Novel friction modifiers

Abstract

This disclosure relates to novel biobased lubricating compositions with high oxidative stability for use in all lubricating applications such as gears, motors, and hydraulics. More particularly, lubricating compositions comprising a base oil and one or more additives and comprising less than 9.9% by weight of one or more of the compounds of Formula 1: wherein n is an integer from 2-6; R is C1-C22 alkyl; R2 is C3-C12 alkyl; R3 is hydrogen or C1-C10 alkyl.

Description

NOVEL FRICTION MODIFIERSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 634,857, filed April 16, 2024, which is incorporated by reference herein in its entirety.TECHNICAL FIELD

[0002] The present disclosure relates to biobased friction modifiers for lubricants that can be used in a variety of industrial applications including gear, engine, and transmission applications. Use of biobased ingredients is increasingly preferred to lower the carbon footprint of industrial products.BACKGROUND

[0003] The lubricants (engine and non-engine) and process fluids industries are increasingly searching for materials that are biobased and biodegradable. One of the largest losses of energy in any mechanical system is friction. When mechanical energy is converted to heat through friction it is lost to the environment and the efficiency of the mechanical system suffers. Lubricants and process fluids are complex systems and vary depending on the particular needs of the application. Often these lubricant systems contain a minor component distinct from the lubricant specifically tailored to reduce friction and accordingly increase the efficiency of the system. These materials are often referred to as friction modifiers or traction control additives. The present disclosure describes novel biobased friction modifiers for use in mechanical systems.

[0004] Biobased means that the materials described herein are derived from sustainable plant sources as opposed to non-regenerable or sustainable sources such as petroleum. Biodegradability means that the lubricants and process fluids (hereinafter "fluids") have the ability in a natural environment to degrade over a period of time, which may be measured by tests such as those promulgated by the Organization of Economic Co-Operation and Development (OECD). Renewable biobased products contain, by definition, high levels of renewable carbons, and standards are being set to encourage increasingly greater levels of renewability. For example, the European Ecolabel now stresses that hydraulic fluids should be biodegradable and preferably contain at least 50 percent by weight renewable carbons.

[0005] While naturally based solutions have continued to evolve, the desire to discover new formulations with exceptional performance endures. Traction additive packages can be expensive and consumed during the lifetime of their use. Therefore, novel biobased additives to improve the traction performance of base oils is highly desired.SUMMARY

[0006] Efficiency of mechanical systems is of utmost importance to the manufacturers of those systems and the users thereof. Making a system more efficient can have numerous benefits such as better and longer performance, reduced wear and down time, lower energy costs, and longer life for battery operated mechanism. Currently this is of extreme importance in the electric vehicle (EV) arena. Consumers have “range anxiety” where they; i) fear depleting batteries before a convenient recharging station is found; or ii) cannot make the length of trips they desire. Reducing the loss of battery energy to heat in an EV allows for longer battery life and accordingly greater range. Alternatively, in some applications battery life may be held constant but the size and weight of the batteries reduced. Even a small or very modest improvement in traction can provide a tremendous benefit over the course of an EV’s lifetime. A small impact accumulates over days and years to a surprising extent.

[0007] The compositions described herein exhibit the surprising ability to reduce the traction, or friction, in lubricant formulations even if utilized in modest quantities in the overall formulation. Compounds of this type are commonly referred to as “friction modifiers”. Typically, the compounds disclosed herein are utilized at less than 10% of the final formulation and even more typically at between 2% and 6%. They can be utilized in low or high viscosity formulations and can be tailored to a variety of end applications. This level of stability for biobased material is unique and highly valuable to the end user. In addition, the compounds of Formula 1 are cheaper and easier to produce than currently utilized alternatives.

[0008] In addition, it was surprisingly discovered that addition of a small percentage of the compounds of Formula 1 or Formula 3 to a base oil can dramatically increase the oxidative stability of the base oil.

[0009] Disclosed are lubricating compositions comprising a base oil wherein the base oil comprises 0.5% to 9.9% of one or more compounds of the Formula 1 :wherein n is an integer from 2-6; R is C1-C12 alkyl; R2 is C5-C11 alkyl; R3 is C4-C10 alkyl.

[0010] Disclosed are lubricating compositions comprising 0.5% to 9.9% of one or more compounds of the Formula 1 :wherein n is an integer from 2-6; R is C1-C12 alkyl; R2 is C5-C11 alkyl; R3 is C4-C10 alkyl.

[0011] The lubricating composition may contain 10%-100% of a base oil. The lubricating composition may comprise 50%-100% of the base oil.BRIEF DESCRIPTION OF THE FIGURES

[0012] Figure 1 shows the GPC data for an Example of the present disclosure (Example 1 IB) where the polymeric distribution of the material is represented.

[0013] Figures 2-7 show the traction curve data for Examples of the present disclosure (as mentioned below) where the traction of a lubricant formulations are compared with and without the compounds of the present disclosure.DETAILED DESCRIPTION

[0014] Reference will now be made in detail to certain aspects of the disclosed subject matter. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter. One aspect described in conjunction with a particular embodiment is not necessarily limited to that embodiment and can be practiced with any other embodiment(s).

[0015] Throughout this document, values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range of “0.1% to 5%” or “0.1% to 5%” should be interpreted to include not just 0.1% to 5%, but also the individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range.

[0016] As used herein the term “less than” means a value lower than the reference value stated. The term “less than” is intended to include situations where presence of the measured variable may be non-detectable but is not intended to mean the absolute absence of a measured variable is possible or desirable. For example, an Acid Value (AV) of less than 0.3 is intended to include the range from 0.3 to an AV that is non-detected but is not intended to mean an absolute value of zero is possible or desired.

[0017] As used herein, the singular forms "a," "an," and "the" and similar referents in the context of describing the elements (especially in the context of the following claims) include plural referents unless the context clearly dictates otherwise. For example, reference to "a substituent" encompasses a single substituent as well as two or more substituents, and the like. It is understood that any term in the singular may include its plural counterpart and vice versa, unless otherwise indicated herein or clearly contradicted by context.

[0018] As used herein, the following terms have the following meanings unless expressly stated to the contrary.

[0019] The term “or” is used to refer to a nonexclusive “or” unless otherwise indicated. The statement “at least one of A and B” has the same meaning as “A, B, or A and B.”

[0020] In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Anyuse of section headings is intended to aid reading of the document and is not to be interpreted as limiting; information that is relevant to a section heading may occur within or outside of that particular section. Any publications, patents, and patent documents referred to in this document are incorporated by reference herein in their entirety, as though individually incorporated by reference. In the event of inconsistent usages between this document and those documents so incorporated by reference, the usage in the incorporated reference should be considered supplementary to that of this document; for irreconcilable inconsistencies, the usage in this document controls.

[0021] As used herein, the terms "for example," "for instance," "such as," or "including" are meant to introduce examples that further clarify more general subject matter. Unless otherwise specified, these examples are provided only as an aid for understanding the applications illustrated in the present disclosure and are not meant to be limiting in any fashion.

[0022] In the methods described herein, the acts can be carried out in any order without departing from the principles of the disclosure, except when a temporal or operational sequence is explicitly recited. Furthermore, specified acts can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.

[0023] The term “substantially” as used herein refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%. In some aspects, substantially means greater than 90%. In some aspects, substantially means greater than 75%.

[0024] The term “alkyl” as used herein means a saturated or unsaturated, branched, or straight-chain monovalent, or divalent, hydrocarbon radical derived by the removal of one, or two, hydrogen atoms from the carbon atoms of a parent alkane, alkene, or alkyne. In some aspects, one or more of the alkyl groups are substantially saturated. In some aspects, one or more of the alkyl groups are fully or partially saturated.

[0025] The terms C1-C22 alkyl; C2-C12, C3-C12; and C1-C10 alkyl means alkyl groups containing 1-22, 2-12, 3-12 and 1-10 carbons. Any similar numerical ranges should be considered likewise. In some aspects alkyl groups may be branched. In other aspects, alkyl groups may be unbranched or straight. In other aspects the alkyl groups may be a mixture of branched or unbranched.One or more of the alkyl groups may be saturated, unsaturated, or a mixture there of. In other aspects, the alkyl groups may substituted, unsubstituted, or a mixture thereof.

[0026] The term “Substituted” as used herein means that one of the hydrogen atoms of the alkyl chain is replaced by another substituent. In some aspects, the alkyl groups are substituted in one more places by hydroxyl, amino, dialkyl amino, alkyl acetylated hydroxyl, an alkyl ester, or an alkyl ether substituent. In some embodiments the alkyl group is substituted with a hydroxyl or alkylacetylated hydroxyl group.

[0027] The term “Base Oil” as used herein means the primary lubricating components of a lubricant formulation not including additional performance additives. The base oil may be a single lubricating components or a mixture of multiple lubricating components depending on the particular needs of the intended application.

[0028] Unless specifically indicated otherwise, all percentage reported herein are intended to be percentages by weight of the final composition referenced (i.e., wt%).

[0029] In 1975, the International Standards Organization (ISO), in unison with American Society for Testing and Materials (ASTM), Society for Tribologists and Lubrication Engineers (STLE), British Standards Institute (BSI), and Deutsches Institute for Normung (DIN) settled upon an approach to minimize the confusion. It is known as the International Standards Organization Viscosity Grade, ISO VG for short. This classification defines 20 viscosity grades in the range of 2 to 3200 square millimeters per second (1 mm2 / s = equals 1 cSt) at 40°C (104°F). For petroleum-based liquids, this covers approximately the range from kerosene to cylinder oils.

[0030] Each viscosity grade is designated by the nearest whole number to its midpoint kinematic viscosity in mm2 / s at 40°C (104°F), and a range of + / - 10 percent of this value is permitted. The 20 viscosity grades with the limits appropriate to each are listed below.Table 1. ISO Viscosity Classification

[0031] The classification is based on the principle that the midpoint (nominal) kinematic viscosity of each grade should be approximately 50 percent greater than that of the preceding one. For example, an ISOIOO oil would define an oil with a kinematic viscosity between 90 cSt and 110 cSt at 40°C and an ISO 320 oil would define an oil with a kinematic viscosity between 288 cSt and 352 cSt at 40°C.wherein n is an integer from 2-6; R is C1-C22 alkyl; R2 is C3-C12 alkyl; 3 is hydrogen or C1-C10 alkyl.

[0032] In some aspects, the compounds of Formula 1 are those wherein R is a C3-C12 alkyl. In other aspects, R is a branched Ce-Cio alkyl. In other aspects, R is 2-ethylhexyl.

[0033] In some aspects, the compounds of Formula 1 are those where R2is a C5-C11 alkyl. In other aspects, R2 is a straight chain saturated or unsaturated C7-C11 alkyl. In other aspects, R2 is a straight chain C11 alkyl.

[0034] In some aspects, the compounds of Formula 1 are those where R3 is a branched C4-C12 alkyl. In other aspects, is a straight chain C4-C8 alkyl. In other aspects, R3 is a straight chain Ce alkyl.

[0035] In some aspects, the compounds of Formula 1 are those where R is 2-ethylhexyl, R2 is a straight chain C9 alkyl, and 3 is a straight chain Ce alkyl.

[0036] In one aspect, a subset of the compounds of Formula 1 can be represented as compounds of Formula 3.wherein n is an integer from 2-6 and R is C1-C22 alkyl.

