Bio-based lubricants

Abstract

This disclosure relates to a novel bio-based lubricant composition having high oxidation stability for use in all lubrication applications such as gears, motors, and hydraulics. More specifically, the lubricant composition comprises a base oil and one or more additives, wherein the base oil comprises more than 10% by weight of one or more compounds of formula 1, where n is an integer from 2 to 6 and R is C1 to C1. 22 It is alkyl, and R2 is C3~C 12 It is an alkyl group, and R3 is hydrogen or C1-C 10 It is alkyl. [Formula 1] JPEG2026513173000028.jpg18128

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims the interests of U.S. Provisional Patent Application No. 63 / 492,655, filed on 28 March 2023, which is incorporated herein by reference in its entirety.

[0002] This disclosure relates to bio-based lubricants that can be used in a variety of industrial applications, including gear, engine, and transmission applications. The use of bio-based components is increasingly preferred to reduce the carbon footprint of industrial products. [Background technology]

[0003] The lubricants (engine and non-engine) and process fluid industries are increasingly seeking bio-based and biodegradable materials. Bio-based means that the materials described herein are derived from sustainable plant sources, as opposed to non-renewable or sustainable sources such as petroleum. Biodegradability means that lubricants and process fluids (hereinafter, "fluids") have the ability to decompose in the natural environment over a period of time, which can be measured by tests such as those published by the Organisation for Economic Co-operation and Development (OECD). Renewable bio-based products, by definition, contain high levels of renewable carbon, and standards are being set to promote increasingly higher levels of renewables. For example, the European ecolabel now emphasizes that hydraulic fluids should be biodegradable and preferably contain at least 50 weight percent renewable carbon.

[0004] Researchers have attempted to meet requirements or recommendations for both biodegradability and renewables by incorporating various types of natural oils into their fluid formulations. Particularly useful are natural esters, including, for example, canola oil, sunflower oil, rapeseed oil, and palm oil, which have a renewable carbon level of 100 percent. Unfortunately, these natural esters often have poor performance at low temperatures and poor oxidation stability. Poor temperature performance is related to a relatively high pour point, which is the highest temperature at which the material stops flowing and is often a result of a significant increase in viscosity caused by crystallization. Another problem with natural esters is that they tend to have commercially undesirable levels of thermal oxidation stability, which is partly due to unsaturation in the acid fraction of their chemical structure.

[0005] In some cases, synthetic esters can be used as substitutes for natural esters. Synthetic esters may, in some cases, have very low pour points (below -50°C) and commercially desirable levels of thermal oxidation stability. However, most synthetic esters are derived from petrochemical feedstocks and therefore have very low (less than 50% by weight), or even zero, renewable carbon levels. Furthermore, they are far more expensive than natural esters and are therefore economically undesirable for many applications.

[0006] However, despite these challenges, there remains a strong motivation to produce fluids with commercially desirable levels of biodegradability and renewable carbon, as well as excellent oxidation stability. Lubricating fluids with exceptional oxidation stability offer longer service lives and limit or eliminate the need for other antioxidant additives. Increased service life offers clear benefits to end users by limiting or reducing downtime due to the need to change the lubricant.

[0007] Natural-based solutions are continuing to evolve, but the desire to discover new formulations with exceptional stability persists. Antioxidant additive packages are expensive and can be consumed during their service life. Therefore, base oils that are more resistant to oxidation can limit or avoid the use of expensive antioxidant packages. SUMMARY OF THE INVENTION

[0008] The concept of reacting a hydroxy-substituted fatty acid with itself to form a polymeric structure is known in the art, for example, by teaching that the hydroxyl value of the preferred compound should be as low as possible (WO / 2011 / 037778A1). Generally, prior art structures are reacted by "end-capping" any residual hydroxyl groups. The Applicants have surprisingly discovered that end-capping is unnecessary and actually harmful to the oxidative stability of these compounds.

[0009] The compositions described herein exhibit surprisingly high oxidative stability and still maintain a high level of renewable carbon content. In some situations, aspects of the invention show an unprecedented increase in stability of 7 to 12 times or more compared to comparable materials. This level of stability of the bio-based materials is unique and highly valuable to the end-user. Furthermore, the compounds of formula 1 are less expensive and easier to manufacture than currently available alternatives.

[0010] A lubricating composition comprising a base oil is disclosed, the base oil comprising 10 to 100% of one or more compounds of formula 1,

[0011]

Chemical formula

[0012] The lubricating composition may contain a base oil comprising 10% to 100% of the compound of formula 1. The lubricating composition may also contain 50% to 100% of the base oil.

[0013] The lubricating composition may contain a base oil having a hydroxyl value greater than 20. The lubricating composition may contain a base oil having a hydroxyl value of 30 to 70. The lubricating composition may contain a base oil, the base oil containing one or more compounds of formula 1, the one or more compounds of formula 1 having a hydroxyl value greater than 20. The lubricating composition may contain a base oil, the base oil containing one or more compounds of formula 1, the one or more compounds of formula 1 having a hydroxyl value of 30 to 70. The lubricating composition may contain one or more additives selected from the group consisting of friction modifiers, viscosity modifiers, antioxidants, wear-resistant additives, extreme pressure additives, defoamers, anti-emulsifiers, and corrosion inhibitors. [Brief explanation of the drawing]

[0014] [Figure 1] The GPC data for an example of this disclosure (Example 11B) is shown, illustrating the polymer distribution of the material. [Modes for carrying out the invention]

[0015] Next, we will refer in detail to specific aspects of the disclosed subject matter. The disclosed subject matter will be described together with the enumerated claims, but it will be understood that the illustrative subject matter is not intended to limit the claims to the disclosed subject matter. One aspect described together with a particular aspect is not necessarily limited to that aspect and may be implemented together with any other aspect.

[0016] Throughout this specification, values ​​expressed in range form should be interpreted flexibly to include not only the numerical values ​​explicitly listed as limits to the range, but also all individual numerical values ​​or subranges contained within that range, as if each numerical value and subrange were explicitly listed. For example, the range "0.1% to 5%" or "0.1% to 5%" shall be interpreted to include not only 0.1% to 5%, but also the individual values ​​within the indicated range (e.g., 1%, 2%, 3%, and 4%), as well as subranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%).

[0017] As used herein, the singular forms “a,” “an,” and “the,” as well as similar referents in contexts describing elements (particularly in the context of the following claims), include multiple referents unless the context explicitly indicates otherwise. For example, a reference to “a substituent” includes a single substituent as well as two or more substituents. Unless otherwise indicated herein or unless explicitly contradicted by the context, any singular term may include its plural counterpart and vice versa.

[0018] As used herein, the following terms have the following meanings unless expressly stated otherwise:

[0019] The term "or" is used to refer to a non-exclusive "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] Furthermore, it should be understood that any expressions or terms used herein, unless otherwise defined, are for illustrative purposes only and not intended to be restrictive. The use of any section headings is intended to aid in the reading of this document and should not be interpreted as restrictive. Information related to a section heading may be located within or outside that particular section. Any publications, patents, and patent documents referenced herein are incorporated herein in whole by reference as if they were incorporated individually by reference. Where there is inconsistency in use between this document and the documents thus incorporated by reference, the use in the incorporated references should be interpreted as supplementing the use in this document. In the event of irreconcilable conflict, the use in this document shall prevail.

[0021] As used herein, the terms “for example,” “for instance,” “such as,” or “including” are intended to introduce examples that further clarify a more general issue. Unless otherwise noted, these examples are provided solely to aid in understanding the uses illustrated in this disclosure and are not intended to limit them in any way.

[0022] In the methods described herein, the actions may be performed in any order without departing from the principles of this disclosure, unless a temporal or operational order is explicitly enumerated. Furthermore, certain actions may be performed in parallel unless explicitly stated to be performed separately by the wording of the claims. For example, the claimed action of performing X and the claimed action of performing Y may be performed simultaneously within a single operation, but the resulting process falls within the literal scope of the claimed process.

[0023] As used herein, the term “substantially” means 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 a majority or most of the portion, such as 100%.

[0024] As used herein, the term "alkyl" means a saturated or unsaturated, branched or linear monovalent or divalent hydrocarbon group derived by removing one or two hydrogen atoms from a carbon atom of a parent alkane, alkene, or alkyne. In some embodiments, one or more alkyl groups are substantially saturated. In some embodiments, one or more alkyl groups are fully or partially saturated.

[0025] C1~C 22 Alkyl, C3~C 12 , and C1~C 10 The term alkyl refers to alkyl groups containing 1 to 22, 3 to 12, and 1 to 10 carbon atoms. Any similar numerical ranges should be considered similarly. In some embodiments, alkyl groups may be branched. In other embodiments, alkyl groups may be unbranched or linear. In other embodiments, alkyl groups may be a mixture of branched and unbranched. One or more alkyl groups may be saturated, unsaturated, or a mixture thereof. In other embodiments, alkyl groups may be substituted, unsubstituted, or a mixture thereof.

[0026] As used herein, the term “substituted” means that one of the hydrogen atoms of an alkyl chain is replaced by another substituent. In some embodiments, the alkyl group is substituted at one or more positions by a hydroxyl, amino, dialkylamino, alkylacetylated hydroxyl, alkyl ester, or alkyl ether substituent. In some embodiments, the alkyl group is substituted with a hydroxyl or alkylacetylated hydroxyl group.

[0027] As used herein, the term “base oil” refers to the primary lubricating component of a lubricant formulation that does not contain additional performance additives. Depending on the specific needs of the intended application, the base oil may be a single lubricating component or a mixture of multiple lubricating components.

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

[0029] In 1975, the International Organization for Standardization (ISO), in collaboration with the American Society for Testing and Materials (ASTM), the Society of Tribologists and Lubrication Engineers (STLE), the British Organization for Standardization (BSI), and the German Institute for Industrial Standards (DIN), decided on an approach to minimize confusion. This is known as the International Organization for Standardization viscosity grade, or ISO VG for short. This classification defines 20 viscosity grades ranging from 2 to 3200 square millimeters / second (1 mm² / s = 1 cSt) at 40°C (104°F). For petroleum-based liquids, this roughly covers the range from kerosene to cylinder oil.

[0030] Each viscosity grade is specified by the integer closest to its midpoint kinematic viscosity in mm² / s at 40°C (104°F), with a range of + / - 10 percent of this value being acceptable. The following are 20 viscosity grades, each with its own appropriate limits.

