Low ash lubricating components

Abstract

To provide a passenger car lubrication composition that reduces or eliminates the level of metal-containing anti-wear additives while meeting the high requirements of industrial performance standards. [Solution] A passenger car lubrication composition having a low sulfated ash content, comprising a base oil, an anti-wear system containing an ashless phosphorus-containing anti-wear compound and optionally a metal-containing anti-wear compound, an anti-wear system in which the phosphorus weight ratio of the ashless anti-wear compound to the optionally metal-containing anti-wear compound is about 50:50 to 100:0, a detergent system having a sulfated ash content of about 0.75 weight percent or less according to ASTM D874, a total phosphorus of the ashless phosphorus-containing anti-wear compound and optionally a metal-containing anti-wear compound of about 700 ppm or less, and a magnesium to calcium weight ratio of about 2.0 or less, and a TBN ratio of about 60 percent TBN according to ASTM D2896 to TBN according to ASTM D4739.

Description

[Technical Field]

[0001] This disclosure relates to low-ash additive systems and lubricating compositions including low-ash additive systems for passenger car engines. [Background technology]

[0002] Automotive manufacturers continue to strive for improved efficiency and fuel economy, and as a result, the demand for engines, lubricants, and their components continues to increase. Lubricants contain many additives to protect engines from wear, oxidation, soot, and / or acid buildup, and it is well known that these additives indicate several performance characteristics of common lubricant additives. One conventional additive for passenger car engine oils is a metal-containing anti-wear compound such as zinc dialkyldithiophosphate (ZDDP), which protects engine components by forming a protective layer on metal surfaces, and has been a major additive in passenger car lubrication compositions to achieve performance in numerous engine oil tests in many applications. ZDDP was a versatile, multi-functional additive that could function, for example, as an anti-wear additive, extreme pressure additive, antioxidant, and / or corrosion inhibitor. While metal-containing compounds like ZDDP are common additives in passenger car engine oils, they also contribute to the ash content of lubricant compositions, and in recent years, there has been a demand to reduce the level of ash contribution from lubricants for several reasons. Unfortunately, removing or reducing levels of metal-containing anti-wear additives like ZDDP in engine oil can be detrimental to many performance targets, and therefore, simply reducing or eliminating ZDDP while still meeting the heightened requirements of manufacturers and industry performance standards tends to be difficult. [Overview of the project]

[0003] In one approach or embodiment, a passenger car lubrication composition having a lower sulfated ash content is described herein. In one embodiment, the passenger car lubrication composition comprises: an anti-wear system comprising one or more base oils of lubrication viscosity, one or more ashless phosphorus-containing anti-wear compounds and optionally one or more metal-containing anti-wear compounds, wherein the phosphorus weight ratio of phosphorus from one or more ashless anti-wear compounds to phosphorus from the optionally one or more metal-containing anti-wear compounds is about 50:50 to about 100:0; a detergent system having a sulfated ash content of about 0.75 weight percent or less as measured according to ASTM D874, total phosphorus contributed by one or more ashless phosphorus-containing anti-wear compounds and optionally one or more metal-containing anti-wear compounds of about 700 ppm or less, and a magnesium-to-calcium weight ratio of about 2.0 or less; and a TBN ratio of at least about 60 percent of TBN measured according to ASTM D4739 to TBN measured according to ASTM D2896.

[0004] In other approaches or embodiments, the passenger car lubrication compositions described in the preceding paragraph include one or more other aspects or embodiments in any combination. These other approaches or embodiments include one or more of the following: when the sulfated ash is less than 0.5 weight percent, the TBN ratio is about 60 percent to 70 percent, and / or when the sulfated ash is greater than 0.5 weight percent, the TBN ratio is greater than 70 to about 80 percent, and / or the ratio of zinc in ppm units to total sash weight percent (ASTM D874) is less than about 400 when the total sash is less than about 0.5 weight percent, and / or the ashless phosphorus-containing anti-wear additive is a dialkyldithiophosphate ester, a dithiophosphate triester, an amyl acid phosphate, a diamyl acid phosphate, a dibutyl hydrogen phosphonate, a dimethyl octadecyl phosphonate, a salt thereof, or a mixture thereof, and / or one or more ashless phosphorus-containing anti-wear additives are a dialkyldithiophosphate anti-wear additive having the structure of formula I, or a salt thereof.

[0005] [ka] In the formula, R1 and R2 of formula I are independently C3-C8 linear or branched alkyl groups, R3 of formula I is hydrogen or methyl, R4 of formula I is a hydroxyl group or a hydrocarbyl group, and / or the ashless phosphorus-containing anti-wear additive is a triester of a dithiophosphate having two oxygen ester moieties and a sulfur ester moiety, each oxygen ester moiety independently containing at least two β-hydrogen atoms on a linear or branched hydrocarbyl group, the sulfur ester moiety containing one or more heteroatoms selected from oxygen or nitrogen and having up to four carbon atoms linking at least one of the heteroatoms to a sulfur atom of the sulfur ester, the ashless phosphorus-containing anti-wear additive has a molecular weight of at least about 490 g / mol, and / or the triester of the dithiophosphate has the structure of formula II.

[0006] [ka] In the formula, R5 and R6 of formula II comprise an oxygen ester moiety and, independently, a linear or branched C3-C100 hydrocarbyl group, and R7 of formula II comprises a sulfur ester moiety having a linear or branched C3-C100 hydrocarbyl group containing one or more heteroatoms, and / or the oxygen ester moieties of R5 and R6 from formula II independently comprise 4-methyl-2-pentyl alcohol, isopropyl alcohol, tert-butyl alcohol, sec-butyl alcohol, 2-octanol, 2-decanol, 2-dodecanol, or the same. Derived from one of the combinations and / or the sulfur ester portion of R7 in formula II is (i) a vinyl ester of a carboxylic acid, selected from vinyl acetate, vinyl propionate, vinyl laurate, vinyl octanoate, vinyl decanoate, vinyl stearate, or a combination thereof; (ii) maleic acid, its ester, diester, or anhydride, such as vinyl acetate, vinyl propionate, vinyl laurate, vinyl octanoate, vinyl decanoate, vinyl stearate, or (iii) an alkyl (meth)acrylate derived from one of the following: (iii) an alkyl (meth)acrylate selected from methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, or a combination thereof, or (iv) a combination thereof, and / or the dithiophosphate triesters comprising each oxygen ester derived from 4-methyl-2-pentyl alcohol and a sulfur ester derived from dibutyl maleate, and / or the molecular weight of the ashless phosphorus-containing anti-wear additive being a maximum of about 650 g / mol, and / or the metal-containing anti-wear additive being one or more zinc dihydrocarbyl dithiophosphate compounds; and / or the zinc dihydrocarbyl dithiophosphate compounds being derived from at least about 60 weight percent of secondary alcohols, and / or the one or more zinc dihydrocarbyl dithiophosphate compounds having the structure of formula III,

[0007] [ka] In the formula, each R group in formula III is independently a linear or branched C3-C16 hydrocarbyl group, and / or each R group in formula III is independently a linear or branched C4-C8 hydrocarbyl group, and / or the hydrocarbyl group of one or more zinc dihydrocarbyl dithiophosphate compounds is selected from one or more of the following: ethylhexyl group, butyl group, methyl isobutyl group, pentyl group, methylpentyl group, isopentyl group, isobutyl group, propyl group, isopropyl group, or a combination thereof, and / or the ashless phosphorus-containing anti-wear compound and the optionally selected metal-containing anti-wear compound contribute a total of approximately 350 ppm or less of phosphorus, and / or the passenger car lubrication composition lubricates a hybrid electric passenger car engine, and / or the passenger car lubrication composition exhibits a rust grade of 70 AGV or higher in the ASTM D6557 rust ball test, and / or the passenger car lubrication composition exhibits a high temperature corrosion bench test in the ASTM D6594 The passenger car lubrication composition has a total copper, lead, and tin content of about 330 ppm or less in total, according to test (HTCBT), and / or exhibits emulsion stability with 0 percent water separation at 0°C and / or 25°C according to ASTM D7563, and / or the cleaning agent system comprises a perbasic calcium sulfonate cleaning agent and a perbasic magnesium sulfonate cleaning agent, contributing about 200 to about 1000 ppm of calcium and about 500 to about 1500 ppm of magnesium to the passenger car lubrication composition, and / or the cleaning agent system has a magnesium-to-calcium weight ratio of at least about 1.0.

[0008] Further approaches or embodiments also disclose methods for lubricating a passenger car engine. In some embodiments, the method includes lubricating the crankcase of a passenger car engine with any embodiment of a passenger car lubricating composition having a low sulfated ash content as described in the preceding two paragraphs.

[0009] In further other approaches or embodiments, the use of passenger car lubrication compositions having a lower sulfated ash content from any embodiment of this outline is described for achieving one or more of the following: (i) a rust grade of 70 AGV or higher in the rust ball test of ASTM D6557, and / or (ii) total copper, lead, and tin of about 330 ppm or less in combination according to the high-temperature corrosion test (HTCBT) of ASTM D6594, and / or (ii) emulsion stability with 0 percent water separation at 0°C and / or 25°C according to ASTM D7563.

[0010] Additional details and benefits of this disclosure are partially described below and / or may be acquired through the practice of this disclosure. These details and benefits may be realized and achieved through the elements and combinations specifically indicated in the attached claims. It should be understood that both the above general description and the following detailed description are illustrative and descriptive only and do not limit the claimed disclosure. [Brief explanation of the drawing]

[0011] [Figure 1] This graph shows the rust ball performance of lower sash lubrication compositions in relation to the ratio of zinc to total sash. [Figure 2] This graph shows the predicted rust ball performance versus the actual rust ball performance in the context of zinc and total sash. [Modes for carrying out the invention]

[0012] In one embodiment, the present application describes a passenger car lubrication composition having a lower ash content, partly due to a reduction or elimination of the amount of a metal-containing anti-wear compound, such as zinc dialkyldithiophosphate (ZDDP) additive in the composition. Sulfated ash is a measure that indicates the total weight percentage of ash contributed by a lubricating oil composition, and the sulfated ash content of a lubricating oil composition is related to the total metal contribution of the various additives therein and can be conveniently measured as described herein, according to ASTM D874 and / or other common evaluation methods known in the art. As described in the background art, metal-containing anti-wear additives such as ZDDP have been major additives in passenger car engine oils for many years, and the metal (e.g., zinc) in such additives is a contributing factor to the ash content of the lubricant. However, simply reducing or eliminating ZDDP to formulate a lubricating composition with a lower ash contribution often results in one or more drawbacks in achieving the desired performance. For example, as shown in the examples, reducing or eliminating metal-containing anti-wear additives in passenger car lubrication compositions presents challenges in achieving desired corrosion resistance (e.g., rust ball test of ASTM D6557), stable emulsions (e.g., ASTM D7563), and / or low corrosion in high-temperature corrosion test (HTCBT) (e.g., ASTM D6594).

