CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Patent Application No.

62/772,672, filed November 29, 2018, the entire disclosure of which is incorporated herein by reference for all purposes.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

[0002] This invention was made with government support under DOE Grant No.

DE-SC0001004 awarded by the Department of Energy. The government has certain rights in the invention.

FIELD OF THE INVENTION

[0003] The present invention relates to lubricant compositions and in particular to bio-based branched aliphatic compounds for use in lubricant compositions and base oils for pharmaceutical and personal care product formulations, and methods of making such compounds.

BACKGROUND OF THE INVENTION

[0004] Lubricants are widely used in industrial machinery, automobiles, aviation machinery, refrigeration compressors, agricultural equipment, marine vessels and many other applications and represent an over $60 billion global chemical enterprise. Base oils are key components (typically, 75-90 wt.%) of commercial formulated lubricants and account for up to 75% of lubricant cost. Base oils are also key components in the formulations of personal care products, greases, and the like. According to the American Petroleum Institute (API), there are five categories of mineral base oils (Groups I - V). (Reference 3) Base oils from Groups I through III are obtained by solvent-refining, distillation, or hydro-processing of petroleum. (Reference 4) Base oils from Group IV have undergone chemical upgrading; for example, 1-decene from petroleum undergoes oligomerization to form poly-a-olefins (PAOs). (Reference 2) Finally, Group V includes all other oils. (Reference 3) ExxonMobil Basestocks 2018 Pulse Report suggests Group III+ oils will experience the greatest increase in demand over the next 10 years (+4% increase) due to their high fuel efficiency and quality. (Reference 5) Nevertheless, their production is expensive and energy intensive, requires petroleum feedstocks, which contribute to greenhouse gas emissions, and harsh reaction conditions, especially when making Group IV PAOs, whose synthesis requires corrosive catalysts (AlCh, BF3, and HF). (References 4, 6) To mitigate these challenges, promising renewable alternatives from bio-derived feedstocks have gained momentum. (References 7-14) Bio-based feedstocks can result in a nearly "closed carbon balance" through CO2 capture during photosynthesis and have unique functional groups that enable site-specific chemistries during processing.

[0005] In one of the early attempts to make bio-based products, Corma and coworkers produced n-tricosane, a linear alkane product with 23 carbons, from lauric acid, a fatty acid found in coconut and palm kernel oils. (Reference 11) This process involved ketonization of lauric acid to form 12-tricosanone, containing 23 carbons, followed by its hydrodeoxygenation (HDO) to produce n-tricosane (58.2% selectivity) and Cio through C22 alkanes (13.9% selectivity total). Although the final product would not be suitable as a Group III base oil (18 to 40 carbons) due to its poor viscosity and high melting point, the short-chain alkanes may be suitable for ultra-low sulfur diesel (ULSD) fuel. Despite these obstacles, the strategy proposed by Corma and coworkers is appealing. The intermediate ketone, 12-tricosanone, can be obtained in 89% yield by ketonization of lauric acid and is an ideal starting material for lubricant synthesis because it contains a high number of carbons and can partake in carbon-carbon coupling reactions due to the presence of a ketonic group.

[0006] Ketones are excellent platforms to incorporate branching due to their acidic -CH group at the a carbon position. (References 3, 14, 17-20) Previously, Bell and coworkers performed multiple cross-ketonization reactions, starting from short-chain length C3 - C5 carboxylic acids, followed by HDO, to produce C12 - C33 branched and cyclic alkane diesel fuels and lubricant base oils. (Reference 12) Wang and coworkers produced C23 bio-lubricant base oil with ~50% yield from acetone and furfural via successive aldol condensation and HDO steps. (Reference 10) While these routes use renewable feedstocks, e.g., carboxylic acid and acetone, which can be produced from sugar fermentation, and lignocellulosic biomass-derived furfural, they require multiple reaction steps and extractions. This results in carbon loss, the need for excessive amounts of solvent, and high production costs.

SUMMARY OF THE INVENTION

[0007] Accordingly, an object of the present invention is to provide novel strategies to synthesize a highly branched bio-lubricant base oil in fewer steps preferably using one or more bio-derived starting materials, for example a long chain ketone obtained from bio-derived fatty acids, and substituted or unsubstituted furfural, obtained from lignocellulosic biomass. The synthesis of 12-tricosanone in high yield from lauric acid is discussed above. In the present invention, selective aldol condensation of a furfural with a ketone such as 12-tricosanone is performed followed by HDO to afford the final products, C28 and C33 branched alkanes, having comparable viscosity to petroleum-derived Group III and Group IV base oils. [0008] Thus, in an aspect of the invention, a lubricant composition is provided, the lubricant composition comprising :

a. 75-99% by weight of a base oil comprising one or more branched aliphatic compounds having the following formula :

R1R2HC-CH2-CH R3R4 (I)

wherein :

(i) Ri and R3 are independently selected from alkyl groups having 8 to 26 carbon atoms,

(ii) R2 and R4 are independently selected from the group consisting of H and alkyl groups having 5 to 7 carbon atoms, with a proviso that at least one of R2 and R4 is not hydrogen,

wherein the alkyl groups are substituted or unsubstituted, or branched or unbranched,

wherein Ri and R3 may be the same or different, and wherein the total carbon content of the branched aliphatic compound of formula (I) is in the range of 26 to 66; and

b. an effective amount of one or more additives.

[0009] In an embodiment of the lubricant composition, at least one of the one or more branched aliphatic compounds has a bio-based content in the range of 20 to 100%, according to ASTM-D6866.

[00010] In another embodiment of the lubricant composition, at least one of the one or more branched aliphatic compounds has one of the following structures:

[00011] In an embodiment of the lubricant composition, the base oil further comprises a minor amount (e.g., up to 25, up to 20, up to 15, up to 10 or up to 5 % by weight, based on the total weight of the lubricant composition) of one or more alkanes having a carbon content in the range of 1 to 25.

[00012] In yet another embodiment of the lubricant composition, the one or more additives are selected from the group consisting of antioxidants, stabilizers, detergents, dispersants, demulsifiers, antioxidants, anti-wear additives, pour point depressants, viscosity index modifiers, friction modifiers, anti-foam additives, defoaming agents, corrosion inhibitors, wetting agents, rust inhibitors, copper passivators, metal deactivators, extreme pressure additives, and combinations thereof.

[00013] The lubricant composition as disclosed hereinabove may further comprise one or more co-base oils selected from the group consisting of API Group I base oil, Group II base oil, Group III base oil, Group IV base oil, Group V base oil, gas-to-liquid (GTL) base oil, and combinations thereof.

[00014] In an embodiment of the lubricant composition, at least one of the one or more branched aliphatic compounds of formula (I) has a kinematic viscosity at 100 °C in the range of 2 to 100 cSt and a kinematic viscosity at 40 °C in the range of 6 to 100 cSt, as measured by ASTM D445. Additionally, at least one of the one or more branched aliphatic compounds of formula (I) has a viscosity index, calculated from kinetic viscosity at 100 °C and 40 °C, in the range of 100 to 200, as measured by ASTM D2270.

[00015] In an embodiment of the lubricant composition, at least one of the one or more branched aliphatic compounds of formula (I) has a pour point in the range of 2 °C to -160 °C, as measured by ASTM D97; and an oxidation stability in the range of 150 °C to 300 °C, as measured by ASTM D6375.

[00016] In an aspect of the lubricant composition, the base oil has a kinematic viscosity of at least 3 cSt, as measured by ASTM D445 and a bio-based content in the range of 30 to 100%, according to ASTM-D6866.

[00017] In another aspect, the lubricant composition is used in one or more of industrial machinery, automobiles, aviation machinery, refrigeration compressors, agricultural equipment, marine vessels, agriculture equipment, medical equipment, hydropower production machinery, and food processing equipment.

[00018] In an aspect, there is provided a composition comprising :

one or more branched aliphatic compounds having the following formula :

R1R2HC-CH2-CH R3R4 (I)

wherein :

(i) Ri and R3 are independently selected from alkyl groups having 8 to 26 carbon atoms,

(ii) R2 and R4 are independently selected from the group consisting of H and alkyl groups having 5 to 7 carbon atoms, with a proviso that at least one of R2 and R4 is not hydrogen,

wherein the alkyl groups are substituted or unsubstituted, or branched or unbranched,

wherein Ri and R3 may be the same or different, and wherein the total carbon content of the branched aliphatic compound of formula (I) is in the range of 26 to 66; and

wherein the composition has a bio-based content in the range of 30 to 100%, according to ASTM-D6866. [00019] In another aspect, there is a method of making the composition comprising one or more branched aliphatic compounds having the formula (I), as disclosed hereinabove, the method comprising the steps of:

a) providing a first component comprising one or more of a furfural or its derivative and a second component comprising a ketone having the formula R1R3CO, wherein each Ri and R3 is independently selected from the group consisting of alkyl groups having 8 to 26 carbon atoms,

wherein at least one of the first component and the second component is bio-derived from a renewable source;

b) condensing the first component with the second component in the presence of a basic catalyst to form a condensed furan compound (CF);

where Rs is hydrogen, methyl, ethyl, or hydroxymethyl group,

c) hydrodeoxygenating the condensed furan compound (CF) in the presence of a hydrodeoxygenation catalyst to obtain one or more branched aliphatic compounds of formula (I).