[0031] [Table 1]

[0032] The classification is based on the principle that the midpoint (nominal) kinematic viscosity of each grade must be approximately 50 percent greater than that of the previous grade. For example, ISO 100 oil is defined as oil with a kinematic viscosity of 90 cSt to 110 cSt at 40°C, and ISO 320 oil is defined as oil with a kinematic viscosity of 288 cSt to 352 cSt at 40°C.

[0033] Compound of formula 1:

[0034]

Chem.

[0035] In some embodiments, the compound of formula 1 is one in which R is C3-C 12 alkyl. In other embodiments, R is branched C6-C 10 alkyl. In other embodiments, R is 2-ethylhexyl.

[0036] In some embodiments, the compound of formula 1 is one in which R2 is C5-C 11 alkyl. In other embodiments, R2 is linear saturated or unsaturated C7-C 11 alkyl. In other embodiments, R2 is linear C 11 alkyl.

[0037] In some embodiments, the compound of formula 1 is one in which R3 is branched C4-C 12 alkyl. In other embodiments, R3 is linear C4-C8 alkyl. In other embodiments, R3 is linear C6 alkyl.

[0038] In some embodiments, the compound of formula 1 is one in which R is 2-ethylhexyl, R2 is linear C9 alkyl, and R3 is linear C6 alkyl.

[0039] In one embodiment, a subset of the compounds of formula 1 can be represented as compounds of formula 3.

[0040]

Chem.

[0041] Preparation of the compounds of formula 1 and 3: The compounds of formulas 1 and 3 can be prepared by oligomerization of hydroxy-substituted fatty acids (or mixtures of hydroxy-substituted fatty acids) and subsequent esterification of the remaining acid group with an alcohol. Hydroxy-substituted fatty acids are known in the art, commercially available, and can be prepared by those skilled in the art. As shown in the examples, the compounds of formula 1 can be prepared using 12-hydroxystearic acid and 10-hydroxystearic acid. Any enantiomer of hydroxystearic acid, or a mixture thereof, is functional in this disclosure. Other hydroxy-substituted fatty acids are known in the art and can be prepared, for example, by epoxidation of an unsaturated fatty acid followed by reductive ring-opening to obtain a variety of monohydroxy fatty acid residues. 10-hydroxystearic acid (CAS: 638-26-6) is known in the art and can be purchased or prepared by enzymatic treatment of oleic acid. 12-Hydroxystearic acid (CAS: 106-14-9) can be derived directly from castor oil and is commercially available from various companies such as Gokl Overseas, Jayant Agro-Organics Ltd, De Monchy UK Ltd, Acme Hardesty, or Hampshire Commodities Ltd. Since commercially available 12-hydroxystearic acid is derived from castor oil, it typically contains some amount of stearic acid as an impurity. Representative examples of commercially available 12-hydroxystearic acid are shown in the examples.

[0042] Hydroxy-substituted fatty acids, or mixtures of acids, can be oligomerized at high temperatures using tin, titanium, or nitrogen-containing catalysts, and the resulting water is removed. The reaction typically proceeds in the absence of a solvent, although a small amount of solvent may be used optionally. Water removal can be achieved by entrainer, reduced pressure, and / or nitrogen sparging. The result of this process is an oligomerized acid containing a distribution of the compound of formula 2, as follows:

[0043] [ka] n is an integer between 2 and 6, and R2 is C3 to C 12 It is an alkyl group, and R3 is hydrogen or C1-C 10 It is alkyl.

[0044] The progress of oligomerization can be tracked by the decrease in the acid value of the reactants. The degree of oligomerization can be limited by the presence of other fatty acids in the starting materials that effectively end-cap the reactive hydroxyl groups. For example, typically, the distribution is achieved such that the majority of oligomers contain 2 to 6 units, and more than 50% contain 3 or more units. However, stopping oligomerization earlier results in a smaller average polymer size (molar weight) and lower viscosity. Conversely, further oligomerization results in a higher average molecular weight and higher viscosity. Depending on the application, either result may be desired. Figure 1 shows the GPC distribution of Example 11B of this disclosure. Furthermore, pre-oligomerized hydroxy fatty acids such as Hypermer LP1 from Croda are also commercially available.

[0045] Next, the compound of formula 2 can be esterified by reaction with a linear or branched alcohol having 1 to 22 carbon atoms. In certain embodiments, the alcohol may be selected from methanol, ethanol, isopropanol, butanol, 2-ethylhexanol, 2-(2-butoxypropoxy)propan-1-ol (DPnB), 1-decanol, 1-octanol, 2-octanol, and Isofol 18 (2-octyldecyl). At this point, an additional tin, titanium, nitrogen, or acid-containing catalyst may be used to remove the formed water and obtain an esterification product of formula 1 having an AV of less than 1.0 KOH / g or less than 0.2 mg KOH / g.

[0046] Alternatively, the compound of formula 1 can be prepared in a single pot by directly reacting a hydroxy fatty acid with an alcohol. In this case, the hydroxy fatty acid is heated under nitrogen in the presence of an excess alcohol. A catalyst such as TNBT is typically added midway through the reaction to reach an AV of less than 0.2 mg KOH / g.

[0047] The base oil may further contain one or more compounds of formula 4,

[0048] [ka] n is an integer from 2 to 6, and R is C1 to C 22 It is alkyl, and R2 is C3~C 12 It is an alkyl group, and R3 is hydrogen or C1-C 10 It is alkyl, and R4 is C1~C 22 It is an acyl. In some embodiments, the compound of formula 4 is such that R is 2-ethylhexyl, R4 is a C18 acyl, R2 is a linear C9 alkyl, and R3 is a linear C6 alkyl.

[0049] The compound of Formula 1 can be used as a base oil in the preparation of lubricant compositions useful as hydraulic fluids, for example, according to the following specifications (ISO 6743-4, ISO 15380, and DIN 51517-3).

[0050] Compounds of formulas 1 and 3 can be used as base oils in the preparation of lubricant compositions useful for lubricating the interface between two mechanical surfaces. The interface can be any two surfaces requiring lubrication, such as, but not limited to, gears, motors, drilling, grinding, and hydraulic surfaces. In some embodiments, the lubricant is gear oil. The gear oil can be either automotive or industrial gear oil. Automotive gear oils include those suitable for use in manual transmissions, transfer cases, and differentials (all of which typically use hypoid gears). A transfer case refers to a part of a four-wheel drive system found in four-wheel drive and all-wheel drive systems. It is connected to the transmission and also to the front and rear axles by drive shafts. It is also called a transfer gear case, transfer gearbox, transfer box, or jockey box in the literature. Industrial gear oils include those suitable for use in spur gears, helical gears, bevel gears, hypoid gears, and worm gears. In particular, those suitable for use in wind turbine gearboxes, which typically have helical gears, are included.

[0051] Automotive gear oils typically have viscosities ranging from SAE 50 to SAE 250, and more commonly from SAE 70W to SAE 140. Suitable automotive base oils also include cross-grades such as 75W-140, S0W-90, 85W-140, and 85W-90. Automotive gear oils are classified by the American Petroleum Institute (API) using GL grades. The API classification subdivides all transmission oils into six classes as follows:

[0052] API GL-1 oils are for light conditions. They consist of base oils without additives. They may contain small amounts of antioxidants, corrosion inhibitors, defoaming additives. API GL-1 oils are designed for spiral bevel gears, worm gears, and manual transmissions without synchronizers in trucks and agricultural machinery.

[0053] API GL-2 is an oil for moderate conditions. It contains anti-wear additives and is designed for worm gears. Proper lubrication of tractor and agricultural machinery transmissions is recommended.

[0054] API GL-3 is a lubricant for moderate conditions and contains up to 2.7% anti-wear additives. It is designed to lubricate bevel gears and other gears in truck transmissions. These are not recommended for hypoid gears.

[0055] API GL-4 oils are suitable for a wide range of conditions—light to heavy. They contain up to 4.0% effective anti-scuffing additives. They are designed for bevel and hypoid gears with small axle displacement, truck gearboxes, and axle units. They are recommended for asynchronous gearboxes in US trucks, tractors, and buses, and for main gears and other gears in all vehicles. These oils form the basis of synchronous gearboxes, particularly in Europe.

[0056] API GL-5 is an oil for heavy-duty applications. It contains up to 6.5% effective anti-scuffing additives. A common application of this class of oil is in hypoid gears with large shaft displacements. These are recommended as general-purpose oils for all other units of mechanical transmissions (except the gearbox). This class of oil may only be used in synchronous manual gearboxes with special approval from the vehicle manufacturer. API GL-5 oil may be used in limited-slip differentials if they meet the requirements of specification MIL-L-2105D or ZF TE-ML-05. In this case, the class designation is different, e.g., API GL-5+ or API GL-5 LS.

[0057] API GL-6 oils are designed for extremely harsh conditions (high-speed slip and significant impact loads). They contain up to 10% high-performance anti-scuffing additives. They are designed for hypoid gears with large shaft displacements. Since API GL-5 is considered to adequately meet the most stringent requirements, API GL-6 is often no longer applicable.

[0058] Most modern gearboxes require GL-4 oil, and any additional differential (if installed) requires GL-5 oil.

[0059] The specifications for industrial gear oils are primarily managed by the American Gear Manufacturers Association (AGMA) in North America or by individual manufacturers. Typical specifications for industrial gear oils in the United States are shown in Table 1 below.

[0060] [Table 2]

[0061] In Europe and most of the rest of the world, specifications for industrial gear oils are typically written by the German Industrial Standards Association (e.g., DIN 51517-3).

[0062] Lubricant compound Compounds of formulas 1, 3, and 4, or mixtures thereof, can be incorporated into lubricating compositions by combining them with additional base oils and / or additives. The preparation of lubricating compositions is known in the art, and any effective method can be used. Typically, the components in the formulation are mixed at ambient temperature or high temperature. Mixing may be carried out in batch or continuous order as desired. In certain embodiments, the lubricating composition contains one or more additives known to those skilled in the art, such as friction modifiers, viscosity modifiers, antioxidants, anti-wear additives, extreme pressure additives, defoamers, anti-emulsifiers, and corrosion inhibitors. Additives are typically included in the final formulation at levels of 1 to 20%, depending on the specific application and user needs. Additives may be included separately or as part of what is known in the art as an additive pack. An additive pack is a commercially available mixture of additives formulated by suppliers for inclusion in a particular base oil and for a particular application. In some embodiments, the lubricating composition contains 1% to 10% by weight of additives. In some embodiments, the lubricating composition contains 2% to 6% by weight of additives.

