JP2021515081A - Lubricating oil composition with low viscosity and providing anti-wear - Google Patents

Abstract

Lubricating oils are provided: (a) major amounts of lubricating oil, (b) dispersant polymethacrylate (DPMA) VII, (c) non-dispersible ethylene-based olefin copolymer viscosity index improver, (d). ) Magnesium-containing detergent; where the lubricating oil composition is substantially free of molybdenum-containing elements. Also provided is a method of improving friction and reducing wear of an internal combustion engine using the engine lubricating oil composition.

Description

Field of Invention The disclosed technology relates to lubricants for internal combustion engines, especially lubricants for spark ignition engines.

Background of the Invention Engine oils are blended with various additives to meet different performance requirements. One of the well-known ways to improve fuel economy is to reduce the viscosity of the lubricant. However, this approach is currently reaching the limits of current equipment functionality and specifications. It is well known that the addition of an organic or organometallic friction modifier at a given viscosity reduces the surface friction of the lubricating oil and allows for better fuel economy. However, these additives often have harmful effects such as increased deposit formation, sealing effects, or compete with wear-resistant components in limited areas of the surface, thereby making them wear-resistant. Film formation becomes impossible and wear increases.

Lowering the viscosity is usually the best way to improve the fuel economy of a lubricating oil (ie, high temperature high shear (HTHS) viscosity). HTHS is an indicator of the viscosity of a lubricant under harsh engine conditions. Deterioration of the viscosity index improver can occur under high temperature and high stress conditions. When this happens, the viscosity of the oil may decrease and engine wear may increase.

Therefore, despite advances in lubricating oil blending technology, there is still a need for engine oil lubricants that effectively improve the fuel economy while providing excellent wear resistance.

Related Techniques WO 2015541891 discloses a method of reducing the aqueous phase separation of an emulsion containing an ethanol-based fuel and a lubricating oil containing a molybdenum ester amide complex and a dispersant polyalkyl (meth) acrylate.

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

WO2014136643 has polymethacrylates with a mass average molecular weight of 30,000 to 600,000, and (B) a shear stability index (SSI) of 40 or less to a lubricating base oil and a 95% loss as measured by differential thermal analysis. An olefin copolymer having a temperature of 500 ° C. or lower is disclosed.

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

EP143369 discloses a biodegradable lubricant that is at least 60% biodegradable and has a gelation index of about 12 or less, and transesterified triglyceride base oils are formulated using with synthetic esters. Can be done. A combination of an ester viscosity index improver and an olefin copolymer viscosity index improver can also be added.

US2017088789 is a lubricant composition comprising an ethylene / olefin copolymer having a weight average molecular weight of about 10,000 to about 250,000; and a (meth) acrylate-containing polymer containing a large number of arms containing at least 20 carbon atoms. The arm is attached to a polyvalent organic moiety).

Abstract of the Invention In one aspect, the present disclosure provides the following lubricating oil compositions:
A lubricating oil composition having an HTHS viscosity in the range of about 1.3 to about 2.9 cP at 150 ° C.
a) A major amount of lubricating viscosity oil with a kinematic viscosity at 100 ° C. in the range of ^{1.5-6.0 mm 2 / s;}
b) Dispersant polymethacrylate (DPMA) VII with Mw of 200,000 g / mol to 450,000 g / mol;
c) Non-dispersible ethylene-based olefin copolymer viscosity index improver having Mw of 50,000 g / mol to 150,000 g / mol and total ethylene content of about 30% by weight to about 70% by weight;
d) Approximately 200-about 1000 ppm magnesium from magnesium-containing detergents;
The lubricating oil composition, wherein the lubricating oil composition is substantially free of molybdenum-containing elements.

In another aspect, the present disclosure provides the following methods:
A method of improving friction and reducing wear of an internal combustion engine, wherein the engine is lubricated with a lubricating oil composition containing the following and having an HTHS viscosity in the range of about 1.3 to about 2.9 cP at 150 ° C. Methods including to do:
a) A major amount of lubricating viscosity oil with a kinematic viscosity at 100 ° C. in the range of ^{1.5-6.0 mm 2 / s;}
b) Dispersant polymethacrylate (DPMA) VII with Mw of 200,000 g / mol to 450,000 g / mol;
c) Non-dispersible ethylene-based olefin copolymer viscosity index improver having Mw of 50,000 g / mol to 150,000 g / mol and total ethylene content of about 30% by weight to about 70% by weight;
d) Approximately 200-about 1000 ppm magnesium from magnesium-containing detergents;
Here, the lubricating oil composition is substantially free of molybdenum-containing elements.

Detailed Description of the Invention To facilitate understanding of the subject matter disclosed herein, some terms, abbreviations, or other abbreviations used herein are defined below. Undefined terms, abbreviations, or abbreviations are understood to have the usual meanings used by those skilled in the art upon filing this application.

Definitions In the present specification, the following terms and expressions have the meanings shown below when and when used.

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

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

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

All reported percentages are% by weight on an active ingredient basis (ie, not related to carriers or diluents) unless otherwise stated.

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.

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

Metals-The term "metal" refers to alkali metals, alkaline earth metals, or mixtures thereof.

Throughout the specification and claims, the expression oil-soluble or dispersible is used. Oil-soluble or dispersible means that the amount 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 a detailed explanation of oil solubility and dispersibility, in particular the term "stable dispersibility," see US Pat. No. 4,320,019, which is expressly incorporated herein by reference in the relevant teaching. Please refer.

As used herein, the term "sulfated ash" refers to nonflammable 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 number of bases" or "TBN" refers to the amount of base equivalent to milligrams of KOH in a gram sample. Therefore, the higher the TBN value, the greater the alkalinity, and therefore the higher the alkalinity. TBN was determined using the ASTM D2896 test.