[00020] In an embodiment of the method, the step of providing a second component comprises a ketone comprises ketonic decarboxylyzing one or more fatty acids from one or more natural oils or waste cooking oils.

[00021] In another embodiment of the method, the basic catalyst is selected from the group consisting of liquid bases (including inorganic liquid bases and organic liquid bases) and solid bases.

[00022] In yet another embodiment of the method, the hydrodeoxygenation catalyst is a solid acid supported metal based catalyst, a physical mixture of a metal based catalyst, or a metal/ metal oxide catalyst and preferably Pd/C, Pd/SiC>2 0r Pt/C, with a solid acid. The solid acid supported metal based catalyst can be selected from Ni/ZSM-5, Pd/ZSM-5, Pd/BEA, or a physical mixture of a metal based catalyst with a solid acid, including Pd/C + ZSM-5, Pd/C + BEA, Pt/C + BEA, and preferably a supported metal-metal oxide catalyst such as Ir-ReOx/SiC>2, Ir-MoOx/SiC>2 or ¹ M ² M0/Si02, wherein ^X M = Ir, Ru, Ni, Co, Pd, Pt, or Rh and ² M = Re, Mo, W, Nb, Mn, V, Ce, Cr, Zn, Co, Y, or Al.

[00023] In an aspect of the invention, the composition prepared according to the method as disclosed hereinabove, is used as a base oil in pharmaceutical and personal care products.

[00024] In an aspect of the invention, a personal care composition is provided, the personal care composition comprising :

a) a base oil comprising the composition as disclosed hereinabove; and

b) an effective amount of one or more additives selected from the group consisting of pigments, fragrances, emulsifiers, wetting agents, thickeners, emollients, rheology modifiers, viscosity modifiers, gelling agents, antiperspirant agents, deodorant actives, fatty acid salts, film formers, anti-oxidants, humectants, opacifiers, monohydric alcohols, polyhydric alcohols, fatty alcohols,

preservatives, pH modifiers, moisturizers, skin conditioners, stabilizing agents, proteins, skin lightening agents, topical exfoliants, antioxidants, retinoids, refractive index enhancers, photo-stability enhancers, SPF improvers, UV blockers, and water.

[00025] In an embodiment, the personal care composition further comprises an active ingredient selected from the group consisting of antibiotic, antiseptic, antifungal, corticosteroid, and anti-acne agent.

[00026] In an aspect of the invention, a pharmaceutical composition is provided, the pharmaceutical composition comprising :

a. a base oil comprising the composition as disclosed hereinabove;

b. an effective amount of one or more pharmaceutically active

ingredients; and

c. optionally, one or more pharmaceutically acceptable excipients.

BRIEF DESCRIPTION OF THE DRAWINGS

[00027] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate various embodiments or aspects of the invention, and together with the written description, serve to explain certain principles of the invention.

[00028] Fig. 1 shows a renewable approach to produce bio-lubricant base oil comprising branched aliphatic compounds. Base-catalyzed aldol condensation (AC) of furfural and 12-tricosanone is performed to form a C33 furan intermediate, along with a small fraction of a C28 intermediate, followed by their hydrodeoxygenation (HDO) over an Ir-ReOx/SiC>2 catalyst to produce base oils containing C33 branched alkane as the major component.

[00029] Fig. 2 shows conversion of 12-tricosanone to C33-CF ("C33 Condensed Furan"), a condensed furan compound, as a function of solvents. Reaction conditions: 0.227 g furfural and 0.1 g 12-tricosanone (mole ratio = 8: 1), 80 °C, 24 hrs. Studies performed with no co-solvent, cyclohexane, and dioxane contained 100 pL of 1 M NaOH. Methanol and water studies contained 1 M NaOH.

[00030] Fig. 3 shows the yields of C28 and C33 furan intermediates obtained from the reaction of 12-tricosanone with furfural. Reaction conditions: 1 mol (0.1 g) tricosanone, 8 mol (0.227 g) furfural, 80 °C. Cyclohexane, dioxane and no co-solvent studies were performed with 100 pL of 1 M NaOH. Methanol and water contained 0.2 g NaOH in 5 mL solvent, 24 h.

[00031] Fig. 4 shows (a) the GC spectra of the aldol condensation (AC) product obtained from a reaction of furfural (0.45 g) and 12-tricosanone (0.10 g). Potential isomers are highlighted in the panels on the right; (b) the GC spectra of product obtained after HDO of aldol condensation product. AC products are C28 and C33 furan isomers (0.40 g). HDO products are primarily chiral isomers of the C28 and C33 alkanes. Eicosane (0.10 g) is used the internal standard to quantify products, post-reaction, in (a) and (b). m/z was obtained separately, using GC-MS. Reaction conditions: 8 hrs, 80 °C, 5 mL methanol, 16: 1 mol ratio furfural : tricosanone, 1 M NaOH.

[00032] Fig. 5 shows the mass fragments of products after (a) aldol condensation and (b) hydrodeoxygenation reactions using HRMS-LIFDI. Solvents for both reactions were removed prior to analysis, and samples were prepared in dichloromethane (1 mg/mL). m/z was obtained from Liquid Injection Field Desorption/Ionization-Mass Spectrometry (LIFDI-MS). Reaction conditions: 16 h, 180 °C, 5 MPa H2, 20 mL cyclohexane, ~0.1 g furans, 0.05 g Ir-ReOx/SiC>2 (experimental). 1 mg/mL in

dichloromethane, catalyst removed (LIFDI-MS).

[00033] Fig. 6 shows the ^X H NMR spectrum obtained to characterize an aldol condensation product. Sample was prepared in CDCI3 (1 mg/mL). The predominant product is the C33 furan, followed by the C28 furan, and their isomers. The highlighted bonds in C33H50O3 are referencing the hydrogen atoms.

[00034] Fig. 7 shows the ¹³ C NMR spectrum obtained to characterize an aldol condensation product. Sample was prepared in CDCI3 (1 mg/mL). The highlighted bonds in C33H50O3 are referencing the carbon atoms.

[00035] Fig. 8 shows the ^X H NMR spectrum obtained to characterize an

hydrodeoxygenation product. Sample was prepared in CDCI3 (1 mg/mL). The highlighted bonds in C33H68 are referencing the hydrogen atoms. High molecular weight oxygenates are likely present, as indicated by the chemical shifts at ~3.7 ppm.

[00036] Fig. 9 shows the ^X H NMR spectrum obtained to characterize a

hydrodeoxygenation product. Sample was prepared in CDC (1 mg/ml_). The highlighted bonds in C33H68 are referencing the hydrogen atoms. High molecular weight oxygenates are likely present, as indicated by the chemical shifts at ~3.7 ppm.

[00037] Fig. 10 shows the ¹³ C NMR spectrum obtained to characterize a

hydrodeoxygenation product. Sample was prepared in CDCb (1 mg/mL). The highlighted bonds in C33H68 are referencing the carbon atoms. Chemical shifts above 60 ppm may correspond to the carbons associated with the unidentified oxygenates.

[00038] Fig. 11A shows yields of furan intermediates from the reaction of 12- tricosanone (0.10 g) with varying amounts of furfural at 80 °C and with 1 M NaOH in methanol (5 mL) for 8 hrs. Error bars correspond to mean ± standard error of the mean (SEM) of three independent reactions.

[00039] Fig. 11B shows the product distribution after performing HDO on the aldol condensation furan intermediates shown in Fig. 11A with a mole ratio of furfural : 12- tricosanone: : 16: 1. HDO reaction conditions: 16 h, 180 °C, 5 MPa, H2, 20 mL cyclohexane, 0.4 g C28 and C33 furans, 0.15 g Ir-ReOx/Si02, 2 replicates.

[00040] Fig. 12 shows (a) Carbon-carbon (C-C) cracking in the tertiary carbon positions of the C33 alkane to produce alkane byproducts, (b) C-C cracking in secondary carbon positions; the dashed line is another possible route to obtain the C14 alkane instead of the C15 alkane.