[0063] Additional base oils used in the compositions of the present disclosure may be obtained from natural oils or synthetic oils, or blends thereof, and may be incorporated into the final base oil formulation, provided that the lubricant has a viscosity suitable for use in the desired application. Gear oils for such use may be mineral oil-based stocks such as conventional and solvent-refined paraffinic neutral and bright stocks, hydrogenated paraffinic neutral and bright stocks, naphthenic oils, cylinder oils, and include straight-run oils and blended oils.

[0064] In certain embodiments, the base oil comprises a blend of one or more base oils of formulas 1, 3, and 4 with at least one other base oil. In some embodiments, 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.

[0065] For example, synthetic base stocks such as PAO, alkylated aromatics, polybutenes, diesters, polyol esters, polyglycols, polyphenyl ethers, and blends thereof can also be used in the implementation of the present invention. Polyalphaolefins are typically produced from C8-C14 olefins, and the results are generally combinations of dimers, trimers, tetramers, pentamers, etc. It is also known that PAO and esters are blended with mineral oil to form semi-synthetic products. Synthetic base oils, particularly base oils having PAO or a mixture of PAOs as the main component, are preferred. PAOs are well known, and Chevron-Synfluid, Exxon-Spectrasyn, INEOS-Durasyn, etc. are readily available. Synthetic esters are also well known, such as Oleon-Radialube, NYCO-NYCOBASE, Lanxess-Hatcol, and Exxon-Esterex. Those skilled in the art are familiar with the technical properties of these materials and how to blend them to achieve the desired results.

[0066] The compounds of Formula 1 may be used as base oils in the preparation of final lubrication formulations. The compounds of Formula 1 may constitute all or substantially all of the base oil, or all or substantially all of the final lubrication formulation. In some embodiments, the base oil contains one or more of the compounds of Formula 1 in an amount greater than 10%. In some embodiments, the compounds of Formula 1 constitute 10-100%, 10-85%, 10-95%, 20-75%, 20-75%, or 50-100% of the base oil or lubrication composition.

[0067] The compound of Formula 3 may be used as a base oil in the preparation of the final lubrication formulation. The compound of Formula 3 may constitute all or substantially all of the base oil, or all or substantially all of the final lubrication formulation. In some embodiments, the base oil contains one or more of the compounds of Formula 3 in an amount greater than 10%. In some embodiments, the compound of Formula 3 constitutes 10-100%, 10-85%, 10-95%, 20-75%, or 50-100% of the base oil or lubrication composition.

[0068] In some embodiments, the base oil comprises one or more compounds of formula 1 in more than 10% and further comprises one or more compounds of formula 4. In some embodiments, the base oil comprises one or more compounds of formula 3 in more than 10% and further comprises one or more compounds of formula 4. [Examples]

[0069] [Table 3]

[0070] The commercially available 12-hydroxystearic acid used had the following fatty acid composition, as shown in Table 3.

[0071] [Table 4]

[0072] Examples 1A-F A 2000 mL five-necked round-bottom flask equipped with a PTFE centrifugal stirrer, a magnetically sealed stirrer guide, a temperature feedback probe and isomanttle, nitrogen inlet and outlet via a distillation head, a Liebig condenser, a receiving flask and outlet bubbler, was filled with 12-hydroxystearic acid (450 g, 1.44 mol; 1.98 equivalents), and the contents were purged with N2 (15 mL). -1The mixture was heated to 190°C while stirring (420 rpm) until it melted. When the reaction temperature was reached, a vacuum of 200 mbar was applied (while maintaining a nitrogen purge). After 1.5 hours, the pressure was reduced to 50 mbar, and after 2.5 hours, the reactants were cooled and the AV was measured at 78.0 mg KOH / g. The reaction was restarted and continued for another 30 minutes to obtain an AV of 70.7 mg KOH / g. The reactants were cooled to a temperature lower than the expected esterification reaction temperature, and the distillation head was replaced with a Dean-Stark trap equipped with a vertical double-surface Liebig condenser. 2-ethylhexane-1-ol (2-EH, 95.0 g, 0.72 mol, 1 equivalent) was added to the reaction vessel, and an additional 33 mL of 2-EH was packed into the Dean-Stark trap. The reactants were heated to 190°C, and a vacuum was applied while taking care to achieve a stable reflux of 2-EH into the trap. Reflux was maintained during the reaction by reducing the pressure as needed. After 8 hours under reaction conditions (total reaction time 11 hours), the AV was measured to be 7.0 mg KOH / g. Catalyst (TNBT, 0.2 mL) was added, and the reaction proceeded for a further 5.5 hours (total reaction time 16.5 hours), after which the AV of the reaction reached <0.2 mg KOH / g. The reaction temperature was adjusted to 125°C, and excess 2-EH was removed through a trap under a complete vacuum. When the distillation of 2-EH stopped, the trap was replaced with a simple distillation arm, 5 g of decolorized carbon was added to the reaction vessel, and the nitrogen headspace purge was replaced with a sparge positioned as low as possible in the vessel without contact with the stirring paddle. The remaining free 2-EH was stripped under a complete vacuum and maintained for 3 hours. The container was repressurized by sparging, and the product oligoester was vacuum filtered through a bed of Celite filter aid to obtain 1A [2-ethylhexyl poly(12-hydroxystearate)] as a pale yellow viscous liquid.

[0073] Example 1B - Example 1B was a repeated experiment using the same stoichiometry as in 1A, but the oligomerization of hydroxystearic acid was carried out for 4 hours up to an AV of 65.3 mg KOH / g before the introduction of 2-EH.

[0074] Example 1C was a repeated experiment using the same stoichiometry as 1A, but the oligomerization of hydroxystearic acid was carried out for 3.5 hours up to an AV of 70 mg KOH / g before the introduction of 2-EH.

[0075] Example 1D is a repeat of Example 1C.

[0076] Example 1E is a repeat of Example 1A, in which 2-EH is increased stoichiometrically by 10%.

[0077] Example 2 The materials from Example 1 were returned to the reaction vessel. 50 mL of distilled water and a considerable amount of anti-bumping granules were placed in a second 250 mL three-necked flask, and a sintered gas distribution pipe was attached via a PTFE tube of a certain length. The gas distribution pipe was introduced into the sample reaction vessel so that the sintered end was as low as possible without contaminating the stirring blades. The steam vessel was placed in a water bath on a hot plate stirrer with a set point of 30°C. The contents of the reaction vessel were heated to 115°C under a separate nitrogen purge. The nitrogen purge was stopped at the set temperature, a vacuum was applied, and low-temperature steam was drawn in through the gas distribution pipe and sparged through the reaction bulk. After about 3 hours, the heat was removed and the vacuum tap was closed. After reaching room temperature, the vacuum was released through the steam sparged by repressurizing the steam generator flask.

[0078] Example 3 A 1000 mL five-necked round-bottom flask equipped with a PTFE centrifugal stirrer, a magnetically sealed stirrer guide, a temperature feedback probe and isomanttle, nitrogen inlet and outlet via a Dean-Stark trap, a Liebig condenser, and an outlet bubbler, was filled with Hypermer LP1 (520.0 g, 0.297 mol CO2H, 1 equivalent) and 2-ethylhexane-1-ol (57.9 g, 0.445 mol, 1.5 equivalents), and the mixture was stirred at a rate of 80 mL / min. -1The mixture was heated to 220°C while purging with nitrogen and stirring at 500 rpm. After 2.5 hours, the temperature was reduced to 180°C, 0.2 mL of TNBT was added, and the reaction was allowed to proceed for a further 16 hours, after which the AV decreased to 1.36 mg KOH / g. An additional 0.2 mL of TNBT was added, and the reaction was continued for a further 24 hours, after which the AV decreased to 0.1 mg KOH / g. The temperature was reduced to 120°C, vacuum was applied for 3 hours by nitrogen spurging, and the product was filtered overnight through SW-10 cellulose filter aid to obtain the material for Example 3.

[0079] Example 4 12-hydroxystearic acid (491.6 g, 1.67 mol) and 2-octanol (108.4 g, 0.83 mol, approximately 50% excess) were placed in a five-necked round-bottom flask equipped with a nitrogen headspace purge (approximately 30 mL / min), an overhead stirrer with a centrifugal stirring rod (approximately 500 rpm), a Dean-Stark receiver with a temperature feedback loop and organic circulation, and a collection flask. A nitrogen atmosphere was maintained in the Dean-Stark receiver by attaching a vertical condenser and a Dreschel bottle. Note: For the molar calculation of 12-hydroxystearic acid, the average Mwt was calculated from the acid value. The reactants were first heated to 180°C, and then the temperature was gradually increased to 200°C, with the heating rate controlled by the water evolution rate, for approximately 2 hours. TnBT catalyst (approximately 0.2 g) and 2-octanol (approximately 10 mL) were added to the reaction vessel, with an acid value of ≤ 20 mg KOH / g. The reaction was maintained at 200°C until the reaction was complete (AV ≤ 0.2 mg KOH / g). After 16 hours, an additional TnBT catalyst (0.2 g) and 2-octanol (approximately 10 mL) were added. The product was cooled to 110°C, then activated carbon (approximately 1 wt%) was added to the reaction vessel, and a vacuum was applied (≤ 5 mbar). After maintaining the reaction conditions for 5 hours, the product was drained and filtered. The material was vacuum filtered using Fibra-cel SW-10 as a filter aid. The product, 2-octyl poly(12-hydroxystearate), was a clear, pale yellow, viscous liquid.

[0080] Example 5 12-hydroxystearic acid (955.4 g, 3.25 mol) and 2-decanol (244.7 g, 1.55 mol, approximately 50% excess) were placed in a five-necked round-bottom flask equipped with a nitrogen headspace purge (approximately 30 mL / min), an overhead stirrer with a centrifugal stirring rod (approximately 450 rpm), a Dean-Stark receiver with a temperature feedback loop, organic circulation, and a collection flask. A nitrogen atmosphere was maintained in the Dean-Stark receiver by attaching a vertical condenser and a Dreschel bottle. Note: For the molar calculation of 12-hydroxystearic acid, the average Mwt was calculated from the acid value. The reactants were first heated to 160°C, and then the temperature was gradually increased to 200°C, with the heating rate controlled by the water evolution rate, for approximately 3 hours. Tyzor TnBT catalyst (approximately 0.4 g) and 1-decanol (approximately 25 mL) were added to the reaction vessel, with an acid value of ≤ 30 mg KOH / g. The reaction was maintained at 200°C for approximately 24 hours until the reaction was complete (AV ≤ 0.2 mg KOH / g). The product was cooled to 145°C, then activated carbon (approximately 1% by weight) was added to the reaction vessel, and a vacuum was applied (≤ 5 mbar). After maintaining the reaction conditions for 5 hours, the product was drained and filtered. The material was vacuum filtered using Fibra-cel SW-10 as a filter aid. The product, 1-decylpoly(12-hydroxystearate), was an off-white paste-like solid.