[0013] This specification has discovered passenger car lubrication compositions with lower levels of sulfated ash content that achieve surprisingly good performance in multiple engine oil tests, even when metal-containing anti-wear compounds such as ZDDP are reduced, or even absent. In one approach or embodiment, the compositions herein are anti-wear systems comprising one or more base oils of lubricating viscosity, one or more ashless phosphorus-containing anti-wear compounds and optionally one or more metal-containing anti-wear compounds (but with reduced amounts of metal), wherein the weight ratio of phosphorus contributed by one or more ashless anti-wear compounds to phosphorus contributed by one or more metal-containing anti-wear compounds is about 25:75 to about 100:0, about 50:50 to about 100:0, about 75:25 to about 100:0, or about 25:75 to about 75:25 (or any other range in between), and ASTM The composition comprises a sulfated ash content of about 0.75% by weight or less (or, in other approaches, about 0.7% by weight or less, about 0.6% by weight or less, about 0.4% by weight or less, or about 0.36% by weight or less) as measured according to D874, and total phosphorus of about 700 ppm or less (or, in other approaches, 600 ppm or less, 500 ppm or less, 400 ppm or less, 350 ppm or less phosphorus, or 300 ppm or less phosphorus) contributed by one or more ashless phosphorus-containing anti-wear compounds, if present, optionally one or more metal-containing anti-wear compounds. In other embodiments, the compositions herein may also balance the zinc level to the total sash contribution, such that in some approaches the composition also has a total zinc of about 300 ppm when the composition has less than 0.5% by weight of total sash, and / or also shows the relationship of zinc in ppm units to total sash, which is reflected by the ratio of zinc of about 400 ppm or less to total sash weight percent.

[0014] In other embodiments, when using an antiwear system as described herein to reduce ash contribution, it has also been found that the passenger vehicle lubricating compositions of the present disclosure also require a specific TBN profile that is compatible with the antiwear system. In one approach, as highlighted by the examples, the lubricating compositions of the present disclosure have a TBN ratio of ASTM D4739 TBN to ASTM D2896 TBN of at least about 60 percent. As shown in the examples, in at least some embodiments, such a TBN relationship combined with an antiwear system selected to reduce ash content helps to achieve performance in the context of compositions having the above lower ash contributing antiwear systems. In still other embodiments, when the sulfuric acid ash content is measured to be less than about 0.5 weight percent, the TBN ratio is from about 60 percent to about 70 percent, and / or when the sulfuric acid ash content is measured to be at least about 0.5 weight percent (e.g., from about 0.5 to about 0.75 weight percent), it has been found that the TBN ratio is greater than 70 to about 80 percent.

[0015] Ashless phosphorus-containing antiwear compound The antiwear system of the passenger vehicle lubricating compositions herein includes one or more ashless phosphorus-containing antiwear compounds. In one approach or embodiment, the ashless phosphorus-containing antiwear compound can be selected from dialkyldithiophosphate esters, triesters of dithiophosphates, amyl phosphates, diamyl phosphates, dibutyl hydrogen phosphonates, dimethyloctadecyl phosphonates, their salts, or mixtures thereof.

[0016] In some embodiments, the ashless phosphorus-containing antiwear compound is an acidic thiophosphate, a thiophosphate ester, or a sulfur-containing phosphate ester and can have one or more sulfur-phosphorus bonds. The thiophosphate ester can be a dithiophosphate ester. In a more specific approach, the acidic thiophosphate or thiophosphate ester can have the structure of Formula I or a salt thereof,

[0017] [Chemical formula] In the formula, R1 and R2 are each independently a linear or branched C1-C10 hydrocarbyl group, and R3 is a C1-C10 linear or branched carboxyl group or a C1-C10 linear or branched alkyl alkanate group. Preferably, R1 and R2 are each a C3-C8 linear or branched alkyl group, and since R3 is derived from 2-methylpropionic acid, the second phosphorus product (or its salt) has the structure of formula Ia below,

[0018]

Chemical formula

[0019] In other embodiments, the ashless phosphorus-containing antiwear compound is a triester of dithiophosphate having a selected structure in which the compound includes two selected oxygen ester moieties and a selected sulfur ester moiety. In one approach, each oxygen ester moiety independently includes a linear or branched hydrocarbyl group having at least two or more β-hydrogens, the sulfur ester moiety includes a linear or branched hydrocarbyl group, includes one or more heteroatoms selected from oxygen or nitrogen, and has up to 4 carbon atoms connecting at least one of the heteroatoms to the sulfur atom of the sulfur ester.

[0020] In some approaches, the triester of the dithiophosphate additive suitable for the ashless phosphorus-containing antiwear compound also has a minimum molecular weight of at least about 490 g / mol and may have the structure of formula II,

[0021]

Chemical formula

[0022] In one approach, the oxygen ester moieties (e.g., R5 and R6 in formula II) each independently comprise a linear or branched C3-C100 hydrocarbyl group, while in the other approach, they comprise a linear or branched C3-C50 hydrocarbyl group, a linear or branched C3-C20 hydrocarbyl group, or preferably a linear or branched C6-C10 hydrocarbyl group, or most preferably a linear or branched C6-C8 hydrocarbyl group, each linear or branched hydrocarbyl group comprising at least two β-hydrogen atoms (or 2-9 β-hydrogen atoms, preferably 2-6 β-hydrogen atoms, more preferably 2-5 β-hydrogen atoms, and most preferably 5 β-hydrogen atoms). As is known to those skilled in the art, a β-hydrogen atom refers to any hydrogen atom on the β-carbon of the hydroxyl group, and an α-carbon is the carbon atom bonded to the oxygen atom of the dithiophosphate (i.e., the α-carbon is the carbon atom bonded to the hydroxyl group in the alcohol used to form the oxygen ester).

[0023] In other approaches or embodiments, the oxygen ester moieties R5 and R6 of Formula II are independently derived from one or more secondary alcohols to provide the described levels of β-hydrogens. For example, suitable secondary alcohols used to form the oxygen ester moieties include, but are not limited to, 4-methyl-2-pentyl alcohol (providing 5 β-hydrogens), isopropyl alcohol (providing 6 β-hydrogens), tert-butyl alcohol (providing 9 β-hydrogens), sec-butyl alcohol (providing 5 β-hydrogens), 2-octanol (providing 5 β-hydrogens), 2-decanol (providing 5 β-hydrogens), 2-dodecanol (providing 5 β-hydrogens), or combinations thereof. Preferably, each oxygen ester of Formula II is derived from 4-methyl-2-pentyl alcohol and provides 5 β-hydrogens to each oxygen ester group. However, this preferred selection of oxygen esters also needs to be adapted to suit the suitable sulfur ester moieties in order to derive the above minimum molecular weight of the additive in order to achieve performance.

[0024] In another approach or embodiment, the sulfur ester moiety (e.g., R7 of formula II) includes a linear or branched C3-C100 hydrocarbyl group (in other approaches, a linear or branched C3-C50 hydrocarbyl group, or a linear or branched C3-C30 hydrocarbyl group) having one or more heteroatoms (preferably oxygen) selected from oxygen or nitrogen, and up to four carbon atoms linking at least one of the heteroatoms (preferably an oxygen atom) to the sulfur atom of the sulfur ester moiety. In other approaches, the sulfur ester has up to two carbon atoms, preferably one or two, linking the heteroatoms to the sulfur atom. In other embodiments, the sulfur ester moiety may also optionally include one or more carbonyl groups in its hydrocarbyl chain.

[0025] In one approach or embodiment, the sulfur ester moiety represented by R7 in Formula II above is derived from, for example, one of (i) vinyl esters, (ii) unsaturated carboxylic acids, their esters, diesters, or anhydrides, (iii) alkyl (meth)acrylates, or (iv) combinations thereof. Furthermore, the sulfur ester moiety needs to be selected in combination with the specific oxygen ester moiety above in order to achieve a minimum molecular weight of at least about 490 g / mol of the additive.

[0026] In one embodiment, the sulfur ester moiety of R7 in formula I can be derived from a vinyl ester. In this approach, suitable vinyl esters include, but are not limited to, vinyl carboxylic acid vinyl esters, such as vinyl acetate, vinyl propionate, vinyl laurate, vinyl octanoate, vinyl decanoate, vinyl stearate, or combinations thereof. When the sulfur ester moiety is formed from a vinyl ester, again, the vinyl ester also needs to have a carboxylic acid moiety sufficient to satisfy the minimum molecular weight mentioned above in order to achieve abrasion and phosphorus retention performance when used with a suitable oxygen ester moiety. In a preferred embodiment, the sulfur ester moiety can be derived from vinyl laurate (and most preferably vinyl laurate combined with each oxygen ester derived from 4-methyl-2-pentyl alcohol). In another embodiment, the sulfur ester moiety can be derived from vinyl stearate.

[0027] In another embodiment, the sulfur ester moiety of R7 may be derived from an unsaturated carboxylic acid, its ester, diester, or anhydride. For example, the unsaturated carboxylic acid, ester, diester, or anhydride may be maleic acid, fumaric acid, its ester, diester, or anhydride. For example, suitable unsaturated acids, esters, or anhydrides may include, but are not limited to, methyl maleate, dimethyl maleate, ethyl maleate, diethyl maleate, butyl maleate, dibutyl maleate, diphenyl maleate, methyl fumarate, dimethyl fumarate, ethyl fumarate, diethyl fumarate, butyl fumarate, dibutyl fumarate, diphenyl fumarate, combinations thereof, their anhydrides, etc. When the sulfur ester moiety is formed from an unsaturated carboxylic acid, ester, diester, or anhydride, again, the desired acid, ester, or anhydride must be selected in combination with the appropriate oxygen ester moiety discussed above so as to satisfy the minimum molecular weight mentioned above in order to achieve wear and phosphorus retention performance. In preferred embodiments, the sulfur ester moiety can be derived from dibutyl maleate (and most preferably, dibutyl maleate combined with each oxygen ester derived from 4-methyl-2-pentyl alcohol).