DETAILED DESCRIPTION OF THE INVENTION

[00041] As used herein, the term "biomass-derived" is used interchangeably with "biologically-derived", "bio-derived" or "bio-based" and refers to compounds that are obtained from renewable resources such as plants and contain either only or

substantially renewable carbon, and no or a very minimal amount fossil fuel-based or petroleum-based carbon.

[00042] Assessment of the content of renewably based carbon in a material can be performed through standard test methods. Using radiocarbon and isotope ratio mass spectrometry analysis, the bio-based content of materials can be determined, using ASTM-D6866-18 (a standard method established by ASTM International, formally known as the American Society for Testing and Materials).

[00043] As used herein, the "bio-based content" is determined in accordance with ASTM-D6866-18 and is built on the same concepts as radiocarbon dating, but without use of the age equations. The analysis is performed by deriving a ratio of the amount of radiocarbon ( ¹⁴ C) in an unknown sample to that of a modern reference standard. The ratio is reported as a percentage with the units "pMC" (percent modern carbon) with modern or present defined as 1950. If the material being analyzed is a mixture of present day radiocarbon and fossil carbon (containing no radiocarbon), then the pMC value obtained correlates directly to the amount of biomass material present in the sample.

[00044] Combining fossil carbon with present day carbon into a material will result in a dilution of the present day pMC content. By presuming 107.5 pMC represents present day biomass materials and 0 pMC represents petroleum derivatives, the measured pMC value for that material will reflect the proportions of the two component types. A material derived 100% from present day plants/trees would give a radiocarbon signature near 107.5 pMC. If that material was diluted with 50% petroleum derivatives, it would give a radiocarbon signature near 54 pMC.

[00045] A bio-mass content result is derived by assigning 100% equal to 107.5 pMC and 0% equal to 0 pMC. In this regard, a sample measuring 99 pMC will give an equivalent bio-based content result of 93%.

[00046] Assessment of the biodegradability of a material, such as of branched aliphatic compounds of formula (I), base oils, or compositions such as lubricant compositions and personal care compositions of the present disclosure, can be

performed through standard test methods, such as those developed by the Organization for Economic Cooperation and Development (OECD), the Coordinating European Council (CEC), and the American Society for Testing and Materials (ASTM), such as, OECD 301B (the Modified Strum test), ASTM D-5864-18, and CEC L-33-A-934. Both OECD 301B and ASTM D-5864-18 measure ready biodegradability, defined as the conversion of 60% of the material to CO2 within a ten day window following the onset of biodegradation, which must occur within 28 days of test initiation. In contrast, the CEC method tests the overall biodegradability of hydrocarbon compounds and requires 80% or greater

biodegradability as measured by the infrared absorbance of extractable lipophilic compounds.

[00047] As used herein, the terms "lubricant", "lubricant composition", and

"lubricant base oil" refer to any substance used to reduce friction by providing a protective film between two moving surfaces. In general, a lubricant exhibits one or more characteristics, such as, high viscosity index, high boiling point, thermal stability, oxidation stability, low pour point, corrosion prevention capability and low surface tension.

[00048] As used herein, a "condensation" reaction refers to a chemical reaction in which two molecules combine to form a larger molecule while producing a small molecule, such as H2O, as a byproduct. [00049] As used herein, a "hydrogenation" reaction refers to a chemical reaction between molecular hydrogen and another compound, typically, in the presence of a catalyst to reduce or saturate organic compounds.

[00050] As used herein, a "hydrodeoxygenation" or "HDO" reaction refers to a chemical reaction whereby a carbon-oxygen bond is cleaved or undergoes lysis (cleavage of a C-0 bond) by hydrogen, typically in the presence of a catalyst. "HDO" is a process for removing oxygen from a compound.

[00051] The term "kinematic viscosity" is used herein to refer to a fluid's inherent resistance to flow when no external force other than gravity is acting on the fluid.

"Kinematic viscosity" is measured as the ratio of absolute (or dynamic) viscosity to density.

[00052] The term "pour point" as used herein refers to the temperature below which a liquid loses its flow characteristics.

[00053] Process of Making a Composition Comprising One or More Branched Aliphatic Compounds Represented bv Formula (I)

[00054] The invention disclosed herein relates to a composition comprising one or more branched aliphatic compounds as represented by the formula (I) from one or more bio-derived reactants, the process of making such compositions and their use as base oils in lubricant compositions, personal care compositions and pharmaceutical

compositions.

[00055] In an aspect of the invention, the composition comprises one or more branched aliphatic compounds having the following formula :

R1R2HC-CH2-CHR3R4 (I)

wherein the composition has a bio-based content in the range of 30 to 100%, according to ASTM-D6866-18.

[00056] In the branched aliphatic compounds of formula (I), Ri and R3 are independently selected from alkyl groups having 8 to 26 carbon atoms, R2 and R4 are independently selected from the group consisting of H and alkyl groups having 5 to 7 carbon atoms, with a proviso that at least one of R2 and R4 is not hydrogen, and the total carbon content of the one or more branched aliphatic compounds of formula (I) is in the range of 26 to 66 (meaning that the compound contains a total of from 26 to 66 carbon atoms).

[00057] As used herein the alkyl groups can be substituted or unsubstituted, or branched or unbranched (linear) or a combination thereof. Suitable examples of alkyl groups include, but are not limited to, C5-C26 alkyl groups, including, but not limited to, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosanyl. [00058] In an embodiment, Ri and R3 may be the same. In another embodiment, Ri and R3 may be different. In yet another embodiment, Ri and R3 are independently chosen from alkyl groups having 8 to 26 carbon atoms, preferably from acyclic unbranched alkyl groups having 8-26 carbon atoms, and most preferably from acyclic unbranched alkyl groups having 8-16 carbon atoms, provided that in total the one or more branched aliphatic compounds of formula (I) contain from 26 to 66 carbon atoms.

[00059] Suitable examples of Ri and R3 include, but are not limited to, C8-C26 alkyl groups including, but not limited to, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosanyl.

[00060] In an embodiment, one of R2 and R4 is hydrogen. In another embodiment, R2 and R4 may be independently chosen from among alkyl groups having 5-7 carbon atoms, or 5-6 carbon atoms, provided that in total the branched aliphatic compound contains from 26 to 66 carbon atoms. Suitable examples of R2 and R4 include, but are not limited to, hydrogen, pentyl, hexyl, and heptyl.

[00061] In an embodiment, at least one of Ri and R3 is a branched alkyl group, having one or more branches. The one or more branches can have any suitable number of carbon atoms, with at least one of the branches having 1-18 carbon atoms, and preferably 1-10 carbon atoms.

[00062] Suitable examples of branched alkyl groups, having one or more branches include, but are not limited to, 2-methylpentane, 3-ethylpentane, and 4-ethylhexane.

[00063] In an aspect, the one or more branched aliphatic compounds of formula (I), have one of the following structures:

where Ri, R2, R3, and R4, are defined as hereinabove, provided that in total the branched aliphatic compound contains 26 to 66 carbon atoms.

[00064] In some embodiments, the composition also comprises a minor amount of one or more alkanes having a carbon content in the range of 1 to 25, or 5 to 20, or 5 to 15.

[00065] In an aspect, there is provided a process of making a composition comprising one or more branched aliphatic compounds as represented by formula (I). The process includes providing a first component comprising one or more of a furfural or its derivative and a second component comprising a ketone having the formula R1R3CO, wherein each Ri and R3 is independently selected from the group consisting of alkyl groups having 8 to 26 carbon atoms and where at least one of the first component and the second component is bio-derived from a renewable source. [00066] Furfural is one of the oldest renewable chemicals. Furfural or its derivatives can be produced by removing water from or dehydrating five-carbon sugars such as xylose and arabinose. These pentose sugars are commonly obtained from the hemicellulose fraction of biomass wastes like cornstalks, corncobs, oat, wheat bran, and sawdust, and the husks of peanuts and oats.

[00067] In an embodiment, the step of providing a second component comprising a ketone comprises ketonic decarboxylyzing one or more fatty acids obtained from one or more natural oils or waste cooking oils. The fatty acids may, for example, be obtained by splitting (hydrolyzing) triglycerides found in such oils. The mixtures of fatty acids thereby typically obtained may be used as mixtures in the ketonic decarboxylation reaction or may be fractionated or purified to produce the fatty acid(s) employed to provide the ketone(s) comprising the second component. Suitable examples of fatty acids include, but are not limited to saturated C10-C24 fatty acids such as lauric acid, palmitic acid and stearic acid. In some embodiments, the fatty acid is an unsaturated fatty acid, including, but not limited to, oleic acid, myristoleic acid, palmitoleic acid, linoleic acid, and sapienic acid. Such fatty acids may be derived from any suitable natural cooking oils including, but not limited, to coconut oil, palm oil, rapeseed oil, vegetable oil, corn oil, peanut oil, olive oil, canola oil, and sunflower oil. The fatty acids may also be derived from any waste cooking oils of one or more natural cooking oils and/or animal fats. The synthesis of ketones of different carbon length via selective hydrogenation of fatty acids from natural oils or WCO is known in the art.

