic acid, 9,10-dihydroxystearic acid, 12-hydroxystearic acid, and 14-hydroxystearic acid.
[0095] The process for preparing the stolide compounds described herein may include the use of any natural or synthetic fatty acid source. However, it may be desirable to source fatty acids from a renewable biological raw material. For example, suitable starting materials of biological origin include, but are not limited to, vegetable fats, vegetable oils, vegetable waxes, animal fats, animal oils, animal waxes, fish fats, fish oils, fish waxes fish, seaweed oils and mixtures of two or more of them. Other potential sources of fatty acids include, but are not limited to, recycled food grade fats and oils, fats, oils, and waxes obtained by genetic engineering, fossil-based materials, and other desired material sources.
[0096] In some embodiments, the compost comprises chain residues of varying lengths. In some modalities, X is, independently for each occurrence, an integer selected from 0 to 20.0 and 18, 0 to 16, 0 to 14, from 1 to 12, 1 to 10, 2 to 8, 6 to 8 , or 4 to 6. In some modalities, X is, independently for each occurrence, an integer selected from 7 to 8. In some modalities, X is, independently for each occurrence, an integer selected from 0, 1, 2,3,4,5,6,7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20. In certain embodiments, for at least one chain residue , x is an integer selected from 7 to 8.
[0097] In some embodiments, y is, independently for each occurrence, an integer selected from 0 to 20.0-18, 0-16, 0-14, 1-12, 1-10, 2-8, 6 -8, or from 4 to 6. In some modalities, y is, independently for each occurrence, an integer selected from 7 to 8. In some modalities, y is, independently for each occurrence, an integer selected from 0 , 1,2,3,4,5,6,7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20. In certain modalities, for at least one chain residue, y is an integer selected from 7 to 8. In some embodiments, at least one chain residue, y is an integer selected from 0 to 6, or 1 and 2. In certain embodiments, y is , independently for each occurrence, an integer selected from 1 to 6, or 1 and 2.
[0098] In some modalities, x + y is, independently, for each chain, an integer selected from 0 to 40.0 to 20, 10 to 20, or 12 to 18. In some modalities, x + y is, independently for each chain, an integer selected from 13 to 15. In some modalities, x + y is 15. In some modalities, x + y is, independently, for each chain, an integer selected from 6, 7, 8 , 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22,23, and 24.
[0099] In some embodiments, the Formula I, II or III stolide compound can comprise any number of fatty acid residues to form an "n-mer" stolide. For example, the stolide can be in its dimer (n = 0), trimer (n = 1), tetramer (n = 2), pentamer (n = 3), hexamer (n = 4), heptamer (n = 5) , octamer (n = 6), nonamer (n = 7), or decamer (n = 8) form. In some modalities, n is an integer selected from 0 to 20.0 to 18, 0 to 16, 0 to 14, 0 to 12, 0 to 10.0 to 8, or 0 to 6. In some modalities, n is an integer selected from 0 to 4. In some embodiments, n is 0 or greater than 0. In some embodiments, n is 1, wherein said at least one compound of Formula I, II, or III comprises the trimer . In some modalities, n is greater than 1. In some modalities, n is an integer selected from 0, 1,2,3,4,5,6,7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.
[00100] In some embodiments, R1 of Formula I, II or III is an optionally substituted alkyl group, which is saturated or unsaturated, and branched or unbranched. In some embodiments, the alkyl group is a Q to C4 alkyl, C1 to C22 alkyl or C1 to C18 alkyl. In some embodiments, the alkyl group is selected from C7 to C17 alkyl. In some embodiments, R1 is selected from C7 alkyl, C9 alkyl, Cn alkyl, C13 alkyl, C15 alkyl, and C17 alkyl. In some embodiments, R1 is selected from C13 to C17 alkyl, such as C13 alkyl, C15 alkyl, and a Cn alkyl group. In some embodiments, R1 is a C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C17, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, or C22 alkyl.
[00101] In some embodiments, R2 of Formula I, II or III is an optionally substituted alkyl group, which is saturated or unsaturated, and branched or unbranched. In some embodiments, the alkyl group is a C1 to C4 alkyl, C1 to C22 alkyl or C1 to C18 alkyl. In some embodiments, the alkyl group is selected from C7 to C17 alkyl. In some embodiments, R2 is selected from C7 alkyl, C9 alkyl, C11 alkyl, C13 alkyl, C15 alkyl, and a Cn alkyl group. In some embodiments, R2 is selected from C13 to C17 alkyl, such as C13 alkyl, C15 alkyl, and a C17 alkyl group. In some embodiments, R2 is a C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C17, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, or C22 alkyl.
[00102] In some embodiments, R3 represents an optionally substituted alkyl group, which is saturated or unsaturated, and branched or unbranched. In some embodiments, the alkyl group is a C1 to C40 alkyl, C1 to C22 alkyl or C1 to C18 alkyl. In some embodiments, the alkyl group is selected from C7 to C17 alkyl. In some embodiments, R3 is selected from C7 alkyl, C9 alkyl, C11 alkyl, C13 alkyl, alkyl, C15 alkyl and C17 alkyl. In some embodiments, R3 is selected from C13 to C17 alkyl, such as from C13 alkyl, C15 alkyl, and C17 alkyl. In some embodiments, R3 represents a C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C17, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, or C22 alkyl.
[00103] In some embodiments, R4 represents an optionally substituted alkyl group, which is saturated or unsaturated, branched or unbranched. In some embodiments, the alkyl group is a C1 to C4 alkyl, C1 to C22 alkyl or C1 to C18 alkyl. In some embodiments, the alkyl group is selected from C7 to C17 alkyl. In some embodiments, R4 is selected from C7 alkyl, C9 alkyl, C11 alkyl, C13 alkyl, C15 alkyl, and C17 alkyl. In some embodiments, R4 is selected from C13 to C17 alkyl, such as from C13 alkyl, C15 alkyl, and C17 alkyl. In some embodiments, R4 represents a C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C17, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, or C22 alkyl.
[00104] As mentioned above, in certain modalities, it may be possible to manipulate one or more of the properties of the stolids by changing the length of R1 and / or its degree of saturation. However, in certain modalities, the level of substitution in R1 can also be changed to change or even improve the properties of the estolides. Without being linked to any particular theory, in certain modalities, it is believed that the presence of polar substituents in R1, such as one or more hydroxy groups, can increase the viscosity of the stolide, increasing the pour point. Therefore, in some embodiments, R1 will be unsubstituted or optionally substituted by a group that is not hydroxyl.
[00105] In some embodiments, stolide is, in its acid-free form, where R2 of Formula I, II, or III is hydrogen. In some embodiments, R2 is selected from optionally substituted alkyl, which is saturated or unsaturated, and branched or unbranched. In certain embodiments, residue R2 may comprise any desired alkyl group, such as those derived from esterification of the stolide with the alcohols identified in the examples presented herein. In some embodiments, the alkyl group is selected from C1 to C40, C1 to C22, C3 to C20, C1 to C18, or C6 to C12. In some embodiments, R2 can be selected from C3 alkyl, C4 alkyl, C8 alkyl, C12 alkyl, C16 alkyl, C18 alkyl, and C20 alkyl. For example, in certain embodiments, R2 can be branched, such as isopropyl, isobutyl, or 2-ethylhexyl. In some embodiments, R2 may be a larger alkyl group, branched or unbranched, comprising C12 alkyl, C16 alkyl, C18 alkyl, or C20 alkyl. Such groups at the R2 position can be derived from the esterification of free acid stolide using the Jarcol ™ line of alcohols marketed by Jarchem Industries, Inc., Newark, New Jersey, including Jarcol ™ I-18CG, 1-20, 1- 12, 1-16, 1-18T, and 85BJ. In some cases, R2 can be obtained from certain alcohols to provide branched alkyls, such as isostearyl and isopalmityl. It is to be understood that such isopalmityl and isostearyl alkyl groups can cover any branched variation of C16 and C18, respectively. For example, the stolides described herein may comprise highly branched isopalmityl or isostearyl groups at the R2 position, derived from the Fineoxocol ® line of isopalmityl and isostearyl alcohols marketed by the Nissan Chemical America Corporation of Houston, Texas, including Fineoxocol ® 180, 180N, and 1600. Without being bound by any particular theory, in certain embodiments, the large, highly branched alkyl groups (for example, isopalmityl and isostearyl) at the R2 position of the stolides can provide at least one way to increase the viscosity of a composition containing stolide, while substantially maintaining or even reducing its pour point.
[00106] In some embodiments, the compounds described herein may comprise a mixture of two or more stolide compounds of Formula I, II, and III. It is possible to characterize the chemical composition of a stolide, a mixture of stolids, or a composition comprising stolides, using the measured stolide number (EN) of the compound, mixture, or composition. The EN represents the average number of fatty acids added to the fatty acid base. The EN also represents the average number of stolide bonds per molecule: EN = n +1
[00107] where n is the number of secondary fatty acids (β). Therefore, a single stolide compound will have an EN which is an integer, for example for dimers, trimers and tetramers: dimer EN = 1 trimer EN = 2 tetramer EN = 3
[00108] However, a composition comprising two or more stolide compounds can have an EN which is an integer or a fraction of an integer. For example, a composition with a 1: 1 molar ratio of dimer and trimer would have an EN of 1.5, while a composition with a 1: 1 molar ratio of tetramer and trimer would have an EN of 2.5.
[00109] In some embodiments, the compositions may comprise a mixture of two or more stolids having an EN that is an integer or fraction of an integer that is greater than 4, 5, or even 5.0. In some modalities, the EN can be an integer or fraction of an integer selected from about 1, 0 to about 5, 0. In some modalities, the EN is an integer or fraction of a selected integer from 1.2 to about 4, 5. In some modalities, the EN is selected from a value greater than 1, 0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2.2.4, 2.6, 2.8, 3.0, 3.2,3.4, 3.6, 3.8, 4.0, 4.2,4.4,4.6, 4.8, 5.0, 5.2.5.4, 5.6 and 5.8. In some modalities, the EN is selected from a value less than 1.2, 1.4, 1.6, 1.8, 2.0, 2.2.2.4, 2.6, 2.8, 3.0, 3.2.3.4, 3.6, 3.8, 4.0, 4.2.4.4.4.6 , 4.8 and 5.0, 5.2,5.4, 5.6, 5.8, and 6.0. In some modalities, the EN is selected from 1, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2.2.4, 2.6, 2.8, 3.0, 3.2.3.4, 3.6, 3.8, 4.0, 4.2.4.4.4.6, 4.8 , 5.0, 5.2,5.4, 5.6, 5.8, and 6.0.
[00110] As noted above, it is to be understood that the chains of the stolide compounds can be independently optionally substituted, in which one or more hydrogens are removed and replaced with one or more of the substituents identified herein. Likewise, two or more of the hydrogen residues can be removed to provide one or more sites of unsaturation, such as a cis or trans double bond. In addition, the chains may optionally comprise branched hydrocarbon residues. For example, in some embodiments the stolides described here can comprise at least one compound of Formula II:

[00111] where
[00112] m is an integer equal to or greater than 1;
[00113] n is an integer equal to or greater than 0;
[00114] R1, independently, for each occurrence, is an optionally substituted alkyl group, which is saturated or unsaturated, branched or unbranched, and;
[00115] R2 is selected from hydrogen and optionally substituted alkyl, which is saturated or unsaturated, branched or unbranched, and; and
[00116] R3 and R4, independently, for each occurrence, are selected from optionally substituted alkyl, which is saturated or unsaturated, and branched or unbranched.
[00117] In certain modalities, m is 1. In some modalities, m is a selected integer of 2,3,4, and 5. In some modalities, n is a selected integer of 1,2,3,4, 5,6,7, 8, 9, 10, 11, and 12. In some embodiments, one or more of R3 differs from one or more other R3 in a Formula II compound. In some embodiments, one or more of R3 other than R4, in a Formula II compound. In some embodiments, if the Formula II compounds are prepared from one or more polyunsaturated fatty acids, it is possible that one or more of R3 and R4 have one or more unsaturation sites. In some embodiments, if the Formula II compounds are prepared from one or more branched fatty acids, it is possible that one or more of R3 and R4 are branched.
[00118] In some modalities, R3 and R4 can be CH3 (CH2) yCH (CH2) x-, where x is, independently for each occurrence, an integer selected from 0, 1,2,3,4,5, 6,7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20, and y is, independently for each occurrence, an integer selected from 0, 1,2 , 3,4,5,6,7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20. Whenever both R3 and R4 are CH3 (CH2) yCH (CH2) x-, the compounds can be composed according to Formula I and III.
[00119] Without being linked to any particular theory, in certain modalities, changing the EN produces compositions containing stolide having desired viscometric properties while substantially retaining or even reducing the pour point. For example, in some types of stolides they exhibit a decrease in the pour point by increasing the value of EN. Therefore, in certain embodiments, a method is provided for maintaining or decreasing the pour point of a stolide base oil by increasing the EN of the base oil, or a method is provided for maintaining or decreasing the pour point of a composition. which comprises an oil stolide base increasing the EN of the base oil. In some embodiments, the method comprises: selecting a base oil having a first stolide EN and an initial pour point, and removing at least a portion of the base oil, said portion having an EN that is less than the initial EN of the base oil, in which the resulting base oil has a stolide EN is greater than the initial EN of the base oil, and a pour point that is equal to or less than the initial pour point of the base oil. In some embodiments, the selected stolide base oil is prepared by oligomerizing at least one first unsaturated fatty acid with at least one second unsaturated fatty acid and / or saturated fatty acid. In some embodiments, removal of at least a portion of the base oil or a composition comprising two or more stolide compounds is accomplished by using at least one distillation, membrane separation chromatography, phase separation, separation by affinity, and solvent extraction. In some embodiments, the distillation takes place at a temperature and / or pressure, which is suitable for separating the stolide base oil or a composition comprising two or more stolide compounds in different "cuts" that exhibit different EN values individually. In some embodiments, this can be achieved by subjecting the base oil or to a composition comprising two or more stolide compounds at a temperature of at least about 250 ° C and an absolute pressure of not more than about 25 microns . In some embodiments, the distillation takes place at a temperature of about 250 ° C to about 310 ° C and an absolute pressure range of about 10 microns to about 25 microns.
[00120] In some embodiments, stolide compounds and compositions exhibit an EN, which is greater than or equal to 1, such as an integer or fraction of an integer selected from about 1.0 to about 2, 0. In some modalities, the EN is an integer or fraction of an integer selected from about 1.0, to about 1, 6. In some modalities, the EN is a fraction of an integer selected from about 1, 1 to about 1, 5. In some modalities, the EN is selected from a value greater than 1, 0, 1, 1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7 , 1.8, and 1.9. In some modalities, the EN is selected from a value less than 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0.
[00121] In some modalities, the EN is greater than or equal to 1, 5, such as an integer or fraction of an integer selected from about 1, 8 to about 2, 8. In some modalities, the EN is an integer or fraction of an integer selected from about 2, 0 to about 2, 6. In some modalities, the EN is a fraction of an integer selected from about 2, 1 to about 2.5. In some modalities, the EN is selected from a value greater than 1, 8, 1, 9, 2.0, 2.1,2.2,2.3, 2.4, 2.5, 2.6, and 2.7. In some modalities, the EN is selected from a value less than 1.9, 2.0, 2.1.2.2.2.3, 2.4, 2.5, 2.6, 2.7, and 2.8. In some modalities, the EN is around 1.8, 2.0, 2.2.2.4, 2.6, or 2.8.
[00122] In some modalities, the EN is greater than or equal to about 4, such as an integer or fraction of an integer selected from about 4, 0 to about 5, 0. In some modalities, the EN is a fraction of an integer selected from about 4, 2 to about 4, 8. In some modalities, the EN is a fraction of an integer selected from about 4, 3 to about 4 , 7. In some modalities, the EN is selected from a value greater than 4.0, 4.1, 4.2.4.3.4.4.4.5, 4.6, 4.7, 4.8, and 4.9. In some modalities, the EN is selected from a value below 4.1, 4.2.4.3.4.4.4.5, 4.6, 4.7, 4.8, 4.9, and 5.0. In some modalities, the EN is around 4.0, 4.2.4.4.4.6, 4.8, or 5.0.
[00123] In some modalities, the EN is greater than or equal to about 5, such as an integer or fraction of an integer selected from about 5, 0 to about 6, 0. In some modalities, the EN is a fraction of an integer selected from about 5, 2 to about 5, 8. In some modalities, the EN is a fraction of an integer selected from about 5, 3 to about 5, 7. In some modalities, the EN is selected from a value greater than 5.0, 5.1, 5.2,5.3,5.4, 5.5, 5.6, 5.7, 5.8, and 5.9. In some modalities, the EN is selected from a value less than 5.1, 5.2,5.3,5.4, 5.5, 5.6, 5.7, 5.8, 5.9, and 6.0. In some modalities, the EN is around 5.0, 5.2.5.4, 5.4, 5.6, 5.8, or 6.0.
[00124] In some modalities, the EN is greater than or equal to 1, such as an integer or fraction of an integer selected from about 1, 0 to about 2, 0. In some modalities, the EN is a fraction of an integer selected from about 1, 1 to about 1, 7. In some embodiments, the EN is a fraction of an integer selected from about 1, 1 to about 1, 5. In some modalities, the EN is selected from a value greater than 1, 0, 1, 1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, or 1.9. In some modalities, the EN is selected from a value less than 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0. In some modalities, the EN is around 1.0, 1.2, 1.4, 1.6, 1.8, or 2.0. In some embodiments, the EN is greater than or equal to 1, such as an integer or fraction of an integer selected from about 1.2 to about 2.2. In some modalities, the EN is an integer or fraction of an integer selected from about 1, 4 to about 2, 0. In some modalities, the EN is a fraction of an integer selected from about 1, 5 to about 1, 9. In some modalities, the EN is selected from a value greater than 1, 0, 1, 1. 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 , 2.0 and 2.1. In some modalities, the EN is selected from a value less than 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2. In some modalities, the EN is around 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, or 2.2.
[00125] In some modalities, the EN is greater than or equal to 2, such as an integer or fraction of an integer selected from about 2, 8 to about 3, 8. In some modalities, the EN is an integer or fraction of an integer selected from about 2, 9 to about 3.5. In some embodiments, the EN is an integer or fraction of an integer selected from about 3.0 to about 3.4. In some modalities, the EN is selected from a value greater than 2, 0, 2, 1,2,2., 2,4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1.3.4, 3.5, 3.6, and 3.7. In some modalities, the EN is selected from a value less than 2.2.2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1,3.2,3.3, 3.4, 3.5, 3.6, 3.7, and 3.8. In some modalities, the EN is around 2.0, 2.2.2.4, 2.6, 2.8, 3.0, 3.2.3.4, 3.6, or 3.8.
[00126] Normally, base stocks and stolide-containing compositions exhibit a certain lubricity, viscosity and / or pour point characteristics. For example, in certain embodiments, base oils, compounds, and compositions may exhibit viscosities ranging from about 10 cSt to about 250 cSt at 40 ° C, and / or about 3 cSt to about 30 cSt at 100 ° C. In some embodiments, base oils, compounds, and compositions may exhibit viscosities within a range of about 50 cSt to about 150 cSt at 40 ° C, and / or about 10 cSt to about 20 cSt to 100 ° C.
[00127] In some embodiments, stolide compounds and compositions may exhibit viscosities less than about 55 cSt at 40 ° C or less than about 45 cSt at 40 ° C, and / or less than about 12 cSt at 100 ° C or less than about 10 cSt at 100 ° C. In some embodiments, the stolide compounds and compositions may exhibit viscosities within a range of about 25 cSt to 55 cSt at 40 ° C, and / or about 5 to about 11 cSt cSt at 100 ° C. In some embodiments, the stolide compounds and compositions may exhibit viscosities within a range of about 35 cSt to about 45 cSt at 40 ° C, and / or from about 6 cSt to about 10 cSt at 100 ° C. In some embodiments, the stolide compounds and compositions may exhibit viscosities within a range of about 38 cSt to about 43 cSt at 40 ° C, and / or about 7 to about 9 cSt cSt at 100 ° C.
[00128] In some embodiments, stolide compounds and compositions may exhibit viscosities less than about 120 cSt at 40 ° C or less than about 100 cSt at 40 ° C, and / or less than about 18 cSt at 100 ° C or less than about 17 cSt at 100 ° C. In some embodiments, the stolide compounds and compositions may have a viscosity within a range of about 70 cSt to about 120 cSt at 40 ° C, and / or about 12 cSt to about 18 cSt at 100 ° C. In some embodiments, the stolide compounds and compositions may exhibit viscosities within a range of about 80 cSt to about 100 cSt at 40 ° C, and / or about 13 cSt to about 17 cSt at 100 ° C. In some embodiments, the stolide compounds and compositions may exhibit viscosities within a range of about 85 cSt to 95 cSt at 40 ° C, and / or about 14 cSt to about 16 cSt at 100 ° C.
[00129] In some embodiments, stolide compounds and compositions may exhibit viscosities greater than about 180 cSt at 40 ° C or greater than about 200 cSt at 40 ° C, and / or greater than about 20 cSt at 100 ° C or greater than about 25 cSt at 100 ° C. In some embodiments, the stolide compounds and compositions may have a viscosity within the range of about 180 cSt to about 230 cSt at 40 ° C, and / or about 25 cSt to about 31 cSt at 100 ° C. In some embodiments, the stolide compounds and compositions may exhibit viscosities within the range of about 200 cSt to about 250 cSt at 40 ° C, and / or about 25 cSt to 35 cSt at 100 ° C. In some embodiments, the stolide compounds and compositions may exhibit viscosities within the range of about 210 cSt to about 230 cSt at 40 ° C, and / or about 28 cSt to about 33 cSt at 100 ° C. In some embodiments, the stolide compounds and compositions may exhibit viscosities within a range of about 200 cSt to about 220 cSt at 40 ° C, and / or about 26 cSt to about 30 cSt at 100 ° C. In some embodiments, the stolide compounds and compositions may exhibit viscosities within a range of about 205 cSt to about 215 cSt at 40 ° C, and / or about 27 cSt to about 29 cSt at 100 ° C.
[00130] In some embodiments, stolide compounds and compositions may exhibit viscosities of less than about 45 cSt at 40 ° C or less than about 38 cSt at 40 ° C, and / or less than about 10 cSt at 100 ° C or less than about 9 cSt at 100 ° C. In some embodiments, the stolide compounds and compositions may have a viscosity within a range of about 20 cSt to about 45 cSt at 40 ° C, and / or about 4 cSt to about 10 cSt at 100 ° C. In some embodiments, the stolide compounds and compositions may exhibit viscosities within a range of about 28 cSt to about 38 cSt at 40 ° C, and / or about 5 to about 9 cSt cSt at 100 ° C. In some embodiments, the stolide compounds and compositions may exhibit viscosities within a range of about 30 cSt to 35 cSt at 40 ° C, and / or from about 6 cSt to about 8 cSt at 100 ° C.
[00131] In some embodiments, stolide compounds and compositions may exhibit viscosities of less than about 80 cSt at 40 ° C or less than about 70 cSt at 40 ° C, and / or less than about 14 cSt at 100 ° C or less than about 13 cSt at 100 ° C. In some embodiments, the stolide compounds and compositions may have a viscosity within a range of about 50 cSt to 80 cSt at 40 ° C, and / or about 8 cSt to about 14 cSt at 100 ° C. In some embodiments, the stolide compounds and compositions may exhibit viscosities within the range of about 60 cSt to 70 cSt at 40 ° C, and / or about 9 to about 13 cSt cSt at 100 ° C. In some embodiments, the stolide compounds and compositions may exhibit viscosities within the range of about 63 cSt to about 68 cSt at 40 ° C, and / or about 10 cSt to about 12 cSt at 100 ° C.