[0037] In one aspect, the compounds of Formula 1 or the compounds of Formula 3 can be present as a mixture of oligomers wherein with the majority of the oligomers contain between 2 and 6 units and greater than 50% of the oligomers contain 3 or more units.Preparation of compounds of Formulas 1 and 3

[0038] Compounds of Formulas land 3 can be prepared through the oligomerization of a hydroxy substituted fatty acid (or mixture of hydroxy substituted fatty acids) and subsequent esterification of the remaining acid groups with an alcohol. Hydroxy substituted fatty acids are known in the art, commercially available, and may be prepared by one of skill in the art. As shown in the Examples 12-hydroxy stearic acid and 10-hydroxy stearic acid maybe used to prepare compounds of Formula 1. Either enantiomer, or a mixture thereof, of the hydroxystearic acid is functional in the present disclosure. Other hydroxy substituted fatty acids are known in the art and may be prepared by example through epoxidation of an unsaturated fatty acid followed by reductive ring opening can yield a variety of monohydroxy fatty acid residues. 10-hydroxy stearic acid (CAS: 638-26-6) is known in the art and can be purchased or prepared by enzymatic treatment of oleic acid. 12-Hydroxy stearic acid (CAS: 106-14-9) can be directly derived from castor oil and is commercially available from a variety of companies such as Gokul Overseas, Jay ant Agro-Organics Ltd, De Monchy UK Ltd; Acme Hardesty, or Hampshire Commodities Ltd. Because commercially available 12-hydroxy stearic acid is derived from castor oil, it typically contains a quantity of stearic acid as an impurity. A representative example of commercially available 12-hydroxystearic acid is shown in the examples.

[0039] A hydroxy substituted fatty acid, or mixture of acids, can be oligomerized at elevated temperature using a tin, titanium, or nitrogen containing catalyst where the formed water is removed. The reaction is typically performed in the absence of a solvent, but some a small amount of solvent could optionally be used. The water removal may be accomplished by means of an entrainer, reduced pressure, and / or nitrogen sparging. The result of this step is an oligomerized acid which includes a distribution of compounds of Formula 2 as follows:wherein n is an integer from 2-6; R2 is C3-C12 alkyl; R3 is hydrogen or C1-C10 alkyl.

[0040] The progress of the oligomerization may be tracked by the reduction in acid value of the reactants. The degree of oligomerization may be limited by the presence of other fatty acids in the starting materials that effectively endcap the reactive hydroxyl group. For example, typically, a distribution is achieved with the majority of the oligomers containing between 2 and 6 units and greater than 50% containing 3 or more units. Figure 1 shows the GPC distribution of an Example 1 IB of the present disclosure. In addition, pre-oligomerized hydroxyfatty acids are also commercially available such a Hyperm er LP1 from Croda.

[0041] The Compounds of Formula 2 can then be esterified by reaction with a straight or branched alcohol having from 1 to 22 carbon atoms. In certain aspects, the alcohol may be selected from methanol, ethanol, isopropanol, butanol, 2-ethylhexanol, 2-(2-butoxypropoxy)propan-l-ol (DPnB), 1-decanol, 1-octanol, 2-octanol, and Isofol 18 (2-Octyl decyl). Additional tin, titanium, nitrogen, or acid containing catalyst may be employed at this point, and formed water is removed, yielding an esterified product of Formula 1 with an AV of less than 1.0 KOH / g or less than 0.2mg KOH / g.

[0042] Alternatively, compounds of Formula 1 can be prepared in a single pot by reacting a hydroxy fatty acid with an alcohol directly. In this case, the hydroxy fatty acid is heated in the presence of an excess of alcohol under nitrogen. Catalyst such as TNBT is typically added part way though the reaction to reach an AV of less than 0.2mg KOH / g.

[0043] Base oils may further comprise one more compounds of Formula 4:wherein, n is an integer from 2-6; R is C1-C22 alkyl; R2 is C3-C12 alkyl; R3 is hydrogen or C1-C10 alkyl, and R4 is C1-C22 acyl. In some aspects, compounds of Formula 4 are those wherein R is 2-ethylhexyl, R4 is a Cl 8 acyl, R2 is a straight chain C9 alkyl, and R3 is a straight chain Ce alkyl.

[0044] The compounds of Formulas 1, 3, and 4, or mixtures thereof, may be formulated into lubricating compositions by combination with base oils and / or additives. Preparation of lubricating compositions is known in the art and any effective method may be utilized. Typically, ingredients in the formulation are mixed at ambient or elevated temperatures. Mixing can be performed batchwise or continuously as desired. In certain embodiments, the lubricating composition further comprises one or more additives known to those in the art such as friction modifiers, viscosity modifiers, antioxidants, anti-wear additives, extreme pressure additives, defoamers, demulsifers, and corrosion inhibitors. Additives are typically included in the final formulations at a level between 1 and 20% depending on the particular application and needs of the user. Additives may be included separately or as part of what is known in the art as an add pack. An add pack is a commercially available mixture of additives formulated by a supplier for inclusion in particular base oils and for particular applications. In some aspects, the lubricating composition comprises l%-10% additives by weight. In some aspects, the lubricating composition comprises 2%-6% additives by weight.

[0045] Base oils in which the compositions of this disclosure are employed can be based on natural or synthetic oils, or blends thereof can be formulated into final gear oil formulations, provided the lubricant has a suitable viscosity for use in desired applications. The base oils for such use can be mineral oil base stocks such as for example conventional and solvent-refined paraffinic neutrals and bright stocks, hydrotreated paraffinic neutrals and bright stocks, naphthenic oils, cylinder oils, etc., including straight run and blended oils.

[0046] In some aspects, base oil is selected from the group consisting of polyalphaolefins (PAOs), synthetic esters such as polyol esters, polyalkylene glycols (PAGs), oil soluble polyalkyleneglycols (OSPs), mineral oils (Groups I, II, and III), fatty acid esters, long chain alkyl esters such as those described and disclosed in WO2022 / 258664, and mixtures thereof.

[0047] Synthetic base stocks can also be used in the practice of this invention, such as for example PAO, alkylated aromatics, polybutenes, diesters, polyol esters, polyglycols, polyphenyl ethers, etc., and blends thereof. Polyalphaolefins are typically manufactured from C8 to Cl 4 olefins, and the result is generally combinations of dimers, trimers, tetramers, pentamers, and so forth. It is also known for PAOs and esters to be blended with mineral oils to form semi synthetics. Synthetic base oils are preferred, especially base oils having PAO or mixtures of PAOs as a major component. PAOs are well known and readily available such as Chevron - Synfluid, Exxon - Spectrasyn, INEOS - Durasyn, and the like. Synthetic esters are also well known such as Oleon - Radialube, NYCO - NYCOBASE, Lanxess - Hatcol, and Exxon - Esterex. The skilled artisan is well aware of the technical properties of these materials and how to blend them to a desired outcome.

[0048] The compounds of Formula 1 may be used in base oils in the preparation of a final lubricating formulation. In some aspects, the base oil comprises 0.5% to 9.9% of one or more of the compounds of Formula 1. In some aspects, compounds of Formula 1 comprise between 2 and 9.9%; between 2% and 8%, between 4% and 8%, or between 4% and 10% of the lubricating composition.

[0049] The compounds of Formula 3 may be used in base oils in the preparation of a final lubricating formulation. In some aspects, the base oil comprises 0.5% to 9.9% of one or more of the compounds of Formula 3. In some aspects, compounds of Formula 3 comprise between 2 and 9.9%; between 2% and 8%, between 4% and 8%, or between 4% and 9.9% of the lubricating composition.

[0050] The compounds of Formula 1 may be used in base oils in the preparation of a final lubricating composition. In some aspects, the lubricating composition comprises 0.5% to 9.9% of one or more of the compounds of Formula 3. In some aspects, compounds of Formula 1 comprise between 2 and 9.9%; between 2% and 8%, between 2% and 6%, or between 4% and 9.9% of the lubricating composition.

[0051] The compounds of Formula 3 may be used in base oils in the preparation of a final lubricating composition. In some aspects, lubricating composition comprises 0.5% to 9.9% of one or more of the compounds of Formula 3. In some aspects, compounds of Formula 3 comprise between 2 and 9.9%; between 2% and 8%, between 2% and 6%, or between 4% and 9.9% of the lubricating composition.

[0052] In some aspects, the base oil comprises 0.5% to 9.9% of one or more of the compounds of Formula 1 and further comprises one more compounds of Formula 4. In some aspects, the base oil comprises 0.5% to 9.9% of one or more of the compounds of Formula 3 and further comprises one more compounds of Formula 4.EXAMPLESTable 2.

[0053] The commercially available 12-hydroxy stearic acid utilized had the following fatty acid composition shown in Table 3.Table 3.Examples 1A-F

[0054] A 2000 ml 5-necked round-bottomed flask equipped with a magnetic sealed stirrer guide with a PTFE centrifugal stirrer, temperature feedback probe and isomantle, a nitrogen inlet and outlet via a distillation head, Liebig condenser, receiver flask and exit bubbler, was charged with 12- hydroxystearic acid (450g, 1.44 mol; 1.98 equiv.) and the contents heated to 190°C with N2 purge (15ml with stirring (420 rpm) once molten. When the reaction temperature was achieved, vacuum was applied to 200 mbar (maintaining a nitrogen purge). After 1 ,5h the pressure was lowered to 50 mbar and after 2.5h the reaction was cooled and the AV measured as 78.0mg KOH / g. The reaction was restarted and continued for a further 30 min to give an AV of 70.7mg KOH / g. The reaction was cooled to below expected esterification reaction temperature, the distillation head was replaced with a Dean and Stark trap with vertical double surface Liebig condenser. 2-Ethylhexan-l- ol (2 -EH; 95.0g, 0.72 mol; 1 equiv.) was charged to the reaction vessel and the Dean and Stark trap filled with an additional 33 ml of 2-EH. The reaction was heated to 190°C and vacuum applied with caution to achieve a steady reflux of 2-EH into the trap. Reflux was maintained during the reaction by lowering the pressure as necessary. After 8h under reaction conditions (l lh total reaction time) the AV was measured to be 7.0mg KOH / g. Catalyst (TNBT, 0.2 ml) was added and the reaction allowed to progress for a further 5.5 h (16.5h total reaction time), after which the AV of the reaction had reached <0.2mg KOH / g. The reaction temperature was adjusted to 125°C and full vacuum applied to remove the excess 2-EH through the trap. When distillation of 2-EH ceased the trap was replaced with a simple distillation arm, 5g decolorizing charcoal was added to the reaction vessel and the nitrogen headspace purge was replaced with a sparge placed as low as possible in the vessel without contacting the stirrer paddle. Full vacuum was applied to strip out the remaining free 2-EH and maintained for 3h. The vessel was re-pressurized through the sparge and the product oligo-ester vacuum filtered through a bed of Celite filter aid to yield 1A [2-ethylhexyl poly(12-hydroxy stearate)] as a pale yellow viscous liquid.

[0055] Example IB was a repeat experiment with the same stoichiometry as 1 A, however, the hydroxystearic acid oligomerization was run for 4 hours to an AV of 65.3mg KOH / g prior to the introduction of the 2-EH.

[0056] Example 1C was a repeat experiment with the same stoichiometry as 1 A, however, the hydroxystearic acid oligomerization was run for 3.5 hours to an AV of 70 mg KOH / g prior to the introduction of the 2-EH.

[0057] Example ID is a repeat of 1C.

