阅读说明：本技术 冷起动模拟机粘度降低基料和含有它们的润滑油制剂 (Cold start simulator viscosity reducing basestocks and lubricating oil formulations containing same ) 是由 K·G·刘易斯 于 2018-03-20 设计创作，主要内容包括：本公开内容涉及冷起动模拟机粘度(“CCSV”)降低基料,其允许低粘度SAE发动机油等级(例如,5W和0W)的灵活性以满足对低温粘度要求的需求同时维持更高的基础油粘度以便改进磨损保护。所述CCSV降低基料包括可衍生自格尔伯特醇和单羧酸的单酯。本公开内容还涉及含所述CCSV降低基料的润滑油,和通过使用含所述CCSV降低基料中的一种或多种的配制油作为润滑性发动机油改进所述发动机中的燃料效率和/或磨损保护的方法。(The present disclosure relates to cold cranking simulator viscosity ("CCSV") reducing basestocks that allow flexibility of low viscosity SAE engine oil grades (e.g., 5W and 0W) to meet the demand for low temperature viscosity requirements while maintaining higher base oil viscosities for improved wear protection. The CCSV reduction base stock comprises a monoester derivable from a Guerbet alcohol and a monocarboxylic acid. The present disclosure also relates to lubricating oils containing the CCSV reducing basestocks, and methods of improving fuel efficiency and/or wear protection in lubricating engine oils by using formulated oils containing one or more of the CCSV reducing basestocks as the engine oil.)

1. An oil composition consisting of a first base stock and a reference oil, wherein:

The first binder comprises a monoester having the formula:

Wherein R is₁And R₂independently of one another, are substituted or unsubstituted C2-C30 alkyl, R₃is substituted or unsubstituted C2-C20 alkyl;

the first base stock is present in the oil composition at a concentration of 0.5 wt% to 14.5 wt%, based on the total weight of the oil composition;

the oil composition has a kinematic viscosity at 100 ℃ KV100(oil) according to ASTM D445 ("KV 100") and a cold cranking simulator viscosity at a given temperature CCSV (oil) according to ASTM 5293 ("CCSV");

The reference oil has KV100 and CCSV of KV100 (reference) and CCSV (reference), respectively, and

The following conditions (i) and (ii) are satisfied:

(i)And

(ii)

2. The oil composition of claim 1 wherein KV100 and CCSV of said oil composition meet the requirements for SAE engine oil grades according to the SAE J300 viscosity grade classification system.

3. The oil composition of claim 1 or claim 2 wherein said first base stock has a KV100 of from 3 to 6cSt, a Noack volatility ("NV") according to ASTM D5800 of at most 20%, and a viscosity index according to ASTM D2271 ("VI") of at least 100.

4. Oil composition according to any one of the preceding claims, wherein R₁and R₂each independently is a linear C2-C24 alkyl group, and R₃Is a linear C2-C12 alkyl group.

5. The oil composition of claim 4, wherein the greater of the two following values is in the range of 18-30: (i) r₁And R₃The total number of carbon atoms taken together; and (ii) R₂And R₃The total number of carbon atoms taken together.

6. The oil composition of claim 1, wherein the monoester comprises 2-octyldodecyl dodecanoate, 2-octyldodecyl nonanoate, or a mixture thereof.

7. The oil composition of any one of claims 1 to 6, wherein said first base stock is present at a concentration of 1 to 10 wt.%, based on the total weight of the oil composition.

8. The oil composition of any one of claims 1 to 7, comprising APC group III base stocks and/or group IV base stocks in the base stock.

9. The oil composition of any one of the preceding claims, further comprising one or more of the following additives in the base oil: dispersants, detergents, viscosity modifiers, antiwear additives, corrosion inhibitors, rust inhibitors, metal deactivators, extreme pressure additives, anti-adhesion agents, viscosity modifiers, defoamers, demulsifiers, and wetting agents.

10. the oil composition of any one of claims 1 to 9, which is an SAE0W engine oil, an SAE 5W engine oil, an SAE10W engine oil, an SAE 15W engine oil, an SAE 20W engine oil or an SAE 25W engine oil.

11. The oil composition of claim 10 having KV100 in one of the following ranges:

7.4-9.3cSt；

10.9-12.5 cSt; and

14.4-16.3cSt。

12. The oil composition of any one of claims 1 to 11, wherein:

The following conditions (i), (ii), and (iii) are satisfied:

(i)-10≤D(kv)<0；

(ii) d is more than or equal to-1000 (ccsv) and less than or equal to-5; and

(iii)D(ccsv)/D(kv)≥3。

13. The oil composition of any one of claims 1 to 11, wherein:

the following conditions (i) and (ii) are satisfied:

(i) d is more than or equal to 0.05 and less than or equal to 20 (kv); and

(ii)-1000≤D(ccsv)≤-5。

14. Use of a monoester having the formula as a first base stock in a lubricating oil composition at a concentration thereof in the range of 0.5 to 14.5 wt.%, based on the total weight of the lubricating oil composition:

wherein R is₁And R₂Independently each is substituted or unsubstituted C2-C30 alkyl, and R₃Is a substituted or unsubstituted C2-C20 alkyl group.

15. The use of claim 14, wherein R₁And R₂Each independently is a linear C2-C24 alkyl group, and R₃Is a linear C2-C12 alkyl group.

16. The use of claim 15, wherein the greater of the two following values is in the range of 18-30: (i) r₁And R₃the total number of carbon atoms taken together; and (ii) R₂and R₃The total number of carbon atoms taken together.

17. Use according to any one of claims 14 to 16, wherein the first binder has a kinematic viscosity at 100 ℃ according to ASTM D445 ("KV 100") of from 3 to 6cSt, a Noack volatility according to ASTM D5800 ("NV") of at most 20%, and a viscosity index according to ASTM D2271 of at least 100.