The contents of boron, calcium, magnesium, molybdenum, phosphorus, sulfur, and zinc were measured according to ASTM D5185.

Nitrogen content was determined according to ASTM D4629.

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

Olefin-The term "olefin" refers to a class of unsaturated aliphatic hydrocarbons with one or more carbon-carbon double bonds obtained in 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 carbons. Examples are 1-octene and 1-octadecene, which are used as starting points for biodegradable surfactants. Linear and branched olefins are also included in the definition of olefins.

Normal Alpha Olefin-The term "normal alpha olefin" refers to an olefin that is a straight, non-branched hydrocarbon with a carbon-carbon double bond at 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 altered distribution of existing olefin species and / or introduction of branching along the alkyl chain. .. The isomerized olefin product isomerizes a linear alpha olefin containing about 10 to about 40 carbon atoms, preferably about 20 to about 28 carbon atoms, preferably about 20 to about 24 carbon atoms. Obtained by

C _10-40 Normal Alpha Olefin-This term defines a fraction of normal alpha olefin with less than 10 carbon atoms removed by distillation or other fractionation method.

Unless otherwise specified, all percentages are weight percent.

Various modifications and alternatives are possible in this disclosure, the particular embodiment of which is described in detail herein. However, the description herein of a particular embodiment is not intended to limit the disclosure to the particular embodiment disclosed, and conversely, the purpose of the disclosure and the purpose of the disclosure as defined by the appended claims. It should be understood that it is intended to cover all modifications, equivalents, and alternatives included in the scope.

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

The benefits, other benefits, and solutions to problems have been described herein for a particular embodiment. However, any benefit, benefit, solution to the problem, and any feature that may cause or become more prominent in any benefit, benefit, or solution is important to the scope of any or all claims. It shall not be construed as a necessary or essential feature.

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

As used herein, "prepared", "prepared", "included", "included", "have", "have", or any other modification thereof is non-exclusive. Intended to include inclusion. For example, a process, method, article, or device that includes a list of features is not necessarily limited to those features and is specific to other features or such processes, methods, articles, or devices that are not explicitly listed. It may include other features. Moreover, unless explicitly stated on the contrary, "or" refers to an inclusive OR rather than an exclusive OR. For example, condition A or B is satisfied by one of the following: A is true (or present) and B is false (or nonexistent), A is false (or nonexistent) and B is true (or nonexistent). Existence), and both A and B are true (or existent).

The use of "one" or "one" is used to describe the elements and components described herein. This is done solely for convenience and to give a general meaning to the scope of the embodiments of the present 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 to mean otherwise. The term "mean" is intended to mean mean, geometric mean, or median when referring to a value. Group numbers corresponding to columns in the Periodic Table of Elements use the rules of "New Notation", as seen in the CRC Handbook of Chemistry and Physics, 81st Edition (2000-2001). To do.

Unless otherwise defined, 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 merely exemplary and are 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 lubricating oil and oil and gas industries.

The specification and description are intended to serve as an exhaustive and comprehensive description of all elements and features of the formulations, compositions, devices and systems that use the structures or methods described herein. Absent. Separate embodiments may also be provided in combination in a single embodiment, and conversely, various features described in the context of a single embodiment for brevity are separate or optional. It may be provided as a sub-combination. In addition, references to values mentioned in a range include any 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 to derive from the present disclosure so that structural substitutions, logical substitutions, or other modifications can be made without departing from the scope of the present disclosure. Therefore, this disclosure should be considered exemplary rather than limiting.

Lubricating Viscosity Oil / Base Oil Component Lubricating viscosity oil (sometimes called "basestock" or "base oil (base oil)") is the main liquid component of a lubricant, in which additives and possible Other oils are blended to produce, for example, the final lubricant (or lubricant composition). The base oil is useful for producing concentrates and from it for producing lubricating oil compositions, and can be selected from natural and synthetic lubricating oils and combinations thereof.

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

Synthetic lubricants include: hydrocarbon oils such as polymerized and copolymerized olefins (eg, polybutylene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylene, poly (1-hexene), poly (1-hexene), poly (1-hexene). Octene), poly (1-decene); alkylbenzene (eg, dodecylbenzene, tetradecylbenzene, dinonylbenzene, di (2-ethylhexyl) benzene; polyphenols (eg, biphenyl, terphenyl, alkylated polyphenols); and alkylation Diphenyl ethers and alkylated diphenyl sulfides and their derivatives, analogs and homologues.

Another suitable class of synthetic lubricants includes: dicarboxylic acids (eg, malonic acid, alkylmalonic acid, alkenylmalonic acid, succinic acid, alkylsuccinic acid and alkenylsuccinic acid, maleic acid, phthalic acid, Azelaic acid, succinic acid, sebacic acid, adipic acid, linoleic acid dimer, phthalic acid) and various alcohols (eg 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 sebacate, dioctyl sebacate, dioctyl azelaite, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, Diecocyl sebacate, 2-ethylhexyl diester of linoleic acid, and composite ester formed by reacting 1 mol of sebacic acid with 2 mol of tetraethylene glycol and 2 mol of 2-ethylhexanoic acid. ..

Esters useful as synthetic oils include esters made from C ₅ to C ₁₂ 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 in an amount of 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% by weight, about 1-6% by weight, about 1-5% by weight, about 1-4% by weight, based on the total weight of the lubricating oil composition. It is present in 1 to 3% by weight and about 1 to 2% by weight.

The base oil may be derived from Fischer-Tropsch synthetic hydrocarbons. Fischer-Tropsch synthetic hydrocarbons are made from synthetic gases containing _{H 2 and CO using a Fischer-Tropsch catalyst.} Such hydrocarbons typically require further treatment in order to be useful as a base oil. For example, hydrocarbons may be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed using processes known to those skilled in the art.

Unrefined, refined and re-refined 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 refining. For example, a shale oil obtained directly from a retort operation, petroleum obtained directly from distillation, or an ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. Refined oils are similar to unrefined oils, except that they have been further processed in one or more refinement steps to improve one or more properties. Many such purification techniques are known to those of skill in the art, such as distillation, solvent extraction, acid or base extraction, filtration and permeation. The rerefined oil is obtained by a process similar to the process used to obtain a refined oil applied to a refined oil already in use. Such rerefined oils are also known as regenerated or reprocessed oils and are often further processed by techniques for approval of used additives and oil cracked products.

Therefore, the base oils that can be used to make this lubricating oil composition are from any of the group 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.

Suitable base oils for use herein are those corresponding to API Group II, Group III, Group IV, and Group V oils and combinations thereof, which are volatile, stable, viscous, and. Group III to Group V oils are preferred because of their very high cleanliness characteristics.

The base oil constitutes the main component of the lubricating oil composition of the present invention and is present in an amount in the range of more than 50% by weight to 99% by weight (for example, 70 to 95% by weight, or 85 to 95% by weight).

The base oil can be selected from either synthetic oils or natural oils commonly used as crankcase lubricants for spark-ignition internal combustion engines. The base oil typically has a kinematic viscosity in the range of ^{1.5-6 mm 2 / s at 100 ° C.} If the kinematic viscosity of the lubricating base oil at 100 ° C. ^{exceeds 6 mm 2} / s, the low temperature viscosity characteristics may deteriorate and sufficient fuel consumption may not be obtained. When the kinematic viscosity is 1.5 mm ² / s or less, the formation of an oil film at the lubricated portion is insufficient; therefore, the lubricity is 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 volatilization prevention tend to decrease, but also the friction coefficient tends to increase, and the wear resistance tends 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 is 2.9 cP or less (eg, 1.0 to 2.9 cP, or 1.3 to 2.9 cP) or 2.6 cP or less (eg, 1.0 to 2.6 cP, or 1.0 to 2.6 cP) at 150 ° C. 1.3-2.6 cP), 2.3 cP or less (eg 1.0-2.3 cP, or 1.3-2.3 cP), for example 2.0 cP or less (eg 1.0-2.0 cP, Or have a high temperature shear (HTHS) viscosity of 1.3-2.3 cP) or 1.7 cP or less (eg, 1.0-1.7 cP, or 1.3-1.7 cP).

Lubricating oil compositions are at least 135 (eg, 135-400, or 135-250), at least 150 (eg, 150-400, or 150-250), at least 165 (eg, 165-400 or 165-250). 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 the 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 solubility of the additive.

The lubricating oil composition is in the range of at 100 ℃ 3~12mm ² / s ^{(e.g., 3~8.2mm 2 /s,3.5~8.2mm} 2 / s or 4~8.2mm ² / s,) Has a kinematic viscosity of.

Generally, the level of sulfur in the lubricating oil composition of the present invention is about 0.7% by weight or less, for example, about 0.01% by weight to about 0.70% by weight, based on the total weight of the lubricating oil composition. 0.01-0.6% by weight, 0.01-0.5% by weight, 0.01-0.4% by weight, 0.01-0.3% by weight, 0.01-0.2% by weight, It is 0.01% by weight to 0.10% by weight. In one embodiment, the level of sulfur in the lubricating oil composition 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 composition of the present invention is about 0.12% by weight or less, eg, about 0.01% by weight to about 0.12, based on the total weight of the lubricating oil composition. By weight%. In one embodiment, the level of phosphorus in the lubricating oil composition of the present invention is about 0.11% by weight or less, eg, about 0.01% by weight to about 0.11 based on the total weight of the lubricating oil composition. By weight%. In one embodiment, the level of phosphorus in the lubricating oil composition of the present invention is about 0.10% by weight or less, eg, about 0.01% by weight to about 0.10, based on the total weight of the lubricating oil composition. By weight%. In one embodiment, the level of phosphorus in the lubricating oil composition of the present invention is about 0.09% by weight or less, eg, about 0.01% by weight to about 0.09, based on the total weight of the lubricating oil composition. By weight%. In one embodiment, the level of phosphorus in the lubricating oil composition of the present invention is about 0.08% by weight or less, eg, about 0.01% by weight to about 0.08, based on the total weight of the lubricating oil composition. By weight%. In one embodiment, the level of phosphorus in the lubricating oil composition of the present invention is about 0.07% by weight or less, eg, about 0.01% by weight to about 0.07, based on the total weight of the lubricating oil composition. By 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, eg, about 0.01% by weight to about 0.05, based on the total weight of the lubricating oil composition. By weight%.

In one embodiment, the level of sulfated ash produced by the lubricating oil composition of the present invention is about 1.60% by weight or less as measured by ASTM D874, eg, about 0. It is a level of 10 to about 1.60 wt% sulfated ash. In one embodiment, the level of sulfated ash produced by the lubricating oil composition of the present invention is about 1.00% by weight or less as measured by ASTM D874, eg, about 0. It is a level of 10 to about 1.00 wt% sulfated ash. In one embodiment, the level of sulfated ash produced by the lubricating oil composition of the present invention is less than or equal to about 0.80% by weight as measured by ASTM D874, eg, as measured by ASTM D874 and sulfated. The ash level is about 0.10 to about 0.80 wt%. 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, as measured by ASTM D874, the level of sulfated ash is from about 0.10 to about 0.60% by weight.

Suitably, the lubricating oil compositions of the present invention have a total base value (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). ) Can have.

Viscosity Adjuster A viscosity modifier (VM) or viscosity index improver (VII) can be used in the lubricant to impart operability at high and low temperatures. The VM can be used to provide its sole function or it can be multifunctional. The multifunction viscosity modifier also provides additional functionality for the dispersant function. Viscosity Adjusters and Dispersants Examples of viscosity modifiers are polymethacrylates, polyacrylates, polyolefins, styrene-maleic acid ester copolymers, and similar polymeric materials including homopolymers, copolymers and graft copolymers.

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

Particularly useful in this disclosure is a combination of the dispersant polymethacrylate VII and the ethylene-based 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. It has a weight average molecular weight of from / 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.

ここで、Ｒは水素またはメチルであり、Ｒ^１は炭素原子数１から５の飽和または不飽和の直鎖または分岐アルキル基かまたは炭素原子数３から５の飽和または不飽和のシクロアルキル基であり、Ｒ^２およびＲ^３はそれぞれ独立して水素または式−ＣＯＯＲ’（式中、Ｒ’は水素または１〜５個の炭素原子を有する飽和または不飽和の直鎖または分岐アルキル基である）；
（ｂ）１０〜９８重量％、好ましくは２０〜９５重量％の、式（ＩＩ）の１つ以上のエチレン性不飽和エステル化合物

ここで、Ｒは水素またはメチル、Ｒ^４は飽和または不飽和の６から１５炭素原子を持つ直鎖または分岐のアルキル基、または６から１５の炭素原子を持つ飽和または不飽和シクロアルキル基であり、Ｒ^５およびＲ^６はそれぞれ独立して水素または式−ＣＯＯＲ”（式中、Ｒ”は水素であるか、または６〜１５個の炭素原子を有する飽和もしくは不飽和の直鎖もしくは分岐鎖アルキル基である）；
（ｃ）０〜３０重量％、好ましくは５〜２０重量％の、式（ＩＩＩ）の１つ以上のエチレン性不飽和エステル化合物：

ここで、Ｒは水素またはメチルであり、Ｒ^７は炭素数１６から４０、好ましくは１６から３０の飽和または不飽和の直鎖または分岐アルキル基、または炭素数１６から４０、好ましくは１６から３０のシクロアルキル基、Ｒ^８およびＲ^９はそれぞれ独立して水素または式−ＣＯＯＲ”’の基であり、ここでＲ”’は水素または１６〜４０個、好ましくは１６〜３０個の炭素原子を有する飽和または不飽和の直鎖または分岐アルキル基であり；
（ｄ）０〜３０重量％のビニルモノマー；
（ｅ）２〜１０重量％の少なくとも１つのＮ−分散剤モノマー。 Polyalkyl (meth) acrylates include the following monomer units:
(A) One or more ethylenically unsaturated ester compounds of the formula (I) from 0 to 40% by weight:

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. Yes, R ² and R ³ are independently hydrogen or formula-COOR'(where R'is hydrogen or a saturated or unsaturated linear or branched alkyl group with 1-5 carbon atoms). ;
(B) One or more ethylenically unsaturated ester compounds of formula (II), 10-98% by weight, preferably 20-95% by weight.

Wherein, R represents hydrogen or methyl, R ⁴ is a saturated or unsaturated cycloalkyl group having carbon atoms of straight-chain or branched alkyl group or a 6 to 15, with 6 to 15 carbon atoms, saturated or unsaturated , R ⁵ and R ⁶ are independently hydrogen or formula-COOR "(in formula, R" is hydrogen or saturated or unsaturated linear or branched alkyl having 6 to 15 carbon atoms. Is the basis);
(C) One or more ethylenically unsaturated ester compounds of formula (III), from 0 to 30% by weight, preferably 5 to 20% by weight:

Here, R is hydrogen or methyl, and R ⁷ is a saturated or unsaturated linear or branched alkyl group having 16 to 40 carbon atoms, preferably 16 to 30 carbon atoms, or 16 to 40 carbon atoms, preferably 16 to 30 carbon atoms. The cycloalkyl groups, R ⁸ and R ⁹ , are independently hydrogen or groups of formula-COOR "', where R"'is hydrogen or 16-40, preferably 16-30 carbon atoms. Saturated or unsaturated linear or branched alkyl group having;
(D) 0 to 30% by weight of vinyl monomer;
(E) At least one N-dispersant monomer of 2-10% by weight.

The DPMA used in the present invention is about 1-10% by weight of methyl methacrylate monomer, about 0.5 to 3% by weight of N-vinylpyrrolidone as a nitrogen-containing monomer, and a longer chain alkyl methacrylate monomer as the rest, in particular. 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-based 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. It has a weight average molecular weight of about 110,000 g / mol.

The ethylene-based viscosity index modifier used in the present invention can be described as follows, the disclosure of which is described in US201320360, which is incorporated herein.

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

In one embodiment, the polymer composition typically comprises from about 30% to about 70% by weight of the first ethylene-α-olefin copolymer (a) and from about 70% to about 30% by weight of the second. Ethylene-α-olefin copolymer (b) of the above is contained 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 2 is contained in the composition based on the total amount of (a) and (b). In certain embodiments, the polymer composition comprises from about 50 to about 54% by weight the first ethylene-α-olefin copolymer (a) and from about 46 to about 50% by weight 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 / mol to about 110,000 g / mol. 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 compositions of the first ethylene-α-olefin copolymer and the second ethylene-α-olefin copolymer in one embodiment is typically from about 60,000 g / mol to about 120,000 g / mol. is there. 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 is typically from about 70,000 g / mol to about 110,000 g / mol. It is a mole. In yet another embodiment, the weight average molecular weight of the compositions of the first ethylene-α-olefin copolymer and the second ethylene-α-olefin copolymer is typically from about 80,000 to about 100,000 g / mol. Is. The molecular weight distribution of each ethylene-α-olefin copolymer is typically less than about 2.5, more typically about 2.1 to about 2.4. The polymer distribution determined by GPC is usually unimodal.

In one embodiment, the polymer composition typically has a total ethylene content of about 40% to about 70% by weight, 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.

ここで、Ｒ”はＣ_１〜Ｃ_３０（例えば、Ｃ_１３〜Ｃ_３０）アルキル基であり；ｎは１から４までの整数であり；Ｍはアルカリ土類金属（例えば、ＣａまたはＭｇ）である。 Salicylic acid detergent Salicylic acid salt can be prepared by reacting a basic metal compound with at least one carboxylic acid and removing water from the reaction product. A cleaning agent made from salicylic acid is a type of cleaning agent prepared from a carboxylic acid. Useful salicylates include long-chain alkyl salicylates. One of the useful families of compositions is the following structure (5).

Where R "is _{an alkyl group C 1 to} C ₃₀ (eg C _{13 to} C ₃₀ ); n is an integer from 1 to 4; M is an alkaline earth metal (eg Ca or Mg). is there.

Hydrocarbyl-substituted salicylic acid can be prepared from phenol by the Kolbe reaction (see US Pat. No. 3,595,791). The metal salt of hydrocarbyl-substituted salicylic acid can be prepared by double decomposition of the metal salt in a polar solvent such as water or alcohol.

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

A typical detergent is an anionic material that contains a long-chain hydrophobic portion of the molecule and a smaller anionic (anionic) or oleophobic hydrophilic moiety of the molecule. The anionic portion of the detergent is typically derived from organic acids such as sulfur acids, carboxylic acids, phosphorous acids, phenols, or mixtures thereof. Counterions are usually alkaline earth or alkali metals.

Salts containing substantially stoichiometric amounts of metal are described as neutral salts and have a total base value (TBN) of 0-80 mg KOH / g. Many compositions are hyperbasic and contain large amounts of metal bases achieved by overreacting metal compounds (eg, metal hydroxides or metal oxides) rich in acid gases (eg, carbon dioxide). Including. Useful detergents can be neutral, moderately hyperbasic, or highly hyperbasic.

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

Suitable cleaning agents include metal salts of sulfonate, phenate, carboxylate, phosphate, and salicylate.

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

Fenates can be prepared by reacting alkali earth metal hydroxides or oxides (eg, CaO, Ca (OH) ₂ , MgO, or Mg (OH) ₂ ) with alkylphenols or alkylphenol sulfides. Useful alkyl groups include straight or branched C _{1 to} C ₃₀ (eg, C _{4 to} 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 alkylphenols may contain multiple alkyl substituents, each independently linear or branched. When non-sulfurized alkylphenols are used, the sulfurized products can be obtained by methods well known in the art. These methods involve heating a mixture of alkylphenols and sulfides (eg, sulfur halides such as elemental sulfur, sulfur dichloride, etc.) and then reacting the phenol sulfides with alkaline earth metal bases.

Magnesium Cleaners Preferred magnesium-containing cleaners include magnesium sulfonate, magnesium phenate, and magnesium salicylate, in particular magnesium sulfonate and magnesium salicylate. These are as described above.

Magnesium-containing detergents are 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 with respect to the lubricating oil composition. , Or can be used in an amount providing a magnesium weight of 400-800 ppm.

In one embodiment that is substantially free of molybdenum elements, the level of molybdenum-containing elements in the lubricating oil composition of the present invention is about 60 ppm or less, eg, about 0.01, based on the total weight of the lubricating oil composition. The level of molybdenum-containing elements is ~ about 60 ppm. In one embodiment, the level of molybdenum-containing elements in the lubricating oil composition of the present invention is about 40 ppm or less, based on the total weight of the lubricating oil composition, for example, about 0.01 to about 40 ppm of molybdenum. The level of the element. In one embodiment, the level of molybdenum-containing elements in the lubricating oil composition of the present invention is about 25 ppm or less, based on the total weight of the lubricating oil composition, for example, about 0.01 to about 25 ppm of molybdenum. The level of the element. In one embodiment, the level of molybdenum-containing elements in the lubricating oil composition of the present invention is about 15 ppm or less, based on the total weight of the lubricating oil composition, for example, about 0.01 to about 15 ppm of molybdenum. The level of the element. In one embodiment, the level of molybdenum-containing elements in the lubricating oil composition of the present invention is about 10 ppm or less, based on the total weight of the lubricating oil composition, for example, about 0.01 to about 10 ppm of molybdenum. The level of the element. In one embodiment, the level of molybdenum-containing elements in the lubricating oil composition of the present invention is about 5 ppm or less, based on the total weight of the lubricating oil composition, for example, about 0.01 to about 5 ppm of molybdenum. The level of the element.

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, It means that it exists in less than 1 ppm, less than 0.5 ppm, and less than 0.1 ppm.

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

The lubricating oil compositions of the present disclosure may also include other conventional additives capable of imparting or improving any desired property of the lubricating oil composition in which these additives are dispersed or dissolved. Any additive known to those of skill in the art can be used in the lubricating oil compositions disclosed herein. Some suitable additives are 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 here by reference. For example, lubricating oil compositions include antioxidants, anti-wear agents, metal cleaners, rust inhibitors, anti-fog agents, de-emulsifiers, metal deactivators, friction modifiers, flow point depressants, defoamers, etc. It can be blended with co-lubricants, corrosion inhibitors, ashless dispersants, multifunction agents, dyes, extreme pressure agents and the like and mixtures thereof. Various additives are known and are commercially available. These additives, or similar compounds thereof, can be used in the preparation of the lubricating oil compositions of the present disclosure by conventional mixing procedures.

