Bio-based lubricants

Abstract

The present disclosure relates to novel bio-based lubricating compositions with high oxidative stability for use in all lubricating applications such as gears, motors and hydraulic devices. More specifically, the lubricating composition comprises a base oil and one or more additives, and the base oil comprises greater than 10% by weight of one or more compounds of Formula 1: wherein n is an integer from 2 to 6; r is a C1-C22 alkyl group; r2 is a C3-C12 alkyl group; and R3 is hydrogen or a C1-C10 alkyl group.

Description

[0001] Cross-reference to related applications

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 492,655, filed March 28, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0003] 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 ingredients is increasingly preferred to reduce the carbon footprint of industrial products. Background Technology

[0004] The lubricant (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, rather than non-renewable or unsustainable sources such as petroleum. Biodegradability means that lubricants and process fluids (hereinafter referred to as “fluids”) have the ability to degrade in the natural environment over a period of time, which can be measured by tests such as those issued by the Organization for Economic Co-operation and Development (OECD). By definition, renewable bio-based products contain high levels of renewable carbon, and standards are being developed to encourage increasingly higher levels of renewability. For example, the European Ecolabel now emphasizes that hydraulic fluids should be biodegradable and preferably contain at least 50% by weight of renewable carbon.

[0005] Researchers have attempted to meet the requirements or recommendations for both biodegradability and renewability by including various types of natural oils in their fluid formulations. Natural esters, including, for example, canola oil, sunflower oil, rapeseed oil, and palm oil, have a 100% renewable carbon content. Unfortunately, these natural esters often exhibit poor performance at low temperatures and demonstrate poor oxidative stability. Poor temperature performance involves a relatively high pour point, the highest temperature at which a material stops flowing, and is often a result of a significant increase in viscosity caused by crystallization. Another problem with natural esters is their tendency to have commercially undesirable levels of thermal oxidative stability, partly due to the unsaturation within the acidic portion of their chemical structure.

[0006] In some cases, synthetic esters can be used as substitutes for natural esters. In some cases, synthetic esters can have very low pour points (below -50°C) and commercially desirable levels of thermal oxidative stability. However, most synthetic esters are derived from petrochemical feedstocks and therefore have very low (less than 50% by weight) and even zero levels of renewable carbon. They are also much more expensive than natural esters and therefore may not be economically ideal for many applications.

[0007] However, despite these challenges, the primary motivation remains to produce fluids with commercially viable levels of biodegradability and renewable carbon, as well as excellent oxidative stability. Lubricating fluids with excellent oxidative stability will have longer service life and will limit or eliminate the need for additional antioxidant additives. Increasing service life by limiting or reducing downtime due to lubricant changes offers significant benefits to end users.

[0008] Despite the ongoing development of natural-based solutions, there remains a desire to discover new formulations with superior stability. Antioxidant additive packages can be expensive and consumed over their lifespan. Therefore, more oxidation-resistant base oils could limit or eliminate the need for costly antioxidant packages. Summary of the Invention

[0009] The concept of reacting hydroxyl-substituted fatty acids with themselves to produce polymeric structures is known in the art, for example (WO / 2011 / 037778A1), which teaches that the hydroxyl value of preferred compounds should be as low as possible. Generally, prior art structures are achieved by “capping” any remaining hydroxyl groups. The applicant has surprisingly found that capping is unnecessary and actually detrimental to the oxidative stability of these compounds.

[0010] The compositions described herein exhibit surprisingly high oxidative stability while maintaining high levels of renewable carbon content. In some cases, aspects of the invention demonstrate an unprecedented increase in stability of 7 to 12 times or more compared to comparable materials. This level of stability in bio-based materials is unique and highly valuable to end users. Furthermore, the compounds of Formula 1 are cheaper and easier to prepare than currently utilized alternatives.

[0011] A lubricating composition comprising a base oil is disclosed, wherein the base oil comprises 10% to 100% of one or more compounds of formula 1:

[0012]

[0013] Where n is an integer from 2 to 6; R is a series of integers from C1 to C2. 12 Alkyl; R2 is C5-C 11 Alkyl; R3 is C4-C 10 alkyl.

[0014] The lubricating composition may contain a base oil comprising 10% to 100% of a compound of formula 1. The lubricating composition may contain 50% to 100% base oil.

[0015] 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 between 30 and 70. The lubricating composition may contain a base oil comprising one or more compounds of Formula 1, wherein one or more compounds of Formula 1 have a hydroxyl value greater than 20. The lubricating composition may contain a base oil comprising one or more compounds of Formula 1, wherein one or more compounds of Formula 1 have a hydroxyl value between 30 and 70. The lubricating composition may contain one or more additives selected from the group consisting of: friction modifiers, viscosity modifiers, antioxidants, anti-wear additives, extreme pressure additives, defoamers, demulsifiers, and corrosion inhibitors. Attached Figure Description

[0016] Figure 1 GPC data for an embodiment of this disclosure (Example 11B) are shown, in which the polymer distribution of the material is presented. Detailed Implementation

[0017] Reference will now be made to certain aspects of the disclosed subject matter in detail. While the disclosed subject matter will be described in conjunction with the enumerated claims, it should be understood that the illustrative subject matter is not intended to limit the claims to the disclosed subject matter. An aspect described in conjunction with a particular embodiment is not necessarily limited to that embodiment and may be practiced in conjunction with any other embodiment.

[0018] Throughout the document, values ​​expressed in range format should be interpreted flexibly to include not only the values ​​explicitly listed as limits of the range, but also all individual values ​​or subranges covered within the range, as if each value and subrange were explicitly listed. For example, the range “0.1% to 5%” or “0.1% to 5%” should be interpreted to include not only 0.1% to 5%, but also individual values ​​(e.g., 1%, 2%, 3%, and 4%) and subranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the specified range.

[0019] Unless the context clearly indicates otherwise, the singular forms “an” and “the” as used herein, and similar indicators, include plural indicators in the context of describing an element (especially in the context of the appended claims). For example, reference to “substituent” covers a single substituent as well as two or more substituents, and so on. It should be understood that, unless otherwise indicated herein or clearly contradicted by the context, any term in the singular form may include its plural counterpart, and vice versa.

[0020] As used herein, unless expressly stated otherwise, the following terms have the following meanings.

[0021] Unless otherwise specified, the term "or" is used to refer to a non-exclusive "or". The statement "at least one of A and B" has the same meaning as "A, B, or A and B".

[0022] Furthermore, it should be understood that the wording or terminology used herein, unless otherwise defined, is for descriptive purposes only and not for limitation. Any use of section headings is intended to aid reading the document and should not be construed as restrictive; information relating to a section heading may appear within or outside that particular section. Any publications, patents, and patent documents cited in this document are incorporated herein by reference in their entirety, as if individually cited. In the event of any inconsistency between the usage in this document and those documents so incorporated by reference, the usage in the incorporated references shall be considered supplementary to the usage in this document; in the case of irreconcilable inconsistencies, the usage in this document shall prevail.

[0023] As used herein, the terms “for example,” “to illustrate,” “such as,” or “including” are intended to provide examples that further illustrate a more general subject. Unless otherwise stated, these examples are provided merely to aid in understanding the application of the descriptions in this disclosure and are not intended to be limiting in any way.

[0024] In the methods described herein, actions can be performed in any order without departing from the principles of this disclosure, except where the timing or order of operations is explicitly specified. Furthermore, unless explicitly stated in writing that the specified actions are performed separately, they can be performed simultaneously. For example, the claimed action X and the claimed action Y can be performed simultaneously in a single operation, and the resulting process will fall within the literal scope of the claimed process.

[0025] As used herein, the term “substantially” means the majority or most, such as at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%.

[0026] As used herein, the term "alkyl" means a saturated or unsaturated, branched or straight-chain 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 respects, one or more alkyl groups are substantially saturated. In other respects, one or more alkyl groups are fully or partially saturated.

[0027] Terminology C1-C 22 Alkyl group; C3-C 12 Alkyl groups; and C1-C 10 Alkyl groups are defined as alkyl groups containing 1-22, 3-12, and 1-10 carbons. Any similar numerical ranges should be considered equally. In some respects, alkyl groups may be branched. In others, alkyl groups may be unbranched or straight-chain. In still others, alkyl groups may be a mixture of branched and unbranched groups. One or more alkyl groups may be saturated, unsaturated, or mixtures thereof. In still others, alkyl groups may be substituted, unsubstituted, or mixtures thereof.

[0028] As used herein, the term "substituted" means that one hydrogen atom of the alkyl chain is replaced by another substituent. In some aspects, the alkyl group is substituted at one or more positions with 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.

[0029] 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, a base oil may be a single lubricating component or a mixture of multiple lubricating components.

[0030] Unless otherwise specifically indicated, all percentages reported herein are intended to be percentages based on the weight of the final composition mentioned (i.e., weight %).

[0031] In 1975, the International Organization for Standardization (ISO), together with the American Society for Testing and Materials (ASTM), the Society for Tribologists and Lubrication Engineers (STLE), the British Standards Institute (BSI), and the German Institute for Standardization (DIN), unanimously decided to adopt a method to minimize confusion. This is known as the International Organization for Standardization Viscosity Grades, or ISO VG for short. This classification defines 20 viscosity grades ranging from 2 mm² / s to 3200 mm² / s (1 mm² / s = 1 cSt) at 40°C (104°F). For petroleum-based liquids, this roughly covers the range from kerosene to cylinder oil.

[0032] Each viscosity grade is represented by the integer closest to its midpoint kinematic viscosity (mm² / s) at 40°C (104°F), and allows a range of + / - 10% of that value. Twenty viscosity grades are listed below, each with appropriate limits.