[00068] The process of making a composition comprising one or more branched aliphatic compounds of formula (I) further includes condensing the first component with the second component in the presence of a basic catalyst to form a condensed furan compound (CF). Any suitable basic catalyst can be used. In an embodiment, the basic catalyst is chosen from liquid bases, including inorganic liquid bases and organic liquid bases. For example, the liquid base may be a solution of a base in a suitable solvent. In another embodiment, the basic catalyst is chosen from among solid bases.

[00069] Exemplary inorganic liquid bases include, but are not limited to, aqueous solutions of sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide. Exemplary organic liquid bases include, but are not limited to, pyridine, methylamine, and imidazole. Exemplary solid bases include, but are not limited to, alumina oxide, titanium oxide, lanthanum oxide, hydrotalcite, magnesium oxide, calcium oxide, and potassium cyanide.

[00070] Exemplary CF compounds include, but are not limited to, 11,13- di((tetrahydrofuran-2-yl)methyl)tricos-l l,13-dien-12-one and l l-di((tetrahydrofuran-2- yl)methyl)tricos-l l-dien-12-one. [00071] The first component comprising one or more of a furfural or a derivative thereof and a second component comprising a ketone having the formula R1R3CO can be provided in any suitable amount. In the context of the present invention, "a derivative thereof" (i.e., a furfural derivative) means a furfural compound substituted with one or more substituents such as alkyl (e.g., methyl) or hydroxyalkyl (e.g., hydroxymethyl) groups. Any suitable furfural derivative may be used including but not limited to methyl furfural and hydroxymethyl furfural.

[00072] In an embodiment, a molar ratio of the first component to the second component can be from 1 : 1 to 25: 1 or from 6: 1 to 25: 1 or from 7: 1 to 20: 1 or from 8: 1 to 16: 1. The condensation reaction can be carried out for any suitable amount of time such as from 1 second to 24 hours.

[00073] In an embodiment, the condensation reaction is carried out in the presence of one or more suitable solvents. Any suitable solvent, preferably capable of dissolving reactants and/or catalyst can be used. In an embodiment, the solvent is a polar, protic solvent, such as methanol, ethanol, isopropanol, butanol, and pentanol.

[00074] The condensation reaction can carried out at any suitable temperature, such as in the range of 25 to 200 °C or 40 to 150 °C or 65 to 85 °C for any suitable amount of time, such as from 1 second to 24 hours or 3 to 20 hours or 5 to 12 hours. In an embodiment, the condensation reaction can be carried out at 80 °C for 8 hours.

[00075] In an embodiment, the process comprises a step of purification of a condensed furan compound prior to a hydrodeoxygenation step. Any suitable method can be used to purify condensed furan compound, such as, for example removal of methanol and unconverted furfural from a condensation reaction product using rotary evaporation. The resulting product can be washed and neutralized with a dilute solution of hydrochloric acid (1 M) and extracted with dichloromethane. Dichloromethane can then be removed by rotary evaporation prior to the hydrodeoxygenation step.

[00076] In an embodiment, the process of making a composition comprising one or more branched aliphatic compounds of formula (I) may also include hydrodeoxygenating the condensed furan compound (CF) in the presence of a hydrodeoxygenation catalyst and molecular hydrogen to obtain one or more branched aliphatic compounds of formula (I)·

[00077] Any suitable hydrodeoxygenation (HDO) catalyst may be used, such as a solid acid supported metal based catalyst or a physical mixture of a metal based catalyst, or a metal/ metal oxide catalyst, and preferably Pd/C, Pd/SiC>2 and Pt/C, with a solid acid. Suitable solid acid supported metal based catalysts includes, but are not limited to, Ni/ZSM-5, Pd/ZSM-5, Pd/BEA; a physical mixture of a metal based catalyst with a solid acid, which includes but is not limited to, Pd/C + ZSM-5, Pd/C + BEA, Pt/C + BEA, and preferably supported metal-metal oxide catalysts such as Ir-ReOx/SiC>2, Ir- can be chosen from among Ir, Ru, Ni, Co, Pd, Pt, Rh and ² M can be chosen from among Re, Mo, W, Nb, Mn, V, Ce, Cr, Zn, Co, Y, Al.

[00078] The HDO reaction can be carried out at any suitable temperature, such as in the range of 100 to 300 °C or 125 to 250 °C or 150 to 210 °C for any suitable amount of time, such as from 1 to 30 hours or 5 to 25 hours or 10 to 22 hours in the presence of hydrogen gas at 0.5 to 15 MPa or 1 to 12 MPa or 2 to 9 MPa. In an embodiment, the condensation reaction can be carried out at 180 °C for about 18 hours at a hydrogen pressure of 5 MPa at 500 rpm. The process can further include a step for

purification/fractionation of hydrodeoxygenation products to remove lower molecular weight C1-C25 minor products, before use as a lubricant composition.

[00079] In an embodiment, the process further comprises reducing the catalyst for the HDO reaction prior to the step of HDO reaction. The catalyst pre-reduction can be carried out at temperature and pressure conditions similar to those used in the HDO reaction, but for a shorter amount of time and preferably in the presence of an organic solvent. Any suitable C2-C8 alkane can be used as a solvent. In an embodiment, the solvent for pre-reduction of catalyst is cyclohexane. In an embodiment, the pre reduction of catalyst is carried out in cyclohexane as a solvent at 200 °C and at a hydrogen pressure of 5MPa for 1 hour with stirring at 240 rpm.

[00080] Exemplary branched aliphatic compounds of formula (I) include, but are not limited to, 11,13-dipentyltricosane and 11-pentyltricosane.

[00081] In an aspect of the invention, the one or more branched aliphatic compounds of formula (I) have a bio-based content in the range of 20% to 100%, e.g., at least 20%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100%; preferably 30 to 100%; and most preferably 50 to 100%, as determined according to ASTM-D6866-18.

[00082] In another aspect, a lubricant composition includes 75-99% by weight of a base oil comprising one or more branched aliphatic compounds of formula (I), in accordance with various embodiments of the present invention, as disclosed

hereinabove, and an effective amount of one or more additives. According to various embodiments, one or more branched aliphatic compounds of formula (I) may comprise at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 99% or even 100% by weight of the base oil. [00083] In an embodiment, the lubricant base oil, as disclosed hereinabove is derived from lauric acid-derived tricosanone and furfural. Laurie acid is primarily found in coconut oil and palm kernel oil. It should be noted that while palm oil comes from the palm fruit, palm kernel oil comes from the palm seed. Both coconut oil and palm kernel oil contain approximately 50 wt.% lauric acid. Therefore, the coconut oil and palm kernel oil are used interchangeably in industry given their similar composition.

Additionally, lauric acid-derived lubricant base oils are promising for multiple reasons, including, but not limited to:

[00084] Climate change will have little effect on coconut oil and palm kernel oil production. Although cyclones are a growing environmental concern that could impact coconut oil production, but it should not impact lauric acid production due to palm trees being located in regions less likely to experience extreme weather and the effects of climate change.

[00085] Copra production requires much less fertilizer as compared to soya bean and rapeseed, which draw large quantities of nitrogen from the soil. Prior art estimates that rapeseed requires 100 kg of nitrogen per ton of oil produced, compared to 25 kg of nitrogen per ton of palm oil produced. Additionally, copra production uses virtually no fossil fuels, as fertilizers are rarely, if ever, applied. Therefore, with the important exception of increasing transportation costs, copra industries will not be affected by rising energy costs.

[00086] Coconut trees and oil palm trees have long lifespans, approximately 60-80 years and 30 years, respectively. At the end of a tree's lifetime, the leftover timber can be used to produce additional products (and revenue). Veneer plywood from copra trees is a profitable venture. Soya beans and rapeseed do not have this functionality.

[00087] In an embodiment of the lubricant composition, the base oil comprising at least one of the one or more branched aliphatic compounds of formula (I) has a bio based content in the range of 20 to 100%, e.g., at least 20%, at least 30%, at least

35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least

65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least

95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100%; preferably 30 to

100%; more preferably 40 to 100%; and most preferably 50 to 100%, as determined according to ASTM-D6866-18.

[00088] In an embodiment of the lubricant composition, at least one of the one or more branched aliphatic compounds has one of the following structures: where Ri, R2, R3, and R4, are defined as hereinabove, provided that in total the branched aliphatic compound contains 26 to 66 carbon atoms.