18. The use of any of claims 14-17, wherein the monoester comprises octyldodecyl dodecanoate, octyldodecyl nonanoate, or a mixture thereof.

19. The use of any of claims 14-18, wherein the first binder is present at a concentration of 1 to 10 wt.%, based on the total weight of the lubricating oil formulation.

20. The use of any one of claims 13-19, wherein:

The lubricating oil formulation has KV100 for KV100(oil) and CCSV for CCSV (oil);

a base oil having a KV100 (base) KV100 and a CCSV (base) cold start simulator viscosity at a given temperature according to ASTM D5293 ("CCSV"), the base oil being the remainder of the lubricating oil formulation absent the first base stock, and

the following conditions (i) and (ii) are satisfied:

(i)And

(ii)

21. The use of claim 20, wherein: 0< D (kv) is less than or equal to 20.

22. The use of claim 20, wherein:

The following conditions (i), (ii), and (iii) are satisfied:

(i)-20≤D(kv)<0；

(ii) d is more than or equal to-1000 (ccsv) and less than or equal to-5; and

(iii)D(ccsv)/D(kv)≥3。

23. A method of improving fuel efficiency and/or wear protection in an engine, comprising lubricating the engine with an engine oil comprising an oil composition according to any one of the preceding claims 1 to 13.

Technical Field

The present disclosure relates to cold cranking simulator viscosity ("CCSV") reduction basestocks that allow flexibility in low viscosity SAE engine oil grades (e.g., 5W and 0W) to meet demands for low temperature viscosity and high temperature viscosity requirements, lubricating oil formulations containing the CCSV reduction basestocks, and methods of improving fuel efficiency and/or wear protection in such engines by using lubricating oil formulations containing one or more of the CCSV reduction basestocks as engine oils.

Background

Continued regulatory pressures to improve fuel efficiency and reduce carbon emissions have driven the automotive industry toward the use of lower viscosity grade engine oils. Lower viscosity engine oils hold promise for maximizing fuel economy, but the more released oils may negatively impact wear protection in automotive engines. This is particularly the case with heavy duty engine oils in commercial vehicles that require lubricants with enhanced wear and deposit protection due to more severe loading and operating conditions.

Today, 15W and 10W grades of engine oil constitute the largest segment of the commercial vehicle lubricating oil market. Increased fuel efficiency requirements will drive the growth of this lower viscosity 5W and 0W grade engine oil market. At the same time, the need for engine oil durability and wear protection will continue to increase.

Automotive engine oils follow the SAE J300 metric system for graded engine oil viscosity. For each SAE engine oil grade (e.g., 5W-30, 10W-30, etc.), there are maximum and minimum viscosity requirements at high and low temperatures. Typically, such high temperature viscosity requirements are expressed as an acceptable range of kinematic viscosity at 100 ℃ as determined in accordance with ASTM D445 ("KV 100"), and such low temperature viscosity requirements are expressed as an acceptable range of cold start simulator viscosity as determined in accordance with ASTM D5583.

within a particular engine oil class, it is theoretically possible to maximize wear performance by increasing the KV100 of the engine oil to the maximum allowable value. In practice, it is difficult to achieve the maximum allowable KV100 in engine oils, particularly those of the 0W or 5W grades, and still meet the required CCSV requirements. Generally, high levels of low viscosity hydrocarbon base stock are required to meet the low temperature viscosity requirements of 0W or 5W engine oils. This may negatively affect wear performance.

There remains a need for engine oils that exhibit a desirable KV100 and an acceptable CCSV that is tolerated by SAE grade standards. In particular, there remains a need for binder materials that can provide the required KV100 and required CCSV profile (profile) for oil formulations that are tolerated by SAE grade standards. There is also a need for a method of determining the effectiveness of a base stock as a CCSV reducing base stock.

The present invention meets this and other needs.

Disclosure of Invention

It has been found that a class of monoesters derived from Guerbet alcohol (Guerbet alcohol) and a monocarboxylic acid can be effectively used as a CCSV reducing base stock to reduce the CCSV of an oil composition without significantly affecting the KV100 of the oil composition, making them particularly useful for formulating engine oils conforming to SAEJ 300.

A first aspect of the present disclosure relates to an oil composition consisting of a first base stock and a reference oil, wherein: (a) the first binder comprises a monoester having the formula:

Wherein R is₁And R₂Independently of one another, are substituted or unsubstituted C2-C30 alkyl, R₃Is substituted or unsubstituted C2-C20 alkyl; (b) the first base stock is present in the oil composition at a concentration of 0.5 wt% to 14.5 wt%, based on the total weight of the oil composition; (c) the oil composition has a kinematic viscosity at 100 ℃ KV100(oil) according to ASTM D445 ("KV 100") and a cold cranking simulator viscosity at a given temperature CCSV (oil) according to ASTM 5293 ("CCSV"); (e) the reference oil respectively has KV100 (reference) and CCSV (reference)Quasi) KV100 and CCSV, and the following conditions (i) and (ii) are satisfied:

And

Wherein: KV100(oil) stands for KV100(oil), KV100(ref) stands for KV100 (reference), CCSV (oil) stands for CCSV (oil), and CCSV (ref) stands for CCSV (reference).

a second aspect of the present disclosure relates to the use of a monoester having the following formula as a first base stock in a lubricating oil composition at a concentration thereof in the range of 0.5 to 14.5 wt.%, based on the total weight of the lubricating oil composition:

Wherein R is₁And R₂Independently of one another, are substituted or unsubstituted C2-C30 alkyl, R₃Is a substituted or unsubstituted C2-C20 alkyl group.

A third aspect of the present disclosure relates to a method of improving fuel efficiency and/or wear protection in an engine comprising lubricating the engine with an engine oil comprising the oil composition of the first aspect of the present disclosure.

Other objects, features and advantages of the present disclosure will be understood with reference to the following drawings and detailed description.