[0033] Table 1. ISO Viscosity Classification

[0034]

[0035] This classification is based on the principle that the midpoint (nominal) kinematic viscosity of each grade should be approximately 50% higher than that of the previous grade. For example, ISO 100 oil is defined as oil with a kinematic viscosity between 90 cSt and 110 cSt at 40°C, and ISO 320 oil is defined as oil with a kinematic viscosity between 288 cSt and 352 cSt at 40°C.

[0036] Compound of Formula 1 :

[0037]

[0038] Where n is an integer from 2 to 6; R is a series of integers from C1 to C2. 22 Alkyl; R2 is C3-C 12 Alkyl; R3 is hydrogen or C1-C 10 alkyl.

[0039] In some respects, the compound of formula 1 is one in which R is C3-C 12Those alkyl compounds. In other respects, R is a branched C6-C... 10 Alkyl group. In other respects, R is 2-ethylhexyl.

[0040] In some respects, the compound of formula 1 is wherein R2 is C5-C 11 Those alkyl compounds. In other respects, R2 is a straight-chain saturated or unsaturated C7-C. 11 Alkyl group. In other respects, R2 is a straight-chain C2. 11 alkyl.

[0041] In some respects, the compound of formula 1 is wherein R3 is a branched C4-C 12 Those alkyl compounds. In other respects, R3 is a straight-chain C4-C8 alkyl. In other respects, R3 is a straight-chain C6 alkyl.

[0042] In some respects, the compounds of Formula 1 are those in which R is 2-ethylhexyl, R2 is a straight-chain C9 alkyl, and R3 is a straight-chain C6 alkyl.

[0043] In one respect, a subset of the compounds of Formula 1 can be represented as compounds of Formula 3.

[0044]

[0045] Where n is an integer from 2 to 6, and R is a C1-C22 alkyl group.

[0046] Preparation of compounds of formula 1 and formula 3 :

[0047] Compounds of Formulas 1 and 3 can be prepared by oligomerization of hydroxylated fatty acids (or mixtures of hydroxylated fatty acids) followed by esterification of the remaining acid group with an alcohol. Hydroxylated fatty acids are known in the art, commercially available, and can be prepared by those skilled in the art. As shown in the examples, 12-hydroxystearic acid and 10-hydroxystearic acid can be used to prepare compounds of Formula 1. Any enantiomer of hydroxystearic acid or a mixture thereof is functional in this disclosure. Other hydroxylated fatty acids are known in the art and can be prepared, for example, by epoxidation of unsaturated fatty acids followed by reductive ring-opening, yielding various 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) is directly derived from castor oil and is commercially available from several companies, such as Gokul Overseas, Jayant Agro-Organics Ltd, De Monchy UK Ltd, Acme Hardesty, or Hampshire Commodities Ltd. Because commercially available 12-hydroxystearic acid is derived from castor oil, it typically contains a certain amount of stearic acid as an impurity. Representative examples of commercially available 12-hydroxystearic acid are shown in the embodiments.

[0048] Mixtures of hydroxylated fatty acids or acids can be oligomerized at elevated temperatures using catalysts containing tin, titanium, or nitrogen, wherein the water formed is removed. The reaction is typically carried out in the absence of a solvent, but optionally with a small amount of solvent. Water removal can be accomplished by entrainers, reduced pressure, and / or nitrogen injection. The result of this step is oligomeric acids comprising a distribution of compounds of formula 2 as follows:

[0049]

[0050] Where n is an integer from 2 to 6; R2 is C3-C 12 Alkyl; R3 is hydrogen or C1-C 10 alkyl.

[0051] 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 other fatty acids with effectively capped reactive hydroxyl groups present in the starting material. For example, typically, a distribution is achieved where the majority of oligomers contain 2 to 6 units, and more than 50% contain 3 or more units. However, premature termination of oligomerization will result in a smaller average polymer size (molecular weight) and lower viscosity. Conversely, further driving oligomerization will result in a higher average molecular weight and higher viscosity. Depending on the application, either outcome may be desired. Figure 1The GPC distribution of Example 11B of this disclosure is shown. Furthermore, pre-oligomeric hydroxy fatty acids are also commercially available, such as Hypermer LP1 from Croda.

[0052] The compound of Formula 2 can then be esterified by reacting with a straight-chain or branched alcohol having 1 to 22 carbon atoms. In some respects, the alcohol can be selected from methanol, ethanol, isopropanol, butanol, 2-ethylhexanol, 2-(2-butoxypropoxy)prop-1-ol (DPnB), 1-decanol, 1-octanol, 2-octanol, and Isofol 18 (2-octyldecyl). Additional catalysts containing tin, titanium, nitrogen, or acid can be used, and the water formed is removed to obtain the esterified product of Formula 1 with an AV of less than 1.0 mg KOH / g or less than 0.2 mg KOH / g.

[0053] Alternatively, compounds of Formula 1 can be prepared in a single vessel 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 achieve an AV of less than 0.2 mg KOH / g.

[0054] Base oils may also contain one or more compounds of formula 4:

[0055]

[0056] Where n is an integer from 2 to 6; R is a set of C1-C2 integers. 22 Alkyl; R2 is C3-C 12 Alkyl; R3 is hydrogen or C1-C 10 Alkyl group, and R4 is C1-C. 22 Acyl group. In some respects, compounds of formula 4 are those in which R is 2-ethylhexyl, R4 is a C18 acyl group, R2 is a straight-chain C9 alkyl group, and R3 is a straight-chain C6 alkyl group.

[0057] The compound of Formula 1 can be used as a base oil for preparing lubricant compositions that can be used, for example, as hydraulic fluids according to the following specifications: (ISO 6743-4, ISO 15380 and DIN 51517-3).

[0058] Compounds of Formulas 1 and 3 can be used as base oils in the preparation of lubricant compositions for lubricating interfaces between two mechanical surfaces. The interface can be any two surfaces requiring lubrication, such as, but not limited to, surfaces of gears, motors, drilled holes, milled surfaces, hydraulic systems, etc. In some respects, the lubricant is gear oil. Gear oil can be automotive or industrial gear oil. Automotive gear oils include those suitable for use in manual transmissions, transfer cases, and differentials, which typically use hypoid gears. The term "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 via a drive shaft and also to the front and rear axles. It is also referred to in the literature as a transfer case housing, transfer gearbox, transfer case, or guide gear box. Industrial gear oils include those suitable for spur gears, helical gears, bevel gears, hypoid gears, and worm gears. Particularly included are those suitable for use in windmill gearboxes, which typically have helical gears.

[0059] Automotive gear oils typically have a viscosity range of SAE 50 to SAE 250, and more commonly SAE 70W to SAE 140. Suitable automotive base oils also include cross-grades such as 75W-140, SOW-90, 85W-140, and 85W-90. The American Petroleum Institute (API) uses GL grades to classify automotive gear oils. The API classification subdivides all transmission fluids into the following six categories.

[0060] API GL-1 is an oil designed for use under light conditions. They consist of additive-free base oils. Sometimes they contain small amounts of antioxidants, corrosion inhibitors, defoamers, and other additives. API GL-1 oils are designed for use in trucks and agricultural machinery with non-synchronized helical-bevel gears, worm gears, and manual transmissions.

[0061] API GL-2 is an oil designed for mild conditions. It contains anti-wear additives and is designed for use with worm gears. Recommended for proper lubrication of tractor and agricultural machinery transmissions.

[0062] API GL-3 is an oil for mild conditions and contains up to 2.7% anti-wear additives. It is designed for lubricating bevel gears and other gears in truck transmissions. It is not recommended for hypoid gears.

[0063] API GL-4 is an oil suitable for a wide range of conditions (light to heavy). They contain up to 4.0% effective anti-scratch additives. Designed for bevel and hypoid gears with small shaft displacements, truck gearboxes, and shaft units. Recommended for use in asynchronous gearboxes of US trucks, tractors, and buses, as well as primary gears and other gears in all vehicles. These oils are fundamental for synchronous gearboxes, especially in Europe.

[0064] API GL-5 is an oil designed for severe conditions. They contain up to 6.5% effective anti-scratch additives. The general application of this type of oil is for hypoid gears with significant shaft displacement. They are recommended as a general-purpose oil for all other mechanical transmission units (except gearboxes). Oils of this type with specific approval from the vehicle manufacturer can only be used in synchronized manual transmissions. If API GL-5 oils correspond to the requirements of specification MIL-L-2105D or ZF TE-ML-05, they can be used in limited-slip differentials. In this case, the category name will be different, such as API GL-5+ or API GL-5 LS.

[0065] API GL-6 is an oil designed for extremely demanding conditions (high sliding speeds and significant shock loads). It contains up to 10% high-performance anti-scratch additives. It is designed for hypoid gears with significant axial displacement. API GL-6 is no longer frequently used because API GL-5 is considered sufficient to meet the most stringent requirements.

[0066] Most modern gearboxes require GL-4 oil, and individual differentials (when assembled) require GL-5 oil.

[0067] Industrial gear oil specifications are primarily managed by the American Gear Manufacturers Association (AGMA) in North America or by individual manufacturers themselves. Typical specifications for industrial gear oils in the United States are shown in Table 1 below.

[0068] Table 1 .

[0069]

[0070] In Europe and most other countries in the world, industrial gear oil specifications are typically written by the German Standards Association (e.g., DIN 51517-3).

[0071] Lubricant formulations

[0072] Compounds of Formulas 1, 3, and 4, or mixtures thereof, can be formulated into lubricating compositions by combination 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 elevated temperature. Mixing can be carried out batch-wise or continuously as needed. In some 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, demulsifiers, and corrosion inhibitors. Depending on the specific application and user requirements, additives are typically included in the final formulation at levels between 1% and 20%. Additives can be included alone or as part of additives known in the art as an additive package. An additive package is a commercially available mixture of additives formulated by a supplier for inclusion in a specific base oil and for use in a specific application. In some aspects, the lubricating composition contains 1% to 10% by weight of additives. In some aspects, the lubricating composition contains 2% to 6% by weight of additives.