[0028] In yet another embodiment, the sulfur ester moiety of R7 may be derived from an alkyl (meth)acrylate. In this approach, suitable alkyl (meth)acrylates may include, but are not limited to, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, or combinations thereof. As with the other approaches for the sulfur ester moiety, when the sulfur ester moiety is formed from an alkyl (meth)acrylate, again, the desired alkyl (meth)acrylate must be selected in combination with a suitable oxygen ester moiety so as to satisfy the minimum molecular weight mentioned above in order to achieve wear and phosphorus retention performance.

[0029] The ashless phosphorus-containing anti-wear compounds described herein can be prepared by many methods, but are preferably prepared by first reacting a selected secondary alcohol with phosphorus pentasulfide. In some approaches, the phosphorus pentasulfide may be its monomer or dimer. The reaction of the selected secondary alcohol with phosphorus pentasulfide forms an intermediate dialkyldithiophosphate, which is then further reacted in a second step with a selected organic compound to form a sulfur ester moiety. The selected organic compound is preferably one of (i) vinyl esters, (ii) unsaturated carboxylic acids, their esters, diesters, or anhydrides, (iii) alkyl (meth)acrylates, or (iv) a combination thereof, forming the ashless anti-wear additive of this application. The reaction in this second step may be carried out at about 70°C to about 150°C for about 2 to about 24 hours, or as needed to obtain the desired final product.

[0030] In one exemplary approach or embodiment, the ash-free phosphorus-containing anti-wear compounds of this specification may be prepared by reacting the above-mentioned secondary alcohol (preferably, for example, 4-methyl-2-pentyl alcohol) with phosphorus pentasulfide in a first reaction step at a molar ratio of secondary alcohol to phosphorus pentasulfide of about 1:1 to about 20:1, or about 2:1 to about 15:1, or about 3:1 to about 10:1, or about 3.5:1 to about 7:1, or about 3.5:1 to about 5:1 to form the above-mentioned intermediate reaction product. The intermediate reaction product is then further reacted in a second reaction step with the above-mentioned organic compound (preferably, for example, vinyl stearate or dibutyl maleate) at a molar ratio of the selected organic compound to the secondary alcohol of about 0.1:1 to about 10:1, or about 0.3:1 to about 5:1, or about 0.5:1 to about 1:1. In some embodiments using preferred reactants, the resulting product may include one or more of 1-((bis((4-methylpentan-2-yl)oxy)phosphorotioyl)thio)ethyl stearate or dibutyl 2-((bis((4-methylpentan-2-yl)oxy)phosphorotioyl)thio)succinate.

[0031] One approach, based on a preferred selection of the oxygen ester moiety (e.g., a secondary alcohol) and the sulfur ester moiety (an organic reactant for the second reaction step), includes, as preferred examples of the ash-free phosphorus-containing anti-wear compounds of this disclosure, compounds of the following formulas IIa and IIb, derived from either 4-methyl-2-pentyl alcohol (each oxygen ester moiety having 5 β-hydrogens) forming the oxygen ester moiety, and either vinyl stearate or dibutyl maleate forming the sulfur ester moiety.

[0032] [ka]

[0033] Exemplary compounds of formula IIa are derived from vinyl stearate, 4-methyl-2-pentyl alcohol, and phosphorus pentasulfide. The additives of formula IIa have five β-hydrogen atoms in the oxygen ester portion, about 5.1% by weight of phosphorus, and a number-average molecular weight of 609.

[0034] [ka]

[0035] Exemplary compounds of formula IIb are derived from dibutyl maleate, 4-methyl-2-pentyl alcohol, and phosphorus pentasulfide. The additive of formula IIb also has 5 β-hydrogens in each oxygen ester moiety, about 5.9 weight percent phosphorus, and a number average molecular weight of 527. Other suitable ashless anti-abrasive additives can be formed in a similar reaction scheme by selecting a suitable starting secondary alcohol and a suitable organic reactant for the second step according to the above construct, thereby deriving additives having the described number of β-hydrogens and minimum molecular weight.

[0036] In the approaches and embodiments described herein, ashless phosphorus-containing anti-wear compounds may be used in passenger car lubrication compositions in amounts of about 0.01 to about 10 weight percent, in other approaches, about 0.1 to about 5.0 weight percent, and in further approaches, about 0.2 to about 3.0 weight percent, about 0.2 to about 2.0 weight percent, or about 0.25 to about 1.5 weight percent. The ashless phosphorus-containing anti-wear compounds described herein can provide a selected amount of phosphorus to passenger car lubrication compositions. In embodiments, for example, an ashless phosphorus-containing anti-wear compound may provide phosphorus up to about 700 ppm, up to about 600 ppm, up to about 500 ppm, up to about 400 ppm, up to about 300 ppm, up to about 200 ppm, or up to about 150 ppm, or about 100 to about 700 ppm, or about 120 to about 680 ppm, or about 150 to about 300 ppm. As described above, the ashless phosphorus-containing anti-wear compound is provided with a phosphorus ratio of about 25:75 to about 100:0 (or other ratios as described in the embodiments above) with respect to the phosphorus content provided by the ashless phosphorus-containing anti-wear compound with respect to the phosphorus content of any metal-containing phosphorus compound.

[0037] Selective metal-containing wear-preventive compounds In further embodiments, the anti-wear systems of the compositions herein may also include one or more optional metal-containing anti-wear compounds, if used, which may be reduced levels of metal phosphates, metal thiophosphates, metal dialkyldialkyldithiophosphates, or combinations thereof, where the metal is selected from aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, zinc, or combinations thereof. In one embodiment, the optional metal-containing anti-wear compounds are one or more dihydrocarbyl dithiophosphate compounds, preferably one or more metal dihydrocarbyl dithiophosphate compounds, and more preferably one or more zinc dihydrocarbyl dithiophosphate compounds (ZDDP). When included in the anti-wear system of the Disclosure, one or more metal dihydrocarbyl dithiophosphate compounds provide phosphorus to the lubricant at a concentration of 350 ppm or less, about 300 ppm or less, 250 ppm or less, 200 ppm or less, or 150 ppm or less. In another approach, one or more metal dihydrocarbyl dithiophosphate compounds of this specification, when used, provide phosphorus in concentrations of about 100 ppm to about 350 ppm, or about 150 ppm to about 300 ppm, or about 125 ppm to about 175 ppm, or about 275 ppm to about 325 ppm. In yet another approach, one or more metal dihydrocarbyl dithiophosphate compounds of the anti-wear system of this specification, when used, provide a lubricant with a metal (e.g., zinc) of 400 ppm or less, a lubricant with a metal (e.g., zinc) of about 350 ppm or less, a lubricant with a metal (e.g., zinc) of about 300 ppm or less, or a lubricant with a metal (e.g., zinc) of about 200 ppm or less. In other approaches, one or more zinc dihydrocarbyl dithiophosphate compounds herein provide, if present, about 100 ppm to about 400 ppm of metal (e.g., zinc), or about 150 ppm to about 350 ppm of metal (e.g., zinc), or about 150 ppm to about 200 ppm of metal (e.g., zinc), or about 300 ppm to about 400 ppm of metal (e.g., zinc). As will be further discussed below, the level of zinc can balance the total sash contribution of the lubricant.The ashless phosphorus-containing anti-wear compounds discussed above, if present, are provided with a phosphorus ratio of approximately 25:75 to approximately 100:0 (or any other ratio mentioned above) with respect to the phosphorus content provided by the ashless phosphorus-containing anti-wear compounds relative to the phosphorus content of the metal-containing phosphorus compounds.

[0038] A suitable metal dihydrocarbyl dithiophosphate compound may contain about 5 to about 10 weight percent of metal (such as about 6 to about 10 weight percent of metal) and about 10 to about 20 weight percent of sulfur (such as about 13 to about 20 weight percent of sulfur, or about 14 to about 19 weight percent of sulfur). A suitable metal dihydrocarbyl dithiophosphate compound may contain a dihydrocarbyl dithiophosphate metal salt, the metal of which may be an alkali metal, an alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, zirconium, zinc, or a combination thereof. Preferably, the metal is zinc.

[0039] The alkyl groups on one or more metal dihydrocarbyl dithiophosphate compounds of the anti-wear systems described herein may be derived from primary alcohols, secondary alcohols, phenols, and / or mixtures thereof. For example, primary alcohols may include, but are not limited to, isobutyl alcohol, amyl alcohol, or 2-ethylhexyl alcohol. Secondary alcohols may include, but are not limited to, methyl isobutylcarbinol or isopropanol. In some optional embodiments, the metal dihydrocarbyl dithiophosphate compound comprises a hydrocarbyl group derived from at least about 50 weight percent of a secondary alcohol, or more preferably a hydrocarbyl group derived from at least about 65 weight percent of a secondary alcohol, a hydrocarbyl group derived from at least about 80 weight percent of a secondary alcohol, or a hydrocarbyl group derived from about 100 weight percent of a secondary alcohol. In other optional embodiments, the anti-wear system includes a hydrocarbyl group derived from about 50% to about 100% by weight of a secondary alcohol, more preferably a hydrocarbyl group derived from about 65% to about 100% by weight of a secondary alcohol, and even more preferably a hydrocarbyl group derived from about 80% to about 100% by weight of a secondary alcohol. In some embodiments, suitable examples of metal dihydrocarbyl dithiophosphate compounds include, but are not limited to, zinc O,O-di(C) 8~14 Examples include zinc O,O-(alkyl) dithiophosphate; zinc O,O-bis(2-ethylhexyl) dithiophosphate; zinc O,O-diisooctyl dithiophosphate; zinc O,O-bis(dodecylphenyl) dithiophosphate; zinc O,O-diisodecyl dithiophosphate; zinc O,O-bis(6-ethylhexyl) dithiophosphate; zinc O,O-dioctyl dithiophosphate; zinc O,O-dipentyl dithiophosphate; zinc O-(2-methylbutyl)-O-(2-methylpropyl) dithiophosphate; and zinc O-(3-methylbutyl)-O-(2-methylpropyl) dithiophosphate; zinc O,O-bis(4-methyl-2-pentyl) dithiophosphate; or combinations thereof.

