FIELD

[0001] This disclosure relates to base stocks including renewable base stocks made from biological materials, blends of base stocks, formulated lubricant compositions containing the base stocks, and uses of base stocks.

BACKGROUND

[0002] Base stock is the major constituent in finished lubricants and contributes significantly to their properties. For example, engine oils are finished crankcase lubricants intended for use in automobile engines and diesel engines and contain two general components, namely, a base stock (one base stock or a blend of base stocks) and additives. In general, a few lubricating base stocks are used to manufacture a variety of engine oils by varying the mixtures of individual lubricating base stocks and individual additives. Base stocks are also used for other purposes such as processing oils for manufacturing various articles such as tires.

[0003] According to the American Petroleum Institute (API) classifications, base stocks are categorized in five groups based on their saturated hydrocarbon content, sulfur level, and viscosity index (Table 1). Lube base stocks are typically produced in large scale from non-renewable petroleum sources. Group I, II, and III base stocks are all derived from crude oil via extensive processing, such as solvent extraction, solvent or catalytic dewaxing, and hydroisomerization. Group III base stocks can also be produced from synthetic hydrocarbon liquids obtained from natural gas, coal or other fossil resources, Group IV base stocks are polyalphaolefins (PAOs), and are produced by oligomerization of alpha olefins, such as 1 -decene. Group V base stocks include all base stocks that do not belong to Groups I-IV, such as naphthenics, polyalkylene glycols (PAG), and esters.

Table 1

[0004] Formulations are undergoing changes driven by a need for increased quality. For example, governing organizations (e.g., the American Petroleum Institute) help to define the specifications for engine oils. Increasingly, the specifications for engine oils are calling for products with excellent low temperature properties and high oxidation stability. Currently, only a small fraction of the base stocks blended into engine oils are able to meet the most stringent of the demanding engine oil specifications. Currently, formulators are using a range of base stocks including Group I, II, III, IV, and V base stocks to formulate their products.

[0005] Industrial oils are also being pressed for improved quality in oxidation stability, cleanliness, interfacial properties and deposit control. Despite advances in lubricating base stocks and lubricant oil formulation technology, there exists a need for improving oxidation performance (for example, for engine oils and industrial oils that have a longer life) and low temperature performance of formulated oils. In particular, there exists a need for improving oxidation performance and low temperature performance of formulated oils without the addition of more additives to the lubricant oil formulation.

[0006] Base stocks are generally produced from the higher boiling fractions recovered from a vacuum distillation operation. They may be prepared from either petroleum-derived or from syncrude-derived feed stocks or from synthesis of lower molecular weight molecules. Additives are chemicals which are added to base stock to improve certain properties in the finished lubricant so that it meets the minimum performance standards for the grade of the finished lubricant. For example, additives added to the engine oils may be used to improve oxidation stability of the lubricant, increase its viscosity, raise the viscosity index, and control deposits. Additives are expensive and may cause miscibility problems the finished lubricant. For these reasons, it is generally desirable to optimize the additive content of the engine oils to the minimum amount necessary to meet the appropriate requirements.

SUMMARY

[0007] Disclosed herein is an example base stock composition comprising: a naphthene component, wherein the naphthene component comprises a naphthene ring comprising two or more paraffinic branches covalently bonded to the naphthene ring, wherein the naphthene component has a carbon number in a range of C28 to C34; and a branched paraffinic component, wherein the branched paraffinic component comprises a paraffinic backbone with a carbon number in a range of C14 to C22, wherein the branched paraffinic component comprises two or more paraffinic branches covalently bonded to the paraffinic backbone, and wherein the branched paraffinic component has a carbon number in a range of C28 to C36.

[0008] Further disclosed herein is an example base stock composition comprising: a naphthene component in an amount of about 15 wt.% to about 30 wt.% based on a total weight of the base stock composition, wherein the naphthene component comprises a naphthene ring comprising two or more paraffinic branches covalently bonded to the naphthene ring, wherein the naphthene component has a carbon number in a range of C28 to C30; and a branched paraffinic component in an amount of about 70 wt.% to about 85 wt.% based on a total weight of the base stock composition, wherein the branched paraffinic component comprises a paraffinic backbone with a carbon number in a range of C14 to C22, wherein the branched paraffinic component comprises two or more paraffinic branches covalently bonded to the paraffinic backbone, wherein the branched paraffinic component has a carbon number in a range of C28 to C34, wherein the base stock composition has a kinematic viscosity at 100 °C of about 3.8 to about 4.3 cSt as measured by ASTM D 445-01, wherein the base stock composition has a viscosity index above 120 as measured by ASTM D2270-93, and wherein the base stock composition has a Noack volatility is less than about 12% as measured by ASTM D5800.

[0009] Further disclosed herein is a method of reducing wear in a mechanical component comprising: contacting two adjacent surfaces with a lubricating oil composition; forming a lubricant film comprising the lubricating oil composition in a space between the two adjacent surfaces; sliding the two adjacent surfaces relative to each other; and reducing wear between the two adjacent surfaces using the lubricant film, wherein the lubricant composition comprises: a base stock comprising: a naphthene component, wherein the naphthene component comprises a naphthene ring comprising two or more paraffinic branches covalently bonded to the naphthene ring, wherein the naphthene component has a carbon number in a range of C28 to C34; and a branched paraffinic component, wherein the branched paraffinic component comprises a paraffinic backbone with a carbon number in a range of C14 to C22, wherein the branched paraffinic component comprises two or more paraffinic branches covalently bonded to the paraffinic backbone, and wherein the branched paraffinic component has a carbon number in a range of C28 to C36.

[0010] These and other features and attributes of the disclosed renewable base stocks made from biological materials, blends of base stocks, formulated lubricant compositions containing the base stocks, and uses of base stocks of the present disclosure and their advantageous applications and/or uses will be apparent from the detailed description which follows.

BRIEF DESCRIPTION OF THE DRAWINGS

[0011] To assist those of ordinary skill in the relevant art in making and using the subject matter hereof, reference is made to the appended drawings, wherein:

[0012] FIG. 1 is a graph that illustrates a volatility to viscosity relationship of selected base stocks.