[0073] The additional base oils used in the compositions of this disclosure may be based on natural or synthetic oils, or blends thereof, and may be formulated into a final base oil formulation, provided that the lubricant has a suitable viscosity for the desired application. Gear oils for such applications may be mineral oil bases, such as conventional and solvent-refined alkane neutral and bright oils, hydrotreated alkane neutral and bright oils, naphthenic oils, cylinder oils, etc., including straight-run oils and blends.

[0074] In some embodiments, the base oil comprises a blend of one or more base oils of formulas 1, 3, and 4 and at least one other base oil. In some aspects, 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.

[0075] Synthetic base oils can also be used in the practice of this invention, such as, for example, PAO, alkylated aromatic compounds, polybutene, diesters, polyol esters, polydiols, polyphenylene ethers, and blends thereof. Polyalphaolefins are typically produced from C8 to C14 olefins, and the result is usually a combination of dimers, trimers, tetramers, pentamers, etc. It is also known to blend PAO and esters with mineral oils to form semi-synthetic compounds. Preferred base oils are synthetic base oils, especially base oils containing PAO or mixtures of PAO as the main component. PAOs are well known and readily available, such as Chevron-Synfluid, Exxon-Spectrasyn, INEOS-Durasyn, etc. Synthetic esters are also well known, such as Oleon-Radiaube, 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 the desired result.

[0076] The compounds of Formula 1 can be used as base oils for preparing final lubricating formulations. The compounds of Formula 1 may comprise all or substantially all of the base oil or all or substantially all of the final lubricating formulation. In some aspects, the base oil comprises more than 10% of one or more compounds of Formula 1. In some aspects, the compounds of Formula 1 comprise between 10% and 100%, between 10% and 85%, between 10% and 95%, between 20% and 75%, between 20% and 75%, or between 50% and 100% of the base oil or lubricating composition.

[0077] The compounds of Formula 3 can be used as base oils for preparing final lubricating formulations. The compounds of Formula 3 may comprise all or substantially all of the base oil or all or substantially all of the final lubricating formulation. In some aspects, the base oil comprises more than 10% of one or more compounds of Formula 3. In some aspects, the compounds of Formula 3 comprise between 10% and 100%, between 10% and 85%, between 10% and 95%, between 20% and 75%, or between 50% and 100% of the base oil or lubricating composition.

[0078] In some aspects, the base oil contains more than 10% of one or more compounds of formula 1, and also contains one or more compounds of formula 4. In some aspects, the base oil contains more than 10% of one or more compounds of formula 3, and also contains one or more compounds of formula 4.

[0079] Example

[0080] Table 2 .

[0081]

[0082] The commercially available 12-hydroxystearic acid used has the following fatty acid composition as shown in Table 3.

[0083] Table 3 .

[0084]

[0085] Examples 1A-F

[0086] 12-hydroxystearic acid (450 g, 1.44 mol; 1.98 equivalents) was added to a 2000 ml five-necked round-bottom flask equipped with a PTFE centrifugal stirrer, temperature feedback probe, and a magnetically sealed stirrer guide with an equal sleeve, nitrogen inlet and outlet through a distillation head, a Liebig condenser, a receiving flask, and an outlet bubbler. Once melted, the contents were purged with N2 (15 ml min). −1 The mixture was heated to 190°C with stirring (420 rpm). When the reaction temperature was reached, a vacuum of 200 mbar was applied (while maintaining nitrogen purging). After 1.5 hours, the pressure was reduced to 50 mbar, and after 2.5 hours, the reaction was cooled, and the AV was measured to be 78.0 mg KOH / g. The reaction was restarted and continued for another 30 minutes, yielding an AV of 70.7 mg KOH / g. The reaction was cooled to below the expected esterification temperature, and a Dean-Stark water separator with a vertical double-surface Liebig condenser was used instead of a distillation head. 2-Ethylhexyl-1-ol (2-EH; 95.0 g, 0.72 mol; 1 equivalent) was added to the reaction vessel, and the Dean-Stark water separator was filled with an additional 33 ml of 2-EH. The reaction was heated to 190°C, and a vacuum was carefully applied to achieve stable reflux of 2-EH into the water separator. Reflux was maintained during the reaction by reducing the pressure as needed. After 8 hours of reaction (total reaction time 11 hours), the AV was measured to be 7.0 mg KOH / g. A catalyst (TNBT, 0.2 ml) was added, and the reaction was allowed to proceed for another 5.5 hours (total reaction time 16.5 hours), after which the AV reached <0.2 mg KOH / g. The reaction temperature was adjusted to 125°C, and a full vacuum was applied to remove excess 2-EH through a water separator. When the distillation of 2-EH stopped, a simple distillation arm was used instead of a water separator, 5 g of decolorizing charcoal was added to the reaction vessel, and the headspace was purged with a sprayer placed as low as possible in the vessel without contacting the agitator instead of nitrogen. A full vacuum was applied to vaporize the remaining free 2-EH and maintained for 3 hours. The vessel was repressurized by spraying, and the product was vacuum filtered through a diatomaceous earth filter bed to obtain 1A [poly(12-hydroxystearic acid) 2-ethylhexyl ester], a pale yellow viscous liquid.

[0087] Example 1B - Example 1B is a repeat experiment using the same stoichiometry as 1A, however, the oligomerization of hydroxystearic acid was carried out for 4 hours until AV was 65.3 mg KOH / g before the introduction of 2-EH.

[0088] Example 1C is a repeat experiment using the same stoichiometry as 1A, however, the oligomerization of hydroxystearic acid was carried out for 3.5 hours until AV was 70 mg KOH / g before the introduction of 2-EH.

[0089] Example 1D is a repeat of 1C.

[0090] Example 1E is a repeat of Example 1A, wherein the stoichiometry of 2-EH is increased by 10%.

[0091] Example 2

[0092] The material from Example 1 was returned to the reaction vessel. 50 ml of distilled water and a substantial amount of anti-burst particles were added to a second 250 ml three-necked flask, and a sintering gas distribution tube was installed through a section of PTFE tubing. The gas distribution tube was introduced into the sample reaction vessel, ensuring the sintering end was as low as possible to avoid contaminating the stirrer blades. The steam vessel was placed in a water bath on a hot plate stirrer set to 30°C. The contents of the reaction vessel were heated to 115°C under separate nitrogen purging. At the set temperature, the nitrogen purging was stopped and a vacuum was applied, allowing the cryogenic steam to be extracted through the gas distribution tube and injected through the reaction body. After approximately 3 hours, the heat was removed and the vacuum stopcock was closed. Once room temperature was reached, the vacuum was released by repressurizing the steam generator flask and injecting steam.

[0093] Example 3

[0094] Hypermer LP1 (520.0 g, 0.297 mol CO2H; 1 equivalent) and 2-ethylhexyl-1-ol (57.9 g, 0.445 mol; 1.5 equivalent) were added to a 1000 ml five-necked round-bottom flask equipped with a PTFE centrifugal stirrer, a temperature feedback probe, a magnetically sealed stirrer guide with a sleeve, a nitrogen inlet and outlet through a Dean-Stark water separator, a Liebig condenser, and an outlet bubbler. The mixture was then stirred in 80 ml of water for 1 minute. -1The mixture was heated to 220°C under nitrogen purging and stirred at 500 rpm. After 2.5 hours, the temperature was lowered to 180°C, 0.2 ml of TNBT was added, and the reaction was allowed to proceed for another 16 hours, after which AV decreased to 1.36 mg KOH / g. Another 0.2 ml of TNBT was added, and the reaction was continued for another 24 hours, after which AV decreased to 0.1 mg KOH / g. The temperature was lowered to 120°C, and a vacuum was applied under nitrogen purging for 3 hours. The product was then filtered overnight through SW-10 cellulose filter aid to obtain the material of Example 3.

[0095] Example 4

[0096] 12-Hydroxystearic acid (491.6 g, 1.67 mol) and 2-octanol (108.4 g, 0.83 mol, approximately 50% excess) were charged into a five-necked round-bottom flask equipped with a nitrogen headspace purging system (approximately 30 mL / min), a centrifugal stir bar (approximately 500 rpm), a temperature feedback loop, a Dean-Stark receiver with organic circulation, and a collection flask. The Dean-Stark receiver was equipped with a vertical condenser and a Dreschel flask to ensure a nitrogen atmosphere. Note: For 12-hydroxystearic acid molar calculations, the average Mwt is calculated from the acid value. The reaction was initially heated to 180 °C, and then gradually increased to 200 °C, with the heating rate controlled by the water escape 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 ≤20 mg KOH / g. The reaction was maintained at 200°C until completion (AV ≤ 0.2 mg KOH / g). After 16 hours, an additional dose of TnBT catalyst (0.2 g) and 2-octanol (approximately 10 ml) were added. The product was cooled to 110°C, and then activated carbon (approximately 1% by weight) was added to the reaction vessel and a vacuum (≤ 5 mbar) was applied. The reaction conditions were maintained for 5 hours before draining and filtering. 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.