[00089] In another embodiment, the base oil further comprises a minor amount of one or more alkanes having a carbon content in the range of 1 to 25, or 5 to 20, or 5 to 15. In an embodiment, where the base oil is derived from furfural and lauric acid, the composition comprises minor amount of one or more alkanes having a carbon content in the range of 10 to 15. While intending not to be bound by any theory, it is believed that such alkanes are products of C-C cracking in the tertiary and secondary carbon positions, such as shown in Figure 12.

[00090] In an embodiment of the lubricant composition, the one or more lubricant additives may be selected from among antioxidants, stabilizers, detergents, dispersants, demulsifiers, antioxidants, anti-wear additives, pour point depressants, viscosity index modifiers, friction modifiers, anti-foam additives, defoaming agents, corrosion inhibitors, wetting agents, rust inhibitors, copper passivators, metal deactivators, extreme pressure additives, and combinations thereof. Any of such lubricant additives may be used in an amount effective to impart one or more desired properties or characteristics to the lubricant composition. Typically, effective concentrations of such lubricant additives will be similar to those utilized in conventional lubricant compositions, although in certain cases lower or higher concentrations may be needed or desired due to the different characteristics of the base oils comprised of one or more branched aliphatic compounds of formula (I) which are present in the lubricant compositions of the present invention.

In certain cases, individual lubricant additives are included in the lubricant composition at only a few ppm, but in other cases an individual lubricant additive is employed in an amount of at least 10 ppm, at least 50 ppm, at least 100 ppm, at least 250 ppm, at least 500 ppm, at least 750 ppm, at least 1000 ppm, at least 2000 ppm, at least 3000 ppm, at least 4000 ppm, at least 5000 ppm, or even higher (e.g., at least 1% by weight), depending upon the type of lubricant additive and the effect desired to be achieved by the inclusion of the lubricant additive. Generally speaking, however, the total amount of lubricant additive does not exceed 25% by weight based on the total weight of the lubricant composition. According to other embodiments, the lubricant composition comprises not more than 20%, not more than 15%, not more than 10% or not more than 5% by weight in total of lubricant additive(s), based on the total weight of the lubricant composition.

[00091] In another embodiment, the lubricant composition may further include one or more co-base oils (i.e., base oils other than the base oil comprised of one or more branched aliphatic compounds of formula (I)). For example, the co-base oil may be selected from the group consisting of American Petroleum Institute (API) Group I base oil, Group II base oil, Group III base oil, Group IV base oil, Group V base oil, gas-to- liquid (GTL) base oil, and combinations thereof.

[00092] According to certain embodiments, the lubricant composition is comprised of a) from 75-99% by weight of a base oil comprised of one or more branched aliphatic compounds of formula (I) and b) from 1-25% by weight in total of one or more additional components selected from the group consisting of lubricant additives and co base oils, the total of a) and b) equaling 100%.

[00093] In yet another embodiment of the lubricant composition, at least one of the one or more branched aliphatic compounds of formula (I) has a kinematic viscosity in the range of 2 to 100 centistokes (cSt) at 100 °C, preferably 2-50 cSt, most preferably 2-30 cSt and in the range of 6 to 100 cSt at 40 °C, preferably 6-50 cSt, most preferably 6-30 cSt, as measured by ASTM D445, such that a viscosity index calculated from kinetic viscosity at 100 °C and 40 °C, is in the range of 100 to 200, as measured by ASTM D2270, and the base oil has a kinematic viscosity of at least 3 cSt, as measured by ASTM D445.

[00094] In one embodiment of the lubricant composition, at least one of the one or more branched aliphatic compounds of formula (I) has a pour point in the range of 2 °C to -160 °C, or 2 °C to -120 °C, or 2 °C to -80 °C, or 2 °C to -65 °C , as measured by ASTM D97.

[00095] In certain embodiments of the lubricant composition, at least one of the one or more branched aliphatic compounds of formula (I) has an oxidation stability in the range of 150 °C to 300 °C, preferably 170 °C to 280 °C, and most preferably 170 °C to 250 °C, as measured by ASTM D6375.

[00096] In an aspect of the invention, the lubricant composition may be used in one or more of industrial machinery, automobiles, aviation machinery, refrigeration compressors, agricultural equipment, marine vessels, agriculture equipment, medical equipment, hydropower production machinery, and/or food processing equipment.

[00097] In another aspect of the invention, the base oil comprising one or more branched aliphatic compounds of formula (I), in accordance with various embodiments of the present invention, as disclosed hereinabove, may be used in one or more of industrial machinery, automobiles, aviation machinery, refrigeration compressors, agricultural equipment, marine vessels, agriculture equipment, medical equipment, hydropower production machinery, and/or food processing equipment. In another embodiment, the base oil comprising one or more branched aliphatic compounds of formula (I), in accordance with various embodiments of the present invention, as disclosed hereinabove, may be used in pharmaceutical formulations and personal care product formulations, e,g, sunscreen, lotion, creams, cosmetics, and the like. [00098] According to still further embodiments, a method is provided of reducing at least one of friction or wear between a first surface and a second surface, wherein the method comprises lubricating at least one of the first surface and the second surface with a base oil or a lubricant composition comprising one or more branched aliphatic compounds of formula (I) in accordance with the present invention. The first surface and the second surface may be the same as or different from each other and may be constructed of any suitable material, including for example metal, coated metal, plastic, and/or ceramic.

[00099] Also provided by the present invention is a method of lowering the coefficient of friction of a substrate surface, wherein the method comprises applying a coating of a base oil or lubricant composition comprised of one or more branched aliphatic compounds of formula (I) to the substrate surface. The substrate may be comprised of any suitable material such as metal, coated metal, plastic and/or ceramic.

[000100] In yet another aspect, a personal care composition is provided, the personal care composition including a base oil comprising one or more branched aliphatic compounds of formula (I), in accordance with various embodiments of the present invention, as disclosed hereinabove, and an effective amount of one or more additives. Any suitable additive could be used, including, but not limited to, pigments, fragrances, emulsifiers, wetting agents, thickeners, emollients, rheology modifiers, viscosity modifiers, gelling agents, antiperspirant agents, deodorant actives, fatty acid salts, film formers, anti-oxidants, humectants, opacifiers, monohydric alcohols, polyhydric alcohols, fatty alcohols, preservatives, pH modifiers, moisturizers, skin conditioners, stabilizing agents, proteins, skin lightening agents, topical exfoliants, antioxidants, retinoids, refractive index enhancers, photo-stability enhancers, SPF improvers, UV blockers, and water. In another embodiment, the personal care composition may further comprise an active ingredient selected from the group consisting of antibiotic, antiseptic, antifungal, corticosteroid, and anti-acne agent. The personal care composition of the present disclosure may be used in any suitable application including, but not limited to, cosmetics, sunscreens, lotions, creams, antiperspirants, deodorants, and medicated ointments, creams, and oils.

[000101] In still another aspect, a pharmaceutical composition is provided, the pharmaceutical composition including a base oil comprising one or more branched aliphatic compounds of formula (I), in accordance with various embodiments of the present invention, as disclosed hereinabove, an effective amount of one or more pharmaceutically active ingredients, and, optionally, one or more excipients (other than base oils comprising one or more branched aliphatic compounds of formula (I)). Any suitable pharmaceutically active ingredient(s) could be used, including in particular oil- soluble drugs, such as anti-inflammatory agents, antibiotics, antifungals, acne treatment agents, scabies/lice treatment agents, corticosteroids and analgesics. The

pharmaceutical composition could, for example, take the form of a cream, lotion, foam, gel, ointment, emulsion (including both water-in-oil and oil-in-water emulsions) or paste and may be a topical preparation, oral formulation or injectable formulation. The base oil comprising one or more branched aliphatic compounds of formula (I) may function, for example, as a carrier, vehicle, solubilizing excipient or filler (such as in soft gelatin capsules and the like).

[000102] Thus, the present invention provides a viable route to obtain a branched alkane based bio-lubricant base oil in fewer steps from long-chain ketone, such as 12- tricosanone, which can be obtained from fatty acid, and an aldehyde such as furfural, which can be obtained from lignocellulosic biomass. This approach involved aldol condensation followed by HDO. The strategy to synthesize renewable base oils described in the present disclosure could be a potential stepping-stone to replace petroleum- derived base oils, which in turn can reduce greenhouse gas emissions. Additionally, low temperature processing compared to the current refinery processing (cracking and distillation for synthetic and mineral base oils), and the use of sustainable feedstock with abundant supply and possible biodegradability could make this process and products competitive and adaptive to the existing market place.