[0058] Example IE is repeat of Example 1A with a 10% stoichiometric increase in 2-EH.Example 2

[0059] The material from Example 1 was returned to a reaction vessel. A second 250ml 3- necked flask was charged with 50ml distilled water and a sizable quantity of anti-bumping granules, and fitted with a sintered gas distribution tube via a length of PTFE tubing. The gas distribution tube was introduced into the sample reaction vessel so that the sintered end was as low as possible without fouling the stirred blade. The steam vessel was placed in a water bath on a hot-plate stirrer with a set point of 30°C. The reaction vessel contents were heated to 115°C under a separate nitrogen purge. At the set temperature the nitrogen purge was shut off and vacuum applied, causing low temperature steam to be drawn through the gas distribution tube and sparge through the reaction bulk. After approximately 3 hours the heat was removed and the vacuum tap closed. Once at room temperature the vacuum was released though the steam sparge by repressurising the steam generator flask.Example 3

[0060] A 1000ml 5-necked round-bottomed flask equipped magnetic sealed stirrer guide with PTFE centrifugal stirrer, temperature feedback probe and isomantle, a nitrogen inlet and outlet via a Dean and Stark trap, Liebig condenser and exit bubbler was charged with Hypermer LP1 (520.0g, 0.297 mol CO2H; 1 equiv.) and 2-ethylhexan-l-ol (57.9g, 0.445 mol; 1.5 equiv.) and the mixture heated to 220°C with a nitrogen purge of 80ml min1and stirring at 500 rpm. After 2.5h the temperature was reduced to 180°C, 0.2 ml TNBT was added and the reaction allowed to progress for a further 16h, after which time the AV had fallen to 1.36mg KOH / g. An additional 0.2ml TNBT was added and the reaction continued for a further 24h after which time the AV had fallen to O.lmg KOH / g. The temperature was reduced to 120°C and vacuum applied with a nitrogen sparge for 3hand the product filtered through SW-10 cellulose filter aid overnight to yield the material of Example 3.Example 4

[0061] 12-hydroxystearic acid (491.6g, 1.67 mol) and 2-octanol (108.4g, 0.83 mol, ~50% excess) were charged to a 5-necked round bottomed flask equipped with a nitrogen headspace purge (~30ml / min), overhead stirrer with centrifugal stirrer bar (~500rpm), temperature feedback loop, Dean-Stark receiver with organic circulation and collection flask. The Dean-Stark receiver was fitted with a vertical condenser and a dreschel bottle to ensure a nitrogen atmosphere. Note: For 12- hydroxystearic acid mol calculation, the average Mwt was calculated from the acid value. The reaction was initially heated to 180°C before gradually increasing the temperature to 200°C, rate of heating controlled by rate of water evolution, ~ 2 hours. TnBT catalyst (~0.2g) and 2-octanol (~10mls) were added to the reaction vessel, Acid Value < 20mgKOH / g. The reaction was maintained at 200°C until the reaction was complete (AV < 0.2mgKOH / g). An additional dose of TnBT catalyst (0.2g) and 2-octanol (~10mls) were added after 16 hours. The product was cooled to 110°C, then activated carbon (~1 wt%) was added to the reaction vessel and vacuum was applied (< 5 mbar). Reaction conditions were maintained for 5 hours before the product was discharged and filtered. The material was vacuum filtered using Fibra-cel SW-10 as the filter aid. The product, 2-octyl poly(12- hydroxystearate), a clear, pale yellow, viscous liquid.Example 5

[0062] 12-hydroxystearic acid (955.4g, 3.25 mol) and 1-decanol (244.7g, 1.55 mol, ~50% excess) were charged to a 5-necked round bottomed flask equipped with a nitrogen headspace purge (~30ml / min), overhead stirrer with centrifugal stirrer bar (~450rpm), temperature feedback loop, Dean-Stark receiver with organic circulation and collection flask. The Dean-Stark receiver was fitted with a vertical condenser and a dreschel bottle to ensure a nitrogen atmosphere. Note: For 12- hydroxystearic acid mol calculation, the average Mwt was calculated from the acid value. The reaction was initially heated to 160°C before gradually increasing the temperature to 200°C, rate of heating controlled by rate of water evolution, ~ 3 hours. Tyzor TnBT catalyst (~0.4g) and 1-decanol (~25mls) were added to the reaction vessel, Acid Value < 30mgKOH / g. The reaction was maintained at 200°C until the reaction was complete (AV < 0.2mgKOH / g), approximately 24 hours. The productwas cooled to 145°C, then activated carbon (~1 wt%) was added to the reaction vessel and vacuum was applied (< 5 mbar). Reaction conditions were maintained for 5 hours before the product was discharged and filtered. The material was vacuum filtered using Fibra-cel SW-10 as the filter aid. The product, 1 -decyl poly( 12-hydroxy stearate) was an off white, paste like solid.Example 6

[0063] 12-hydroxy stearic acid (327.2g, 5.29 mol total) and 2-ethyl hexanol (344.1, 2.64 mol,-50% excess) were charged to a 5-necked round bottomed flask equipped with a nitrogen headspace purge (~30ml / min), overhead stirrer with centrifugal stirrer bar (~500rpm), temperature feedback loop, and a Dean-Stark receiver with organic circulation and collection flask. The Dean-Stark receiver was fitted with a vertical condenser and a dreschel bottle to ensure a nitrogen atmosphere. Note: For 12-hydroxy stearic acid mol calculation, the average Mwt was calculated from the acid value. The reaction was initially heated to 165°C before gradually increasing the temperature to 190°C, rate of heating controlled by rate of water evolution, - 1 hours until and AV of less than 15 was achieved actual AV = 13.2 mgKOH / g. The reaction was maintained at 190°C as TnBT catalyst was added (~1.7g). The reaction was maintained at 190°C until the reaction was complete (AV < 0.2mgKOH / g), approximately 38 hours. The reaction was cooled to 120°C. The reaction was then reconfigured, removing the Dean-stark receiver and replacing with a simple distillation arm, the nitrogen headspace purge was reconfigured to a sub-surface nitrogen sparge and then vacuum was applied (< 5 mbar, to strip off any free 2-ethylhexanol. Reaction conditions were maintained for 5 hours before the reaction was repressurized and sampled for acid value (AV = 0. 12 mgKOH / g) and GC analysis to determine the free 2-ethyl hexanol content of ~l,500ppm.

[0064] The reaction was reconfigured for steam stripping: a subsurface nitrogen sparge was connected to a 1 liter, 3 necked round bottomed flask filled with water, ~500g, and anti-bumping granules. The nitrogen / steam exhaust tube from the 3 necked flask was connected to a sub-surface sparge in the reactor vessel. The reaction was heated to 110°C and vacuum applied (<20 mbar), the nitrogen flow to the vessel was reduced to a minimal amount. The water in the flask was heated gently with a heat gun to allow the water to remain at room temperature and a vigorous bubbling of gas (nitrogen + steam) in the reaction vessel observed: for a constant vacuum, the temperature of the water will dictate the vigor of the steam strip process. These conditions were maintained for 3 hours before re-pressurizing and replacing the steam sparge with the nitrogen purge. The product wassampled for acid value (AV= 0.12mg KOH / g) and GC analysis to determine the free 2-ethyl hexanol content (<60ppm, Target <100 ppm). The product was discharged, filtered (filter aid: Celite® 512) and subject to full analytical work up. The product, 2-ethylhexyl poly 12-hydroxy stearate, a clear, amber, viscous liquid.

[0065] Material from Example 6 was analyzed by GPC to determine the distribution of repeating units.Table 4.Example 7

[0066] Material prepared according to Example 6 (550.0g), activated carbon (~1 wt%) and Tonsil Optium 210-ff (~1 wt%) were charged to a 5-necked round bottomed flask equipped with a sub-surface nitrogen sparge (~30ml / min), overhead stirrer with centrifugal stirrer bar (~400rpm), temperature feedback loop, condenser set for distillation removal and collection flask. The collection flask was fitted with both a dreschel bottle, to ensure a nitrogen atmosphere, and vacuum capabilities. The reaction was heated to 110°C and then vacuum was applied (< 5 mbar). Reaction conditions were maintained for 3 hours before the reaction was re-pressurized and the product discharged and filtered, using Celite® 512 as a filter aid. The product was a clear, amber, viscous liquid.Example 8

[0067] Material prepared according to Example 6 (550.0g) and acetic anhydride (110 mis, large excess) were charged to a 5-necked round bottomed flask equipped with a sub-surface nitrogen sparge (~30ml / min), overhead stirrer with centrifugal stirrer bar (~400rpm), temperature feedback loop, condenser set for distillation removal and collection flask. The collection flask was fitted with both a dreschel bottle, to ensure a nitrogen atmosphere, and vacuum capabilities. The reaction was heated to and maintained at 100°C for approximately 5 hours before the reaction was reconfigured for steam stripping: a subsurface nitrogen sparge was connected to a 1 liter, 3 necked round bottomed flask filled with water, ~500g, and anti-bumping granules. The nitrogen / steam exhaust tube from the 3 necked flask was connected to a sub-surface sparge in the reactor vessel. The reaction was heated to 110°C and vacuum applied (<20 mbar), the nitrogen flow to the vessel was reduced to a minimal amount. The water in the flask was heated gently with a heat gun to allow the water to remain at room temperature and a vigorous bubbling of gas (nitrogen + steam) in the reaction vessel observed: for a constant vacuum, the temperature of the water will dictate the vigor of the steam strip process. These conditions were maintained for 3 hours before repressurizing and replacing the steam sparge with the nitrogen purge. Activated carbon (~1 wt%) was added to the vessel and vacuum was applied (< 5 mbar). Reaction conditions were maintained for 3 hours before the reaction was repressurized and the product discharged and filtered, using Celite® 512 as a filter aid. The product, 2-ethylhexyl poly-12-hydroxystearyl acetylate, a clear, pale yellow, viscous liquid.Example 9

[0068] A 2000 ml 5-necked round-bottomed flask equipped magnetic sealed stirrer guide with PTFE centrifugal stirrer, temperature feedback probe and isomantle, a nitrogen inlet and outlet via a Dean and Stark trap, Liebig condenser and exit bubbler was charged with 12-hydroxy stearic acid (1000 g, 3.19 mol; 1 equiv.) and 2-ethylhexan- 1 -ol (519.2 g, 3.99 mol; 1.25 equiv.) and the mixture heated with a set point 200°C with N2 purge (15 ml min ') and stirring (520 rpm) once molten. The Dean and Stark trap initially filled with 2-EH but once this was displaced by the water of reaction the level of water in the trap was held at greater than ca. 80% maintained the excess of alcohol in the reaction vessel. After 3 h the temperature of the reaction had reached 200°C and the set point was increased to 220°C. After a further 1.5 h a total of 54 ml water had been removed from the reaction vessel. Catalyst (TNBT, 0.2 ml) was added and the reaction allowed to progress for a further 16 hafter which the AV of the reaction had reached <0.2mg KOH / g. An additional 0.2 ml TNBT was added and the reaction continued for a further 3 h. The mixture was cooled to 110°C, de-colorizing charcoal (5g) added and vacuum applied cautiously to prevent foaming to remove excess 2-EH for 2h. The charcoal was removed by filtration and full vacuum applied at 125°C with a nitrogen sparge until no free 2-EH was detected in the product by GC or odor.Example 10

[0069] A 1000 ml 5-necked round-bottomed flask equipped magnetic sealed stirrer guide with PTFE centrifugal stirrer, temperature feedback probe and isomantle, a nitrogen inlet and outlet via a Liebig condenser was charged with a sample of 2-ethylhexyl 12-hydroxy stearate (from Example 9, 550g; nom. 1.333 mol) and the reactant heated to 90°C. Slow addition of acetic anhydride (125ml; 136.0g, 1.333 mol) was started Only a minimal exotherm was observed and when the reaction temperature began to fall heating was applied to raise the temperature to 110°C. After 50ml of acetic anhydride was added the addition was stopped and a sample taken to ensure reaction was occurring. Addition was completed more rapidly and 0.1ml methanesulphonic acid was added as catalyst. After completion of the reaction the excess acetic anhydride and formed acetic acid was distilled out under vacuum. De-colorizing charcoal (5g) was added and heating at 125°C under vacuum was continued for a further 3 h before fdtration of the final product with SW-10 cellulose filter aid.