[0013] FIG. 2 illustrates an embodiment of a process for producing a base stock including a naphthene component and a branched paraffinic component in accordance with some embodiments of the present disclosure. DETAILED DESCRIPTION

[0014] Disclosed herein are renewable base stocks derived from biological materials. These base stocks, derived from various biological sources such as seed oil or other biological feeds, do not have the same structure nor the same properties as established by petroleum processing to make hydrocarbon feed stocks. Such bio-base stocks often have excellent volatility to viscosity relationships driven by the narrow molecular weight range and may have exceptional low temperature performance driven by their unique composition. These base stocks have exceptional properties especially when controlled for cyclic composition in the base stock.

[0015] All numerical values within the detailed description and the claims herein are modified by “about” or “approximately” the indicated value, and take into account experimental error and variations that would be known to a person of ordinary skill in the art.

[0016] As used herein, the term “major component” means a component (e.g., base stock) present in a lubricating oil of this disclosure in an amount greater than about 50 weight percent (wt. %).

[0017] As used herein, the term “minor component” means a component (e.g., one or more lubricating oil additives) present in a lubricating oil of this disclosure in an amount less than 50 weight percent.

[0018] As used herein, the term “single ring naphthenes” means a saturated hydrocarbon group having the general formula Cnthn arranged in the form of a single closed ring, where n is the number of carbon atoms. It is also denoted herein as 1RN.

[0019] As used herein, the term “multi-ring naphthenes” means a saturated hydrocarbon group having the general formula CnH2(n+i-r) arranged in the form of multiple closed rings, where n is the number of carbon atoms and r is the number of rings (here, r>l). It is also denoted herein as 2+RN. [0020] As used herein, “kinematic viscosity at 100° C.” will be used interchangeably with “KV100” and “kinematic viscosity at 40° C.” will be used interchangeably with “KV40.”

[0021] The viscosity -temperature relationship of a lubricating oil is one of the critical criteria which must be considered when selecting a lubricant for a particular application. Viscosity Index (VI) is an empirical, unitless number which indicates the rate of change in the viscosity of an oil within a given temperature range. Fluids exhibiting a relatively large change in viscosity with temperature are said to have a low viscosity index. A low VI oil, for example, will thin out at elevated temperatures faster than a high VI oil. A high VI oil maintains better low temperature fluidity than a low VI oil. Usually, the high VI oil is more desirable because better properties at low and high temperatures.

[0022] In another aspect, as the oil operating temperature decreases, the viscosity of a high VI oil will not increase as much as the viscosity of a low VI oil. This is advantageous because the excessive high viscosity of the low VI oil will decrease the efficiency of the operating machine. Thus high VI (HVI) oil has performance advantages in both high and low temperature operation. VI is determined according to ASTM method D2270-93 [1998], VI is related to kinematic viscosities measured at 40° C. and 100° C. using ASTM Method D 445-01.

[0023] Bio-base stocks, that is base stocks that have a fraction derived from a non-petroleum- based source, have previously been developed but these base stocks often highly isoparaffinic leading to poor low temperature viscosity properties that then require subsequent dewaxing. Biobase stocks have also been developed which contain a cyclic hydrocarbon fraction. These cyclic hydrocarbon fraction tends to have short branches such as methyl and ethyl. Although base stocks that are 100% iso-paraffinic are known, having a cyclic hydrocarbon moiety often raises viscosity above the required target for blending high performance engine oils at a given Noack volatility. Cyclic hydrocarbons in the bio-base stock also negatively affect the viscosity/volatility relationship.

[0024] Managing the composition of the bio-base stock to ensure an optimum balance of properties has not yet been done in base stocks. Such properties include viscosity versus molecular weight, volatility versus viscosity, low temperature viscosity versus volatility, low temperature viscosity versus expected (CCS ratio), presence of cyclic structure in the molecule to provide solubility for additives, and presence of cyclic structure in the molecule to provide solubility deposits in use in formulated engine oils.

[0025] The renewable base stock of the present disclosure includes a naphthene component and a branched paraffinic component. The renewable base stock disclosed herein has several advantages over previous bio-derived base stocks and petroleum-derived base stocks, only some of which may be alluded to herein. One of the advantages of the renewable base stock includes advantaged positioning of the naphthene ring in the middle or near the middle of the naphthene component which shortens the paraffinic chains for a given molecular weight range thereby providing better low temperature properties while still providing for solubility of polar materials such as additives in a lubricating composition. Petroleum based stream tend to have the ring structure towards the end of the molecule with leaves less longer (>C3) branching and therefore poorer lower temperature properties as compared the base stock of the present disclosure. The branched paraffinic component has a relatively long carbon backbone with few methyl groups leading to advantaged properties such as excellent low temperature viscosity and pour point.

[0026] The process to make the base stock disclosed herein utilizes renewable resources such as seed oils or other biological feeds to make renewable base stock, however, the base stock disclosed herein can also be prepared from hydrocarbon sources. There may be several synthetic routes to produce the base stock, only some of which include biogenic carbon from a renewable source such as seed oils. As used herein renewable base stock and base stock should be read equivalently. In some embodiments, base stocks are derived from seed oils and other biological feeds.

[0027] In embodiments, the base stock includes the naphthene component in an amount of 15 wt.% to 30 wt.% based on a total weight of the base stock. Alternatively, the naphthene component is present in an amount of 15 wt.% to 20 wt.% based on a total weight of the base stock, in an amount of 20 wt.% to 25 wt.% based on a total weight of the base stock, in an amount of 25 wt.% to 30 wt.% based on a total weight of the base stock, or any ranges therebetween. In embodiments, the base stock includes the branched paraffinic component in an amount of 70 wt.% to 85 wt.% based on a total weight of the base stock. Alternatively, the branched paraffinic component is present in an amount of 70 wt.% to 75 wt.% based on a total weight of the base stock, in an amount of 75 wt.% to 80 wt.% based on a total weight of the base stock, in an amount of 80 wt.% to 85 wt.% based on a total weight of the base stock, or any ranges therebetween. In embodiments, the base stock is substantially free of any other components other than the naphthene component and the branched paraffinic component, such as from 0 wt.% to 1 wt.%, from 0 wt.% to 0.5 wt.%, from 0 wt.% to 0.1 wt.%, from 0 wt.% to 0.01 wt.% components other than the naphthene component and the branched paraffinic component or any ranges therebetween.