[0097] Example 5

[0098] 12-hydroxystearic acid (955.4 g, 3.25 mol) and 1-decyl alcohol (244.7 g, 1.55 mol, approximately 50% excess) were charged into a five-necked round-bottom flask equipped with a nitrogen headspace purging (approximately 30 mL / min), a centrifugal stir bar (approximately 450 rpm), a temperature feedback loop, a Dean-Stark receiver with organic circulation, and a collection flask. The Dean-Stark receiver was equipped with a vertical condenser and a Dreschel flask to ensure a nitrogen atmosphere. Note: For 12-hydroxystearic acid molar calculations, the average Mwt is calculated from the acid value. The reaction was initially heated to 160 °C, and then gradually increased to 200 °C, with the heating rate controlled by the water escape rate, for approximately 3 hours. Tyzor TnBT catalyst (approximately 0.4 g) and 1-decyl alcohol (approximately 25 mL) were added to the reaction vessel, with an acid value ≤30 mg KOH / g. The reaction was maintained at 200°C until completion (AV ≤ 0.2 mg KOH / g), approximately 24 hours. The product was cooled to 145°C, and then activated carbon (approximately 1% by weight) was added to the reaction vessel and a vacuum (≤ 5 mbar) was applied. The reaction conditions were maintained for 5 hours before draining and filtering the product. The material was vacuum filtered using Fibra-cel SW-10 as a filter aid. The product, 1-decyl poly(12-hydroxystearate), was a grayish-white paste-like solid.

[0099] Example 6

[0100] 12-hydroxystearic acid (327.2 g, 5.29 mol total) and 2-ethylhexanol (344.1 g, 2.64 mol, approximately 50% excess) were charged into a five-necked round-bottom flask equipped with a nitrogen headspace purging system (approximately 30 ml / min), a centrifugal stir bar (approximately 500 rpm), a temperature feedback loop, a Dean-Stark receiver with organic circulation, and a collection flask. The Dean-Stark receiver was equipped with a vertical condenser and a Dreschel flask to ensure a nitrogen atmosphere. Note: For 12-hydroxystearic acid molar calculations, the average Mwt was calculated from the acid value. The reaction was initially heated to 165 °C, and then gradually increased to 190 °C at a rate controlled by the water escape rate for approximately 1 hour until an AV of less than 15 was reached (actual AV = 13.2 mg KOH / g). When adding TnBT catalyst (approximately 1.7 g), the reaction was maintained at 190 °C. The reaction was maintained at 190°C until completion (AV ≤ 0.2 mg KOH / g), approximately 38 hours. The reaction was then cooled to 120°C. The reaction was then reconfigured by removing the Dean-Stark receiver and replacing it with a simple distillation arm, reconfiguring the nitrogen headspace purging to subsurface nitrogen injection, and then applying a vacuum (≤ 5 mbar) to strip away any free 2-ethylhexanol. The reaction conditions were maintained for 5 hours, and then the reaction was repressurized and samples were taken for acid value (AV = 0.12 mg KOH / g) and GC analysis to determine the content of free 2-ethylhexanol at approximately 1,500 ppm.

[0101] The reaction was reconfigured for steam stripping: a subsurface nitrogen jet was connected to a 1-liter, three-necked round-bottom flask filled with approximately 500 g of water and anti-snap boiling particles. A nitrogen / steam vent from the three-necked flask was connected to the subsurface jet in the reaction vessel. The reaction was heated to 110 °C and a vacuum (<20 mbar) was applied, minimizing the nitrogen flow to the vessel. The water in the flask was gently heated with a hot air gun to maintain room temperature, and vigorous bubbling of the gases (nitrogen + steam) in the reaction vessel was observed: for a constant vacuum, the water temperature will determine the strength of the steam stripping process. These conditions were maintained for 3 hours before repressurization and purging with nitrogen instead of the steam jet. Samples of the product were taken 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 and filtered (filter aid: Celite). ® 512) and underwent complete analytical processing. The product, poly(2-ethylhexyl 12-hydroxystearic acid), is a clear, amber-colored viscous liquid.

[0102] GPC analysis was used to determine the distribution of repeating units in the material from Example 6.

[0103] Table 4 .

[0104]

[0105] Example 7

[0106] The material prepared according to Example 6 (550.0 g), activated carbon (approximately 1 wt%), and Tonsil Optium 210-ff (approximately 1 wt%) were loaded into a five-necked round-bottom flask equipped with a subsurface nitrogen injection (approximately 30 ml / min), a centrifugal stirring bar (approximately 400 rpm), a temperature feedback loop, a condenser assembly for distillation removal, and a collection flask. The collection flask was equipped with a Dreschel flask to ensure a nitrogen atmosphere and vacuum capability. The reaction was heated to 110 °C, and then a vacuum (≤5 mbar) was applied. The reaction conditions were maintained for 3 hours, then the reaction was pressurized again, and the product was discharged and used with Celite. ® 512 was used as a filter aid. The product was a clear, amber-colored viscous liquid.

[0107] Example 8

[0108] The material prepared according to Example 6 (550.0 g) and acetic anhydride (110 ml, a large excess) were charged into a five-necked round-bottom flask equipped with a subsurface nitrogen jet (approximately 30 ml / min), a top-mounted stirrer with a centrifugal stirring bar (approximately 400 rpm), a temperature feedback loop, a condenser assembly for distillation removal, and a collection flask. The collection flask was equipped with a Dreschel flask to ensure a nitrogen atmosphere and vacuum capability. The reaction was heated to 100°C and held at 100°C for approximately 5 hours, and then the reaction was reconfigured for steam stripping: the subsurface nitrogen jet was connected to a 1-liter three-necked round-bottom flask filled with approximately 500 g of water and anti-spilling particles. A nitrogen / steam vent pipe from the three-necked flask was connected to the subsurface jet in the reaction vessel. The reaction was heated to 110°C and a vacuum (<20 mbar) was applied, and the nitrogen flow to the vessel was reduced to a minimum. Gently heat the water in the flask with a hot air gun to keep the water at room temperature and observe vigorous bubbling of the gas (nitrogen + steam) in the reaction vessel: for a constant vacuum, the temperature of the water will determine the strength of the steam stripping process. Maintain these conditions for 3 hours before repressurizing and purging with nitrogen instead of steam jetting. Add activated carbon (approximately 1% by weight) to the vessel and apply a vacuum (≤5 mbar). Maintain the reaction conditions for 3 hours, then repressurize the reaction and drain the product using Celite. ® 512 was used as a filter aid. The product, 2-ethylhexyl poly-12-hydroxystearoyl acetylate, was a clear, pale yellow, viscous liquid.

[0109] Example 9

[0110] 12-hydroxystearic acid (1000 g, 3.19 mol; 1 equivalent) and 2-ethylhexyl-1-ol (519.2 g, 3.99 mol; 1.25 equivalent) were charged into a 2000 ml five-necked round-bottom flask equipped with a PTFE centrifugal stirrer, a temperature feedback probe, and a magnetically sealed stirrer guide with an equal sleeve, a nitrogen inlet and outlet through a Dean-Stark water separator, a Liebig condenser, and an outlet bubbler. Once melted, the mixture was purged with N2 (15 ml min). −1 The mixture was heated to a set point of 200°C with stirring (520 rpm). The Dean-Stark water separator was initially filled with 2-EH, but once displaced by the reaction water, the water level in the separator remained above approximately 80%, maintaining 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 was allowed to proceed for another 16 hours, after which the AV of the reaction reached <0.2 mg KOH / g. Another 0.2 ml of TNBT was added, and the reaction was continued for another 3 hours. The mixture was cooled to 110°C, and decolorizing char (5 g) was added, with a vacuum carefully applied to prevent bubbling, thereby removing excess 2-EH for 2 hours. The char was removed by filtration, and a full vacuum was applied at 125°C under nitrogen injection until free 2-EH was undetectable in the product by GC or odor.

[0111] Example 10

[0112] A sample of 2-ethylhexyl 12-hydroxystearate (from Example 9, 550 g; nom. 1.333 mol) was loaded into a 1000 ml round-bottom flask equipped with a PTFE centrifugal stirrer, a temperature feedback probe, and a magnetically sealed stirrer guide tube with a Liebig condenser nitrogen inlet and outlet, and the reactants were heated to 90 °C. Acetic anhydride (125 ml; 136.0 g, 1.333 mol) was slowly added. Only minimal exothermic reaction was observed, and heating was applied to raise the temperature to 110 °C when the reaction temperature began to decrease. After adding 50 ml of acetic anhydride, the addition was stopped and a sample was taken to ensure that the reaction had occurred. The addition was completed more quickly, and 0.1 ml of methanesulfonic acid was added as a catalyst. After the reaction was complete, excess acetic anhydride and the acetic acid formed were distilled off under vacuum. Decolorizing charcoal (5 g) was added, and heating was continued at 125 °C under vacuum for another 3 hours, followed by filtration of the final product with SW-10 cellulose filter aid.

[0113] Table 5 shows the oxidation stability (induction time) of the above embodiments.

[0114] Table 5 .

[0115]

[0116] Reference 1 is a commercially available capped lactone sold by Biosynthetic under product code BT22. Reference 2 is a commercially available high-performance pentaerythritol tetraisostearate sold by Cargill Incorporated under the trademark Priolube 3987.

[0117] Tables 5, 6, and 7 show a comparison of the stability of the acetylated forms with end caps and two commercial benchmarks of Formula 1 compounds. Surprisingly, the examples of Formula 1 containing free hydroxyl groups (as demonstrated by the hydroxyl value) are approximately 7 times more stable than the corresponding acetylated forms. This is a significant and unexpected increase in oxidative stability, which will be highly advantageous for end users.

[0118] Table 6 .

[0119]

[0120] Table 7 .

[0121]

[0122] Example 11 - Scale-up Experiment of Poly(12-hydroxystearic acid) 2-ethylhexyl ester

[0123] Before setting the oil jacket to a constant oil temperature of 90°C, inspect the container to ensure it is clean and operational. Seal the container, ensuring the main vent valve is closed before applying full vacuum to assess vacuum tightness. Release the vacuum with nitrogen, then fill with 12-hydroxystearic acid through the sight glass port. Batch sizes are shown in Table 8 below. Once filled, close the sight glass port and raise the constant oil temperature to 160°C with nitrogen headspace at 100 ml / min.