[000103] Aspects of the Invention

[000104] Certain illustrative, non-limiting aspects of the invention may be summarized as follows:

Aspect 1. A lubricant composition comprising :

a. 75-99% by weight of a base oil comprising one or more branched aliphatic compounds having the following formula :

R1R2HC-CH2-CHR3R4 (I)

wherein :

(i) Ri and R3 are independently selected from alkyl groups having 8 to 26 carbon atoms,

(ii) R2 and R4 are independently selected from the group consisting of H and alkyl groups having 5 to 7 carbon atoms, with a proviso that at least one of R2 and R4 is not hydrogen,

wherein the alkyl groups are substituted or unsubstituted, or branched or unbranched,

wherein Ri and R3 may be the same or different, and

wherein the total carbon content of the branched aliphatic compound of formula (I) is in the range of 26 to 66; and b. an effective amount of one or more additives.

Aspect 2. The lubricant composition according to Aspect 1, wherein at least one of the one or more branched aliphatic compounds has a bio-based content in the range of 20 to 100%, according to ASTM-D6866.

Aspect 3. The lubricant composition according to either of Aspects 1 or 2, wherein at least one of the one or more branched aliphatic compounds has one of the following structures:

Aspect 4. The lubricant composition according to any of Aspects 1-3, wherein the base oil further comprises a minor amount of one or more alkanes having a carbon content in the range of 1 to 25.

Aspect 5. The lubricant composition according to any of Aspects 1-4, wherein the one or more additives are selected from the group consisting of antioxidants, stabilizers, detergents, dispersants, demulsifiers, antioxidants, anti-wear additives, pour point depressants, viscosity index modifiers, friction modifiers, anti-foam additives, defoaming agents, corrosion inhibitors, wetting agents, rust inhibitors, copper passivators, metal deactivators, extreme pressure additives, and combinations thereof.

Aspect 6. The lubricant composition according to any of the Aspects 1-5, further comprising one or more co-base oils selected from the group consisting of API Group I base oil, Group II base oil, Group III base oil, Group IV base oil, Group V base oil, gas-to-liquid (GTL) base oil, and combinations thereof.

Aspect 7. The lubricant composition according to any of Aspects 1-6, wherein at least one of the one or more branched aliphatic compounds of formula (I) has a kinematic viscosity at 100 °C in the range of 2 to 100 cSt, as measured by ASTM D445.

Aspect 8. The lubricant composition according to any of Aspects 1-6, wherein at least one of the one or more branched aliphatic compounds of formula (I) has a kinematic viscosity at 40 °C in the range of 6 to 100 cSt, as measured by ASTM D445.

Aspect 9. The lubricant composition according to any of Aspects 1-8, wherein at least one of the one or more branched aliphatic compounds of formula (I) has a viscosity index, calculated from kinetic viscosity at 100 °C and 40 °C, in the range of 100 to 200, as measured by ASTM D2270. Aspect 10. The lubricant composition according to any of Aspects 1-9, wherein at least one of the one or more branched aliphatic compounds of formula (I) has a pour point in the range of 2 °C to -120 °C, as measured by ASTM D97.

Aspect 11. The lubricant composition according to any of Aspects 1-10,

wherein at least one of the one or more branched aliphatic compounds of formula (I) has an oxidation stability in the range of 150 °C to 300 °C, as measured by ASTM D6375.

Aspect 12. The lubricant composition according to any of Aspects 1-11,

wherein the base oil has a kinematic viscosity of at least 3 cSt, as measured by ASTM D445.

Aspect 13. The lubricant composition according to any of Aspects 1-12,

wherein the base oil has a bio-based content in the range of 30 to 100%, according to ASTM-D6866.

Aspect 14. Use of the lubricant composition according to any of Aspects 1-13, in one or more of industrial machinery, automobiles, aviation machinery, refrigeration compressors, agricultural equipment, marine vessels, agriculture equipment, medical equipment, hydropower production machinery, and food processing equipment.

Aspect 15. A composition comprising :

one or more branched aliphatic compounds having the following formula :

R1R2HC-CH2-CH R3R4 (I)

wherein :

(i) Ri and R3 are independently selected from alkyl groups having 8 to 26 carbon atoms,

(ii) R2 and R4 are independently selected from the group consisting of H and alkyl groups having 5 to 7 carbon atoms, with a proviso that at least one of R2 and R4 is not hydrogen,

wherein the alkyl groups are substituted or unsubstituted, or branched or unbranched,

wherein Ri and R3 may be the same or different, and

wherein the total carbon content of the branched aliphatic compound of formula (I) is in the range of 26 to 66; and

wherein the composition has a bio-based content in the range of 30 to 100%, according to ASTM-D6866. Aspect 16. A method of making the composition of Aspect 15, the method comprising the steps of:

a) providing a first component comprising one or more of a furfural or its derivative and a second component comprising a ketone having the formula R1R3CO, wherein each Ri and R3 is independently selected from the group consisting of alkyl groups having 8 to 26 carbon atoms, wherein at least one of the first component and the second component is bio-derived from a renewable source;

b) condensing the first component with the second component in the presence of a basic catalyst to form at least one condensed furan compound (CF) selected from the group consisting of:

where Rs is hydrogen, methyl, ethyl, or hydroxymethyl group; and c) hydrodeoxygenating the at least one condensed furan compound (CF) in the presence of a hydrodeoxygenation catalyst to obtain one or more branched aliphatic compounds of formula (I).

Aspect 17. The method according to Aspect 16, wherein the step of providing a second component comprising a ketone comprises ketonic decarboxylyzing one or more fatty acids from one or more natural oils or waste cooking oils.

Aspect 18. The method according to either Aspect 16 or Aspect 17, wherein the basic catalyst is selected from the group consisting of liquid bases

(including inorganic liquid bases and organic liquid bases) and solid bases.

Aspect 19. The method according to any of Aspects 16-18, wherein the

hydrodeoxygenation catalyst is a solid acid supported metal based catalyst, a physical mixture of a metal based catalyst, or a metal/ metal oxide catalyst and preferably Pd/C, Pd/SiC>2 0r Pt/C, with a solid acid. Aspect 20. The method according to Aspect 19, wherein the

hydrodeoxygenation catalyst is a solid acid supported metal based catalyst selected from Ni/ZSM-5, Pd/ZSM-5, Pd/BEA, or a physical mixture of a metal based catalyst with a solid acid, including Pd/C + ZSM-5, Pd/C + BEA, Pt/C + BEA, and preferably a supported metal-metal oxide catalyst such as Ir- ReOx/Si0 ₂ , Ir-MoOx/SiC>2 or WMO/SiOz, wherein ^X M = Ir, Ru, Ni, Co, Pd, Pt, or Rh and ² M = Re, Mo, W, Nb, Mn, V, Ce, Cr, Zn, Co, Y, or Al.

Aspect 21. Use of the composition prepared according to any of Aspects 16-20, as a base oil in pharmaceutical and personal care products.

Aspect 22. A personal care composition comprising :

a. a base oil comprising the composition of Aspect 15; and

b. an effective amount of one or more additives selected from the group

consisting of pigments, fragrances, emulsifiers, wetting agents, thickeners, emollients, rheology modifiers, viscosity modifiers, gelling agents, antiperspirant agents, deodorant actives, fatty acid salts, film formers, anti-oxidants, humectants, opacifiers, monohydric alcohols, polyhydric alcohols, fatty alcohols, preservatives, pH modifiers, moisturizers, skin conditioners, stabilizing agents, proteins, skin lightening agents, topical exfoliants, antioxidants, retinoids, refractive index enhancers, photo stability enhancers, SPF improvers, UV blockers, and water.

Aspect 23. The personal care composition of Aspect 22, further comprising an active ingredient selected from the group consisting of antibiotic, antiseptic, antifungal, corticosteroid, and anti-acne agent.

Aspect 24. A pharmaceutical composition comprising :

a. a base oil comprising the composition of Aspect 15;

b. an effective amount of one or more pharmaceutically active ingredients; and

c. optionally, one or more pharmaceutically acceptable excipients.

[000105] As used herein, when an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range. [000106] The term "about" refers to the variation in the numerical value of a measurement, e.g., temperature, weight, percentage, length, concentration, and the like, due to typical error rates of the device used to obtain that measure. In one embodiment, the term "about" means within 5% of the reported numerical value.

[000107] As used herein, the singular form of a word includes the plural, and vice versa, unless the context clearly dictates otherwise. Thus, the references "a", "an", and "the" are generally inclusive of the plurals of the respective terms. Likewise the terms "include", "including" and "or" should all be construed to be inclusive, unless such a construction is clearly prohibited from the context. Similarly, the term "examples," particularly when followed by a listing of terms, is merely exemplary and illustrative and should not be deemed to be exclusive or comprehensive.

[000108] The term "comprising" is intended to include embodiments encompassed by the terms "consisting essentially of" and "consisting of". Similarly, the term

"consisting essentially of" is intended to include embodiments encompassed by the term "consisting of".