[0081] Example 6 12-hydroxystearic acid (327.2 g, 5.29 mol total) and 2-ethylhexanol (344.1 g, 2.64 mol, approximately 50% excess) were placed in a five-necked round-bottom flask equipped with a Dean-Stark receiver with a nitrogen headspace purge (approximately 30 mL / min), an overhead stirrer with a centrifugal stirring rod (approximately 500 rpm), a temperature feedback loop, and organic circulation, and a collection flask. A nitrogen atmosphere was maintained in the Dean-Stark receiver by attaching a vertical condenser and a Dreschel bottle. Note: For the molar calculation of 12-hydroxystearic acid, the average Mwt was calculated from the acid value. The reactants were first heated to 165°C, then the temperature was gradually increased to 190°C, with the heating rate controlled by the water evolution rate, for approximately 1 hour until an AV of less than 15 was achieved, resulting in an actual AV of 13.2 mg KOH / g. The reaction was maintained at 190°C while adding TnBT catalyst (approximately 1.7 g). The reaction was maintained at 190°C for approximately 38 hours until the reaction was complete (AV ≤ 0.2 mg KOH / g). The reactants were then cooled to 120°C. The reaction was then reconstituted, the Dean-Stark receiver was removed and replaced with a simple distillation arm, the nitrogen headspace purge was reconstituted with a subsurface nitrogen purge, and then vacuum was applied (≤ 5 mbar) to strip off any free 2-ethylhexanol. After maintaining the reaction conditions for 5 hours, the reactants were repressurized, and samples were taken for acid value (AV = 0.12 mg KOH / g) and GC analysis to determine a free 2-ethylhexanol content of approximately 1,500 ppm.

[0082] The reaction was reconfigured for vapor stripping: a subsurface nitrogen sparge was connected to a 1-liter three-necked round-bottom flask filled with approximately 500 g of water and anti-bumping granules. The nitrogen / vapor outlet from the three-necked flask was connected to the subsurface sparge in the reaction vessel. The reactants were heated to 110°C, a vacuum was applied (<20 mbar), and the nitrogen flow into the vessel was reduced to a minimum. The water in the flask was gently heated with a heat gun to maintain the water at room temperature, and vigorous bubbling of the gas (nitrogen + vapor) in the reaction vessel was observed: for a constant vacuum, the water temperature determines the vigor of the vapor stripping process. After maintaining these conditions for 3 hours, the mixture was repressurized, and the vapor sparge was replaced with a nitrogen sparge. The product was sampled for acid value (AV = 0.12 mg KOH / g) and GC analysis to determine the free 2-ethylhexanol content (<60 ppm, target <100 ppm). The product was drained, filtered (using Celite® 512 as a filter aid), and subjected to complete analysis. The product, 2-ethylhexyl poly-12-hydroxystearate, was a clear, amber-colored, viscous liquid.

[0083] The materials from Example 6 were analyzed by GPC to determine the distribution of repeating units.

[0084] [Table 5]

[0085] Example 7 The materials (550.0 g), activated carbon (approximately 1 wt%), and Tonsil Optium 210-ff (approximately 1 wt%) prepared according to Example 6 were placed in a five-necked round-bottom flask equipped with a subsurface nitrogen sparge (approximately 30 mL / min), an overhead stirrer with a centrifugal stirring rod (approximately 400 rpm), a temperature feedback loop, a condenser set for distillation removal, and a collection flask. Both a Dreschel bottle and a nitrogen atmosphere were attached to the collection flask to ensure vacuum capacity. The reaction mixture was heated to 110°C, and then a vacuum was applied (≤5 mbar). After maintaining the reaction conditions for 3 hours, the reaction mixture was repressurized, the product was discharged, and the mixture was filtered using Celite® 512 as a filter aid. The product was a clear, amber-colored viscous liquid.

[0086] Example 8 The material (550.0 g) prepared according to Example 6, and acetic anhydride (110 mL, large excess) were placed in a five-necked round-bottom flask equipped with a subsurface nitrogen sparge (approximately 30 mL / min), an overhead stirrer with a centrifugal stirring rod (approximately 400 rpm), a temperature feedback loop, a condenser set for distillation removal, and a collection flask. Both a Dreschel bottle and a nitrogen atmosphere were attached to the collection flask to ensure vacuum capacity. The reaction mixture was heated and maintained at 100°C for approximately 5 hours, after which the reaction mixture was reconstituted for vapor stripping: a subsurface nitrogen sparge was connected to a 1-liter three-necked round-bottom flask filled with approximately 500 g of water and anti-bumping granules. A nitrogen / vapor outlet from the three-necked flask was connected to the subsurface sparge in the reaction vessel. The reaction mixture was heated to 110°C, a vacuum was applied (<20 mbar), and the nitrogen flow into the vessel was reduced to a minimum. The water in the flask was gently heated with a heat gun to maintain the water at room temperature, and vigorous bubbling of the gas (nitrogen + vapor) in the reaction vessel was observed: under constant vacuum, the water temperature determines the vigor of the vapor stripping process. After maintaining these conditions for 3 hours, the vessel was repressurized and the vapor spur was replaced with a nitrogen spur. Activated carbon (approximately 1 wt%) was added to the vessel, and a vacuum was applied (≤5 mbar). After maintaining the reaction conditions for 3 hours, the reactants were repressurized, the product was discharged, and the mixture was filtered using Celite® 512 as a filter aid. The product, 2-ethylhexyl poly-12-hydroxystearyl acetylate, was a clear, pale yellow, viscous liquid.

[0087] Example 9 A 2000 mL five-necked round-bottom flask equipped with a PTFE centrifugal stirrer, a magnetically sealed stirrer guide, a temperature feedback probe and isomanttle, nitrogen inlet and outlet via a Dean-Stark trap, a Liebig condenser, and an outlet bubbler, was filled with 12-hydroxystearic acid (1000 g, 3.19 mol, 1 equivalent) and 2-ethylhexane-1-ol (519.2 g, 3.99 mol, 1.25 equivalents), and the mixture was purged with N2 (for 15 mL). -1The mixture was heated to a set point of 200°C while stirring (520 rpm) until it melted. The Dean-Stark trap was initially filled with 2-EH, but after this was replaced with reaction water, the water level in the trap was maintained at over 80%, preserving the excess alcohol in the reaction vessel. After 3 hours, the reaction temperature reached 200°C, and the set point was raised to 220°C. After another 1.5 hours, a total of 54 mL of water was removed from the reaction vessel. Catalyst (TNBT, 0.2 mL) was added, and the reaction proceeded for a further 16 hours, after which the AV of the reaction reached <0.2 mg KOH / g. An additional 0.2 mL of TNBT was added, and the reaction was continued for a further 3 hours. The mixture was cooled to 110°C, decolorized carbon (5 g) was added, and the excess 2-EH was removed for 2 hours, with vacuum carefully applied to prevent foaming. The activated carbon was removed by filtration, and the product was subjected to a complete vacuum at 125°C using a nitrogen spurge until no free 2-EH was detected in the product by GC or odor analysis.

[0088] Example 10 A 1000 mL five-necked round-bottom flask equipped with a PTFE centrifugal stirrer, a magnetically sealed stirrer guide, a temperature feedback probe, and an isomalt, was fitted with nitrogen inlet and outlet via a Liebig condenser. The sample of 2-ethylhexyl 12-hyhydroxystearate (from Example 9, 550 g, nom. 1.333 mol) was placed in the flask, and the reaction mixture was heated to 90°C. The slow addition of acetic anhydride (125 mL, 136.0 g, 1.333 mol) was started. Only minimal exothermic reaction was observed, and as the reaction temperature began to decrease, heating was applied to raise the temperature to 110°C. After adding 50 mL of acetic anhydride, the addition was stopped, and a sample was taken to confirm that the reaction was occurring. The addition was completed more rapidly, and 0.1 mL of methanesulfonic acid was added as a catalyst. After the reaction was complete, the excess acetic anhydride and the formed acetic acid were removed by distillation under vacuum. Decolorized carbon (5g) was added, and heating at 125°C under vacuum was continued for another 3 hours. The final product was then filtered using SW-10 cellulose filter aid.

[0089] Table 5 shows the oxidation stability (induction time) of the above examples.

[0090] [Table 6] Benchmark 1 is a commercially available end-capped estolide sold by Biosynthetics under product code BT22. Benchmark 2 is a commercially available high-performance pentaerythritol tetraisostearate ester sold by Cargill Incorporated under the trade name Priolube 3987.

[0091] Tables 5, 6, and 7 show the stability of the compound of Formula 1 and a comparison with the end-capped acylated version and two commercially available benchmarks. It is quite surprising that the example of Formula 1 containing a free hydroxyl group (indicated by the hydroxyl value) is approximately seven times more stable than the corresponding acylated version. This represents a dramatic and unexpected increase in oxidative stability, which is highly advantageous for end-users.

[0092] [Table 7]

[0093] [Table 8]

[0094] Example 11 - Scale-up of 2-ethylhexyl poly(12-hydroxystearate) The container was inspected to ensure it was clean and functioning correctly before setting the oil jacket to a constant oil temperature of 90°C. The container was sealed, and the main drain valve was securely closed before applying a full vacuum to assess whether the container was vacuum-sealed. After releasing the vacuum with nitrogen, 12-hydroxystearic acid was filled through the sight glass port. See Table 8 below for batch quantities. After filling, the sight glass port was closed, and the constant oil temperature was raised to 160°C using a nitrogen headspace of 100 mL / min.

[0095] After 12-HSA was completely melted, the stirrer was activated (150 rpm) to raise the temperature to a constant reactor temperature of 190°C and the nitrogen headspace was increased to 200 mL / min. When the contents temperature reached 190°C, an initial pressure of 800 mbar was applied, then the pressure was reduced to 200 mbar over 10 minutes and held for 1.5 hours. After that, the pressure was reduced to <50 mbar and held for another hour. The vacuum was released with nitrogen and the container was pressurized to 1100 mbar. The contents were sampled through a sparge valve and the acid value was measured. After sampling, nitrogen was blown into the sparge for 10 minutes. Acid value of 70-80 mg KOH g -1 If within this range, the reaction is considered complete and the next step is initiated. If not within specifications, the pressure is reduced to <50 mbar and the reaction is continued until the desired AV is reached.

[0096] After cooling the container to a constant reactor temperature of <140°C, the small access port on the container lid was twisted off. After filling the container with the required amount of 2-ethylhexanol, the port was closed again. Furthermore, the binary separator was filled with 1 / 3 water and 2 / 3 2-ethylhexanol. The container was then set to a constant reactor temperature of 190°C, and upon reaching this temperature, the pressure was reduced to 800 mbar. The pressure was then periodically reduced to maintain an appropriate reflux level.

[0097] After approximately 6-7 hours, the vacuum was released with nitrogen and the container was pressurized to 1100 mbar. The contents were sampled through a sparge valve and the acid value was measured. If the acid value was ≤10 mg KOH g -1 If this was the case, the pressure was released and tetra-n-butanol titanate (TnBT) was added through the small access port on the lid. The reaction was then continued by reducing the pressure until reflux was achieved. Acid value >10 mg KOH g -1 If this was the case, the reaction was continued and a sample was taken again after 1 hour. After sampling, nitrogen was blown into the sparge for 10 minutes.

[0098] After adding TnBT, the reaction continued, and the pressure was reduced to ensure proper reflux was maintained. Acid value <0.2 mg KOH g-1 The container was then sampled periodically using the same procedure detailed above until the reaction was considered complete.

[0099] After completion, the vessel was set to a constant reactor temperature of 125°C and the stirring speed was increased to 200 rpm. The binary separator was drained, the water was discarded, and the 2-ethylhexanol was retained for further batches. After reaching this temperature, the pressure in the vessel was reduced to <50 mbar and the free 2-ethylhexanol was distilled from the vessel into the binary separator. After the distillation of 2-ethylhexanol stopped, the vessel was set to 110°C and the vacuum was released with nitrogen.

[0100] A vacuum-grade nylon tube was attached to the reactor, and the other end was attached to a valve mounted on a 500 mL three-necked flask. A thermometer and a second valve were attached to the other neck of the flask. This three-necked flask was then placed in a DrySyn block on a hot plate, which had a feedback probe inside the block. Water and anti-bumping granules were added to the flask, and the block was heated to 110°C.

[0101] The pressure in the 50L container was reduced to <50 mbar, the second valve of the 500mL flask was closed, the first valve was opened, and the reactor valve was opened. This reduced the pressure in the 500mL flask, generating vapor, which was drawn into the 50L container via a sparge. The generated vapor, along with 2-ethylhexanol, was collected in a binary separator. After stopping the removal of 2-ethylhexanol from the container, the valve was closed and the vacuum in the container was released with nitrogen.

[0102] After pressurizing the container to 1100 mbar, the contents were sampled through a sparge valve and the acid value was measured. Following sampling, nitrogen was blown into the sparge for 10 minutes. The 2-ethylhexanol content was measured, and if it was >100 ppm, vapor stripping was continued. If the 2-ethyl content was <100 ppm, stripping was considered complete.

[0103] In batches 11B, 11C, and 11D, the containers were dried by setting them to a constant reactor temperature of 90°C and reducing the pressure to <50 mbar. These conditions were maintained for 1-2 hours. The vacuum was released with nitrogen, and the containers were pressurized to 1100 mbar. The valve at the bottom was opened, and the material was discharged into a pre-weighed container.

[0104] Using batch 11A, the vessel was set to a constant reactor temperature of 90°C and pressurized to 1100 mbar. The bottom valve was opened and the material was discharged into a pre-weighed container. The material was then filled into a 30 L glass container with Norit SA. The oil jacket was set to 90°C and a vacuum of <50 mbar was applied. After maintaining these conditions for 1-2 hours, the vacuum was released with nitrogen. The material was then discharged into a pre-weighed container.

[0105] All four batches were filtered through a Buncher funnel using Celite 545 filter aid and Whatman 54 filter paper. After filtration, the material was discharged into pre-weighed containers.

[0106] [Table 9]

[0107] [Table 10]

[0108] Example 12 - Fractionation Effect The material from Example 11B was passed through a 4-inch pop-wiped film evaporator (WFE) under various conditions under vacuum to separate the low molecular weight components. Four different WFE conditions were evaluated to obtain four sets of residues and distillates, as listed in Table 10 below.

[0109] [Table 11]

[0110] Table 10 shows that the polymer content and properties can be modified by separation of components via treatment with WFE. Materials with higher polymer content can be produced. Depending on the desired properties, component separation may be desirable in some applications.

[0111] Example 13 - Effect of hydroxyl position change Example 13A-2-ethylhexyl poly-10-hydroxystearic acid 10-Hydroxystearic acid (900 g, 95% purity, prepared by the enzymatic method and subsequent recrystallization described in Example 17) was heated to 190°C over approximately 1 hour in a 2-liter round-bottom flask equipped with a nitrogen inlet and an outlet adapter connected to a horizontal water condenser. After reaching that temperature, the pressure was gradually reduced to 175 mbar over 3 hours, and then further reduced to <50 mbar. After reaching the acid value (75 mg KOH / g), the reaction was stopped and cooled to obtain poly-10HSA.

[0112] Poly-10HSA and 190 g of 2-ethylhexanol from the above were heated to 190°C over approximately 1 hour in a 2-liter round-bottom flask equipped with a nitrogen inlet and an outlet adapter connected to a horizontal water condenser. A vacuum of 300 mbar was applied during heating. The vacuum was slowly reduced to 100 mbar over 6 hours. 0.6 g of TBT was added to an AV of 19 mg KOH / g. After a further 7 hours, the pressure was reduced further to 90 mbar, and the reaction was stopped when the AV reached 0.2 mg KOH / g. Excess 2-ethylhexanol was removed by distillation. The final product was bleached (10 g Norit SA4) and steam stripped at 110°C for 4 hours. The product was dried and 4 g of Supercel filter aid was added. After time-consuming filtration (24 hours), product 13A was isolated and analyzed (see below).

[0113] Example 13: B-Ethylhexyl poly10-hydroxystearate / stearate (86 / 14) To mimic the stearic acid content of commercially available 12-hydroxystearic acid, a comparison was made by adding stearic acid to the starting 10-hydroxystearic acid.

[0114] 810 g of 10-hydroxystearic acid (95% purity, prepared by enzymatic method and subsequent recrystallization) and 90 g of stearic acid (98% purity) were heated to 190°C over approximately 1 hour in a 2 L round-bottom flask equipped with a nitrogen inlet and an outlet adapter connected to a horizontal water condenser. After reaching this temperature, the pressure was gradually reduced to 200 mbar over 2 hours, and then further reduced to <50 mbar. After reaching the acid value (73 mg KOH / g), the reaction was stopped and cooled to obtain poly-10HAS / stearic acid.

[0115] Poly-10HSA / stearic acid and 190 g of 2-ethylhexanol were heated to 190°C over approximately 1 hour in a 2-liter round-bottom flask equipped with a nitrogen inlet and an outlet adapter connected to a horizontal water condenser. After reaching the reaction temperature, the pressure was reduced to 300 mbar over 2 hours. 0.6 g of TBT was added with an AV of 25 mg KOH / g. The pressure was reduced to 100 mbar. After a further 7.5 hours, the reaction was stopped with an AV of 0.2 mg KOH / g. Excess 2-ethylhexanol was removed by distillation. The final product was bleached (10 g Norit SA4) and steam stripped at 110°C for 3.5 hours. The product was dried and 4 g of Supercel filter aid was added. After time-consuming filtration (approximately 5 hours), product 13B was isolated and analyzed (see below).

[0116] Example 14 - Effect of unsaturation in the main chain Example 14 A-2-ethylhexyl poly12-hydroxystearate / ricinolate (971 / 2 / 21 / 2) 877.5 g of 12-hydroxystearic acid and 22.5 g of ricinoleic acid were heated to 190°C over approximately 1 hour in a 2-liter round-bottom flask equipped with a nitrogen inlet and an outlet adapter connected to a horizontal water condenser. After reaching this temperature, the pressure was gradually reduced to 200 mbar over 2.5 hours, and then further reduced to <50 mbar. After reaching the acid value (73 mg KOH / g), the reaction was stopped and the mixture was cooled.

[0117] Poly-12HSA / ricinoleic acid and 190 g of 2-ethylhexanol were heated to 190°C over approximately 1 hour in a 2-liter round-bottom flask equipped with a nitrogen inlet and an outlet adapter connected to a horizontal water condenser. After reaching the reaction temperature, the pressure was reduced to 300 mbar over 3.5 hours. 0.6 g of TBT was added with an AV of 20 mg KOH / g. The pressure was reduced to 100 mbar over 2.5 hours. After a further 7.5 hours, the reaction was stopped with an AV of 0.2 mg KOH / g. Excess 2-ethylhexanol was removed by distillation. The final product was bleached (10 g Norit SA4) and steam stripped at 110°C for 4 hours. The product was dried and 4.4 g of Supercel filter aid was added. After filtration, product 14A was isolated and analyzed (see Table 11).

[0118] Example 14B-2-ethylhexyl poly-12-hydroxystearate / ricinolate (95 / 5) 978 g of 12-hydroxystearic acid and 51.5 g of ricinoleic acid were heated to 190°C over approximately 1 hour in a 2-liter round-bottom flask equipped with a nitrogen inlet and an outlet adapter connected to a horizontal water condenser. After reaching this temperature, the pressure was gradually reduced to 200 mbar over 3.5 hours, and then further reduced to <50 mbar. After reaching the acid value (72 mg KOH / g), the reaction was stopped and cooled to obtain poly-12HSA / ricinoleic acid.

[0119] The poly-12HSA / ricinoleic acid and 217 g of 2-ethylhexanol from the above were heated to 190°C over approximately 1 hour in a 2-liter round-bottom flask equipped with a nitrogen inlet and an outlet adapter connected to a horizontal water condenser. After reaching the reaction temperature, the pressure was reduced to 300 mbar over 4 hours. 0.68 g of TBT was added with an AV of 16.6 mg KOH / g. The pressure was reduced to 100 mbar over 1.5 hours. After a further 6 hours, the reaction was stopped with an AV of 0.12 mg KOH / g. Excess 2-ethylhexanol was removed by distillation. The final product was bleached (11 g Norit SA4) and steam stripped at 110°C for 4 hours. The product was dried and 4.8 g of Supercel filter aid was added. After filtration, the product was isolated and analyzed. The acid value was higher than expected (0.86 mg KOH / g). Therefore, 975 g of the product was mixed with 50 g of 2-ethylhexanol and esterified at 190°C and 150 mbar until the AV was 0.12 mg KOH / g. Excess 2-ethylhexanol was removed by distillation. The final product was bleached (11 g Norit SA4) and steam stripped at 110°C for 4 hours. The product was dried and 4.8 g of Supercel filter aid was added. After filtration, the final product 14B was isolated and analyzed (see Table 11).