[0028] In embodiments, the naphthene component includes hydrocarbons containing a naphthene ring and two or more paraffinic branches covalently bonded to the naphthene ring such that the naphthene component has a carbon number in a range of C28 to C34. Alternatively, the naphthene component has a carbon number in a range of C28 to C30, in a range of C30 to C32, in a range of C32 to C34, or any ranges therebetween. In embodiments, the molecular weight range of the naphthene component is 6 or less. Alternatively, the molecular weight range of the naphthene component is 5 or less, the molecular weight range of the naphthene component is 4, or the molecular weight range of the naphthene component is 3 or less. In embodiments the naphthene ring comprises cyclohexane. In embodiments, the paraffinic branches covalently bonded to the naphthene ring have a carbon number in a range of C3 to Cl 8. Alternatively, the paraffinic branches have a carbon number in a range of C3 to CIO, in a range of CIO to Cl 4, in a range of C14 to Cl 8, or any ranges therebetween. In embodiments, the paraffinic branches covalently bonded to the naphthene ring each have a carbon number of C3 or greater. For example, the naphthene component includes greater than 95% wt.% paraffinic branches of C3 or greater. For example, 95 w.t% to 97% wt.% paraffinic branches of C3 or greater, 95 w.t% to 99% wt.% paraffinic branches of C3 or greater, or 95 w.t% to 99.9% wt.% paraffinic branches of C3 or greater, or any ranges therebetween. Alternatively, the paraffinic branches covalently bonded to the naphthene ring each have a carbon number of C5 or greater. For example, the naphthene component includes greater than 95% wt.% paraffinic branches of C5 or greater. For example, 95 w.t% to 97% wt.% paraffinic branches of C5 or greater, 95 w.t% to 99% wt.% paraffinic branches of C5 or greater, or 95 w.t% to 99.9% wt.% paraffinic branches of C5 or greater, or any ranges therebetween. In embodiments, the naphthene component comprises limited multi-ring components. In embodiments, the naphthene component is substantially free of multi-ring components, such as less than 1 wt.% multi-ring components. For example, from 0 wt.% to 1 wt.%, from 0 wt.% to 0.5 wt.%, from 0 wt.% to 0.1 wt.%, from 0 wt.% to 0.5 wt.% multi -ring components, or any ranges therebetween. The presence of multi-ring components can be verified by standard methods including C13 NMR and proton NMR, for example. Alternatively, the naphthene component contains up 10 wt.% of multi-ring components. For example, from 0 wt.% to 10 wt.%, from 0 wt.% to 8 wt.% of multi-ring components, from 0 wt.% to 6 wt.% of multi -ring components, from 0 wt.% to 4 wt.% of multi-ring components, from 0 wt.% to wt.% of multi-ring components, or any ranges therebetween.

[0029] In embodiments, the branched paraffinic component includes hydrocarbons with a paraffinic backbone and two or more paraffinic branches covalently bonded to the paraffinic backbone such that the branched paraffinic component has a carbon number in a range of C28 to C36. Alternatively, the branched paraffinic component has a carbon number in a range of C28 to C30, in a range of C30 to C32, in a range of C32 to C34, in a range of C34 to C36, in a range of C28 to C34, or any ranges therebetween. In embodiments, the molecular weight range of the branched paraffinic component is 6 or less. Alternatively, the molecular weight range of the branched paraffinic component is 5 or less, the molecular weight range of the branched paraffinic component is 4, or the molecular weight range of the branched paraffinic component is 3 or less. In embodiments, the paraffinic backbone of the branched paraffinic component includes paraffins with carbon numbers of at least C12. Alternatively, the branched paraffinic component includes a paraffinic backbone with carbon numbers of at least C14 or at least C16. In embodiments, the paraffinic backbone of the branched paraffinic component has a carbon number in a range of C12 to C22. Alternatively, the backbone of the branched paraffinic component has a carbon number in a range of C12 to Cl 6, in a range of C16 to C20, in a range of C20 to C24, or any ranges therebetween. In embodiments, the paraffinic branches covalently bonded to the paraffinic backbone have a carbon number in a range of C3 to Cl 8. Alternatively, the paraffinic branches have a carbon number in a range of C3 to CIO, in a range of CIO to Cl 4, in a range of C 14 to Cl 8, or any ranges therebetween. In embodiments, the paraffinic branches covalently bonded to the paraffinic backbone each have a carbon number of C3 or greater. For example, the branched paraffinic component includes greater than 95% wt.% paraffinic branches of C3 or greater. For example, 95 w.t% to 97% wt.% paraffinic branches of C3 or greater, 95 w.t% to 99% wt.% paraffinic branches of C3 or greater, or 95 w.t% to 99.9% wt.% paraffinic branches of C3 or greater, or any ranges therebetween. Alternatively, the paraffinic branches covalently bonded to the paraffinic backbone each have a carbon number of C5 or greater. For example, the branched paraffinic component includes greater than 95% wt.% paraffinic branches of C5 or greater. For example, 95 w.t% to 97% wt.% paraffinic branches of C5 or greater, 95 w.t% to 99% wt.% paraffinic branches of C5 or greater, or 95 w.t% to 99.9% wt.% paraffinic branches of C5 or greater, or any ranges therebetween.

[0030] The viscosity -temperature relationship of a lubricating oil is one of the criteria which may be considered when selecting a lubricant for a particular application. Viscosity Index (VI) is an empirical, unitless number which indicates the rate of change in the viscosity of an oil within a given temperature range. Fluids exhibiting a relatively large change in viscosity with temperature are said to have a low viscosity index. A low VI oil, for example, will thin out at elevated temperatures faster than a high VI oil. Usually, the high VI oil is more desirable because it has higher viscosity at higher temperature, which translates into better or thicker lubrication film and better protection of the contacting machine elements. In embodiments, the base stocks of the present disclosure have a viscosity index (VI) of at least 120, such as a VI at a point in a range of 120-150. Alternatively, the base stocks of the present disclosure have a viscosity index in a range of 120-130, from 130-140, from 140 to 150, or any ranges therebetween. Viscosity index is determined according to ASTM method D 2270-93 [1998], VI is related to kinematic viscosities measured at 40° C. and 100° C. using ASTM Method D 445-01.

[0031] The high temperature stability of a lubricating oil is often an important consideration when selecting a base stock for a particular application. The Noack volatility of a base stock measures the evaporative loss of engine oils exposed to elevated temperatures. The Noack volatility is measured by ASTM B3952 or D5800, Method B test. In embodiments, the base stocks of the present disclosure have a Noack volatility of less than 12. wt.%. In embodiments, the base stock has a Noack volatility in a range of 0 wt.% to 12. wt.%. Alternatively, the base stock has a Noack volatility in a range of 0 wt.% to 4. wt.%, in a range of 4 wt.% to 8. wt.%, in a range of 8 wt.% to 12. wt.%, or any ranges therebetween.