[00132] In some embodiments, stolide compounds and compositions may exhibit viscosities greater than about 120 cSt at 40 ° C or greater than about 130 cSt at 40 ° C, and / or greater than about 15 cSt at 100 ° C or greater than about 18 cSt at 100 ° C. In some embodiments, the stolide compounds and compositions may have a viscosity within the range of about 120 cSt to about 150 cSt at 40 ° C, and / or about 16 cSt to about 24 cSt at 100 ° C. In some embodiments, the stolide compounds and compositions may exhibit viscosities within a range of about 130 cSt to about 160 cSt at 40 ° C, and / or about 17 cSt to about 28 cSt at 100 ° C. In some embodiments, the stolide compounds and compositions may exhibit viscosities within a range of about 130 cSt to about 145 cSt at 40 ° C, and / or about 17 cSt to about 23 cSt at 100 ° C. In some embodiments, the stolide compounds and compositions may exhibit viscosities within a range of about 135 cSt to about 140 cSt at 40 ° C, and / or about 19 cSt to about 21 cSt at 100 ° C. In some embodiments, the stolide compounds and compositions may exhibit viscosities of about 1,2,3,4,5,6,7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22,23, 24, 25, 26, 27, 28, 29, 30, 32,34, 36, 38, 40, 42,44,46, 48, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 350, or 400 cSt. at 40 ° C. In some embodiments, the stolide compounds and compositions may exhibit viscosities of about 1,2,3,4,5,6,7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22,23, 24, 25, 26, 27, 28, 29, and 30 cSt at 100 ° C.
[00133] In some embodiments, stolide compounds and compositions may exhibit viscosities less than about 200, 250, 300, 350, 400, 450, 500, or 550 cSt at 0 ° C. In some embodiments, the stolide compounds and compositions may have a viscosity within the range of about 200 cSt to about 250 cSt at 0 ° C. In some embodiments, the stolide compounds and compositions may have a viscosity within the range of about 250 cSt to about 300 cSt at 0 ° C. In some embodiments, the stolide compounds and compositions may have a viscosity within the range of about 300 cSt to about 350 cSt at 0 ° C. In some embodiments, the stolide compounds and compositions may have a viscosity within the range of about 350 cSt to about 400 cSt at 0 ° C. In some embodiments, the stolide compounds and compositions may have a viscosity within the range of about 400 cSt to about 450 cSt at 0 ° C. In some embodiments, the stolide compounds and compositions may exhibit a viscosity in the range of about 450 cSt to about 500 cSt at 0 ° C. In some embodiments, the stolide compounds and compositions may have a viscosity within the range of about 500 cSt to about 550 cSt at 0 ° C. In some embodiments, the stolide compounds and compositions may exhibit viscosities of about 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, or 550 cSt at 0 ° C.
[00134] In some embodiments, the stolide compounds and compositions may exhibit desirable low temperature dumping point properties. In some embodiments, the stolide compounds and compositions may have a pour point of less than about -20 ° C, about -25 ° C, about -35 ° C, -40 ° C, or even about -50 ° C. In some embodiments, the stolide compounds and compositions have a pour point of about -25 ° C to about -45 ° C. In some embodiments, the pour point falls within a range of about -30 ° C to about -40 ° C, about -34 ° C to about -38 ° C, about -30 ° C to about -45 ° C, -35 ° C and about - 45 ° C, 34 ° C to about -42 ° C, about -38 ° C to about -42 ° C, or about 36 ° C to about -40 ° C. In some embodiments, the pour point falls within the range of about -27 ° C to about -37 ° C, or about -30 ° C to about -34 ° C. In some embodiments, the pour point falls within the range of about -25 ° C to about -35 ° C, or about -28 ° C to about -32 ° C. In some embodiments, the pour point falls within the range of about -28 ° C to about -38 ° C, or about -31 ° C to about -35 ° C. In some embodiments, the pour point falls within the range of about -31 ° C to about -41 ° C, or about -34 ° C to about -38 ° C. In some embodiments, the pour point falls within the range of about -40 ° C to about -50 ° C, or about -42 ° C to about -48 ° C. In some embodiments, the pour point falls within the range of about -50 ° C to about -60 ° C, or about -52 ° C to about -58 ° C. In some embodiments, the upper pour point limit is less than about -35 ° C, about -36 ° C, about -37 ° C, about -38 ° C, about -39 ° C, about -40 ° C, about - 41 ° C, about -42 ° C, about -43 ° C, about -44 ° C, or about - 45 ° C. In some embodiments, the lower pour point limit is greater than about -70 ° C, about -69 ° C, about -68 ° C, about -67 ° C, about -66 ° C, about -65 ° C, about -64 ° C, about - 63 ° C, about -62 ° C, about -61 ° C, about -60 ° C, about -59 ° C, about -58 ° C, about -57 ° C, approximately - 56 ° C, -55 ° C, about -54 ° C, about -53 ° C, about -52 ° C, -51, about -50 ° C, about -49 ° C, about -48 ° C, about-47 ° C, about -46 ° C, or about -45 ° C.
[00135] In addition, in certain modalities, stolids may exhibit reduced Iodine (IV) Values, when compared to stolids prepared by other methods. IV is a measure of the degree of total unsaturation of an oil, and is determined by measuring the amount of iodine per gram of stolide (cg / g). In certain cases, oils that have a higher degree of unsaturation may be more susceptible to creating corrosivity and deposits, and may exhibit lower levels of oxidative stability. Compounds that have a higher degree of unsaturation will have more points of unsaturation for the iodine to react, which results in a higher IV. Thus, in certain embodiments, it may be desirable to reduce the IV of the stolide in an effort to increase the oxidative stability of the oil, while decreasing the harmful deposits and corrosivity of the oil.
[00136] In some embodiments, the stolide compounds and compositions described herein have an IV of less than about 40 cg / g or less than about 35 cg / g. In some embodiments, stolids have an IV of less than about 30 cg / g, less than about 25 cg / g, less than about 20 cg / g, less than about 15 cg / g, less than about 10 cg / g, or less than about 5 cg / g. In some embodiments, stolids have an IV of about 0 cg / g. The IV of a composition can be reduced by decreasing the degree of unsaturation. This can be achieved by, for example, increasing the amount of saturated leveling materials in relation to unsaturated leveling materials when synthesizing stolides. Alternatively, in certain embodiments, IV can be reduced by hydrogenating stolids with unsaturated lids.
[00137] In certain embodiments, the composition is a lubricating composition. In certain embodiments, the composition comprises a stolide base oil, wherein the stolide base oil comprises at least one stolide compound. In certain embodiments, the composition comprises a combination of a stolide base oil and at least one antioxidant. Unless otherwise indicated, an indication of the characteristics of the "combination" of a stolide base oil and at least one antioxidant refers specifically to the properties of a mixture of stolide base oil and at least one antioxidant, in the absence of any other components that may be present in the overall composition. In certain embodiments, one or more properties of the composition will be similar to, or substantially the same as, the properties of the combination of the stolide base oil and the at least one antioxidant.
[00138] In certain embodiments, the composition has a kinematic viscosity, essentially the same as the kinematic viscosity of the stolide base oil included in the composition. In certain embodiments, the composition has a kinematic viscosity, within approximately 1% or about 2% of the kinematic viscosity of the stolide base oil included within the composition. In certain embodiments, the composition has a kinematic viscosity of 0, 2%, 0, 4%, 0, 6%, 0, 8%, 1, 0%, 1.2%, 1, 4%, 1, 6% , 1, 8%, or 2% of the kinematic viscosity of the stolide base oil included in the composition. In certain embodiments, the composition has a kinematic viscosity, which is less than or equal to about 15 cSt at 100 ° C. In certain embodiments, the composition has a kinematic viscosity, which is less than or equal to about 50 cSt at 40 ° C. In certain embodiments, the composition has a kinematic viscosity, which is less than or equal to about 500 cSt at 0 ° C.
[00139] In certain embodiments, the stolide base oil has a total acid number of about 0, 5, 0, 4, 0, 3, 0, 2, or even 0.1 mg KOH / g. In certain embodiments, the stolide base oil has a total acid number of less than about 0.1 mg KOH g, such as about 0.05 to about 0.1 mg KOH / g. In certain embodiments, the stolide base oil has a total acid number of about 0.05 mg KOH / g or less. In certain embodiments, the stolide base oil has a total acid number of about 0.02 to about 0.06 mg KOH / g. In certain embodiments, the stolide base oil has a total acid number of about 0.0, 01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0 , 08, 0.09, or 0.1 mg KOH g. In certain embodiments, the composition has a total acid number of essentially the same as the total acid number for the stolide base oil included in the composition.
[00140] In certain embodiments, the compositions described herein comprise or consist essentially of a stolide base oil, wherein said base oil comprises at least one compound of Formulas I, II and / or III. In certain embodiments, the composition additionally comprises at least one additive, wherein the at least one additive can be selected from one or more of an antioxidant, an antimicrobial agent, an extreme pressure agent, a friction modifier, a depressant from the pour point, a metal chelating agent, a metal deactivator, a defoaming agent, or a demulsifier. In certain embodiments, the composition essentially comprises or consists of a stolide base oil and at least one antioxidant. In certain embodiments, the composition additionally comprises at least one lubricating oil. In certain embodiments, the lubricating oil is not a stolide base oil. In certain embodiments, the lubricating oil is selected from a Group I oil, a Group II oil, a Group III oil, a polyalphaolefin, a polyol ester, a polyalkylene glycol, and an oil soluble polyalkylene glycol.
[00141] In certain embodiments, the composition essentially comprises or consists of a combination of a stolide base oil and at least one additive. In certain embodiments, at least one additive is an antioxidant. In certain embodiments, at least one antioxidant is selected from phenolic antioxidants, amine antioxidants, and organometallic antioxidants. In certain embodiments, the at least one antioxidant is a phenolic antioxidant. In certain embodiments, the at least one antioxidant is an impaired phenolic antioxidant. In certain embodiments, the at least one antioxidant is an amine antioxidant, such as a diarylamine, benzylamine, or polyamines. In certain embodiments, the at least one antioxidant is a diarylamine antioxidant, such as an alkylated diphenylamine antioxidant. In certain embodiments, the at least one antioxidant is a phenyl-α-naphthylamine or an alkylated phenyl-α-naphthylamine. In certain embodiments, the at least one antioxidant comprises an antioxidant package. In certain embodiments, the antioxidant package comprises one or more phenolic antioxidants and one or more amine antioxidants, such as a combination of an impaired phenolic antioxidant and an alkylated diphenylamine antioxidant. Examples of antioxidants include, but are not limited to, zinc dithiophosphates (ZDDP), butylated hydroxy anisol (BHA), 2,6-ditherciary-butyl paracresol (DBPC), tertiary mono-butyl hydroquinone (TBHQ), hydro tetra hydro butyrophenone (THBP), hydroquinone, pyrogallol, propyl gall, phenothiazine, and one or more tocopherols. Other exemplary antioxidants include, but are not limited to, hydroxylamines, amine N-oxides, oximes and nitrones. In certain embodiments, the at least one antioxidant is dithiocarbamate. In certain embodiments, dithiocarbamate is a metal dialkyl dithiocarbamate, such as, for example, zinc diamyl dithiocarbamate (ZDDC). In certain embodiments, diamyl zinc dithiocarbamate may have a synergistic effect with one or more extreme pressure agents, such as antimony dialkyl dithiocarbamate (ADDC).
[00142] In certain embodiments, the at least one antioxidant is an amine antioxidant. In certain embodiments, the at least one antioxidant is alkylated diphenylamine selected from nonylated diphenylamine and butylated / octyl diphenylamine. In certain embodiments, the at least one antioxidant is selected from N, N'-diisopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1 , 4-dimethylpentyl) - p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methyl-heptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethyl-butyl) -N'-phenyl-p-phenylenediamine, N- (1-methyl-heptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl -p- phenylenediamine, 4 - (p-toluenesulfamoyl) diphenylamine, N, N'-dimethyl- N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyiphenylamine, 4-isopropoxyphenylamine, N-phenyl- 1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, e.g. p, p'-di-tert-octyldiphenylamine, 4-n-butylaminophen1,4-butyrylaminophenol, 4 - * skip pp. 32/33. nonailaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2,6-di-tert-butyl-4-dimethylamino methylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N , N ', N'-tetramethyl- 4,4'-diaminodiphenylmethane, 1,2-bis [(2-methyl-phenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3'-dimethylbutyl) phenyl] amine, N-phenyl-1-naphthylamine tert-octyl, tert-butyl / tert-octyl diphenylamines mono- and dialkylated, isopropyl / isohexyldiphenylamines mono- and dialkylated, tert- mono- and dialkylated butyldiphenylamines, mono- and dialkylated nonyl diphenylamines, mono- and dialkylated octyl / butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, N-alkylphenothiazine, N , N, N ', N'-tetrafenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine, bis (2,2,6 , 6-tetramethyl piperid-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one and 2,2,6,6-tetramethyl piperidin-4-ol.