Drawings

Figure 1 is a schematic showing the effect of a CCSV reducing base on CCSV and KV100 for a formulation consisting of a base oil and the CCSV reducing base.

Figure 2 graphically shows the CCSV reducing efficacy of various monoester binders and comparative esters.

Detailed Description

definition of

"alkyl" refers to a saturated hydrocarbon group consisting of carbon and hydrogen atoms.

"hydrocarbyl" refers to a group consisting only of hydrogen and carbon atoms. The hydrocarbyl groups may be saturated or unsaturated, linear or branched, cyclic or acyclic, aromatic or non-aromatic.

A "Cn" group or compound refers to a group or compound that contains carbon atoms in the total number n. Thus, a "Cm-Cn" group or compound refers to a group or compound comprising carbon atoms in the total number of m to n. Thus, C1-C50 alkyl refers to alkyl groups containing carbon atoms in a total number of 1-50.

"carbon backbone" refers to the longest straight carbon chain in the molecule of the compound or group in question. "branched" refers to any non-hydrogen group attached to a carbon backbone.

"monoester" refers to compounds having one ester (-C (O) -O-) functional group therein.

"Tertiary amide" refers to a compound that contains a tertiary amide (> N-C (O) -) functional group.

"SAE" refers to the SAE International (formerly known as the society of automotive Engineers), which is a specialized organization that sets standards for internal combustion engine lubricating oils.

"SAE J300" refers to the viscosity grade classification system for engine oils established by SAE, which defines the limits of the classification in rheological terms only.

"lubricating oil" refers to a substance that can be introduced between two or more surfaces and reduce the level of friction between two adjoining surfaces moving relative to each other. A lubricant "base stock" is a material used to formulate lubricants by blending it with other components, typically fluids at various viscosity levels at the operating temperature of the lubricant. Non-limiting examples of suitable base stocks in lubricants include API group I, group II, group III, group IV and group V base stocks. PAOs, especially hydrogenated PAOs, have recently become widely used in lubricant formulations as group IV base stocks, and are especially preferred. If one base stock is designated as the primary base stock in the lubricant, the additional base stock may be referred to as a co-base stock (a co-base stock).

All kinematic viscosity values in this disclosure are determined according to ASTM D445. The kinematic viscosity at 100 ℃ is reported herein as KV100 and the kinematic viscosity at 40 ℃ is reported herein as KV 40. All KV100 and KV40 values herein are in units of cSt unless otherwise specified.

All viscosity index ("VI") values in this disclosure are determined according to ASTM D2270.

All Noack volatility ("NV") values in this disclosure are determined according to ASTM D5800, unless otherwise specified. All NV values are in wt% unless otherwise specified.

All CCS viscosity ("CCSV") values in this disclosure are determined according to ASTM 5293. All CCSV values herein are in centipoise unless otherwise specified. All CCSV values are measured at the temperature of interest for the lubricating oil formulation or oil composition in question. Thus, for the design and manufacture of engine oil formulations, the temperature of interest is the temperature at which SAE J300 assumes maximum CCSV. Thus, the CCSV measurement temperatures are: -35 ℃ for SAE0W grade oil; for SAE 5W grade oil, -30 ℃; -25 ℃ for SAE10W grade oil; for SAE 15W grade oil, -20 ℃; -15 ℃ for SAE 20W grade oil; for SAE 25W grade oil, -10 ℃.

All percentages describing chemical compositions herein are by weight unless otherwise specified. "Wt%" refers to weight percent.

All numbers expressing "about" or "approximately" the numerical values used in the detailed description and claims are to be understood as being modified in light of the experimental error and deviation as would be expected by one of ordinary skill in the art.

CCSV reducing base stock

Summary of I.1

The binder of the present disclosure desirably has KV100 in the range of k1 to k2cSt, where k1 and k2 can be independently 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, and 7.5, so long as k1< k 2. Preferably, k1 is 3.0 and k2 is 6.0. Thus, the base stocks of the present disclosure have a relatively "low" viscosity at normal operating temperatures of internal combustion engine lubricating oils.

the base stock may desirably have a VI in the range of v1-v2, where v1 and v2 may be independently 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 and 200, as long as v1< v 2.

The base stocks of the present disclosure desirably have NV values in the range of n1-n2 wt%, where n1 and n2 can be independently 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, so long as n1< n 2. Preferably, n1 is 1 and n2 is 16. In general, for the same type of CCSV reducing base stock, the larger the molecular weight of the molecule, the lower the NV value. For engine oils and basestocks for them, typically, low NV values are preferred, all other parameters remaining equal.

Desirably, the CCSV reducing base of the present disclosure has a high thickening effect at the relatively "low" temperatures (e.g., -35 ℃) that an automobile engine may experience from time to time during its normal life. The CCSV reducing base of the present disclosure may thus manifest itself as a solid, wax, or viscous fluid at-35 ℃,0 ℃, and even 25 ℃.

The basestocks of the present disclosure, when incorporated into a lubricating oil formulation or oil composition, desirably result in a reduced CCSV for the formulation or oil composition as compared to the remainder of the lubricating oil formulation or oil composition. Thus, it is referred to as a CCSV reducing base. Such CCSV reducing base stocks of the present disclosure may be used as a base stock or co-base stock in any lubricating oil composition. Preferably, the CCSV reducing base (sometimes referred to as a "first base") of the present disclosure is used as a co-base in combination with a second base that is a primary base. In certain applications, it may be desirable to include two or even more additional basestocks in the lubricating oil formulation or oil composition of the present disclosure in addition to the CCSV reducing basestocks of the present disclosure. For ease of description, the CCSV reducing base will hereinafter be referred to only as a general base, whether designated as a primary base or a co-base.