[0032] The low temperature viscosity of a lubricating oil is often an important consideration when selecting a base stock for a particular application. The cold cranking simulator (CCS) as outlined in ASTM D5293 can be used to estimate the low temperature performance of the base stock. In embodiments, the base stock of the present application has a -35 °C of less than 3000 cP (centipoise). Alternatively, the base stock of the present application has a CCS at -35 °C in a range of 1000 cP to 3000 cP, in a range of 1000 cP to 2000 cP, in a range of 2000 cP to 3000 cP, in a range of 1000 cP to 1500 cP, in a range of 1500 cP to 2000 cP, in a range of 2000 cP to 2500 cP, in a range of 2500 cP to 3000 cP, or any ranges therebetween. Alternatively, the base stock of the present application has a CCS at 35 °C of less than 2900 cP, or less than 2800 cP, or less than 2700 cP, or less than 2600 cP, or less than 2500 cP, or less than 2400 cP, or less than 2300 cP, or less than 2200 cP, or less than 2100 cP, or less than 2000 cP.

[0033] In embodiments, the CCS ratio of the base stock, that is, a measured low temperature viscosity and the predicted low temperature viscosity from CCS measurement as described in ASTM D5293 at -35 °C is 0.7 or lower. Alternatively, the CCS ratio at -35 °C is in a range of 0 to 0.7, in a range of 0 to 0.6, in a range of 0 to 0.5, in a range of 0 to 0.4, in a range of 0 to 0.3, in a range of 0 to 0.2, in a range of 0 to 0.1, or any ranges therebetween.

[0034] As mentioned above, the low temperature viscosity versus volatility of a base stock is often an important consideration when selecting a base stock for a particular application. In embodiments, the CCS measured by ASTM D5293 and the Noack volatility as measured by ASTM B3952 or D5800, Method B, can be compared. FIG. 1 is a graph that illustrates a volatility to viscosity relationship of selected base stocks including an embodiment of a base stock disclosed herein. It can be seen from FIG. 1 that the embodiment of the disclosed bast stock has lower Noack volatility as a function of CCS viscosity at -35 °C as compared to a polyalphaolefin base stock, a group III - hi base stock, and a group III low base stock. For example, the base stocks of the present application have a 35 °C CCS of less than 3000 cP and a Noack volatility of less than 12 wt.%. Alternatively, the base stocks of the present application have a 35 °C CCS of less than 3000 cP and a Noack volatility of less than 10 wt.%. Alternatively, the base stocks of the present application have a 35 °C CCS of less than 3000 cP and a Noack volatility of less than 8 wt.%. Alternatively, the base stocks of the present application have a 35 °C CCS of less than 3000 cP and a Noack volatility of less than 6 wt.%.

[0035] In embodiments, the base stock has a kinematic viscosity at 100 °C (KV100) at a point in a range of 3.8 cSt (centistokes) to about 4.3 cSt. Alternatively, the base stock has a kinematic viscosity at 100 °C of 3.8 cSt to 4 cSt, from 3.9 cSt to 4.1 cSt, from 3.9 cSt to 4 cSt, from 4.1 cSt to 4.2 cSt, or any ranges therebetween. KV100 is determined using ASTM D445.

[0036] In embodiments, base stock of the present disclosure has a pour point at a point in a range of -30° C to -70° C. Alternatively, a point in a range of from -30° C to -40° C, at a point in a range of from -40° C to -50° C, at a point in a range of from -50° C to -60° C, at a point in a range of from -60° C to -70° C, or any ranges therebetween. The pour point is measured by ASTM B3983 or D5950-l.

[0037] As mentioned above, the base stock of the present disclosure can include a biogenic carbon component when a portion the base stock is produced from renewable sources such as seed oils. The biogenic carbon is disparate from non-biogenic carbon, such as petroleum carbon, and can be identified using radiometric analysis techniques. In embodiments, the base stock of the present disclosure contains at least 98% biogenic carbon as measured by ASTM D6866. Alternatively, the base stock of the present disclosure contains at least 95% biogenic carbon, at least 90% biogenic carbon, at least 85% biogenic carbon, at least 80% biogenic carbon, at least 75% biogenic carbon, at least 70% biogenic carbon, at least 65% biogenic carbon, at least 60% biogenic carbon, at least 55% biogenic carbon, or at least 50% biogenic carbon. In embodiments, the base stock contains from 50% to 99.9% biogenic carbon, from 60% to 99.9% biogenic carbon, from 70% to 99.9% biogenic carbon, from 80% to 99.9% biogenic carbon, from 90% to 99.9% biogenic carbon, or any ranges therebetween. In embodiments, the base stock consists of greater than 99.9% biogenic carbon.

[0038] The composition of the base stock is dependent upon the processing steps and severity of the processing steps involved in producing the base stock. In embodiments, the base stock is produced in a manner to minimize contaminants such as heteroatoms present in the base stock. In embodiments, the production of the base stock includes a deoxygenation and hydrotreating step to remove heteroatoms. In embodiments, the base stock contains less than 1 wt.% oxygen. Alternatively, the base stock includes less than 500 ppm (parts per million) oxygen. Alternatively, the base stock includes less than 400 ppm oxygen, less than 300 ppm oxygen, less than 200 ppm oxygen, less than 100 ppm oxygen, or less than 50 ppm oxygen. In embodiments, the base stock contains less than 0.1 wt.% sulfur. Alternatively, the base stock includes less than 50 ppm sulfur. Alternatively, the base stock includes less than 40 ppm sulfur, less than 30 ppm sulfur, less than 20 ppm sulfur, less than 10 ppm sulfur, or less than 5 ppm sulfur. In embodiments, the base stock contains less than 0.1 wt.% nitrogen. Alternatively, the base stock includes less than 50 ppm nitrogen. Alternatively, the base stock includes less than 40 ppm nitrogen, less than 30 ppm nitrogen, less than 20 ppm nitrogen, less than 10 ppm nitrogen, or less than 5 ppm nitrogen. Heteroatoms concentration can be measured by any suitable methods including those outlines in ASTM D8149-20, for example.