[0124] Once 12-HSA is completely melted, turn on the stirrer (150 rpm), raise the temperature to a constant reactor temperature of 190°C, and increase the nitrogen headspace to 200 ml / min. When the contents reach 190°C, apply an initial pressure of 800 mbar; then reduce the pressure to 200 mbar over 10 minutes and maintain this pressure for 1.5 hours. Afterward, reduce the pressure to <50 mbar and maintain this pressure for another hour. Break the vacuum with nitrogen and pressurize the container to 1100 mbar. Sample the contents through the ejector valve and measure the acid value. After sampling, purge the ejector with nitrogen for 10 minutes. If the acid value is between 70 mg KOH / g... -1 Up to 80mgKOH g -1 If the reaction is complete, proceed to the next stage; if it does not meet specifications, reduce the pressure to <50 mbar and continue the reaction until the desired AV is reached.

[0125] Cool the container to a constant reactor temperature of <140°C before unscrewing the small inlet port on the container lid. Before re-closing the port, fill the container with the required amount of 2-ethylhexanol. Additionally, the binary separator is filled with 1 / 3 water and 2 / 3 2-ethylhexanol. Then set the container to a constant reactor temperature of 190°C, and once reached, reduce the pressure to 800 mbar. The pressure is then periodically reduced to maintain a suitable reflux level.

[0126] After approximately 6 to 7 hours, the vacuum is broken with nitrogen and the container is pressurized to 1100 mbar. The contents are sampled through the injection valve, and the acid value is measured. If the acid value is ≤10 mg KOH / g... -1 Then release the pressure and add tetrabutyl titanate (TnBT) through the small inlet port on the cap. Continue the reaction by reducing the pressure until reflux is achieved. If the acid value is >10 mg KOH g -1 If the reaction continues, a sample is taken again after one hour. After sampling, nitrogen gas is blown into the injector for 10 minutes.

[0127] After adding TnBT, continue the reaction under reduced pressure to ensure proper reflux is maintained. Using the same procedure detailed above, periodically sample the vessel until the acid value is <0.2 mg KOH / g. -1 And it is considered that the reaction is complete.

[0128] Once complete, set the vessel to a constant reactor temperature of 125°C and increase the stirrer speed to 200 rpm. Drain the binary separator; discard any water and retain any 2-ethylhexanol for another batch. Once this temperature is reached, reduce the pressure in the vessel to <50 mbar and distill the free 2-ethylhexanol from the vessel into the binary separator. Once the 2-ethylhexanol distillation stops, set the vessel to 110°C and break the vacuum with nitrogen.

[0129] Connect the vacuum-grade nylon tubing to the reactor, and the other end to a valve mounted on a 500ml three-necked flask. Attach a thermometer and a second valve to the other neck of the flask. Then place the three-necked flask in a DrySyn block on a hot plate, which contains a feedback probe. Add water and anti-spilling particles to the flask and heat the block to 110°C.

[0130] Reduce the pressure in the 50L container to <50 mbar, and with the second valve on the 500ml flask closed and the first valve open, open the reactor valve. This reduces the pressure in the 500ml flask and generates vapor that is injected into the 50L container. Collect the generated vapor along with any 2-ethylhexanol in a binary separator. After stopping the removal of 2-ethylhexanol from the container, close the valve and break the vacuum in the container with nitrogen.

[0131] Pressurize the container to 1100 mbar, then sample the contents through the ejector valve and measure the acid value. After sampling, purge the ejector with nitrogen for 10 minutes. Determine the 2-ethylhexanol content, and if >100 ppm, continue steam stripping. If the 2-ethylhexanol content is <100 ppm, stripping is considered complete.

[0132] For batches 11B, 11C, and 11D, set the vessel to a constant reactor temperature of 90°C and reduce the pressure to <50 mbar for drying. Maintain these conditions for 1 to 2 hours. Break the vacuum with nitrogen and pressurize the vessel to 1100 mbar. Open the bottom valve and discharge the material into a pre-weighed vessel.

[0133] For batch 11A, set the container to a constant reactor temperature of 90°C and pressurize to 1100 mbar. Open the bottom valve and discharge the material into a pre-weighed container. Then, transfer the material into a 30L glass container fitted with Norit SA. Set the oil jacket to 90°C and apply a vacuum of <50 mbar. Maintain these conditions for 1 to 2 hours before breaking the vacuum with nitrogen. Then, discharge the material into a pre-weighed container.

[0134] All four batches were filtered through a Buncher funnel using Celite 545 filter aid and Whatman 54 filter paper. Once filtered, the material was discharged into pre-weighed containers.

[0135] Table 8. 50L reaction volume and details

[0136]

[0137] Table 9 .

[0138]

[0139] Example 12 - Fractionation Effect

[0140] Material from Example 11B was fed through a 4" Pope wiped-film evaporator (WFE) under vacuum and various conditions to separate the lower molecular weight components. Four different WFE conditions were evaluated, resulting in four groups of residues and distillates listed in Table 10 below.

[0141] Table 10 .

[0142]

[0143]

[0144] Table 10 shows that polymer content and properties can be altered by treating the separated components with WFE. Materials with higher polymer content can be produced. Depending on the desired characteristics, component separation may be necessary in some applications.

[0145] Example 13 - Effect of hydroxyl position change

[0146] Example 13A - Poly-10-hydroxystearic acid 2-ethylhexyl ester

[0147] 10-hydroxystearic acid (900 g, 95% purity, prepared by an enzymatic process as described in Example 17, followed by recrystallization) was heated to 190°C in a 2-liter round-bottom flask equipped with a nitrogen inlet and a take-off adapter connected to a horizontal water condenser over approximately 1 hour. Once this temperature was reached, 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 produce poly(10HSA).

[0148] The poly(10HSA) and 190 g of 2-ethylhexanol were heated to 190 °C in a 2 L round-bottom flask equipped with a nitrogen inlet and a take-off adapter connected to a horizontal water condenser for about 1 hour. During heating, a vacuum of 300 mbar was applied. The vacuum was slowly reduced to 100 mbar over 6 hours. 0.6 g of TBT was added at 19 mg KOH / g AV. After another 7 hours of further reducing the pressure to 90 mbar, the reaction was stopped at 0.2 mg KOH / g AV. Excess 2-ethylhexanol was distilled off. 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 a lengthy filtration (24 hours), product 13A was separated and analyzed (see below).

[0149] Example 13B - Poly(10-hydroxystearyl ethylhexyl) stearate (86 / 14)

[0150] To simulate the stearic acid content of commercially available 12-hydroxystearic acid, the comparison was made by adding a measured amount of stearic acid to the starting 10-hydroxystearic acid.

[0151] 10-Hydroxystearic acid (810 g) (95% purity, prepared via an enzymatic process followed by recrystallization) and 90 g 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 a take-off adapter connected to a horizontal water condenser. Once this temperature was reached, 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 produce poly(10HAS / stearic acid).

[0152] Poly(10HSA) / stearic acid and 190 g of 2-ethylhexanol were heated to 190 °C in a 2 L round-bottom flask equipped with a nitrogen inlet and a take-off adapter connected to a horizontal water condenser over approximately 1 hour. After reaching the reaction temperature, the pressure was reduced to 300 mbar over 2 hours. 0.6 g of TBT was added at 25 mg KOH / g AV. The pressure was reduced to 100 mbar. After another 7.5 hours, the reaction was stopped at 0.2 mg KOH / g AV. Excess 2-ethylhexanol was distilled off. 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 a lengthy filtration (approximately 5 hours), product 13B was separated and analyzed (see below).

[0153] Example 14 - The Influence of Unsaturation in the Main Chain

[0154] Example 14A - Poly(2-ethylhexyl 12-hydroxystearate) / ricinoleate (97½ / 2½)

[0155] 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 a take-off adapter connected to a horizontal water condenser. Once this temperature was reached, 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.

[0156] The poly(12HSA) / ricinoleate and 190 g of 2-ethylhexanol were heated to 190 °C in a 2 L round-bottom flask equipped with a nitrogen inlet and a take-off adapter connected to a horizontal water condenser over approximately 1 hour. After reaching the reaction temperature, the pressure was reduced to 300 mbar over 3.5 hours. 0.6 g of TBT was added at 20 mg KOH / g AV. The pressure was reduced to 100 mbar over 2.5 hours. After another 7.5 hours, the reaction was stopped at 0.2 mg KOH / g AV. Excess 2-ethylhexanol was distilled off. 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 separated and analyzed (see Table 11).

[0157] Example 14B - Poly-12-hydroxystearic acid 2-ethylhexyl ester / ricinoleate (95 / 5)

[0158] 978 g of 12-hydroxystearic acid and 51.5 g of ricinoleic acid were heated to 190 °C in a 2-liter round-bottom flask equipped with a nitrogen inlet and a take-off adapter connected to a horizontal water condenser over approximately 1 hour. Once this temperature was reached, 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 the mixture was cooled to obtain poly(12-hydroxystearic acid) / ricinoleic acid ester.

[0159] The poly(12HSA) / ricinoleate and 217 g of 2-ethylhexanol were heated to 190 °C in a 2 L round-bottom flask equipped with a nitrogen inlet and a take-off adapter connected to a horizontal water condenser over approximately 1 hour. After reaching the reaction temperature, the pressure was reduced to 300 mbar over 4 hours. 0.68 g of TBT was added at 16.6 mg KOH / g AV. The pressure was reduced to 100 mbar over 1.5 hours. After another 6 hours, the reaction was stopped at 0.12 mg KOH / g AV. Excess 2-ethylhexanol was distilled off. 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 separated 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 AV was 0.12 mg KOH / g. Excess 2-ethylhexanol was distilled off. 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 separated and analyzed (see Table 11).

[0160] Example 14C - Poly-12-hydroxystearic acid ethylhexyl ester / ricinoleate (92½ / 7½)

[0161] 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 a take-off adapter connected to a horizontal water condenser. Once this temperature was reached, 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.

[0162] The poly(12HSA) / ricinoleate prepared above and 196 g of 2-ethylhexanol were heated to 190 °C in a 2 L round-bottom flask equipped with a nitrogen inlet and a take-off adapter connected to a horizontal water condenser over approximately 1 hour. After reaching the reaction temperature, the pressure was reduced to 250 mbar over 1.5 hours. 0.6 g of TBT was added at 16 mg KOH / g AV. The pressure was reduced to 100 mbar over 3 hours. After another 5 hours, the reaction was stopped at 0.13 mg KOH / g AV. Excess 2-ethylhexanol was distilled off. 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 separated and analyzed (see Table 11).

[0163] Table 11 .

[0164]

[0165] Example 15 - Effects of acetylation and decrease in hydroxyl value

[0166] Example 15A - Acetylated to 29 mg KOH g -1 hydroxyl value

[0167] Poly(12-HSA) (1264.2 g, 1.01 mol) from Example 11B was placed in a round-bottom five-necked flask. The flask was equipped with a stirrer, temperature probe, pressure equalization dropping funnel, and a nitrogen headspace (30 ml / min). -1 The condenser is connected to a collection flask equipped with a nitrogen outlet that leads to a Dreschel bottle filled with a weak potassium hydroxide aqueous solution and phenolphthalein indicator.

[0168] Raise the temperature of the container to 130°C and place acetic anhydride (48.8 g, 0.48 mol) into a dropping funnel. Once the temperature is reached, slowly add the acetic anhydride to the container over 2 hours. Increase the nitrogen flow to 50 ml / min. -1 It is kept for 1.75 hours, and then the material is steam stripped.

[0169] By changing the nitrogen headspace to nitrogen injection (50ml min) -1 Steam stripping was performed. An ejector was connected to an auxiliary container filled with reverse osmosis water and a nitrogen inlet. The auxiliary container was placed in a water bath maintained at 60°C. A vacuum pump was used instead of the Dreschel flask, and the pressure in the main container was reduced to approximately 60 mbar, thereby reducing the pressure in the auxiliary container and causing steam generation. The generated steam was carried into the main container by a nitrogen injection. After 15 minutes, the container temperature was lowered to 110°C and maintained for 30 minutes. The container pressure was then reduced to 40 mbar and maintained for another 20 minutes, after which the vacuum was broken with nitrogen.

[0170] Nitrogen headspace was used instead of injection, and the container pressure was reduced to 20 mbar for drying. After approximately 2 hours, the vacuum was broken with nitrogen, and the material was sampled (S1). The acid value was measured to be 0.28 mg KOH / g. -1 And the hydroxyl value is 29 mg KOH g -1 Nitrogen headspace was replaced with nitrogen injection, and steam stripping continued at a container pressure of 20 mbar. After 5.5 hours, the vacuum was broken with nitrogen, and nitrogen headspace was replaced with nitrogen injection. The container temperature was lowered to 90°C, and the material was dried again at a container pressure of <30 mbar. After another 3.25 hours, the vacuum was broken with nitrogen, and a sample was taken (S2). The acid value was measured to be 0.19 mg KOH / g.-1 And the hydroxyl value is 29 mg KOH g -1 When the acid value is <0.2 mg KOH g -1 Then, another larger sample was taken. A total of approximately 220g of material was taken as Example 15A.

[0171] Example 15B - Acetylated to 11 mg KOH g -1 hydroxyl value

[0172] 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. Once the temperature was reached, acetic anhydride was added over 2.25 hours, allowing the reaction to proceed for another 1.5 hours, after which the container was cooled to 110 °C and stripped. The nitrogen headspace was changed to a nitrogen injection (50 ml / min). -1 Steam stripping is performed. An ejector is connected to an auxiliary container filled with reverse osmosis water and a nitrogen inlet. The auxiliary container is placed in a water bath maintained at 60°C. A vacuum pump is used instead of the Dreschel flask, and the pressure in the main container is reduced to <30 mbar, thereby reducing the pressure in the auxiliary container and generating steam. The generated steam is carried into the main container by a nitrogen injection.

[0173] After 5 hours, steam stripping was stopped by breaking the vacuum with nitrogen and the jet was replaced with nitrogen headspace. The container was cooled to 90°C, and then the pressure was reduced to <80 mbar for 2 hours. A sample (S3) with an acid value of 0.16 mg KOH was taken. -1 The hydroxyl value was measured to be 11 mg KOH g. -1 When the acid value is <0.2 mg KOH g -1 Then, another larger sample was taken. A total of approximately 235g of material was taken as Example 15B.

[0174] Example 15C - Acetylated to 3 mg KOH g -1 hydroxyl value

[0175] The remaining material was further acetylated by adding acetic anhydride (20.0 g, 0.20 mol) to a dropping funnel and heating the container to 130 °C. Once the temperature was reached, acetic anhydride was added over 1 hour, and the reaction was allowed to proceed for another 4 hours. The container was then cooled to 110 °C and stripped. The nitrogen headspace was changed to a nitrogen injection (50 ml / min). -1 Steam stripping is performed. An ejector is connected to an auxiliary container filled with reverse osmosis water and a nitrogen inlet. The auxiliary container is placed in a water bath maintained at 60°C. A vacuum pump is used instead of the Dreschel flask, and the pressure in the main container is reduced to <20 mbar, thereby reducing the pressure in the auxiliary container and generating steam. The generated steam is carried into the main container by a nitrogen injection.

[0176] After 5.4 hours, steam stripping was stopped by breaking the vacuum with nitrogen and the jet was replaced with nitrogen headspace. The container was cooled to 90°C, and then the pressure was reduced to <20 mbar for 2.5 hours. A sample (S4) with an acid value of 0.05 mg KOH was taken. -1 The hydroxyl value was measured to be 3 mg KOH g. -1 Because the acid value is <0.2 mg KOH g -1 Therefore, the reaction was considered complete, and the material was separated as in Example 15C.

[0177] Table 12 clearly demonstrates the significant and surprising effect of increasing the proportion of free hydroxyl groups (as measured by the hydroxyl value) on oxidative stability. A modest increase in hydroxyl value from 3 to 11 resulted in a threefold increase in oxidative stability. There is a difference of more than 10-fold between the starting material of Example 11 and the most acylated example at 15C.

[0178] Table 12 .

[0179]

[0180] Example 16 - Effect of different esterified alcohols

[0181] Poly(12-hydroxystearic acid)

[0182] 1100 g of 12-hydroxystearic acid was heated to 190 °C in a 2-liter round-bottom flask equipped with a nitrogen inlet and a take-off adapter connected to a horizontal water condenser over approximately 1 hour. Once this temperature was reached, the pressure was gradually reduced to 200 mbar over 1.5 to 2 hours, and then further reduced to <50 mbar. After reaching the acid value (70 mg KOH / g to 75 mg KOH / g), the reaction was stopped and

[0183] Example 16A - Poly(12-hydroxyhexyl stearate)

[0184] The poly-12HSA (860 g) and hexanol (160 g) prepared above were heated to 190 °C in a 2 L round-bottom flask equipped with a nitrogen inlet and a Dean Stark separator over approximately 1 hour. 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 at 10.3 mg KOH / g AV. After another 6.5 hours of further reducing the pressure to 200 mbar, the reaction was stopped at 0.2 mg KOH / g AV.

[0185] Excess hexanol was distilled off at 120°C. 947 g of the final product was bleached (10 g Norit SA4) and steam-stripped at 110°C for 3 hours. The product was dried and 5 g of Supercel filter aid was added. After filtration, the product was analyzed (see below).

[0186] Example 16B - Poly-12-hydroxystearic acid 2-octyldecyl ester

[0187] The prepared poly-12HSA (900 g) and 495 g Isofol 18 were heated to 190 °C in a 2 L round-bottom flask equipped with a nitrogen inlet and a take-off adapter connected to a horizontal water condenser over approximately 1 hour. During heating, a vacuum of 600 mbar was applied. Subsequently, the vacuum was slowly reduced to 125 mbar over 4 hours. 0.46 g TBT was added at 11.9 mg KOH / g AV. The reaction was stopped after another 7 hours of further pressure reduction to 25 mbar at 0.2 mg KOH / g AV.

[0188] The product was distilled using a two-stage molecular distillation apparatus. Excess Isofol 18 was distilled off (stage 1, 155°C-160°C / 10). -3 millibars; Level 2 185℃ / 10 -3 (mbar). 1064 g of the final product was bleached (10 g Norit SA4) and steam stripped at 110 °C for 4 hours. The product was dried and 5 g Supercel filter aid was added. After filtration, the product was analyzed (see below).

[0189] Example 16C-Poly-12-hydroxystearic acid isostearyl ester

[0190] The prepared poly(12HSA) (900 g) and 493 g isostearyl alcohol (3515) were heated to 190 °C in a 2 L round-bottom flask equipped with a nitrogen inlet and a take-off adapter connected to a horizontal water condenser over approximately 1 hour. 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 at 9.1 mg KOH / g AV. The reaction was stopped after a further 6.25 hours of pressure reduction to 25 mbar at 0.14 mg KOH / g AV.

[0191] The product was distilled using a two-stage molecular distillation apparatus. Excess isostearyl alcohol was distilled off (stage 1, 150°C-160°C / 10). -3 millibars; Level 2 185℃ / 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 Supercel filter aid was added. After filtration, the product was analyzed (see below).

[0192] Example 16D-poly-12-hydroxystearic acid stearyl ester

[0193] The prepared poly(12HSA) (900 g) and 495 g stearyl alcohol were heated to 190 °C in a 2 L round-bottom flask equipped with a nitrogen inlet and a take-off adapter connected to a horizontal water condenser for approximately 1 hour. During heating, a vacuum of 300 mbar was applied. Subsequently, the vacuum was slowly reduced to 100 mbar over 5 hours. 2.4 g of 20% TBT solution was added at 9.1 mg KOH / g AV. The reaction was stopped at 0.14 mg KOH / g AV after an additional 6.25 hours of further pressure reduction to 25 mbar.

[0194] The product was distilled using a two-stage molecular distillation apparatus. Excess isostearyl alcohol was distilled off (stage 1, 150°C-160°C / 10). -3 millibars; Level 2 185℃ / 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 Supercel filter aid was added. After filtration, the product was analyzed (see below).

[0195] Example 16E - Poly(12-hydroxystearic acid methyl ester)

[0196] The 12HSA (900 g) prepared above was heated to 190 °C in a 2 L round-bottom flask equipped with a nitrogen inlet and a take-off adapter connected to a horizontal water condenser. Methanol was metered into the reactor (approximately 350 mL / h). 0.5 g TBT was added at 25 mg KOH / g AV. After 5 hours, the reaction temperature was raised to 205 °C. After a total reaction time of 10 hours, the reaction was stopped at 0.17 mg KOH / g AV (initial product).

[0197] The reaction was repeated using 400 g of 12 HSA. The product was then subjected to a reaction at 280 °C and 3.5 × 10⁻⁶ ppm. -3 Molecular distillation is performed at millibars to produce top and bottom fractions.

[0198] The final product (poly-12-hydroxystearic acid methyl ester) is a mixture of 837g of the initial product and 148g of the top fraction from a molecular distillation repeat.

[0199] The final product (985 g) was bleached (10 g Norit SA4) and steam stripped at 110 °C for 3 hours. The product was dried and 5 g Supercel filter aid was added. After filtration, the product was analyzed (see below).

[0200] Example 16F - Poly(12-hydroxystearic acid isopropyl)

[0201] The first batch was prepared by esterifying poly12HSA with isopropanol. For the second batch, isopropyl ester was prepared by esterifying 12HSA with isopropanol to a low acid value. Both batches were subjected to molecular distillation to separate the low molecular weight components from the mixture. Isopropyl ester was prepared by mixing the top and bottom fractions of the molecular distillation in the following ratio.

[0202] The 12HSA (1000 g) prepared as described above was heated to 190 °C in a 2 L round-bottom flask equipped with a nitrogen inlet and a take-off adapter connected to a horizontal water condenser. The product was esterified to an AV of 75 mg KOH / g. IPA was metered into the mixture. After 7 hours, an AV of 34 mg KOH / g was reached, and 0.3 g TBT was added. After a total reaction time of 21 hours, an additional 0.3 g TBT was added, and the temperature was raised to 210 °C. After 4 hours, an AV of 0.25 mg KOH / g was reached, and the reaction was stopped. A total of 5 L of IPA was metered into the reactor. The recovered product was heated to 280 °C and 3.5 × 10⁻⁶ ppm. -3 Molecular distillation was performed at millibars (approximately 100 ml / h) to obtain the product, namely the top fraction (16F1).

[0203] The 12HSA (1250 g) prepared as described above was heated to 190 °C in a 2 L round-bottom flask equipped with a nitrogen inlet and a take-off adapter connected to a horizontal water condenser. IPA was metered into the reactor (approximately 350 mL / h). After 4 hours, 0.5 g TBT was added at an AV of 35 mg KOH / g. After 10.5 hours, an additional 0.3 g TBT was added at an AV of 3.7. Over the next 3 hours, the AV was increased to 9.4 mg KOH / g. A new IPA flask was then added. After a total reaction time of 26 hours, the reaction was stopped at an AV of 0.3 mg KOH / g. The product was then heated at 280 °C and 3.5 × 10⁻⁶ ppm. -3 Molecular distillation was performed at millibars (approximately 100 ml / h) to produce a top fraction (16F2) and a bottom fraction (16F3).

[0204] The final product is a mixture of 360g of the top fraction of 16F1 from molecular distillation, 120g of the top fraction of 16F2 from molecular distillation, and 700g of the bottom fraction of 16F3 from molecular distillation.

[0205] The combined fractions were bleached (12 g Norit SA4) and steam stripped at 110 °C for 3 hours. The product was dried and 5 g Supercel filter aid was added. After filtration, the product (16F) was analyzed (see below).

[0206] Table 13 .

[0207]

[0208] Example 17 - Preparation of 10-hydroxystearic acid

[0209] The tank was filled with 280 liters of softened water. Citric acid (473 g) and Na₂HPO₄ (1.65 kg) were added to the tank. The pH of the entire mixture was 7.0 ± 0.5. MgSO₄·7H₂O (689 g) was added to the tank and the mixture was stirred for 15 minutes. The temperature of the resulting mixture was adjusted to 20°C to 25°C. Oleic acid (7 kg) was added to the solution, followed by hydratase PDN C100 V2 (140 g) from Biocatalysts Ltd., and the resulting mixture was stirred at 20°C to 25°C for 24 hours. The mixture was then heated to 50°C and held at that 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.

[0210] Example 18 - Lubricant Formulation

[0211] Three exemplary lubricant compositions were prepared by mixing commercially available additive packages into the material of Example 11 according to the proportions in Table 14.

[0212] Table 14 .

[0213]

[0214] Preparation of blends

[0215] To prepare the blend, first add the additive packet to a beaker in the required amount, then add the base oil to reach 100g. Stir the mixture at 60°C for 20 minutes using a mixer set to 400rpm. Repeat this process for all desired blends.

[0216] Measure the properties of the blends and report them in Table 15 below.

[0217] Table 15 .

[0218]

[0219] For the material in Example 11, Hitec 307 exhibited the least desirable performance compared to the other additive packages used. Both King additive packages showed good performance, with oxidation times nearly doubled compared to the base material. King BL-1232EL performed slightly better. Hitec 307 is an additive package designed for mineral oils, so its performance being inferior to the King additive package designed for esters is not surprising.

[0220] Analytical methods

[0221] Viscosity

[0222] The viscosity of the sample was measured on an Anton Parr Stabinger Viscometer 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 machine also measures the viscosity index (VI) and density.

[0223] RapidOxy

[0224] The materials disclosed herein exhibit excellent oxidative stability. This stability may make assessing stability at lower temperatures time-consuming. Samples were evaluated at three different temperatures to more fully understand their stability. All samples were evaluated on an Anton Parr RapidOxy 100 instrument according to ASTM D8206. Method conditions are listed in Table 16. A 4-gram sample size was used in a standard glass dish. Temperatures utilized were 140°C, 160°C, or 180°C, as indicated. The apparatus was pressurized to 700 kPa with pure oxygen, and the test completion was determined by the time taken for the peak pressure to decrease by 10% or 50%. Thus, a 10% or 50% reduction was used as an indication of rapid oxidation start or oxidation induction time (OIT). OIT should be determined on compounds of Formulas 1 and 3, as well as on base oils and lubricant formulations without the addition of any additives or antioxidants. In some respects, the OIT of lubricating compositions, base oils, compounds of Formula 1, and compounds of Formula 3 is greater than 500 hours, as determined at 160°C according to ASTM D8206. In some respects, the lubricating compositions, base oils, compounds of Formula 1, and compounds of Formula 3 have an OIT greater than 750 hours, as determined according to ASTM D8206 at 160°C. In some respects, the lubricating compositions, base oils, compounds of Formula 1, and compounds of Formula 3 have an OIT greater than 1000 hours, as determined according to ASTM D8206 at 160°C.

[0225] Table 16 .

[0226]

[0227] We also evaluated the thermal degradation of the samples from Example 11B by thermogravimetric analysis (TGA) under a nitrogen atmosphere to ensure that the oxidative stability data were not biased towards degradation at higher temperatures. The samples were evaluated on standard equipment under nitrogen from 90°C to 900°C. No significant degradation was observed at temperatures below 240°C.

[0228] As used herein, the term "acid value" (AV) is defined as the weight (mg) of KOH required to neutralize 1g of organic acid present in a sample, and it is a measure of the free fatty acids present in the composition. AV can be determined by the AOCS official method Cd 3d-63.

[0229] As used herein, the term "hydroxyl value" is defined as the hydroxyl value expressed in milligrams of potassium hydroxide and corresponds to the number of hydroxyl groups present in 1 g of sample; it is one of the traditional characteristics of oils and fats. The hydroxyl value can be determined using the AOCS standard method Cd 13-60.

[0230] GPC analysis was performed using an Agilent 1260 Infinity GPC / SEC multi-detector kit. Solvent: tetrahydrofuran; detector refractive index: 1% (w / v); sample concentration: 50 μl; injection volume: 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 Column. Results are shown in Table 4 below.

[0231] All aspects of this disclosure

[0232] In some respects, the base oil may have a hydroxyl value between 30 and 60. In some respects, the lubricating composition may have a hydroxyl value greater than 10, or greater than 20, or greater than 30. In some respects, the base oil may have a hydroxyl value between 10 and 70, or between 20 and 70. In some respects, the base oil may have a hydroxyl value between 30 and 60.

[0233] In some aspects, the compound of Formula 1 may have a hydroxyl value greater than 10, or greater than 20, or greater than 30. In some aspects, the compound of Formula 1 may have a hydroxyl value between 10 and 70 or between 30 and 70. In some aspects, the compound of Formula 1 may have a hydroxyl value between 30 and 60.

[0234] In some aspects, compounds of Formula 3 may have a hydroxyl value greater than 10, or greater than 20, or greater than 30. In some aspects, compounds of Formula 3 may have a hydroxyl value between 10 and 70 or between 30 and 70. In some aspects, compounds of Formula 3 may have a hydroxyl value between 30 and 60.

[0235] In some aspects, the compounds of Formula 1 and Formula 4 may have hydroxyl values ​​greater than 10, 20, or 30. In some aspects, the compounds of Formula 1 and Formula 4 may have hydroxyl values ​​between 10 and 70 or between 20 and 70. In some aspects, the compounds of Formula 1 and Formula 4 may have hydroxyl values ​​between 30 and 60.

[0236] In some aspects, the compounds of Formula 3 and Formula 4 may have hydroxyl values ​​greater than 10, 20, or 30. In some aspects, the compounds of Formula 3 and Formula 4 may have hydroxyl values ​​between 10 and 70 or between 20 and 70. In some aspects, the compounds of Formula 3 and Formula 4 may have hydroxyl values ​​between 30 and 60.

[0237] Another aspect of this disclosure is a method for lubricating two surfaces, the method comprising contacting the interface of the surfaces with a lubricating composition of any composition described herein.

[0238] In some respects, the surface is part of the hydraulic system.

[0239] In some respects, the surface is gear-like.

[0240] In some applications, gears are used in industrial gearboxes, marine gearboxes, vehicle gearboxes, or vehicle transmissions.

[0241] In some respects, the surface is the drill bit surface or the milled surface.

[0242] The use of compounds of Formula 1 or Formula 3 as lubricants.

[0243] In some respects, the lubricating composition comprises a base oil and an additive, wherein the base oil comprises 10% or more of one or more compounds of formula 3, wherein R is 2-ethylhexyl.

[0244] In some aspects, the lubricating composition comprises a base oil and an additive, wherein the base oil comprises 10% or more of one or more compounds of formula 1, wherein R is C1-C2. 22 Alkyl group, R2 is a saturated or unsaturated C7 or C9 alkyl group; and R3 is a C6 or C8 alkyl group.

[0245] In some respects, the lubricating composition comprises a base oil and an additive, wherein the base oil comprises 30% or more of one or more compounds of formula 3, wherein R is 2-ethylhexyl.

[0246] In some respects, the lubricating composition comprises a base oil and an additive, wherein the base oil comprises 50% or more of one or more compounds of formula 3, wherein R is 2-ethylhexyl.

[0247] In some respects, the lubricating composition comprises a base oil and an additive, wherein the base oil comprises 10% or more of one or more compounds of formula 3, wherein R is 2-ethylhexyl; and also comprises 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.

[0248] In some respects, the lubricating composition comprises a base oil and an additive, wherein the base oil comprises 10% or more of one or more compounds of formula 3, wherein R is 2-ethylhexyl; and also comprises a polyalphaolefin (PAO).

[0249] In some respects, the lubricating composition comprises a base oil and an additive, wherein the base oil comprises 30% or more of one or more compounds of formula 3, wherein R is 2-ethylhexyl; and also comprises a polyalphaolefin (PAO).

[0250] In some aspects, the lubricating composition comprises a base oil and an additive, wherein the base oil comprises 10% or more of one or more compounds of formula 3, wherein R is 2-ethylhexyl; and also comprises 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.

[0251] In some respects, the lubricating composition comprises a base oil and an additive, wherein the base oil comprises 10% or more of one or more compounds of formula 3, wherein R is 2-ethylhexyl; and also comprises a polyalphaolefin (PAO) having a hydroxyl value greater than 10.

[0252] In some respects, the lubricating composition comprises a base oil and an additive, wherein the base oil comprises 30% or more of one or more compounds of formula 3, wherein R is 2-ethylhexyl; and also comprises a polyalphaolefin (PAO) having a hydroxyl value greater than 10.

[0253] In some aspects, the lubricating composition comprises a base oil and an additive, wherein the base oil comprises 10% or more of one or more compounds of formula 3, wherein R is 2-ethylhexyl; and also comprises 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.

[0254] In some respects, the lubricating composition comprises a base oil and an additive, wherein the base oil comprises 10% or more of one or more compounds of formula 3, wherein R is 2-ethylhexyl; and also comprises a polyalphaolefin (PAO) having a hydroxyl value greater than 20.

[0255] In some respects, the lubricating composition comprises a base oil and an additive, wherein the base oil comprises 30% or more of one or more compounds of formula 3, wherein R is 2-ethylhexyl; and also comprises a polyalphaolefin (PAO) having a hydroxyl value greater than 20.

[0256] In some respects, the lubricating composition comprises a base oil and an additive, wherein the base oil comprises 30% or more of one or more compounds of formula 3, wherein R is 2-ethylhexyl; and also comprises a polyalphaolefin (PAO) and has a hydroxyl value between 10 and 70.

[0257] In some respects, the lubricating composition comprises a base oil and additives, wherein the base oil comprises 30% or more of one or more compounds of formula 3, wherein R is 2-ethylhexyl, and also comprises a polyalphaolefin (PAO) and has a hydroxyl value between 20 and 70.

[0258] In some respects, the lubricating composition comprises a base oil and an additive, wherein the base oil comprises 30% or more of one or more compounds of formula 3, wherein R is 2-ethylhexyl; and also comprises a polyalphaolefin (PAO), and wherein the lubricating composition has a hydroxyl value between 20 and 70.

[0259] In some respects, the lubricating composition comprises a base oil and an additive, wherein the base oil comprises 30% or more of one or more compounds of formula 3, wherein R is 2-ethylhexyl, and wherein the base oil has an oxidation induction time (OIT) of more than 500 hours, and wherein the base oil does not contain any additional additives or antioxidants.

[0260] In some respects, the lubricating composition comprises a base oil and an additive, wherein the base oil comprises 50% or more of one or more compounds of formula 3, wherein R is 2-ethylhexyl.

[0261] In some respects, the lubricating composition comprises a base oil and an additive, wherein the base oil contains 10% or more of one or more compounds of formula 3, wherein R is 2-ethylhexyl, and the base oil has an OIT of more than 500 hours as determined by ASTM D8206 at 160°C.

[0262] In some respects, the lubricating composition comprises a base oil and additives, wherein the base oil contains 10% or more of one or more compounds of Formula 1, and the base oil has an OIT of more than 500 hours as determined by ASTM D8206 at 160°C.

[0263] In some respects, the lubricating composition comprises a base oil and an additive, wherein the base oil contains 30% or more of one or more compounds of formula 3, wherein R is 2-ethylhexyl, and the base oil has an OIT of more than 750 hours as determined by ASTM D8206 at 160°C.

[0264] In some respects, the lubricating composition comprises a base oil and an additive, wherein the base oil contains 30% or more of one or more compounds of formula 3, wherein R is 2-ethylhexyl, and the base oil has an OIT of more than 1000 hours as determined by ASTM D8206 at 160°C.

[0265] In some respects, the lubricating composition comprises a base oil and an additive, wherein the base oil comprises 50% or more of one or more compounds of formula 3, wherein R is 2-ethylhexyl, and the base oil has an OIT of more than 1000 hours as determined by ASTM D8206 at 160°C.

[0266] In some respects, the lubricating composition comprises a base oil and an additive, wherein the base oil comprises 30% or more of one or more compounds of formula 3, wherein R is 2-ethylhexyl, has an OIT of more than 750 hours as determined by ASTM D8206 at 160°C, has a hydroxyl value between 20 and 70, and also comprises a polyalphaolefin (PAO).

Claims

1. A lubricating composition comprising a base oil and one or more additives, wherein: The base oil comprises 10% to 100% by weight of one or more compounds of formula 1: Where n is an integer from 2 to 6; R is a series of integers from C1 to C2. 22 Alkyl; R2 is C3-C 12 Alkyl; R3 is hydrogen or C1-C 10 alkyl.

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

3. The 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 greater than 20.

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

6. The composition according to claim 1, wherein the compound of formula 1 has a hydroxyl value between 30 and 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, anti-wear additives, extreme pressure additives, defoamers, demulsifiers, and corrosion inhibitors.

8. The composition according to any one of claims 1 to 7, wherein the composition comprises at least 30%, at least 50%, or at least 70% of a compound of formula 1.

9. The composition according to any one of claims 1 to 8, wherein the composition further comprises additional base oil selected from the group consisting of: polyalphaolefin (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 of claim 9, wherein the additional base oil comprises a polyalphaolefin.

11. The composition of claim 1, wherein the base oil further comprises one or more compounds of formula 4: in, n is an integer from 2 to 6; R is a C1-C2 integer. 22 Alkyl; R2 is C3-C 12 Alkyl; R3 is hydrogen or C1-C 10 Alkyl group, and R4 is C1-C. 22 Acyl group.

12. The composition according to claim 8, wherein the base oil has a hydroxyl value greater than 20.

13. The composition according to claim 9, wherein R is 2-ethylhexyl and R4 is C 18 Acyl group.

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: Where n is an integer from 2 to 6, and R is a C1-C2 sequence. 22 alkyl.

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

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

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

18. The composition of claim 14, wherein the base oil has a hydroxyl value greater than 20.

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

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

21. The composition of claim 14, wherein the one or more additives are selected from the group consisting of: friction modifiers, viscosity modifiers, antioxidants, anti-wear additives, extreme pressure additives, defoamers, demulsifiers, and corrosion inhibitors.

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

23. The composition according to any one of claims 14 to 22, wherein the composition further comprises an additional base oil selected from the group consisting of: polyalphaolefin (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.

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

25. The composition according to any one of claims 1 to 24, wherein the base oil further comprises one or more compounds of formula 4: in, n is an integer from 2 to 6; R is a C1-C2 integer. 22 Alkyl; R2 is C3-C 12 Alkyl; R3 is hydrogen or C1-C 10 Alkyl group, and R4 is C1-C. 22 Acyl group.

26. The composition of claim 25, wherein the base oil has a hydroxyl value greater than 20.

27. The composition according to claim 25, wherein R is 2-ethylhexyl and R4 is C 18 Acyl group.

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

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

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

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

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

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

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