Desirably, the CCSV reducing base stock is readily soluble in low viscosity hydrocarbon base stocks at ambient temperature for a given treat rate.

the basestocks of the present disclosure are preferably used to formulate automotive engine lubricating oils, preferably those meeting SAE J300 classification standards. However, it is contemplated that the basestocks of the present disclosure may be used to formulate other lubricating oils (e.g., automotive driveline oils, industrial lubricating oils, gear oils, greases, etc.), heat transfer oils (e.g., transformer oils), hydraulic power transmission oils, processing oils, and the like.

I.2 monoesters derived from Guerbet alcohols and monocarboxylic acids

Monoesters derived from guerbet alcohols and monocarboxylic acids are particularly advantageous CCSV reducing basestocks of the present disclosure. The monoester has the formula:

Wherein R is₁、R₂And R₃Independently each is a C2-C30 substituted or unsubstituted alkyl group. Preferably, R₁、R₂And R₃each independently a linear alkyl group containing from 2 to 24 carbon atoms.

The monoester can be prepared by reacting a Guerbet alcohol having the formula

With monocarboxylic acids of the formula

under reaction conditions sufficient to produce the monoester, wherein: r₁、R₂And R₃as defined above. For example, 2-octyldodecyl nonanoate may be prepared by reacting 2-octyl-1-dodecanol with a linear C9 monocarboxylic acid. Similarly, 2-octyldodecyl dodecanoate can be prepared by reacting 2-octyl-1-dodecanol with a linear C12 monocarboxylic acid.

Exemplary monoesters useful as CCSV reducing binders of the present disclosure include, for example, 2-octyldodecyl nonanoate, 2-octyldodecyl dodecanoate, mixtures thereof, and the like.

Exemplary guerbet alcohols that can be used to prepare the monoester CCSV reducing binders of the present disclosure include, for example, 2-octyl-1-dodecanol, mixtures thereof, and the like.

The alcohol reactant is a mono-alcohol, preferably a single branched alcohol containing 16 to 24 carbons. More preferably, the alcohol has 20 carbons. The preferred alcohol is Guerbet alcohol.

the monocarboxylic acid is preferably a linear acid having 7 to 16 carbons. More preferably, the monocarboxylic acid contains 9 to 12 carbons. Exemplary monocarboxylic acids useful in preparing the monoester CCSV reducing binders of the present disclosure include, for example, linear C9 monocarboxylic acid (nonanoic acid), linear C10 monocarboxylic acid (decanoic acid), linear C11 monocarboxylic acid (undecanoic acid), linear C12 monocarboxylic acid (dodecanoic acid), mixtures thereof, and the like.

II. determination method of CCSV reduction performance of base material

Different base stocks may have different CCSV reducing potency when used in different amounts relative to the same base oil. The same base stock may have the same, similar or different CCSV reducing potency relative to different base oils. The following method can be used to determine the effectiveness of a particular first basestock at a given concentration to act as a CCSV reducing basestock in a lubricating oil.

The method comprises the following steps: the base oil to be combined with the first base stock is measured at low temperatures of interest for the lubricating oil formulation or oil composition (e.g., the temperature at which the SAE J300 standard imposes the maximum CCSV requirement, i.e., for SAE0W grade oil, -35 ℃, for SAE 5W grade oil, -30 ℃, for SAE10W grade oil, -25 ℃, for SAE 15W grade oil, -20 ℃, for SAE 20 grade oil, -15 ℃, for SAE 25 grade oil, -10 ℃) KV100 and CCSV (KV 100 (base) and CCSV (base), respectively)), and the blend oil consisting of the base oil and the first base stock at the desired concentration of the first base stock in the blend oil at the same low temperature KV100 and CCSV (oil, respectively)).

Next, if CCSV (oil) is less than CCSV (baseline) and KV100(oil) is greater than KV100 (baseline), the first basestock is determined to be a CCSV-reduced basestock at the first concentration.

If CCSV (oil) is less than CCSV (base), and KV100(oil) is less than KV100 (base), meaning that the addition of the first basestock to the base oil results in a reduction in KV100 as compared to the base oil, the following values are calculated:

And

Wherein: KV100(oil) stands for KV100(oil), KV100(ref) stands for KV100 (reference), CCSV (oil) stands for CCSV (oil), and CCSV (ref) stands for CCSV (reference).

if D (CCSV)/D (kv) ≧ 3.0, the first basestock is determined as a CCSV reduced basestock relative to the base oil at the first concentration. Those CCSV reducing binders exhibiting a D (CCSV) of ≦ -5 at the first concentration thereof are considered excellent CCSV reducing binders at said first concentration. In general, for negative number d (CCSV), the greater its absolute value | d (CCSV) | the more effective it is in reducing the CCSV of the mixture oil compared to the base oil, and the more desirable it is, all other parameters remaining equal.

The above method can be reduced to a representation in an x-y coordinate system, where the x-axis is d (kv) and the y-axis is d (ccsv). The two axes intersect at (0,0), which represents the reference oil. Thus, all of the first basestocks in the quadrants where x >0 and y <0 are CCSV reduced basestocks. All of the first basestocks in the quadrant where y >0 are not CCSV reducing basestocks because their introduction results in an increase in CCSV. For any first web belonging to the quadrant where x <0 and y <0, it is a CCSV reducing web in the sense of this disclosure if it is on or below the line defined by the equation y — 3 x. It is not a CCSV reducing base stock in the sense of this disclosure. Those CCSV reducing binders having a d (CCSV) falling on or below the line defined by y ═ 5 are considered to be excellent (preferred) CCSV reducing binders at their given concentrations. Such a diagrammatic representation is shown in fig. 1.