[0039] In embodiments, the base stock of the present application includes the branched paraffinic component which has a carbon number in a range of C28 to C36 and the naphthene component which has a carbon number in a range of C28 to C34. In further embodiments, the base stock can further include a lighter component, a heavier component, or both which have carbon numbers outside the range of C28-C34 of the branched paraffinic component and the naphthene component. [0040] For example, a lighter component including hydrocarbons with carbon numbers in a range of C24 to C27 may be included in the base stock. In embodiments, the lighter component includes lighter branched paraffinic hydrocarbons with carbon numbers from C24 to C27, wherein the lighter branched paraffinic hydrocarbons include a paraffinic backbone and two or more paraffinic branches covalently bonded to the paraffinic backbone such that the branched paraffinic component has a carbon number in a range of C24 to C27. For example, the lighter branched paraffinic hydrocarbons include greater than 95% wt.% paraffinic branches of C3 or greater. For example, 95 w.t% to 97% wt.% paraffinic branches of C3 or greater, 95 w.t% to 99% wt.% paraffinic branches of C3 or greater, or 95 w.t% to 99.9% wt.% paraffinic branches of C3 or greater, or any ranges therebetween. Alternatively, the paraffinic branches covalently bonded to the paraffinic backbone each have a carbon number of C5 or greater. For example, lighter branched paraffinic hydrocarbons includes greater than 95% wt.% paraffinic branches of C5 or greater. For example, 95 w.t% to 97% wt.% paraffinic branches of C5 or greater, 95 w.t% to 99% wt.% paraffinic branches of C5 or greater, or 95 w.t% to 99.9% wt.% paraffinic branches of C5 or greater, or any ranges therebetween.

[0041] In further embodiments, the lighter component includes a lighter naphthene component containing a naphthene ring and two or more paraffinic branches covalently bonded to the naphthene ring such that the lighter naphthene component has a carbon number in a range of C24 to C27. In embodiments, the paraffinic branches covalently bonded to the naphthene ring each have a carbon number of C3 or greater. For example, the naphthene component includes greater than 95% wt.% paraffinic branches of C3 or greater. For example, 95 w.t% to 97% wt.% paraffinic branches of C3 or greater, 95 w.t% to 99% wt.% paraffinic branches of C3 or greater, or 95 w.t% to 99.9% wt.% paraffinic branches of C3 or greater, or any ranges therebetween. Alternatively, the paraffinic branches covalently bonded to the paraffinic backbone each have a carbon number of C5 or greater. For example, lighter branched paraffinic hydrocarbons includes greater than 95% wt.% paraffinic branches of C5 or greater. For example, 95 w.t% to 97% wt.% paraffinic branches of C5 or greater, 95 w.t% to 99% wt.% paraffinic branches of C5 or greater, or 95 w.t% to 99.9% wt.% paraffinic branches of C5 or greater, or any ranges therebetween.

[0042] In embodiments, a heavier component including hydrocarbons with carbon numbers in a range of C37 to C44 may be included in the base stock. In embodiments, the heavier component includes heavier branched paraffinic hydrocarbons with carbon numbers from C37 to C44, wherein the heavier branched paraffinic hydrocarbons include a paraffinic backbone and two or more paraffinic branches covalently bonded to the paraffinic backbone such that the branched paraffinic component has a carbon number in a range of C37 to C44. In embodiments, the paraffinic branches of the heavier branched paraffinic hydrocarbons include 95 w.t% to 97% wt.% paraffinic branches of C3 or greater, 95 w.t% to 99% wt.% paraffinic branches of C3 or greater, or 95 w.t% to 99.9% wt.% paraffinic branches of C3 or greater, or any ranges therebetween. Alternatively, the paraffinic branches each have a carbon number of C5 or greater. For example, 95% wt.% paraffinic branches of C5 or greater. For example, 95 w.t% to 97% wt.% paraffinic branches of C5 or greater, 95 w.t% to 99% wt.% paraffinic branches of C5 or greater, or 95 w.t% to 99.9% wt.% paraffinic branches of C5 or greater, or any ranges therebetween. In further embodiments, the heavier component includes hydrocarbons containing a naphthene ring and two or more paraffinic branches covalently bonded to the naphthene ring such that the naphthene component has a carbon number in a range of C37 to C44. In embodiments, the paraffinic branches covalently bonded to the naphthene ring each have a carbon number of C3 or greater. For example, the naphthene component includes greater than 95% wt.% paraffinic branches of C3 or greater, greater than 99% wt.% paraffinic branches of C3 or greater, or greater than 99.9% wt.% paraffinic branches of C3 or greater.

[0043] In embodiments, the heavier component may be present the base stock of the present application in an amount of 0.1 wt.% to 10 wt.% based on a total weight of the base stock. Alternatively, from 0.1 wt.% to 1 wt.%, 1 wt.% to 5 wt.%, 5 wt.% to 10 wt.%, or any ranges therebetween. Alternatively, the heavier component may be present the base stock of the present application in an amount of less than 5 wt.%, less than 3 wt.%, or less than 1 wt.%.

[0044] If a lubricant base stock product is desired, the lubricant base stock product can be further fractionated to form a plurality of products. For example, lubricant base stock products can be made corresponding to a 2 cSt cut, a 4 cSt cut, a 6 cSt cut, and/or a cut having a viscosity higher than 6 cSt. For example, a lubricant base stock product fraction having a viscosity of at least 2 cSt can be a fraction suitable for use in low pour point application such as transformer oils, low temperature hydraulic oils, or automatic transmission fluid. A lubricant base stock product fraction having a viscosity of at least 4 cSt can be a fraction having a controlled volatility and low pour point, such that the fraction is suitable for engine oils made according to SAE J300 in 0W- or 5W- or lOW-grades. This fractionation can be performed at the time the diesel (or other fuel) product from the second stage is separated from the lubricant base stock product, or the fractionation can occur at a later time. Any hydrofinishing and/or aromatic saturation can occur either before or after fractionation. After fractionation, a lubricant base stock product fraction can be combined with appropriate additives for use as an engine oil or in another lubrication service. [0045] A base stock constitutes the major component of the engine or other mechanical component oil lubricant composition of the present disclosure and typically is present in an amount from about 50 to about 99 weight percent, preferably from about 70 to about 95 weight percent, and more preferably from about 85 to about 95 weight percent, based on the total weight of the composition. As described herein, additives constitute the minor component of the engine or other mechanical component oil lubricant composition of the present disclosure and typically are present in an amount ranging from about less than 50 weight percent, preferably less than about 30 weight percent, and more preferably less than about 15 weight percent, based on the total weight of the composition.