[000109] Within this specification, embodiments have been described in a way which enables a clear and concise specification to be written, but it is intended and will be appreciated that embodiments may be variously combined or separated without departing from the invention. For example, it will be appreciated that all preferred features described herein are applicable to all aspects of the invention described herein.

[000110] In some embodiments, the invention herein can be construed as excluding any element or process step that does not materially affect the basic and novel characteristics of the compounds for use as a lubricant base oil, lubricant base oil compositions based on such compounds and process for making such compounds.

Additionally, in some embodiments, the invention can be construed as excluding any element or process step not specified herein.

[000111] Although the invention is illustrated and described herein with reference to specific embodiments, the invention is not intended to be limited to the details shown. Rather, various modifications may be made in the details within the scope and range of equivalents of the claims and without departing from the invention.

EXAMPLES

[000112] Examples of the present invention will now be described. The technical scope of the present invention is not limited to the examples described below.

[000113] Abbreviations

[000114] The meaning of abbreviations is as follows: "cm” means centimeter(s), "g" means gram(s), "h" or "hr" means hour(s), "HPLC” means high pressure liquid chromatography, "m" means meter(s), "min" means minute(s), "mL" means milliliter(s), "mm" means millimeter(s), "MPa" means megapascal(s), "psi" means pound(s) per square inch, "rpm" means revolutions per minute, "wt %" means weight percent(age).

[000115] Example 1. General materials and methods.

[000116] Materials

[000117] Furfural and 12-tricosanone were purchased from Tokyo Chemical Industry

Co. Methanol (>99.8%), sodium hydroxide pellets, hydrochloric acid (36.5 to 38.0%), and cyclohexane (99.9%) were purchased from Fisher Scientific. Eicosane (99%) and hydrogen hexachloroiridate hydrate (99.98%, metal basis) were purchased from Sigma- Aldrich. Ammonium perrhenate (VII) (99.999% metals basis) was purchased from Alfa Aesar. Fuji Silysia Chemical Ltd. G6 (BET surface area, 535 m ² /g) supplied silica gel.

[000118] Catalyst Preparation

[000119] The Ir-ReOx/SiC>2 (Ir 4 wt% loading, Re/Ir =2, molar) catalyst was prepared by a sequential impregnation method. ^[21] First, Ir/SiC>2 was prepared by impregnating Ir on S1O2 (Fuji Silysia G-6) using an aqueous solution of hydrogen hexachloroiridate hydrate. Next, the solvent was evaporated at 75 °C on a hotplate (IKA) and dried at 110 °C for 12 hrs in an oven (Fisher Scientific). The resulting Ir/SiC>2 was impregnated with ReOx using an aqueous solution of ammonium perrhenate(VII). The catalyst was calcined in a crucible in air at 500 °C for 3 hrs at a 10 °C/min temperature ramp. The reported metal loadings in the catalyst are based on the theoretical amount of metals used for impregnation. The catalyst was used in powder form with a granule size of <400 mesh. BET surface area measurements were performed on a Micromeritics ASAP 2020 Accelerated Surface Area and Porosimetry instrument at the Advanced Materials Characterization Laboratory at the University of Delaware. The measured BET surface area of Ir-ReOx/SiC>2 was 368.6 m ² /g.

[000120] Reaction procedures

[000121] Process of Making a Condensed Furan Compound ( CF ) bv Aldol

Condensation Reaction

[000122] All reactions were conducted in 10 mL glass vials (Sigma-Aldrich) heated in an aluminum heating block with controlled stirring (Fisher Scientific). In a standard reaction, the reactants, furfural (4.68 mmol, 0.45 g) and 12-tricosanone (0.295 mmol, 0.10 g), were combined with the solvent, methanol (5 mL), and catalyst, sodium hydroxide (1 M, 0.20 g). The catalyst concentration was selected from a prior report (Reference 10). Temperature and stirring rate were maintained at 80 °C and 400 rpm, respectively. After reaction for the set time, the reaction vials were removed from the heating block and cooled to room temperature. Methanol and unconverted furfural were removed by rotatory evaporation (Buchi). The products were washed and neutralized with a dilute solution of hydrochloric acid (1 M) and extracted with dichloromethane (20 ml_). Dichloromethane was removed by rotary evaporation prior to HDO. The products formed by aldol condensation were solids at room temperature.

[000123] Process of Making a Branched Alkane Compound (BA) bv

Hvdrodeoxyaenation (HDO) Reaction

[000124] HDO reactions of aldol condensation products were conducted in a 50 mL Parr reactor with an inserted Teflon liner and a magnetic bar. The catalyst, Ir-ReOx/Si02 (0.15 g), and solvent, cyclohexane (5 mL), were added to the reactor for catalyst prereduction. The reactor was sealed with a fitted reactor head that contained a

thermocouple, a rupture disk, a pressure gauge, and a gas release valve. The mixture was heated at 200 °C and 5 MPa H2 for 1 hr at 240 rpm. Upon pre-reduction, the reactor was cooled to room temperature and H2 was released. Next, the aldol condensation products (0.40 g) were mixed with cyclohexane (15 mL) and added to the reactor. The reactor head was immediately closed, purged with 1 MPa H2 three times, and pressurized to 5 MPa H2. The reaction occurred over 18 hrs at 180 °C and with continuous stirring at 500 rpm. The heating time to reach the set temperature was approximately 25 min and was not included in the total reaction time. Upon completion, the reactor was

immediately transferred to a water bath. The catalyst was separated from the solution by centrifugation.

[000125] Analysis of products

[000126] The products were analyzed using a gas chromatograph (GC, Agilent 7890A), equipped with an HP-1 column and a flame ionization detector. Products were quantified using eicosane (C20) as the internal standard (0.10 g). The products were identified by a GC (Agilent 7890B) mass spectrometer (MS, Agilent 5977A with a tripleaxis detector), equipped with a DB-5 column. High resolution mass spectrometry-liquid injection field desorption ionization (HRMS-LIFDI, Waters GCT Premier) data were obtained from the Mass Spectrometry Facility at the University of Delaware. ^X H and ¹³ C nuclear magnetic resonance spectroscopy (NMR, Bruker AV400, CDCI3 solvent) were also used to identify the products from aldol condensation and HDO.

The conversion and the yield of all products from aldol condensation and HDO reactions were calculated on carbon basis using the following equations:

mol of initial reactant - mol of unreacted reactant

Conversion [%] = x 100

mole of initial reactant

mo I product x C atoms in product

Yield of detected products [%-C]= x 100

mol of total C atoms of initial reactants

[000127] Lubricant Base Oil Properties Measurements

[000128] Cyclohexane and lower boiling point alkanes (<Oe) in the products were removed by rotary evaporation prior to viscosity measurements. [000129] The lubricant properties of the final HDO products were evaluated according to the American Society for Testing and Materials (ASTM) methods.

[000130] The kinematic viscosities at 100 °C and 40 °C (KV100 and KV40) were determined following the ASTM D445 method.

[000131] The viscosity index (VI) was calculated using the KV100 and KV40, following the ASTM D2270 method.

[000132] An extra low charge semi-micro viscometer (Cannon, size 150, calibrated model # : 9722-H62) apparatus was used for all measurements. The sample charge volume was 300 pL. To demonstrate the accuracy of this method, the viscosity of a Cannon ® N35 Standard and an Exxon Mobil SpectraSyn Plus™ PAO-4 (Group IV) were measured and found that as-measured viscosities were in agreement with the reported values, as shown below in Table 1.

Table 1. Viscosities measured by the micro-viscometer compared to the reported viscosities.

Viscosity Index (VI) from ASTM D2270 can be calculated as follows:

io ^w - 1

vi = + 100

0.00715 log (H) - \og(U)

log(T)

where

H is kinematic viscosity at 40 °C of an oil of 100 viscosity index having the same kinematic viscosity at 100 °C as the oil whose viscosity index is to be calculated, mm ² /s; obtained using Table 1 in ASTM D2270,

U is kinematic viscosity at 40 °C, and

Y is kinematic viscosity at 100 °C. [000133] Example 2. Synthesis of Condensed Furan Compound. C33-CF bv Aldol Condensation of Furfural and 12-tricosanone using different solvents

[000134] All reactions were catalyzed by 1 M NaOH (unless otherwise specified), and the reaction temperature was 80 °C for all experiments to ensure 12-tricosanone (melting point = 68 °C) was a liquid at reaction temperature.