Alternatively, the CCSV reducing efficacy of a given first binder can be determined by measuring the high temperature kinematic viscosity at a temperature other than 100 ℃, for example 40 ℃. Likewise, the low temperature viscosity measurement may be performed at temperatures other than-35 deg.C, such as-30 deg.C, -25 deg.C, -20 deg.C, -15 deg.C, -10 deg.C, etc., as long as such temperatures are of importance for the oil formulation. As described above, SAE J300 imposes minimum CCSV requirements for different grades of engine oil. The most preferred temperature to achieve CCSV for a given SAE J300 engine oil grade is the temperature required to impose the maximum CCSV by the SAE J300 standard.

a first base identified as a CCSV reducing base at a first concentration can be tested for CCSV reducing efficacy at a second concentration, or even more. Typically, CCSV reducing base stocks exhibit higher CCSV reducing efficacy at higher concentrations in the blend oil. Thus, a CCSV reducing base is considered to be an overall superior (preferred) CCSV reducing base if it exhibits a D (CCSV). ltoreq.5 at a concentration of 5 wt% thereof, based on the total weight of the mixture oil. It is expected that an overall excellent CCSV reducing base stock will be an excellent CCSV reducing base stock at its higher concentration in the blend oil, for example at 6, 7, 8, 9, 10, 11, 12, 13, 14, 14.5 wt%. Such CCSV reduction base stocks are particularly desirable that exhibit high | d (CCSV) | over a wide concentration range with CCSV reduction potency, especially high CCSV reduction potency. Preferably, the overall superior CCSV reducing base stock exhibits a D (CCSV) in the blend oil of no more than-8, -10, -12, -15, -16, -18, -20, -25, -30, -35, -40, -45, -50, -60, -70, -80, -90, -100, -200, -500, -800, or even-1000 at a concentration of 5 wt% thereof. Certain highly advantageous CCSV reducing binders of the present disclosure may exhibit D (CCSV) ≧ 5 even at concentrations such as 1, 2, 3, or 4 wt%, based on the total weight of the miscella. It was found that a first base stock which is a CCSV reducing base stock in a first base stock is a good indicator, so that it will also be a CCSV reducing base stock in a different second base stock having a similar chemical composition as the first base stock.

Preferably, a blend oil consisting of a base oil and a first basestock found to be a CCSV reducing basestock is an interesting lubricating oil.

in practice, the base oil may be selected as a combination of various base stocks for the final lubricating oil formulation. Once the blend oil consisting of the base oil and the first base stock is determined to have the desired CCSV and KV100, additional components, such as additive packages typically used in the lubricating oil types described, can then be added to prepare the final lubricating oil.

It is still possible that a specific base stock may be used as a base stock in the final formulation of the lubricating oil. Such base stock base oils desirably may be base stocks having the KV100 closest to the first base stock, i.e., the CCSV reducing base stock, among all base stocks other than the first base stock contained in the lubricating oil formulation. Alternatively, such base stock reference oil may desirably be the base stock having the closest CCSV (base) to the first base stock at a given temperature of interest, among all base stocks other than the first base stock contained in the formulation. For engine oil formulations, commercial group IV basestocks may be used, such as a conventional catalyzed (i.e., non-metallocene catalyzed) PAO having a KV100 of about 4cSt ("PAO-4", such as SpectraSyn commercially available from ExxonMobil Chemical Company having the address 4500Bayway Drive, Baytown, Texas, U.S. A^TM4) As a reference oil.

In addition, it is also possible that additional base stocks may be added, preferably in small amounts, to the blend oil consisting of the base oil and the first base stock to fine-tune the final lubricating oil formulation to a desired chemical composition with optimum properties, such as KV100 and CCSV. Desirably, such KV100 and CCSV meet the SAE J300 grade designation for engine oils, particularly oils of grades 0W20, 0W30, 0W40, 5W20, 5W30, 5W40, 10W20, 10W30, 10W40, 15W20, 15W30, 15W40, 20W20, 20W30, or 20W 40.

Of course, once the final oil formulation is determined, the product may be formed by mixing the various components in any order deemed appropriate by one of ordinary skill in the art. For example, the various components of the first base stock, the base oil, and the various additives and additional components can all be mixed simultaneously to obtain an oil formulation product, wherein the step of forming a blended oil of the first base stock and the base oil is omitted. Additionally, the base oil may be replaced in the lubricating oil formulation with similar basestocks or basestock mixtures (e.g., those having KV100 in the range of f1 x KV100 (base) to f2 x KV100 (base) and those in the same API group as the base oil, where f1 and f2 may independently be 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, so long as f1< f2), which are known to reduce the first basestock will perform similarly in mixtures with those replacement oils replacing the base oil.

Oil compositions containing CCSV reducing base stock

III.1 overview

The CCSV reducing basestocks of the present disclosure are useful in formulating lubricating oils. The oil composition of the first aspect of the present disclosure outlined above may be part or all of a lubricating oil formulation. Thus, the oil composition may be: (i) a mixture of a first base and the remainder of the formulation in the absence of said first base; (ii) a mixture of the first base stock with one or more other base stocks included in a lubricating oil formulation in the absence of an additive component in the lubricating oil formulation; (iii) a mixture of the first base stock and all other base stocks contained in the lubricating oil formulation but absent any additive components that may be present in the lubricating oil formulation; (iv) a mixture of a first base stock and one or more other base stocks (but not all other base stocks) contained in a lubricating oil formulation and at least a portion of the additive components contained in the lubricating oil formulation; and (v) a mixture of the first base stock and all additive components contained in the lubricating oil formulation (but no other base stocks contained in the lubricating oil formulation).

Thus, additional components, such as other base stocks, additional amounts of materials already present in the oil composition, additive components, and the like, may be added to the oil composition of the present disclosure in order to prepare the final lubricating oil formulation of the product. However, one particularly preferred embodiment of the oil composition of the present disclosure is a lubricating oil formulation, in which case the base oil is the remainder of the lubricating oil formulation in the absence of the first basestock.