[0040] In a further approach or embodiment, metal dihydrocarbyl dithiophosphate compounds suitable for wear-resistant systems according to this specification are also, formula III:

[0041] [ka] The structure may be such that each R in formula III independently contains 3 to 18 carbon atoms, or 3 to 12 carbon atoms, or about 3 to 10 carbon atoms, provided that each phosphorus atom has an average of at least 10 total carbon atoms, preferably at least 12 total carbon atoms or 10 to 12 total carbon atoms. For example, each R may independently be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl, methyl-pentyl, and / or 4-methyl-2-pentyl, or a combination thereof. The number of carbon atoms in each R group in the above formula is generally about 3 or more, about 4 or more, about 6 or more, or about 8 or more. In formula III, A is a metal, such as aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, zirconium, zinc, or a combination thereof, preferably A is zinc. When the metal dihydrocarbyl dithiophosphate compound has the structure shown in formula III and A is zinc, the compound may contain about 4 to about 9 weight percent phosphorus and about 6 to about 10 weight percent zinc.

[0042] In other approaches or embodiments, it is understood in the art that a more precise representation of the sulfur-zinc coordination sequence can be represented by the symmetric sequence shown below, and that the chemical structure of formula IIIa, which may be used herein, is interchangeable with that of formula III shown above. It is also understood that the structures shown in formulas I and II may exist as monomers, dimers, trimers, or oligomers (e.g., tetramers).

[0043] [ka]

[0044] Dihydrocarbyl dithiophosphate metal salts can be prepared according to known techniques, usually by first reacting one or more alcohols or phenols with P2S5 to form dihydrocarbyl dithiophosphoric acid (DDPA), and then neutralizing the formed DDPA with a metal compound such as zinc oxide. For example, DDPA can be prepared by reacting a mixture of alcohols containing suitable amounts of primary and / or secondary alcohols with P2S5.

[0045] TBN profile When reducing the ash contribution using the selected anti-wear system of this disclosure, it has also been found that, in some embodiments, it is preferable that the lubricant also has a specific TBN profile that is compatible with the selected anti-wear system. In one approach, as highlighted by the examples, the lubricants herein have a TBN ratio comprising TBN measured according to ASTM D4739 to TBN measured according to ASTM D2896, at least about 60 percent. As shown in the examples, in at least some embodiments, such a TBN profile combined with an anti-wear system selected to reduce the ash content helps achieve performance in the context of compositions having an anti-wear system with a lower ash contribution. In yet other embodiments, it has been found that to achieve performance, the TBN ratio is about 60 percent to about 70 percent when the sulfated ash content is measured at less than about 0.5 weight percent, or the TBN ratio is greater than 70 to about 80 percent when the sulfated ash content is measured at at least about 0.5 weight percent (e.g., about 0.5 to about 0.75 weight percent).

[0046] Alternatively, the passenger car lubrication compositions herein include a detergent system that contributes to the TBN ratio, and in preferred embodiments, a magnesium and / or calcium-based detergent. The preferred TBN contributed by the detergent system additives is at least 3 mg KOH / g, at least 4 mg KOH / g, at least 5 mg KOH / g, or at least 6 mg KOH / g to about 10 mg KOH / g or less, about 8 mg KOH / g or less, or about 6 mg KOH / g or less, and the TBN of the additives is measured by ASTM D4739. In embodiments, the detergent system herein generally includes one or more alkali or alkali metal salts of sulfonates, phenates, calixalates, salixalates, salicylates, carboxylic acids, their sulfurized derivatives, or combinations thereof, and may be neutral, low basic, or overbasic as long as the above TBN relationships described herein are satisfied. Preferably, the cleaning agent is a perbasic magnesium and / or calcium-based cleaning agent, and most preferably, a perbasic magnesium and / or calcium-based sulfonate.

[0047] Suitable detergents and methods for preparing them are described in detail in numerous patent publications, including U.S. Patents No. 7,732,390, No. 4,165,291, and / or No. 4,206,062 (and the references cited herein), which are incorporated herein by reference. The lubricant compositions herein may include about 0.1 to about 5 weight percent of individual and / or total detergent additives, about 0.15 to about 3 weight percent in other approaches, about 0.2 to about 2.5 weight percent in yet other approaches, or about 0.3 to about 2.0 weight percent of individual and / or total detergent additives, insofar as the detergent additives satisfy the sulfonate amount and other TBN relationships described herein.

[0048] The detergent systems herein may provide amounts of total detergent metal, based on the total lubricating composition, greater than about 250 ppm of total metal; in other approaches, about 250 ppm to about 2500 ppm of total metal, about 300 ppm to about 2100 ppm of total metal, about 350 ppm to about 2000 ppm of total metal, about 400 ppm to about 1950 ppm, or about 400 ppm to about 1900 ppm of total metal. In other approaches, the detergent metal is calcium, sodium, and / or magnesium, preferably calcium, sodium, and magnesium provided by sulfonates, most preferably calcium, sodium, and / or magnesium sulfonates alone. Preferably, the detergent metal is calcium, magnesium, or a combination thereof.

[0049] Generally, suitable cleaning agents in the system may include petroleum sulfonic acid, and long-chain mono- or dialkylaryl sulfonic acid having an aryl group of benzyl, tolyl, and xylyl, and / or linear or branched alkali metal salts or alkaline earth metal salts of various phenates or derivatives of phenates, such as calcium, sodium, or magnesium. Examples of suitable cleaning agents include, in addition to the necessary TBN relationships of this specification, the following cleaning agents: calcium carbonate, calcium sulfur-containing phenate, calcium sulfonate, calcium calixalate, calcium salixalate, calcium salicylate, calcium carboxylic acid, calcium phosphate, calcium mono- and / or dithiophosphate, calcium alkylphenol, calcium sulfur-linked alkylphenol compounds, calcium methylene crosslinked phenol, magnesium carbonate, magnesium sulfur-containing phenate, magnesium sulfonate, magnesium calixalate, magnesium salixalate, magnesium salicylate, magnesium carboxylic acid, magnesium phosphate, magnesium mono- and / or dithiophosphate, magnesium alkylphenol, magnesium sulfur-linked alkylphenol compounds, magnesium methylene crosslinked phenol, sodium phenate, sodium sulfur-containing phenate, sodium sulfonate, sodium calixalate, sodium salixalate, sodium salicylate, sodium carboxylic acid, sodium phosphate, sodium mono- and / or dithiophosphate, sodium alkylphenol, sodium sulfur-linked alkylphenol compounds, or low-basic / neutral and overbasic variations of sodium methylene crosslinked phenol.

[0050] The detergent additive may be neutral, low-basic, or overbasic, preferably an overbasic detergent or a mixture of a neutral to low-basic detergent and an overbasic detergent, and may satisfy the minimum detergent TBN number and other relationships described above as necessary. As can be understood, overbasic detergent additives are well known in the art and may be alkali metal or alkaline earth metal overbasic detergent additives. Such detergent additives can be prepared by reacting a metal oxide or metal hydroxide with a base and carbon dioxide gas. The base is typically an acid, such as an aliphatic-substituted sulfonic acid, an aliphatic-substituted carboxylic acid, or an aliphatic-substituted phenol.

[0051] The term "overbasic" refers to metal salts in which the amount of metal present exceeds the stoichiometric amount, such as metal salts of sulfonates, carboxylates, salicylates, and / or phenates. Such salts may have a conversion level greater than 100% (i.e., such salts may contain more than 100% of the theoretical amount of metal required to convert an acid to its "standard" or "neutral" salt). The expression "metal ratio," often abbreviated as MR (metal ratio), is used to indicate the ratio of the total stoichiometric equivalents of metal in an overbasic salt to the stoichiometric equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. For standard or neutral salts, MR is 1, and for overbasic salts, MR is greater than 1. They are generally referred to as overbasic, highly basic, or ultrabasic salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.

[0052] Where used herein, unless otherwise specified, the term "TBN" is used to represent the total base number in mg KOH / g units of a detergent additive as measured by the method of ASTM D4739. Detergents can be neutral to overbasic. For example, a low-basic to neutral detergent additive may have a total base number (TBN) of less than about 200 mg KOH / gram. In another example, an overbasic detergent in the lubricating oil composition herein may have a total base number (TBN) of about 200 mg KOH / gram or more, or about 250 mg KOH / gram or more, or about 350 mg KOH / gram or more, or about 375 mg KOH / gram or more, or about 400 mg KOH / gram or more. The overbasic cleaning agent may have a metal-to-substrate ratio of 1.1:1 or less, or 2:1 or less, or 4:1 or less, or 5:1 or less, or 7:1 or less, or 10:1 or less, or 12:1 or less, or 15:1 or less, or 20:1 or less.

[0053] Examples of suitable overbasic detergents include, but are not limited to, overbasic calcium carbonate, overbasic calcium sulfur-containing phenates, overbasic calcium sulfonates, overbasic calcium calixalates, overbasic calcium salixalates, overbasic calcium salicylates, overbasic calcium carboxylic acids, overbasic calcium phosphates, overbasic calcium mono and / or dithiophosphates, overbasic calcium alkylphenols, overbasic calcium sulfur-coupled alkylphenol compounds, overbasic calcium methylene crosslinked phenols, overbasic magnesium phenates, overbasic magnesium sulfur-containing phenates, overbasic magnesium sulfonates, overbasic magnesium calixalates, overbasic magnesium salixalates, overbasic magnesium salicylates, overbasic magnesium carboxylic acids, overbasic magnesium phosphates, overbasic magnesium mono and / or dithiophosphates, overbasic magnesium alkylphenols, overbasic magnesium sulfur-coupled alkylphenol compounds, or overbasic magnesium methylene crosslinked phenols.

[0054] If a low-basic or neutral detergent is optionally incorporated into the detergent system, it generally has a TBN of less than 200 mg KOH / g, up to 175 mg KOH / g, up to 150 mg KOH / g, up to 100 mg KOH / g, or up to 50 mg KOH / g. The low-basic / neutral detergent may include a calcium or magnesium-containing detergent. Suitable examples of low-basic / neutral detergents include, but are not limited to, calcium sulfonate, calcium carbohydrate, calcium salicylate, magnesium sulfonate, magnesium phenate, and / or magnesium salicylate (as long as the TBN relationships described herein are satisfied).