[0120] Example 14C-ethylhexyl poly-12-hydroxystearate / ricinolate (921 / 2 / 71 / 2) 865 g of 12-hydroxystearic acid and 65 g of ricinoleic acid were heated to 190°C over approximately 1 hour in a 2-liter round-bottom flask equipped with a nitrogen inlet and an outlet adapter connected to a horizontal water condenser. After reaching that temperature, the pressure was gradually reduced to 200 mbar over 2 hours, and then further reduced to <50 mbar. After reaching the acid value (73 mg KOH / g), the reaction was stopped and the mixture was cooled.

[0121] The poly-12HSA / ricinoleic acid prepared above and 196 g of 2-ethylhexanol were heated to 190°C over approximately 1 hour in a 2-liter round-bottom flask equipped with a nitrogen inlet and an outlet adapter connected to a horizontal water condenser. After reaching the reaction temperature, the pressure was reduced to 250 mbar over 1.5 hours. 0.6 g of TBT was added with an AV of 16 mg KOH / g. The pressure was reduced to 100 mbar over 3 hours. After a further 5 hours, the reaction was stopped with an AV of 0.13 mg KOH / g. Excess 2-ethylhexanol was removed by distillation. The final product was bleached (10 g Norit SA4) and steam stripped at 110°C for 4 hours. The product was dried and 4.4 g of Supercel filter aid was added. After filtration, product 14C was isolated and analyzed (see Table 11).

[0122] [Table 12]

[0123] Example 15 - Effects of acetylation and reduction of hydroxyl value Example 15A - 29 mg KOH g -1 Acetylation of the hydroxyl value Poly-12-HSA (1264.2 g, 1.01 mol) from Example 11B was placed in a round-bottom five-neck flask. The flask was equipped with a stirrer, a temperature probe, a pressure-equalizing dropping funnel, and a nitrogen headspace (30 mL). -1 A take-off arm leading to a horizontal condenser was attached. The condenser was mounted on a collection flask equipped with a nitrogen outlet leading to a Dressel bottle filled with a weak potassium hydroxide solution and phenolphthalein indicator.

[0124] The temperature of the container was raised to 130°C, and acetic anhydride (48.8 g, 0.48 mol) was placed in a dropping funnel. After reaching this temperature, the acetic anhydride was slowly added to the container over 2 hours. A nitrogen stream of 50 mL / min was applied. -1 The temperature was increased and held for 1.75 hours, after which the material was steam-stripped.

[0125] Nitrogen headspace is cleared by nitrogen sparging (50 mL) -1Steam stripping was performed by changing the configuration. The sparge was connected to an auxiliary vessel filled with reverse osmosis water and a nitrogen inlet. The auxiliary vessel was placed in a water bath maintained at 60°C. The Dreschel bottle was replaced with a vacuum pump, and the pressure in the main vessel was reduced to approximately 60 mbar, and therefore the pressure in the auxiliary vessel was reduced, generating steam. The generated steam was transported into the main vessel through a nitrogen sparge. After 15 minutes, the temperature of the vessel was reduced to 110°C and held for 30 minutes. Then, the pressure in the vessel was reduced to 40 mbar and held for a further 20 minutes, after which the vacuum was released with nitrogen.

[0126] The sparge was replaced with nitrogen headspace, and the container pressure was reduced to 20 mbar for drying. After approximately 2 hours, the vacuum was released with nitrogen, and the material was sampled (S1). 0.28 mg KOH g -1 Acid value and 29 mg KOH g -1 The hydroxyl value was measured. The nitrogen headspace was replaced with a nitrogen sparge, and vapor stripping was continued at a container pressure of 20 mbar. After 5.5 hours, the vacuum was released with nitrogen, and the nitrogen sparge was replaced with a nitrogen headspace. The container temperature was reduced to 90°C, and the material was dried again at a container pressure of <30 mbar. After a further 3.25 hours, the vacuum was released with nitrogen, and the sample (S2) was taken. 0.19 mg KOH g -1 Acid value and 29 mg KOH g -1 The hydroxyl value was measured. Acid value <0.2 mg KOH g -1 Therefore, a larger sample was taken. A total of approximately 220g of material was sampled as Example 15A.

[0127] Example 15B - 11 mg KOH g -1 Acetylation of the hydroxyl value The remaining material was further acetylated by adding acetic anhydride (30.4 g, 0.30 mol) to a dropping funnel and heating the container to 130°C. After reaching this temperature, the acetic anhydride was added over 2.25 hours, followed by a further 1.5 hours of reaction. The container was then cooled to 110°C and steam stripped. The nitrogen headspace was sparged with nitrogen (50 mL). -1Steam stripping was performed by changing the configuration. The sparge was connected to an auxiliary vessel filled with reverse osmosis water and a nitrogen inlet. The auxiliary vessel was placed in a water bath maintained at 60°C. The Dreschel bottle was replaced with a vacuum pump to reduce the pressure in the main vessel to <30 mbar, and therefore the pressure in the auxiliary vessel, thereby generating steam. The generated steam was transported into the main vessel through a nitrogen sparge.

[0128] After 5 hours, vapor stripping was stopped by releasing the vacuum with nitrogen, and the spurge was replaced with nitrogen headspace. After cooling the vessel to 90°C, the pressure was reduced to <80 mbar over 2 hours. Acid value 0.16 mg KOH g -1 A sample (S3) containing the following was collected, with a hydroxyl value of 11 mg KOH g -1 The acid value was measured. <0.2 mg KOH g -1 Therefore, a larger sample was taken. A total of approximately 235g of material was sampled as Example 15B.

[0129] Example 15C - 3 mg KOH g -1 Acetylation of the hydroxyl value Acetic anhydride (20.0 g, 0.20 mol) was added to a dropping funnel, and the container was heated to 130°C to further acetylate the remaining material. After reaching this temperature, acetic anhydride was added over 1 hour, followed by a further 4 hours of reaction. The container was then cooled to 110°C and steam stripped. Nitrogen headspace was sparged with nitrogen (50 mL). -1 Steam stripping was performed by changing the configuration. The sparge was connected to an auxiliary vessel filled with reverse osmosis water and a nitrogen inlet. The auxiliary vessel was placed in a water bath maintained at 60°C. The Dreschel bottle was replaced with a vacuum pump to reduce the pressure in the main vessel to <20 mbar, and therefore the pressure in the auxiliary vessel, thereby generating steam. The generated steam was transported into the main vessel through a nitrogen sparge.

[0130] After 5.4 hours, vapor stripping was stopped by releasing the vacuum with nitrogen, and the spurge was replaced with nitrogen headspace. After cooling the vessel to 90°C, the pressure was reduced to <20 mbar over 2.5 hours. Acid value 0.05 mg KOH g -1 A sample (S4) containing the following was collected, with a hydroxyl value of 3 mg KOH g -1 The acid value was measured. <0.2 mg KOH g -1 Therefore, the reaction was considered complete, and the substance was isolated as Example 15C.

[0131] Table 12 clearly demonstrates the dramatically surprising effect that increasing the proportion of free hydroxyl groups (measured by the hydroxyl value) has on oxidative stability. A slight increase in the hydroxyl value from 3 to 11 results in more than a threefold increase in oxidative stability. There is more than a tenfold difference between the starting material of Example 11 and the most acylated example of 15C.

[0132] [Table 13]

[0133] Example 16 - Effects of different esterified alcohols Poly-12-hydroxystearic acid 1100 g of 12-hydroxystearic acid was heated to 190°C over approximately 1 hour in a 2-liter round-bottom flask equipped with a nitrogen inlet and an outlet adapter connected to a horizontal water condenser. After reaching this temperature, the pressure was gradually reduced to 200 mbar over 1.5–2 hours, and then further reduced to <50 mbar. After reaching an acid value (70–75 mg KOH / g), the reaction was stopped and cooled.

[0134] Example 16 A-hexyl poly-12-hydroxystearate The poly-12HSA (860 g) and hexanol (160 g) prepared above were heated to 190°C over approximately 1 hour in a 2-liter round-bottom flask equipped with a nitrogen inlet and a Dean-Stark separator. After 1.5 hours, a vacuum of 750 mbar was applied. Subsequently, the vacuum was slowly reduced to 375 mbar over 5 hours. 0.43 g of TBT was added to an AV of 10.3 mg KOH / g. After a further 6.5 hours, the pressure was reduced further to 200 mbar, and the reaction was stopped when the AV reached 0.2 mg KOH / g.

[0135] Excess hexanol was removed by distillation at 120°C. 947g of the final product was bleached (10g Norit SA4) and steam stripped at 110°C for 3 hours. The product was dried and 5g of Supercel filter aid was added. After filtration, the product was analyzed (see below).

[0136] Example 16B-2-octyldecylpoly-12-hydroxystearate The poly-12HSA (900 g) and 495 g of Isofol 18 prepared above were heated to 190°C over approximately 1 hour in a 2-liter round-bottom flask equipped with a nitrogen inlet and an outlet adapter connected to a horizontal water condenser. A vacuum of 600 mbar was applied during heating. Subsequently, the vacuum was slowly reduced to 125 mbar over 4 hours. 0.46 g of TBT was added to an AV of 11.9 mg KOH / g. After a further 7 hours, the pressure was reduced further to 25 mbar, and the reaction was stopped when the AV reached 0.2 mg KOH / g.

[0137] The product was distilled using a two-stage molecular distillation apparatus. Excess Isofol 18 was removed by distillation (first stage 155-160°C / 10 -3 mbar, second stage 185℃ / 10 -3 (mbar). 1064g of the final product was bleached (10g Norit SA4) and steam stripped at 110°C for 4 hours. The product was dried and 5g of Supercel filter aid was added. After filtration, the product was analyzed (see below).

[0138] Example 16: C-Isostearyl Poly-12-Hydroxystearate The poly-12HSA (900 g) and 493 g of isostearyl alcohol (3515) prepared above were heated to 190°C over approximately 1 hour in a 2-liter round-bottom flask equipped with a nitrogen inlet and an outlet adapter connected to a horizontal water condenser. A vacuum of 300 mbar was applied during heating. The vacuum was slowly reduced to 100 mbar over 5 hours. 2.4 g of 20% TBT solution was added to an AV of 9.1 mg KOH / g. After a further 6.25 hours, the pressure was further reduced to 25 mbar, and the reaction was stopped when the AV reached 0.14 mg KOH / g.

[0139] The product was distilled using a two-stage molecular distillation apparatus. Excess isostearyl alcohol was removed by distillation (first stage 150-160°C / 10 -3 mbar, second stage 185℃ / 10 -3 (mbar). 935g of the final product was bleached (10g Norit SA4) and steam stripped at 110°C for 4 hours. The product was dried and 5g of Supercel filter aid was added. After filtration, the product was analyzed (see below).

[0140] Example 16: D-Stearyl Poly-12-Hydroxystearate The poly-12HSA (900 g) and 495 g of stearyl alcohol prepared above were heated to 190°C over approximately 1 hour in a 2-liter round-bottom flask equipped with a nitrogen inlet and an outlet adapter connected to a horizontal water condenser. A vacuum of 300 mbar was applied during heating. Subsequently, the vacuum was slowly reduced to 100 mbar over 5 hours. 2.4 g of 20% TBT solution was added to an AV of 9.1 mg KOH / g. After a further 6.25 hours, the pressure was reduced further to 25 mbar, and the reaction was stopped when the AV reached 0.14 mg KOH / g.

[0141] The product was distilled using a two-stage molecular distillation apparatus. Excess isostearyl alcohol was removed by distillation (first stage 150-160°C / 10 -3 mbar, second stage 185℃ / 10 -3(mbar). 935g of the final product was bleached (10g Norit SA4) and steam stripped at 110°C for 4 hours. The product was dried and 5g of Supercel filter aid was added. After filtration, the product was analyzed (see below).

[0142] Example 16: E-methylpoly12-hydroxystearate The 12HSA (900g) prepared above was heated to 190°C in a 2-liter round-bottom flask equipped with a nitrogen inlet and an outlet adapter connected to a horizontal water condenser. Methanol was added to the reactor (approximately 350 mL / h). 0.5 g of TBT was added with an AV of 25 mg KOH / g. After 5 hours, the reaction temperature was raised to 205°C. After a total reaction time of 10 hours, the reaction was stopped with an AV of 0.17 mg KOH / g (preliminary product).

[0143] This reaction was repeated with 400g of 12HSA. The product was heated at 280°C and 3.5x10⁻⁶ -3 Molecular distillation was performed at mbar to obtain the upper and lower fractions.

[0144] The final product (methyl poly-12-hydroxystearate) was a mixture of 837 g of the preliminary product and 148 g of the upper fraction obtained from repeated molecular distillation.

[0145] The final product (985g) was bleached (10g Norit SA4) and steam stripped at 110°C for 3 hours. The product was dried and 5g of Supercel filter aid was added. After filtration, the product was analyzed (see below).

[0146] Example 16: F-isopropyl poly-12-hydroxystearate The first batch was prepared by esterifying poly-12HSA with isopropanol. For the second batch, isopropyl ester was prepared by esterifying 12HSA with isopropanol to obtain a low acid value. Both batches were subjected to molecular distillation to separate the low molecular weight components from the mixture. The isopropyl ester was prepared by mixing the molecularly distilled upper and lower fractions in the ratios described below.

[0147] The 12HSA (1000g) prepared above was heated to 190°C in a 2-liter round-bottom flask equipped with a nitrogen inlet and an outlet adapter connected to a horizontal water condenser. The product was esterified to AV with 75 mg KOH / g. IPA was added to the mixture. After 7 hours, AV reached 34 mg KOH / g, and 0.3 g TBT was added. After a total reaction time of 21 hours, another 0.3 g TBT was added, and the temperature was raised to 210°C. After 4 hours, AV was 0.25 mg KOH / g, and the reaction was stopped. A total of 5 liters of IPA was added to the reactor. The recovered product was sterilized at 280°C and 3.5 × 10⁻⁶ -3 Molecular distillation was performed at mbar (approximately 100 mL / hour) to obtain the upper fraction product (16F1).

[0148] The 12HSA (1250g) prepared above was heated to 190°C in a 2-liter round-bottom flask equipped with a nitrogen inlet and an outlet adapter connected to a horizontal water condenser. IPA was added to the reactor (approximately 350 mL / h). After 4 hours, 0.5 g of TBT was added with an AV of 35 mg KOH / g. After 10.5 hours, when the AV was 3.7, a further 0.3 g of TBT was added. Over the next 3 hours, the AV increased to 9.4 mg KOH / g. It was decided to switch to a new bottle of IPA. After a total reaction time of 26 hours, the reaction was stopped with an AV of 0.3 mg KOH / g. The product was heated at 280°C and 3.5 × 10⁻⁶ -3 Molecular distillation was performed at mbar (approximately 100 mL / hour) to produce the upper fraction (16F2) and the lower fraction (16F3).

[0149] The final product was a mixture of 360 g of molecularly distilled upper fraction of 16F1, 120 g of molecularly distilled upper fraction of 16F2, and 700 g of molecularly distilled lower fraction of 16F3.

[0150] The combined fractions were bleached (12g Norit SA4) and steam stripped at 110°C for 3 hours. The product was dried and 5g of Supercel filter aid was added. After filtration, the product (16F) was analyzed (see below).

[0151] [Table 14]

[0152] Example 17 - Preparation of 10-hydroxystearic acid 280 liters of demineralized water were filled into a tank. 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 hydratase enzyme PDN C100 V2 (140 g) from Biocatalysts Ltd., and the resulting mixture was stirred at 20-25°C for 24 hours. The mixture was then heated to 50°C and maintained at this temperature for 1 hour. The mixture was then cooled to 30°C and filtered through a 1 mm nylon filter. The solid precipitate was dried and removed from the filter to obtain 10-hydroxystearic acid.

[0153] Example 18 - Lubricant Compound Three exemplary lubricant compositions were prepared by mixing commercially available additive packages with the materials of Example 11 according to the proportions shown in Table 14.

[0154] [Table 15]

[0155] Blend preparation To prepare the blends, the desired amount of additive package was first weighed into a beaker, and then the base oil was added to make a total of 100g. The mixture was stirred at 60°C for 20 minutes using a mixer set to 400 rpm. This procedure was performed for all the required blends.

[0156] The performance of the blend was measured and reported in Table 15 below.

[0157] [Table 16]

[0158] For the material in Example 11, Hitec 307 exhibited the least desirable performance compared to the other additive packs used. Both King additive packs showed good performance, nearly doubling the oxidation time compared to the base material. King BL-1232EL performed slightly better. Hitec 307 is an additive pack designed for use with mineral oil, and therefore it is not surprising that its performance is inferior to that of the King additive packs, which are designed for use with esters.

[0159] Analysis method: viscosity The viscosity of the samples was measured using an Anton Parr Stabinger SVM3001 viscometer according to Method ASTM D445. The material was added to the viscometer, and the kinematic viscosity was measured at 40°C (KV40) and 100°C (KV100). The viscosity index (VI) and density were also measured using the same instrument.

[0160] RapidOxy The materials disclosed herein possess excellent oxidation stability. This stability may make it time-consuming to evaluate stability at lower temperatures. Samples were evaluated at three different temperatures to gain a more complete understanding of their stability. All samples were evaluated in an Anton Parr RapidOxy 100 instrument according to ASTM D8206. The method conditions are listed in Table 16. Sample size 4 grams was used in a standard glass dish. The temperatures used were 140°C, 160°C, or 180°C, as indicated. The instrument was pressurized to 700 kPa with pure oxygen, and the completion of the test was determined by the time it took for the peak pressure to drop by 10% or 50%. Thus, a 10% or 50% drop was used as an indicator of rapid onset of oxidation or oxidation induction time (OIT). OIT should be determined for the compounds of formulas 1 and 3, as well as for base oils and lubricant formulations without additives or antioxidants. In some embodiments, the OIT of the lubricating composition, base oil, compound of formula 1, and compound of formula 3 is greater than 500 hours when determined at 160°C according to ASTM D8206. In some embodiments, the OIT of the lubricating composition, base oil, compound of formula 1, and compound of formula 3 is greater than 750 hours when determined at 160°C according to ASTM D8206. In some embodiments, the OIT of the lubricating composition, base oil, compound of formula 1, and compound of formula 3 is greater than 1000 hours when determined at 160°C according to ASTM D8206.

[0161] [Table 17]

[0162] Samples from Example 11B were also evaluated for thermal decomposition by thermogravimetric analysis (TGA) under a nitrogen atmosphere to ensure that the oxidation stability data was not distorted at high temperatures due to decomposition. Samples were evaluated under nitrogen at 90°C to 900°C using standard equipment. It was found that no significant decomposition occurred at temperatures below 240°C.

[0163] The term "Acid Value" (AV), as used herein, is defined as the weight (mg) of KOH required to neutralize the organic acid present in 1 g of a test sample, and is a measure of the free fatty acids present in the composition. AV can be determined by AOCS Official Method Cd 3d-63.

[0164] As used herein, the term "Hydroxyl Value" is defined as the number of hydroxyl groups present in milligrams of potassium hydroxide in one g of sample, and is one of the conventional properties of oils and fats. The hydroxyl value may also be determined by the AOCS standard method Cd13-60.

[0165] GPC analysis was performed using the following instrument: Agilent 1260 infinity GPC / SEC multi detector suite. Solvent: tetrahydrofuran, detector refractive index: 1%, sample concentration: 1% (w / v), injection volume: 50 μl, temperature: 40°C, flow rate: 1 mL / min, 2×(PLGel 3 μm 100 Å, 300 × 7.5 mm) and 1×(PLGel, 3 μm, 50 × 7.5 mm) guard columns. The results are shown in Table 4 below.

[0166] The nature of this disclosure In some embodiments, the base oil may have a hydroxyl value of 30 to 60. In some embodiments, the lubricating composition may have a hydroxyl value greater than 10, greater than 20, or greater than 30. In some embodiments, the base oil may have a hydroxyl value of 10 to 70 or 20 to 70. In some embodiments, the base oil may have a hydroxyl value of 30 to 60.

[0167] In some embodiments, the compound of formula 1 may have a hydroxyl value greater than 10, greater than 20, or greater than 30. In some embodiments, the compound of formula 1 may have a hydroxyl value of 10 to 70 or 30 to 70. In some embodiments, the compound of formula 1 may have a hydroxyl value of 30 to 60.

[0168] In some embodiments, the compound of formula 3 may have a hydroxyl value greater than 10, greater than 20, or greater than 30. In some embodiments, the compound of formula 3 may have a hydroxyl value of 10 to 70 or 30 to 70. In some embodiments, the compound of formula 3 may have a hydroxyl value of 30 to 60.

[0169] In some embodiments, the compounds of formula 1 and formula 4 may have a hydroxyl value greater than 10, greater than 20, or greater than 30. In some embodiments, the compounds of formula 1 and formula 4 may have a hydroxyl value of 10 to 70 or 20 to 70. In some embodiments, the compounds of formula 1 and formula 4 may have a hydroxyl value of 30 to 60.