Oil compositions (preferably, lubricating oil formulations) having KV100 for KV100(oil) and CCSV for CCSV (oil) at the given low temperatures described above; the base oils having the chemical composition of the remainder of the oil composition in the absence of the first base stock have KV100 and CCSV of KV100 (base) and CCSV (base), respectively, and satisfy the following conditions (i) and (ii):

wherein d1 and d2 may independently be-20, -18, -16, -15, -14, -12, -10, -8, -6, -5, -4, -2, 0, 2,4, 6, 8, 10, 12, 14, 15, 16, 18, 20, 22, 24, 25, 26, 28, 30, 32, 34, 36, 38, 40, provided that d1<d 2; preferably d1 ═ 10, d2 ═ 20; (wherein KV100(oil) stands for KV100(oil) and KV100(ref) stands for KV100 (reference)) and

Wherein d3 and d4 may independently be-1000, -800, -600, -500, -400, -200, -100, -80, -60, -50, -48, -46, -45, -44, -42, -40, -30, -38, -36, -35, -34, -32, -30, -28, -26, -25, -24, -22, -20, -18, -16, -15, -14, -12, -10, -8, -6, -5, -4, -2, provided that d3<d 4; preferably d3 ═ 100, d4 ═ 5; more preferably, d3 is-50, d4 is-10 (wherein: CCSV (oil) stands for CCSV (oil), and CCSV (ref) stands for CCSV (base)).

In a preferred embodiment, the following conditions (i) and (ii) are satisfied:

(i) d5 ≦ D (kv) ≦ d6, where d5 and d6 may independently be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 16, 18, 20, 25, 30, 35, 40, provided that d5< d 6; preferably d 5-1, d 6-20; more preferably d 5-2, d 6-15; and

(ii) d 7. ltoreq. D (ccsv.). ltoreq.d 8, where d7 and d8 may independently be-1000, -800, -600, -500, -400, -200, -100, -80, -60, -50, -48, -46, -45, -44, -42, -40, -30, -38, -36, -35, -34, -32, -30, -28, -25, -22, -20, -18, -16, -15, -14, -12, -10, -8, -6, -5, -4, -3, -2 or-1, provided that d7< d 8; preferably d7 ═ 100, d8 ═ -3; more preferably, d 7-50 and d 8-5.

In these embodiments, inclusion of the CCSV reducing base into the formulation results in a reduction in CCSV in the formulation compared to the base oil, and an increase or maintenance in KV100 in the formulation compared to the base oil, both of which are highly desirable for formulating engine oils with high wear protection.

In another embodiment, the following conditions (i), (ii), and (iii) are satisfied:

(i) d 9. ltoreq. D (kv). ltoreq.d 10, where d9 and d10 may independently be-0.01, -0.05, -0.1, -0.5, -1, -2, -4, -5, -6, -8, -10, -12, -14, -15, -16, -18, -20, -22, -24, -25, provided that d9< d 10; preferably d9 ═ 0.05, d10 ═ -20; more preferably d9 ═ 0.1, d10 ═ -10;

(ii) d 11. ltoreq.D (ccsv.). ltoreq.d 12, where d11 and d12 may independently be-1000, -800, -600, -500, -400, -200, -100, -80, -60, -50, -48, -46, -45, -44, -42, -40, -30, -38, -36, -35, -34, -32, -30, -28, -26, -25, -24, -22, -20, -18, -16, -15, -14, -12, -10, -8, -6, -5, -4, -2, 0, provided that d11< d 12; preferably d11 ═ 30, d12 ═ 5; more preferably d11 ═ 25, d12 ═ 10; and

(iii) r1 ≦ D (ccsv)/D (kv), preferably but not necessarily D (ccsv)/D (kv) r2, where r1 and r2 may independently be 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 500, 1000, 5000, 10,000, 50, 000, provided that r1< r 2. Preferably, r1 is 5, more preferably r1 is 10. Preferably, r2 is 10,000, more preferably r2 is 1,000.

In these embodiments, inclusion of the CCSV reducing base into the formulation results in a reduction in both CCSV and KV100 in the formulation compared to the baseline oil. In order to obtain an engine oil with high anti-wear protection of the metal surface, it is preferred that the ratio of d (ccsv)/d (kv) which meets the classification requirements for SAE J300 of the grades therein should be desirably high, i.e. at least 3, preferably at least 5, more preferably at least 10.

The CCSV reducing base stock is preferably present in an amount sufficient to provide the desired CCSV reducing effect in the oil composition while balancing the other properties of the oil composition, especially KV 100. The CCSV reducing base stock may be present in the oil composition of the present disclosure in an amount of about c1-c2 wt%, wherein c1 and c2 may be independently 0.1, 0.3, 0.5, 0.6, 0.8, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, 11.0, 12.0, 13.0, 14.0, 14.1, 14.2, 14.3, 14.4, 14.5, 14.6, 14.7, 14.8, or 14.9, based on the total weight of the oil composition, provided that c1< c 2. More preferably, c1 is 3.0 and c2 is 14.0. More preferably, c1 is 5.0 and c2 is 12.0. In general, it is desirable that the oil composition contain a CCSV reducing base stock as a co-base stock.

Preferred oil compositions containing CCSV reducing base stocks of the present disclosure exhibit KV100 in the range of KV1-KV2, where KV1 and KV2 can be 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, 15.0, so long as KV1< KV 2.

The engine oil lubricant grade was determined according to SAE J300 specifications. Low temperature (W) ratings (i.e., 10W-xx, 5W-xx, 0W-xx) are determined by performance in a combination of viscosity tests including Cold Cranking Simulation (CCS) (ASTM D5293) and low temperature pump viscosity (ASTM D4684). The high temperature classification of engine oils (i.e., XW-20, XW-30) is determined by the kinematic viscosity at 100 ℃ (ASTM D445) and the high temperature high shear viscosity (ASTM D4683).

Advantageously, the use of the CCSV reducing binder of the present invention in an engine oil formulation can result in such oils having a particularly desirably high KV100 while maintaining an acceptable CCSV, all within the acceptable range specified by the SAE J300 grade classification.