[0055] In some embodiments, the detergents used in the lubricants herein comprise at least overbasic calcium sulfonate, overbasic sodium sulfonate, and / or overbasic magnesium sulfonate, each having a total base number of 200 to 400, or in other approaches, about 200 to about 350. The above TBN values ​​reflect the values ​​of the finished detergent components diluted in the base oil. In other approaches, the detergent system comprises a blend of neutral to low-basic and overbasic sulfonate detergents.

[0056] In other embodiments, the TBN of the cleaning agents herein may reflect undiluted or undiluted versions of the cleaning agent components. For example, the fluids herein may include calcium or sodium overbasic sulfonate as an undiluted additive having a TBN of about 300 to about 450, or in other approaches, about 380 to about 420, and / or magnesium overbasic sulfonate as an undiluted additive having a TBN of about 500 to about 700, or in other approaches, about 600 to about 700.

[0057] More specifically, the detergent systems of this specification include neutral, low-basic, and / or over-basic detergents (preferably neutral to over-basic calcium sulfonate, neutral to over-basic sodium sulfonate, and / or neutral to over-basic magnesium sulfonate) to achieve a detergent additive TBN of at least about 3 mg KOH / g, at least about 4 mg KOH / g, at least about 5 mg KOH / g, or at least about 6 mg KOH / g to about 10 mg KOH / g or less, about 8 mg KOH / g or less, or about 6 mg KOH / g or less as measured by ASTM D4739. As described above and as shown in the examples, the lubricant also has a selected TBN profile in which the TBN ratio of TBN measured according to ASTM D4739 to TBN measured according to ASTM D2896 is at least about 60 percent. In other embodiments, as shown in the examples, it was also found that to achieve performance, the TBN ratio is about 60 percent to about 70 percent when the sulfated ash content is measured to be more than about 0.5 weight percent, or when the sulfated ash content is measured to be at least about 0.5 weight percent (e.g., about 0.5 to about 0.75 weight percent), the TBN ratio is more than 70 to about 80 percent.

[0058] The cleaning agent system also provides at least one of calcium, sodium, magnesium, or a combination thereof, and therefore one or more of the following metal content.

[0059] Sodium: Up to approximately 100 ppm sodium, up to approximately 75 ppm sodium, up to approximately 50 ppm sodium, up to approximately 25 ppm sodium, up to approximately 10 ppm sodium, up to approximately 5 ppm sodium, or zero.

[0060] Magnesium: at least about 90 ppm of magnesium, at least about 180 ppm of magnesium, at least about 200 ppm of magnesium, at least 300 ppm of magnesium, or at least about 400 ppm of magnesium (preferably about 90 to about 3,500 ppm of magnesium, about 180 ppm to about 3,000 ppm, about 200 ppm to about 2,000 ppm of magnesium, 300 ppm to about 1,500 ppm of magnesium, or about 400 ppm to about 1,300 ppm of magnesium, or about 500 to about 1,300 ppm of magnesium).

[0061] Calcium: at least about 90 ppm of calcium, at least about 180 ppm of calcium, at least about 200 ppm of calcium, at least 300 ppm of calcium, or at least about 400 ppm of calcium (preferably about 90 to about 3,500 ppm of calcium, about 180 ppm to about 3,000 ppm, about 180 ppm to about 2,000 ppm of calcium, 200 ppm to about 1,500 ppm of calcium, or 300 ppm to about 1,000 ppm of calcium, or 300 to about 800 ppm, or 300 to about 700 ppm).

[0062] In some approaches, the detergent systems of the passenger car lubrication compositions herein may also have a selected relationship between magnesium and calcium (e.g., preferred detergent metal) in the system herein. For example, the magnesium-to-calcium ratio (preferably contributed by a sulfonate detergent) may be less than about 2.0, preferably greater than about 1.0, and in some embodiments, the magnesium-to-calcium detergent ratio is about 1.1:1 to about 2.0:1, about 1.3:1 to about 2.0:1, or about 1.5:1 to about 2.0:1, or about 1.5:1 to about 1.9:1 (or other ranges in between).

[0063] Low-ash passenger car lubricant composition The low-ash passenger car lubricant compositions of this disclosure include selected anti-abrasive systems and selected detergent systems, which provide compositions having detergent and anti-abrasive additives to contribute to sulfated ash levels of about 0.75% by weight or less, about 0.7% by weight or less, about 0.6% by weight or less, about 0.5% by weight or less, about 0.4% by weight or less, or about 0.36% by weight or less (ASTM D874). Alternatively, the lubricant compositions of this specification may also include additives that contribute to sulfated ash levels of about 0.05% by weight or more, about 0.1% by weight or more, about 0.2% by weight or more, or about 0.3% by weight or more, as measured according to ASTM D874.

[0064] As used herein, “sulfated ash” or “SASH” refers to the amount of sulfated ash as measured using ASTM D874. Alternatively, sulfated ash may also be calculated based on the amount of metal in the lubricant. For example, sulfated ash (SASH) may be calculated based on the total metallic elements contributing to SASH in the lubricant composition, optionally adjusted by coefficients for each metallicity type. Metals contributing to SASH include (with adjustment coefficients) barium (1.7), boron (3.22), calcium (3.4), copper (1.252), lead (1.464), lithium (7.92), magnesium (4.95), manganese (1.291), molybdenum (1.5), potassium (2.33), sodium (3.09), and zinc (1.5). Specifically, the ppmw content of each metallic element present in the lubricating oil composition that is considered to contribute to sulfated ash is multiplied by its corresponding coefficient as described above, the products of each metallic element / coefficient adjustment are then summed, and the total is divided by 10,000 to calculate the weight percentage of sash in the lubricating composition. Unless otherwise specified, all sulfated ash levels herein are measured using ASTM D874.

[0065] In some embodiments, the lubricating compositions herein include a relationship that balances the contribution of detergent sash with respect to the contribution of metal-containing wear-preventive sash, in particular, a relationship that balances the amount of zinc with respect to the total sash level. For example, in some embodiments, if the composition has additives that contribute less than about 0.5 weight percent to total sash (preferably less than about 0.4 weight percent to total sash, or more preferably less than about 0.36 weight percent to total sash), the composition may also have less than about 300 ppm of total zinc (preferably less than about 250 ppm to total zinc, or more preferably less than about 200 ppm to total zinc) and / or may balance the total zinc level in ppm with respect to the total sash contribution, such that the relationship of zinc in ppm with respect to the total sash contribution is reflected by a ratio of less than about 400 ppm of zinc to weight percent of total sash (or a ratio of less than about 300, less than about 200, or less than about 100), as is generally shown in Figure 1 and the following examples.

[0066] In further embodiments, the lubricant rust ball performance (ASTM D6557) may also be related to the lubricant zinc content and the lubricant total sash contribution (ASTM D874), as is generally shown in Figure 2 and / or in the relationship of Equation 1 below. For example, the rust ball AGV of ASTM D6557 can be determined from the lubricant zinc content in ppm and the total sash contribution in weight percent using the relationship of Equation (1). AGV=(SASH * 196.0269) + (zinc * -0.01975)-4.17252(Formula 1) Figure 2 shows the correlation between the AGV determined from equation (1) and the actual AGV measured by ASTM D6557 for several representative samples.

[0067] lubricating oil composition The additives herein, in combination with one or more further optional additives, may be combined with a main amount of a base oil or base oil blend (described below) to produce a lubricating oil composition. In this approach, the lubricating oil composition comprises a base oil blend of about 50 weight percent or more, about 60 weight percent or more, about 70 weight percent or more, or about 80 weight percent to about 95 weight percent, about 90 weight percent or less, or about 85 weight percent or less, such blends of which are further discussed below. The lubricating compositions herein may have a KV100 of about 2 to about 15 cSt (ASTM D445), preferably about 5 to about 12 cSt, more preferably 6 to about 10 cSt.

[0068] Base Oil Blend: The base oils used in the lubricating oil compositions herein may be oils of lubricating viscosity and are selected from any of the base oils in Groups I through V, as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five base oil groups are as follows:

[0069] [Table 1]

[0070] Groups I, II, and III are mineral oil process raw materials. Group IV base oils contain true synthetic molecular species produced by the polymerization of olefinic unsaturated hydrocarbons. Many Group V base oils are also true synthetic products and may include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers, and / or polyphenyl ethers, but can also be natural oils such as vegetable oils. It should be noted that Group III base oils are derived from mineral oils, but due to the rigorous processing these fluids undergo, their physical properties become very similar to those of some true synthetics such as PAO. Therefore, oils derived from Group III base oils can be referred to as synthetic fluids in industry. Group II+ may include high viscosity index Group II.

[0071] The base oil blends used in the disclosed lubricating oil compositions may be mineral oils, animal oils, vegetable oils, synthetic oils, synthetic oil blends, or mixtures thereof. Suitable oils may be derived from hydrocracking, hydrotapping, hydrofinishing, unrefined oils, refined oils, and re-refined oils, as well as mixtures thereof.

[0072] Unrefined oils are derived from natural, mineral, or synthetic sources that undergo little to no further refining. Refined oils are similar to unrefined oils except that they have been treated with one or more refining steps that may result in an improvement in one or more properties. Examples of preferred refining techniques include solvent extraction, secondary distillation, acid or base extraction, filtration, and osmosis. Oils refined to a quality suitable for consumption may or may not be useful. Edible oils are sometimes called white oils. In some embodiments, lubricating oil compositions do not contain edible oils or white oils.

[0073] Refined oil is also known as recycled oil or reprocessed oil. These oils are obtained in the same way as refined oil using the same or similar processes. Often, these oils are further treated by techniques that target the removal of spent additives and oil degradation products.

[0074] Mineral oils may include oils obtained by drilling or from plants and animals, or any mixture thereof. For example, such oils may include, but are not limited to, castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as mineral lubricants, such as liquid petroleum, and paraffinic, naphthenic, or mixed paraffin-naphthenic type solvent-treated or acid-treated mineral lubricants. Such oils may be partially or completely hydrogenated if desired. Oils derived from coal or shale may also be useful.

[0075] Useful synthetic lubricants include hydrocarbon oils, for example, polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylene, polypropylene, propylene-isobutylene copolymer); trimers or oligomers of poly(1-hexene), poly(1-octene), and 1-decene, for example, poly(1-decene) (such materials are often referred to as α-olefins), and mixtures thereof; alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers, and alkylated diphenyl sulfides, as well as their derivatives, analogs, and homologs, or mixtures thereof. Polyalphaolefins are typically hydrogenated materials.