[0046] Mixtures of base stocks may be used if desired, for example, a base stock component and a co-base stock component. The co-base stock component is present in the lubricating oils of this disclosure in an amount from about 1 to about 99 weight percent, preferably from about 5 to about 95 weight percent, and more preferably from about 10 to about 90 weight percent, based on the total weight of the composition. The base stock blend can be present in the engine or other mechanical component oil lubricant composition from 15 wt.% to 99 wt. %, based on the total weight of the oil lubricant composition. Alternatively, from 15 wt.% to 30 wt. %, 30 wt.% to 60 wt. %, 60 wt.% to 80 wt. %, 80 wt.% to 90 wt. %, 90 wt.% to 95 wt. %, 95 wt.% to 99 wt. %, or any ranges therebetween.

[0047] In embodiments, the base stocks further include an additional base stock such as a group I, group II, group III, group IV, group V, or combinations thereof. In embodiments, the additional base stock is present in an amount of 1 wt.% to 99 wt.% by weight of the base stock. Alternatively, from 1 wt.% to 20 wt.%, 20 wt.% to 50 wt.%, 50 wt.% to 70 wt.%, 70 wt.% to 99 wt.%, or any ranges therebetween.

[0048] The formulated lubricating oil useful in the present disclosure may contain one or more of the other commonly used lubricating oil performance additives including but not limited to antiwear additives, detergents, dispersants, viscosity modifiers, corrosion inhibitors, rust inhibitors, metal deactivators, extreme pressure additives, anti-seizure agents, wax modifiers, other viscosity modifiers, fluid-loss additives, seal compatibility agents, lubricity agents, anti-staining agents, chromophoric agents, anti-foam agents, antioxidants, anti-rust additives, anti-wear additives, pour point depressant, demulsifiers, emulsifiers, densifiers, wetting agents, gelling agents, tackiness agents, colorants, and others. These additives are commonly delivered with varying amounts of diluent oil that may range from 5 weight percent up to greater than 90 weight percent. [0049] The additives useful in this disclosure do not have to be soluble in the lubricating oils. Insoluble additives such as zinc stearate in oil can be dispersed in the lubricating oils of this disclosure.

[0050] When lubricating oil compositions contain one or more additives, the additive(s) are blended into the composition in an amount sufficient for it to perform its intended function. As stated above, additives are typically present in lubricating oil compositions as a minor component, typically in an amount of less than 50 weight percent, preferably less than about 30 weight percent, and more preferably less than about 15 weight percent, based on the total weight of the composition. Additives are most often added to lubricating oil compositions in an amount of at least 0.1 weight percent, preferably at least 1 weight percent, more preferably at least 5 weight percent. Typical amounts of such additives useful in the present disclosure are shown in Table 1 below.

[0051] The lube base stocks and lubricant compositions can be employed in the present disclosure in a variety of lubricant-related end uses, such as a lubricant oil or grease for a device or apparatus requiring lubrication of moving and/or interacting mechanical parts, components, or surfaces. Useful apparatuses include engines and machines. The lube base stocks of the present disclosure are suitable for use in the formulation of automotive crank case lubricants, automotive gear oils, transmission oils, many industrial lubricants including circulation lubricant, industrial gear lubricants, grease, compressor oil, pump oils, refrigeration lubricants, hydraulic lubricants and metal working fluids. Furthermore, the lube base stocks of this disclosure may be derived from renewable sources; such base stocks may qualify as sustainable product and can meet “sustainability” standards set by industry groups or government regulations. The lube base stocks and lubricant compositions can be useful to reduce wear between surfaces such as metal surfaces in internal combustion engines, electric motors, crankcases, gearboxes, transmissions, differentials, and other mechanical devices. The base stock or lubricant composition containing the base stock can form a film on the surfaces of mechanical devices to protect the surfaces from wear. [0052] The components of the base stock including the naphthene component and a branched paraffinic component each of which can be prepared by dimerizing unsaturated fatty acids, followed by deoxygenation and/or hydrotreatment. Fatty acids can be sourced from various renewable sources including seed oils. Seed oils such as soy, castor oil, com oil, coconut oil, cottonseed oil, linseed oil, hemp oil, jojoba oil, palm kernel oil, canola oil, safflower oil, sunflower oil, olive oil, rapeseed oil, and combinations thereof can be used in embodiments disclosed herein. Such seeds oils are typically too low in viscosity and molecular weight to be directly used in lubricant applications. Seed oils contain fatty acids with carbon numbers typically ranging from C14 to C22 and typically contain a degree of unsaturation as well as a variety of oxygen-containing functional group. The unsaturation makes it possible to react fatty acid via molecules together to double the molecular weight by dimerization over the proper catalyst at the proper conditions. Additionally, molecules of differing carbon number may be reacted to form the corresponding larger molecule. Increasing the molecular weight is needed to make the viscosity required for lubricant applications. Removing the oxygen in the dimerized product such that the resultant base stock will not quickly degrade in use as a lubricant. The deoxygenated dimerized product can be separated using conventional techniques such as distillation to select for product fractions which are blended to make the renewable base stock disclosed herein. While the process to make the base stock disclosed herein can be practiced with renewable resources such as seed oils, the base stock can also be prepared from hydrocarbon sources. As will be used from herein renewable base stock and base stock should be read equivalently.

[0053] One challenge with using dimerization followed by deoxygenation to produce high performance lubricant base stock is that the chemistry forms cyclic compounds either as part of the dimerization and/or part of the deoxygenation. An example of a dimerization reaction that forms a cyclic compound is shown in Reaction 1. Molecules with these cyclic structures occur in a significant proportion of the molecules when seed oils are dimerized. The cyclic structures are detrimental to a lubricant because with lubricants it is desirable to produce low viscosity fluids for a given molecular weight range. The presence of cyclic structures in hydrocarbon molecules is well known to increase viscosity of molecule for a given molecular weight, that is, for a specified molecular weight increasing the number of cyclic structures increases the viscosity. Dimerization of seed oils typically produces about half of the molecules with ring structures with carbon numbers ranging from C32 to C36.

Reaction 1

[0054] Dimerization can produce a branched paraffinic component with few methyl groups such as in Structure 1. The structure leads to an advantaged set of properties such as excellent low temperature viscosity and pour point. Dimerization can also lead to the presence of ring structures such as in Structure 2. These are unusual structures in that the ring position is predominantly in the center of the molecule.

Structure 1

[0055] Dimerization connects typically two C18 or C16 molecules and leads to the following typical structures: the first is branched paraffinic with very few methyl groups. This leads to an advantaged set of properties typically excellent low temperature viscosity and pour point.