Desirably, the oil composition of the present disclosure is a mW20 engine oil having a KV100 of 7.4 to 9.3cSt, preferably 8.4 to 9.3cSt, where m can be 0, 5, 10, 15, 20, 25, meeting the requirements of SAE J300.

Desirably, the oil composition of the present disclosure is a mW30 engine oil having a KV100 of 10.9 to 12.5cSt, preferably 11.7 to 12.5cSt, where m can be 0, 5, 10, 15, 20, 25, meeting the requirements of SAE J300.

Desirably, the oil composition of the present disclosure is a mW40 engine oil having a KV100 of 14.4 to 16.3cSt, preferably 15.4 to 16.3cSt, where m can be 0, 5, 10, 15, 20, 25, meeting the requirements of SAE J300.

5W-20 grade engine oils allow KV100 of 5.6-9.3 cSt. The fuel efficiency improvement provided by the lubricant is due to the reduction in KV 100. However, in practice, it is difficult to reach a KV100 minimum of 5.6cSt without simultaneously reducing the low temperature CCSV to less than the 5W limit (6200 centipoise at-35 ℃) and into the 0W range. This is particularly the case with engine oils of high quality group III/IV basestocks having very low CCSV. Thus, conventional attempts to maximize fuel efficiency of 5W engine oils by minimizing KV100 via strategies to increase the amount of high quality group III/IV basestocks may result in the modified oil being re-classified as a 0W engine oil. Thus, there is a practical limit to how low it can be lowered before a grade 5W engine oil is removed from the grade. There is also a fuel efficiency limit for class 5W engine oils.

The CCSV reducing base of the present disclosure described above may be used to reduce the low temperature CCSV of the formulation. Ideally, the CCSV reducing basestock does not reduce the high temperature KV100 viscosity relative to the remainder of the engine oil formulation (i.e., the remainder of the oil in the absence of the CCSV reducing basestock). The incorporation of the CCSV reducing base stocks of the present disclosure in engine oils allows the formulation to maintain high temperature viscosity while maintaining a sufficiently high CCSV to maintain grade.

The CCSV reducing base stock-containing oil compositions of the present disclosure may advantageously exhibit a VI in the range of from about 30 to about 200, preferably from about 35 to about 180, more preferably from about 40 to about 150.

The CCSV reducing base stock-containing oil compositions of the present disclosure advantageously exhibit an NV value of at most 20%, preferably at most 18%, 16%, 15%, 14%, 12%, 10%, or even 8%.

The oil composition of the present disclosure is particularly advantageous as an engine oil for internal combustion engines, including gas engines, diesel engines, natural gas engines, four-stroke engines, two-stroke engines, and rotary engines. The engine oil may be thrown into the crankcase of the engine to provide the necessary lubrication and cooling of the engine during normal operation. The high KV100 combined with the CCSV of the oil that can be achieved by lowering the base stock with CCSV makes it particularly wear-resistant. The engine oil is particularly advantageous as a passenger car engine oil (PVEO) product.

While the lubricating oil formulation or oil composition of the present disclosure may contain a CCSV reducing base stock as the main base stock, or even as a single base stock, it is preferred to include a CCSV reducing base stock as a co-base stock in combination with a main base stock and optionally one or more additional co-base stocks. In addition to the base stock, the lubricating oil formulation or oil composition of the present disclosure may further comprise an additive component.

III.2 other base stocks which can be used in lubricating oils

A wide range of lubricating oil basestocks known in the art may be used with the CCSV reducing basestocks in the lubricating oil formulations of the present disclosure as either the main basestock or the co-basestock. Such other base stocks may be derived from natural sources or synthetic, including unrefined, refined, or re-refined oils. Unrefined oil bases include shale oil obtained directly from a retorting operation, petroleum oil obtained directly from primary distillation, and ester oil obtained directly from natural sources (e.g., plant matter and animal tissue) or obtained directly from a chemical esterification process. Refined oil base stocks are those unrefined base stocks that have been further subjected to one or more purification steps such as solvent extraction, secondary distillation, acid extraction, base extraction, filtration, and percolation to improve the properties of at least one lubricant. Rerefined oil base stocks are obtained by processes similar to refined oils except that oils which have previously been used as feedstocks are used.

API groups I, II, III, IV and V are broad categories of base stocks developed and specified by the American Petroleum Institute (API Publication 1509; www.API.org) to establish guidelines for lubricant base stocks. Group I bases generally have a viscosity index of about 80-120 and contain greater than about 0.03% sulfur and less than about 90% saturates. Group II bases generally have a viscosity index of about 80 to 120 and contain less than or equal to about 0.03% sulfur and greater than or equal to about 90% saturates. Group III basestocks generally have a viscosity index greater than about 120 and contain less than or equal to about 0.03% sulfur and greater than about 90% saturates. Group IV includes Polyalphaolefins (PAO). Group V materials include base materials not included in groups I-IV. The following table summarizes the properties of each of these five groups.

Natural oils include animal oils (e.g., lard), vegetable oils (e.g., castor oil), and mineral oils. Animal and vegetable oils with advantageous thermo-oxidative stability can be used. Among natural oils, mineral oils are preferred. Mineral oils vary widely according to their natural source, for example, according to whether they are paraffinic, naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal or shale are also useful in the present disclosure. Natural oils also vary in the process used for their production and purification, such as their distillation range and whether they are straight-run or cracked, hydrofinished or extracted with a solvent.

Group II and/or group III basestocks are typically hydrotreated or hydrocracked basestocks derived from a crude oil refinery process.

Synthetic binders include polymerized and interpolymerized olefins (e.g., polybutylene, polypropylene, propylene isobutylene copolymer, ethylene-olefin copolymer, and ethylene-alpha olefin copolymer).