The lubricating oil composition of the present invention can contain one or more wear resistant agents that can reduce friction and excessive wear. Any wear resistant agent known to those of skill in the art can be used in the lubricating oil composition. Non-limiting examples of suitable abrasion resistant agents include: zinc dithiophosphate, metal dithiophosphate (eg Pb, Sb, Mo, etc.) salts, metal dithiocarbamate (eg Zn). , Pb, Sb, Mo, etc.) salt, fatty acid metal (eg, Zn, Pb, Sb, etc.) salt, boron compound, phosphate ester, phosphite ester, phosphate ester or thiophosphate ester amine salt, dicyclo Reaction products of pentadiene and thiophosphate, and combinations thereof. The amount of abrasion resistant agent is from about 0.01% to about 5% by weight, from about 0.05% to about 3% by weight, or about 0.1% by weight to about 0.1% by weight, based on the total weight of the lubricating oil composition. It can fluctuate by 1% by weight.

In certain embodiments, the abrasion resistant 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 alkaline 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 (dihydrocarbyl dithiophosphate metal salt) has about 3 to about 22 carbon atoms, about 3 to about 18 carbon atoms, and about 3 to about 12 carbon atoms. It has an atom, or about 3 to about 8 carbon atoms. In a further embodiment, the alkyl group is linear or branched.

The amount of dihydrocarbyl dithiophosphate metal salt containing the zinc dialkyldithiophosphate salt in the lubricating oil composition 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 composition of the present invention may contain one or more friction modifiers capable of reducing friction between moving parts. Any friction modifier known to those of skill in the art can be used in the lubricating oil composition. Non-limiting examples of suitable friction modifiers include: aliphatic carboxylic acids; derivatives of aliphatic carboxylic acids (eg, alcohols, esters, borate esters, amides, metal salts, etc.); , Di or trialkyl substituted phosphoric acid or phosphonic acid; mono, di or trialkyl substituted phosphoric acid or phosphonic acid derivatives (eg, 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; booxide fatty epoxides; fatty phosphites, fatty epoxides, fatty amines, Epoxide-alkylated fatty amines, metal salts of fatty acids, fatty acid amides, glycerin esters, glycerin booxide esters; and fatty imidazolines, according to US Pat. No. 6,372,696, the contents of which are incorporated herein by reference. Disclosed); _{Reactions of nitrogen-containing compounds selected from the group consisting of C 4 to} C ₇₅ , or C _{6 to} C ₂₄ , or C _{6 to} C ₂₀ , fatty acid esters, and ammonia and alkanolamines, and mixtures thereof. A friction modifier obtained from the product. The amount of friction modifier is about 0.01% to about 10% by weight, about 0.05% to about 5% by weight, or about 0.1% by weight to about 0.1% 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 an organic antioxidant in an amount of 0.01 to 5% by weight, preferably 0.1 to 3% by weight. The antioxidant can be a hindered phenolic antioxidant or a diallylamine antioxidant. Diarylamine antioxidants are advantageous in imparting a base value derived from the nitrogen atom. Hindered phenol oxidants are advantageous in that they do not generate _{NO x gas.}

Examples of hindered phenol 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'-isopropyridenebis (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) octadecyl propionate, octyl 3- (3,54-butyl-4-hydroxy-3-methylphenyl) propionate, and, but not limited to, IrganoxL135® (registered trademark). Commercial products such as BASF), Naugarube 531® (Chemtura), and Ethanox 376® (SI Group).

Examples of diarylamine antioxidants include alkyldiphenylamines having a mixture of alkyl groups having 4-9 carbon atoms, p, p'-dioctyldiphenylamines, phenylnaphthylamines, phenylnaphthylamines, alkylated naphthylamines, alkylated phenylnaphthylamines and the like. Can be mentioned.

Each of the hindered phenol oxidants and the diallylamine oxidants can be used alone or in combination. If desired, other oil-soluble antioxidants can be used.

In the preparation of lubricant formulations, it is common practice to introduce the additive in the form of a 10-80% by weight active ingredient concentrate in a hydrocarbon oil, such as a mineral lubricant, or other suitable solvent. Is.

Generally, these concentrates may be diluted with 3 to 100 parts by weight of the additive package, for example 5 to 40 parts by weight, in forming the finished lubricant, for example, crankcase motor oil. it can. Of course, the purpose of the concentrate is to make the handling of the various materials less difficult and less cumbersome, 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. In some cases, one or more other things 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 with one or more additions, the additions can be in any order. In other embodiments, the additive is added to the base oil at the same time, optionally in the form of an additive concentrate. In some embodiments, solubilization of the additives 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 device known to those of skill in the art can be used to blend, mix or solubilize the ingredients. Blending, mixing or solubilizing can be done in blenders, stirrers, dispersers, mixers (eg planetary mixers and dual planetary mixers), homogenizers (eg gaulin homogenizers and laney homogenizers), mills (eg colloid mills, ball mills and sand mills). Alternatively, it can be carried out with any other mixing or dispersing device known in the art.

Applications of Lubricating Oil Compositions Lubricating oil compositions disclosed herein are suitable for use as motor oils (ie, engine oils or crankcase oils) in spark-ignition internal combustion engines, especially direct injection and boosted engines. May be.

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

Examples The examples below are for purposes of illustration only and are by no means limiting the scope of the invention.