[0056] FIG. 2 illustrates an embodiment of a process 200 for producing the base stock including a naphthene component and a branched paraffinic component in accordance with some embodiments of the present disclosure. Process 200 begins by introducing feed 202 into dimerization unit 204. In embodiments, feed 202 includes triacylglycerols with fatty acid chains with carbon numbers in a range of C14-C28 wherein at least a portion of the fatty acid chains include at least one degree of unsaturation. Feed 202 may also include free fatty acids carbon numbers in a range of C14-C28 wherein at least a portion of the fatty acid chains include at least one degree of unsaturation. In embodiments feed 202 includes free fatty acids with carbon numbers in a range of C14-C28 wherein at least a portion of the free fatty acids include at least one degree of unsaturation. In embodiments, feed 202 includes seed oils, including those seed oils disclosed herein. When utilized, seed oils may be of any grade or quality including refined seed oils. Seed oils may be sourced from plant materials whereby the plant material may be pressed or otherwise made to produce seed oil. In dimerization unit 204, the fatty acids including at least one degree of unsaturation are contacted with a dimerization catalyst at conditions sufficient to react at least a portion of the fatty acids by dimerization of the fatty acids to produce a corresponding dimer acid. The dimer acid can include fatty acids with the same carbon length or disparate carbon lengths. From dimerization unit 204, the dimerization unit effluent 206 is introduced into deoxygenation/hydrogenation unit 208. In deoxygenation/hydrogenation unit 208, the components of the dimerization unit effluent 206 are subjected to conditions effective to deoxygenate and/or hydrogenate at least a portion of the components of the dimerization unit effluent to produce the naphthene component and the branched paraffinic component described herein. From deoxygenation/hydrogenation unit 208, effluent 210 containing the naphthene component and the branched paraffinic component are introduced into fractionation and blending unit 212. Fractionation and blending unit 212 includes equipment suitable to separate components of effluent 210, such as distillation equipment, and equipment to blend the resultant distillation cuts to form the base stock described herein. In some embodiments, hydrocarbons from refinery stream 114 can be blended in fractionation and blending unit 212. Refinery stream 214 can be sourced from a refining process such as fractionation of crude oil or any other suitable source for lubricant range hydrocarbons. A product stream 216 includes a base stock disclosed herein including a naphthene component and a branched paraffinic component.

ADDITIONAL EMBODIMENTS

[0057] Accordingly, the present disclosure may provide to base stocks and renewable base stocks made from biological materials, blends of base stocks, formulated lubricant compositions containing the base stocks, and uses of base stocks and may include any of the various features disclosed herein, including one or more of the following statements.

[0058] Statement 1. A base stock composition comprising: a naphthene component, wherein the naphthene component comprises a naphthene ring comprising two or more paraffinic branches covalently bonded to the naphthene ring, wherein the naphthene component has a carbon number in a range of C28 to C34; and a branched paraffinic component, wherein the branched paraffinic component comprises a paraffinic backbone with a carbon number in a range of C14 to C22, wherein the branched paraffinic component comprises two or more paraffinic branches covalently bonded to the paraffinic backbone, and wherein the branched paraffinic component has a carbon number in a range of C28 to C36. [0059] Statement 2. The base stock composition of statement 1, wherein the base stock composition has a Noack volatility is that less than about 12% as measured by ASTM D5800.

[0060] Statement 3. The base stock composition of any of statements 1-2, wherein the base stock composition has a kinematic viscosity at 100 °C of about 3.8 to about 4.3 cSt as measured by ASTM D 445-01.

[0061] Statement 4. The base stock composition of any of statements 1-3, wherein the base stock composition has a viscosity index of at least 120 as measured by ASTM D2270-93.

[0062] Statement 5. The base stock composition of statements 1-4, wherein the base stock composition has a cold cranking simulator viscosity value at -35 °C of less than 3000 cP as measured by ASTM D5203.

[0063] Statement 6. The base stock composition of any of statements 1-5, wherein the base stock composition comprises at least 98% biogenic carbon as measured by ASTM D6866.

[0064] Statement 7. The base stock composition of any of statements 1-6, wherein the base stock composition has a cold pour point of less than -30 °C as measured by ASTM D5950.

[0065] Statement 8. The base stock composition of any of statements 1-7, wherein the base stock further comprises a lighter component wherein the lighter component comprises lighter branched paraffinic hydrocarbons and lighter naphthenic hydrocarbons with carbon numbers from C24 to C27, wherein the lighter branched paraffinic hydrocarbons comprise a lighter paraffinic backbone and two or more lighter paraffinic branches covalently bonded to the lighter paraffinic backbone such that the lighter branched paraffinic hydrocarbons have a carbon number in a range of C24 to C27, wherein the lighter naphthenic hydrocarbons comprise a lighter naphthene ring and two or more lighter paraffinic branches covalently bonded to the lighter naphthene ring such that the lighter naphthenic hydrocarbons have a carbon number in a range of C24 to C27.

[0066] Statement 9. The base stock composition of any of statements 1-8, wherein the base stock further comprises a heavier component wherein the heavier component comprises heavier branched paraffinic hydrocarbons and heavier naphthenic hydrocarbons with carbon numbers from C37 to C44, wherein the heavier branched paraffinic hydrocarbons comprise a heavier paraffinic backbone and two or more heavier paraffinic branches covalently bonded to the heavier paraffinic backbone such that the heavier branched paraffinic hydrocarbons have a carbon number in a range of C37 to C44, wherein the heavier naphthenic hydrocarbons comprise a heavier naphthene ring and two or more heavier paraffinic branches covalently bonded to the heavier naphthene ring such that the heavier naphthenic hydrocarbons have a carbon number in a range of C37 to C44. [0067] Statement 10. The base stock composition of any of statements 1-9, comprising the naphthene component in an amount of about 15 wt.% to about 30 wt.% based on a total weight of the base stock composition.

[0068] Statement 11. The base stock composition of any of statements 1-10, wherein the naphthene component comprises paraffinic branches with carbon numbers of C3 or greater.

[0069] Statement 12. The base stock composition of any of statements 1-11, comprising the branched paraffinic component in an amount of about 70 wt.% to about 85 wt.% based on a total weight of the base stock composition.

[0070] Statement 13. The base stock composition of any of statements 1-12, wherein the branched paraffinic component comprises paraffinic branches with carbon numbers of C3 or greater.

