JP6669442B2 - Lubricating oil composition - Google Patents

Description

FIELD OF THE INVENTION The present invention relates to automotive lubricating oil compositions. More specifically, but not exclusively, the present invention relates to automotive crankcase lubricating oil compositions for use in gasoline (spark ignition) and diesel (compression ignition) internal combustion engines, which compositions are referred to as crankcase lubricating oils; And addition to the lubricating oil composition to improve the corrosion resistance properties of non-ferrous metal engine parts, especially those containing copper and / or lead (eg, bearings) (i.e., to inhibit corrosion of non-ferrous metal engine parts). On the use of agents.

BACKGROUND OF THE INVENTION Crankcase lubricating oil is the oil used for general lubrication of internal combustion engines, in which a sump is generally located below the engine's crankshaft and to which circulating oil returns.
Antiwear agents are typically used as additives in crankcase lubricating oils to reduce excessive wear of metal engine parts. The antiwear agent is usually based on a compound containing sulfur or phosphorus or both, such as a compound capable of depositing a polysulfide film on the surface of a metal engine component. A common antiwear agent always utilized in crankcase lubricants is dihydrocarbyl dithiophosphate metal salt.
It is also desirable to reduce the energy and fuel consumption requirements of the engine, and therefore, there is also a need for a crankcase lubricant that reduces the overall friction of the engine. Reduction of the engine friction loss greatly contributes to improving the fuel economy performance and fuel economy retention characteristics of the engine. Accordingly, ashless organic friction modifiers, such as ashless nitrogen-free organic friction modifiers (e.g., esters formed from carboxylic acids and alkanols, such as glycerol monooleate (GMO), etc.) have been used as additives in crankcase lubricating oils. To obtain improved friction characteristics and improved fuel economy performance.
Thus, to provide a crankcase lubricating oil having the desired antiwear performance and desired frictional properties, lubricating oil formulators typically combine the lubricating oil composition with an ashless organic friction modifying additive such as a GMO. Dihydrocarbyl dithiophosphate metal salt antiwear additives have been utilized.
It has now been found that the use of ashless organic friction modifier additives such as GMOs in lubricating oils typically results in significant amounts of lead and copper corrosion. In addition, the use of ashless organic friction modifiers such as GMO in combination with a metal dihydrocarbyl dithiophosphate antiwear additive typically further increases the amount of lead corrosion. The corrosive properties of ashless organic friction modifiers such as GMOs, and the increased lead corrosion that can be attributed to the combination of ashless organic friction modifiers and dihydrocarbyl dithiophosphate metal salts are problematic for lubricating oil formulators. For example, the corrosive nature of the additive components, particularly when used in combination, may necessitate a reduction in the throughput of the additive, thereby affecting the antiwear and / or fuel economy performance of the lubricating oil; or, or It may be necessary to include even more expensive anti-corrosion additives in the lubricating oil to combat the corrosive properties of metal dihydrocarbyl dithiophosphates and ashless organic friction modifiers.

  Accordingly, metal dihydrocarbyl dithiophosphate antiwear agents and ashless organic friction modifying additives that exhibit improved corrosion performance characteristics with respect to non-ferrous metal engine components, particularly those containing copper and / or lead, or alloys thereof, are disclosed. There is a need for a lubricating oil composition containing the same.

According to a first aspect Summary of the Invention, the present invention provides a lubricating oil composition having a phosphorus content of 0.12 wt% or less as determined in 1.2 mass% of sulfated ash content and ASTM D5185 as determined by ASTM D874 Wherein the lubricating oil composition comprises the following components:
(A) a large amount of oil of lubricating viscosity;
(B) an oil-soluble or oil-dispersible polymer friction modifier as an effective small amount of an additive (this polymer friction modifier is as follows:
(i) a functionalized polyolefin;
(ii) polyalkylene glycol;
(iii) a polyol; and
(iv) a reaction product of only a polycarboxylic acid);
as well as
(C) There is provided a lubricating oil composition comprising at least one oil-soluble or oil-dispersible metal dihydrocarbyl dithiophosphate as an effective minor additive or made by mixing these components.
Preferably, the lubricating oil composition of the present invention is a crankcase lubricating oil.

Unexpectedly, in a lubricating oil composition comprising a large amount of oil of lubricating viscosity, the use of the polymeric friction modifier (B) as defined by the first aspect of the present invention as an effective small amount of an additive, Corrosion of non-ferrous metal (eg, copper and / or lead) containing engine components can be suppressed as compared to comparable lubricating oils without the friction modifier (B). In other words, the polymeric friction modifier (B) can function as an anti-corrosion agent for non-ferrous metal-containing engine parts, especially those containing copper and / or lead or alloys containing such metals.
Further, in a lubricating oil composition comprising a large amount of oil of lubricating viscosity, an oil-soluble or oil-dispersible polymer friction modifier (B) as defined in the first aspect of the present invention as an effective small amount of an additive, The use of an effective minor additive in combination with an oil-soluble or oil-dispersible metal dihydrocarbyl dithiophosphate salt as defined in the first aspect of the invention, typically comprises an oil-soluble or oil-soluble or diisocyanate as defined in the first aspect of the invention. Improved corrosion of engine parts containing non-ferrous metals (e.g., copper and / or lead) compared to comparable lubricating oils containing an ashless organic friction modifier such as GMO in combination with an oil dispersible metal dihydrocarbyl dithiophosphate. It has also been found to provide lubricating oils that exhibit prevention and / or reduction (ie, inhibit corrosion).
Still further, in a lubricating oil composition comprising a large amount of oil of lubricating viscosity, an oil-soluble or oil-dispersible polymer friction modifier (B) as defined in the first aspect of the present invention as an effective small amount of an additive. The use in combination with an oil-soluble or oil-dispersible metal dihydrocarbyl dithiophosphate as defined in the first aspect of the invention as an effective minor additive typically comprises (i) metal dihydrocarbyl dithiophosphate. A comparable lubricating oil without the polymeric friction modifier (B); and (ii) a comparable lubricating oil without the metal dihydrocarbyl dithiophosphate and the polymeric friction modifier (B). It has also been found to provide lubricating oils that exhibit improved prevention and / or reduction of corrosion of copper-containing metal engine components (ie, inhibit corrosion).
Accordingly, such reduced levels of non-ferrous metal corrosion (eg, reduced copper and / or lead corrosion levels) associated with the use of polymeric friction modifiers (B) as compared to ashless organic friction modifiers such as GMOs are particularly desirable for dihydrocarbyl. When used in combination with a metal dithiophosphate, it may allow for increased throughput of the combination of additives in lubricating oils. Additionally or alternatively, such a reduction in non-ferrous metal corrosion levels can reduce the need for the use of relatively expensive auxiliary corrosion-resistant additives. Thus, the use of polymeric friction modifier (B) in combination with a metal dihydrocarbyl dithiophosphate typically results in severe abrasion resistance as set forth in industrial lubricant specifications and original equipment manufacturer specifications. It provides the formulator with a high degree of flexibility when formulating lubricating oil compositions that must meet performance and fuel economy performance standards.