Example 1
The 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) With respect to calcium content, a cleaning agent at 1120 ppm, mostly _{derived from C 14-} C ₁₈ normal alpha olefin-derived hyperbasic calcium salicylate, and a small amount derived from low-perbasic calcium sulfonate;
(C) 240 ppm highly perbasic magnesium sulfonate detergent with respect to magnesium;
(D) Ethylene carbonate-treated succinimide booxide dispersant;
(E) Alkylated diphenylamine antioxidant, hindered phenol antioxidant;
(F) Conventional amount of pour point depressant,
(G) A combination of viscosity index improvers, a non-dispersant OCP derived from ethylene propylene (ethylene propylene-based copolymer containing 55-65% ethylene, weight average molecular weight of 80,000 to about 100,000 g / mol. , And 1.50% by weight polymer concentrate containing 0.70% by weight polymer concentrate containing SSI (about 20 to about 26) and 1.50% by weight polymer concentrate containing dispersant type PMA (1 to 10% by weight methyl methacrylate monomer, It has about 0.5 to 3% by weight of N-vinylpyrrolidone as a nitrogen-containing monomer, and the rest has a longer chain alkyl methacrylate monomer, especially lauryl methacrylate, and 200,000 to 250,000 MW, which is about. It has an SSI of 40 to about 50,
(H)
(I) Additional additives including organic friction modifiers, Mannich reaction products, corrosion inhibitors, markers, foam inhibitors; and (j) the rest is a mixture of Group III and Group IV PAO base oils.

Example 2
Example 1 was repeated, except that _{calcium salicylate was derived from C 20-} C ₂₄ isomerized normal alpha olefins with an alpha olefin isomerization level of about 0.16. The additive contained 6.4 wt% Ca and about 20 wt% diluted oil and had a TBN of about 180 mg KOH / g and a basicity index of about 2.4. On an active ingredient basis, the TBN of this additive is approximately 225 mg KOH / g.

The isomerization level was measured by the 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 with Bruker Ultrashield Plus 400 in chloroform-d1 at 400 MHz using TopSpin 3.2 spectrum processing software.

The isomerization level (I) is _{the methyl group (-CH 3 ) bonded to the methylene main chain group (-CH 2-} ) (chemical shift 1.01-1.38 ppm) (chemical shift 0.30 to 1.01 ppm). Represents the relative quantity of, and is defined by equation (6) shown below:
I = m / (m + n) Equation (6)
Here, m is an NMR integral of a methyl group having a chemical shift of 0.30 ± 0.03 to 1.01 ± 0.03 ppm, and n is an NMR integral of a methyl group having a chemical shift of 1.01 ± 0.03 to 1.38 ± 0. . NMR integration of 10 ppm methylene group.

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

Example 4
Example 3 was repeated, except that the overbasified calcium salicylate from the normal alpha olefins _{C 14-} C _{18 was removed.}

Example 5
Example 1 was repeated, except that 3 wt% ester base oil was added to the finished oil.

Example 6
Example 1 was repeated except that calcium salicylate was replaced with magnesium salicylate derived from _{C 20-} C ₂₄ isomerized normal alpha olefins with an alpha olefin isomerization level of about 0.16. The additive contained 4.3% by weight Mg and about 35% by weight diluted 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 calcium salicylate was derived from C 14-} C ₁₈ alpha olefins and replaced with magnesium salicylate having about 236 mg KOH / g TBN and 5.34 wt% Mg. It was.

Comparative Example 1
Example 1 was repeated, but a 0.7% by weight polymer concentrate containing an ethylene propylene-induced non-dispersant OCP and a hydrogenated polyisoprene star polymer bonded to divinylbenzene having 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 sulfur-free molybdenum compound was added to the lubricating oil composition in an amount providing 320 ppm of molybdenum.

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

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

Comparative Example 5
Example 1 was repeated, but 4.50% by weight of the ethylene propylene-induced non-dispersant OCP and the dispersant PMA containing a hydrogenated polyisoprene star polymer bonded to divinylbenzene with an SSI of 4 and a molecular weight of 35,000. Replaced with a polymer concentrate, 0.4 wt% sulfur-containing molybdenum succinimide complex was added in an amount providing 200 ppm molybdenum to the lubricating oil composition.

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

Comparative Example 7
Example 1 was repeated, but the ethylene propylene-induced non-dispersant OCP was replaced with a polymer concentrate of 6.25 wt% dispersant OCP.

Table 2 shows the performance evaluation of the test formulation. The following bench tests were performed to measure wear. FZG wear scuffing load capacity test. In order to evaluate the wear performance of automobile engine oil, FZG test rig (FZG square test machine) using A10 gear compliant with CEC-L-84-A-02, various engine oils with different chemical properties Evaluate the load characteristics of. This method helps to assess the scuffing load capacity of oils commonly used in highly stressed cylindrical gear devices found in many vehicles and fixed applications. The minimum load stage fail of the A10 gear at 16.6 m / s and 130 ° C. was 8.

Claims (18)

A lubricating oil composition having an HTHS viscosity in the range of about 1.3 to about 2.9 cP at 150 ° C.
a) A major amount of lubricating viscosity oil with a kinematic viscosity at 100 ° C. in the range of ^{1.5-6.0 mm 2 / s;}
b) Dispersant polymethacrylate (DPMA) VII with Mw of 200,000 g / mol to 450,000 g / mol;
c) Non-dispersible ethylene-based olefin copolymer viscosity index improver having Mw of 50,000 g / mol to 150,000 g / mol and total ethylene content of about 30% by weight to about 70% by weight;
d) Approximately 200-about 1000 ppm magnesium from magnesium-containing detergents;
The lubricating oil composition, wherein the lubricating oil composition is substantially free of molybdenum-containing elements. The lubricating oil composition according to claim 1, further comprising 1 to 10% by weight of an ester base oil. The lubricating oil composition according to claim 1, wherein the magnesium-containing detergent is _{magnesium salicylate derived from a C 20-} C _{24 isomerized normal alpha olefin.} The lubricating oil composition according to claim 1, wherein the non-dispersible ethylene-based olefin copolymer viscosity index improver has a total ethylene content of about 55 to 65% by weight. The lubricating oil composition according to 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. The lubricating oil composition according to claim 1, wherein the dispersant polymethacrylate (DPMA) VII has an Mw of 200,000 g / mol to 300,000 g / mol. The lubricating oil composition according to claim 1, wherein the dispersant polymethacrylate VII contains the following monomer units:
(A) One or more ethylenically unsaturated ester compounds of the formula (I) from 0 to 40% by weight:

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 independently hydrogen or formula-COOR'(where R'is hydrogen or a saturated or unsaturated linear or branched alkyl group having 1 to 5 carbon atoms);
(B) One or more ethylenically unsaturated ester compounds of formula (II), 10-98% by weight, preferably 20-95% by weight.

Where R is hydrogen or methyl and R ⁴ is a linear or branched alkyl group with 6 to 15 carbon atoms of saturated or unsaturated, or saturated or unsaturated with 6 to 15 carbon atoms. Cycloalkyl groups, R ⁵ and R ⁶ are independently hydrogen or formula-COOR "(in formula, R" is hydrogen or saturated or unsaturated direct with 6 to 15 carbon atoms. Chain or branched alkyl group);
(C) One or more ethylenically unsaturated ester compounds of formula (III), from 0 to 30% by weight, preferably 5 to 20% by weight:

Here, R is hydrogen or methyl, and R ⁷ is a saturated or unsaturated linear or branched alkyl group having 16 to 40 carbon atoms, preferably 16 to 30 carbon atoms, or 16 to 40 carbon atoms, preferably 16 to 30 carbon atoms. R ⁸ and R ⁹ are independently hydrogen or groups of formula-COOR "', where R"'is hydrogen or 16-40, preferably 16-30 carbons. Saturated or unsaturated linear or branched alkyl groups with atoms;
(D) 0 to 30% by weight of vinyl monomer;
(E) At least one N-dispersant monomer of 2-10% by weight. The lubricating oil composition according to claim 1, wherein the non-dispersible ethylene-based olefin copolymer is an ethylene-propylene copolymer. The lubricating oil composition according to claim 1, wherein the magnesium content from the magnesium-containing cleaning agent is about 200 to about 850 ppm. A method of improving friction and reducing wear of an internal combustion engine, wherein the engine is lubricated with a lubricating oil composition containing the following and having an HTHS viscosity in the range of about 1.3 to about 2.9 cP at 150 ° C. Methods including to do:
a) A major amount of lubricating viscosity oil with a kinematic viscosity at 100 ° C. in the range of ^{1.5-6.0 mm 2 / s;}
b) Dispersant polymethacrylate (DPMA) VII with Mw of 200,000 g / mol to 450,000 g / mol;
c) Non-dispersible ethylene-based olefin copolymer viscosity index improver having Mw of 50,000 g / mol to 150,000 g / mol and total ethylene content of about 30% by weight to about 70% by weight;
d) Approximately 200-about 1000 ppm magnesium from magnesium-containing detergents;
Here, the lubricating oil composition is substantially free of molybdenum-containing elements. The method of claim 10, wherein the lubricating oil composition further comprises 1 to 10% by weight of an ester base oil. The method of claim 10, wherein the magnesium-containing detergent is _{magnesium salicylate derived from a C 20-} C _{24 isomerized normal alpha olefin.} 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. The method according to 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. 10. The method of claim 10, wherein the dispersant polymethacrylate (DPMA) VII has a Mw of 200,000 g / mol to 300,000 g / mol. 10. The method of claim 10, wherein the dispersant polymethacrylate VII comprises the following monomer units:
(A) One or more ethylenically unsaturated ester compounds of the formula (I) from 0 to 40% by weight:

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 independently hydrogen or formula-COOR'(where R'is hydrogen or a saturated or unsaturated linear or branched alkyl group having 1 to 5 carbon atoms);
(B) One or more ethylenically unsaturated ester compounds of formula (II), 10-98% by weight, preferably 20-95% by weight.

Where R is hydrogen or methyl and R ⁴ is a linear or branched alkyl group with 6 to 15 carbon atoms of saturated or unsaturated, or saturated or unsaturated with 6 to 15 carbon atoms. Cycloalkyl groups, R ⁵ and R ⁶ are independently hydrogen or formula-COOR "(in formula, R" is hydrogen or saturated or unsaturated direct with 6 to 15 carbon atoms. Chain or branched alkyl group);
(C) One or more ethylenically unsaturated ester compounds of formula (III), from 0 to 30% by weight, preferably 5 to 20% by weight:

Here, R is hydrogen or methyl, and R ⁷ is a saturated or unsaturated linear or branched alkyl group having 16 to 40 carbon atoms, preferably 16 to 30 carbon atoms, or 16 to 40 carbon atoms, preferably 16 to 30 carbon atoms. R ⁸ and R ⁹ are independently hydrogen or groups of formula-COOR "', where R"'is hydrogen or 16-40, preferably 16-30 carbons. Saturated or unsaturated linear or branched alkyl groups with atoms;
(D) 0 to 30% by weight of vinyl monomer;
(E) At least one N-dispersant monomer of 2-10% by weight. The method according to claim 10, wherein the non-dispersible ethylene-based olefin copolymer is an ethylene-propylene copolymer. The method of claim 10, wherein the magnesium from the magnesium-containing detergent is from about 200 to about 850 ppm.