[0170] In some embodiments, the compounds of formula 3 and formula 4 may have a hydroxyl value greater than 10, greater than 20, or greater than 30. In some embodiments, the compounds of formula 3 and formula 4 may have a hydroxyl value of 10 to 70 or 20 to 70. In some embodiments, the compounds of formula 3 and formula 4 may have a hydroxyl value of 30 to 60.

[0171] Another aspect of the present disclosure is a method for lubricating two surfaces, comprising bringing the interface of the surfaces into contact with a lubricating composition of any of the compositions described herein.

[0172] In some embodiments, the surface is part of the hydraulic system.

[0173] In some embodiments, the surface is a gear.

[0174] In some embodiments, the gear is located in an industrial gearbox, a marine gearbox, a vehicle gearbox, or a vehicle transmission.

[0175] In some embodiments, the surface is a drill bit or a milling surface.

[0176] Use of compounds of formula 1 or formula 3 as lubricants.

[0177] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 10% or more of one or more compounds of formula 3, where R is 2-ethylhexyl.

[0178] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 10% or more of one or more compounds of formula 1, where R is C1 to C 22 It is an alkyl group, where R2 is a saturated or unsaturated C7 or C9 alkyl group, and R3 is a C6 or C8 alkyl group.

[0179] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 30% or more of one or more compounds of formula 3, where R is 2-ethylhexyl.

[0180] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 50% or more of one or more compounds of formula 3, where R is 2-ethylhexyl.

[0181] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 10% or more of one or more compounds of formula 3, where R is 2-ethylhexyl, and further comprising another base oil selected from the group consisting of polyalphaolefins (PAO), synthetic esters such as polyol esters, polyalkylene glycols (PAG), oil-soluble polyalkylene glycols (OSP), mineral oils (groups I, II, and III), fatty acid esters, and mixtures thereof.

[0182] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 10% or more of one or more compounds of formula 3, where R is 2-ethylhexyl, and further comprising polyalphaolefin (PAO).

[0183] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 30% or more of one or more compounds of formula 3, where R is 2-ethylhexyl, and further comprising polyalphaolefin (PAO).

[0184] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 10% or more of one or more compounds of formula 3, where R is 2-ethylhexyl, and further comprising another base oil selected from the group consisting of polyalphaolefins (PAO), synthetic esters such as polyol esters, polyalkylene glycols (PAG), oil-soluble polyalkylene glycols (OSP), mineral oils (groups I, II, and III), fatty acid esters, and mixtures thereof, and having a hydroxyl value greater than 10.

[0185] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 10% or more of one or more compounds of formula 3, where R is 2-ethylhexyl, and further comprising polyalphaolefin (PAO), having a hydroxyl value of 10 or more.

[0186] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 30% or more of one or more compounds of formula 3, where R is 2-ethylhexyl, and further comprising polyalphaolefin (PAO), having a hydroxyl value of 10 or more.

[0187] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 10% or more of one or more compounds of formula 3, where R is 2-ethylhexyl, and further comprising another base oil selected from the group consisting of polyalphaolefins (PAO), synthetic esters such as polyol esters, polyalkylene glycols (PAG), oil-soluble polyalkylene glycols (OSP), mineral oils (groups I, II, and III), fatty acid esters, and mixtures thereof, and having a hydroxyl value greater than 20.

[0188] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 10% or more of one or more compounds of formula 3, where R is 2-ethylhexyl, and further comprising polyalphaolefin (PAO), having a hydroxyl value greater than 20.

[0189] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 30% or more of one or more compounds of formula 3, where R is 2-ethylhexyl, and further comprising polyalphaolefin (PAO), having a hydroxyl value greater than 20.

[0190] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 30% or more of one or more compounds of formula 3, where R is 2-ethylhexyl, and further comprising polyalphaolefin (PAO), having a hydroxyl value of 10 to 70.

[0191] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 30% or more of one or more compounds of formula 3, where R is 2-ethylhexyl, and further comprising polyalphaolefin (PAO), having a hydroxyl value of 20 to 70.

[0192] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 30% or more of one or more compounds of formula 3, where R is 2-ethylhexyl, and further comprising polyalphaolefin (PAO), and the lubricating composition having a hydroxyl value of 20 to 70.

[0193] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 30% or more of one or more compounds of formula 3, where R is 2-ethylhexyl, the base oil having an oxidation induction time (OIT) of more than 500 hours, and the base oil not containing any additional additives or antioxidants.

[0194] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 50% or more of one or more compounds of formula 3, where R is 2-ethylhexyl.

[0195] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 10% or more of one or more compounds of formula 3, where R is 2-ethylhexyl, and the base oil having an OIT of more than 500 hours as measured at 160°C according to ASTM D8206.

[0196] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 10% or more of one or more compounds of formula 1, and the base oil having an OIT of more than 500 hours as measured at 160°C according to ASTM D8206.

[0197] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 30% or more of one or more compounds of formula 3, where R is 2-ethylhexyl, and the base oil having an OIT of more than 750 hours as measured at 160°C according to ASTM D8206.

[0198] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 30% or more of one or more compounds of formula 3, where R is 2-ethylhexyl, and the base oil having an OIT of more than 1000 hours, as measured at 160°C according to ASTM D8206.

[0199] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 50% or more of one or more compounds of formula 3, where R is 2-ethylhexyl, and the base oil having an OIT of more than 1000 hours, as measured at 160°C according to ASTM D8206.

[0200] In some embodiments, the lubricating composition comprises a base oil and an additive, the base oil comprising 30% or more of one or more compounds of formula 3, where R is 2-ethylhexyl, having an OIT of more than 750 hours as measured at 160°C according to ASTM D8206, and having a hydroxyl value of 20 to 70, and further comprising polyalphaolefin (PAO).

Claims

1. A lubricating composition comprising a base oil and one or more additives, The base oil comprises 10 to 100% by weight of one or more compounds of formula 1. 【Chemistry 1】 n is an integer from 2 to 6, and R is C １ ~C ２２ It is alkyl, R ２ C ３ ~C １２ It is alkyl, R ３ is hydrogen or C １ ~C １０ A lubricating composition that is alkyl.

2. The composition according to claim 1, wherein the base oil comprises 20 to 100% by weight of the compound of formula 1.

3. The lubricating composition according to claim 2, wherein the lubricating composition comprises 10 to 100% of the compound of formula 1.

4. The composition according to claim 1, wherein the base oil has a hydroxyl value of 20 or more.

5. The composition according to claim 1, wherein the base oil has a hydroxyl value of 30 to 70.

6. The composition according to claim 1, wherein the compound of formula 1 has a hydroxyl value of 30 to 70.

7. The composition according to claim 1, wherein the one or more additives are selected from the group consisting of friction modifiers, viscosity modifiers, antioxidants, wear-resistant additives, extreme pressure additives, defoaming agents, anti-emulsifiers, and corrosion inhibitors.

8. A composition according to any one of claims 1 to 7, comprising at least 30%, at least 50%, or at least 70% of the compound of formula 1.

9. The composition according to any one of claims 1 to 8, further comprising an additional base oil selected from the group consisting of polyalphaolefins (PAO), synthetic esters such as polyol esters, polyalkylene glycols (PAG), oil-soluble polyalkylene glycols (OSP), mineral oils (groups I, II, and III), fatty acid esters, and mixtures thereof.

10. The composition according to claim 9, wherein the additional base oil comprises a polyalphaolefin.

11. The base oil further comprises one or more compounds of formula 4, 【Chemistry 2】 n is an integer from 2 to 6, and R is C １ ~C ２２ alkyl, R ２ is C ３ ~C １２ alkyl, R ３ is hydrogen or C １ ~C １０ alkyl, R ４ is C １ ~C ２２ acyl. The composition according to claim 1.

12. The composition according to claim 8, wherein the base oil has a hydroxyl value of 20 or more.

13. R is 2-ethylhexyl, and R ４ C １８ The composition according to claim 9, wherein it is an acyl.

14. A lubricating composition comprising a base oil and an additive, wherein the base oil comprises 10 to 100% by weight of one or more compounds of formula 3, 【Transformation 3】 In the formula, n is an integer from 2 to 6, and R is C １ ~C ２２ A lubricating composition that is alkyl.

15. The composition according to claim 14, wherein R is 2-ethylhexyl.

16. The composition according to claim 15, wherein the base oil comprises 20 to 100% of the compound of formula 3.

17. The lubricating composition according to claim 15, wherein the lubricating composition comprises 10 to 100% of the compound of formula 3.

18. The composition according to claim 14, wherein the base oil has a hydroxyl value of 20 or more.

19. The composition according to claim 14, wherein the base oil has a hydroxyl value of 30 to 70.

20. The composition according to claim 14, wherein the compound of formula 3 has a hydroxyl value of 30 to 70.

21. The composition according to claim 14, wherein the one or more additives are selected from the group consisting of friction modifiers, viscosity modifiers, antioxidants, wear-resistant additives, extreme pressure additives, defoaming agents, anti-emulsifiers, and corrosion inhibitors.

22. The composition according to any one of claims 14 to 21, comprising at least 30%, at least 50%, or at least 70% of the compound of formula 3.

23. The composition according to any one of claims 14 to 22, further comprising an additional 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.

24. The composition according to claim 23, wherein the additional base oil comprises a polyalphaolefin.

25. The base oil further comprises one or more compounds of formula 4, 【Chemistry 4】 n is an integer from 2 to 6, and R is C １ ~C ２２ It is alkyl, R ２ C ３ ~C １２ It is alkyl, R ３ is hydrogen or C １ ~C １０ It is alkyl, R ４ C １ ~C ２２ The composition according to any one of claims 1 to 24, wherein it is an acyl.

26. The composition according to claim 25, wherein the base oil has a hydroxyl value of 20 or more.

27. R is 2-ethylhexyl, and R ４ C １８ The composition according to claim 25, wherein it is an acyl.

28. A method for lubricating two surfaces, comprising bringing the interface of the surfaces into contact with a lubricating composition according to any one of claims 1 to 27.

29. The method according to claim 28, wherein the surface is part of a hydraulic system.

30. The method according to claim 28, wherein the surface is a gear.

31. The method according to claim 28, wherein the gear is located in an industrial gearbox, a marine gearbox, a vehicle gearbox, or a vehicle transmission.

32. The method according to claim 28, wherein one of the aforementioned surfaces is a drill bit or a milling surface.

33. Use of compounds of formula 1 or formula 3 as lubricants.

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