[0071] Statement 14. The base stock composition of any of statements 1-13, wherein the naphthene component has a carbon number in a range of C28 to C30 and wherein the branched paraffinic component has a carbon number in a range of C28 to C34.

[0072] Statement 15. The base stock composition of any of statements 1-14, wherein the naphthene component, the branched paraffinic component, or both, are at least partially derived from dimerization of an unsaturated fatty acid with a carbon number in a range of C14 to C22.

[0073] Statement 16. The base stock composition of statement 15, wherein the unsaturated fatty acid is at least partially derived from a seed oil.

[0074] Statement 17. The base stock composition of any of statements 1-16, wherein the naphthene component, the branched paraffinic component, or both, are at least partially derived from a stream of a refining process.

[0075] Statement 18. The base stock composition of any of statements 1-17, wherein the base stock composition comprises less than 100 ppm (parts per million) oxygen.

[0076] Statement 19. The base stock composition of any of statements 1-18, wherein the base stock composition comprises less than 10 ppm (parts per million) sulfur.

[0077] Statement 20. The base stock composition of any of statements 1-19, wherein the base stock composition comprises less than 100 ppm (parts per million) nitrogen.

[0078] Statement 21. A base stock composition comprising: a naphthene component in an amount of about 15 wt.% to about 30 wt.% based on a total weight of the base stock composition, wherein the naphthene component comprises a naphthene ring comprising two or more paraffinic branches covalently bonded to the naphthene ring, wherein the naphthene component has a carbon number in a range of C28 to C30; and a branched paraffinic component in an amount of about 70 wt.% to about 85 wt.% based on a total weight of the base stock composition, wherein the branched paraffinic component comprises a paraffinic backbone with a carbon number in a range of C14 to C22, wherein the branched paraffinic component comprises two or more paraffinic branches covalently bonded to the paraffinic backbone, wherein the branched paraffinic component has a carbon number in a range of C28 to C34, wherein the base stock composition has a kinematic viscosity at 100 °C of about 3.8 to about 4.3 cSt as measured by ASTM D 445-01, wherein the base stock composition has a viscosity index above 120 as measured by ASTM D2270-93, and wherein the base stock composition has a Noack volatility is less than about 12% as measured by ASTM D5800.

[0079] Statement 22. The base stock composition of statement 21, wherein the naphthene component, the branched paraffinic component, or both, are at least partially derived from dimerization of an unsaturated fatty acid with a carbon number in a range of C14 to C22.

[0080] Statement 23. A lubricating oil composition comprising: a base stock; and an additive, wherein the base stock comprises: a naphthene component, wherein the naphthene component comprises a naphthene ring comprising two or more paraffinic branches covalently bonded to the naphthene ring, wherein the naphthene component has a carbon number in a range of C28 to C34; and a branched paraffinic component, wherein the branched paraffinic component comprises a paraffinic backbone with a carbon number in a range of C14 to C22, wherein the branched paraffinic component comprises two or more paraffinic branches covalently bonded to the paraffinic backbone, and wherein the branched paraffinic component has a carbon number in a range of C28 to C36.

[0081] Statement 24. The lubricating oil composition of statement 23, wherein the additive is an anti-wear additive, a viscosity modifier, an antioxidant, a detergent, a pour point depressant, a corrosion inhibitor, a metal deactivator, a seal compatibility additive, an anti-foam agent, an inhibitor, an anti-rust additive, or any combination thereof.

[0082] Statement 25. The lubricating oil composition of any of statements 23-24, further comprising at least one additional base stock, wherein the at least one additional base stock is a group I base stock, group II base stock, group III base stock, group IV base stock, group V base stock, and combinations thereof.

[0083] Statement 26. The lubricating oil composition of any of statements 23-25, wherein the lubricating oil composition has a kinematic viscosity at 100 °C of about 3.8 to about 4.3 cSt as measured by ASTM D 445-01, wherein the base stock composition has a viscosity index above 120 as measured by ASTM D2270-93, and wherein the base stock composition has a Noack volatility is less than about 12% as measured by ASTM D5800. [0084] Statement 27. The lubricating composition of any of statements 23-26, wherein the lubricating composition is suitable for use as an automotive crank case lubricant, an automotive gear oil, a transmission oil, a circulation lubricant, a gear lubricant, a grease, a compressor oil, a pump oil, a hydraulic lubricant, or combinations thereof.

[0085] Statement 28. A method of reducing wear in a mechanical component comprising: contacting two adjacent surfaces with a lubricating oil composition; forming a lubricant film comprising the lubricating oil composition in a space between the two adjacent surfaces; sliding the two adjacent surfaces relative to each other; and reducing wear between the two adjacent surfaces using the lubricant film, wherein the lubricant composition comprises: a base stock comprising: a naphthene component, wherein the naphthene component comprises a naphthene ring comprising two or more paraffinic branches covalently bonded to the naphthene ring, wherein the naphthene component has a carbon number in a range of C28 to C34; and a branched paraffinic component, wherein the branched paraffinic component comprises a paraffinic backbone with a carbon number in a range of C14 to C22, wherein the branched paraffinic component comprises two or more paraffinic branches covalently bonded to the paraffinic backbone, and wherein the branched paraffinic component has a carbon number in a range of C28 to C36.

[0086] Statement 29. The method of statement 28, wherein the lubricating oil composition is suitable for use as an automotive crank case lubricant, an automotive gear oil, a transmission oil, a circulation lubricant, a gear lubricant, a grease, a compressor oil, a pump oil, a hydraulic lubricant, or combinations thereof.

[0087] Statement 30. The method of any of any of statements 28-29, wherein the mechanical component comprises an internal combustion engine, an electric motor, a crankcase, a gearbox, a transmission, a differential, or any combination thereof.

[0088] While the disclosure has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the disclosure as disclosed herein. Although individual embodiments are discussed, the present disclosure covers all combinations of all those embodiments.

[0089] While compositions, methods, and processes are described herein in terms of “comprising,” “containing,” “having,” or “including” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components and steps. The phrases, unless otherwise specified, “consists essentially of’ and “consisting essentially of’ do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, so long as such steps, elements, or materials, do not affect the basic and novel characteristics of the disclosure, additionally, they do not exclude impurities and variances normally associated with the elements and materials used.

[0090] All numerical values within the detailed description are modified by “about” the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art. [0091] Many alterations, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description without departing from the spirit or scope of the present disclosure and that when numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated