KR20230011331A - Lubricating oil composition comprising a comb polymethacrylate and an ethylenic olefin copolymer viscosity modifier - Google Patents

Abstract

A lubricating oil composition, for example, comprising (a) a major amount of an oil of lubricating viscosity, (b) a non-dispersible comb polymethacrylate (PMA) and (c) a non-dispersible ethylenic olefin copolymer and having a viscosity grade of SAE 0W-20 or lower. A composition is provided. In addition, by lubricating the engine with a lubricating oil composition A method for reducing wear on an internal combustion engine is provided.

Description

Lubricating oil composition comprising a comb polymethacrylate and an ethylenic olefin copolymer viscosity modifier

The disclosed technology relates to lubricating oils for internal combustion engines, particularly lubricating oils for spark-ignited engines.

Engine oil is blended with various additives to meet performance requirements. The challenge of engine oil formulation is to achieve wear, deposit and varnish control while achieving improved fuel economy.

One known method of increasing the fuel economy of a lubricating oil composition is to reduce its viscosity (ie, high temperature high shear (HTHS) viscosity). HTHS is a measure of the viscosity of a lubricating oil composition under severe engine conditions. However, this approach is currently reaching the limits of equipment capabilities and specifications. At a given viscosity, the addition of an organic or organometallic friction reducer reduces the surface friction of the lubricating oil composition and allows for better fuel economy. However, these additives often have detrimental effects such as increased deposit formation, seal impact, or increase wear by not allowing the formation of a wear-resistant film beyond the wear-resistant component for a limited surface area.

Viscosity modifiers are also widely used to improve the viscosity index (VI) of a lubricating oil composition, thereby thickening the oil with increasing temperature. However, under high temperature and high stress conditions, viscosity modifier degradation may occur. When this occurs, the viscosity of the lubricating oil composition may decrease, resulting in increased engine wear.

Therefore, despite advances in lubricating oil blending technology, there remains a need for an engine lubricating oil, particularly a lubricating oil having a viscosity grade of SAE 0W-20 or lower, that provides excellent anti-wear performance while providing sufficient fuel economy.

In one aspect, the present disclosure provides a lubricating oil composition having a kinematic viscosity at 100° C. of less than 9.3 mm ² /s comprising:

a) large amounts of oil of lubricating viscosity;

b) non-dispersible comb polymethacrylate (PMA); and

c) non-dispersible ethylenic olefin copolymers.

Another aspect of the present disclosure provides a method of reducing wear in an internal combustion engine comprising lubricating the engine with a lubricating oil composition having a kinematic viscosity at 100° C. of less than 9.3 mm ² /s, the lubricating oil composition comprising:

a) large amounts of oil of lubricating viscosity;

b) non-dispersible comb polymethacrylate (PMA); and

c) non-dispersible ethylenic olefin copolymers.

In another aspect, the present disclosure provides a lubricating oil composition comprising:

a) large amounts of oil of lubricating viscosity;

b) 0.4 to 1.9% by weight, based on the total weight of the lubricating oil composition, of a non-dispersible comb polymethacrylate (PMA); and

c) 0.01 to 0.36% by weight, based on the total weight of the lubricating oil composition, of a non-dispersible ethylene-based olefin copolymer.

Another aspect of the present disclosure provides a method of reducing wear in an internal combustion engine comprising lubricating the engine with a lubricating oil composition comprising:

a) large amounts of oil of lubricating viscosity;

b) 0.4 to 1.9% by weight, based on the total weight of the lubricating oil composition, of a non-dispersible comb polymethacrylate (PMA); and

c) 0.01 to 0.36% by weight, based on the total weight of the lubricating oil composition, of a non-dispersible ethylene-based olefin copolymer.

To facilitate understanding of the subject matter disclosed herein, a number of terms, abbreviations, or other shorthands used herein are defined below. Any undefined terms, abbreviations or abbreviations are understood to have the ordinary meanings used by those skilled in the art at the time this application was filed.

Justice

In this application, the following words and expressions, when used, have the meanings given below.

"Majority" means greater than 50% by weight of the composition.

"Minor amount" means less than 50% by weight of the composition, expressed relative to the specified additive, calculated as the active ingredient of the additive or additives, and relative to the total mass of all additives present in the composition.

“Active ingredient” or “active agent” means an additive material that is not a diluent or solvent.

All percentages reported are weight percent (wt.%) on an active ingredient basis (ie, regardless of carrier or diluent oil) unless otherwise specified.

The abbreviation "ppm" means parts per million by weight based on the total weight of the lubricating oil composition.

Kinematic viscosity (KV) at 100° C. is measured in mm ² /s and is determined according to ASTM D445.

High Temperature High Shear (HTHS) viscosity at 150 ^° C. is measured according to ASTM D4683.

Apparent viscosity at a temperature of -35°C to -5°C is measured with a Cold Cranking Simulator according to ASTM D5293.

The term “metal” refers to alkali metals, alkaline earth metals, or mixtures thereof.

An oil-soluble or dispersible material means that the amount of the material required to provide the desired level of activity or performance can be incorporated by dissolving, dispersing or suspending in an oil of lubricating viscosity. Usually, this means that at least about 0.001% by weight of the material can be incorporated into the lubricating oil composition. For further discussion of solubility and dispersibility, particularly the term "stable dispersibility," see U.S. Patent No. 4,320,019, which is incorporated herein by reference for its relevant teachings.

As used herein, the term "sulfated ash" refers to non-combustible residues resulting from detergents and metallic additives in lubricating oils. Sulfuric acid ash can be measured according to ASTM D874.

As used herein, the term "Total Base Number" or "TBN" refers to the amount of base equivalent to a milligram of KOH in 1 gram of sample. Therefore, a higher TBN number reflects more alkaline products and thus indicates greater alkalinity. TBN is measured according to ASTM D2896.

Boron, calcium, magnesium, molybdenum, phosphorus, sulfur and zinc contents are measured according to ASTM D5185.

Weight average molecular weight (Mw) and number average molecular weight (Mn) are measured by gel permeation chromatography (GPC) based on polystyrene.

Shear Stability Index (SSI) is measured according to ASTM D7109.

All ASTM standards referred to herein are the most current versions as of the filing date of this application.

The term "olefin" refers to a class of unsaturated aliphatic hydrocarbons having one or more carbon-carbon double bonds obtained in a number of processes. Those containing one double bond are called mono-alkenes and those with two double bonds are called dienes, alkyldienes or diolefins. Alpha olefins are particularly reactive because the double bond is between the first and second carbons. Examples of alpha olefins are 1-octene and 1-octadecene, which are used as starting points for intermediate-biodegradable surfactants. Linear and branched olefins are also included in the definition of olefins.

Although this invention is subject to many variations and many substitutions in form, specific embodiments are described in detail herein. It should be understood, however, that there is no intention to limit the disclosure to the specific embodiments disclosed, but on the contrary, it is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the disclosure as defined by the appended claims.

Not all activities described in the general description or examples may be required, and some of the specific activities may not be required, and one or more additional activities may be performed in addition to the activities described. Moreover, the order in which the activities are listed may not necessarily be the order in which the activities are performed.

Advantages, other advantages, and solutions to problems have been described herein in connection with specific embodiments. However, an advantage, advantage, solution to a problem, and any features that can give rise to or distinguish any advantage, advantage, or solution are essential, or essential, or essential features of all or part of the claims. should not be regarded as

The specification and examples of embodiments described herein are intended to provide a general understanding of the structure of various embodiments.

As used herein, the terms "comprises", "comprising", "includes", "includes", "is", "having" or any other variation thereof are intended to include a non-exclusive inclusion. do. For example, a process, method, article, or device comprising a list of features is not necessarily limited to only those features and may include other features not explicitly listed or other features unique to such process, method, article, or device. there is. Also, to the contrary, unless expressly stated, “or” indicates an inclusive or exclusive or not. For example, condition A or B is satisfied by any one of the following. A is true (or present) and B is false (or not present) A is false (or not present) and B is true (or present) and both A and B are true (or present) Ham) Im.

The use of "a" or "an" is used to describe the elements and components described herein. This is done merely for convenience and to provide a general sense of the scope of the embodiments of the present disclosure. This description should be read as including one or at least one, and the singular also includes the plural and vice versa, unless it is clear to the contrary.

The term “average” when referring to values is intended to mean the mean, geometric mean or median. Group numbers corresponding to columns of the periodic table of elements use the "New Notation" convention found in the CRC Handbook of Chemistry and Physics, 81st Edition (2000-2001).

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. The materials, methods and examples are illustrative only and are not intended to be limiting. To the extent not disclosed herein, many details regarding specific materials and processing operations are conventional and can be found in textbooks and other sources within the oil and gas industry as well as lubricants.

The specifications and examples are not intended to provide an exhaustive and comprehensive description of all elements and features of formulations, compositions, devices and systems using the structures or methods described herein. Separate embodiments may also be provided in a single combination, and conversely, for brevity, various features that are described in the context of a single embodiment may be provided separately or in any sub-combination. Also, references to values specified in a range include all values within that range. Many other embodiments may become apparent to the skilled artisan only after reading this disclosure. Other embodiments may be used and derived from the present invention so that structural, logical, or other changes may be made without departing from the scope of the present invention. Accordingly, this disclosure is to be regarded as illustrative rather than restrictive.

lubricating viscosity oil/ base oil ingredient

An oil of lubricating viscosity (sometimes referred to as "base stock" or "base oil") is, for example, the primary liquid component of a lubricating oil composition that is blended with additives and possibly other oils to create the final lubricating oil composition. . Base oils are useful for preparing concentrates as well as for preparing lubricating oil compositions therefrom, and may be selected from natural and synthetic oils and combinations thereof.

Natural oils include animal and vegetable oils, liquid petroleum oils and hydrorefined and solvent treated mineral lubricating oils of paraffinic, naphthenic and paraffinic-naphthenic mixed types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.

Synthetic oils include hydrocarbon oils such as polymerized and interpolymerized olefins such as polybutylene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexene), poly(1-octene) , poly(1-decene)); Alkylbenzenes such as dodecylbenzene, tetradecylbenzene, dinonylbenzene, and di(2-ethylhexyl)benzene; polyphenols such as biphenyls, terphenyls, and alkylated polyphenols; and alkylated diphenyls ethers and alkylated diphenyl sulfides and their derivatives, analogs and homologues.

Another class of suitable synthetic oils includes dicarboxylic acids such as malonic acid, alkyl malonic acid, alkenyl malonic acid, succinic acid, alkyl succinic acid, and alkenyl succinic acid, maleic acid, fumaric acid, azelaic acid, suberic acid, sebacic acid, azelaic acid, dipic acid, linoleic acid dimer, and phthalic acid) with various alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, ethylene glycol monoether, and propylene glycol. Specific examples of such esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, 2-ethylhexyl diesters of linoleic acid dimers, and complex esters formed by the reaction of 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid .

The base oil may be a renewable or bio-derived engine oil. Examples of such engine oils are disclosed in WO2016061050, incorporated herein by reference. According to some embodiments, the renewable or bio-derived base oil includes bio-based hydrocarbons such as isoparaffinic hydrocarbons derived from hydrocarbon terpenes such as myrcene, ocimene and farnesene.

Esters useful as synthetic oils also include those prepared from C ₅ to C ₁₂ monocarboxylic acids with polyols and polyol esters such as neopentyl glycol, trimethylopropane, pentaerythritol, dipentaerythritol, tripentaerythritol. do.

Base oils may be derived from Fischer-Tropsch synthetic hydrocarbons. Fischer-Tropsch synthetic hydrocarbons are produced from synthesis gas containing H ₂ and CO using a Fischer-Tropsch catalyst. These hydrocarbons require further processing to be useful as base oils. For example, hydrocarbons may be hydroisomerized using processes known to those skilled in the art; hydrocracking and hydroisomerization; dewaxing; or hydroisomerization and dewaxing; can be processed

Unrefined, refined and re-refined oils can be used as the base oil in the lubricating oil composition of the present invention. Unrefined oils are obtained from natural or synthetic sources without further refining. Examples of crude oils are shale oil obtained directly from a retorting operation, petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment. Refined oil is similar to crude oil except that the crude oil is further processed in one or more refining steps to improve one or more properties. Purification techniques such as distillation, solvent extraction, acid or base extraction, filtration and percolation are known to those skilled in the art.

Accordingly, the base oil that may be used to prepare the present lubricating oil composition may be selected from Groups I-V base oils as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines (API Publication 1509). These base oil groups are summarized in Table 1 below.

base oil characteristic group ^(a) Saturate ^(b) , % by weight Sulfur ^(c) , % by weight Viscosity index ^(d) group I < 90 and/or >0.03 80 ~ < 120 group II ≥90 ≤0.03 80 ~ < 120 group III ≥90 ≤0.03 ≥120 group IV Polyalphaolefin (PAO) group V Any base ingredient not included in Groups I, II, III or IV

^(a) Groups I to III are mineral oil based raw materials. ^{( b)} Measured according to ASTM D2007.

^(c) Measured according to ASTM D2622, ASTM D3120, ASTM D4294 or ASTM D4927.

^(d) Measured according to ASTM D2270.

Base oils suitable for use herein are those corresponding to API Group II, Group III, Group IV, Group V oils and mixtures thereof, preferably Group III to Group V oils, due to their excellent volatility, stability, viscosity and cleanliness characteristics. any of a variety of oils.

The base oil constitutes a major component of the lubricating oil composition and is present in an amount ranging from 50 to 99% by weight (eg 70 to 95% by weight or 85 to 95% by weight).

The base oil may be selected from any of the synthetic or natural oils commonly used as crankcase lubricants for spark-ignition internal combustion engines. Base oils generally have a kinematic viscosity at 100° C. in the range of 1.5 to 6 mm ² /s. When the kinematic viscosity at 100°C of the lubricating base oil exceeds 6 mm ² /s, the low-temperature viscosity characteristic deteriorates and sufficient fuel economy may not be obtained. At a kinematic viscosity of less than 1.5 mm ² /s, the formation of an oil film in the lubrication area is insufficient. For this reason, lubricity may decrease and evaporation loss of the lubricating oil composition may increase.

However, in some embodiments, a base oil having a kinematic viscosity greater than 6 mm ² /s is required. For example, the whole base oil may include a small amount of a high cut base oil such as 10 cSt polyalphaolefin.

Preferably, the base oil has a viscosity index of at least 90 (eg, at least 95, at least 105, at least 110, at least 115 or at least 120). When the viscosity index is less than 90, not only the viscosity-temperature characteristics, heat and oxidation stability, and anti-volatilization properties deteriorate, but also the friction coefficient tends to increase, and the wear resistance tends to deteriorate.

The lubricating oil composition may be a multi-grade oil having a viscosity grade of SAE 0W-XX, where XX is any one of 8, 10, 12, 16, 20. According to a preferred embodiment, the lubricating oil composition has a viscosity grade of SAE 0W-20.

The lubricating oil composition has a high temperature, high shear (HTHS) viscosity of 3.0 cP or less (eg, 1.0 to 3.0 cP or 1.3 to 3.0 cP), 2.8 cP or less (eg, 1.0 to 2.8 cP or 1.3 to 2.8 cP), or 2.7 cP at 150 ° C. or less (eg 1.0 to 2.7 cP or 1.3 to 2.7 cP), 2.6 cP or less (eg 1.0 to 2.6 cP or 1.3 to 2.6 cP), such as 2.5 cP or less (eg 1.0 to 2.5 cP or 1.3 to 2.5 cP), or 2.0 cP or less (eg, 1.0 to 2.0 cP or 1.3 to 2.0 cP). According to exemplary embodiments, the lubricating oil composition has an HTHS viscosity at 150° C. of 2.5 to 2.6 cP, 2.55 to 2.9 cP or 2.55 to 2.58 cP.

The lubricating oil composition is at least 135 (eg 135 to 400 or 135 to 250), at least 150 (eg 150 to 400 or 150 to 250), at least 165 (eg 165 to 400 or 165 to 250), at least 190 (eg 150 to 400 or 165 to 250). 190 to 400 or 190 to 250) or at least 200 (eg 200 to 400 or 200 to 250). If the viscosity index of the lubricating oil composition is less than 135, it may be difficult to improve fuel economy while maintaining a desired HTHS viscosity at 150°C. If the viscosity index of the lubricating oil composition exceeds 400, evaporation may decrease, and defects may occur due to lack of solubility of additives and matching with a seal material. According to exemplary embodiments, the lubricating oil composition has a viscosity index of 200 to 240, 203 to 235, 200 to 210, 220 to 225 or 230 to 240.

The lubricating oil composition has a kinematic viscosity at 100°C in the range of 3 to 12 mm ² /s (eg, 3 to 11 mm ² /s, 5 to 9 mm ² /s, or 6 to 8 mm ² /s). According to exemplary embodiments, the lubricating oil composition may have a concentration of less than 6.9 to 9.3 mm ² /s, 7.4 to 7.8 mm ² /s, 7.45 to 7.76 mm ² /s, 7.4 to 7.5 mm ² /s, 7.5 to 7.6 mm at 100 °C. ² /s, from 7.6 to 7.7 mm ² /s or from 7.7 to 7.8 mm ² /s.

The lubricating oil composition has an apparent viscosity of 3600 to 3900 mPa·s as measured by a Cold Cranking Simulator (CCS) at a temperature ranging from 35° C. to -5° C. According to exemplary embodiments, the lubricating oil composition has an apparent viscosity of 3600 to 3700 mPa·s, 3700 to 3800 mPa·s or 3800 to 3900 mPa·s.

Generally, the sulfur level of the lubricating oil composition is less than or equal to about 0.7 weight percent based on the total weight of the lubricating oil composition. For example, the lubricating oil composition may have a sulfur level of about 0.01 to 0.5 weight percent, 0.01 to 0.4 weight percent, 0.01 to 0.3 weight percent, 0.01 to 0.2 weight percent, or 0.01 to 0.10 weight percent. In one embodiment, the sulfur level in the lubricating oil composition is about 0.60% or less, about 0.50% or less, about 0.40% or less, about 0.30% or less, about 0.20% or less by weight, based on the total weight of the lubricating oil composition. or about 0.10% by weight or less.

In one embodiment, the phosphorus level in the lubricating oil composition is at a level of about 0.08 weight percent or less, such as about 0.01 to about 0.08 weight percent phosphorus, based on the total weight of the lubricating oil composition. In one embodiment, the phosphorus level in the lubricating oil composition is at a level of about 0.07 weight percent or less, such as about 0.01 to about 0.07 weight percent phosphorus, based on the total weight of the lubricating oil composition. In one embodiment, the phosphorus level in the lubricating oil composition is at a level of about 0.05 weight percent or less, such as about 0.01 to about 0.05 weight percent phosphorus, based on the total weight of the lubricating oil composition.

In one embodiment, the level of sulfate ash produced by the lubricating oil composition is less than or equal to about 1.00 weight percent sulfate ash as measured by ASTM D874, eg, from about 0.10 to about 1.00 weight percent sulfate ash as measured by ASTM D874. In one embodiment, the level of sulfate ash produced by the lubricating oil composition is less than or equal to about 0.80 weight percent sulfate ash as measured by ASTM D874, eg, from about 0.10 to about 0.80 weight percent sulfate ash as measured by ASTM D 874. In one embodiment, the level of sulfate ash produced by the lubricating oil composition is less than or equal to about 0.60 weight percent sulfate ash as measured by ASTM D874, eg, from about 0.10 to about 0.60 weight percent sulfate ash as measured by ASTM D874.

Suitably, the lubricating oil composition may have a total number (TBN) of 4 to 15 mg KOH/g (eg, 5 to 12 mg KOH/g, 6 to 12 mg KOH/g, or 8 to 12 mg KOH/g).

viscosity modifier

Viscosity modifiers (VMs), sometimes referred to as viscosity index improvers (VII), are present in lubricating oil compositions to impart high and low temperature operability. Viscosity modifiers increase the viscosity of the lubricating oil composition at high temperatures, thereby increasing film thickness, while having a limited effect on viscosity at low temperatures.

Viscosity modifiers may be used to impart their unique function or may be multifunctional. Multifunctional viscosity modifiers can also act as dispersants.

Examples of suitable viscosity modifiers are polymers and copolymers of methacrylates, butadienes, olefins or alkylated styrenes. Other suitable viscosity modifiers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (eg, copolymers of various chain length acrylates).

The viscosity modifier may be present in the lubricating oil composition in a total amount of about 0.001% to about 10% by weight based on the total weight of the lubricating oil composition. In another embodiment, the viscosity modifier is present in an amount of 0.01 to 8%, 0.1 to 5%, 0.4 to 4%, 0.6 to 3%, 0.7 to 2%, 1 to 1.5%, based on the total weight of the lubricating oil composition. % or from 1.05 to 1.44% by weight total. In some exemplary embodiments, the viscosity modifier is present in a total amount of 1.0 to 1.2 weight percent, 1.3 to 1.4 weight percent, or 1.4 to 1.5 weight percent based on the total weight of the lubricating oil composition.

Particularly useful in lubricating oil compositions is the combination of a non-dispersible comb polymethacrylate (comm PMA) and one or more non-dispersible ethylenic olefin copolymers (OCP).

non-dispersibility comb polymethacrylate

Non-dispersible comb polymethacrylate (comb PMA) is a comb-shaped polymer with a main chain having one long branch per repeating unit.

In one embodiment, the non-dispersible comb PMA has a weight average molecular weight (Mw) of 300,000 to 600,000 g/mol, 350,000 to 550,000 g/mol, 375,000 to 500,000 g/mol or 390,000 to 460,000 g/mol.

In one embodiment, the non-dispersible comb PMA has a number average molecular weight (Mn) of 35,000 to 105,000 g/mol, 45,000 to 95,000 g/mol, 55,000 to 85,000 g/mol, or 65,000 to 75,000 g/mol. In another embodiment, the non-dispersible comb PMA has a number average molecular weight (Mn) of 150,000 to 250,000 g/mol or 200,000 to 215,000 g/mol.

In one embodiment, the non-dispersible comb PMA has a shear stability index (SSI) of 0.1 to 1.0, 0.2 to 0.9 or 0.3 to 0.8.

Non-dispersible comb PMA of lubricating oil composition are described in US2017/0298287A1 and JP2019014802, the disclosures of which are incorporated herein by reference. The non-dispersible comb PMA can be provided by Viscoplex® Viscosity Index Improvers 3-201 and/or 3-162 available from Evonik.

According to one embodiment, the non-dispersible comb PMA is provided by a compound referred to as Viscoplex® 3-201 comprising comb PMA as a major resin component. The weight average molecular weight (Mw) of this non-dispersible comb PMA was 420,000 g/mol, the number average molecular weight (Mn) was 70,946 g/mol, and the Mw/Mn was 5.92. The compound has at least a structural unit derived from a macromonomer having an Mn of 500 or more. The non-dispersible comb PMA is present in an amount of 19% by weight based on the total weight of the compound.

According to another embodiment, the non-dispersible comb PMA is provided by a compound referred to as Viscoplex® 3-162 which also contains comb PMA as a major resin component. This non-dispersible comb PMA had a weight average molecular weight (Mw) of 399,292 g/mol, a number average molecular weight (Mn) of 205,952 g/mol, Mw/Mn of 1.94, and a shear stability index (SSI) of 0.6.

According to another embodiment, the non-dispersible comb PMA is provided by a combination of compounds, for example Viscoplex® 3-201 and Viscoplex® 3-162.

The non-dispersible comb PMA is generally present in an amount of 0.4 to 2.0%, 0.5 to 1.9%, 0.6 to 1.8%, 0.77 to 1.5% or 0.76 to 1.33% by weight based on the total weight of the lubricating oil composition. According to one embodiment, the non-dispersible comb PMA is present in an amount of 0.4 to 1.9 weight percent based on the total weight of the lubricating oil composition.

non-dispersibility Ethylene-based olefin copolymer

The lubricating oil composition also includes a non-dispersible ethylenic olefin copolymer (OCP) as a viscosity modifier. In one embodiment, the non-dispersible ethylene-based olefin copolymer has a weight average molecular weight (Mw) of 50,000 to 200,000 g/mol, 70,000 to 180,000 g/mol, or 90,000 to 160,000 g/mol. For example, the non-dispersible ethylene-based olefin copolymer can have a weight average molecular weight of 95,000 to 105,000 g/mol, 110,000 to 115,000 g/mol or 145,000 to 150,000 g/mol.

In one embodiment, the non-dispersible ethylene-based olefin copolymer has a weight average molecular weight (Mw) of 20,000 to 100,000 g/mol, 30,000 to 90,000 g/mol, or 35,000 to 85,000 g/mol.

In certain embodiments, the non-dispersible ethylenic olefin copolymer has a shear stability index (SSI) of 10 to 70, 15 to 65, or 20 to 60.

Non-dispersible ethylenic olefin copolymers may be described as follows and as described in US 2013/0203640, the disclosure of which is incorporated herein by reference.

In one embodiment, the non-dispersible ethylene-based olefin copolymer is an ethylene propylene copolymer.

In one embodiment, the non-dispersible ethylene-olefin copolymer has a total ethylene content of 35 to 70 weight percent or 40 to 65 weight percent based on the total weight of the non-dispersible ethylene-olefin copolymer. In another embodiment, the non-dispersible ethylenic olefin copolymer has a total ethylene content of 45 to 60 weight percent based on the total weight of the non-dispersible ethylene-olefin copolymer.

The lubricating oil composition may include more than one non-dispersible ethylenic olefin copolymer. In one embodiment, the lubricating oil composition comprises a combination of (a) a first ethylene-a-olefin copolymer and (b) a second ethylene-a-olefin copolymer. In this case, the lubricating oil composition is generally about 30 to about 70% by weight of the first ethylene-α-olefin copolymer (a) and about 30 to 70% by weight based on the total amount of (a) and (b) in the lubricating oil composition. % of the second ethylene-α-olefin copolymer (b). In another embodiment, the lubricating oil composition comprises about 40 to about 60 weight percent of a first ethylene-a-olefin copolymer (a) and about 60 to 40 weight percent based on the total amount of (a) and (b) in the lubricating oil composition. % of the second ethylene-α-olefin copolymer (b). In certain embodiments, the lubricating oil composition comprises about 50 to about 54 weight percent of a first ethylene-a-olefin copolymer (a) and about 46 to 50 weight percent, based on the total amount of (a) and (b) in the lubricating oil composition. of the second ethylene-α-olefin copolymer (b).

In one embodiment, the weight average molecular weight of the first ethylene-α-olefin copolymer is generally from about 60,000 to about 120,000 g/mol. In one embodiment, the weight average molecular weight of the first ethylene-α-olefin copolymer is generally from about 70,000 to about 110,000 g/mol. In one embodiment, the weight average molecular weight of the second ethylene-α-olefin copolymer is generally about 60,000 to about 120,000 g/mol. In one embodiment, the weight average molecular weight of the second ethylene-α-olefin copolymer is generally about 70,000 to about 110,000 g/mol in one embodiment. In one embodiment, the weight average molecular weight of the composition of the first ethylene-α-olefin copolymer and the second ethylene-α-olefin copolymer is generally about 60,000 to about 120,000 g/mol. In another embodiment, the weight average molecular weight of the first ethylene-a-olefin copolymer and the second ethylene-a-olefin copolymer composition is generally from about 70,000 to about 110,000 g/mol. In another embodiment, the weight average molecular weight of the composition of the first ethylene-a-olefin copolymer and the second ethylene-a-olefin copolymer is generally from about 80,000 to about 100,000 g/mol. The molecular weight distribution of each ethylene-α-olefin copolymer is generally less than about 2.5, more typically from about 2.1 to about 2.4. The polymer distribution determined by GPC is usually unimodal.

The one or more non-dispersible ethylenic olefin copolymers are generally present in an amount of 0.01 to 1.5%, 0.05 to 1.0%, 0.08 to 0.4%, 0.1 to 0.5% or 0.15 to 0.4% by weight based on the total weight of the lubricating oil composition. exist in quantity. According to one embodiment, the one or more non-dispersible ethylenic olefin copolymers are present in an amount of 0.01 to 0.36 weight percent based on the total weight of the lubricating oil composition.

additional additives

In addition to the aforementioned non-dispersible comb PMA and non-dispersible ethylenic olefin copolymer viscosity modifier, the lubricating oil compositions of the present disclosure may include one or more additional performance additives that may impart or improve any desirable properties of the lubricating oil composition. Any additive known to those skilled in the art may be used in the lubricating oil compositions disclosed herein. Some suitable additives are described by Mortier et al., “Chemistry and Technology of Lubricants,” 3rd Edition, Springer (2010) and L. R. Rudnick, “Lubricant Additives: Chemistry and Applications,” Second Edition, CRC Press (2009).

For example, the lubricating oil composition may contain antioxidants, antiwear agents, metal detergents, dispersants, additional friction reducers, corrosion inhibitors, demulsifiers, additional viscosity modifiers, pour point depressants, foam inhibitors, and the like.

Generally, when used, the concentration of each additive in the lubricating oil composition may range from 0.001 to 10 weight percent (eg, 0.01 to 5 weight percent or 0.05 to 2.5 weight percent) based on the total weight of the lubricating oil composition. In addition, the total weight of the additives in the lubricating oil composition may be in the range of 0.001 to 20% by weight (eg, 0.01 to 15% by weight or 0.1 to 10% by weight) based on the total weight of the lubricating oil composition.

antioxidant

Antioxidants retard oxidative degradation of base oils during use. This deterioration may result in the presence of deposits, sludge on the metal surface or an increase in the viscosity of the lubricating oil composition. Useful antioxidants include hindered phenols, aromatic amines and sulfurized alkylphenols and their alkali and alkaline earth metal salts.

Hindered phenol antioxidants may contain secondary butyl and/or tertiary butyl groups as sterically hindering groups. The phenol group may be further substituted with a bridging group linked to a hydrocarbyl group and/or a secondary aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 2,2'-methylenebis(6-tert-butyl-4 -methylphenol), 4,4'-bis(2,6-di-tert-butylphenol) and 4,4'-methylenebis(2,6-di-tert-butylphenol). The hindered phenol antioxidant may be an ester or adduct derived from 2,6-di-tert-butylphenol and an alkyl acrylate, wherein the alkyl group may contain 1 to 18 carbon atoms.

Suitable aromatic amine antioxidants include diarylamines such as alkylated diphenylamines (eg dioctyl diphenylamine, dinonyl diphenylamine), phenyl-alpha-naphthalenes and alkylated phenyl-alpha-naphthalenes.

According to an exemplary embodiment, the lubricating oil composition includes an amine antioxidant.

antiwear agent

Antiwear agents help reduce wear of metal parts lubricated with the lubricating oil composition. Examples of antiwear agents include phosphorus containing antiwear agents/extreme pressure agents such as metal thiophosphates, phosphoric acid esters and salts thereof; phosphorus-containing carboxylic acids, esters, ethers and amides; and phosphites. The antiwear agent may be zinc dialkyldithiophosphate (ZnDTP). Phosphorus-free antiwear agents include borate esters (including boric acid epoxides), dithiocarbamate compounds, molybdenum-containing compounds and sulfurized olefins.

According to one embodiment, the lubricating oil composition includes ZnDTP as an antiwear agent.

metal cleaner

Common detergents are anionic materials comprising a long-chain hydrophobic portion of the molecule and a smaller anionic or oleophobic hydrophilic portion of the molecule. The anionic portion of the detergent is usually derived from an organic acid such as sulfuric acid, carboxylic acid, phosphoric acid, phenol or mixtures thereof. The counter ion is usually an alkaline earth or alkali metal.

In some embodiments, a lubricating oil composition provided herein includes at least a neutral or overbased metal detergent as an additive or additive component. In certain embodiments, the metal detergent in the lubricating oil composition acts as a neutralizer of acidic products in the lubricating oil composition. In certain embodiments, the metal cleaner prevents the formation of deposits on engine surfaces. Depending on the nature of the acid used, the detergent may have additional functions such as antioxidant properties. In certain embodiments, the lubricating oil composition includes a metal detergent comprising an overbased detergent or a mixture of neutral and overbased detergents. The term “overbased” is intended to define additives that contain a higher metal content than required by the stoichiometry of the specific metal and specific organic acid used. The excess metal is in the form of particles of an inorganic base (eg hydroxide or carbonate) surrounded by a sheath of metal salt. The sheath serves to keep the particles dispersed in the liquid oleaginous vehicle. The amount of excess metal is generally expressed as the ratio of the total equivalents of excess metal to the equivalents of organic acid and is generally in the range of 0.1 to 30.

Some examples of suitable metal detergents include sulphurised or unsulfurized alkyl or alkenyl phenates, alkyl or alkenyl aromatic sulfonates, borated sulfonates, sulphurised or unsulfurized multi-hydroxy alkyl or alkenyl aromatic compounds. metal salts of alkanoic acids, metal salts of alkyl or alkenyl polyacids, and chemical and physical mixtures thereof. . Other examples of suitable metal detergents include metal sulfonates, phenates, salicylates, phosphonates, thiophosphonates, and combinations thereof. The metal can be any metal suitable for making sulfonate, phenate, salicylate or phosphonate detergents. Non-limiting examples of suitable metals include alkali metals, alkaline metals and transition metals. In some embodiments, the metal is Ca, Mg, Ba, K, Na, Li, or the like.

The metal cleaner may be an overbased cleaner such as a low overbased (LOB), medium basic (MOB) or high overbased (HOB) cleaner.

The low overbased detergent may be an overbased salt having a base number (BN) of less than 100. In one embodiment, the low overbased salt may have a BN between about 5 and 50. In another embodiment, the low overbased salt may have a BN between about 10 and 30. In another embodiment, the low overbased salt may have a BN between about 15 and 20. The base value of the overbased detergent was measured in the presence of diluted oil, not oil-free.

Moderate overbased detergents can be overbased salts with a BN of about 100 to 250. In one embodiment, the BN of the medium overbased salt may be between about 100 and 200. In another embodiment, the BN of the medium overbased salt may be between about 125 and 175. The base value of the overbased detergent was measured in the presence of diluted oil, not oil-free.

High overbased detergents can be overbased salts with a BN greater than 250. In one embodiment, the highly overbased salt may have a BN between about 250 and 550. The base value of the overbased detergent was measured in the presence of diluted oil, not oil-free.

Exemplary metal cleaners that may be used in the lubricating oil composition include overbased calcium phenate. According to another embodiment, the lubricating oil composition includes LOB Ca sulfonate, HOB Ca salicylate and MOB Ca salicylate as detergents.

no regrets dispersant

Dispersants are additives whose main function is to reduce sludge deposits by keeping solid and liquid contaminants in suspension while passivating them and reducing engine deposits. For example, the dispersant keeps in a suspended state oil-insoluble substances resulting from oxidation during use of the lubricating oil composition to prevent sludge agglomeration and settling or deposition on metal parts.

Dispersants are generally "ashless", non-metallic organic materials that do not form substantially ash upon combustion in contrast to metal-containing and thus ash-forming materials. They contain long hydrocarbon chains with a polar head, the polarity being derived from the inclusion of at least one nitrogen, oxygen or phosphorus atom. Hydrocarbons are useful oleophilic groups having, for example, 40 to 500 carbon atoms. Thus, the ashless dispersant may include an oil soluble polymer backbone.

A preferred class of olefin polymers consists of polybutylenes, specifically polyisobutylenes (PIBs) or poly-n-butylenes, which may be prepared, for example, by polymerization of C4 refinery streams.

Dispersants include, for example, derivatives of long-chain hydrocarbon-substituted carboxylic acids, examples of which are derivatives of high molecular weight hydrocarbyl-substituted succinic acids. Noteworthy dispersants consist, for example, of hydrocarbon-substituted succinimides prepared by reacting said acids (or derivatives) with nitrogen-containing compounds, advantageously polyalkylene polyamines such as polyethylene polyamines. Commercially available polyisobutylene-based succinimide dispersants contain a polyisobutylene polymer having a number average molecular weight of 900 to 2500, functionalized with maleic anhydride, and derivatized with a polyamine having a molecular weight of 100 to 350.

Other suitable dispersants include succinic acid esters and ester-amides, Mannich bases, polyisobutylene succinic acid (PIBSA) and other related ingredients.

Succinic acid esters are formed by the condensation reaction between a hydrocarbon-substituted succinic anhydride and an alcohol or polyol. For example, condensation products of hydrocarbon-substituted succinic anhydrides and pentaerythritol are useful dispersants.

Succinic acid ester-amides are formed by the condensation reaction between a hydrocarbon-substituted succinic anhydride and an alkanol amine. For example, suitable alkanol amines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines and polyalkenylpolyamines such as polyethylene polyamines. One example is propoxylated hexamethylenediamine.

Mannich bases are prepared by the reaction of alkylphenols, formaldehyde and polyalkylene polyamines. The molecular weight of the alkylphenol may range from 800 to 2500.

Nitrogen-containing dispersants may be post-treated in conventional manner to improve properties by reaction with any of a variety of agents. Among these are boron compounds (eg boric acid) and cyclic carbonates (eg ethylene carbonate).

According to one exemplary embodiment, the lubricating oil composition includes borated succinimide and ethylene carbonate (EC) treated succinimide as an ashless dispersant.

friction reducer

The lubricating oil composition may include a friction reducing agent. A friction reducer is any substance capable of altering the coefficient of friction of a surface being lubricated by a lubricant or fluid containing such substance(s). Friction reducing agents include alkoxylated fatty amines, borated fatty epoxides, fatty phosphites, fatty epoxides, fatty amines, borated alkoxylated fatty amines, metal salts of fatty acids, fatty acid amides, glycerol esters, borated glycerol esters and fats. imidazoline included. As used herein, the term "fat" means a hydrocarbon chain, usually a straight chain hydrocarbon chain, having from 10 to 22 carbon atoms.

According to an exemplary embodiment, the lubricating oil composition includes an organomolybdenum compound, also referred to as a molybdenum-containing compound. The organomolybdenum compound contains at least molybdenum, carbon and hydrogen atoms, but may also contain sulfur, phosphorus, nitrogen and/or oxygen atoms. Suitable organomolybdenum compounds include various organic molybdenum complexes such as molybdenum dithiocarbamates, molybdenum dithiophosphates and molybdenum carboxylates, molybdenum esters, molybdenum amines, molybdenum amides, which can be used to dissolve molybdenum oxide or ammonium molybdate in fatty, It can be obtained by reaction with glycerides or fatty acids, or fatty acid derivatives such as esters, amines and amides. The term “fat” refers to a carbon chain, usually a straight chain, having from 10 to 22 carbon atoms.

Molybdate esters can be prepared by methods disclosed in US 4,889,647 and US 6,806,241 B2. A commercial example is R.T. MOLYVAN® 855 additive manufactured by Vanderbilt Company, Inc.

According to an exemplary embodiment, the lubricating oil composition includes molybdenum dithiocarbamate (MoDTC). Molybdenum dithiocarbamate (MoDTC) is an organic molybdenum compound represented by the following structure (1).

In the above structure, R ¹ , R ² , R ³ and R ⁴ independently of each other are linear or branched alkyl groups having 4 to 18 carbon atoms (eg, 8 to 13 carbon atoms).

The preparation of these compounds is described in the literature and in US Pat. Nos. 3,356,702 and 4,098,705, incorporated herein by reference. Commercial examples include R.T. MOLYVAN® 807, MOLYVAN® 822 and MOLYVAN® 2000 manufactured by Vanderbilt Company Inc., SAKURA-LUBE® 165 and SAKURA-LUBE® 515 manufactured by ADEKA CORPORATION and Naugalube® MolyFM manufactured by Chemtura Corporation.

Trinuclear molybdenum dialkyldithiocarbamates are also described in US Pat. Nos. 5,888,945 and 6,010,987, incorporated herein by reference, incorporated herein by reference. The trinuclear molybdenum compound preferably has the formula Mo ₃ S ₄ (dtc) ₄ , Mo ₃ S ₇ (dtc) ₄ and mixtures thereof, wherein dtc represents independently selected diorganodithiocarbamate ligands containing independently selected organic groups, wherein said ligands are all organic compounds of the compound ligand to render the compound soluble or dispersible in the lubricating oil composition. has a sufficient number of carbon atoms in the group.

According to another embodiment, the lubricating oil composition includes molybdenum dithiophosphate (MoDTP). MoDTP is an organic molybdenum compound represented by the following structure (2).

In the above structure, R ⁵ , R ⁶ , R ⁷ and R ⁸ independently of each other are linear or branched alkyl groups having 4 to 18 carbon atoms (eg, 8 to 13 carbon atoms).

Molybdenum carboxylates are described in US Patent RE 38,929 and US Patent No. 6,174,842, incorporated herein by reference. Molybdenum carboxylates can be derived from any fat-soluble carboxylic acid. Common carboxylic acids include naphthenic acid, 2-ethylhexanoic acid and linolenic acid. Commercial sources of carboxylates produced from these specific acids are MOLYBDENUM NAP-ALL, MOLYBDENUM HEX-CEM and MOLYBDENUM LIN-ALL, respectively. The manufacturer of this product is OMG OM Group.

Ammonium molybdate is optionally prepared from an acidic molybdenum source such as molybdenum trioxide, molybdic acid, ammonium molybdate and ammonium thiomolybdate in the presence of a sulfur source such as sulfur, inorganic sulfides, polysulfides and carbon disulfide as an oil soluble amine. It is prepared by reacting with Preferred amine compounds are polyamine dispersants commonly used in engine oil compositions. Examples of such dispersants are succinimides and Mannich type dispersants. References to these dispersants are provided in US Pat. Nos. 4,259,194, 4,259,195, 4,265,773, 4,265,843, 4,727,387, 4,283,295 and 4,285,822.

In one embodiment, the molybdenum amine is a molybdenum-succinimide complex. Suitable molybdenum-succinimide complexes are described, for example, in US Pat. No. 8,076,275. These complexes are prepared by a process comprising reacting an acidic molybdenum compound with an alkyl or alkenyl succinimide of a polyamine of structure (3), (4) or mixtures thereof.

In the above structure, R is a C ₂₄ to C ₃₅₀ (eg C ₇₀ to C ₁₂₈ ) alkyl or alkenyl group; R' is a straight or branched chain alkylene group of 2 to 3 carbon atoms; x is 1 to 11; y is 1 to 10;

The molybdenum compound used to prepare the molybdenum-succinimide complex compound is an acidic molybdenum compound or a salt of an acidic molybdenum compound. “Acidic” means that the molybdenum compound will react with a basic nitrogen compound as determined by ASTM D664 or D2896. Generally acidic molybdenum compounds are hexavalent. Representative examples of suitable molybdenum compounds are molybdenum trioxide, molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate and other molybdenum salts such as other alkali metal molybdates and hydrogen salts such as sodium hydrogen molybdate, MoOCl ₄ , MoO ₂ Br ₂ , Mo ₂ O ₃ Cl ₆ Include etc.

Succinimides that can be used to prepare molybdenum succinimide complexes are disclosed in numerous references and are well known in the art. Certain root types of succinimides and related substances encompassed by the technical term “succinimide” are taught in U.S. Pat. Nos. 3,172,892, 3,219,666 and 3,272,746. The term "succinimide" is also understood in the art to include a number of amide, imide and amidine species that may be formed. However, the predominant product is succinimide, and the term is generally accepted to mean the reaction product of an alkenyl substituted succinic acid or anhydride with a nitrogen-containing compound. Particularly preferred are polyisobutenyl succinic anhydrides of 70 to 128 carbon atoms and corresponding succinimides prepared from tetraethylene pentamine or triethylene tetramine or mixtures thereof.

In one embodiment, the molybdenum containing compound is sulfur free.

The molybdenum-succinimide complex may be post-treated with a sulfur source at a suitable pressure and temperature not exceeding 120° C. to provide a sulfurized molybdenum-succinimide complex. The sulfiding step may be performed for a time of about 0.5 to 5 hours (eg, 0.5 to 2 hours). Suitable sulfur sources include elemental sulfur, hydrogen sulfide, phosphorus pentasulfide, organic polysulfides of the formula R ₂ S _x , where R is hydrocarbyl (eg, C ₁ to C ₁₀ alkyl) and x is at least 3, C ₁ to C 10 C ₁₀ mercaptans, inorganic sulfides and polysulfides, thioacetamides and thioureas.

The molybdenum containing compound is used in an amount to provide molybdenum to the lubricating oil composition in an amount of 50 ppm to 1200 ppm, 50 ppm to 1000 ppm, 50 ppm to 800 ppm, 50 ppm to 600 ppm, 50 ppm to 400 ppm or 50 ppm to 200 ppm.

In some embodiments, the lubricating oil composition is substantially free of molybdenum containing compounds.

During use of the lubricating oil composition in an engine, the molybdenum-containing compound can promote the formation of a molybdenum-containing lubricating film on the metal surfaces of the engine.

According to an exemplary embodiment, the lubricating oil composition includes MoDTC in an amount ranging from 0.6 to 0.8% by weight based on the total weight of the lubricating composition.

corrosion inhibitor

Corrosion inhibitors protect lubricated metal surfaces from chemical attack by water or other contaminants. Suitable corrosion inhibitors include polyoxyalkylene polyols and their esters, polyoxyalkylene phenols, thiadiazoles and anionic alkyl sulfonic acids.

pour point depressant

Pour point depressants lower the minimum temperature at which a fluid can flow or pour. Suitable pour point depressants include C8 to C18 dialkyl fumarate/vinyl acetate copolymers, polyalkylmethacrylates, and the like.

anti-foaming agent

Anti-foaming agents retard stable foam formation. Examples of suitable antifoaming agents include polysiloxanes, polyacrylates, and the like.

Manufacturing process of lubricating oil composition

The lubricating oil compositions disclosed herein may be prepared by any method known to those skilled in the art for making lubricating oils. Viscosity modifiers and other additives may be added separately or simultaneously to the base oil. In some embodiments, the additives are individually added to the base oil in one or more additions to the base oil and the additions may be in any order. In another embodiment, additives are simultaneously added to the base oil, optionally in the form of an additive concentrate. According to another embodiment, some of the additives are added individually and some are added in the form of an additive concentrate. In some embodiments, solubilization of the additive in the base oil may be assisted by heating the mixture to a temperature of about 25 to 200°C, about 50 to 150°C, or about 75 to about 125°C.

Any mixing or dispersing equipment known to those skilled in the art may be used for blending, mixing or solubilizing the ingredients to form the lubricating oil composition. Blending, mixing or solubilization may be performed using a blender, stirrer, disperser, mixer (e.g. planetary mixer and double planetary mixer), homogenizer (e.g. Gaulin homogenizer and Rannie homogenizer), mill (e.g. colloid mill, ball mill, sand mill) or any other mixing or dispersing equipment known in the art.

Application of lubricating oil composition

The lubricating oil compositions disclosed herein may be suitable for use as motor oil (engine oil or crankcase oil) in spark-ignition internal combustion engines. The lubricating oil composition is preferably used for engines or crankcases requiring a viscosity grade of SAE 0W-20, 0W-16 or 0W-12. For example, the lubricating oil composition may be used to lubricate an engine comprising a valve train system with roller follower rocker arms.

The following inventive examples are presented to illustrate embodiments of the invention, but are not intended to limit the invention to the specific embodiments presented. Unless otherwise indicated, all parts and percentages are by weight. All numerical values are approximate. When numerical ranges are given, it is to be understood that embodiments outside the stated ranges may still fall within the scope of the invention. Specific details set forth in each embodiment should not be construed as essential features of the present invention.

Example

Reference formulations for all inventive examples and comparative examples were prepared by blending together the following ingredients provided in weight percent based on the total weight of the lubricating oil composition.

(a) 1% by weight boric acid succinimide;

(b) succinimide treated with 3% by weight ethylene carbonate (EC);

(c) 0.34% by weight auxiliary ZnDTP;

(d) 0.72% by weight basic ZnDTP;

(e) 0.5% by weight LOB Ca sulfonate;

(f) 0.77% by weight HOB Ca salicylate;

(g) 0.5 wt % MOB Ca salicylate;

(h) 2% by weight amine antioxidant;

(i) 0.004% by weight anti-foaming agent and

(h) Diluted oil.

The weight percentages of components (a)-(h) are not based on active ingredient as they include all diluents and/or solvents that may be present.

All examples of the present invention and comparative examples are listed in Tables 2 and 3 viscosity modifier(s) (comb PMA and/or OCP) to top-treat the baseline formulation to obtain a lubricating oil composition having a SAE 0W-20 viscosity grade. Example compositions of the present invention are provided in Table 2, and comparative example compositions are provided in Table 3.

inventive Example Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 ¹ PMA 7 6 4 7 6 4 7 6 4 ² OCP1 One. 1.85 3.5 - - - - - - ³ OCP2 - - - 1.1 2. 3.8 - - - ⁴ OCP3 - - - - - - 0.95 1.85 3.4 KV 100℃ 7.45 7.46 7.53 7.50 7.53 7.68 7.50 7.59 7.76 KV 40℃ 29.59 30.89 33.47 29.85 31.31 34.16 29.84 31.80 34.44 VI 235 222 203 235 222 204 235 221 206 CCS 3640 3768 3833 3635 3753 3816 3675 3713 3764 HTHS150 2.58 2.56 2.55 2.58 2.57 2.56 2.57 2.57 2.55 HTHS100 4.96 5.02 5.16 4.96 5.03 5.15 4.92 5.01 5.10 HTHS80 7.38 7.55 7.79 7.38 7.51 7.74 7.36 7.50 7.70

comparative example Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 ¹ PMA 8.1 - - - ² OCP1 - 7 - - ³ OCP2 - - 7.5 - ⁴ OCP3 - - - 6.8 KV 100℃ 7.41 7.90 8.19 8.38 KV 40℃ 28.29 39.78 41.42 42.33 VI 248 175 177 179 CCS 3610 4288 4162 4070 HTHS150 2.58 2.58 2.59 2.59 HTHS100 4.89 5.52 5.02 5.52 HTHS80 7.19 8.28 7.55 8.30

¹ PMA (Viscoplex®3-201) is a compound comprising 19% by weight non-dispersible comb-type polymethacrylate with Mw of 420,000 g/mol and Mw/Mn of 5.92.

² OCP1 is a concentrate containing 10% by weight of a non-dispersible ethylene-propylene copolymer having an ethylene content of 57% by weight, Mw of about 100,000, Mn of about 40,000, and SSI of 24.

³ OCP2 is a concentrate containing 8.75 wt% of a non-dispersible ethylene-propylene copolymer having an ethylene content of 57 wt%, Mw of 112,000, Mn of 49,000, and SSI of 35.

⁴ OCP3 is a concentrate containing 8.8 wt% of a non-dispersible ethylene-propylene copolymer having an ethylene content of 49 wt%, Mw of 146,000, Mn of 84,000, and SSI of 50.

toyota 2ZR -Fuel economy test of FE motor engine

The lubricating oil compositions of Examples 1 to 9 and Comparative Examples 1 to 4 of the present invention were tested for fuel economy performance in a gasoline motor engine test. The engine was a Toyota 2ZR-FE 1.8L in-line four-cylinder arrangement. A torque meter was placed between the motor and the engine's crankshaft and measured the percent torque change between the reference and candidate lubricant compositions. Percent (%) torque change was measured at oil temperatures of 60°C, 80°C and 100°C and engine speeds of 400 rpm, 550 rpm, 750 rpm, 1000 rpm, 1500 rpm and 2000 rpm. A lower percent torque change (i.e. more negative) reflects better fuel economy. The configuration and test conditions of the motor engine friction torque test are described in detail in SAE Paper 2013-01-2606. Table 4 provides average % torque at oil temperatures of 60°C, 80°C and 100°C for inventive example compositions, and Table 5 provides average % torque at oil temperatures of 60°C, 80°C and 100°C for comparative example compositions. Provides the average % torque change over temperature.

Electric Engine Friction Torque - Invention Example Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 60℃
rpm -2.99 -3.16 -2.77 -2.71 -3.08 -2.75 -2.99 -2.91 -2.61 80℃ -1.93 -1.89 -1.72 -1.29 -1.83 -1.84 -1.45 -1.63 -1.53 100℃ -1.51 -1.72 -1.60 -1.41 -1.73 -1.80 -1.31 -1.59 -1.51 Sum -2.14 -2.26 -2.03 -1.80 -2.21 -2.13 -1.92 -2.04 -1.88

Electric Engine Friction Torque - Comparison Example Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 60℃
rpm -2.95 -2.35 -2.08 -1.69 80℃ -1.51 -1.54 -1.22 -1.10 100℃ -1.41 -1.69 -1.48 -1.39 Sum -1.96 -1.86 -1.59 -1.39

Claims (23)

In the lubricating oil composition,
a) a large amount of oil of lubricating viscosity;
b) non-dispersible comb polymethacrylate (PMA); and
c) a non-dispersible ethylenic olefin copolymer;
The lubricating oil composition has a kinematic viscosity of less than 9.3 mm ² /s at 100 ^° C. The lubricating oil composition according to claim 1, wherein the non-dispersible comb PMA has a weight average molecular weight (Mw) of 390,000 to 460,000 g/mol. The lubricating oil composition according to claim 1, wherein the non-dispersible comb PMA has a shear stability index (SSI) of 0.3 to 0.8. The lubricating oil composition according to claim 1, wherein the non-dispersible comb PMA is present in an amount of 0.4 to 2.0% by weight based on the total weight of the lubricating oil composition. The lubricating oil composition according to claim 1, wherein the non-dispersible ethylene-based olefin copolymer has a weight average molecular weight (Mw) of 90,000 to 160,000 g/mol. The lubricating oil composition according to claim 1, wherein the non-dispersible ethylenic olefin copolymer has a shear stability index (SSI) of 10 to 70. The lubricating oil composition according to claim 1, wherein the non-dispersible ethylenic olefin copolymer is present in an amount of 0.08 to 0.4% by weight based on the total weight of the lubricating oil composition. The lubricating oil composition according to claim 1, wherein the non-dispersible ethylene-based olefin copolymer has a total ethylene content of 45 to 60% by weight based on the total weight of the non-dispersible ethylene-based olefin copolymer. The lubricating oil composition according to claim 1, wherein the non-dispersible ethylene-based olefin copolymer is an ethylene propylene copolymer. The method of claim 1, based on the total weight of the lubricating oil composition, the non-dispersible comb PMA is present in an amount of 0.76 to 1.33% by weight and the amount of the non-dispersible ethylenic olefin copolymer is present in an amount of 0.08 to 0.4% by weight. , a lubricating oil composition. The lubricating oil composition according to claim 1, wherein the non-dispersible comb PMA and the non-dispersible ethylenic olefin copolymer are present in a total amount of 0.4 to 4% by weight based on the total weight of the lubricating oil composition. The lubricating oil composition according to claim 1, wherein the oil of lubricating viscosity is an API Group III base oil. The lubricating oil composition according to claim 1, wherein the composition further comprises a molybdenum compound. The lubricating oil composition according to claim 13, wherein the molybdenum compound is molybdenum dithiocarbamate (MoDTC). 14. The lubricating oil composition of claim 13, wherein the molybdenum compound provides an amount of molybdenum in the lubricating oil composition in the range of 50 to 1200 ppm. The lubricating oil composition according to claim 1, wherein the lubricating oil composition has a viscosity grade of SAE 0W-20, 0W-16 or 0W-12. The lubricating oil composition according to claim 1, wherein the lubricating oil composition has a High Temperature High Shear (HTHS) viscosity of 2.55 to less than 2.9 cP at 15 °C. The lubricating oil composition according to claim 1, wherein the lubricating oil composition has a viscosity index of 200 to 240. In a method for reducing wear of an internal combustion engine comprising lubricating the engine with a lubricating oil composition having a kinematic viscosity of less than 9.3 mm ² /s at 100 ° C, the lubricating oil composition comprises:
a) a large amount of oil of lubricating viscosity;
b) non-dispersible comb polymethacrylate (PMA); and
c) A method for reducing wear in an internal combustion engine comprising a non-dispersible ethylene-based olefin copolymer. 20. The method of claim 19, wherein the engine includes roller arms and rocker arms. In the lubricating oil composition,
a) a large amount of oil of lubricating viscosity;
b) a non-dispersible comb polymethacrylate (PMA) in an amount of from 0.4 to 1.9% by weight, based on the total weight of the lubricating oil composition; and
c) a non-dispersible ethylenic olefin copolymer in an amount of from 0.01 to 0.36 weight percent, based on the total weight of the lubricating oil composition. In a method for reducing wear of an internal combustion engine comprising lubricating the engine with a lubricating oil composition, the lubricating oil composition comprising:
a) a large amount of oil of lubricating viscosity;
b) a non-dispersible comb polymethacrylate (PMA) in an amount of from 0.4 to 1.9% by weight, based on the total weight of the lubricating oil composition; and
c) the non-dispersible ethylenic olefin copolymer in an amount of from 0.01 to 0.36% by weight, based on the total weight of the lubricating oil composition. 23. The method of claim 22, wherein the engine includes a roller follower rocker arm.