[000135] Figure 2 shows the yield of products and conversion of 12-tricosanone in different solvents. Previous works have shown that aldol condensation may occur with ^[10] or without a solvent. (Reference 22) As shown in Figure 2, conversion of 12-tricosanone was low (<25%) and no C28 or C33 furan intermediates were detected without a solvent, indicating the observed conversion of 12-tricosanone was likely due to its oligomerization with itself and/or furfural. Rio et al. suggested that carboxyl and hydroxyl groups may promote oligomerization to form high molecular weight organic compounds found in oils and source rocks. (Reference 23) These oligomers, however, are difficult to detect by conventional GC columns due to their high molecular weights (>C4o). (References 21,

24) Without wishing to be bound by any particular theory, it is believed that the carboxyl and hydroxyl groups in 12-tricosanone and furfural promote the formation of high molecular weight, solid oligomeric species called humins, whose characterization is reported in prior work. (Reference 25)

[000136] Since having no solvent led to low conversion of 12-tricosanone, next different solvents were screened as a function of their polarity. As shown in Figure 2, non-polar, aprotic solvents, such as cyclohexane and dioxane, resulted in very low yield of condensation product, which is likely due to their poor ability to dissolve the reactants and catalyst, combined with their inability to donate protons. In contrast, as shown in Figure 2, a polar, protic solvent, such as methanol resulted in the highest conversion of 12-tricosanone, likely due to methanol's ability to dissolve the reactants and catalyst. Given the propensity of methanol, water was also tested, but it resulted in no yield of product. The observed conversion of 12-tricosanone with water as the solvent, as shown in Figure 2 is likely due to the formation of humins. Water was most likely ineffective because it is a product of aldol condensation, and when used as a solvent, it shifts equilibrium towards the reactants, according to Le Chatelier's principle. Therefore, subsequent aldol condensation were performed in methanol.

[000137] Example 3. Synthesis of Condensed Furan Compound, C33-CF bv Aldol Condensation of Furfural and 12-Tricosanone with Different Mole Ratios and Reaction Times

[000138] Next, experiments were conducted as a function of reaction time and feed ratio to achieve high yields in desired condensation product, i.e., C33 furan intermediate. Initially, reactions were carried out for 24 hrs and with mole ratios of furfural: 12- tricosanone ranging from 1 : 1 to 16: 1, as shown in Figure 3. GC-MS detected two fragments with a mass to charge ratio (m/z) of 416 and nine fragments with an m/z of 464, which correspond to geometric isomers of the C28 and C33 furans, respectively, as shown in Figure 4a. All isomers corresponding to the same m/z fragment as one product were considered for yield calculation. Additional analysis by HRMS-LIFDI shown in Figures 5a and 5b and ^X H and ¹³ C NMR spectra shown in Figures 6 and 7, were consistent with the C28 and C33 products identified from GC-MS.

[000139] As shown in Figure 11A, the product distribution, i.e. yield of C33 versus C28, could be tuned by changing the feed ratio of reactants, where high amounts of furfural favored the C33 furan (Yc ₃₃ furan = 64.8% when furfural: 12-tricosanone is 8: 1).

The yields of total detected C28 and C33 furans are lower than the 12-tricosanone conversion, which could be due to the formation of humins. Higher selectivity to desired condensation products was achieved by decreasing the reaction time from 24 hrs, shown in Figure 3 to 8 hrs, shown in Figure 11A. A maximum 94.3% yield of branched furan intermediates containing C33 as the major product (Yc ₂₈ ^furan = 14.8% and Vc _33furan = 79.5%, Fig. 11A) is obtained for 8 hrs and at furfural to 12-tricosanone molar ratio of 16: 1. Excess furfural can be recycled upon separation using rotary evaporation. Higher feed ratio beyond 16: 1, such as 25: 1 resulted in a slight decrease in the yield of C33 furan and the overall yield, as shown in Fig. 11A.

[000140] Example 4. Synthesis of Branched Alkane C33-BA bv Hvdrodeoxyaenation of C33-CF

[000141] Aldol condensation product, after neutralizing and removing methanol and any unconverted furfural, was dissolved in cyclohexane and transferred to the Parr reactor for hydrodeoxygenation (HDO) using the procedure described hereinabove in Example 1.

[000142] HDO of C28 and C33 condensed furan compounds mixture (Yc ₂₈ ^furan =

14.8% and Y^furan = 79.5%) over Ir-ReOx/Si02 at 180 °C and 5 MPa H2 in cyclohexane for 18 hrs yielded 61.4% of total lubricant-ranged branched alkanes (C28 and C33) . Figure 1 IB shows that the major products are C33 (Yc ₃₃ = 50.5%) and C28 (Yc ₂₈ = 10.9%) alkanes, followed by C15, C14, C13 and C10 alkanes (/combine < 11%), which likely result from carbon-carbon (C-C) cracking in the tertiary and secondary carbons of the C33 and C28 alkanes, as shown in Figure 11. In the present synthesis of branched alkanes via HDO, C5 alkane is likely to form via C-C cracking as shown in Figure 12, but it was not quantified because of difficulty arising from the solvent, cyclohexane, forming Ci - C6 alkanes during pre-reduction of the catalyst and during the HDO reaction. Thus, alkanes with less than six carbons were not quantified. In addition to C5 alkane, gaseous Ci - C4 alkanes could also form from the substrates in the HDO step to account for some of the carbon loss, but gas phase products were not quantified in this work. Furthermore, coke formation on the catalyst and unidentified oxygenated intermediates may contribute to the remaining carbon loss. Coke formation is not expected to hinder recycling the catalyst, as Liu et al. have demonstrated that upon re-calcination, the catalyst can be regenerated with similar activity to that of the fresh catalyst. (Reference 26) GC-MS and HRMS-LIFDI detected mass fragments expected for C28 and C33 alkane products, as shown in Figures 5 and 6 respectively. Additionally, the NMR spectra were congruent with that expected for the C33 alkane product, as shown in Figures 9 and 10.

[000143] Example 5. Properties of C33-BA based base oils of the present invention and commercial formulated lubricants

[000144] The bio-lubricant base oil having branched alkane (C33-BA) compounds, such as obtained in Example 4, is a viscous liquid at room temperature and even at low temperature, ~3 °C, while n-tricosane, containing 23 carbons and produced by HDO of 12-tricosanone, is solid. (Reference 11) This suggests the addition of branches on linear alkanes by method in accordance with the present invention can significantly improve the low temperature flow property. The viscous properties of as-synthesized base oil are determined by extra-low charge, micro-viscosity measurements and are compared to those of Phillips 66 Ultra-S 3™ (Group III) and Exxon Mobil SpectraSyn Plus™ PAO-3.6 (Group IV) base oils.

[000145] When considering lubricant base oils, at high temperatures (100 °C), an oil's viscosity (KV100) should be high to create a thick hydrodynamic film between surfaces. Upon decreasing temperature (40 °C), an oil's viscosity (KV40) should be low, or less resistant to flow, to promote fluidity. The VI, calculated using the KV100 and KV40 values, measures viscosity stability of a fluid as a function of temperature.

Maximizing VI ensures that the oil's viscosity varies as little as possible with

temperature.

[000146] Table 2 shows that KV100, KV40, and VI of the C33-BA based base oil are comparable to commercial Group III and Group IV base oils. The VI of the C33-BA based base oil is 115, which is higher than 100, suggesting the C33-BA based base oil of the present invention has high quality. (Reference 6) [000147] Table 2. Properties of C33-BA based base oil ( c ₃₃ = 50.5% and Y _C28 = 10.9%) compared to Group III and Group IV commercial lubricants.

^* KV40 and KV100 are kinematic viscosities at 40 °C and 100 °C, respectively (ASTM D445).

^† VI calculated from KV40 and KV100 (ASTM D2270).

*The properties of commercial products were obtained from the product specifications datasheet disclosed by the manufacturers.

[000148] Thus, as disclosed herein above, the present invention provides a viable route to obtain a branched alkane based bio-lubricant base oil in fewer steps from long- chain ketone, such as 12-tricosanone, which can be obtained from fatty acid, and and an aldehyde such as furfural, which can be obtained from lignocellulosic biomass. This approach involved aldol condensation followed by HDO. Aldol condensation of 12- tricosanone and furfural at 16: 1 molar ratio resulted in maximum 93.5% yield of branched C28 and C33 furan intermediates in 8 hrs. C33 furan intermediate was the major product, 79.5%, with balance being C28 furan intermediate. Subsequent HDO of aldol condensation product over an Ir-ReOx/Si02 (Re/Ir molar ratio = 2) yielded 72% total alkanes, in which lubricant-ranged branched alkanes, C28 and C33, were 61%. Small amounts (11%) of low carbon alkanes (>Cio) were detected. Micro-viscosity

measurements indicated that the base oil of the present invention has viscous properties comparable to petroleum-derived Group III and IV oils. The strategy to synthesize renewable base oils described in the present disclosure could be a potential stepping- stone to replace petroleum-derived base oils, which in turn can reduce greenhouse gas emissions.

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