JP2024015129A - Lubricating oil composition providing wear protection at low viscosity - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lubricating oil comprising the following.

SOLUTION: The lubricating oil comprises: (a) a major amount of an oil of lubricating viscosity; (b) a dispersant polymethacrylate (DPMA) VII; (c) a non-dispersant ethylene-based olefin copolymer viscosity index improver; and (d) a magnesium-containing detergent; where the lubricating oil composition is substantially free of molybdenum-containing element. Also provided is a method for improving friction and reducing wear in an internal combustion engine using the engine lubricating oil composition.

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

FIELD OF THE INVENTION The disclosed technology relates to lubricants for internal combustion engines, particularly lubricants for spark ignition engines.

BACKGROUND OF THE INVENTION Engine oils are blended with various additives to meet various performance requirements. One well-known method of improving fuel economy is to reduce the viscosity of lubricating oils. However, this approach is currently reaching the limits of current equipment capabilities and specifications. It is well known that at a given viscosity, the addition of organic or organometallic friction modifiers reduces the surface friction of a lubricating oil, allowing for better fuel efficiency. However, these additives often have deleterious effects such as increased deposit formation, sealing effects, or compete with anti-wear components in limited locations on the surface, thereby reducing wear resistance. Film formation becomes impossible and wear increases.

To improve the fuel economy performance of lubricating oils, it is usually best to reduce the viscosity (i.e., high temperature high shear (HTHS) viscosity). HTHS is a measure of lubricant viscosity under harsh engine conditions. Under high temperature and high stress conditions, degradation of the viscosity index improver can occur. When this occurs, oil viscosity decreases and engine wear can increase.

Therefore, despite advances in lubricant formulation technology, there remains a need for engine oil lubricants that effectively improve fuel economy while providing superior antiwear performance.

Related art WO2015041891 discloses a method for reducing aqueous phase separation of an emulsion comprising an ethanol-based fuel and a lubricating oil comprising a molybdenum ester amide complex and a dispersant polyalkyl (meth)acrylate.

US Pat. No. 6,303,548 discloses a SAE 0W-40 lubricant comprising a mixture of base oil and a polymethacrylate and an olefin copolymer or hydrogenated diene VI modifier.

WO2014136643 describes a polymethacrylate having a mass average molecular weight of 30,000 to 600,000, and (B) a shear stability index (SSI) of 40 or less and a 95% loss as measured by differential thermal analysis to a lubricant base oil. Olefin copolymers having temperatures below 500°C are disclosed.

US20090270294 discloses a mixture of at least two polymers with a difference in permanent shear stability index (PSSI).

EP1436369 discloses biodegradable lubricants that are at least 60% biodegradable and have a gelling index of about 12 or less and are formulated using transesterified triglyceride base oils together with synthetic esters. I can do it. Combinations of ester viscosity index improvers and olefin copolymer viscosity index improvers can also be added.

US20170088789 describes a lubricant composition comprising an ethylene/olefin copolymer having a weight average molecular weight of about 10,000 to about 250,000; the arm is attached to a polyvalent organic moiety).

SUMMARY OF THE INVENTION In one aspect, the present disclosure provides lubricating oil compositions that:
A lubricating oil composition having an HTHS viscosity ranging from about 1.3 to about 2.9 cP at 150°C,
a) a predominant amount of oil of lubricating viscosity with a kinematic viscosity at 100° C. in the range 1.5-6.0 mm ² /s;
b) dispersant polymethacrylate (DPMA) VII with Mw from 200,000 g/mol to 450,000 g/mol;
c) a non-dispersible ethylene-based olefin copolymer viscosity index improver having a Mw of 50,000 g/mol to 150,000 g/mol and a total ethylene content of about 30% to about 70% by weight;
d) about 200 to about 1000 ppm magnesium from a magnesium-containing detergent;
wherein the lubricating oil composition is substantially free of molybdenum-containing elements.

In another aspect, the disclosure provides a method of:
A method of improving friction and reducing wear in an internal combustion engine, the method comprising: lubricating the engine with a lubricating oil composition having an HTHS viscosity in the range of about 1.3 to about 2.9 cP at 150°C. The method includes:
a) a predominant amount of oil of lubricating viscosity with a kinematic viscosity at 100° C. in the range 1.5-6.0 mm ² /s;
b) dispersant polymethacrylate (DPMA) VII with Mw from 200,000 g/mol to 450,000 g/mol;
c) a non-dispersible ethylene-based olefin copolymer viscosity index improver having a Mw of 50,000 g/mol to 150,000 g/mol and a total ethylene content of about 30% to about 70% by weight;
d) about 200 to about 1000 ppm magnesium from a magnesium-containing detergent;
wherein the lubricating oil composition is substantially free of molybdenum-containing elements.

DETAILED DESCRIPTION OF THE INVENTION To facilitate an understanding of the subject matter disclosed herein, certain terms, abbreviations, or other shorthand notations used herein are defined below. Undefined terms, abbreviations, or shorthand expressions are understood to have their ordinary meanings as used by those skilled in the art upon the filing of this application.

DEFINITIONS As used herein, the following terms and expressions have the meanings indicated below when and where they are used.

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

"Minor amount" means less than 50% by weight of the composition, expressed with respect to the specified additive and with respect to the total mass of all additives present in the composition; Considered as an active ingredient.

"Active ingredient" or "active substance" refers to an additive material that is not a diluent or solvent.

All percentages reported are weight percent on an active ingredient basis (i.e., without reference to 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.

High temperature high shear (HTHS) viscosity at 150° C. was measured according to ASTM D4683.

Kinematic viscosity at 100° C. (KV ₁₀₀ ) was determined according to ASTM D445.

Metal - The term "metal" refers to an alkali metal, an alkaline earth metal, or a mixture thereof.

Throughout the specification and claims the expression oil-soluble or dispersible is used. Oil-soluble or dispersible means that it can be incorporated by dissolving, dispersing, or suspending in an oil of lubricating viscosity in the amount necessary to provide the desired level of activity or performance. Typically, this means that at least about 0.001% by weight of the material can be incorporated into the lubricating oil composition. For a detailed explanation of oil solubility and dispersibility, particularly the term "stably dispersible," see U.S. Pat. No. 4,320,019, expressly incorporated herein by reference for related teachings. Please refer.

The term "sulfated ash" as used herein refers to non-combustible residues resulting from detergents and metal additives in lubricating oils. Sulfated ash can be measured using ASTM Test D874.

As used herein, the term "total base number" or "TBN" refers to the amount of base equivalent to milligrams of KOH in one gram of sample. Therefore, the higher the TBN value, the more alkaline products and therefore the higher the alkalinity. TBN was determined using the ASTM D2896 test.

Boron, calcium, magnesium, molybdenum, phosphorus, sulfur, and zinc content were determined according to ASTM D5185.

Nitrogen content was determined according to ASTM D4629.

All ASTM standards referenced herein are the current versions as of the filing date of this application.

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

Normal alpha olefin - The term "normal alpha olefin" refers to an olefin that is a straight chain, unbranched hydrocarbon in which a carbon-carbon double bond is present in the alpha or primary position of the hydrocarbon chain.

Isomerized normal alpha olefin. As used herein, the term "isomerized normal alpha olefin" refers to an alpha olefin that has been subjected to isomerization conditions that result in a change in the distribution of olefin species present and/or the introduction of branching along the alkyl chain. . The isomerized olefin product isomerizes linear alpha olefins containing about 10 to about 40 carbon atoms, preferably about 20 to about 28 carbon atoms, preferably about 20 to about 24 carbon atoms. It can be obtained by

C _10-40 Normal Alpha Olefins - This term defines a fraction of normal alpha olefins from which fewer than 10 carbons have been removed by distillation or other fractionation methods.

All percentages are by weight unless otherwise specified.