[0076] Other synthetic lubricants include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl esters of decanephosphonic acid), or polymeric tetrahydrofurans. Synthetic oils may be produced by the Fischer-Tropsch reaction and are typically hydrogenated isomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil may be prepared by the Fischer-Tropsch gas-liquid synthesis procedure and other gas-liquid oils.

[0077] In another embodiment, the main amount of base oil contained in the lubricating composition may be selected from the group consisting of Group I, Group II, Group III, Group IV, Group V, and any combination of two or more of the aforementioned, but the main amount of base oil is other than base oil resulting from the provision of additive components or viscosity index improvers in the composition.

[0078] The amount of oil with lubricating viscosity present may be the difference remaining after subtracting the total amount of performance additives, including viscosity index improvers and / or pour point depressants and / or other top-treatment additives, from 100% by weight. For example, the amount of oil with lubricating viscosity that may be present in the final fluid may be the main amount, e.g., more than about 50% by weight, more than about 60% by weight, more than about 70% by weight, more than about 80% by weight, more than about 85% by weight, or more than about 90% by weight.

[0079] Optional additives: The lubricating oil compositions described herein may also contain a number of optional additives, which are described in the following paragraphs.

[0080] Boron-containing compounds: In some approaches, the lubricating oil compositions herein may optionally contain one or more boron-containing compounds. Examples of boron-containing compounds include borate esters, borate fatty amines, borate epoxides, borate detergents, and borate dispersants such as succinimide borate dispersants, as disclosed in U.S. Patent No. 5,883,057. If present, boron-containing compounds may be used in amounts sufficient to provide up to about 8% by weight, about 0.01% to about 7% by weight, about 0.05% to about 5% by weight, or about 0.1% to about 3% by weight of the lubricating oil composition.

[0081] Extreme pressure agents: The lubricating compositions of this specification may optionally contain one or more extreme pressure agents. Oil-soluble extreme pressure (EP) agents include sulfur and chlorosulfur-containing EP agents, chlorinated hydrocarbon EP agents, and phosphorus EP agents. Examples of such EP agents include chlorinated waxes; organic sulfides and polysulfides such as dibenzyl disulfide, bis(chlorobenzyl) disulfide, dibutyltetrasulfide, methyl sulfide esters of oleic acid, alkylphenol sulfides, dipentene sulfides, terpenes sulfides, and Diels-Alder sulfide adducts; phosphorus sulfide hydrocarbons such as reaction products of phosphorus sulfide with terpentine or methyl oleate; phosphate esters such as dihydrocarbyl and trihydrocarbyl phosphite, e.g., dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, and pentylphenyl phosphite; dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene-substituted phenyl phosphite; metal thiocarbamates such as zinc dioctyl dithiocarbamate and barium heptylphenol dioate; amine salts of alkyl and dialkyl phosphates, e.g., amine salts of reaction products of dialkyldithiophosphate and propylene oxide; and mixtures thereof.

[0082] Friction modifiers: The lubricating compositions of this specification may optionally contain one or more friction modifiers. Suitable friction modifiers may include metal-containing and metal-free friction modifiers, and may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated etheramines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonates, metal-containing compounds, glycerol esters, sulfurized fatty compounds and olefins, sunflower oil, other naturally occurring vegetable or animal oils, dicarboxylic acid esters, esters or partial esters of polyols with one or more aliphatic or aromatic carboxylic acids, and the like.

[0083] Suitable friction modifiers may contain hydrocarbyl groups selected from linear, branched, or aromatic hydrocarbyl groups, or mixtures thereof, and may be saturated or unsaturated. Hydrocarbyl groups may consist of carbon and a heteroatom such as hydrogen or sulfur or oxygen. Hydrocarbyl groups may range from about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long-chain fatty acid ester. In other embodiments, the long-chain fatty acid ester may be a mono-ester, di-ester, or (tri)glyceride. Friction modifiers may be long-chain fatty amides, long-chain fatty esters, long-chain fatty epoxide derivatives, or long-chain imidazolines.

[0084] Other suitable friction modifiers may include organic, ashless (metal-free), and nitrogen-free organic friction modifiers. Such friction modifiers may contain esters formed by reacting a carboxylic acid and an anhydride with an alkanol, and may generally contain polar end groups (e.g., carboxyl or hydroxyl) covalently bonded to a lipophilic hydrocarbon chain. An example of an organic ashless nitrogen-free friction modifier is commonly known as glycerol monooleate (GMO), which may contain mono-, di-, and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. Patent No. 6,723,685, which is incorporated herein by reference in whole.

[0085] Amineral friction modifiers may include amines or polyamines. Such compounds may have hydrocarbyl groups that are linear, saturated, unsaturated, or mixtures thereof, and may contain about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated etheramines. Such compounds may have hydrocarbyl groups that are linear, saturated, unsaturated, or mixtures thereof. These may contain about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated etheramines.

[0086] Amines and amides may be used on their own or as adducts or reaction products with boron compounds such as boron oxide, boron halides, metaborates, boric acid, or mono-, di-, or tri-alkylborates. Other suitable friction modifiers are described in U.S. Patent No. 6,300,291, which is incorporated herein by reference in whole.

[0087] The friction modifier may be optionally present in a range such as approximately 0% to 10% by weight, approximately 0.01% to 8% by weight, or approximately 0.1% to 4% by weight.

[0088] Transition metal-containing compounds: In another embodiment, in accordance with the above considerations regarding total metal content, the lubricants herein may optionally contain transition metal-containing compounds or metalloids. Examples of transition metals include, but are not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, and tungsten. Examples of preferred metalloids include, but are not limited to, boron, silicon, antimony, and tellurium.

[0089] Viscosity Index Modifiers: The lubricating oil compositions of this specification may optionally contain one or more viscosity index modifiers, such as dispersant olefin copolymer viscosity index modifiers. Suitable viscosity index modifiers include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, styrene-isoprene hydrogenated polymers, styrene / maleate copolymers, styrene-butadiene hydrogenated copolymers, isoprene hydrogenated polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrated alkenylaryl conjugated diene copolymers, or mixtures thereof. Viscosity index modifiers may include star polymers, but a preferred example is described in U.S. Patent Application Publication No. 20120101017(A1).

[0090] The lubricating oil compositions herein may optionally contain one or more dispersing viscosity index improvers in addition to, or in place of, a viscosity index improver. Suitable viscosity index improvers include functionalized polyolefins, such as ethylene-propylene copolymers functionalized with the reaction product of an acylating agent (such as maleic anhydride) and an amine, amine-functionalized polymethacrylates, or esterified maleic anhydride-styrene copolymers reacted with an amine.

[0091] In one approach, a preferred dispersant olefin copolymer viscosity index improver comprises a reaction product of an acylated olefin copolymer and a polyamine, wherein the acylated olefin copolymer is an olefin copolymer grafted with about 0.3 to about 0.75 carboxylic acid groups per 1,000 number-average molecular weight units of the olefin copolymer, the olefin copolymer having a number-average molecular weight of about 40,000 to about 150,000, and the polyamine is N-arylphenylenediamine. In an optional approach, the lubricating composition comprises about 1 weight percent to about 4 weight percent of the dispersant olefin copolymer viscosity index improver.

[0092] Other optional additives: Other additives may be selected to perform one or more functions required of the lubricating fluid. Furthermore, one or more of the additives mentioned may be polyfunctional and may provide functions in addition to or other than those specified herein. Other performance additives may be additions to the additives specified herein and / or may include one or more of the following: metal deactivators, viscosity index improvers, ashless TBN boosters, friction modifiers, anti-wear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam inhibitors, deemulsifiers, emulsifiers, pour point depressants, seal swelling agents, and mixtures thereof. Typically, a fully formulated lubricating oil contains one or more of these performance additives, in accordance with the above considerations regarding the components, amounts, and relationships of the various compositional components.

[0093] Suitable metal deactivators include derivatives of benzotriazole (typically toltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzothiazole; foam inhibitors comprising copolymers of ethyl acrylate, 2-ethylhexyl acrylate, and optionally vinyl acetate; demulsifiers comprising trialkyl phosphates, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers; and pour point depressants comprising esters of maleate-styrene anhydride, polymethacrylate, polyacrylate, or polyacrylamide.

[0094] Suitable foam inhibitors include silicon-based compounds such as siloxanes.

[0095] Suitable pour point depressants include polymethyl methacrylate or mixtures thereof. The pour point depressant may be present in an amount sufficient to provide about 0% to about 1% by weight, about 0.01% to about 0.5% by weight, or about 0.02% to about 0.04% by weight, based on the final weight of the lubricating oil composition.

[0096] Suitable additional rust inhibitors may be a single compound or a mixture of compounds having properties that inhibit corrosion of metal surfaces. Additional rust inhibitors may be provided as long as they do not compete with the selected rust inhibitors considered above. In addition to those described above, non-limiting examples of rust inhibitors include oil-soluble high molecular weight organic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid, as well as oil-soluble polycarboxylic acids including dimeric and trimeric acids such as those derived from tall oil fatty acids, oleic acid, and linoleic acid. Other suitable rust inhibitors include long-chain alpha- and omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000, and alkenyl succinates containing about 10 or more carbon atoms in an alkenyl group, such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Another useful type of acidic corrosion inhibitor is a semi-ester of alkenyl succinic acid, which has about 8 to 24 carbon atoms in the alkenyl group, with an alcohol such as polyglycol. The corresponding semi-amides of such alkenyl succinic acid are also useful. Molecular weight organic acids are also useful rust inhibitors.

[0097] If present, the rust inhibitor can be used in an amount sufficient to provide about 0% to about 5% by weight, about 0.01% to about 3% by weight, and about 0.1% to about 2% by weight, based on the final weight of the lubricating oil composition.

[0098] Generally speaking, preferred lubricants according to this specification may contain additive components within the range listed in the table below.

[0099] [Table 2]

[0100] The percentages of each component listed above represent the weight percentage of each component based on the weight of the final lubricating oil composition. The remainder of the lubricating oil composition consists of one or more base oils. The additives used in formulating the compositions described herein may be blended with the base oils individually or in various partial combinations. However, it may be preferable to blend all the components simultaneously using an additive concentrate (i.e., the additive plus a diluent such as a hydrocarbon solvent). A complete lubricant conventionally contains an additive package, referred herein as a dispersant / inhibitor package or DI package, which provides the properties required in the formulation.

[0101] The lubricants described herein are configured for use in a variety of lubricants, including automotive lubricants and / or greases, internal combustion engine oils, hybrid engine oils, electric engine lubricants, drivetrain lubricants, transmission lubricants, gear oils, hydraulic lubricants, tractor hydraulic fluids, metal working fluids, turbine engine lubricants, stationary engine lubricants, tractor lubricants, motorcycle lubricants, power steering fluids, clutch fluids, axle fluids, and wet brake fluids. Suitable engine types may include, but are not limited to, heavy-duty diesels, passenger cars, light-duty diesels, medium-speed diesels, or marine engines. Internal combustion engines may be diesel-fueled engines, gasoline-fueled engines, natural gas-fueled engines, biofuel engines, diesel / biofuel blended-fuel engines, gasoline / biofuel blended-fuel engines, alcohol-fueled engines, gasoline / alcohol-fuel blended-fuel engines, compressed natural gas (CNG)-fueled engines, or mixtures thereof. Diesel engines may be compression-ignition engines. Gasoline engines may be spark-ignition engines. Internal combustion engines may also be used in combination with electric or battery power sources. Engines configured in this way are generally known as hybrid engines. Internal combustion engines can be two-stroke, four-stroke, or rotary engines. Suitable internal combustion engines include marine diesel engines (such as those for inland vessels), aircraft piston engines, low-load diesel engines, and engines for motorcycles, automobiles, locomotives, and trucks. Engines can be coupled with turbochargers.

[0102] The terms “oil composition,” “lubrication composition,” “lubricating oil composition,” “lubricating oil,” “lubricant composition,” “lubricating composition,” “completely formulated lubricant composition,” “lubricant,” “crankcase oil,” “crankcase lubricant,” “engine oil,” “engine lubricant,” “motor oil,” and “motor lubricant” are considered synonymous, fully interchangeable technical terms referring to the final lubrication product which contains a small amount of additive composition in addition to a main amount of base oil.

[0103] As used herein, the terms “additive package,” “additive concentrate,” “additive composition,” “engine oil additive package,” “engine oil additive concentrate,” “crankcase additive package,” “crankcase additive concentrate,” “motor oil additive package,” and “motor oil concentrate” are considered synonymous, fully interchangeable technical terms referring to a portion of a lubricating oil composition excluding the main amount of base oil raw material mixture. An additive package may or may not contain viscosity index improvers or pour point depressants.

[0104] The term "overbasic" refers to metal salts such as sulfonates, carboxylates, salicylates, and / or phenates in which the amount of metal present exceeds the stoichiometric amount. Such salts can have a conversion level greater than 100% (i.e., such salts may contain more than 100% of the theoretical amount of metal required to convert an acid to its "standard" or "neutral" salt). The expression "metal ratio," often abbreviated as MR (metal ratio), is used to indicate the ratio of the total stoichiometric equivalents of metal in an overbasic salt to the stoichiometric equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the metal ratio is 1, while in overbasic salts, the MR is greater than 1. These are commonly referred to as overbasic, highly basic, or ultrabasic salts and may be salts of organic sulfur acids, carboxylic acids, salicylates, sulfonates, and / or phenols.

[0105] The term "alkaline earth metals" refers to calcium, barium, magnesium, and strontium, while the term "alkali metals" refers to lithium, sodium, potassium, rubidium, and cesium.

[0106] As used herein, the terms “hydrocarbyl,” “hydrocarbyl substituent,” or “hydrocarbyl group” are used in their ordinary sense as is well known to those skilled in the art. Specifically, they refer to a group having carbon atoms directly bonded to the rest of the molecule and having primarily hydrocarbon characteristics. Each hydrocarbyl group is independently selected from the hydrocarbon substituents, the substituted hydrocarbon substituents comprising one or more of the following: halo, hydroxyl, alkoxy, mercapto, nitro, nitroso, amino, pyridyl, furyl, imidazolyl, oxygen, and nitrogen, and two or fewer non-hydrocarbon substituents present for every 10 carbon atoms in the hydrocarbyl group.

[0107] As used herein, the terms “hydrocarbilene substituent” or “hydrocarbilene group” are used in their ordinary sense as is well known to those skilled in the art. Specifically, they refer to groups that are directly bonded to the rest of the molecule by carbon atoms at two locations on the molecule and that have primarily hydrocarbon characteristics. Each hydrocarbilene group is independently selected from divalent hydrocarbon substituents, the substituted divalent hydrocarbon substituents include halo groups, alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, hydroxyl groups, alkoxy groups, mercapto groups, nitro groups, nitroso groups, amino groups, pyridyl groups, furyl groups, imidazolyl groups, oxygen, and nitrogen, and two or fewer non-hydrocarbon substituents are present for every 10 carbon atoms in the hydrocarbilene group.

[0108] As used herein, the term “weight percent” means the percentage of the listed components relative to the total weight of the composition, unless otherwise expressly stated.

[0109] As used herein, the terms "ppm" or "ppmw" refer to parts per million by weight unless otherwise expressly stated.

[0110] As used herein, the terms “soluble,” “oil-soluble,” and “dispersible” may indicate, but are not necessarily, that a compound or additive is soluble, soluble, miscible, or suspendable in oil in any proportion. However, the aforementioned terms mean that they are soluble, suspendable, soluble, or stably dispersible in oil to a degree sufficient to exert their intended effect, for example, in an environment in which oil is used. Furthermore, if desired, it may be possible to incorporate other additives to incorporate a higher level of specific additives.

[0111] As used herein, the term "TBN" is used to express the total base number in mg KOH / g as measured by either ASTM D2896 or ASTM D4739, as specified herein.

[0112] As used herein, the term “alkyl” refers to a linear, branched, cyclic, and / or substituted saturated chain moiety of about 1 to about 100 carbon atoms. As used herein, the term “alkenyl” refers to a linear, branched, cyclic, and / or substituted unsaturated chain moiety of about 3 to about 10 carbon atoms. As used herein, the term “aryl” refers to monocyclic and polycyclic aromatic compounds that may contain heteroatoms, including but not limited to alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and / or nitrogen, oxygen, and sulfur.

[0113] The molecular weight of any embodiment described herein may be determined using a gel permeation chromatography (GPC) instrument or similar instrument available from Waters, and data processed with Waters Empower Software or similar software. GPC instruments may be provided with a Waters separation module and a Waters refractive index detector (or similar optional instrument). GPC operating conditions may include a guard column, four Agilent PLgel columns (300 × 7.5 mm in length, 5 μm in particle size, and pore sizes ranging from 100 to 10,000 Å), and a column temperature of approximately 40°C. Unstabilized HPLC-grade tetrahydrofuran (THF) may be used as a solvent at a flow rate of 1.0 mL / min. The GPC instrument may be calibrated with commercially available polystyrene (PS) standards having a narrow molecular weight distribution ranging from 500 to 380,000 g / mol. Calibration curves can be extrapolated for samples with a mass of less than 500 g / mol. The sample and PS standard can be dissolved in THF and prepared at a concentration of 0.1–0.5% by weight, and can be used without filtration. GPC measurement is also described in U.S. Patent No. 5,266,223, incorporated herein by reference. The GPC method provides additional molecular weight distribution information; see, for example, WWYau, JJKirkland and DDBly, "Modern Size Exclusion Liquid Chromatography," John Wiley and Sons, New York, 1979, incorporated herein by reference.

[0114] As used herein, “sulfated ash” or “SASH” refers to the amount of sulfated ash as measured using ASTM D874. Alternatively, sulfated ash may also be calculated based on the amount of metal in the lubricant. For example, sulfated ash (SASH) may be calculated based on the total metallic elements contributing to SASH in the lubricant composition, optionally adjusted by coefficients for each metallicity type. Metals contributing to SASH include (with adjustment coefficients) barium (1.7), boron (3.22), calcium (3.4), copper (1.252), lead (1.464), lithium (7.92), magnesium (4.95), manganese (1.291), molybdenum (1.5), potassium (2.33), sodium (3.09), and zinc (1.5). Specifically, the ppmw content of each metallic element present in the lubricating oil composition that is considered to contribute to sulfated ash is multiplied by its corresponding coefficient as described above, the products of each metallic element / coefficient adjustment are then summed, and the total is divided by 10,000 to calculate the weight percentage of sash in the lubricating composition. Unless otherwise specified, all sulfated ash levels herein are measured using ASTM D874. See also Nadkarni, R., Ledesma, R., and Via G., "Sulfated Ash Test Method: Limitations of Reliability and Reproducibility," SAE Technical Paper 952548, 1995, or Takatoshi Kunihiro, "Method of Estimating Sulfated Ash in Engine Oils by Metal Element Analyses," Journal of the Japan Petroleum Institute, 1992, volume 35, issue 6, pages 460-465, both of which are reproduced herein. [Examples]

[0115] A better understanding of this disclosure and its many advantages can be made apparent by the following examples. The following examples are illustrative and not limiting in any way to their scope or intent. Those skilled in the art will readily understand that variations of the components, methods, steps, and devices described in these examples can be used. Unless otherwise stated or made apparent from the context of the discussion throughout the following examples and this disclosure, all percentages, ratios, and parts described in this disclosure are by weight. Any standardized test method described in the examples, disclosure or claims refers to a version of the test method that was publicly published at the time of filing of this disclosure, unless it is apparent from the context of its use.

[0116] Example 1 In this example, the passenger car lubrication compositions of the present invention were evaluated, comprising in various amounts: (1) a detergent system containing overbasic calcium sulfonate with a TBN of approximately 300 (ASTM D4739) and overbasic magnesium sulfonate with a TBN of approximately 400 (ASTM 4739); and (2) an anti-wear system containing an ash-free phosphorus-containing anti-wear compound (e.g., 3-[[bis(2-methylpropoxy)phosphinothioi]thio]-2-methyl-propanoic acid) and an optional amount of a metal-containing anti-wear compound (e.g., zinc dialkyldithiophosphate with 100% alkyl groups derived from a primary alcohol). Each composition in this example also contained the same amounts of other additives, including antioxidants, dispersants, friction modifiers, antifoaming additives, pour point depressants, viscosity modifiers, and the remainder being base oil, to achieve the KV100 listed in the table. Fluid relationships are provided in Table 3, and performance results are provided in Table 4.