[00143] In certain embodiments, the at least one antioxidant is an alkylated monophenol. In certain embodiments, the at least one antioxidant is an alkylated diphenol. In certain embodiments, the at least one antioxidant is a bisphenol alkylidene. In certain embodiments, the at least one antioxidant is selected from 2,6-di-tert-butylphenol, 4,4'-methylene-bis (2,6-di-tert-butylphenol), 4,4'-bis (2,6-di-tert-butylphenol), 4,4'-bis (2-methyl-6-tert-butylphenol), 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol), 4,4'-isopropylidene-bis (2,6-di-tert-butylphenol), 2,2'-methylene-bis (4 -methyl-6 -nonylphenol), 2,2'-isobutylidene-bis (4,6-dimethylphenol), 2,2'-methylene-bis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-tert-butyl -4-ethylphenol), 2,2'-methylenebis [4-methyl-6- (a-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclo- hexylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidene bis (4,6-di-tert-butylphenol), 2,2'-ethylidene bis (6- tert-butyl-4-isobutylphenol), 2,2'-methylene-bis [6 - (a-methylbenzyl) -4-nonylphenol], 2,2'-methylene-bis [6 - (a, a-dimethylbenzyl) - 4-nonylphenol], 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-met ylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) - 4-methylphenol, 1, 1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl ) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methyl-phenyl) -3-n-dodecylmercapto butane, ethylene glycol bis [3, 3-bis (3'-tert-butyl- 4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methyl-phenyl) dicyclopentadiene, bis [2 - (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis- (3,5-dimethyl -2-hydroxyphenyl) butane, 2,2-bis- (3,5-di-tert-butyl-4 -hydroxyphenyl) propane, 2,2-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra- (5-tert-butyl- 4-hydroxy-2-methyl-phenyl) -pentane, 2,6-di-tert-butyl-4-methylphenol (butylated hydroxytoluene (BHT)), 2,6-di-tert-butyl-4-ethylphen1,2, 4-dimethyl-6-tert-butyl-phenol, 2,6-di-tert-butyl-N, N'-dimethylamino-p-chloro, 2,6-di-tert-4- (N, N'-dimethylaminomethylphenol ), heptyl 3 - (3 ', 5'-di-butyl-4'-hydroxyphenyl) propionate, octyl 3 - (3', 5'-di-butyl-4'-hydroxyphenyl) propionate, nonyl 3 - (3 ', 5'-di-butyl-4'-hydroxyphenyl) propionate, octadecyl 3 - (3', 5'-di-butyl-4'-hydroxyphenyl) propionate, 2-tert-butyl- 4,6-dimethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl -4-methylphenol, 2 - (α -methylcyclohexyl) -4,6- dimethylphenol, 2,6-dioctadecyl-4-methylphen-1,2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2, 6-di-nonyl-4-methylphenene 1,2,2-dimethyl-6 (l'-methylundec-1'-yl) phenol-1,2,4-dimethyl-6- (l'-methylheptadec-1'-yl ) phenol, and 2,4-dimethyl-6- (1'-methyltridec-1'-yl) phenol.
[00144] In certain embodiments, the at least one antioxidant is selected from an alkylthiomethylphenol and a hydroxylated thiodienyl ether. In certain embodiments, the at least one antioxidant is selected from 4,4'-thio-bis (2-methyl-6-tert-butylphenol), 2,2'-thio-bis (4-methyl-6-tert -butylphenol), bis (3-methyl-4-hydroxy-5-tert-butylbenzyl) - sulfide, thiodiethylene-bis- (3,5-di-t-butyl-4-hydroxyhydrocinamate), tetquis- (methylene- (3 , 5-di-t-butyl-4-hydrocinamate)) methane, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 2,4-dioctyltomethyl-6-tert-butylphen1,2,4- dioctyltethomethyl-6-methylphenene 1,2,4-dioctyltomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol, 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl) -3-methylphenol), 4,4'-thio-bis- (3,6-di-sec-amylphenol), and 4,4'-bis- (2,6-dimethyl-4-hydroxyphenyl) -disulfide.
[00145] In certain embodiments, at least one antioxidant is selected from hydroquinones and alkylated hydroquinones. In certain embodiments, the at least one antioxidant is selected from 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amyl- hydroquinone, 2,6 - diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxyaniso1,3,5-di-tert-butyl- 4- hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, and bis- (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
[00146] In certain embodiments, the at least one antioxidant is selected from 0-, N-and S-benzyl compounds. In certain embodiments, the at least one antioxidant is selected from 3,5, 3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol terephthalate, bis (3,5-di-tert- butyl-4-hydroxybenzyl) sulfide, and that-octyl-3,5-di-tert-butyl-4-hydroxy benzylmercaptoacetate.
[00147] In certain embodiments, at least one antioxidant is selected from hydroxybenzylated malonates. In certain embodiments, the at least one antioxidant is selected from dioctadecyl-2,2-bis- (3,5-di-tert-butyl-2-hydroxybenzyl) -malonate, di-octadecyl-2- (3-tert -butyl-4-hydroxy-5-methylbenzyl) -malonate, di-dodecylmercaptoethyl-2,2-bis- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, and bis [4 - (l, 1 , 3, 3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.
[00148] In certain embodiments, at least one antioxidant is selected from triazine compounds. In certain embodiments, the at least one antioxidant is selected from 2,4-bis (octylmercapto) -6 - (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2 - octylmercapto -4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-terti- butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3, 5 - tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) - 1,3,5-triazine, 1,3,5-tris (3,5-di-propionyl-tert-butyl-4-hydroxyphenyl) -hexa - hydro-1,3,5-triazine, and 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
[00149] In certain embodiments, at least one antioxidant is selected from aromatic hydroxybenzyl compounds. In certain embodiments, the at least one antioxidant is selected from 1 -2,4,6-trimethylbenzene, 1,4-bis-, 3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl ) (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5, 6-tetramethylbenzene, and 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol. In certain embodiments, at least one antioxidant is selected from benzylphosphonates. In certain embodiments, the at least one antioxidant is selected from dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5 -di -tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy 3-methylbenzylphosphonate, and the calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester. In certain embodiments, at least one antioxidant is selected from acylaminophenols. In certain embodiments, the at least one antioxidant is selected from 4-hydroxyluranilide, 4-hydroxystearanilide, and octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.
[00150] In certain embodiments, the at least one antioxidant is selected from esters of [3 - (3,5-di-tert-butyl-4-hydroxyphenyl) propionic with mono- or polyhydric alcohols, such as, with methanol, ethanol, octadecanol, 1,6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N '-bis (hydroxyethyl) oxamide, 3-thiaundecane1,3-thiapentadecanol, trimethylhexanediol, trimethylalpropane, or 4-hydroxymethyl-1-phosphate-2,6,7-trioxabicyclo [2.2.2] octane. In certain embodiments, the at least one antioxidant is selected from esters of P- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols, such as with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'- bis (hydroxyethyl) oxamide, 3-thiaundecane1,3-thiapentadecanol, trimethylhexanediol, trimethylalpropane, or 4-hydroxymethyl-1-phosfa-2, 6, 7-trioxabicyclo [2.2.2] octane. In certain embodiments, the at least one antioxidant is selected from esters of 13 - (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, such as with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis ( hydroxyethyl) oxamide, 3-thiaundecane1,3-thiapentadecanol, trimethylhexanediol, trimethylalpropane, and 4-hydroxymethyl-1-phosphate-2,6,7-trioxabicyclo [2.2.2] octane. In certain embodiments, the at least one antioxidant is selected from esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols, such as with methanol, ethanol, octadecanol , 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) ) oxamide, 3-thiaundecane1,3-thiapentadecanol, trimethylhexanediol, trimethylalpropane, and 4-hydroxymethyl-1-phosphor-2,6,7-trioxabicyclo [2.2.2] octane.
[00151] Other exemplary, non-limiting examples of suitable antioxidants include those that include nitrogen, such as β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid amides, such as N, N'- bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) - trimethylenediamine, and N, N'-bis ( 3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine. Even additional non-limiting examples of suitable antioxidants include aliphatic or aromatic phosphites, esters of thiodipropionic acid or thiodiacetic acid, or salts of dithiocarbamic or dithiophosphoric acid, 2,2,12,12-tetramethyl-5, 9-dihydroxy-3 , 7, 1-tritiamidecane and 2,2,15,15-tetramethyl-5,12-dihydroxy-3,7,10,14-tetratiahexadecane.
[00152] Other exemplary antioxidants include, but are not limited to, those marketed under the trademarks of Vanlube® (RT Vanderbilt Corp.), Na-Lube® (King Industries), Irganox® (BASF), Irgalube® (BASF) , Ethanox® (Albermarle), and Naugalube® (Chemtura), such as Irganox® L06, Irganox® L55, Irganox® L-57, Irganox® L115, Irganox® L118, Irganox® L134, Irganox®-L135, Irganox® L150 , Irganox® 1010, Irganox® 1035, rgalube® F20, Na Lube® AO-130, Naugalube® 438L, Na Lube® AO-142, Na Lube® AO-210, Na-Lube® AO- 242, Vanlube® NA, Vanlube® SL, Ethanox® 4701, Ethanox® 376, Ethanox® 4716, Ethanox® 4783, Ethanox® 4702, Ethanox® 4710, Ethanox® 4782J, Ethanox® 4727J, Ethanox® 4703, and Ethanox® 5057.
[00153] In certain embodiments, the at least one antioxidant comprises about 0 to about 5% by weight of the overall combination or composition, such as about 0.01% to about 5%. In certain, the at least one antioxidant comprises about 0 to about 3% by weight of the combination or the overall composition, such as about 0.1 to about 3% by weight. In certain embodiments, the at least antioxidant is present in amounts of about 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, or 3.0% by weight of the combination or overall composition. In certain embodiments, the at least antioxidant is present in amounts of about 1,2,3,4,5,6,7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 , 19, or 20% by weight of the overall combination or composition. In certain embodiments, the oxidation stability of olive oil can be determined by AOM (anaerobic oxidation of methane) or OSI (oxidation stability index) of methods known to those skilled in the art.
[00154] In certain embodiments, the composition additionally comprises at least one extreme pressure agent. In certain embodiments, the at least one extreme pressure agent is an extreme phosphorus pressure agent. In certain embodiments, the extreme phosphorus pressure agent comprises one or more compounds selected from phosphoric acid esters, phosphoric acid esters, phosphoric acid amine salts, amine salts of phosphoric acid esters, acid phosphates of amine, chlorinated phosphoric acid esters, phosphorus acid esters, phosphorylated carboxylic acid compounds, phosphorothionates and metal salts of phosphorus-containing compounds. In certain embodiments, the at least one extreme pressure agent comprises one or more compounds selected from phosphoric acid esters, phosphoric acid esters, amine salts of acidic phosphoric acid esters, chlorinated phosphoric acid esters, and esters phosphorous acid. In certain embodiments, the at least one extreme pressure agent comprises a phosphorus-containing ester prepared from phosphoric acid and / or phosphorous acid, such as those derived from alkanol or polyether alcohols.
[00155] Examples of phosphoric acid esters include, but are not limited to, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, riheptyl phosphate, trioctyl phosphate, trinonyl phosphate, tridecyl phosphate, triundecyl, tridodecyl phosphate, tritridecyl phosphate, tritetradecyl phosphate, tripentadecyl phosphate, trihexadecyl phosphate, triheptadecyl phosphate, trioctadecyl phosphate, triphenyl phosphate, triphenyl phosphate, triphenyl phosphate, triphenyl phosphate, triphenyl phosphate and xylyldiphenyl phosphate.
Exemplary phosphoric acid esters include, but are not limited to, monoalkyl phosphoric acid esters, such as monopropyl acid phosphate, butyl acid phosphate, monopentyl acid phosphate, monohexyl acid phosphate, monoheptyl acid phosphate , mono-octyl acid phosphate, monononyl acid phosphate, monodecyl acid phosphate, monoundecyl acid phosphate, monododecyl acid phosphate, monotridecyl acid phosphate, mono-tetradecyl acid phosphate, monopentadecyl acid phosphate, monopentadic acid phosphate hexadecyl, monoheptadecyl acid phosphate, monooctadecyl acid phosphate and monoololic acid phosphate, and dialkyl phosphoric acid esters and phosphoric di (alkyl esters) aryl phosphate, such as dibutyl acid phosphate, dipentyl acid phosphate, di-phosphate acid hexyl, diheptylic acid phosphate, dioctyl acid phosphate, dinonyl acid phosphate, didecyl acid phosphate co, diundecyl acid phosphate, didodecyl acid phosphate, ditridecyl acid phosphate, ditetradecyl acid phosphate, dipentadecyl acid phosphate, dihexadecyl acid phosphate, diheptadecyl acid phosphate and dioctadecyl acid phosphate and dihydrate phosphate.
[00157] Examples of amine salts of phosphoric acid ester include, but are not limited to, the exemplary acid phosphoric acid esters mentioned above with amines such as methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine , octylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptilamine, dioctylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptilamine, trioctilamine.
[00158] Examples of acid chlorinated phosphoric acid esters include, but are not limited to, dichloro propyl tphosphate, trischlorethyl phosphate, tris chlorophenyl phosphate, and bis [di (chloroalkyl)] polyoxyalkylene phosphate.
[00159] Exemplary phosphorus acid esters include, but are not limited to, dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, dihexyl phosphite, dioctyl phosphite, dinonyl phosphite, didecyl phosphite, phosphite diundecyl, didodecyl phosphite, dioleyl phosphite, diphenyl phosphite, dicresyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, trinonyl phosphite, trinidyl phosphite tridodecyl phosphite, triolela phosphite, triphenyl phosphite, and tricresyl phosphite.
[00160] Exemplary phosphorus-containing carboxylic acids include, but are not limited to, the compounds represented by Formula A:

[00161] where X is an alkylene residue and R1, R2 and R3 are independently selected from hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkylalkyl, optionally substituted aryl, optionally substituted arylalkyl, optionally substituted heteroarylalkyl, heteroarylalkyl optionally substituted, optionally substituted hetero-cycloalkyl, and optionally substituted hetero-cycloalkylalkyl.
[00162] Exemplary phosphorothionate compounds include, but are not limited to, compounds represented by Formula B:

[00163] wherein R1, R2 and R3 are independently selected from hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkylalkyl, optionally substituted aryl, optionally substituted arylalkyl, optionally substituted heteroaryl, optionally substituted heteroarylalkyl, optionally hetero-cycloalkyl optionally substituted, and optionally substituted heterocycloalkylalkyl.
[00164] Examples of amine salts of phosphorus-containing compounds include, but are not limited to, amine or alkanolamine salts of phosphoric acid, butylamine phosphates, propanolamine phosphates, and triethanolamine phosphates, monoethanolamine, dibutyl-, dimethyl-, and monoisopropanol amine.
[00165] Examples of metal salts of phosphorus-containing compounds include, but are not limited to, metal salts of the phosphorous compounds described herein. In certain embodiments, metal salts of phosphorous compounds are prepared by neutralizing some or all of the acidic hydrogen of the phosphorous compound with a metal base. Examples of metal bases include, but are not limited to, metal oxides, metal hydroxides, metal carbonates, and metal chlorides, wherein said metal is selected from alkali metals, such as lithium, sodium, potassium and cesium, metals alkaline earth, such as calcium, magnesium and barium, and heavy metals, such as zinc, copper, iron, lead, nickel, silver, and manganese.
[00166] In certain embodiments, the at least one extreme pressure agent is selected from one or more sulfur compounds. In certain embodiments, the at least one extreme pressure agent comprises one or more compounds selected from sulfides and polysulfides, such as benzildisulfide, bis- (chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfur oils and fats, sulfur glyceride oils, fatty acids sulfur compounds, sulfur esters, sulfur olefins, dihydrocarbyl (poly) sulfides, thiadiazole compounds, alkylthiocarbamoyl compounds, tioterpene alkylthiocarbamate compounds, dialkyl compounds, thiodipropionate compounds, sulfur compound mineral oils, zinc dithiocarbamates and molten dihydrocarbons. , sulfur dipentenes, sulfur terpenes and sulfur Diels-Alder adducts. Other exemplary sulfur compounds include, but are not limited to, phosphorous hydrocarbons, such as the phosphorus sulfide reaction product with turpentine or methyl oleate.
[00167] Examples of dihydrocarbyl (poly) sulfides include, but are not limited to, dibenzyl polysulfides, dinonyl polysulfides, didodecyl polysulfides, dibutyl polysulfides, dioctyl polysulfides, diphenyl polysulfides, and dicyclohexyl polysulfides . Exemplary thiadiazole compounds include, but are not limited to, 1,3,4-thiadiazols, 1,2,4-thiadiazols, 1, 4, 5-thiadiazoles and, like 2,5-bis (n-hexyldithio) - 1,3,4-thiadiazole, 2,5-bis (n-octyldithium) -1,3,4 - thiadiazole, 2,5-bis (n-nonildithio) -1,3,4-thiadiazole, 2,5- bis (1, 1,3, 3-tetramethylbutyldithium) -1,3,4-thiadiazo1,3,5 - of bis (n-hexyldithium) -1,2,4-thiadiazo1,3,5-bis (n-octyltium ) - 1,2,4-thiadiazo1,3,5-bis (n-nonildithio) -1,2,4-thiadiazo1,3,5-bis (1, 1,3, 3-tetramethylbutildithio) -1,2, 4-thiadiazole, 4,5-bis (n-hexyldithium) - 1,2,3-thiadiazole, 4,5-bis (n-octyltium) - 1,2,3-thiadiazole, 4,5-bis (n- nonildithio) -1,2,3-thiadiazole, and 4,5-bis (1, 1,3, 3 - tetramethylbutildithio) -1,2,3-thiadiazole.
Exemplary alkylthiocarbamoyl compounds include, but are not limited to, bis (dimethylthiocarbamoyl) monosulfide, bis (dibutylthiocarbamoyl) disulfide, bis (dibutylthiocarbamoyl) disulfide, bis (diamylthiocarbamoyl) and bis (diamylthiocarbamoyl) disulfide. Exemplary alkylthiocarbamate compounds include, but are not limited to, methylene bis (dibutyldithiocarbamate) and methylene-bis [di (2-ethyl) dithiocarbamate]. Exemplary tioterpene compounds include, but are not limited to, phosphorus and pinene pentasulfide reaction products. Exemplary dialkyl thiodipropionate compounds include, but are not limited to, dilauryl thiodipropionate and distearyl thiodipropionate.
[00169] In certain embodiments, the at least one extreme pressure agent is present in amounts of about 0 to about 25% by weight of the composition. In certain embodiments, the at least one extreme pressure agent is present in amounts of about 0 to about 20, about 0 to about 15, about 0 to about 10, about 0 to about 8, about from 0 to about 6, about 0 to about 4, or about 0 to about 2% by weight of the composition. In certain embodiments, the at least one extreme pressure agent is present in amounts of about 0 to about 5% by weight of the composition, such as about 0.1 to about 3% by weight. In certain embodiments, the at least one extreme pressure agent is present in amounts of about 1,2,3,4,5,6,7, 8, 9, 10, 11, 12, 13, 14, 15, 16 , 17, 18, 19, or 20% by weight of the composition. In certain embodiments, the at least one extreme pressure agent is present in amounts of about 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2 , 2.4, 2.6, 2.8, or 3.0% by weight of the composition.
[00170] In certain embodiments, the composition additionally comprises at least one antifoaming agent. Exemplary antifoam agents include, but are not limited to, silicones, such as dimethylsilicone and fluorosilicone, and their polymers, such as polyacrylates, polymethacrylates and perfluoroalkyl ethers. In certain embodiments, at least one defoaming agent is present in amounts of about 0 to about 25% by weight of the composition. In certain embodiments, the at least one defoaming agent is present in amounts of about 0 to about 20, about 0 to about 15, about 0 to about 10, about 0 to about 8, about 0 at about 6, about 0 to about 4, or about 0 to about 2% by weight of the composition. In certain embodiments, at least one defoaming agent is present in amounts of about 0 to about 5% by weight of the composition, such as about 0.1 to about 3% by weight. In certain embodiments, at least one defoaming agent is present in amounts of about 1,2,3,4,5,6,7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20,% by weight of the composition. In certain embodiments, at least one antifoaming agent is present in amounts of about 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, or 3.0% by weight of the composition.
[00171] In certain embodiments, the composition additionally comprises at least one demulsifier. In certain embodiments, the at least one demulsifier is an anionic surfactant, such as an alkyl naphthalene sulfonate or an alkyl benzene. In certain embodiments, the at least one demulsifier is non-ionic. In certain embodiments, the at least one demulsifier is selected from a nonionic alkoxylated alkylphenol resin, an alkylene oxide polymer, such as polyethylene oxide, polypropylene oxide, an ethylene oxide block copolymer, or propylene oxide, an ester of an oil-soluble acid, and a polyoxyethylene of sorbitan. Other exemplary demulsifiers include, but are not limited to, block copolymers of propylene oxide or ethylene oxide and initiators such as glycerol, phenol, formaldehyde resins, soloxanes, polyamines, and polyols. In certain embodiments, the polymers contain about 20 to about 50% ethylene oxide. Low molecular weight materials, such as, for example, alkali metals or alkaline earth metal salts of dialkylnaphthalene sulfonic acids, may also be useful in certain applications. In certain embodiments, the at least one demulsifier can be present from about 0.01% by weight to about 10% by weight, from about 0.05% by weight to about 5% by weight, or from about 0.1% by weight to about 3% by weight of the composition. In certain embodiments, the at least one demulsifier is present in amounts of about 1,2,3,4,5,6,7, 8, 9, or 10% by weight of the composition. In certain embodiments, the at least one demulsifier is present in amounts of about 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, or 3.0% by weight of composition.
[00172] In certain variants, at least one additive includes at least one antimicrobial agent. In certain embodiments, the at least one antimicrobial agent inhibits the growth of microorganisms. In certain embodiments, the at least one antimicrobial agent is any antimicrobial substance that is compatible with the composition can be mixed into the composition. In certain embodiments, compounds that are useful as antioxidants can also be used as antimicrobial agents. For example, in certain embodiments, phenolic antioxidants such as BHA may also have some activity against one or more of bacteria, fungi, viruses and protozoa. In certain embodiments, the at least one antioxidant can be added with at least one antimicrobial agent selected from one or more of potassium sorbate, sorbic acid, and monoglycerides. Other exemplary antimicrobials include, but are not limited to, vitamin E and ascorbyl palmitate, as well as morpholine-based compounds, such as 4 - (2-nitrobutyl) morpholine, 4,4'- (2-ethyl-2- nitrotrimethylene) dimorpholine and methylene dimorpholine, which may be commercially available under the designations BIOBAN P-1487 ™, BIOBAN CS-1135 ™, and Kaython ™ EDC 1, 5 (marketed by Dow Chemical Co.). Other exemplary antimicrobial agents include, but are not limited to, those comprising the poly (oxy-1,2-ethanediyl (dimethylimino) - 1,2-ethanediyl (dimethylimino) - 1,2-ethanediyl dichloride material, sold under the Busan 77 ® designation (marketed by Buckman Laboratories, Inc. of Memphis, Tennessee).
[00173] In certain variants, at least one chelating agent additive includes at least one metal and / or at least one metal deactivator. Since metals, such as copper may be present, in certain embodiments, the composition may include at least one metal deactivator. Exemplary metal deactivators include, but are not limited to, yellow metal deactivators, such as copper deactivators and copper alloys. Exemplary metal deactivators include, but are not limited to, benzotriazoles and their derivatives, such as 4 - or 5-alkylbenzotriazols (e.g., triazole), 4,5,6,7-tetrahydrobenzotriazole and 5, 5'-methylenebisbenzotriazole, Mannich bases of benzotriazole or triazole, such as triazole 1- [bis (2-ethylhexyl) -aminomethyl) and 1- [bis (2-ethylhexyl) aminomethyl) - benzotriazole, and alkoxyalkylbenzotriazols such as 1 - ( nonilaximethyl) benzotriazole, 1- (1-butoxyethyl) benzotriazole and 1 - (1-cyclohexyloxybutyl) triazole. Non-limiting examples include 1,2,4-triazoles and their derivatives, such as 3-alkyl (or aryl) - 1,2,4-triazols, Mannich bases and 1,2,4-triazoles, such as 1 - [ bis (2-ethylhexyl) -aminomethyl-1,2,4-triazole, alkoxyalkyl-1,2,4-triazoles such as 1- (1-butoxyethyl) -1,2,4-triazole, and 3- acylated amino -1,2,4-triazoles and imidazole derivatives, such as 4,4'-methylene-bis (2-undecyl-5-methylimidazole) and bis - [(N-methyl) imidazol-2-yl] carbinol octyl ether. In certain embodiments, the deactivator of at least one metal is selected from 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole and its derivatives, and 3,5-bis [di (2-ethyl- hexyl) - aminomethyl] - 1,3,4-thiadiazolin-2-one. Other examples of metal deactivators may include amino compounds, for example salicylidenepropylenediamine, salicylaminoguanidine and their salts. Exemplary metal deactivators include those available under the trade name K-Corr ® (King Industries), including K-Corr ® 100 and K-Corr ® NF-200.
[00174] In certain embodiments, the composition comprises at least one metal deactivator in an amount equal to or less than about 1% by weight, such as about 0.1% by weight to about 0.5% by weight. In certain embodiments, the composition comprises at least one metal deactivator in an amount of about 0, 1, 0, 2, 0, 3, 0, 4, 0, 5, 0, 6, 0, 7, 0, 8 , 0, 9, or 1.0% by weight of the composition. In certain embodiments, the composition includes a combination of additives, such as a combination of amines and phenolic antioxidant compounds and / or triazole metal deactivators. An exemplary combination includes, but is not limited to, Irganox® G-57 antioxidant, Irganox® L-109 antioxidant, and metal deactivator Irgamet® -30, which are each commercially available from Ciba-Geigy, Inc (now BASF).
[00175] In certain embodiments, one or more of the optional additives, such as certain metal deactivator packages, may comprise a fatty acid or fatty acid derivative or a precursor, which can increase the acid value (for example, the total acid number) of the composition. Without being linked to any particular theory, in certain modalities, it is believed that the increase in the acidity index of the composition may result in the reduction of the oxidative stability of the formulation. Therefore, in certain embodiments, the composition is substantially free of fatty acid components, such as free fatty acids, and / or has a low acid value.
[00176] In certain embodiments, a method of preparing a stolide composition is described, said method comprising selecting a stolide base oil; reduce the acid number of the stolide base oil to provide a low acid stolide base oil, and combine the low acid stolide base oil with at least one antioxidant. In certain embodiments, the reduction of the acidity index of the stolide base oil to provide a low acidity stolide base oil which comprises contacting said stolide base oil with at least one acid reducing agent. In certain embodiments, the at least one acid reducing agent is selected from any suitable agent, such as, for example, one or more of activated carbon, magnesium silicate (for example, Magnesol ®), aluminum oxide (for example, Alumina), silicon dioxide, a zeolite, a base resin, and an anion exchange resin. In certain embodiments, the acid value of at least one stolide base oil is reduced to any of the levels described herein, such as about 0.1 mg KOH / g or less. In certain embodiments, the combination of low acid stolide base oil and at least one antioxidant that has a time value similar to the times described here for other stolide base oils when tested in a rotary pressurized container oxidation test using ASTM method 2272-11, such as about 1000 minutes or more.
[00177] In certain embodiments, the composition additionally comprises at least one friction modifier. In certain embodiments, at least one friction modifier is selected from amine, imide, fatty acid friction modifiers, each of which may comprise at least one alkyl group having 6 to 30 carbon atoms, such as one straight chain alkyl group having 6 to 30 carbon atoms. Examples of amine-type friction modifiers include, but are not limited to, straight chain or branched amines, such as straight chain aliphatic monoamines, aliphatic alkanolamines, and aliphatic polyamines, and alkylene oxide adducts of such aliphatic amines . Examples of imide-type friction modifiers include, but are not limited to, succinimide-type friction modifiers, such as mono- and / or bis-succinimides having one or two straight or branched chain hydrocarbon groups, such as those that have a hydrocarbon group of 6 to 30 or 8 to 18 carbon atoms, and succinimide-modified compounds produced allowing such succinimides to react with one or more compounds selected from boric acid, phosphoric acid, carboxylic acids, such as those having 1 to 20 carbon atoms, and sulfur-containing compounds. Examples of amide-type friction modifiers include, but are not limited to, amide-type fatty acid friction modifiers, such as straight or branched chain fatty acid amides (including those having 7 to 31 carbon atoms) and ammonia , aliphatic monoamines, or aliphatic polyamines.
[00178] In certain embodiments, at least one friction modifier is a friction modifier of the fatty acid type, such as a straight or branched chain fatty acid, fatty acid esters of such fatty acids and aliphatic monohydric alcohols or aliphatic polyhydric alcohols, a metal fatty acid salt, such as alkaline earth metal salts of these fatty acids (magnesium and calcium salts) and zinc salts of such fatty acids. In certain embodiments, the friction modifier is present from about 0.01 to about 5.0% by weight of the composition, such as about 0.03 to about 3.0% by weight. In certain embodiments, at least one friction modifier is present in amounts of about 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, or 3.0% in weight of the composition.
[00179] In certain embodiments, the composition additionally comprises at least one viscosity modifier. In certain embodiments, the at least one viscosity modifier provides high and low operating temperature for the lubricating oil and allows it to remain shear stable at high temperatures, while providing acceptable viscosity or fluidity at low temperatures. In certain embodiments, the at least one viscosity modifier comprises one or more compounds selected from high molecular weight hydrocarbon polymers, such as polyesters. In certain embodiments, the at least one viscosity modifier is derivatized to include other properties or functions, such as the addition of dispersion properties. Examples of viscosity modifiers include, but are not limited to, polybutene, polyisobutylene (PIB), ethylene and propylene copolymers, polymethacrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and the vinyl compound, styrene interpolymers and acrylic esters, and partially hydrogenated copolymers of styrene / isoprene, styrene / butadiene, and isoprene / butadiene, as well as partially hydrogenated homopolymers of butadiene and isoprene.
[00180] In certain embodiments, the composition comprises at least one polybutene polymer. In certain embodiments, the at least one polybutene polymer comprises a mixture of poly-n-butenes and polyisobutylene, which may result from the polymerization of C4 olefins and will generally have an average molecular weight number of about 300 to 1500, or a polyisobutylene or polybutene having an average molecular weight number of about 400 to 1300. In certain embodiments, polybutene and / or polyisobutylene may have an average molecular weight (PM) number of about 950 MW can be measured by gel permeation chromatography. Polymers composed of 100% polyisobutylene or 100% poly-n-butene are to be understood as falling within the scope of this description and within the meaning of the term "polybutene polymer". An exemplary polyisobutylene includes "PIB SI 054", which has a molecular weight of about 950 and is sold by Infineum USA of LindeN, New Jersey.
[00181] In certain embodiments, the at least one polybutene polymer comprises a mixture of polybutenes and polyisobutylene prepared from a C4 olefin refinery stream containing about 6% by weight to about 50% by weight of isobutylene , with the balance of a mixture of butene (cis- and trans-) isobutylene and less than 1% by weight of butadiene. For example, at least one polybutene polymer can be prepared by Lewis acid catalysis from a C4 flow composed of 6-45% by weight of isobutylene, 25 to 35% by weight of saturated butenes and 15 to 50% by weight of 1- and 2-butenes. In certain embodiments, the composition comprises from about 0% by weight to about 80% by weight, such as about 0% by weight to about 60% by weight or about 0% by weight to about 40% by weight. weight of at least one viscosity modifier. In certain embodiments, the at least one viscosity modifier is present in amounts of about 1% by weight to about 30% by weight, about 1% by weight to about 25% by weight, or about 5% by weight. weight about 20% by weight of the composition. In certain embodiments, the at least one viscosity modifier comprises about 0, 5, 1, 1, 5, 2,2,5, 3, 3,5, 4.4, 5, 5, 5, 5, 6, 6, 5, 7, 7, 5, 8, 8.5, 9, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22,23, 24, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80% by weight of the composition.
[00182] In certain embodiments, the composition additionally comprises at least one pour point depressant. Examples of pour point depressants include, but are not limited to, polyvinyl acetate oligomers and polymers and / or acrylic oligomers and polymers, including (meth) acrylates, such as those available from Rohmax, Philadelphia, Pennsylvania, under the trade name of VISCOPLEX ®. In certain embodiments, the at least one pour point depressant is an alkyl methacrylate with a molecular weight of about 200,000, such as VISCOPLEX ® 10-310. Other suitable pour point depressants may include methacrylates available from functional products, Macedonia, Ohio, under the trade name DP-551. In certain embodiments, the at least one pour point depressant is present in the composition from about 0% by weight to about 5% by weight, such as about 0.2% by weight to about 3% by weight, or about 0.4 wt% to about 2 wt%. In certain embodiments, the at least one pour point depressant is present in amounts of about 1, 2, 3, 4, or 5% by weight of the composition. In certain embodiments, at least one pour point depressant is present in amounts of about 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, or 3.0 % by weight of the composition.
[00183] In certain embodiments, the composition comprises at least one dye. In certain embodiments, at least one dye is selected from dyes and pigments. In certain embodiments, any known dyes and / or pigments can be used, such as those commercially available as food additives. In certain embodiments, dyes and pigments can be selected from oil-soluble dyes and pigments. In certain embodiments, at least one dye is present in the composition in smaller amounts, for example, less than about 1 ppm.
[00184] In some embodiments, a composition including stolide base oil. In some embodiments, the composition includes a combination of a stolide base oil and at least one antioxidant. In some embodiments, the composition and / or a combination has a time of at least 200 minutes when tested in a rotary pressurized container oxidation test using ASTM method 2272-11. In some embodiments, the composition and / or combination has a time of at least 300 minutes when tested in a rotary pressurized container oxidation test using ASTM method 2272-11. In some embodiments, the composition and / or combination has a time of at least 400 minutes when tested in a rotary pressurized container oxidation test using ASTM method 2272-11. In some embodiments, the composition and / or combination has a time of at least 420, 440, 460, or even 480 minutes when tested in a rotary pressurized container oxidation test using ASTM method 2272-11. In certain embodiments, the composition and / or combination has a time of at least 500, 520, 540, 560, 580, 600, 620, 640, 660, 680, 700, 720, 740, 760, 780, 800, 820 , 840, 860, 880, 900, 920, 940, 960, or even 980 minutes, when tested in a rotary pressurized container oxidation test using ASTM method 2272-11. In certain embodiments, the composition and / or combination has a time of at least 1000, 1100, 1200, 1300, 1400, or even 1500 minutes, when tested in a rotary pressurized container oxidation test using ASTM method 2272-11.
[00185] In certain embodiments, the composition and / or combination has an oxidation initiation temperature of at least 200 ° C, as determined by non-isothermal pressurized differential scanning calorimetry under dynamic O2 conditions. In certain embodiments, the composition and / or combination has an oxidation initiation temperature of at least 205 ° C, 210 ° C, 215 ° C, 220 ° C, 225 ° C, 230 ° C, 235 ° C, 240 ° C, 245 ° C, 250 ° C, 255 ° C, 260 ° C, 265 ° C, 270 ° C, 275 ° C, 280 ° C, 285 ° C, 290 ° C, 295 ° C, 300 ° C , 305 ° C, 310 ° C, 315 ° C, 320 ° C, or up to 325 ° C, as determined non-isothermal pressurized differential scanning calorimetry under dynamic O2 conditions.
[00186] In certain embodiments, the composition includes a blend of at least one stolide base oil and at least one other base oil selected from polyalphaolefins (PAO), synthetic esters such as polyol esters, polyalkylene glycols (pags) ), soluble oil polyalkylene glycols (OPS), mineral oils (Groups I, II and III), vegetable and animal oils (eg mono-, di- and triglycerides), and fatty acid esters. In certain embodiments, the composition comprises at least one stolide base oil and at least one OPS. In certain embodiments, at least one PSO is prepared by reacting an alcohol with a mixed butylene oxide and feeding with propylene oxide. In certain embodiments, the alcohol is selected from one or more C8-C20 alcohols. In certain embodiments, the ratio of butylene oxide to propylene oxide is from about 3: 1 to about 1: 3. In certain embodiments, at least one OPS may provide greater hydrolytic stability for the composition containing stolide. Exemplary OPS includes, but is not limited to, those marketed under the trade name UCON ™ by Dow.
[00187] The present invention also relates to methods of preparing stolides according to Formula I, II, and III. As an example, the reaction of an unsaturated fatty acid with an organic acid, and the esterification of the resulting free acid stolide are illustrated and discussed in the following Schemes 1 and 2. The particular structural formulas used to illustrate the reactions correspond to those for the synthesis of compounds according to Formula I and III, however, the methods apply equally to the synthesis of compounds according to Formula II, with the use of compounds having the structure that corresponds to R3 and R4 with a reactive site unsaturation.
[00188] As illustrated below, compound 100 represents an unsaturated fatty acid that can serve as a basis for the preparation of the stolide compounds described herein.

[00189] In scheme 1, where x is, independently for each occurrence, an integer selected from 0 to 20, y is, independently for each occurrence, an integer selected from 0 to 20, n is an integer greater than or equal to 1, and R1 is an optionally substituted alkyl group, which is saturated or unsaturated, branched and unbranched, or unsaturated fatty acid 100 can be combined with compound 102, and a proton from a source of protons, to form free acid stolide 104. In certain embodiments, compound 102 is not included, and unsaturated fatty acid 100 can be exposed to acidic conditions alone to form free acid stolide 104, in which R1 would represent a group unsaturated alkyl. In certain embodiments, if compound 102 is included in the reaction, R1 may represent one or more optionally substituted alkyl residues that are saturated or unsaturated and branched or unbranched. Any suitable proton source can be implemented to catalyze the formation of free acid stolide 104, including, but not limited to, homogeneous acids and / or strong acids such as hydrochloric acid, sulfuric acid, perchloric acid, nitric acid, triflic acid, and the like. Layout 2

[00190] Likewise, in Scheme 2, where x is, independently for each occurrence, an integer selected from 0 to 20, y is, independently for each occurrence, an integer selected from 0 to 20, n is an integer greater than or equal to 1, and R1 and R2 are each an alkyl group that is saturated or unsaturated, branched and unbranched, or free acid stolid 104 can be esterified by any suitable process known to those skilled in the art. technique, such as acid-catalyzed reduction with alcohol 202, to obtain esterified stolide 204. Other exemplary methods may include other types of Fischer esterification, such as those using Lewis acid catalysts, such as BF3.
[00191] In all of the previous examples, the described compounds can be useful by themselves, in the form of mixtures, or in combination with other compounds, compositions, and / or materials.
[00192] The methods for obtaining the new compounds described herein will be evident to those skilled in the art, the appropriate procedures being described, for example, in the examples below, and in the references cited here. EXAMPLES Analytics
[00193] Nuclear Magnetic Resonance: NMR spectra were collected using a Bruker Avance 500 spectrometer with an absolute frequency of 500, 113 MHz to 300 K using CDCI3 as solvent. Chemical shifts have been reported as parts per million from tetramethylsilane. The formation of an ester bond between the fatty acid derivative, indicating the formation of stolide, was verified with a peak NMR at about 4.84 ppm.
[00194] Stolide Number (EN): The EN was measured by GC analysis. It should be understood that the EN of a composition refers specifically to the EN characteristics of any stolide compounds present in the composition. Therefore, a stolide composition having a particular EN can also comprise other components, such as natural or synthetic additives, other non-stolide base oils, fatty acid esters, for example, triglycerides and / or fatty acids, but EN, as used herein, unless otherwise stated, refers to the value of the stolide fraction of the stolide composition.
[00195] Iodine value (IV): The iodine value is a measure of the degree of total unsaturation of an oil. IV is expressed in terms of centigrams of iodine absorbed per gram of oil sample. Therefore, the higher the iodine value of an oil, the greater the level of unsaturation in that oil. The IV can be measured and / or estimated by GC analysis. When a composition includes unsaturated compounds other than stolides as defined in Formula I, II, and III, the stolides can be separated from other unsaturated compounds present in the composition before measuring the iodine value of the constituent stolids. For example, if a composition includes unsaturated fatty acids or triglycerides that comprise unsaturated fatty acids, it can be separated from the stolids present in the composition before measuring the iodine value for the one or more stolides.
[00196] Acid Value: The acid value is a measure of the acid present in the total of an oil. The acid number can be determined by any suitable titration method known to those skilled in the art. For example, acid values can be determined by the amount of KOH that is required to neutralize a given oil sample, and thus can be expressed in terms of mg KOH / g of oil.
[00197] Gas Chromatography (GC): GC analysis was performed to evaluate the number of stolides (EN) and iodine index (IV) of the stolides. This analysis was performed using an Agilent 6890N series gas chromatograph equipped with a flame ionization detector and an auto-sampler / injector together with a SP-2380 30 m x 0.25 mm i.d.
[00198] The parameters of the analysis were as follows: column flow at 1.0 mL / min with a helium head pressure of 14, 99 psi; 50: 1 split ratio; programmed ramp from 120-135 ° C to 20 ° C / min, 135-265 ° C to 7 ° C / min, maintained for 5 minutes at 265 ° C; injector and detector temperatures set at 250 ° C.
[00199] Measurement of EN and IV by GC: To perform these analyzes, the fatty acid components of a sample of stolide reacted with MeOH to form methyl esters of fatty acids through a method that left behind a hydroxy group in places where the stolide bonds were once present. Patterns of fatty acid methyl esters were first analyzed to establish elution times.
[00200] Sample preparation: To prepare the samples, 10 mg of stolide was combined with 0.5 ml of 0.5 M KOH / MeOH in a flask and heated at 100 ° C for 1 hour. This was followed by the addition of 1.5 ml of 1.0 MH2SO4 / MeOH and heated to 100 ° C for 15 minutes and then allowed to cool to room temperature. One (1) ml of H2O and 1 ml of hexane was then added to the flask and the resulting liquid phases were mixed very well. The layers were then allowed to phase separate for 1 minute. The lower H2O layer was removed and discarded. A small amount of drying agent (anhydrous Na2SO4) was then added to the organic phase, after which the organic layer was then transferred to a 2 ml capped vial and analyzed.
[00201] Calculation of EN: EN is measured as the percentage of hydroxy fatty acids divided by the percentage of non-hydroxy fatty acids. As an example, a stolide dimer results in half of the fatty acids containing a hydroxyl functional group, with the other half missing a hydroxyl functional group. Therefore, the EN would be 50% hydroxy fatty acids divided by 50% non-hydroxy fatty acids, resulting in an EN value of 1 that corresponds to the only stolide bond between the capped fatty acid and the dimer base fatty acid .
[00202] Calculation of IV: The iodine value is calculated using the following equation based on the ASTM D97 method standard (ASTM International, Conshohocken, PA):
Af = fraction of fatty compound in the sample MWI = 253.81, atomic weight of two iodine atoms added to a double bond db = number of double bonds in the fatty compound MWf = molecular weight of the fatty compound
[00203] The properties of the exemplary stolide compounds and compositions described herein are identified in the following examples and tables.
[00204] Other Measurements: Except when described, pour point is measured by the ASTM D97-96a method, cloud point is measured by the ASTM D2500 method, kinematic viscosity / viscosity is measured by the ASTM D445-97 method, viscosity index is measured by method ASTM D2270-93 (re-approved 1998), specific gravity is measured by method ASTM D4052, fire point and flash point are measured by method ASTM D92, evaporative loss is measured by method ASTM D5800, vapor pressure is measured by method ASTM D5191, rotary pressurized container oxidation tests are measured by the ASTM 2272-11 method, and acute aqueous toxicity is measured by the Organization for Economic Cooperation and Development (OECD) 203. Example 1
[00205] The acid catalyst reaction was carried out in a 50 gallon Pfaudler RT-Series glass-lined reactor. Oleic acid (65 kg, OL700, Twin Rivers) was added to the reactor with 70% perchloric acid (992.3 mL, Aldrich Cat # 244252) and heated to 60 ° C under vacuum (10 torr abs (absolute Torr, 1 torr = ~ 1 mmHg)) for 24 hours while stirring continuously. After 24 hours, the vacuum was released. 2-ethylhexanol (29, 97 kg) was then added to the reactor and the vacuum was restored. The reaction was allowed to proceed under the same conditions (60 ° C, 10 torr abs) for another 4 hours. At the same time, KOH (645, 58 g) was dissolved in 90% ethanol / water (5000 mL, 90% EtOH by volume) and added to the reactor to cool the acid. The solution was then allowed to cool for approximately 30 minutes. The reactor contents were then pumped through a 1 micron (μ) filter to an accumulator to filter the salts. The water was then added to the accumulator to wash the oil. The two liquid phases were thoroughly mixed together for about 1 hour. The solution was then left in phase separation for about 30 minutes. The water layer was drained and removed. The organic layer was again pumped through a 1 μ filter back into the reactor. The reactor was heated to 60 ° C under vacuum (10 torr abs) until all the ethanol and water finished distilling from the solution. The reactor was then heated to 100 ° C under vacuum (10 torr abs) and that temperature was maintained until 2-ethylhexanol stopped distilling from the solution. The remaining material was then distilled using a Myers 15 distillation centrifuge still at 200 ° C under an absolute pressure of about 12 microns (0.012 Torr) to remove all monoester material leaving the stolids (Ex. 1). Certain data are reported below in Tables 1 and 8. Example 2
[00206] The acid catalyst reaction was carried out in a 50 gallon Pfaudler RT-Series glass-lined reactor. Oleic acid (50 kg, OL 700, Twin Rivers) and completely cut coconut fatty acid (18, 754 kg, TRC 110, Twin Rivers) were added to the reactor with 70% perchloric acid (1, 145 mL, Aldrich Cat # 244252) and heated to 60 ° C under vacuum (10 torr abs) for 24 hours, while stirring continuously. After 24 hours, the vacuum was released. 2-ethylhexanol (34, 58 kg) was then added to the reactor and the vacuum was restored. The reaction was allowed to proceed under the same conditions (60 ° C, 10 torr abs) for another 4 hours. At the same time, KOH (744, 9 g) was dissolved in 90% ethanol / water (5000 ml, 90% EtOH by volume) and added to the reactor to cool the acid. The solution was then allowed to cool for approximately 30 minutes. The reactor contents were then pumped through a 1 μ filter to an accumulator to filter the salts. The water was then added to the accumulator to wash the oil. The two liquid phases were thoroughly mixed together for about 1 hour. The solution was then left in phase separation for about 30 minutes. The water layer was drained and discarded. The organic layer was again pumped through a 1 μ filter back into the reactor. The reactor was heated to 60 ° C under vacuum (10 torr abs) until all ethanol and water finished distilling from the solution. The reactor was then heated to 100 ° C under vacuum (10 torr abs) and that temperature was maintained until 2-ethylhexanol finished distilling from the solution. The remaining material was then distilled using a Myers 15 distillation centrifuge still at 200 ° C under an absolute pressure of about 12 microns (0.012 Torr) to remove all monoester material leaving the stolids (Ex. 2). Certain data are reported below in Tables 2 and 7. Example 3
[00207] The stolids produced in Example 1 (Ex. 1) were subjected to distillation conditions in a Myers 15 distillation centrifuge still at 300 ° C under an absolute pressure of about 12 microns (0.012 Torr). This resulted in a primary distillate having a lower EN average (Ex. 3A), and a distillation residue having a higher EN average (Ex. 3B). Certain data are reported below in Tables 1 and 8. Table 1

[00208] Stolides produced in Example 2 (Ex. 2) were subjected to distillation conditions in a Myers 15 distillation centrifuge still at 300 ° C under an absolute pressure of about 12 microns (0.012 Torr). This resulted in a primary distillate having a lower EN average (Ex. 4A), and a distillation residue with a higher EN average (Ex. 4B). Certain data are reported below in Tables 2 and 7. Table 2
Example 5
[00209] Stolids produced by the method presented in Example 1, were subjected to distillation conditions (ASTM D-6352 standard) at 1 atm (atmosphere) during the temperature range of about 0 ° C to about 710 ° C, resulting in 10 different stolide cuts recovered at increased temperatures. The amount of material distilled from the sample in each cut and the temperature at which each cut distilled (and recovered) are shown below in Table 3: Table 3
Example 6
[00210] Stolids made according to the method of Example 2 were subjected to distillation conditions (ASTM D-6352 standard) at 1 atm, in the temperature range of about 0 ° C to about 730 ° C, which resulted in 10 different stolide cuts. The quantity of each cut and the temperature at which each cut was recovered are shown in Table 4. Table 4

Example 7
[00211] Stolide base oil 4B (from Example 4) was subjected to distillation conditions (ASTM D-6352 standard) at 1 atm, in the temperature range of about 0 ° C to about 730 ° C, which resulted in 9 different stolide cuts. The amount of each cut and the temperature at which each cut was recovered are reported in Table 5 um. Table 5a
Example 8
[00212] Stolides were made according to the method set out in Example 1, except that the 2-ethylhexanol esterifying alcohol used in Example 1 was replaced by other alcohols. The alcohols used for esterification include those identified in Table 5b below. The properties of the resulting stoles are shown in Table 9. Table 5b
Example 9
[00213] Stolides were made according to the method set out in Example 2, except that the esterifying alcohol 2-ethylhexanol was replaced by isobutanol. The properties of the resulting stoles are shown in Table 9. Example 10
[00214] Stolides of Formula I, II, and III, are prepared according to the method referred to in Examples 1 and 2, except that the esterification alcohol 2-ethylhexanol is replaced by several other alcohols. The alcohols to be used for esterification include those identified in Table 6 below. Esterification of alcohols to be used, including those listed below, can be saturated or unsaturated, branched or unbranched and, or substituted by one or more groups selected from alkyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec -butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl, and the like, to form a residue, branched or unbranched at the R2 position. Examples of combinations of esterification of alcohols and R2 substituents are shown below in Table 6:


Example 11
[00215] Saturated and unsaturated stolids varying the acid values were subjected to various corrosion and deposit tests. These tests included the High Temperature Corrosion Bench Test (HTCBT) for various metals, the ASTM D130 corrosion test, and the MHT-4 TEOST test (ASTM D7097) to correlate piston deposits. The tested stoles with higher acid values (0.67 mg KOH / g) were produced using the method referred to in Examples 1 and 4 for the production of Ex. 1 and Ex. 4A (Ex. 1 * and * Ex.4A below). The tested stolides with lower acid values (0.08 mg KOH / g) were produced using the method referred to in Examples 1 and 4 for the production of Ex. 1 and Ex. 4A, except the crude acid-free stolide was treated and purified before esterification with BF3 - OET2 (0.15 equiv ;. reacted with stolide and 2-EH in Dean Stark trap, at 80 ° C under vacuum (10 torr abs) for 12 hours, while continuously stirring; reaction product crude washed 4x with H2O; excess 2-EH removed by heating the washed reaction product to 140 ° C under vacuum (10 torr abs) for 1 h) (Ex.4A # below). Solids having an IV of 0 were hydrogenated by means of 10% by weight of palladium on incorporated carbon, at 75 ° C for 3 hours under a pressurized hydrogen atmosphere (200 psig) (Ex.4A * H and Ex.4A # H below) Corrosion tests and deposits were made with a package of Dexos ™ additives. The results were compared with a mineral oil standard:
Example 12
[00216] "Ready" and "Final" biodegradability of the stolide produced in Ex. 1 was tested according to standard OECD procedures. The results of the OECD biodegradability studies are shown below in Table 11:
Example 13
[00217] The stolide base stock Ex. 1 of Example 1 was tested under OECD 203 for Acute Aquatic Toxicity. Tests have shown that stolids are non-toxic, as well as no deaths have been reported for the concentration ranges of 5,000 mg / L and 50,000 mg / L. Example 14
[00218] Stolides were prepared according to the method established in Example 2, except that the reaction was initially loaded with 41.25 kg of oleic acid and 27, 50 kg of fully cut coconut fatty acids. Properties of the resulting stoles are set out below in Table 12. Example 15
[00219] The stolids produced in Example 14 (Ex. 14) were subjected to distillation conditions in a Myers 15 distillation centrifuge still at 300 ° C under an absolute pressure of about 12 microns (0.012 Torr). This resulted in a primary distillate having a lower viscosity (Ex. 15A), and a distillation residue of a higher viscosity (Ex. 15B). Properties of the resulting stoles are set out below in Table 12.
Example 16
[00220] Stolides were prepared according to the methods set out in Examples 14 and 15 to provide Ex. 14 stolide products, ex. 15A, e.g. 15B, which were subsequently subjected to a basic anion exchange resin wash to decrease acidity of the stolids: separately, each of the stolide products (1 equiv) was added to a 30-gallon stainless steel reactor (equipped with a rotor) , together with 10% by weight of Amber IRA-402 ™ resin. The mixture was stirred for 4 to 6 hours, with the speed of the rotor tip running at no more than about 1200 feet / min. After stirring, the stolide / resin mixture was filtered, and the recovered resin was set aside. The properties of the resulting low acid stoles are shown below in Table 13, which are labeled Ex. 14 *, Ex. 15A * and Ex. 15B *. Example 17
[00221] Stolides were prepared according to the methods set out in Examples 15. The resulting Ex. 15A stolides were subsequently hydrogenated through 10 wt% palladium on incorporated carbon, at 75 ° C for 3 hours under a hydrogen atmosphere. pressurized to supply hydrogenated stolide compounds (Ex. 17). The hydrogenated Ex. 17 stolids were then subjected to a basic anion exchange resin wash according to the method set out in Example 16 to provide low acidity stolides (Ex. 17 *). The properties of the resulting low acidity Ex 17 * stolides are shown below in Table 13. Table 13

Example 18
[00222] Stolides were prepared according to the methods established above. For the resulting stoles, several antioxidants and additive packages containing antioxidants were added. Heat and agitation were applied when necessary to dissolve the antioxidant and / or additive package in the stolide base oil. The oxidative stability of the resulting formulated stolids was then tested using a rotating pressure vessel (RPVOT) oxidative stability test - ASTM 2272-11, at 150 ° C. The results for the various formulations are shown below in Table 14, together with the results of the comparative tests of various non-stolide base oil formulations. Table 14






Example 19
[00223] Stolides were prepared according to the methods established above. For the resulting stoles, several antioxidants and additive packages containing antioxidants were added. Heat and agitation were applied when necessary to dissolve the antioxidant and / or additive package in the stolide base oil. The oxidative stability of the resulting formulated stolids was tested by the modified P-DSC test, in which the oxidation onset temperature (OT) was determined by non-isothermal pressurized differential scanning calorimetry (P-DSC) under dynamic O2 conditions (see , for example, Dunn, Dunn, "Effect of antioxidants on the oxidative stability of methyl soyate (biodiesel)," Fuel Process. Tech., 86: 1071-85 (2005) incorporated herein by reference in its entirety for all purposes) . The results for the various formulations are shown below in Table 15, together with the results of comparative tests for different formulations of base oils containing non-stolide.




Example 20
[00224] Stolides were prepared according to the methods established above. For the resulting stolides, several antioxidants were added. Heat and agitation were applied when necessary to dissolve the antioxidant and / or additive package in the stolide base oil. The oxidative stability of the resulting formulated stolids was then tested by pressurized differential scanning calorimetry (P-DSC) at different temperatures, with the oxidation induction time (OIT) in minutes. The results for the various formulations are shown below in Table 16. Table 16
Additional modalities 1. A composition comprising a combination of a stolide base oil and at least one antioxidant, said combination having a time of at least 500 minutes, when tested in a rotary pressurized container oxidation test using ASTM method 2272- 11,
[00225] wherein the stolide base oil comprises at least one stolide compound selected from compounds of Formula I:

[00226] where
[00227] x is, independently for each occurrence, an integer selected from 0 to 20;
[00228] y is, independently for each occurrence, an integer selected from 0 to 20;
[00229] n is an integer greater than or equal to 0;
[00230] R1 is an optionally substituted alkyl group, which is saturated or unsaturated, branched or unbranched, and; and
[00231] R2 represents an optionally substituted alkyl group, which is saturated or unsaturated, and branched or unbranched,
[00232] wherein each fatty acid residue chain of said at least one compound is independently optionally substituted. 2. The composition according to claim 1, in
[00233] x is, independently for each occurrence, an integer selected from 1 to 10;
[00234] y is, independently for each occurrence, an integer selected from 1 to 10;
[00235] n is an integer selected from 0 to 8;
[00236] R1 is an optionally substituted C1 to C22 alkyl, which is saturated or unsaturated, branched or unbranched, and
[00237] R2 represents an optionally substituted C1 to C22 alkyl, which is saturated or unsaturated, branched or unbranched and,
[00238] in which each fatty acid chain residue is unsubstituted. The composition according to any one of claims 1 and 2, wherein
[00239] x + y is, independently, for each chain, an integer selected from 13 to 15; and
[00240] n is an integer selected from 0 to 6. 4. The composition according to any one of claims 1-3, wherein R2 represents an unsubstituted alkyl group that is saturated or unsaturated, branched or unbranched and 5. The composition according to any one of claims 1-4, wherein R2 is a C1 to C22 branched or unbranched alkyl that is saturated or unsaturated. The composition according to claim 5, wherein R2 is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decanyl, undecanyl, dodecanyl, tridecanyl, tetradecanyl, pentadecanyl, hexadecanyl , heptadecanila, octadecanila, nonadecanila, and icosanila, which are saturated or unsaturated and branched or unbranched. The composition according to claim 5, wherein R2 is selected from C6 to C12 alkyl. The composition according to claim 7, wherein R2 is 2-ethylhexyl. The composition according to any one of claims 1-8, wherein R1 is a branched or unbranched C1 to C20 alkyl that is saturated or unsaturated. The composition according to claim 9, wherein R1 is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decanyl, undecanyl, dodecanyl, tridecanyl, tetradecanyl, pentadecanyl, hexadecanil , heptadecanila, octadecanila, nonadecanila, and icosanila, which are saturated or unsaturated and branched or unbranched. The composition according to claim 9, wherein R1 is selected from C7 to C17 unsubstituted alkyl that is unbranched and saturated or unsaturated. The composition according to claim 11, wherein R1 is selected from C13 to C17 alkyl which is unsubstituted, unbranched, and saturated or unsaturated. The composition according to claim 11, wherein R1 is selected from C7 saturated alkyl, C9 saturated alkyl, Cn saturated alkyl, C13 alkyl, C15 saturated alkyl, and C17 saturated or unsaturated alkyl, which is unsubstituted and unbranched. The composition according to claim 12, wherein R1 is selected from C13 saturated alkyl, C15 saturated alkyl, and C17 saturated or unsaturated alkyl, which are unsubstituted and unbranched. The composition according to any one of claims 1-5, wherein R1 and R2 are independently selected from optionally substituted C1 to C18 alkyl, which is saturated or unsaturated, and branched or unbranched. The composition according to any one of claims 1-5, wherein R1 is selected from C7 to C17 optionally substituted alkyl, which is saturated or unsaturated, and branched or unbranched, and R2 is selected from a C3 the optionally substituted C2 alkyl which is saturated or unsaturated, and branched or unbranched. 17. The composition according to any one of claims 1-16, wherein said composition has an EN selected from an integer or fraction of an integer that is equal to or greater than 4, wherein the EN is the average number of bonds in compounds according to Formula I. 18. The composition according to claim 17, wherein said composition has an EN which is an integer or fraction of an integer selected from 4 to 5, wherein the EN is the average number of bonds in compounds according to Formula I. 19. The composition according to claim 17, wherein said composition has an EN which is a fraction of a selected integer 4.2 to 4.8, where the EN is the average number of bonds in compounds according to Formula I. 20. The composition according to any one of claims 1-16, wherein said composition has an EN selected from of an integer or fraction of an integer that is equal to or greater than 5, where EN is the number average number of bonds in compounds according to Formula I. 21. The composition according to any one of claims 17-20, wherein said stolide base oil has a kinematic viscosity equal to or greater than 200 cSt, when measured at 40 ° C. The composition according to claim 21, wherein said stolide base oil has a kinematic viscosity of 200 cSt to 250 cSt at 40 ° C. The composition according to claim 21, wherein said stolide base oil has a kinematic viscosity of 210 cSt to 230 cSt at 40 ° C. The composition according to any one of claims 17-23, wherein said stolide base oil has a pour point of -40 ° C or less. The composition according to claim 24, wherein said stolide base oil has a pour point of -40 ° C to -50 ° C. The composition according to claim 24, wherein said stolide base oil has a pour point of -42 ° C to -48 ° C. The composition according to claim 24, wherein said stolide base oil has a pour point below - 50 ° C. The composition according to claim 27, wherein said stolide base oil has a pour point of -50 ° C to -60 ° C. The composition according to claim 27, wherein said stolide base oil has a pour point of -52 ° C to -58 ° C. The composition according to any one of claims 1-16, wherein said composition has an EN selected from an integer or fraction of an integer that is equal to or greater than 3, where the EN is the average number of bonds in compounds according to Formula I. 31. The composition according to claim 30, wherein said composition has an EN which is an integer or fraction of an integer selected from 3 to 4 , wherein the EN is the average number of bonds in compounds according to Formula I. 32. The composition according to claim 30, wherein said composition has an EN which is an integer or fraction of a number selected integer from 3 to 3.5, where the EN is the average number of bonds in compounds according to Formula I. 33. The composition according to claim 30, wherein said composition has an EN selected from from an integer or fraction of an integer that is equal to or greater than 3, 5, wherein the EN is the average number of bonds in compounds according to Formula I. 34. The composition according to claim 30, wherein said composition has an EN selected from an integer or fraction of an integer that is equal to or greater than 4, where the EN is the average number of bonds in compounds according to Formula I. 35. The composition according to claim 30, wherein said composition has an EN that is an integer or fraction of an integer selected from 4 to 5, where EN is the average number of bonds in compounds according to Formula I. 36. The composition according to claim 30, wherein said composition has an EN which is a fraction of a selected integer 4, 2-4, 8, where EN is the average number of bonds in compounds according to Formula I. 37. The composition according to any one of claims 30, wherein said composition has an EN selected from an integer or fra an integer that is equal to or greater than 5, where EN is the average number of bonds in compounds according to Formula I. 38. The composition according to any one of claims 30-37, wherein the said stolide base oil has a kinematic viscosity equal to or greater than 130 cSt, when measured at 40 ° C. 39. The composition according to claim 38, wherein said stolide base oil has a kinematic viscosity of 130 cSt to 160 cSt at 40 ° C. 40. The composition according to claim 38, wherein said stolide base oil has a kinematic viscosity of 130 cSt to 145 cSt at 40 ° C. 41. The composition according to any one of claims 30-40, wherein said stolide base oil has a pour point of -30 ° C or less. 42. The composition of claim 41, wherein said stolide base oil has a pour point of -30 ° C to -40 ° C. 43. The composition of claim 41, wherein said stolide base oil has a pour point of -34 ° C to -38 ° C. 44. The composition of claim 41, wherein said stolide base oil has a pour point of less than - 35 ° C. 45. The composition of claim 41, wherein said stolide base oil has a pour point of -35 ° C to -45 ° C. 46. The composition of claim 41, wherein said stolide base oil has a pour point of -38 ° C to -42 ° C. 47. The composition of claim 41, wherein said stolide base oil has a pour point of less than - 40 ° C. 48. The composition according to claim 41, wherein said stolide base oil has a pour point of -40 ° C to -50 ° C. 49. The composition according to claim 41, wherein said stolide base oil has a pour point of -42 ° C to -48 ° C. 50. The composition of claim 41, wherein said stolide base oil has a pour point of less than - 50 ° C. 51. The composition according to claim 41, wherein said stolide base oil has a pour point of -50 ° C to -60 ° C. 52. The composition of claim 41, wherein said stolide base oil has a pour point of -52 ° C to -58 ° C. 53. The composition according to any one of claims 1-16, wherein the composition has an EN selected from an integer or fraction of an integer that is equal to or less than 2, where the EN is the number average of bonds in compounds according to Formula I. 54. The composition according to claim 53, wherein said composition has an EN which is an integer or fraction of an integer selected from 1 to 2, in that the EN is the average number of bonds in compounds according to Formula I. 55. The composition according to claim 53, wherein said composition has an EN which is a fraction of an integer selected from 1 to 1 , 6, wherein the EN is the average number of bonds in compounds according to Formula I. 56. The composition according to any one of claims 53-55, wherein said stolide base oil has a kinematic viscosity equal to or less than 55 cSt, when measured at 40 ° C. 57. The composition of claim 56, wherein said stolide base oil has a kinematic viscosity of 25 CST at 55 cSt at 40 ° C. 58. The composition of claim 56, wherein said stolide base oil has a kinematic viscosity of 35 CST at 45 cSt at 40 ° C. 59. The composition according to any one of claims 53-58, wherein said stolide base oil has a pour point of -25 ° C or less. 60. The composition according to claim 59, wherein said stolide base oil has a pour point of -27 ° C to -37 ° C. 61. The composition according to claim 59, wherein said stolide base oil has a pour point of -30 ° C to -34 ° C. 62. The composition of claim 59, wherein said stolide base oil has a pour point of less than - 50 ° C. 63. The composition according to claim 59, wherein said stolide base oil has a pour point of -50 ° C to -60 ° C. 64. The composition of claim 59, wherein said stolide base oil has a pour point of -52 ° C to -58 ° C. 65. The composition according to any one of claims 1-16, wherein said composition has an EN selected from an integer or fraction of an integer that is equal to or less than 2, where the EN is the average number of bonds in compounds according to Formula I. 66. The composition according to claim 65, wherein said composition has an EN which is an integer or fraction of an integer selected from 1 to 2, wherein the EN is the average number of bonds in compounds according to Formula I. 67. The composition according to claim 65, wherein said composition has an EN which is a fraction of an integer selected from 1.1 to 1.7, where EN is the average number of bonds in compounds according to Formula I. 68. The composition according to any one of claims 65-67, wherein said stolide base oil has a kinematic viscosity equal to or less than 45 cSt, when measured at 40 ° C. 69. The composition of claim 68, wherein said stolide base oil has a kinematic viscosity of 20 cSt to 45 cSt at 40 ° C. 70. The composition of claim 68, wherein said stolide base oil has a kinematic viscosity of 28 CST at 38 cSt at 40 ° C. 71. The composition according to any one of claims 65-70, wherein said stolide base oil has a pour point of -25 ° C or less. 72. The composition of claim 71, wherein said stolide base oil has a pour point of -25 ° C to -35 ° C. 73. The composition according to claim 71, wherein said stolide base oil has a pour point of -28 ° C to -32 ° C. 74. The composition of claim 71, wherein said stolide base oil has a pour point of less than - 50 ° C. 75. The composition of claim 71, wherein said stolide base oil has a pour point of -50 ° C to -60 ° C. 76. The composition of claim 71, wherein said stolide base oil has a pour point of -52 ° C to -58 ° C. 77. The composition according to any one of claims 1 to 76, wherein said combination has a time of at least 600 minutes, when tested in a rotary pressurized container oxidation test using ASTM method 2272-11. 78. The composition of claim 77, wherein said combination has a time of at least 700 minutes, when tested in a rotary pressurized container oxidation test using ASTM method 2272-11. 79. The composition according to claim 77, wherein said combination has a time of at least 800 minutes, when tested in a rotary pressurized container oxidation test using ASTM method 2272-11. 80. The composition according to claim 77, wherein said combination has a time of at least 900 minutes, when tested in a rotary pressurized container oxidation test using ASTM method 2272-11. 81. The composition according to claim 77, wherein said combination has a time of at least 1000 minutes, when tested in a rotary pressurized container oxidation test using ASTM method 2272-11. 82. The composition according to claim 77, wherein said combination has a time of at least 1, 100 minutes, when tested in a rotary pressurized container oxidation test using ASTM method 2272-11. 83. The composition of claim 77, wherein said combination has a time of at least 1200 minutes when tested in a rotary pressurized container oxidation test using ASTM method 2272-11. 84. The composition according to claim 77, wherein said combination has a time of at least 1300 minutes, when tested in a rotary pressurized container oxidation test using ASTM method 2272-11. 85. The composition according to claim 77, wherein said combination has a time of at least 1, 400 minutes, when tested in a rotary pressurized container oxidation test using ASTM method 2272-11. 86. The composition according to any one of claims 1-85, wherein the at least one antioxidant is selected from one or more of a phenolic antioxidant or an amine antioxidant. 87. The composition of claim 86, wherein the at least one antioxidant is selected from one or more hindered phenolic antioxidants. 88. The composition of claim 86, wherein the at least one antioxidant is selected from one or more diarylamine antioxidants. 89. The composition according to claim 88, wherein the at least one antioxidant is selected from one or more diphenylamine antioxidants. 90. The composition according to claim 89, wherein the at least one antioxidant is selected from one or more alkylated diphenylamine antioxidants. 91. The composition according to claim 90, wherein the at least one antioxidant is selected from one or more of nonylated diphenylamines, octylated diphenylamines and butylated diphenylamines. 92. The composition according to claim 88, wherein the at least one antioxidant is selected from one or more of phenyl-α-naphthylamine and alkylated phenyl-α-naphthylamines. 93. The composition of claim 86, wherein the at least one antioxidant comprises at least one phenolic antioxidant and at least one amine antioxidant. 94. The composition of claim 93, wherein the at least one antioxidant comprises at least one hindered phenolic antioxidant and at least one alkylated diphenylamine antioxidant. 95. The composition according to any one of claims 1-94, wherein the stolide base oil has an acid value of 0.5 mg or less KOH / g. 96. The composition of claim 95, wherein the stolide base oil has an acid value of 0.4 mg KOH / g or less. 97. The composition according to claim 95, wherein the stolide base oil has an acid value of 0.3 mg KOH / g or less. 98. The composition according to claim 95, wherein the stolide base oil has an acid value equal to or less than 0.2 mg KOH / g. 99. The composition according to claim 95, wherein the stolide base oil has an acid value of 0.1 mg KOH / g or less. 100. The composition according to any one of claims 1 to 99, wherein said composition additionally comprises a lubricant selected from a Group I oil, A Group II oil, a Group III oil, a polyalphaolefin, a polyalkylene glycol, and an oil soluble polyalkylene glycol. 101. The composition according to any one of claims 1 to 100, wherein said composition additionally comprises at least one additive selected from one or more of an antimicrobial agent, an extreme pressure agent, a cold flow modifier , a friction modifier, a viscosity modifier, a pour point depressant, a metal chelating agent, a metal deactivator, an anti-foam agent, and a demulsifier. 102. The composition according to any one of claims 1 to 101, wherein the combination of the stolide base oil and at least one antioxidant comprises at least 50% by weight of the composition. 103. The composition of claim 102, wherein the combination of the stolide base oil and at least one antioxidant comprises at least 70% by weight of the composition. 104. The composition according to claim 102, wherein the combination of the stolide base oil and at least one antioxidant comprises at least 80% by weight of the composition. 105. The composition according to claim 102, wherein the combination of the stolide base oil and at least one antioxidant comprises 50 to 90% by weight of the composition. 106. The composition according to claim 102, wherein the combination of the stolide base oil and at least one antioxidant comprises 80 to 90% by weight of the composition. 107. The composition according to claim 102, wherein the combination of the stolide base oil and at least one antioxidant comprises at least 90% by weight of the composition. 108. The composition of claim 102, wherein the combination of the stolide base oil and the at least one antioxidant comprises 85 and 99% by weight of the composition. 109. The composition according to any one of claims 1-99, wherein said composition consists essentially of a combination of stolide base oil and at least one antioxidant. 110. The composition according to any one of claims 1-109, wherein said at least one antioxidant comprises 0.01 to 5% by weight of the combination. 111. The composition according to claim 110, wherein said at least one antioxidant comprises 0.1 to 3 weight. % Of the combination. 112. The composition according to any one of claims 1 to 109, wherein said at least one antioxidant comprises 0.01 to 5% by weight of the composition. 113. The composition according to any one of claims 112, wherein said at least one antioxidant is 0, 1 and 3% by weight of the composition. 114. The composition according to any one of claims 1 to 108, wherein said composition comprises 50 to 70% by weight of the stolide base oil; 25 to 49.99% by weight of a lubricating oil, and 0.01 to 5% by weight of at least one antioxidant. 115. The composition according to any one of claims 1-114, wherein the composition has an acid value of 0.5 mg or less KOH / g. 116. The composition of claim 115, wherein the composition has an acid value of 0.4 mg KOH / g or less. 117. The composition according to claim 115, wherein the composition has an acid value of 0.3 mg KOH / g or less. 118. The composition according to claim 115, wherein the composition has an acid value equal to or less than 0.2 mg KOH / g. 119. The composition according to claim 115, wherein the composition has an acid value of 0.1 mg KOH / g or less. 120. The composition according to any one of claims 1 to 119, wherein the composition is substantially free of fatty acids. 121. The composition according to any one of claims 1-120, wherein said composition comprises a hydraulic fluid, a passenger car engine oil, or a crankcase oil. 122. The composition according to any one of claims 1-121, wherein R1 is saturated. 123. The composition according to any one of claims 1 to 122, wherein R2 is saturated. 124. A method for improving the oxidative stability of a stolide base oil, the method comprising selecting a stolide base oil; reduce the acid number of the stolide base oil to provide a low acid stolide base oil, and combine the low acid stolide base oil with at least one antioxidant. 125. The method of claim 124, wherein reducing the acidity index of the stolide base oil to provide a low acidity stolide base oil comprises contacting said stolide base oil with at least one reducing agent of acid. 126. The method of claim 125, wherein the at least one acid reducing agent is selected from one or more of activated carbon, magnesium silicate, aluminum oxide, silicon dioxide, a zeolite, a base resin, and an anion exchange resin. 127. The method according to any of claims 124 to 126, wherein the at least antioxidant is an amine antioxidant. 128. The method according to any of claims 124 to 127, wherein the low acid stolide base oil has an acid number of 0.5 mg or less KOH / g. 129. The method of claim 128, wherein the low acid stolide base oil has an acid number of 0.5 mg or less KOH / g. 130. The methods according to any one of claims 124-129, wherein the combination of the low acid stolide base oil and the at least one antioxidant has a time of at least 500 minutes when tested in an oxidation test of pressurized rotating container using ASTM method 2272-11. 131. The methods according to any of claims 124-130, wherein the combination of the low acid stolide base oil and the at least one antioxidant has a time of at least 1000 minutes when tested in an oxidation test of pressurized rotating container using ASTM method 2272-11.

权利要求:
Claims (33)
[0001]
1. Composition, characterized by the fact that it comprises a combination of a stolide base oil and at least one amine antioxidant, said combination having a time of at least 1000 minutes, when tested in a rotary pressurized container oxidation test using ASTM method 2272-11, wherein said at least one amine antioxidant comprises 0.01 to 5% by weight of the combination, wherein the stolide base oil has an acid value of 0.2 or less mg KOH / g, and comprises at least one stolide compound selected from compounds of Formula I:
[0002]
2. Composition according to claim 1, characterized by the fact that x is, independently for each occurrence, an integer selected from 1 to 10; y is, independently for each occurrence, an integer selected from 1 to 10; n is an integer selected from 0 to 8; R1 is an unsubstituted C1 to C22 alkyl that is saturated, branched or unbranched; and R2 is an unsubstituted C1 to C22 alkyl, which is saturated, and branched or unbranched, where each fatty acid chain residue is unsubstituted.
[0003]
3. Composition according to claim 1 or 2, characterized by the fact that x + y is, independently, for each chain, an integer selected from 13 to 15; and n is an integer selected from 0 to 6.
[0004]
Composition according to any one of Claims 1 to 3, characterized in that R2 is an unsubstituted alkyl group, which is saturated, and branched or unbranched
[0005]
Composition according to any one of Claims 1 to 4, characterized in that R2 is a saturated branched or unbranched C1 to C20 alkyl.
[0006]
6. Composition according to claim 5, characterized by the fact that R2 is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decanyl, undecanyl, dodecanyl, tridecanyl, tetradecanil, pentadecanil , hexadecanila, heptadecanila, octadecanila, nonadecanila, and icosanila, which are saturated and branched or unbranched.
[0007]
7. Composition according to claim 5, characterized by the fact that R2 is selected from C6 to C12 alkyl.
[0008]
Composition according to any one of Claims 1 to 7, characterized in that R1 is a saturated branched or unbranched C1 to C20 alkyl.
[0009]
9. Composition according to claim 8, characterized by the fact that R1 is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyla, octyl, nonyl, decanyl, undecanyl, dodecanyl, tridecanyl, tetradecanil, pentadecanil , hexadecanila, heptadecanila, octadecanila, nonadecanila, and icosanila, which are saturated and branched or unbranched.
[0010]
10. Composition according to any one of claims 1 to 9, characterized by the fact that the composition has an EN selected from an integer or fraction of an integer that is equal to or less than 2, where the EN is the average number of bonds in compounds according to Formula I.
[0011]
Composition according to any one of Claims 1 to 10, characterized in that said stolide base oil has a kinematic viscosity equal to or less than 55 cSt, when measured at 40 ° C.
[0012]
Composition according to any one of claims 1 to 11, characterized in that said stolide base oil has a pour point equal to or less than -25 ° C.
[0013]
Composition according to any one of claims 1 to 12, characterized in that said combination has a time of at least 1,200 minutes, when tested in a rotary pressurized container oxidation test using ASTM method 2272-11.
[0014]
Composition according to any one of claims 1 to 12, characterized in that said combination has a time of at least 1,400 minutes, when tested in a rotary pressurized container oxidation test using ASTM method 2272-11.
[0015]
Composition according to any one of claims 1 to 14, characterized in that the at least one amine antioxidant is selected from one or more diarylamine antioxidants.
[0016]
16. Composition according to claim 15, characterized in that the at least one amine antioxidant is selected from one or more diphenylamine antioxidants.
[0017]
17. Composition according to claim 16, characterized in that the at least one amine antioxidant is selected from one or more alkylated diphenylamine antioxidants.
[0018]
18. Composition according to claim 17, characterized in that the at least one amine antioxidant is selected from one or more of nonylated diphenylamines, octylated diphenylamines and butylated diphenylamines.
[0019]
19. Composition according to any one of claims 1 to 18, characterized in that the combination additionally comprises at least one phenolic antioxidant.
[0020]
Composition according to any one of claims 1 to 19, characterized in that the stolide base oil has an acid value equal to or less than 0.1 mg KOH / g.
[0021]
21. Composition according to any one of claims 1 to 20, characterized in that said composition additionally comprises at least one lubricating oil chosen from one or more Group I oil, Group II oil, group oil III, polyalphaolefin, polyalkylene glycol, or oil soluble polyalkylene glycol.
[0022]
22. Composition according to any one of claims 1 to 21, characterized in that said composition additionally comprises at least one additive selected from one or more of antimicrobial agent, extreme pressure agent, cold flow modifier, modifier friction, viscosity modifier, depressive pour point, metal chelating agent, metal deactivator, antifoaming agent, or demulsifier.
[0023]
23. Composition according to any one of claims 1 to 22, characterized in that the combination of the stolide base oil and the antioxidant at least one amine comprises at least 50% by weight of the composition.
[0024]
24. Composition according to any one of claims 1 to 18, characterized in that said composition consists essentially of a combination of stolide base oil and the antioxidant with at least one amine.
[0025]
25. Composition according to any one of claims 1 to 24, characterized in that said composition comprises 50 to 70% by weight of the stolide base oil; 25 to 49.99% by weight of a lubricating oil, and 0.01 to 5% by weight of the antioxidant at least one amine.
[0026]
26. Composition according to any one of claims 1 to 25, characterized in that the composition has an acid value equal to or less than 0.1 mg KOH / g.
[0027]
27. Method for improving the oxidative stability of a stolide base oil, characterized by the fact that it comprises: selecting a stolide base oil; reduce the acid number of the stolide base oil to provide a low acid stolide base oil, where the low acid stolide base oil has an acid value of 0.2 mg KOH / g or less , and combining the low acid stolide base oil with at least one antioxidant, that said at least one amine antioxidant comprises 0.01 to 5% by weight of the combination.
[0028]
28. The method of claim 27, characterized in that the reduction in the acidity index of the stolide base oil to provide a low acidity stolide base oil comprises contacting said stolide base oil with at least one acid reducing agent.
[0029]
29. The method of claim 28, characterized by the fact that at least one acid reducing agent is selected from one or more of activated carbon, magnesium silicate, aluminum oxide, silicon dioxide, one zeolite, a base resin, and an anion exchange resin.
[0030]
30. The method of any one of claims 27 to 29, characterized in that the antioxidant is at least an amine antioxidant.
[0031]
31. Method according to claim 27, characterized in that the low acid stolide base oil has an acid number equal to or less than 0.1 mg KOH / g.
[0032]
32. Method according to any of claims 27 to 31, characterized in that the combination of the low acid stolide base oil and the at least one antioxidant has a time of at least 500 minutes, when tested in a test of oxidation of pressurized rotating vessel using ASTM method 2272-11.
[0033]
33. Method according to any one of claims 27 to 32, characterized in that the combination of the low acid stolide base oil and the at least one antioxidant has a time of at least 1,000 minutes when tested in a test of oxidation of pressurized rotating vessel using ASTM method 2272-11.

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法律状态:
2018-12-11| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-07-02| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2020-02-04| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-08-25| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-12-01| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 30/05/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201161498499P| true| 2011-06-17|2011-06-17|

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US61/498,499|2011-06-17|

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US201161569046P| true| 2011-12-09|2011-12-09|

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US61/569,046|2011-12-09|

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US201261643072P| true| 2012-05-04|2012-05-04|

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US61/643,072|2012-05-04|

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PCT/US2012/039937|WO2012173774A1|2011-06-17|2012-05-30|Estolide compositions exhibiting high oxidative stability|

---