Synthetic polyalphaolefin ("PAO") base stocks are placed in group IV. Advantageous group IV base stocks are those made from one or more of C6, C8, C10, C12, and C14 linear alpha-olefins ("LAO"). These binders are commercially available in a wide range of viscosities, for example KV100 in the range of 1.0 to 1,000 cSt. The PAO binder may be prepared by polymerizing LAO(s) in the presence of a lewis acid type catalyst in the presence of a catalyst system based on a metallocene compound. High quality group IV PAO commercial binders include SpectraSyn available from ExxonMobil Chemical Company having addresses 4500Bayway drive, Baytown, Texas 77450, United States^TMAnd SpectraSyn Elite^TMAnd (4) series.

All other synthetic binders, including but not limited to alkylaromatics and synthetic esters, are in group V.

Minor amounts of esters are usefulthe lubricating oil formulation of the present disclosure. Additive solvency and seal compatibility characteristics can be imparted by utilizing esters such as esters of dibasic acids with monoalkanols and polyol esters of monocarboxylic acids. The former type of esters include, for example, esters of dicarboxylic acids such as phthalic acid, succinic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, caronic acid, alkyl caronic acids, alkenyl caronic acids, and the like with various alcohols such as butanol, hexanol, dodecanol, 2-ethylhexanol, and the like. Specific examples of these types of esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, eicosyl sebacate, and the like. Useful ester group V base stocks include Esterex, commercially available from ExxonMobil Chemical Company^TMAnd (4) series.

One or more of the following may also be used as base stocks in the lubricating oils of the present disclosure: (1) one or more gas-to-liquid (GTL) materials; and (2) hydrodewaxing, hydroisomerization, solvent dewaxing or catalytic dewaxing base stocks derived from synthetic waxes, natural waxes, waxy feedstocks, slack waxes, gas oils, waxy fuels, hydrocracker bottoms, waxy raffinates, hydrocrackers, thermal cracked products, oil bottoms, and waxy materials derived from coal liquefaction or shale oils. Such waxy feeds may be derived from mineral oil or non-mineral oil processing or may be synthetic (e.g., fischer-tropsch feedstock). Such binders preferably comprise C20 or higher, more preferably C30 or higher linear or branched hydrocarbyl compounds.

the lubricating oil formulation or oil composition of the present disclosure may comprise one or more group I, II, III, IV or V basestocks in addition to the CCSV reducing basestock. Preferably, group I basestocks, if any, are present at lower concentrations if a high quality lubricant is desired. Group I binders may be introduced in small amounts as diluents for the additive package. Group II and group III basestocks may be included in the lubricating oil formulations or oil compositions of the present disclosure, but preferably only those having high quality, such as those having a VI of 100-120. Group IV and group V basestocks, preferably those of high quality, are desirably included in the lubricating oil formulations or oil compositions of the present disclosure.

III.3 lubricating oil additives

Formulated lubricating oils useful in the present disclosure may also contain one or more conventional lubricating oil performance additives including, but not limited to, dispersants, detergents, viscosity modifiers, antiwear additives, corrosion inhibitors, rust inhibitors, metal deactivators, extreme pressure additives, anti-adhesion agents, wax modifiers, viscosity modifiers, fluid loss additives, seal compatibilisers, lubricants, anti-staining agents, colourants, antifoamants, demulsifiers, thickeners, wetting agents, gelling agents, adhesives, colorants and the like. For a review of many commonly used additives and amounts used, see: (i) klamann in Lubricants and Related Products, Verlag Chemie, Deerfield Beach, FL; ISBN 0-89573-177-0; (ii) "Lunbricnt Additives," M.W.Ranney, published by the Noyes Data Corporation of Parkridge, NJ (1973); (iii) "Synthesis, Mineral Oils, and Bio-Based Lubricants," eds., L.R. Rudnick, CRCTaylor and Francis, 2006, ISBN 1-57444-; (iv) "contamination Fundamentals", J.G.Wills, Marcel Dekker Inc. (New York, 1980); (v) synthetic Lubricants and high-Performance Functional Fluids,2nd Ed., Rudnick and Shunkin, Marcel Dekker Inc., (New York, 1999); and (vi) "polyalphaolephins," L.R. Rudnick, Chemical Industries (Boca Raton, FL, United States) (2006),111 (Synthesis, Mineral Oils, and Bio-base Lubricants), 3-36. Reference is also made to: (a) U.S. patent nos. 7,704,930B 2; (b) U.S. patent No. 9,458,403B 2 from column 18, line 46 to column 39, line 68; (c) U.S. patent No. 9,422,497B 2 at column 34, line 4 to column 40, line 55; and (d) U.S. patent No. 8,048,833B 2, column 17, line 48 to column 27, line 12, the disclosures of which are incorporated herein in their entirety. These additives are typically delivered prior to introduction into the formulated oil with varying amounts of diluent oil, which may range from 5 wt% to 50 wt%, based on the total weight of the additive package. Additives useful in the present disclosure need not be soluble in the lubricating oil formulation. Insoluble in oil additives may be dispersed in the lubricating oil formulations of the present disclosure.

When the lubricating oil formulation contains one or more of the above-described additives, the additive(s) are blended into the oil composition in an amount sufficient to perform their intended function.

It should be noted that many additives are shipped from additive manufacturers as concentrates that contain one or more additives along with a certain amount of base oil diluent. Accordingly, the amounts by weight in the following table, as well as other amounts referred to herein, refer to the amount of active ingredient (i.e., the non-diluent portion of the ingredient). The weight percentages (wt%) indicated below are based on the total weight of the lubricating oil formulation.

Examples of techniques that may be employed to characterize the above-described CCSV reduced base include, but are not limited to, analytical gas chromatography, nuclear magnetic resonance, thermogravimetric analysis (TGA), inductively coupled plasma mass spectrometry, Differential Scanning Calorimetry (DSC), and volatility and viscosity measurements.

The invention is further illustrated by the following non-limiting examples.