While this disclosure is susceptible to various modifications and alternative forms, specific embodiments thereof are described herein in detail. However, this description of particular embodiments is not intended to limit the disclosure to the particular forms disclosed, but rather to the spirit and scope of the disclosure as defined by the appended claims. It is to be understood that the intent is to cover all modifications, equivalents, and alternatives within the scope.

Not all activities described in the general description or examples may be required, some specific activities may not be required, and one or more activities may be performed in addition to those described. In some cases. Additionally, the order in which activities are listed is not necessarily the order in which they are performed.

Benefits, other advantages, and solutions to problems are described herein with respect to particular embodiments. However, any benefit, advantage, solution to a problem, and any feature that may give rise to or make any benefit, advantage, or solution more prominent is material to any or all claims. shall not be construed as necessary or mandatory features.

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

As used herein, "comprising," "comprising," "comprising," "included," "having," "having," or any other variation thereof is a non-exclusive term. Inclusions are intended to be included. For example, a process, method, article, or apparatus that includes a list of features is not necessarily limited to those features and may include other features not explicitly listed or specific to such process, method, article, or apparatus. may include other features. Further, unless explicitly stated to the contrary, "or" refers to inclusive disjunctions rather than exclusive disjunctions. For example, condition A or B is satisfied by either: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

The use of "an" or "a" is used to describe the elements and components described herein. This is done solely for convenience and to give a general sense of the scope of the embodiments of this disclosure. This description should be read to include one or at least one, and the singular also includes the plural and vice versa, unless it is clear that it is meant otherwise. The term "average" when referring to a value is intended to mean the average, geometric mean, or median. Group numbers corresponding to columns in the Periodic Table of Elements use the “New Notation” conventions, as found in the CRC Handbook of Chemistry and Physics, 81st Edition (2000-2001). do.

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 not intended to be limiting. To the extent not described herein, many details regarding specific materials and processing practices are conventional and may be found in textbooks and other sources within the lubricant and oil and gas industries.

This specification and description is intended to serve as an exhaustive and comprehensive description of all elements and features of formulations, compositions, devices and systems employing the structures or methods described herein. do not have. Separate embodiments may also be provided in combination in a single embodiment, and conversely, various features that are, for brevity, described in the context of a single embodiment, may be provided separately or in combination. May be provided in sub-combinations. Further, references to values stated in ranges include each and every value within that range. Many other embodiments will be apparent to those skilled in the art only after reading this specification. Other embodiments may be used and derived from this disclosure, so that structural substitutions, logical substitutions, or other changes may be made without departing from the scope of this disclosure. Accordingly, this disclosure should be considered illustrative rather than restrictive.

Oil of lubricating viscosity/base oil component Oil of lubricating viscosity (sometimes referred to as "base stock" or "base oil") is the main liquid component of a lubricant, in which additives or and other oils are blended, for example, to form the final lubricant (or lubricant composition). Base oils are useful for making concentrates, as well as for making lubricating oil compositions therefrom, and can be selected from natural and synthetic lubricating oils and combinations thereof.

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

Synthetic lubricating oils include: hydrocarbon oils such as polymerized and copolymerized olefins (e.g., polybutylene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylene, poly(1-hexene), poly(1-hexene), octene), poly(1-decene); alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene); polyphenols (e.g., biphenyl, terphenyl, alkylated polyphenols); and alkylation Diphenyl ethers and alkylated diphenyl sulfides, and derivatives, analogs and homologs thereof.

Another suitable class of synthetic lubricating oils includes dicarboxylic acids (e.g., malonic acid, alkylmalonic acid, alkenylmalonic acid, succinic acid, alkylsuccinic acid and alkenylsuccinic acid, maleic acid, fumaric acid, azelaic acid, suberic acid, sebacic acid, adipic acid, linoleic acid dimer, phthalic acid) and various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene) glycol) ester. Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, dioctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, These include dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid. .

Esters useful as synthetic oils also include esters made from _C5 to _C12 monocarboxylic acids and polyols, and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol. included.
In one embodiment, the ester base oil is present at about 1-10% by weight, based on the total weight of the lubricating oil composition. In other embodiments, the ester base oil is about 1-8%, about 1-6%, about 1-5%, about 1-4%, about Present at 1-3% by weight, about 1-2% by weight.

The base oil may be derived from Fischer-Tropsch synthetic hydrocarbons. Fischer-Tropsch synthetic hydrocarbons are made from synthesis gas containing _H2 and CO using a Fischer-Tropsch catalyst. Such hydrocarbons typically require further processing in order to be useful as base oils. For example, the hydrocarbons may be hydroisomerized; hydrocracking and hydroisomerizing; dewaxing; or hydroisomerizing and dewaxing using processes known to those skilled in the art.

Unrefined, refined and rerefined oils can be used in the lubricating oil compositions of the present invention. Unrefined oils are oils obtained directly from natural or synthetic sources without further purification treatment. For example, shale oil obtained directly from retorting operations, petroleum oil obtained directly from distillation, or ester oil obtained directly from an esterification process and used without further processing would be unrefined oils. Refined oils are similar to unrefined oils, except that they have been further processed with one or more refining steps to improve one or more properties. Many such purification techniques are known to those skilled in the art, such as distillation, solvent extraction, acid or base extraction, filtration and osmosis. Rerefined oils are obtained by processes similar to those used to obtain refined oils that are applied to already used refined oils. Such rerefined oils are also known as reclaimed or reprocessed oils and are often further processed by techniques for the approval of used additives and oil cracking products.

Accordingly, the base oil that may be used to make the present lubricating oil compositions may be from any of the Groups IV base oils specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines (API Publication 1509). You can choose. Such base oil groups are summarized in Table 1 below.

Base oils suitable for use herein are a variety of API Group II, Group III, Group IV, and Group V oils and combinations thereof, with varying volatility, stability, viscosity, and Group III to Group V oils are preferred because of their very high cleanliness characteristics.

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

The base oil can be selected from either synthetic or natural oils commonly used as crankcase lubricants for spark ignition internal combustion engines. Base oils typically have kinematic viscosities in the range of 1.5 to 6 mm ² /s at 100°C. When the kinematic viscosity at 100° C. of the lubricating base oil exceeds 6 mm ² /s, low-temperature viscosity characteristics may deteriorate and sufficient fuel efficiency may not be obtained. If the kinematic viscosity is 1.5 mm ² /s or less, the formation of an oil film at the lubricated location will be insufficient; therefore, the lubricity may be poor and the evaporation loss of the lubricating oil composition may be large.

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, thermal and oxidative stability, and prevention of volatilization will decrease, but also the coefficient of friction will tend to increase, and the wear resistance will also tend to decrease. .

In one embodiment, the lubricating oil composition is a multigrade oil. In another embodiment, the multigrade oil is a viscosity grade SAE 0W-XX oil, where XX is any of 8, 10, 12, 16, and 20.

The lubricating oil composition has a temperature of 2.9 cP or less (e.g., 1.0 to 2.9 cP, or 1.3 to 2.9 cP), 2.6 cP or less (e.g., 1.0 to 2.6 cP, or 1.3 to 2.6 cP), 2.3 cP or less (for example, 1.0 to 2.3 cP, or 1.3 to 2.3 cP), such as 2.0 cP or less (for example, 1.0 to 2.0 cP, or 1.3 to 2.3 cP), or 1.7 cP or less (eg, 1.0 to 1.7 cP, or 1.3 to 1.7 cP).

The lubricating oil composition has 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), It has a viscosity index of at least 190 (eg, 190-400, or 190-250), or at least 200 (eg, 200-400, or 200-250). If the viscosity index of the lubricating oil composition is less than 135, it may be difficult to improve fuel efficiency while maintaining HTHS viscosity at 150°C. If the viscosity index of the lubricating oil composition exceeds 400, the evaporability may decrease, and disadvantages may occur due to insufficient matching with the sealing material and insufficient solubility of additives.

The lubricating oil composition has a viscosity in the range of 3 to 12 mm ² /s (e.g., 3 to 8.2 mm ² /s, 3.5 to 8.2 mm ² /s, or 4 to 8.2 mm ² /s) at 100°C. It has a kinematic viscosity of

Generally, the level of sulfur in the lubricating oil compositions of the present invention will be about 0.7% by weight or less, such as from about 0.01% to about 0.70% by weight, based on the total weight of the lubricating oil composition. 0.01 to 0.6% by weight, 0.01 to 0.5% by weight, 0.01 to 0.4% by weight, 0.01 to 0.3% by weight, 0.01 to 0.2% by weight, It is 0.01% to 0.10% by weight. In one embodiment, the level of sulfur in the lubricating oil compositions of the present invention is about 0.60% by weight or less, about 0.50% by weight or less, about 0.40% by weight, based on the total weight of the lubricating oil composition. % or less, about 0.30% by weight or less, about 0.20% by weight or less, about 0.10% by weight or less.

In one embodiment, the level of phosphorus in the lubricating oil compositions of the present invention is about 0.12% by weight or less, such as from about 0.01% to about 0.12% by weight, based on the total weight of the lubricating oil composition. Weight%. In one embodiment, the level of phosphorus in the lubricating oil compositions of the present invention is about 0.11% by weight or less, such as from about 0.01% to about 0.11% by weight, based on the total weight of the lubricating oil composition. Weight%. In one embodiment, the level of phosphorus in the lubricating oil compositions of the present invention is about 0.10% by weight or less, such as from about 0.01% to about 0.10% by weight, based on the total weight of the lubricating oil composition. Weight%. In one embodiment, the level of phosphorus in the lubricating oil compositions of the present invention is about 0.09% by weight or less, such as from about 0.01% to about 0.09% by weight, based on the total weight of the lubricating oil composition. Weight%. In one embodiment, the level of phosphorus in the lubricating oil compositions of the present invention is about 0.08% by weight or less, such as from about 0.01% to about 0.08% by weight, based on the total weight of the lubricating oil composition. Weight%. In one embodiment, the level of phosphorus in the lubricating oil compositions of the present invention is about 0.07% by weight or less, such as from about 0.01% to about 0.07% by weight, based on the total weight of the lubricating oil composition. Weight%. In one embodiment, the level of phosphorus in the lubricating oil composition of the present invention is about 0.05% by weight or less, such as from about 0.01% to about 0.05% by weight, based on the total weight of the lubricating oil composition. Weight%.

In one embodiment, the level of sulfated ash produced by the lubricating oil compositions of the present invention is about 1.60% by weight or less, as measured by ASTM D874, for example, about 0.0% by weight, as measured by ASTM D874. The level of sulfated ash is from 10 to about 1.60% by weight. In one embodiment, the level of sulfated ash produced by the lubricating oil compositions of the present invention is about 1.00% by weight or less, as measured by ASTM D874, for example, about 0.0% by weight, as measured by ASTM D874. The level of sulfated ash is from 10 to about 1.00% by weight. In one embodiment, the level of sulfated ash produced by the lubricating oil compositions of the present invention is about 0.80% by weight or less, as measured by ASTM D874, e.g., sulfated ash, as measured by ASTM D874. The ash level is about 0.10 to about 0.80% by weight. In one embodiment, the level of sulfated ash produced by the lubricating oil composition of the present invention is about 0.60% by weight or less, as measured by ASTM D874. For example, the level of sulfated ash is about 0.10 to about 0.60% by weight as measured by ASTM D874.

Suitably, the lubricating oil compositions of the present invention have a total base number (TBN) of 4 to 15 mg KOH/g (e.g., 5 to 12 mg KOH/g, 6 to 12 mg KOH/g, or 8 to 12 mg KOH/g). ).

Viscosity Modifiers Viscosity modifiers (VM) or viscosity index improvers (VII) can be used in lubricants to provide high and low temperature operability. A VM can be used to provide that sole function or it can be multi-functional. Multifunctional viscosity modifiers also provide additional functionality for dispersant functionality. Examples of viscosity modifiers and dispersants are polymethacrylates, polyacrylates, polyolefins, styrene-maleate copolymers, and similar polymeric materials including homopolymers, copolymers and graft copolymers.

In one embodiment, VII can be present in the lubricating oil composition at 0.001 to 10% by weight, based on the lubricating oil composition. In other embodiments, VII is 0.01 to 8%, 0.01 to 5%, 0.01 to 4%, 0.01 to 3%, 0% by weight, based on the lubricating oil composition. It can be present in the lubricating oil composition in amounts of .01 to 2.5%, 0.1 to 2.5% by weight.

Particularly useful in this disclosure is the combination of a dispersant polymethacrylate VII and an ethylenic non-dispersant VII.

Dispersant polymethacrylate (DPMA) VII
In one embodiment, the dispersant PMA is 200,000 g/mol to 450,000 g/mol, 200,000 g/mol to 400,000 g/mol, 200,000 g/mol to 350,000 g/mol, or 200,000 g/mol /mol to 300,000 g/mol.

The dispersant polymethacrylate (DPMA) viscosity index modifier used in the present invention can be described as follows, the disclosure of which is described in WO 2013/182581, which is incorporated herein. Compounds within this definition include Viscoplex® viscosity index improvers 6-054, 6-565, 6-850, 6-950 and 6-954, all available from Evonik RohMax Additives GmbH of Darmstadt, Germany. will be included.

Polyalkyl (meth)acrylates contain the following monomer units:
(a) 0 to 40% by weight of one or more ethylenically unsaturated ester compounds of formula (I):

Here, R is hydrogen or methyl, and R ¹ is a saturated or unsaturated straight-chain or branched alkyl group having 1 to 5 carbon atoms or a saturated or unsaturated cycloalkyl group having 3 to 5 carbon atoms. and R ² and R ³ are each independently hydrogen or of the formula -COOR', where R' is hydrogen or a saturated or unsaturated straight-chain or branched alkyl group having 1 to 5 carbon atoms. ;
(b) 10 to 98% by weight, preferably 20 to 95% by weight of one or more ethylenically unsaturated ester compounds of formula (II)

where R is hydrogen or methyl, ^R4 is a saturated or unsaturated straight-chain or branched alkyl group with 6 to 15 carbon atoms, or a saturated or unsaturated cycloalkyl group with 6 to 15 carbon atoms; , R ⁵ and R ⁶ are each independently hydrogen or a group of the formula -COOR", where R" is hydrogen or a saturated or unsaturated straight or branched alkyl group having 6 to 15 carbon atoms. is the basis);
(c) 0 to 30% by weight, preferably 5 to 20% by weight of one or more ethylenically unsaturated ester compounds of formula (III):

Here, R is hydrogen or methyl, R ⁷ is a saturated or unsaturated straight chain or branched alkyl group having 16 to 40 carbon atoms, preferably 16 to 30 carbon atoms, or a C 16 to 40, preferably 16 to 30 cycloalkyl group, R ⁸ and R ⁹ are each independently hydrogen or a group of the formula -COOR'', where R'' is hydrogen or has 16 to 40, preferably 16 to 30 carbon atoms. a saturated or unsaturated straight-chain or branched alkyl group having;
(d) 0 to 30% by weight of vinyl monomer;
(e) 2-10% by weight of at least one N-dispersant monomer.

The DPMA used in the present invention comprises about 1-10% by weight of methyl methacrylate monomer, about 0.5-3% by weight of N-vinylpyrrolidone as nitrogen-containing monomer, and the balance longer chain alkyl methacrylate monomer, especially It is believed to contain lauryl methacrylate and has a MW of 200,000 to 250,000. It has an SSI of about 40 to about 50.

Non-dispersible ethylene olefin copolymer (OCP) VII
In one embodiment, the non-dispersible ethylene-based olefin copolymer VII is from 50,000 g/mol to about 150,000 g/mol, from about 60,000 g/mol to about 120,000 g/mol, or from about 70,000 g/mol to It has a weight average molecular weight of approximately 110,000 g/mol.

The ethylene-based viscosity index modifier used in the present invention can be described as follows and is described in US2013203640, the disclosure of which is incorporated herein.

In one embodiment, the ethylene VII is an ethylene propylene copolymer.

In one embodiment, the polymer composition typically comprises about 30% to about 70% by weight of the first ethylene-α-olefin copolymer (a) and about 70% to about 30% by weight of the second copolymer (a). of ethylene-α-olefin copolymer (b) is included in the composition based on the total amount of (a) and (b). In another embodiment, the polymer composition typically comprises from about 40% to about 60% by weight of the first ethylene-α-olefin copolymer (a) and from about 60% to about 40% by weight of the first ethylene-α-olefin copolymer (a). The ethylene-α-olefin copolymer (b) of No. 2 is included in the composition based on the total amount of (a) and (b). In certain embodiments, the polymer composition comprises about 50 to about 54 weight percent of the first ethylene-α-olefin copolymer (a) and about 46 to about 50 weight percent of the second ethylene-α-olefin copolymer (a). b) is included in the composition based on the total amount of (a) and (b).

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

In one embodiment, the polymer composition typically has a total ethylene content of about 40% to about 70%, or about 50% to about 70% by weight. In another embodiment, the polymer composition typically has a total ethylene content of about 55% to about 65% by weight. In other embodiments, the polymer composition has a total ethylene content of about 57% to about 63% by weight.

Salicylate Detergents Salicylates can be prepared by reacting a basic metal compound with at least one carboxylic acid and removing water from the reaction product. Detergents made from salicylic acid are a type of detergent prepared from carboxylic acids. Useful salicylates include long chain alkyl salicylates. One useful family of compositions is the following structure (5).

where R'' is a C ₁ -C ₃₀ (e.g., C ₁₃ -C ₃₀ ) alkyl group; n is an integer from 1 to 4; M is an alkaline earth metal (e.g., Ca or Mg); be.

Hydrocarbyl-substituted salicylic acids can be prepared from phenol by the Kolbe reaction (see US Pat. No. 3,595,791). Metal salts of hydrocarbyl-substituted salicylic acids can be prepared by double decomposition of the metal salts in polar solvents such as water or alcohols.

In one aspect of the disclosure, the salicylate is derived from C ₁₀ -C ₄₀ isomerized NAO and has an isomerization level (i) of about 0.10 to about 0.40, preferably about 0.10. It is made from an alkylphenol having alkyl groups derived from isomerized NAO of from to about 0.35, preferably from about 0.10 to about 0.30, more preferably from about 0.12 to about 0.30.

Typical detergents are anionic substances that include long chain hydrophobic portions of the molecule and smaller anionic or lipophobic hydrophilic portions of the molecule. The anionic portion of the detergent is typically derived from an organic acid such as sulfuric acid, carboxylic acid, phosphorous acid, phenol, or mixtures thereof. The counterion is usually an alkaline earth or alkali metal.

Salts containing substantially stoichiometric amounts of metal are described as neutral salts and have a total base number (TBN) of 0 to 80 mg KOH/g. Many compositions are overbased and contain large amounts of metal base, which is achieved by overreacting a metal compound (e.g., metal hydroxide or metal oxide) enriched with an acidic gas (e.g., carbon dioxide). include. Useful detergents can be neutral, moderately overbased, or highly overbased.

It is desirable that at least some of the detergents used in the detergent mixture be overbased. Overbased detergents help neutralize acidic impurities produced by the combustion process so that they become trapped in the oil. Typically, the overbased material has a ratio of metal ion to anionic portion of the detergent of from 1.05:1 to 50:1 (e.g., from 4:1 to 25:1) on an equivalent basis. . The resulting detergent is typically an overbased detergent having a TBN of 150 mg KOH/g or greater (eg, 250-450 mg KOH/g or greater). Mixtures of detergents with different TBNs can be used.

Suitable detergents include metal salts of sulfonates, phenates, carboxylates, phosphates, and salicylates.

Sulfonates can be prepared from sulfonic acids, which are typically obtained by sulfonation of alkyl-substituted aromatic hydrocarbons, such as those obtained from the fractionation of petroleum, or by alkylation of aromatic hydrocarbons. Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl or their halogen derivatives. Alkylation can be carried out using alkylating agents having from about 3 to more than 70 carbon atoms in the presence of a catalyst. Alkaryl sulfonates typically contain about 9 to 80 or more carbon atoms (eg, about 16 to 60 carbon atoms) per alkyl-substituted aromatic moiety.

Phenates can be prepared by reacting alkaline earth metal hydroxides or oxides (eg, CaO, Ca(OH) ₂ , MgO, or Mg(OH) ₂ ) with alkylphenols or sulfurized alkylphenols. Useful alkyl groups include straight or branched C ₁ -C ₃₀ (eg, C ₄ -C ₂₀ ) alkyl groups, or mixtures thereof. Examples of suitable phenols include isobutylphenol, 2-ethylhexylphenol, nonylphenol, dodecylphenol, and the like. It should be noted that the starting alkylphenol may contain multiple alkyl substituents, each independently linear or branched. When non-sulfurized alkylphenols are used, the sulfurized product can be obtained by methods well known in the art. These methods involve heating a mixture of an alkylphenol and a sulfiding agent (eg, elemental sulfur, a sulfur halide such as sulfur dichloride, etc.) and then reacting the sulfurized phenol with an alkaline earth metal base.

Magnesium Detergents Preferred magnesium-containing detergents include magnesium sulfonates, magnesium phenates, and magnesium salicylates, especially magnesium sulfonates and magnesium salicylates. These are as described above.

The magnesium-containing detergent is present at least 200 ppm to 1000 ppm, 240 ppm to 1000 ppm, 240 to 900 ppm, 240 to 840 ppm, 240 to 800 ppm, 250 to 800 ppm, 300 to 1000 ppm, 300 to 800 ppm, 400 to 1000 ppm, relative to the lubricating oil composition. , or 400 to 800 ppm by weight of magnesium.

In one embodiment that is substantially free of elemental molybdenum , the level of molybdenum-containing elements in the lubricating oil compositions of the present invention is about 60 ppm or less, such as about 0.01 ppm or less, based on the total weight of the lubricating oil composition. Molybdenum-containing element levels of ~60 ppm. In one embodiment, the level of molybdenum-containing elements in the lubricating oil compositions of the present invention is about 40 ppm or less, such as from about 0.01 to about 40 ppm molybdenum-containing elements, based on the total weight of the lubricating oil composition. It is at the elemental level. In one embodiment, the level of molybdenum-containing elements in the lubricating oil compositions of the present invention is about 25 ppm or less, for example, about 0.01 to about 25 ppm molybdenum-containing elements, based on the total weight of the lubricating oil composition. It is at the elemental level. In one embodiment, the level of molybdenum-containing elements in the lubricating oil compositions of the present invention is about 15 ppm or less, for example, about 0.01 to about 15 ppm molybdenum-containing elements, based on the total weight of the lubricating oil composition. It is at the elemental level. In one embodiment, the level of molybdenum-containing elements in the lubricating oil compositions of the present invention is about 10 ppm or less, for example, about 0.01 to about 10 ppm molybdenum-containing elements, based on the total weight of the lubricating oil composition. It is at the elemental level. In one embodiment, the level of molybdenum-containing elements in the lubricating oil compositions of the present invention is about 5 ppm or less, such as from about 0.01 to about 5 ppm molybdenum-containing elements, based on the total weight of the lubricating oil composition. It is at the elemental level.

In other embodiments, the lubricating oil composition is substantially free of molybdenum-containing elements. In some embodiments, substantially free of molybdenum-containing elements means that the molybdenum-containing elements are less than 10 ppm, less than 9 ppm, less than 8 ppm, less than 7 ppm, less than 6 ppm, less than 5 ppm, less than 4 ppm, less than 3 ppm, less than 2 ppm, Means present at less than 1 ppm, less than 0.5 ppm, less than 0.1 ppm.

Other Lubricating Oil Additives In addition to the additive compounds described herein, the lubricating oil compositions can include additional lubricating oil additives.

The lubricating oil compositions of the present disclosure may also include other conventional additives that can impart or improve any desirable properties of the lubricating oil composition in which these additives are dispersed or dissolved. Any additive known to those skilled in the art may be used in the lubricating oil compositions disclosed herein. Some suitable additives include Mortier et al., “Chemistry and Technology of Lubricants”, 2nd Edition, London, Springer, (1996); and Leslie R. Rudnick, “Lubricant Additives: Chemistry and Applications”, New York , Marcel Dekker (2003), incorporated herein by reference. For example, lubricating oil compositions include antioxidants, antiwear agents, metal detergents, rust inhibitors, antifog agents, demulsifiers, metal deactivators, friction modifiers, pour point depressants, antifoaming agents, Can be blended with cosolvents, corrosion inhibitors, ashless dispersants, multifunctional agents, dyes, extreme pressure agents, etc. and mixtures thereof. Various additives are known and commercially available. These additives, or similar compounds thereof, can be used in preparing the lubricating oil compositions of the present disclosure by conventional mixing procedures.

The lubricating oil compositions of the present invention can include one or more antiwear agents that can reduce friction and excessive wear. Any antiwear agent known to those skilled in the art can be used in the lubricating oil composition. Non-limiting examples of suitable antiwear agents include: zinc dithiophosphates, metal (e.g., Pb, Sb, Mo, etc.) salts of dithiophosphates, metal (e.g., Zn) salts of dithiocarbamates. , Pb, Sb, Mo, etc.) salts, metal (e.g. Zn, Pb, Sb, etc.) salts of fatty acids, boron compounds, phosphoric acid esters, phosphorous acid esters, amine salts of phosphoric acid esters or thiophosphoric acid esters, dicyclo Reaction products of pentadiene and thiophosphoric acid, and combinations thereof. The amount of antiwear agent is from about 0.01% to about 5%, from about 0.05% to about 3%, or from about 0.1% to about 0.1% by weight, based on the total weight of the lubricating oil composition. 1% by weight and may vary.

In certain embodiments, the antiwear agent is or comprises a dihydrocarbyl dithiophosphate metal salt, such as a zinc dialkyldithiophosphate compound. The metal of the dihydrocarbyl dithiophosphate metal salt can be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. In some embodiments, the metal is zinc. In other embodiments, the alkyl group of the dihydrocarbyl dithiophosphate metal salt has about 3 to about 22 carbon atoms, about 3 to about 18 carbon atoms, about 3 to about 12 carbon atoms, atoms, or about 3 to about 8 carbon atoms. In further embodiments, the alkyl group is straight or branched.

The amount of dihydrocarbyl dithiophosphate metal salts, including zinc dialkyldithiophosphate salts, in the lubricating oil compositions disclosed herein is measured by its phosphorus content. In some embodiments, the phosphorus content of the lubricating oil compositions disclosed herein is from about 0.01% to about 0.14% by weight, based on the total weight of the lubricating oil composition.

The lubricating oil compositions of the present invention can include one or more friction modifiers that can reduce friction between moving parts. Any friction modifier known to those skilled in the art can be used in the lubricating oil composition. Non-limiting examples of suitable friction modifiers include: fatty carboxylic acids; derivatives of aliphatic carboxylic acids (e.g., alcohols, esters, borates, amides, metal salts, etc.); , di- or trialkyl-substituted phosphoric or phosphonic acids; mono-, di- or trialkyl-substituted phosphoric or phosphonic acids derivatives (e.g. esters, amides, metal salts, etc.); mono-, di- or trialkyl-substituted amines; mono- or dialkyl Substituted amides and combinations thereof. In some embodiments, examples of friction modifiers include, but are not limited to: alkoxylated fatty amines; borated fatty epoxides; fatty phosphites, fatty epoxides, fatty amines; Borated alkoxylated fatty amines, metal salts of fatty acids, fatty acid amides, glycerin esters, borated glycerin esters; and fatty imidazolines (see U.S. Pat. No. 6,372,696, the contents of which are incorporated herein by reference). (disclosed); reaction of nitrogen-containing compounds and mixtures thereof selected from the group consisting of C ₄ -C ₇₅ , or C ₆ -C ₂₄ , or C ₆ -C ₂₀ , fatty acid esters, and ammonia and alkanolamines, etc. Friction modifier obtained from the product. The amount of friction modifier is from about 0.01% to about 10%, from about 0.05% to about 5%, or from about 0.1% to about 10% by weight, based on the total weight of the lubricating oil composition. It can vary by 3% by weight.

The lubricating oil composition of the present invention preferably contains 0.01 to 5% by weight, preferably 0.1 to 3% by weight, of an organic antioxidant. The antioxidant can be a hindered phenol antioxidant or a diarylamine antioxidant. Diarylamine antioxidants are advantageous in providing a base number derived from the nitrogen atom. Hindered phenol antioxidants are advantageous in that they do not generate NO _x gas.

Examples of hindered phenolic antioxidants include: 2,6-di-t-butyl-p-cresol, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-methylenebis(6-t-butyl-o-cresol), 4,4'-isopropylidenebis(2,6-di-t-butylphenol), 4,4'-bis(2,6-di -t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-thiobis(2-methyl-6-t-butylphenol), 2,2-thio-diethylenebis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate -di-t-butyl-4-hydroxyphenyl) octadecyl propionate, octyl 3-(3,54-butyl-4-hydroxy-3-methylphenyl) propionate, and Irganox L135® ( Commercial products such as BASF), Naugalube 531® (Chemtura), and Ethanox 376® (SI Group).

Examples of diarylamine antioxidants include alkyldiphenylamines having a mixture of alkyl groups having 4 to 9 carbon atoms, p,p'-dioctyldiphenylamine, phenylnaphthylamine, phenylnaphthylamine, alkylated naphthylamine, and alkylated phenylnaphthylamine. Can be mentioned.

Each of the hindered phenol antioxidants and diarylamine antioxidants can be used alone or in combination. Other oil-soluble antioxidants can be used if desired.

In the preparation of lubricating oil formulations, it is common practice to introduce additives in the form of 10 to 80% by weight active ingredient concentrates in hydrocarbon oils, such as mineral lubricating oils, or other suitable solvents. It is.

Typically, these concentrates can be diluted with 3 to 100, such as 5 to 40, parts by weight of lubricating oil per part by weight of additive package in forming a finished lubricant, e.g., crankcase motor oil. can. Of course, the purpose of the concentrate is to make handling of the various materials less difficult and unwieldy, as well as to facilitate dissolution or dispersion in the final blend.

Process for Preparing Lubricating Oil Compositions The lubricating oil compositions disclosed herein can be prepared by any method known to those skilled in the art for making lubricating oils. In some embodiments, the base oil can be blended or mixed with the zirconium-containing compounds described herein. Optionally, one or more others can be added. Additives can be added to the base oil individually or simultaneously. In some embodiments, the additives are added individually to the base oil in one or more additions, and the additions can be in any order. In other embodiments, the additive is added to the base oil simultaneously, optionally in the form of an additive concentrate. In some embodiments, solubilizing the additive in the base oil is by heating the mixture to a temperature of about 25°C to about 200°C, about 50°C to about 150°C, or about 75°C to about 125°C. can be supported.

Any mixing or dispersing equipment known to those skilled in the art can be used to blend, mix or solubilize the ingredients. Blending, mixing or solubilization can be carried out using blenders, agitators, dispersers, mixers (e.g. planetary mixers and double planetary mixers), homogenizers (e.g. Gaulin homogenizers and Runny homogenizers), mills (e.g. colloid mills, ball mills and sand mills) or any other mixing or dispersing equipment known in the art.

Uses of Lubricating Oil Compositions The lubricating oil compositions disclosed herein are suitable for use as motor oils (i.e., engine oils or crankcase oils) in spark-ignition internal combustion engines, particularly direct injection and boosted engines. There may be cases where

The following examples are presented to illustrate embodiments of the invention and are not intended to limit the invention to the particular embodiments described. All parts and percentages are by weight unless stated to the contrary. All numbers are approximate. It should be understood that where numerical ranges are given, embodiments outside the stated ranges may still be within the scope of the invention. Specific details described in each example should not be construed as necessary features of the invention.

EXAMPLES The following examples are for illustrative purposes only and are not intended to limit the scope of the invention in any way.

Example 1
A lubricating oil composition was prepared by blending the following ingredients together to obtain a molybdenum-free SAE 0W-20 viscosity grade formulation:
(a) 740 ppm secondary zinc dialkyldithiophosphate with respect to phosphorus content;
(b) a detergent with respect to calcium content of 1120 ppm, mostly derived from overbased calcium salicylate derived from C ₁₄ to C ₁₈ normal alpha olefins and a small amount derived from low overbased calcium sulfonate;
(c) a highly overbased magnesium sulfonate detergent with 240 ppm of magnesium;
(d) ethylene carbonate treated borated succinimide dispersant;
(e) alkylated diphenylamine antioxidant, hindered phenol antioxidant;
(f) a conventional amount of pour point depressant;
(g) a combination of viscosity index improvers, comprising an ethylene propylene-derived non-dispersing agent OCP (an ethylene propylene-based copolymer containing 55 to 65% ethylene, weight average molecular weight of 80,000 to about 100,000 g/mole; , and SSI of about 20 to about 26) and 1.50 wt.% polymer concentrate containing dispersant type PMA (1 to 10 wt.% methyl methacrylate monomer, about 0.5 to 3% by weight N-vinylpyrrolidone as the nitrogen-containing monomer, and the remainder longer chain alkyl methacrylate monomers, especially lauryl methacrylate, and having a MW of 200,000 to 250,000, which is about having an SSI of 40 to about 50;
(h)
(i) additional additives including organic friction modifiers, Mannich reaction products, corrosion inhibitors, markers, foam suppressants; and (j) the remainder is a mixture of Group III and Group IV PAO base oils.

Example 2
Example 1 was repeated except that the calcium salicylate was derived from a C ₂₀ to C ₂₄ isomerized normal alpha olefin with an alpha olefin isomerization level of about 0.16. The additives included 6.4 wt% Ca and about 20 wt% diluent oil and had a TBN of about 180 mg KOH/g and a basicity index of about 2.4. Based on active ingredient, the TBN of this additive is approximately 225 mg KOH/g.

The isomerization level was measured by NMR method.

Isomerization level (I) and NMR method The isomerization level (I) of the olefin was determined by hydrogen-1 (1H) NMR. NMR spectra were acquired on a Bruker Ultrashield Plus 400 in chloroform-d1 at 400 MHz using TopSpin 3.2 spectral processing software.

The isomerization level (I) is a methyl group (-CH ₃ ) (chemical shift 0.30-1.01 ppm) attached to a methylene backbone group (-CH ₂ -) (chemical shift 1.01-1.38 ppm). represents the relative amount of and is defined by equation (6) shown below:
I=m/(m+n) Formula (6)
Here, m is the NMR integral of the methyl group with a chemical shift of 0.30±0.03 to 1.01±0.03 ppm, and n is a chemical shift of 1.01±0.03 to 1.38±0. .10 ppm methylene group NMR integral.

Example 3
Example 1 was repeated except that the magnesium sulfonate detergent was present in an amount to provide 840 ppm magnesium.

Example 4
Example 3 was repeated except that the overbased calcium salicylate from C ₁₄ to C ₁₈ normal alpha olefins was removed.

Example 5
Example 1 was repeated except that 3% by weight of ester base oil was added to the finished oil.

Example 6
Example 1 was repeated except that the calcium salicylate was replaced with magnesium salicylate derived from a C ₂₀ -C ₂₄ isomerized normal alpha olefin with an alpha olefin isomerization level of about 0.16. The additive contained 4.3 wt% Mg, and about 35 wt% diluent oil, and had a TBN of about 200 mg KOH/g. The isomerization level was measured in the same manner as in Example 1.

Example 7
Example 1 was repeated except that the calcium salicylate was replaced with magnesium salicylate derived from a C ₁₄ -C ₁₈ alpha olefin and having about 236 mg KOH/g TBN and 5.34 wt% Mg. Ta.

Comparative example 1
Example 1 was repeated, but the ethylene propylene derived non-dispersant OCP was added to a 0.7 wt% polymer concentrate containing a hydrogenated polyisoprene star polymer combined with divinylbenzene with an SSI of 4 and a molecular weight of 35,000. Replaced with

Comparative example 2
Example 1 was repeated, but 0.4% by weight of a sulfur-free molybdenum compound was added to the lubricating oil composition in an amount to provide 320 ppm of molybdenum.

Comparative example 3
Example 1 was repeated, but 0.4% by weight of a sulfur-free molybdenum compound and 0.4% by weight of a sulfur-containing molybdenum succinimide complex were added in amounts to provide 490 ppm of molybdenum to the lubricating oil.

Comparative example 4
Example 1 was repeated, but 1.0% by weight of a sulfur-free molybdenum compound was added in an amount to provide 780 ppm of molybdenum in the lubricating oil.

Comparative example 5
Example 1 was repeated, but the ethylene propylene derived non-dispersant OCP and the dispersant PMA were combined with 4.50 wt. The polymer concentrate was replaced and 0.4% by weight sulfur-containing molybdenum succinimide complex was added in an amount to provide 200 ppm of molybdenum to the lubricating oil composition.

Comparative example 6
Comparative Example 3 was repeated, but the non-dispersant OCP and the dispersant PMA derived from ethylene propylene were combined with 4.50% by weight hydrogenated polyisoprene star polymer combined with divinylbenzene with an SSI of 4 and a molecular weight of 35,000. of polymer concentrate.

Comparative example 7
Example 1 was repeated, but the ethylene propylene derived non-dispersant OCP was replaced with 6.25% by weight of the polymer concentrate of the dispersant OCP.

Performance evaluation of the test formulations is shown in Table 2. To measure wear, the following bench test was performed. FZG wear scuffing load capacity test. In order to evaluate the wear performance of automotive engine oils, various engine oils with different chemical properties were tested on an FZG test rig (FZG four-sided test machine) using A10 gears in accordance with CEC-L-84-A-02. Evaluate the load characteristics of. This method is useful for evaluating the scuffing load-bearing capacity of oils commonly used in highly stressed cylindrical gearing found in many vehicles and stationary applications. The minimum load phase fail of the A10 gear at 16.6 m/s and 130°C was 8.

In another aspect, the disclosure provides a method of:
A method of improving friction and reducing wear in an internal combustion engine, the method comprising: lubricating the engine with a lubricating oil composition having an HTHS viscosity in the range of about 1.3 to about 2.9 cP at 150°C. The method includes:
a) a predominant amount of oil of lubricating viscosity with a kinematic viscosity at 100° C. in the range 1.5-6.0 mm ² /s;
b) dispersant polymethacrylate (DPMA) VII with Mw from 200,000 g/mol to 450,000 g/mol;
c) a non-dispersible ethylene-based olefin copolymer viscosity index improver having a Mw of 50,000 g/mol to 150,000 g/mol and a total ethylene content of about 30% to about 70% by weight;
d) about 200 to about 1000 ppm magnesium from a magnesium-containing detergent;
wherein the lubricating oil composition is substantially free of molybdenum-containing elements.

In connection with the present invention, the following contents are further disclosed.
[1]
A lubricating oil composition having an HTHS viscosity ranging from about 1.3 to about 2.9 cP at 150°C,
a) a predominant amount of oil of lubricating viscosity with a kinematic viscosity at 100° C. in the range 1.5-6.0 mm ² /s;
b) dispersant polymethacrylate (DPMA) VII with Mw from 200,000 g/mol to 450,000 g/mol;
c) a non-dispersible ethylene-based olefin copolymer viscosity index improver having a Mw of 50,000 g/mol to 150,000 g/mol and a total ethylene content of about 30% to about 70% by weight;
d) about 200 to about 1000 ppm magnesium from a magnesium-containing detergent;
wherein the lubricating oil composition is substantially free of molybdenum-containing elements.
[2]
The lubricating oil composition according to [1], further comprising 1 to 10% by weight of ester base oil.
[3]
The lubricating oil composition according to [1], wherein the magnesium-containing detergent is magnesium salicylate derived from a C ₂₀ -C ₂₄ isomerized normal alpha olefin.
[4]
The lubricating oil composition of [1], wherein the non-dispersible ethylene-based olefin copolymer viscosity index improver has a total ethylene content of about 55-65% by weight.
[5]
The lubricating oil composition according to [1], wherein the non-dispersible ethylene-based olefin copolymer viscosity index improver has a Mw of 70,000 g/mol to 110,000 g/mol.
[6]
The lubricating oil composition according to [1], wherein the dispersant polymethacrylate (DPMA) VII has a Mw of 200,000 g/mol to 300,000 g/mol.
[7]
The lubricating oil composition according to [1], wherein the dispersant polymethacrylate VII contains the following monomer units:
(a) 0 to 40% by weight of one or more ethylenically unsaturated ester compounds of formula (I):

Here, R is hydrogen or methyl, and R ¹ is a saturated or unsaturated linear or branched alkyl group having 1 to 5 carbon atoms or a saturated or unsaturated cycloalkyl group having 3 to 5 carbon atoms. , R ² and R ³ are each independently hydrogen or of the formula -COOR', where R' is hydrogen or a saturated or unsaturated straight-chain or branched alkyl group having 1 to 5 carbon atoms;
(b) 10 to 98% by weight, preferably 20 to 95% by weight of one or more ethylenically unsaturated ester compounds of formula (II)

where R is hydrogen or methyl, and R4 ^is a saturated or unsaturated straight-chain or branched alkyl group with 6 to 15 carbon atoms, or a saturated or unsaturated alkyl group with 6 to 15 carbon atoms. is a cycloalkyl group, and R ⁵ and R ⁶ are each independently hydrogen or of the formula -COOR", where R" is hydrogen or a saturated or unsaturated straight chain having 6 to 15 carbon atoms. chain or branched alkyl group);
(c) 0 to 30% by weight, preferably 5 to 20% by weight of one or more ethylenically unsaturated ester compounds of formula (III):

Here, R is hydrogen or methyl, R ⁷ is a saturated or unsaturated straight chain or branched alkyl group having 16 to 40 carbon atoms, preferably 16 to 30 carbon atoms, or a C 16 to 40, preferably 16 to 30 and R ⁸ and R ⁹ are each independently hydrogen or a group of the formula -COOR'', where R'' is hydrogen or a cycloalkyl group of 16 to 40, preferably 16 to 30 carbon atoms. a saturated or unsaturated straight-chain or branched alkyl group having atoms;
(d) 0 to 30% by weight of vinyl monomer;
(e) 2-10% by weight of at least one N-dispersant monomer.
[8]
The lubricating oil composition according to [1], wherein the non-dispersible ethylene-based olefin copolymer is an ethylene propylene copolymer.
[9]
The lubricating oil composition of [1], wherein the magnesium from the magnesium-containing detergent is about 200 to about 850 ppm.
[10]
A method of improving friction and reducing wear in an internal combustion engine, the method comprising: lubricating the engine with a lubricating oil composition having an HTHS viscosity in the range of about 1.3 to about 2.9 cP at 150°C. The method includes:
a) a predominant amount of oil of lubricating viscosity with a kinematic viscosity at 100° C. in the range 1.5-6.0 mm ² /s;
b) dispersant polymethacrylate (DPMA) VII with Mw from 200,000 g/mol to 450,000 g/mol;
c) a non-dispersible ethylene-based olefin copolymer viscosity index improver having a Mw of 50,000 g/mol to 150,000 g/mol and a total ethylene content of about 30% to about 70% by weight;
d) about 200 to about 1000 ppm magnesium from a magnesium-containing detergent;
wherein the lubricating oil composition is substantially free of molybdenum-containing elements.
[11]
The method according to [10], wherein the lubricating oil composition further comprises 1 to 10% by weight of an ester base oil.
[12]
The method according to [10], wherein the magnesium-containing detergent is magnesium salicylate derived from a C ₂₀ -C ₂₄ isomerized normal alpha olefin.
[13]
The method of [10], wherein the non-dispersible ethylene-based olefin copolymer viscosity index improver has a total ethylene content of about 55-65% by weight.
[14]
The method according to [10], wherein the non-dispersant ethylene-based olefin copolymer viscosity index improver has a Mw of 70,000 g/mol to 110,000 g/mol.
[15]
The method according to [10], wherein the dispersant polymethacrylate (DPMA) VII has a Mw of 200,000 g/mol to 300,000 g/mol.
[16]
The method according to [10], wherein the dispersant polymethacrylate VII contains the following monomer units:
(a) 0 to 40% by weight of one or more ethylenically unsaturated ester compounds of formula (I):

Here, R is hydrogen or methyl, and R ¹ is a saturated or unsaturated linear or branched alkyl group having 1 to 5 carbon atoms or a saturated or unsaturated cycloalkyl group having 3 to 5 carbon atoms. , R ² and R ³ are each independently hydrogen or of the formula -COOR', where R' is hydrogen or a saturated or unsaturated straight-chain or branched alkyl group having 1 to 5 carbon atoms;
(b) 10 to 98% by weight, preferably 20 to 95% by weight of one or more ethylenically unsaturated ester compounds of formula (II)

where R is hydrogen or methyl, and R4 ^is a saturated or unsaturated straight-chain or branched alkyl group with 6 to 15 carbon atoms, or a saturated or unsaturated alkyl group with 6 to 15 carbon atoms. is a cycloalkyl group, and R ⁵ and R ⁶ are each independently hydrogen or of the formula -COOR", where R" is hydrogen or a saturated or unsaturated straight chain having 6 to 15 carbon atoms. chain or branched alkyl group);
(c) 0 to 30% by weight, preferably 5 to 20% by weight of one or more ethylenically unsaturated ester compounds of formula (III):

Here, R is hydrogen or methyl, R ⁷ is a saturated or unsaturated straight chain or branched alkyl group having 16 to 40 carbon atoms, preferably 16 to 30 carbon atoms, or a C 16 to 40, preferably 16 to 30 and R ⁸ and R ⁹ are each independently hydrogen or a group of the formula -COOR'', where R'' is hydrogen or a cycloalkyl group of 16 to 40, preferably 16 to 30 carbon atoms. a saturated or unsaturated straight-chain or branched alkyl group having atoms;
(d) 0 to 30% by weight of vinyl monomer;
(e) 2-10% by weight of at least one N-dispersant monomer.
[17]
The method according to [10], wherein the non-dispersible ethylene-based olefin copolymer is an ethylene propylene copolymer.
[18]
The method of [10], wherein the magnesium from the magnesium-containing detergent is about 200 to about 850 ppm.

Claims (18)

A lubricating oil composition having an HTHS viscosity ranging from about 1.3 to about 2.9 cP at 150°C,
a) a predominant amount of oil of lubricating viscosity with a kinematic viscosity at 100° C. in the range 1.5-6.0 mm ² /s;
b) dispersant polymethacrylate (DPMA) VII with Mw from 200,000 g/mol to 450,000 g/mol;
c) a non-dispersible ethylene-based olefin copolymer viscosity index improver having a Mw of 50,000 g/mol to 150,000 g/mol and a total ethylene content of about 30% to about 70% by weight;
d) about 200 to about 1000 ppm magnesium from a magnesium-containing detergent;
wherein the lubricating oil composition is substantially free of molybdenum-containing elements. The lubricating oil composition of claim 1 further comprising 1 to 10% by weight of an ester base oil. The lubricating oil composition of claim 1, wherein the magnesium-containing detergent is magnesium salicylate derived from a _C20 - _C24 isomerized normal alpha olefin. The lubricating oil composition of claim 1, wherein the non-dispersible ethylene-based olefin copolymer viscosity index improver has a total ethylene content of about 55-65% by weight. The lubricating oil composition of claim 1, wherein the non-dispersible ethylene-based olefin copolymer viscosity index improver has a Mw of 70,000 g/mol to 110,000 g/mol. 2. The lubricating oil composition of claim 1, wherein the dispersant polymethacrylate (DPMA) VII has a Mw of 200,000 g/mol to 300,000 g/mol. The lubricating oil composition of claim 1, wherein the dispersant polymethacrylate VII comprises the following monomer units:
(a) 0 to 40% by weight of one or more ethylenically unsaturated ester compounds of formula (I):

Here, R is hydrogen or methyl, and R ¹ is a saturated or unsaturated linear or branched alkyl group having 1 to 5 carbon atoms or a saturated or unsaturated cycloalkyl group having 3 to 5 carbon atoms. , R ² and R ³ are each independently hydrogen or of the formula -COOR', where R' is hydrogen or a saturated or unsaturated straight-chain or branched alkyl group having 1 to 5 carbon atoms;
(b) 10 to 98% by weight, preferably 20 to 95% by weight of one or more ethylenically unsaturated ester compounds of formula (II)

where R is hydrogen or methyl, and ^R4 is a saturated or unsaturated straight-chain or branched alkyl group with 6 to 15 carbon atoms, or a saturated or unsaturated alkyl group with 6 to 15 carbon atoms. is a cycloalkyl group, and R ⁵ and R ⁶ are each independently hydrogen or of the formula -COOR", where R" is hydrogen or a saturated or unsaturated straight chain having 6 to 15 carbon atoms. chain or branched alkyl group);
(c) 0 to 30% by weight, preferably 5 to 20% by weight of one or more ethylenically unsaturated ester compounds of formula (III):

Here, R is hydrogen or methyl, R ⁷ is a saturated or unsaturated straight chain or branched alkyl group having 16 to 40 carbon atoms, preferably 16 to 30 carbon atoms, or a C 16 to 40, preferably 16 to 30 and R ⁸ and R ⁹ are each independently hydrogen or a group of the formula -COOR'', where R'' is hydrogen or a cycloalkyl group of 16 to 40, preferably 16 to 30 carbon atoms. a saturated or unsaturated straight-chain or branched alkyl group having atoms;
(d) 0 to 30% by weight of vinyl monomer;
(e) 2-10% by weight of at least one N-dispersant monomer. The lubricating oil composition of claim 1, wherein the non-dispersible ethylene-based olefin copolymer is an ethylene propylene copolymer. The lubricating oil composition of claim 1, wherein the magnesium from the magnesium-containing detergent is about 200 to about 850 ppm. A method of improving friction and reducing wear in an internal combustion engine, the method comprising: lubricating the engine with a lubricating oil composition having an HTHS viscosity in the range of about 1.3 to about 2.9 cP at 150°C. The method includes:
a) a predominant amount of oil of lubricating viscosity with a kinematic viscosity at 100° C. in the range 1.5-6.0 mm ² /s;
b) dispersant polymethacrylate (DPMA) VII with Mw from 200,000 g/mol to 450,000 g/mol;
c) a non-dispersible ethylene-based olefin copolymer viscosity index improver having a Mw of 50,000 g/mol to 150,000 g/mol and a total ethylene content of about 30% to about 70% by weight;
d) about 200 to about 1000 ppm magnesium from a magnesium-containing detergent;
wherein the lubricating oil composition is substantially free of molybdenum-containing elements. 11. The method of claim 10, wherein the lubricating oil composition further comprises 1 to 10% by weight ester base oil. 11. The method of claim 10, wherein the magnesium-containing detergent is magnesium salicylate derived from a _C20 - _C24 isomerized normal alpha olefin. 11. The method of claim 10, wherein the non-dispersible ethylene-based olefin copolymer viscosity index improver has a total ethylene content of about 55-65% by weight. 11. The method of claim 10, wherein the non-dispersant ethylene-based olefin copolymer viscosity index improver has a Mw of 70,000 g/mol to 110,000 g/mol. 11. The method of claim 10, wherein the dispersant polymethacrylate (DPMA) VII has a Mw of 200,000 g/mol to 300,000 g/mol. 11. The method of claim 10, wherein the dispersant polymethacrylate VII comprises the following monomer units:
(a) 0 to 40% by weight of one or more ethylenically unsaturated ester compounds of formula (I):

Here, R is hydrogen or methyl, and R ¹ is a saturated or unsaturated linear or branched alkyl group having 1 to 5 carbon atoms or a saturated or unsaturated cycloalkyl group having 3 to 5 carbon atoms. , R ² and R ³ are each independently hydrogen or of the formula -COOR', where R' is hydrogen or a saturated or unsaturated straight-chain or branched alkyl group having 1 to 5 carbon atoms;
(b) 10 to 98% by weight, preferably 20 to 95% by weight of one or more ethylenically unsaturated ester compounds of formula (II)

where R is hydrogen or methyl, and ^R4 is a saturated or unsaturated straight-chain or branched alkyl group with 6 to 15 carbon atoms, or a saturated or unsaturated alkyl group with 6 to 15 carbon atoms. is a cycloalkyl group, and R ⁵ and R ⁶ are each independently hydrogen or of the formula -COOR", where R" is hydrogen or a saturated or unsaturated straight chain having 6 to 15 carbon atoms. chain or branched alkyl group);
(c) 0 to 30% by weight, preferably 5 to 20% by weight of one or more ethylenically unsaturated ester compounds of formula (III):

Here, R is hydrogen or methyl, R ⁷ is a saturated or unsaturated straight chain or branched alkyl group having 16 to 40 carbon atoms, preferably 16 to 30 carbon atoms, or a C 16 to 40, preferably 16 to 30 and R ⁸ and R ⁹ are each independently hydrogen or a group of the formula -COOR'', where R'' is hydrogen or a cycloalkyl group of 16 to 40, preferably 16 to 30 carbon atoms. a saturated or unsaturated straight-chain or branched alkyl group having atoms;
(d) 0 to 30% by weight of vinyl monomer;
(e) 2-10% by weight of at least one N-dispersant monomer. 11. The method of claim 10, wherein the non-dispersible ethylene-based olefin copolymer is an ethylene propylene copolymer. 11. The method of claim 10, wherein the magnesium from the magnesium-containing detergent is about 200 to about 850 ppm.