[0117] [Table 3] * For example, the TBN ratio of Invention Example 1 is calculated as follows: 3.8 / 5.7 * 100 = 66.7% **For Invention Example 3, for example, the zinc / total SASH ratio is calculated as follows: 172 ppm zinc / 0.71 wt% total SASH

[0118]

Table 4

[0119] Comparative Example 1 In this comparative example, as described in Table 5, (1) a detergent system containing calcium overbased sulfonate with a TBN of about 300 (ASTM D4739) and magnesium overbased sulfonate with a TBN of about 400 (ASTM D4739), and (2) an antiwear system or a mixed antiwear system containing only a metal-containing phosphorus compound (e.g., zinc dialkyldithiophosphate in which 100% of the alkyl groups are derived from primary alcohols) were evaluated in various amounts in a non-conforming passenger vehicle lubricating composition. Each comparative composition also contained the same amounts of other additives including antioxidants, dispersants, friction modifiers, antifoaming additives, pour point depressants, viscosity modifiers, and the balance base oil to achieve the KV100 described in the table. Fluid relationships are provided in Table 5 and performance results are provided in Table 6.

[0120]

Table 5

[0121]

Table 6

[0122] Example 3 This embodiment includes a predictive formula for determining rust ball performance (ASTM D6557). For example, the rust ball AGV of ASTM D6557 can be determined from the lubricant zinc content in ppm and the total SASH contribution in weight percent using the relationship in formula (1): AGV = (SASH * 196.0269) + (zinc * -0.01975)-4.17252 (Equation 1).

[0123] Table 7 and Figure 2 below show the correlation between the AGV determined from formula (1) and the actual AGV measured by ASTM D6557 for several representative samples consistent with those described in Example 1 and Comparative Example 1.

[0124] [Table 7]

[0125] Where used herein and in the appended claims, the singular forms “a,” “an,” and “the” include multiple references unless explicitly and clearly limited to one. For example, a reference to “antioxidants” includes two or more different antioxidants. Where used herein, the term “includes” and its grammatical variations are intended to be non-limiting so as not to exclude other similar items that may be substituted for or added to the items in the list.

[0126] For the purposes of this specification and the appended claims, unless otherwise indicated, all numbers representing quantities, percentages, or proportions, and other numerical values ​​used herein and in the claims should be understood in all cases as being modified by the term “approximately.” Therefore, unless otherwise indicated, the numerical parameters described herein and in the appended claims are approximations that may vary depending on the desired characteristics sought by this disclosure. Each numerical parameter should be interpreted at least in terms of the number of significant figures reported and by applying common rounding techniques, not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims.

[0127] It should be understood that each component, compound, substituent, or parameter disclosed herein is disclosed for use alone or in combination with any one or more other components, compounds, substituents, or parameters disclosed herein.

[0128] It should be further understood that each range disclosed herein should be interpreted as a disclosure of each specific value within the disclosure range having the same number of significant figures. Therefore, for example, the range 1 to 4 should be interpreted as a clear disclosure of any range of such values, not just the values ​​1, 2, 3, and 4.

[0129] It should be further understood that each lower limit of each range disclosed herein should be interpreted as being disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compound, substituent, or parameter. Therefore, this disclosure should be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or each specific value within each range, or by combining each upper limit of each range with each specific value within each range. That is, it should also be further understood that any range between endpoint values ​​within a broad range is also considered herein. Therefore, the range 1-4 also means ranges such as 1-3, 1-2, 2-4, 2-3, etc.

[0130] Furthermore, any specific amounts / values ​​of components, compounds, substituents, or parameters disclosed in the description or examples should be interpreted as disclosures of either a lower or upper limit of a range, and can therefore be combined with any other lower or upper limit or specific amounts / values ​​in the range for the same component, compound, substituent, or parameter disclosed elsewhere in this application to form a range for that component, compound, substituent, or parameter.

[0131] While specific embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents may emerge that are not currently anticipated or can not be anticipated by the applicants or others skilled in the art. Therefore, the attached claims, as filed and as may be amended, are intended to encompass all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A passenger car lubricant composition having a low sulfated ash content, One or more base oils with lubricating viscosity, An anti-wear system comprising one or more ashless phosphorus-containing anti-wear compounds and optionally one or more metal-containing anti-wear compounds, wherein the phosphorus weight ratio of phosphorus from the one or more ashless anti-wear compounds to phosphorus from the optionally one or more metal-containing anti-wear compounds is approximately 50:50 to approximately 100:

0. A sulfated ash content of approximately 0.75% by weight or less, as measured according to ASTM D874, Total phosphorus, contributed by the one or more ashless phosphorus-containing anti-wear compounds and the one or more optionally selected metal-containing anti-wear compounds, is approximately 700 ppm or less. A cleaning agent system having a magnesium-to-calcium weight ratio of approximately 2.0 or less, A passenger car lubricant composition comprising a TBN ratio of at least approximately 60 percent of TBN measured according to ASTM D4739 to TBN measured according to ASTM D2896.

2. The passenger car lubrication composition according to claim 1, wherein when the sulfated ash content is less than 0.5 weight percent, the TBN ratio is about 60 percent to 70 percent, and / or when the sulfated ash content is greater than 0.5 weight percent, the TBN ratio is greater than 70 percent to about 80 percent.

3. The passenger car lubricant composition according to claim 1, wherein the ratio of zinc in ppm units to total SASH weight percent (ASTM D874) is less than about 400 when the total SASH is less than about 0.5 weight percent.

4. The ashless phosphorus-containing anti-wear additive is a dialkyldithiophosphate ester, a dithiophosphate triester, an amyl acid phosphate, a diamyl acid phosphate, a dibutyl hydrogen phosphonate, a dimethyl octadecyl phosphonate, a salt thereof, or a mixture thereof, and / or one or more of the ashless phosphorus-containing anti-wear additives is a dialkyldithiophosphate anti-wear additive having the structure of formula I, or a salt thereof. 【Chemistry 1】 In the formula, R １ and R ２ However, independently, they are C3-C8 linear or branched alkyl groups, R ３ However, it is hydrogen or methyl, R ４ The passenger car lubrication composition according to claim 1, wherein the phosphorus-containing anti-wear additive is a hydroxyl group or a hydrocarbyl group and / or the phosphorus-containing anti-wear additive is a triester of a dithiophosphate having two oxygen ester moieties and a sulfur ester moiety, each oxygen ester moiety independently containing at least two β-hydrogen atoms on a linear or branched hydrocarbyl group, the sulfur ester moiety contains one or more heteroatoms selected from oxygen or nitrogen and has up to four carbon atoms linking at least one of the heteroatoms to a sulfur atom of the sulfur ester, and the phosphorus-containing anti-wear additive has a molecular weight of at least about 490 g / mol.

5. The dithiophosphate triester has the structure of formula II, 【Chemistry 2】 During the ceremony, R ５ and R ６ However, the oxygen ester portion and independently include linear or branched C3-C100 hydrocarbyl groups, R ７ The passenger car lubricant composition according to claim 4, wherein the sulfur ester portion having a linear or branched hydrocarbyl group of C3 to C100 containing one or more heteroatoms.

6. R ５ and R ６ wherein the oxygen ester moieties of R and R are independently derived from one of 4-methyl-2-pentanol, isopropyl alcohol, tert-butyl alcohol, sec-butyl alcohol, 2-octanol, 2-decanol, 2-dodecanol, or combinations thereof, the passenger car lubricating composition according to claim 5.

7. R ７ The passenger car lubricant composition according to claim 5, wherein the sulfur ester portion is derived from one of the following: (i) a vinyl ester of a carboxylic acid, selected from vinyl acetate, vinyl propionate, vinyl laurate, vinyl octanoate, vinyl decanoate, vinyl stearate, or a combination thereof; (ii) maleic acid, its ester, diester, or anhydride, selected from vinyl acetate, vinyl propionate, vinyl laurate, vinyl octanoate, vinyl decanoate, vinyl stearate, or a combination thereof; (iii) an alkyl (meth)acrylate, selected from methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, or a combination thereof; or (iv) a combination thereof.

8. The passenger car lubricant composition according to claim 5, wherein the triester of the dithiophosphate comprises each oxygen ester derived from 4-methyl-2-pentyl alcohol and the sulfur ester derived from dibutyl maleate.

9. The passenger car lubrication composition according to claim 6, wherein the molecular weight of the ash-free phosphorus-containing anti-wear additive is a maximum of approximately 650 g / mol.

10. The passenger car lubrication composition according to claim 1, wherein the metal-containing wear-preventing additive is one or more zinc dihydrocarbyl dithiophosphate compounds.

11. The zinc dihydrocarbyl dithiophosphate compound is derived from at least about 60 weight percent of a secondary alcohol, and / or the one or more zinc dihydrocarbyl dithiophosphate compounds have the structure of formula III. 【Transformation 3】 The passenger car lubricant composition according to claim 10, wherein each R group in formula III is independently a linear or branched C3-C16 hydrocarbyl group and / or each R group is independently a linear or branched C4-C8 hydrocarbyl group.

12. The passenger car lubricant composition according to claim 11, wherein the hydrocarbyl group of the one or more zinc dihydrocarbyl dithiophosphate compounds is selected from one or more of the following: ethylhexyl group, butyl group, methyl isobutyl group, pentyl group, methylpentyl group, isopentyl group, isobutyl group, propyl group, isopropyl group, or a combination thereof.

13. The passenger car lubrication composition according to claim 1, wherein the ash-free phosphorus-containing anti-wear compound and the optionally selected metal-containing anti-wear compound contribute to a total phosphorus content of approximately 350 ppm or less.

14. The passenger car lubrication composition according to claim 1, wherein the passenger car lubrication composition lubricates a hybrid electric passenger car engine, and / or the passenger car lubrication composition exhibits a rust grade of 70 AGV or higher in the rust ball test of ASTM D6557, and / or the passenger car lubrication composition has a total of about 330 ppm or less of total copper, lead, and tin in combination according to the high temperature corrosion test (HTCBT) of ASTM D6594, and / or the passenger car lubrication composition exhibits emulsion stability with 0 percent water separation at 0°C and / or 25°C according to ASTM D7563.

15. The passenger car lubrication composition according to claim 1, wherein the detergent system comprises a perbasic calcium sulfonate detergent and a perbasic magnesium sulfonate detergent, contributing about 200 to about 1000 ppm of calcium and about 500 to about 1500 ppm of magnesium to the passenger car lubrication composition, and / or the detergent system has a magnesium-to-calcium weight ratio of at least about 1.0.

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