[0070] Table 5 shows the oxidative stability (induction time) of the Examples described above.Table 5.Benchmark 1 is a commercially available endcapped estolide sold by Biosynthetics under the product code BT22. Benchmark 2 is a commercially available high performing pentaerythritol tetraisostearate esters sold by Cargill Incorporated under the brand name Priolube 3987.

[0071] Tables 5, 6, and 7 show the comparison of the stability of a compounds of Formula 1 with an endcapped acylated version as well with two commercial benchmarks. It is very surprising that the Examples of formula 1 containing free hydroxyl groups (as demonstrated by the hydroxyl value) are approximately 7 times more stable than the corresponding acylated version. This is a dramatic and unexpected increase in oxidative stability that would be highly advantageous to an end user.Table 6.Table 7.Example 11 : 2-ethylhexyl poly(T2-hydroxy stearate) scale up

[0072] The vessel was inspected to ensure it was clean and in working order before the oil jacket was set to 90°C constant oil temperature. The vessel was sealed, ensuring the main drain valves were shut before a full vacuum was applied to assess if the vessel was vacuum tight. The vacuum was released with nitrogen before the 12-hydroxy stearic acid was charged via the sight glass port. Forbatch quantities Table 8 below. Once charged the sight glass port was closed and the constant oil temperature was increased to 160°C with 100 ml / min nitrogen headspace.

[0073] Once the 12-HSA was fully molten the stirrer was turned on (150 rpm), the temperature was increased to 190°C constant reactor temperature and the nitrogen headspace was increased to 200 ml / min. An initial pressure of 800 mbar was applied as the contents temperature reached 190°C; pressure was then reduced to 200 mbar over 10 minutes and then held for 1.5 hrs. After which the pressure was reduced to <50 mbar and held for a further 1 hr. The vacuum was broken with nitrogen and the vessel pressurized to 1100 mbar. The contents were sampled via the sparge valves and an acid value was measured. After sampling, nitrogen was blown down the sparge for 10 minutes. If the acid value was between 70-80 mg KOH g-1and the reaction was deemed complete and progressed to the next stage; if it was not in specification the pressure was reduced to <50 mbar and the reaction continued. Until the desired AV was reached.

[0074] The vessel was cooled to <140°C constant reactor temperature before a small access port on the lid of the vessel was unscrewed. The required 2-ethyl hexanol was charged to the vessel before the port was reclosed. Additionally, the binary separator was filled with l / 3rdwater and 2 / 3rd2-ethyl hexanol. The vessel was then set to 190°C constant reactor temperature and once reached the pressure was reduced to 800 mbar. The pressure was then reduced periodically to maintain a suitable level of reflux.

[0075] After approximately 6-7 hours, the vacuum was broken with nitrogen and the vessel pressurized to 1100 mbar. The contents were sampled via the sparge valves and an acid value was measured. If the acid value was <10 mg KOH g’1, the pressure was released, and tetra n-butanol titanate (TnBT)was added via the small access port on the lid. The reaction was then continued by decreasing the pressure until reflux was achieved. If the acid value was >10 mg KOH g'1, the reaction was just continued and sampled again an hour later. After sampling, nitrogen was blown down the sparge for 10 minutes.

[0076] After the TnBT was added, the reaction was continued, and the pressure reduced to ensure a suitable reflux was maintained. Periodically the vessel was sampled, using the same procedure detailed above, until the acid value was <0.2 mg KOH g'1and the reaction was deemed complete.

[0077] Once complete the vessel was set to 125°C constant reactor temperature and the stirrer speed was increased to 200 rpm. The binary separator was drained; with any water being discardedand any 2-ethyl hexanol kept for further batches. Once at temperature the pressure in the vessel was reduced to <50 mbar and free 2-ethyl hexanol distilled out of the vessel into the binary separator. Once the 2-ethyl hexanol had stopped distilling, the vessel was set to 110°C and the vacuum was broken with nitrogen.

[0078] A vacuum rated nylon tube was attached to the reactor and the other end was attached to a valve fitted to a 500 ml three-neck flask. A thermometer and a second valve were fitted to the other necks of the flask. The three-neck flask was then placed into a DrySyn block on a hotplate with a feedback probe in the block. Water and anti-bumping granules were placed into the flask and the block was heated to 110°C.

[0079] The pressure of the 50 L vessel was reduced to <50 mbar and, with the second valve on the 500 ml flask closed and the first valve open, reactor valves were opened. This reduced the pressure in the 500 ml flask and generated steam that was drawn into the 50 L vessel via the sparge. The generated steam was collected in the binary separator along with any 2-ethyl hexanol. After the 2-ethyl hexanol had stopped being removed from the vessel, valves were closed and the vacuum of the vessel was broken with nitrogen.

[0080] The vessel was pressurized to 1100 mbar before the contents were sampled via the sparge valves and an acid value was measured. After sampling, nitrogen was blown down the sparge for 10 minutes. A 2-ethyl hexanol content was determine and if >100 ppm the steam stripping was continued. If the 2-ethyl content was <100 ppm the stripping was deemed complete.

[0081] With batches 1 IB, 11C, and 1 ID, the vessel was set to a constant reactor temperature of 90°C and the pressure was reduced to <50 mbar to dry. These conditions were maintained for 1 - 2 hours. The vacuum was broken with nitrogen and the vessel was pressurized to 1100 mbar. The bottom valves were opened and the material was discharged into pre-weighed containers.

[0082] With batch 11 A, the vessel was set to a constant reactor temperature of 90°C and pressurized to 1100 mbar. The bottom valves were opened and the material was discharged into preweighed containers. The material was then charged to the 30 L glass vessel with Norit SA. The oil jacket was set to 90°C and a vacuum of <50 mbar was applied. These conditions were maintained for 1-2 hours before the vacuum was broken with nitrogen. The material was then discharged into preweighed containers.

[0083] All four batches were fdtered via Buncher funnel using Celite 545 fdter aid and a Whatman 54 filter paper. Once filtered the material was discharged into pre-weighed containers.Table 8. 50 L Reaction Quantities and DetailsTable 9.Example 12: Fractionation Effects

[0084] The material from Example 1 IB was sent through a 4” Pope wiped film evaporator (WFE) under vacuum at various condition to separate out the lower molecular weight components. Four different WFE conditions were evaluated leading to 4 sets of residues and distillates set out in Table 10 below.Table 10.

[0085] TablelO, shows that polymer content and properties may be modified by separation of components via treatment with a WFE. Materials with higher polymer content may be produced.Depending on desired characteristics, separation of components may be desirable in some applications.Example 13: Effects of change in hydroxyl positionExample 13 A: 2-Ethylhexyl poly- 10-hydroxy stearic acid

[0086] 10-Hydroxy stearic acid (900g, 95% purity, prepared via enzymatic process as described in Example 17 with subsequent recrystallisation) was heated in a 2 liter round bottom flask equipped with nitrogen inlet and a take-off adaptor connected to a horizonal water condenser to 190°C in approx. 1 h. Once at temperature the pressure was gradually decreased to 175 mbar in 3 hrs and then further reduced to <50 mbar. After reaching the acid value (75 mg KOH / g) the reaction was stopped and cooled to yield poly 10HSA.

[0087] Poly-IOHSA from above and 190 g 2-ethylhexanol were heated in a 2 liter round bottom flask equipped with nitrogen inlet and a take-off adaptor connected to a horizonal water condenser to 190°C in approx. 1 h. During heating up a vacuum of 300 mbar was applied. The vacuum was slowly decreased in 6 h to 100 mbar. At an AV of 19 mg KOH / g 0.6g TBT was added. After another 7h in which the pressure was further decreased to 90 mbar the reaction was stopped at an AV of 0.2mg KOH / g. The excess 2-ethylhexanol was distilled off. The final product was bleached (10g Norit SA4) and steam stripped at 110°C for 4 hours. The product was dried and 4g Supercel filter aid was added. After a time consuming filtration (24 h) the product 13A was isolated and analyzed (see below).Example 13B: Ethylhexyl poly 10-hydroxy stearate / stearate (86 / 14)

[0088] To mimic the stearic acid content of the commercially available 12-hydroxy stearic acid, a comparison was done by dosing stearic acid into the starting 10-hydroxystearic acid.

[0089] 10-Hydroxy stearic acid (810g) (95% purity, prepared via enzymatic process with subsequent recrystallisation) and 90g Stearic acid (98% pure) were heated in a 2L round bottom flask equipped with nitrogen inlet and a take-off adaptor connected to a horizonal water condenser to 190°C in approx. Ih. Once at temperature the pressure was gradually decreased to 200 mbar in 2 hrs and then further reduced to <50 mbar. After reaching the acid value (73mg KOH / g) the reaction was stopped and cooled to yield poly lOHAS / stearic acid.

[0090] Poly lOHSA / stearic and 190g 2-ethylhexanol were heated in a 2 liter round bottom flask equipped with nitrogen inlet and a take-off adaptor connected to a horizonal water condenser to 190°C in approx. Ih. After reaching the reaction temperature the pressure was decreased in 2 hours to 300 mbar. At an AV of 25mg KOH / g 0.6g TBT was added. The pressure was reduced to 100 mbar. After another 7.5h the reaction was stopped at an AV of 0.2mg KOH / g. The excess 2-ethylhexanol was distilled off. The final product was bleached (10g Norit SA4) and steam stripped at 110°C for 3.5 hours. The product was dried and 4g Supercel filter aid was added. After a time consuming filtration (~ 5 h) the product 13B was isolated and analyzed (see below).Example 14: Effects of unsaturation in backbone.Example 14A: 2-Ethylhexyl poly 12-hvdroxystearate / ricinoleate (O?1 / ^1 / ?)

[0091] 12 Hydroxy stearic acid (877.5g) and 22.5g Ricinoleic acid were heated in a 2 liter round bottom flask equipped with nitrogen inlet and a take-off adaptor connected to a horizonal water condenser to 190°C in approx. Ih. Once at temperature the pressure was gradually decreased to 200 mbar in 2.5 hrs and then further reduced to <50 mbar. After reaching the acid value (73mg KOH / g) the reaction was stopped and cooled.

[0092] Poly 12HSA / ricinoleic from above and 190g 2-ethylhexanol were heated in a 2 liter round bottom flask equipped with nitrogen inlet and a take-off adaptor connected to a horizonal water condenser to 190°C in approx. Ih. After reaching the reaction temperature the pressure was decreased in 3.5 hours to 300 mbar. At an AV of 20 mg KOH / g 0.6g TBT was added. The pressure was reduced to 100 mbar in 2.5 h. After another 7.5 h the reaction was stopped at an AV of 0.2mg KOH / g. The excess 2-ethylhexanol was distilled off. The final product was bleached (10g Norit SA4) and steam stripped at 110°C for 4 hours. The product was dried and 4.4g Supercel filter aid was added. After filtration the product 14A was isolated and analysed (see Table 11).Example 14B: 2-Ethylhexyl polv-12-hvdroxystearate / ricinoleate (95 / 5)

[0093] 12 Hydroxy stearic acid (978g) and 51 ,5g ricinoleic acid were heated in a 2 liter round bottom flask equipped with nitrogen inlet and a take-off adaptor connected to a horizonal water condenser to 190°C in approx. Ih. Once at temperature the pressure was gradually decreased to 200 mbar in 3.5 hrs and then further reduced to <50 mbar. After reaching the acid value (72 mg KOH / g) the reaction was stopped and cooled to yield poly 12HSA / ricinoleic.

[0094] Poly 12HSA / ricinoleic from above and 217g 2-ethylhexanol were heated in a 2 liter round bottom flask equipped with nitrogen inlet and a take-off adaptor connected to a horizonal water condenser to 190°C in approx. Ih. After reaching the reaction temperature the pressure was decreased in 4 hours to 300 mbar. At an AV of 16.6mg KOH / g 0.68g TBT was added. The pressure was reduced to 100 mbar in 1.5h. After another 6 h the reaction was stopped at an AV of 0.12 mg KOH / g. The excess 2-ethylhexanol was distilled off. The final product was bleached (11g Norit SA4) and steam stripped at 110°C for 4 hours. The product was dried and 4.8g Supercel filter aid was added. After filtration the product was isolated and analyzed. The acid value was higher than expected (0.86mg KOH / g). Therefore 975 g product was mixed with 50g 2-ethylhexanol and esterified at 190°C and 150 mbar until the AV was 0.12mg KOH / g. The excess 2-ethylhexanol was distilled off. The final product was bleached (11g Norit SA4) and steam stripped at 110°C for 4 hours. The product was dried and 4.8g Supercel filter aid was added. After filtration the final product 14B was isolated and analyzed (see Table 11).Example 14C: Ethylhexyl Dolv-12-hydroxystearate / ricinoleate (921 / 2 / 71 / 2)

[0095] 12-Hydroxy stearic acid (865g) and 65 g ricinoleic acid were heated in a 2 liter round bottom flask equipped with nitrogen inlet and a take-off adaptor connected to a horizonal water condenser to 190°C in approx. 1 h. Once at temperature the pressure was gradually decreased to 200 mbar in 2 hrs and then further reduced to <50 mbar. After reaching the acid value (73mg KOH / g) the reaction was stopped and cooled.

[0096] Poly 12HSA / ricinoleic prepared above and 196g 2-ethylhexanol were heated in a 2 liter round bottom flask equipped with nitrogen inlet and a take-off adaptor connected to a horizonal water condenser to 190°C in approx. 1 h. After reaching the reaction temperature the pressure was decreased in 1.5 hours to 250 mbar. At an AV of 16mg KOH / g 0.6g TBT was added. The pressure was reduced to 100 mbar in 3 h. After another 5 h the reaction was stopped at an AV of 0.13mg KOH / g. The excess 2-ethylhexanol was distilled off. The final product was bleached (10g Norit SA4) and steam stripped at 110°C for 4 hours. The product was dried and 4.4g Supercel filter aid was added. After filtration the product 14C was isolated and analysed (see Table 11).Table 11.Example 15: Effect of Acetylation and reduction of hydroxyl valueExample 15 A: Acetylation to Hydroxyl Value of 29 mg KOH g-1

[0097] Poly-12-HSA from Example 11B, (1264.2g, 1.01 mol) was placed into a round bottom 5-neck flask. The flask was fitted with a stirrer, temperature probe, pressure equalizing dropping funnel, nitrogen headspace (30ml min-1) and a takeoff arm leading to a horizontal condenser. The condenser was attached to a collection flask that was fitted with a nitrogen outlet leading to a Dreschel bottle filled with weak potassium hydroxide solution in water and phenolphthalein indicator.

[0098] The temperature of the vessel was increased to 130°C and acetic anhydride (48.8g, 0.48 mol) was placed into the dropping funnel. Once at temperature, acetic anhydride was slowly added to the vessel over 2 hours. The nitrogen flow was increased to 50ml min-1and held for 1.75 hours before the material was steam stripped.

[0099] Steam stripping was carried out by changing the nitrogen headspace to a nitrogen sparge (50ml min-1). The sparge was connected to an auxiliary vessel filled with reverse osmosis water and with a nitrogen inlet. The auxiliary vessel was placed in a water bath held at 60°C. The Dreschel bottle was replaced with a vacuum pump and the pressure in the main vessel was reduced to ~60 mbar, thus reducing the pressure of the auxiliary vessel and causing steam to be generated. The generated steam was carried into the main vessel through the sparge by the nitrogen. After 15 minutes the temperature of the vessel was reduced to 110°C and held for 30 minutes. The pressure of the vessel was then reduced to 40 mbar and held for a further 20 minutes before the vacuum was broken with nitrogen.

[0100] The sparge was replaced with a nitrogen headspace and the vessel pressure reduced to 20 mbar to dry. After ~2 hours the vacuum was broken with nitrogen and the material was sampled (SI). An acid value of 0.28mg KOH g-1and a hydroxyl value of 29mg KOH g-1was measured. The nitrogen headspace was replaced with a nitrogen sparge, and the steam stripping was continued with a vessel pressure of 20 mbar. After 5.5 hours the vacuum was broken with nitrogen and the nitrogen sparge replaced with nitrogen headspace. The temperature of the vessel was reduced to 90°C and the material was dried again at a vessel pressure <30 mbar. After a further 3.25 hours, the vacuum was broken with nitrogen and a sample (S2) was taken. An acid value of 0.19mg KOH g-1and a hydroxylvalue of 29mg KOH g’1was measured. As the acid value was <0.2mg KOH g’1a further, larger, sample was taken. In total ~220g of material was sampled as Example 15 A.Example 15B: Acetylation to Hydroxyl Value of 1 Img KOH g'1

[0101] The remaining material was acetylated further by placing acetic anhydride (30.4g, 0.30 mol) into the dropping funnel and heating the vessel to 130°C. Once at temperature, acetic anhydride over 2.25 hours and then allowed to react for a further 1.5 hours before the vessel was cooled to 110°C and steam stripped. Steam stripping was carried out by changing the nitrogen headspace to a nitrogen sparge (50ml min’1). The sparge was connected to an auxiliary vessel filled with reverse osmosis water and with a nitrogen inlet. The auxiliary vessel was placed in a water bath held at 60°C. The Dreschel bottle was replaced with a vacuum pump and the pressure in the main vessel was reduced to <30 mbar, thus reducing the pressure of the auxiliary vessel and causing steam to be generated. The generated steam was carried into the main vessel through the sparge by the nitrogen.

[0102] After 5 hours the steam stripping was stopped by breaking the vacuum with nitrogen and the sparge was replaced with nitrogen headspace. The vessel was cooled to 90°C before the pressure was reduced to <80 mbar for 2 hours. A sample (S3) was taken with an acid value of 0.16mg KOH g’1and a hydroxyl value of 1 Img KOH g’1was measured. As the acid value was <0.2mg KOH g’1a further, larger, sample was taken. In total ~235g of material was sampled as Example 15B.Example 15C: Acetylation to Hydroxyl Value of 3 mg KOH g'1

[0103] The remaining material was acetylated further by placing acetic anhydride (20.0g, 0.20 mol) into the dropping funnel and heating the vessel to 130°C. Once at temperature, acetic anhydride over 1 hour and then allowed to react for a further 4 hours before the vessel was cooled to 110°C and steam stripped. Steam stripping was carried out by changing the nitrogen headspace to a nitrogen sparge (50ml min’1). The sparge was connected to an auxiliary vessel filled with reverse osmosis water and with a nitrogen inlet. The auxiliary vessel was placed in a water bath held at 60°C. The Dreschel bottle was replaced with a vacuum pump and the pressure in the main vessel was reduced to <20 mbar, thus reducing the pressure of the auxiliary vessel and causing steam to be generated. The generated steam was carried into the main vessel through the sparge by the nitrogen.

[0104] After 5.4 hours the steam stripping was stopped by breaking the vacuum with nitrogen and the sparge was replaced with nitrogen headspace. The vessel was cooled to 90°C before thepressure was reduced to <20 mbar for 2.5 hours. A sample (S4) was taken with an acid value of 0.05mg KOH g-1and a hydroxyl value of 3mg KOH g-1was measured. As the acid value was <0.2mg KOH g’1the reaction was deemed complete and the material isolated as Example 15C.

[0105] Table 12 clearly demonstrates the dramatically surprising effect that increasing the proportion of free hydroxyl groups (as measured by hydroxyl value) has on oxidative stability. A modest increase in hydroxyl value from 3 to 11 over triples the oxidative stability. There is greater than a 10 fold difference between the starting material of Example 11 and the most acylated Example of 15C.Table 12.Example 16: Effects of Differing Esterifying AlcoholsPoly 12-hydroxy stearic acid

[0106] 12 Hydroxy stearic acid (1100g) was heated in a 2 liter round bottom flask equipped with nitrogen inlet and a take-off adaptor connected to a horizonal water condenser to 190°C in approx. Ih. Once at temperature the pressure was gradually decreased to 200 mbar in 1.5-2 hrs and then further reduced to <50 mbar. After reaching the acid value (70-75mg KOH / g) the reaction was stopped and cooled.Example 16A: Hexyl poly 12-hydroxy stearate

[0107] Poly-12HSA (860g) as prepared above and Hexanol (160g) were heated in a 2 liter round bottom flask equipped with nitrogen inlet and a Dean Stark separator to 190°C in approx. Ih. After 1 ,5h a vacuum of 750 mbar was applied. Subsequently the vacuum was slowly decreased in 5h to 375 mbar. At an AV of 10.3mg KOH / g 0.43g TBT was added. After another 6.5h in which the pressure was further decreased to 200 mbar the reaction was stopped at an AV of 0.2mg KOH / g.

[0108] The excess of hexanol was distilled off at 120°C. 947g final product was bleached (10g Norit SA4) and steam stripped at 110°C for 3 hours. The product was dried and 5g Supercel filter aid was added. After filtration the product was analyzed (see below).Example 16B: 2-Octyl decyl polv-12-hydroxystearate

[0109] Poly-12HSA (900g) as prepared above and 495g of Isofol 18 were heated in a 2 liter round bottom flask equipped with nitrogen inlet and a take-off adaptor connected to a horizonal water condenser to 190°C in approx. 1 h. During heating up a vacuum of 600 mbar was applied. Subsequently the vacuum was slowly decreased in 4h to 125 mbar. At an AV of 11 ,9mg KOH / g 0.46g TBT was added. After another 7 h in which the pressure was further decreased to 25 mbar the reaction was stopped at an AV of 0.2mg KOH / g.

[0110] The product was distilled using a 2-stage molecular distillation set-up. The excess of Isofol 18 was distilled off (1ststage 155-160°C / 10’3mbar ; 2ndstage 185°C / 10'3mbar). 1064g final product was bleached (10g Norit SA4) and steam stripped at 110°C for 4 hours. The product was dried and 5 g Supercel filter aid was added. After filtration the product was analyzed (see below).Example 16C: Isostearyl poly 12-hydroxy stearate

[0111] Poly 12HSA (900g) as prepared above and 493 g Isostearyl alcohol (3515) were heated in a 2 liter round bottom flask equipped with nitrogen inlet and a take-off adaptor connected to a horizonal water condenser to 190°C in approx. 1 h. During heating up a vacuum of 300 mbar was applied. The vacuum was slowly decreased in 5 h to 100 mbar. At an AV of 9.1 mg KOH / g 2.4g 20% TBT solution was added. After another 6.25 h in which the pressure was further decreased to 25 mbar the reaction was stopped at an AV of 0.14 mg KOH / g.

[0112] The product was distilled using a 2-stage molecular distillation set-up. The excess of isostearyl alcohol was distilled off (1ststage 150-160°C / 10'3mbar ; 2ndstage 185°C / 10’3mbar). 935 g final product was bleached (10g Norit SA4) and steam stripped at 110°C for 4 hours. The product was dried and 5 g Supercel filter aid was added. After filtration the product was analyzed (see below).Example 16D: Stearyl poly- 12-hydroxy stearate

[0113] Poly 12HSA (900g) as prepared above and 495g Stearyl alcohol were heated in a 2 liter round bottom flask equipped with nitrogen inlet and a take-off adaptor connected to a horizonal water condenser to 190°C in approx. Ih. During heating up a vacuum of 300 mbar was applied. Subsequently the vacuum was slowly decreased in 5 h to 100 mbar. At an AV of 9.1mg KOH / g 2.4g 20% TBT solution was added. After another 6.25h in which the pressure was further decreased to 25 mbar the reaction was stopped at an AV of 0.14mg KOH / g.

[0114] The product was distilled using a 2-stage molecular distillation set-up. The excess of isostearyl alcohol was distilled off (1ststage 150-160°C / 10'3mbar ; 2ndstage 185°C / 10‘3mbar). 935g final product was bleached (10g Norit SA4) and steam stripped at 110°C during 4 hours. The product was dried and 5g Supercel filter aid was added. After filtration the product was analyzed (see below).Example 16E: Methyl poly 12-hydroxy stearate

[0115] 12HSA (900g) as prepared above was heated in a 2 liter round bottom flask equipped with nitrogen inlet and a take-off adaptor connected to a horizonal water condenser to 190°C. Methanol was dosed to reactor (approx. 350 ml / h). At an AV of 25mg KOH / g 0.5 g TBT was added. After 5 h the reaction temperature was increased to 205 °C. After a total reaction time of lOh the reaction was stopped at an AV of 0.17mg KOH / g (preliminary product).

[0116] This reaction was repeated with 400 g 12HSA. The product was molecular distilled at 280°C and 3.5xl0’3mbar to create a top and bottom fraction.

[0117] The final product (methyl poly- 12-hydroxy stearate) was a mixture of 837g of the preliminary product and 148g of the top fraction of the molecular distilled repeat.

[0118] The final product (985g) was bleached (10g Norit SA4) and steam stripped at 110°C during 3 hours. The product was dried and 5g Supercel filter aid was added. After filtration the product was analyzed (see below).Example 16F: Isopropyl poly 12-hydroxy stearate

[0119] The first batch was prepared by esterifying poly 12HSA with isopropanol. For the second batch the isopropyl ester was prepared by esterifying 12HSA with isopropanol to a low acid value. Both batches were molecular distilled to separate the low molecular components from the mix. The isopropyl ester was prepared by mixing molecular distilled top and bottom fractions in the ratio described below.

[0120] 12HSA (1000g) as prepared above was heated in a 2 liter round bottom flask equipped with nitrogen inlet and a take-off adaptor connected to a horizonal water condenser to 190°C. The product was esterified to an AV of 75mg KOH / g. IPA was dosed to the mix. After 7h an AV of 34mg KOH / g was reached and 0.3g TBT was added. After a total reaction time of 21h another 0.3g TBT was added and the temperature was increased to 210°C. In 4h the AV was 0.25mg KOH / g and the reaction was stopped. In total 5 liter of IPA was dosed to the reactor. The recovered product was molecular distilled at 280°C and 3.5xl0’3mbar (approx. lOOml / hr) to yield product a top fraction product (16F1).

[0121] 12HSA (1250g) as prepared above was heated in a 2 liter round bottom flask equipped with nitrogen inlet and a take-off adaptor connected to a horizonal water condenser to 190°C. IPA was dosed to reactor (approx. 350 ml / h). After 4h at an AV of 35mg KOH / g 0.5g TBT was added. After 10.5h at an AV of 3.7 another 0.3g of TBT was added. During the following 3hthe AV increased to 9.4mg KOH / g. It was decided to switch to a new bottle of IPA. After a total reaction time of 26h the reaction was stopped at an AV of 0.3mg KOH / g. The product was molecular distilled at 280°C and 3.5xl0’3mbar (approx. lOOml / hr) to create a top fractional 6F2) and a bottom fraction (16F3).

[0122] The final product was a mixture of 360g top fraction of molecular distilled 16F1, 120g top fraction of molecular distilled 16F2 and 700g bottom fraction of molecular distilled 16F3.

[0123] The combined fractions were bleached (12g Norit SA4) and steam stripped at 110°C during 3 hours. The product was dried and 5g Supercel filter aid was added. After filtration the product (16F) was analyzed (see below).Table 13.Example 17: Preparation of IQ-hydroxystearic acid

[0124] A tank was filled with 280 liters of demineralized water. Citric acid (473 g) and Na2HPO4 (1.65 kg) were added to the tank. The pH of the entire mixture was 7.0 ± 0.5. MgSO4.7H2O (689 g) was added to the tank and the mixture was stirred for 15 minutes. The temperature of the resulting mixture was adjusted to 20-25 °C. Oleic acid (7 kg) was added to the solution, followed by the addition the of the hydratase enzyme PDN Cl 00 V2 from Biocatalysts Ltd (140 g) and the resulting mixture was stirred for 24 hours 20-25 °C. The mixture was then heated to 50°C and kept at this temperature for 1 hour. The mixture was then cooled to 30°C and filtered over a 1pm nylon filter. The solid precipitate was dried and taken from the filter affording 10-hydroxy stearic acid.Example 18: Ester Examples

[0125] The following esters were prepared by standard esterification techniques through the dehydration of an acid and an alcohol or were acquired commercially from Cargill, Incorporated.Table 14.Antioxidant EffectBlend preparation

[0126] To prepare the blends, the appropriate ingredients were measured first into the beaker in the desired quantities to reach 100g. The mixture was stirred using a mixer set at 400 rpm, at 60°C for 20 minutes. This procedure was carried out for all required blends.

[0127] Performance of the blends was measure and reported in Table 15 below.Table 15.Rapid Oxy run at 140C as described below.

[0128] From Table 15 a surprising antioxidant affect can be seen. Inclusion of 4% of a either material from Example 3 or 1 lb or can double or triple the oxidative stability of an ester based lubricant.Example 19: Traction Effects

[0129] The lubricant blends in Table 16 below were prepared as follows. The lubricant blends in Table 16 below were prepared by measuring each component into a suitable 250 ml glass beaker using a Mettler Toledo G2002-S balance. Where used, Example 3 and Example 1 IB were measured into the beaker first. Once all the required components were measured into the beaker, the beaker was placed on an IKA C-MAG HS7 hotplate and was stirred using an appropriate stirrer placed in an IKAOS20-S overhead stirrer. The material was blended at 300 rpm with the temperature set at 60°C for 1 hour.

[0130] All blends were standardized to a kV100°C of 5.5 cSt.Table 16.*PAOs were commercially sourced under the trade name SpectraSyn 4, 6, 7, or 8 fromExxon Mobile

[0131] Figures 2 and 3 are a comparison of Examples 19A (control) with Examples 19D and 19G at 40°C and 100°C.

[0132] Figures 4 and 6 are a comparison of Examples 19B (control) with Examples 19E and 19H at 40°C and 100°C.

[0133] Figures 6 and 7 are a comparison of Examples 19C (control) with Examples 19F and 19I at 40°C and 100°C.Example 20: Inclusion rate traction study

[0134] The lubricant blends in Table 17 below were prepared as follows. The lubricant blends in Table 17 below were prepared by measuring each component into a suitable 250 ml glass beaker using a Mettler Toledo G2002-S balance. Where used, Example 3 and Example 1 IB were measured into the beaker first. Once all the required components were measured into the beaker, the beaker was placed on an IKA C-MAG HS7 hotplate and was stirred using an appropriate stirrer placed in an IKA OS20-S overhead stirrer. The material was blended at 300 rpm with the temperature set at 60°C for 1 hour.

[0135] All blends were standardized to a kV100°C of 5.5 cSt.Table 17. Inclusion rate formulationsTable 18. Stribeck comparison - 60CTable 19. Stribeck comparison - 80CTable 20. Traction curve - 20 mm / s at 60CTable 21. Traction curve - 10 mm / s 60CTable 22. Traction curve - 20 mm / s at 80CTable 23. Traction curve at 10 mm / s at 80C

[0136] The MTM for Example 20 was run according to the following method. Stribeck and traction curves were measured at two different temperatures specifically 60°C and finally 80°C. The idle speed when the temperature in the pot is being established is set to 1,000 mms-1 with a slide roll ratio of 0% and a load of 5N. During an initial rubbing step, the test is performed at 60°C with a rolling speed of 50 mms-1 with a slide roll ratio of 50% and a load of 30N for 30 minutes. Following the rubbing step, the Stribeck and traction curves are measured at 60°C before the temperature is increased to 80°C and the Stribeck and traction curves measured again.

[0137] For the Stribeck curve, the test was performed at 60°C or 80°C using a mean slide roll ratio of 50% and a load of 36N. The Stribeck curve was run from 3200 mms-1 to 10 mms-1 in 50 steps evenly distributed in a logarithmic manner.

[0138] For the traction curves, two different tests were performed at each temperature. The first test was performed using a mean speed of 0.2 mms-1 with a ball load of 26N. The second testwas performed using a mean speed of 0.1 mms-1 with a ball load of 60N. Both traction curves themselves are run according to the following slide roll ratio parameters: a) Starting at 0.00% increasing in steps of 0.1% to 2.00% b) Then increasing in steps of 0.2% to 5.00% c) Then increasing in steps of 1 .00% to 10.00% d) Then increasing in steps of 10.00% to 100.00%

[0139] The data was saved and used to prepare the appropriate slide roll and Stribeck curves.

[0140] This Example demonstrates the high performance at an inclusion rate of 4%-10%. Improvements of 20%-50% are typically achieved.Analytical MethodsViscosity

[0141] Viscosity of the samples was measured on an Anton Parr Stabinger Viscometer SVM3001 Viscometer in accordance with method ASTM D445. Material was added to the viscometer and the kinematic viscosity measured at 40°C (KV40) and at 100°C (KV100); with the machine also measuring the viscosity index (VI) and density.RapidOxy

[0142] Materials of the present disclosure have exceptional oxidative stability. This stability can make it time consuming to assess stability at lower temperature. The samples were evaluated at three different temperatures to understand more fully their stability. Samples were all evaluated on an Anton Parr RapidOxy 100 instrument in accordance with ASTM D8206. Method conditions are listed in Table 16. A sample size of 4grams was used in a standard glass dish. The temperature utilized was either 140°C, 160°C, or 180°C as indicated. The apparatus was pressurized to 700kPa with pure oxygen and test completion is determined by the time it takes for the peak pressure to drop by 10% or 50%. Accordingly, 10% or 50% reduction was used as an indication of rapid onset of oxidation or Oxidation Induction Time (OIT). OIT should be determined on compounds of Formulas 1 and 3, and on base oils, and lubricant formulations, without addition of any additives or antioxidants. In some aspects, the OIT of the lubricating compositions, base oils, compounds of Formula 1, and Compounds of Formula 3 is greater than 500hr as determined according to ASTM D8206 at 160°C. In some aspects, the OIT of the lubricating compositions, base oils, compounds of Formula, 1 and Compoundsof Formula 3 is greater than 750hr as determined according to ASTM D8206 at 160°C. In some aspects, the OIT of the lubricating compositions, base oils, compounds of Formula, 1 and Compounds of Formula 3 is greater than lOOOhr as determined according to ASTM D8206 at 160°C.Table 24.

[0143] Samples from Example 11B we also evaluated for thermal degradation via Thermogravimetric analysis (TGA) under a nitrogen atmosphere to ensure the oxidative stability data was not skewed at a higher temperature do to degradation. Samples were evaluated from 90°C to 900°C under nitrogen on standard equipment. No significant degradation was seen to occur at temperatures under 240°C.

[0144] The term “Acid Value” (AV) as used herein is defined as the weight of KOH in mg needed to neutralize the organic acids present in 1g of test sample and it is a measure of the free fatty acids present in the composition. AV can be determined by the AOCS Official Method Cd 3d-63.

[0145] The term “Hydroxyl Value” as used herein is defined as the hydroxyl value, expressed in milligrams of potassium hydroxide and corresponds to the number of hydroxyl groups present in 1g of a sample, is one of the traditional characteristics of oils and fats. Hydroxyl Value may be determined by AOCS Standard Method Cd 13-60.

[0146] The GPC analysis was carried out using Instrument: Agilent 1260 infinity GPC / SEC multi detector suite. Solvent: Tetrahydrofuran, Detector Refractive Index, sample concentration 1% (w / v), Injection Volume 50pl, Temperature: 40°C, Flow rate: Iml / minute, 2 x (PLGel 3pm 100A, 300x7.5mm) and 1 x (PLGel, 3pm, 50x7.5mm) Guard Colum. Results are shown in Figure 1.MTM Slide Roll Test

[0147] For Example 18, all testing was completed using a standard MTM-2 from PCS Instruments. During the test, standard MTM test specimens specifically a %” diameter steel ball and a 46mm diameter steel disc. Both the ball and disc were produced by PCS using AISI 5200 bearing grade steel and polished to a surface finish of respectively Ra < 0.01 and <0.02.

[0148] Before the test was completed, the test chamber in the MTM was cleaned with N- heptane and then dried and followed by laboratory grade nitrogen. The ball and disc along with the test pieces required by the MTM were sonicated in N-heptane in separate pots for 15 minutes. The test pieces include: a ball retaining screw, a splash guard, a disc holder, a disc securing nut, pot lid, tweezers and a hex torque drive supplied by PCS. After this period, the N-heptane is drained and more N-heptane is poured into the pots and sonicated again for a further 15 minutes for a total cleaning time of 30 minutes. The heptane is drained from the containers and then all test components were dried using nitrogen.

[0149] When all components are dried, the ball is installed by placing the disc into the MTM chamber such that is aligns with the pins at the bottom of the chamber. The disc holder is then placed on top of the disc and the disc securing nut is placed onto the screw in the bottom of the chamber and tightened. The securing nut is tightened until the torque drive supplied by PCS clicks three times. The ball retaining screw is then placed inside the ball and this is placed into the ball adaptor on the MTM using the tweezers. The securing nut is tightened until the torque drive supplied by PCS clicks three times. The splash guard is then installed on top of the disc and the appropriate lubricant is added until the oil covers the top of the splash guard. The ball is then lowered using the PCS software and the pot lid and plastic lid placed on top of the pot. The securing handle is then moved such that it rests in the divot in the top of the plastic lid and the PCS software displays the ‘locked’ sign.

[0150] The MTM is run using a 6 temperature traction profile. All traction tests are performed using a mean speed of 2,000 mm-1 with a ball load of 16N. The idle speed when the temperature in the pot is being established is set to 1,000 mm-1 with a slide roll ratio of 0% and a load of 5N. During the test, 6 different traction curves are recorded at different temperatures specifically 40°C, 60°C, 75°C, 100°C, 120°C and finally 150°C. The traction curves themselves are run according to the following slide roll ratio parameters: a) Starting at 0.00% increasing in steps of 0.1% to 2.00% b) Then increasing in stepsc) Then increasing in steps of 1.00% to 10.00% d) Then increasing in steps of 10.00% to 100.00%The data is saved and used to prepare the appropriate slide roll curves.Aspects of the disclosure

[0151] Any of the following aspects may be combined in any fashion to define the invention described herein and the inventors have specifically conceived of such combinations.

[0152] In some aspects, the compounds of Formula 1 may have an acid value (AV) of less than 0.25, or less than 0.2, or between 0.05 and 0.2.

[0153] In some aspects, the compounds of Formula 3 may an acid value (AV) of less than 0.25, or less than 0.2, or between 0.05 and 0.2.

[0154] In some aspects, the compounds of Formula 1 may have a hydroxyl value of more than 10, or more than 20 or more than 35. In some aspects, the compounds of Formula 1 may have a hydroxyl value of between 10 and 70 or between 35 and 70. In some aspects, the compounds of Formula 1 may have a hydroxyl value of between 35 and 60.

[0155] In some aspects, the compounds of Formula 3 may have a hydroxyl value of more than 10, or more than 20 or more than 35. In some aspects, the compounds of Formula 3 may have a hydroxyl value of between 10 and 70 or between 35 and 70. In some aspects, the compounds of Formula 3 may have a hydroxyl value of between 35 and 60.

[0156] In some aspects, the compounds of Formula 1 and compounds of Formula 4 may have a hydroxyl value of more than 10, or more than 20 or more than 35. In some aspects, the compounds of Formula 1 and compounds of Formula 4 may have a hydroxyl value of between 10 and 70 or between 35 and 70. In some aspects, the compounds of Formula 1 and compounds of Formula 4 may have a hydroxyl value of between 35 and 60.

[0157] In some aspects, the compounds of Formula 3 and compounds of Formula 4 may have a hydroxyl value of more than 10, or more than 20 or more than 35. In some aspects, the compounds of Formula 3 and compounds of Formula 4 may have a hydroxyl value of between 10 and 70 or between 35 and 70. In some aspects, the compounds of Formula 3 and compounds of Formula 4 may have a hydroxyl value of between 35 and 60.

[0158] Another aspect of the present disclosure is a method of lubricating two surfaces comprising contacting the interface of the surfaces with a lubricating composition of any of the compositions described herein.

[0159] In some aspects, the surfaces are part of hydraulic system.

[0160] In some aspects, the surfaces are gears.

[0161] In some aspects, the gears are in an industrial gear box, marine gear box, vehicle gear box, or vehicle transmission.

[0162] The use of a compound of Formula 1 or Formula 3 as a friction modifier.

[0163] In some aspects, the lubricating composition comprises 0.5 - 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl.

[0164] In some aspects, the lubricating composition comprises 0.5 - 9.9% of one or more compounds of the Formula 1 wherein R is C1-C22 alkyl, R2 is a saturated or unsaturated C7 or C9 alkyl; and R3 is a C6 or C8 alkyl.

[0165] In some aspects, the lubricating composition comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl.

[0166] In some aspects, the lubricating composition comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl and the base oil is selected from the group consisting of polyalphaolefins (PAOs), synthetic esters such as polyol esters, polyalkylene glycols (PAGs), oil soluble polyalkylene glycols (OSPs), mineral oils (Groups I, II, and III), fatty acid esters, and mixtures thereof.

[0167] In some aspects, the lubricating composition comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl and the base oil comprises a polyalphaolefin (PAO).

[0168] In some aspects, the lubricating composition comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl and the base oil selected from the group consisting of polyalphaolefins (PAOs), synthetic esters such as polyol esters, polyalkylene glycols (PAGs), oil soluble polyalkylene glycols (OSPs), mineral oils (Groups I, II, and III), fatty acid esters, and mixtures thereof, and has a hydroxyl value greater than 10.

[0169] In some aspects, the lubricating composition comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl and further comprises a polyalphaolefin (PAO) and the base oil has a hydroxyl value greater than 35.

[0170] In some aspects, the lubricating composition comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl and the base oil comprises a polyalphaolefin (PAO) and the compounds of Formula 3 have a hydroxyl value greater than 35.

[0171] In some aspects, the lubricating composition comprises comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl and the base oil is selected from the group consisting of polyalphaolefins (PAOs), synthetic esters such as polyol esters, polyalkylene glycols (PAGs), oil soluble polyalkylene glycols (OSPs), mineral oils (Groups I, II, and III), fatty acid esters, and mixtures thereof, and the compounds of Formula 3 have a hydroxyl value greater than 35.

[0172] In some aspects, the lubricating composition comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl and the base oil comprises a polyalphaolefin (PAO) and the compounds of Formula 3 have a hydroxyl value greater than 35 and an acid value of less than 0.2 or less than 0.15.

[0173] In some aspects, the lubricating composition comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl and the base oil is selected from the group consisting of polyalphaolefins (PAOs), synthetic esters such as polyol esters, polyalkylene glycols (PAGs), oil soluble polyalkylene glycols (OSPs), mineral oils (Groups I, II, and III), fatty acid esters, and mixtures thereof, and the compounds of Formula 3 have a hydroxyl value greater than 35 and an acid value of less than 0.2 or less than 0.15.

[0174] In some aspects, the lubricating composition comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl and the base oil comprises a polyalphaolefin (PAO), and the Compounds of Formula 3 have a hydroxyl value greater than 35.

[0175] In some aspects, the lubricating composition comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl, the base oil comprises a polyalphaolefin (PAO) and has a hydroxyl value between 35 and 70.

[0176] In some aspects, the lubricating composition comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl, and wherein the base oil has an oxidation induction time (OIT) is improved by 25% as determined according to ASTM D8206 at 160°C and wherein the base oil does not contain any additional additives or antioxidants.

[0177] In some aspects, the lubricating composition comprises 2% to 8% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl, and wherein the base oil has an oxidationinduction time (OIT) is improved by 25% as determined according to ASTM D8206 at 160°C and wherein the base oil does not contain any additional additives or antioxidants.

[0178] In some aspects, the lubricating composition comprises 2% to 8% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl, and wherein the base oil has an oxidation induction time (OIT) is improved by 25% as determined according to ASTM D8206 at 160°C and wherein the base oil does not contain any additional additives or antioxidants.

[0179] In some aspects, the lubricating composition 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl, and wherein the base oil has an oxidation induction time (OIT) is improved by 25% as determined according to ASTM D8206 at 160°C and wherein the base oil does not contain any additional additives or antioxidants.

[0180] In some aspects, the lubricating composition comprises 2% to 9.9% of one or more compounds of the Formula 1 and the base oil is improved by 25% as determined according to ASTM D8206 at 160°C.

[0181] In some aspects, the lubricating composition comprises a base oil and additives wherein the base oil comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl and the base oil has an OIT is improved by 25% as determined according to ASTM D8206 at 160°C.

[0182] In some aspects, the lubricating composition comprises a base oil and additives wherein the base oil comprises a PAO and 2% 9.9% to of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl and the base oil has an OIT is improved by 25% as determined according to ASTM D8206 at 160°C.

[0183] In some aspects, the lubricating composition comprises a base oil wherein the base oil comprises 0.5 - 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl.

[0184] In some aspects, the lubricating composition comprises a base oil wherein the base oil comprises 0.5 - 9.9% of one or more compounds of the Formula 1 wherein R is C1-C22 alkyl, R2 is a saturated or unsaturated C7 or C9 alkyl; and R3 is a Ce or alkyl.

[0185] In some aspects, the lubricating composition comprises a base oil and additives wherein the base oil comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl.

[0186] In some aspects, the lubricating composition comprises a base oil and additives wherein the base oil comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein Ris 2-ethylhexyl and the base oil is selected from the group consisting of polyalphaolefins (PAOs), synthetic esters such as polyol esters, polyalkylene glycols (PAGs), oil soluble polyalkylene glycols (OSPs), mineral oils (Groups I, II, and III), fatty acid esters, and mixtures thereof.

[0187] In some aspects, the lubricating composition comprises a base oil and additives wherein the base oil comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl and the base oil comprises a polyalphaolefin (PAO).

[0188] In some aspects, the lubricating composition comprises a base oil wherein the base oil comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl and the base oil selected from the group consisting of polyalphaolefins (PAOs), synthetic esters such as polyol esters, polyalkylene glycols (PAGs), oil soluble polyalkylene glycols (OSPs), mineral oils (Groups I, II, and III), fatty acid esters, and mixtures thereof, and has a hydroxyl value greater than 10.

[0189] In some aspects, the lubricating composition comprises a base oil wherein the base oil comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl and further comprises a polyalphaolefin (PAO) and the base oil has a hydroxyl value greater than 35.

[0190] In some aspects, the lubricating composition comprises a base oil wherein the base oil comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl and the base oil comprises a polyalphaolefin (PAO) and the compounds of Formula 3 have a hydroxyl value greater than 35.

[0191] In some aspects, the lubricating composition comprises a base oil and additives wherein the base oil comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl and the base oil is selected from the group consisting of polyalphaolefins (PAOs), synthetic esters such as polyol esters, polyalkylene glycols (PAGs), oil soluble polyalkylene glycols (OSPs), mineral oils (Groups I, II, and III), fatty acid esters, and mixtures thereof, and the compounds of Formula 3 have a hydroxyl value greater than 35.

[0192] In some aspects, the lubricating composition comprises a base oil wherein the base oil comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl and the base oil comprises a polyalphaolefin (PAO) and the compounds of Formula 3 have a hydroxyl value greater than 35 and an acid value of less than 0.2 or less than 0.15.

[0193] In some aspects, the lubricating composition comprises a base oil and additives wherein the base oil comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein Ris 2-ethylhexyl and the base oil is selected from the group consisting of polyalphaolefins (PAOs), synthetic esters such as polyol esters, polyalkylene glycols (PAGs), oil soluble polyalkylene glycols (OSPs), mineral oils (Groups I, II, and III), fatty acid esters, and mixtures thereof, and the compounds of Formula 3 have a hydroxyl value greater than 35 and an acid value of less than 0.2 or less than 0.15.

[0194] In some aspects, the lubricating composition comprises a base oil wherein the base oil comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl and the base oil comprises a polyalphaolefin (PAO), and the Compounds of Formula 3 have a hydroxyl value greater than 35.

[0195] In some aspects, the lubricating composition comprises a base oil and additives wherein the base oil comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl, the base oil comprises a polyalphaolefin (PAO) and has a hydroxyl value between 35 and 70.

[0196] In some aspects, the lubricating composition comprises a base oil and additives wherein the base oil comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl, and wherein the base oil has an oxidation induction time (OIT) is improved by 25% as determined according to ASTM D8206 at 160°C and wherein the base oil does not contain any additional additives or antioxidants.

[0197] In some aspects, the lubricating composition comprises a base oil and additives wherein the base oil comprises 2% to 8% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl, and wherein the base oil has an oxidation induction time (OIT) is improved by 25% as determined according to ASTM D8206 at 160°C and wherein the base oil does not contain any additional additives or antioxidants.

[0198] In some aspects, the lubricating composition comprises a base oil and additives wherein the base oil comprises 2% to 8% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl, and wherein the base oil has an oxidation induction time (OIT) is improved by 25% as determined according to ASTM D8206 at 160°C and wherein the base oil does not contain any additional additives or antioxidants.

[0199] In some aspects, the lubricating composition comprises a base oil and additives wherein the base oil comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl, and wherein the base oil has an oxidation induction time (OIT) is improved by 25%as determined according to ASTM D8206 at 160°C and wherein the base oil does not contain any additional additives or antioxidants.

[0200] In some aspects, the lubricating composition comprises a base oil and additives wherein the base oil comprises 2% to 9.9% of one or more compounds of the Formula 1 and the base oil is improved by 25% as determined according to ASTM D8206 at 160°C.

[0201] In some aspects, the lubricating composition comprises a base oil and additives wherein the base oil comprises 2% to 9.9% of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl and the base oil has an OIT is improved by 25% as determined according to ASTM D8206 at 160°C.

[0202] In some aspects, the lubricating composition comprises a base oil and additives wherein the base oil comprises a PAO and 2% 9.9% to of one or more compounds of the Formula 3 wherein R is 2-ethylhexyl and the base oil has an OIT is improved by 25% as determined according to ASTM D8206 at 160°C.

[0203] In one aspect, the compounds of Formula 1 or the compounds of Formula 3 can be present as a mixture of oligomers wherein with the majority of the oligomers contain between 2 and 6 units and greater than 50% of the oligomers contain 3 or more units.

Claims

CLAIMS1. A lubricating composition comprising:0.5%-9.9% by weight of one or more compounds of the Formula 1 :wherein n is an integer from 2-6; R is C1-C22 alkyl; R2 is C3-C12 alkyl; R3 is hydrogen or Ci- C10 alkyl.

2. The composition of claim 1 comprising 2-8% of the compounds of Formula 1.

3. The composition of claim 2, wherein the compounds of Formula 1 have an acid value of less than 0.25 or an acid value between 0.05 and 0.2.

4. The composition of claims 1-3, wherein the compounds of Formula 1 have a hydroxyl value of greater than 35 or a hydroxyl value between 35 and 70.

5. The composition of any of claims 1-4, wherein the lubricating composition comprises a base oil selected from the group consisting of polyalphaolefins (PAOs), synthetic esters such as polyol esters, polyalkylene glycols (PAGs), oil soluble polyalkylene glycols (OSPs), mineral oils (Groups I, II, and III), fatty acid esters, and mixtures thereof.

6. The composition of claim 5, wherein the base oil comprises a polyalphaolefin.

7. The composition of claim 1, further comprising one or more compounds of Formula 4:wherein, n is an integer from 2-6; R is C1-C22 alkyl; R2 is C3-C12 alkyl; R3 is hydrogen or Ci- C10 alkyl, and R4 is C1-C22 acyl.

8. The composition of claim 7, wherein R is 2-ethylhexyl and R4 is Cis acyl.

9. The lubricating composition of claim 1, comprising 0.5% - 9.9% by weight of one or more compounds of the Formula 3:wherein n is an integer from 2-6 and R is C1-C22 alkyl.

10. The composition of claim 9, wherein R is 2-ethylhexyl.

11. The composition of claims 9 and 10, wherein the compounds of Formula 1 have an acid value of less than 0.25 or an acid value between 0.05 and 0.2.

12. The composition of claims 9-11, wherein the compounds of Formula 1 have a hydroxyl value of greater than 35 or a hydroxyl value between 35 and 70.

13. The composition of any of claims 9-12, further comprising a base oil selected from the group consisting of polyalphaolefins (PAOs), synthetic esters such as polyol esters, polyalkylene glycols (PAGs), oil soluble polyalkylene glycols (OSPs), mineral oils (Groups I, II, and III), fatty acid esters, and mixtures thereof.

14. The composition of claim 13, wherein the base oil comprises a polyalphaolefin.

15. The composition of any of claims 9-14, further comprising one or more compounds of Formula 4:wherein, n is an integer from 2-6; R is C1-C22 alkyl; R2 is C3-C12 alkyl; 3 is hydrogen or Ci- C10 alkyl, and R4 is C1-C22 acyl.

16. The composition of claim 15, wherein R is 2-ethylhexyl and R4 is Cis acyl.

17. A method of reducing the traction of a base oil comprising including in the base oil any of the compounds of the preceding claims.

18. A method of lubricating two surfaces comprising contacting the interface of the surfaces with a lubricating composition of any of claims 1-16.

19. The method of claim 18, wherein the surfaces are part of hydraulic system.

20. The method of claim 18, wherein the surfaces are gears.

21. The method of claim 18, wherein the gears are in an industrial gear box, marine gear box, vehicle gear box, or vehicle transmission.

22. A lubricating composition comprising a base oil wherein: the base oil comprises 0.5%-9.9% by weight of one or more compounds of the Formula 1 :wherein n is an integer from 2-6; R is C1-C22 alkyl; R2 is C3-C12 alkyl; R3 is hydrogen or Ci- C10 alkyl.

23. The composition of claim 22, wherein the base oil comprises 2-8% of the compounds of Formula 1.

24. The composition of claim 23, wherein the compounds of Formula 1 have an acid value of less than 0.25 or an acid value between 0.05 and 0.2.

25. The composition of claims 22-24, wherein the compounds of Formula 1 have a hydroxyl value of greater than 35 or a hydroxyl value between 35 and 70.

26. The composition of any of claims 22-25, wherein the base oil selected from the group consisting of polyalphaolefins (PAOs), synthetic esters such as polyol esters, polyalkylene glycols (PAGs), oil soluble polyalkylene glycols (OSPs), mineral oils (Groups I, II, and III), fatty acid esters, and mixtures thereof.

27. The composition of claim 26, wherein the base oil comprises a polyalphaolefin.

28. The composition of claim 22, wherein the base oil further comprises one or more compounds of Formula 4:wherein, n is an integer from 2-6; R is C1-C22 alkyl; R2 is C3-C12 alkyl; 3 is hydrogen or Ci- C10 alkyl, and R4 is C1-C22 acyl.

29. The composition of claim 28, wherein R is 2-ethylhexyl and R4 is Cis acyl.

30. The lubricating composition of claim 22, wherein the base oil comprises 0.5% - 9.9% by weight of one or more compounds of the Formula 3 :wherein n is an integer from 2-6 and R is C1-C22 alkyl.

31. The composition of claim 22, wherein R is 2-ethylhexyl.

32. The composition of claims 22 and 23, wherein the compounds of Formula 1 have an acid value of less than 0.25 or an acid value between 0.05 and 0.2.

33. The composition of claims 22-24, wherein the compounds of Formula 1 have a hydroxyl value of greater than 35 or a hydroxyl value between 35 and 70.

34. The composition of any of claims 22-24, wherein the base oil selected from the group consisting of polyalphaolefins (PAOs), synthetic esters such as polyol esters, polyalkylene glycols (PAGs), oil soluble polyalkylene glycols (OSPs), mineral oils (Groups I, II, and III), fatty acid esters, and mixtures thereof.

35. The composition of claim 24, wherein the base oil comprises a polyalphaolefin.

36. The composition of any of claims 22-25, wherein the base oil further comprises one or more compounds of Formula 4:wherein, n is an integer from 2-6; R is C1-C22 alkyl; R2 is C3-C12 alkyl; i is hydrogen or Ci- C10 alkyl, and R4 is C1-C22 acyl.

37. The composition of claim 36, wherein R is 2-ethylhexyl and R4 is Cis acyl.

38. A method of reducing the traction of a base oil comprising including in the base oil any of the compounds of the preceding claims.

39. A method of lubricating two surfaces comprising contacting the interface of the surfaces with a lubricating composition of any of the compounds of the preceding claims.

40. The method of claim 39, wherein the surfaces are part of hydraulic system.

41. The method of claim 39, wherein the surfaces are gears.

42. The method of claim 39, wherein the gears are in an industrial gear box, marine gear box, vehicle gear box, or vehicle transmission.

43. The use of any of the compounds of Formula 1 or Formula 3 as a friction modifier.

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