According to a second aspect, the present invention provides a method of lubricating a spark ignition or compression ignition internal combustion engine, comprising the step of lubricating the engine with a lubricating oil composition as defined according to the first aspect of the present invention.
According to a third aspect, the present invention provides a method of lubricating a spark-ignition or compression-ignition internal combustion engine, wherein the high-volume, high-volume, non-ferrous-metal-containing engine components are provided with a reduced amount of corrosion during operation of the engine. There is provided the use of an oil-soluble or oil-dispersible polymeric friction modifier (B) as defined in the first aspect of the present invention as an effective small amount of additive in a lubricating oil composition comprising an oil of lubricating viscosity. Preferably, the non-ferrous metal-containing component comprises copper, lead, or an alloy of said metal.
Preferably, the lubricating oil composition as defined in the third aspect of the present invention further comprises an effective minor amount of a metal dihydrocarbyl dithiophosphate as defined in the first aspect of the present invention.
According to a fourth aspect, the present invention relates to a method for lubricating a spark-ignition or compression-ignition internal combustion engine, wherein the high-volume, high-speed, high-speed, high-speed, high-speed, low-frequency, high-temperature, low-temperature, high-temperature, high-temperature, high-temperature, high-temperature engine components are provided. In a lubricating oil composition comprising an oil of lubricating viscosity, an effective small amount of an oil-soluble or oil-dispersible polymer friction modifier (B) as defined in the first aspect of the present invention as an effective small amount of an additive, There is provided the use as an agent in combination with the oil-soluble or oil-dispersible metal dihydrocarbyl dithiophosphate (C) as defined in the first aspect of the present invention. Preferably, the non-ferrous metal-containing engine component comprises copper, lead or an alloy of said metal, especially copper or an alloy thereof.
According to a fifth aspect, the present invention provides a method for reducing and / or preventing (i.e., suppressing corrosion) corrosion of a non-ferrous metal containing engine component during operation of an engine in the operation of a spark ignition or compression ignition internal combustion engine. There is provided a use of a lubricating oil composition according to the first aspect of the invention. Preferably, the non-ferrous metal-containing engine component comprises copper, lead or an alloy of said metal, especially copper or an alloy thereof.

According to a sixth aspect, the present invention is a method for preventing and / or reducing (i.e., inhibiting corrosion) corrosion of non-ferrous metal-containing engine parts of an engine, comprising a large amount of oil of lubricating viscosity and an effective small amount of an additive. A method comprising lubricating an engine with a lubricating oil composition comprising the oil-soluble or oil-dispersible polymeric friction modifier (B) as defined in the first aspect of the present invention, and operating the engine. Preferably, the non-ferrous metal-containing component comprises copper, lead or an alloy of said metal. Preferably, the engine as defined in the sixth aspect of the invention is a spark ignition or compression ignition internal combustion engine.
According to a seventh aspect, the present invention is a method for preventing and / or reducing (ie, inhibiting corrosion) of non-ferrous metal-containing engine parts of an engine, wherein the engine is lubricated with the lubricating oil composition of the first aspect of the present invention. A method comprising lubricating and operating an engine is provided. Preferably, the non-ferrous metal-containing component comprises copper, lead or an alloy of said metal, especially copper or an alloy thereof. Preferably, the engine as defined in the seventh aspect of the invention is a spark ignition or compression ignition internal combustion engine.
Preferably, the oil-soluble or oil-dispersible metal dihydrocarbyl dithiophosphate (C) is an oil-soluble or oil-dispersible zinc dihydrocarbyl dithiophosphate (i.e., zinc dihydrocarbyl dithiophosphate (ZDDP)), more preferably an oil-soluble or Oil-dispersible zinc dialkyldithiophosphate.

Preferably, the lubricating oil composition of the first aspect of the present invention and the lubricating oil composition as defined in the second, third, fourth, fifth, sixth and seventh aspects of the present invention comprise an additive component ( In addition to B) and (C), select from ashless dispersants, metal detergents, corrosion inhibitors, antioxidants, pour point depressants, antiwear agents, friction modifiers, demulsifiers, defoamers and viscosity modifiers An effective minor amount (0.1-30% by weight) of one or more co-additives.
The lubricating oil composition of the present invention has a sulfated ash content (ASTM D874) of 1.2% by weight or less, preferably 1.1% by weight or less, more preferably 1.0% by weight or less based on the total weight of the composition.
Preferably, the lubricating oil compositions of the present invention contain low levels of phosphorus. The lubricating oil composition is 0.12% by mass or less based on the total mass of the composition, preferably up to 0.11% by mass, more preferably 0.10% by mass or less, still more preferably 0.09% by mass or less, still more preferably 0.08% by mass. Below, most preferably it contains phosphorus in an amount of not more than 0.06% by weight of phosphorus (ASTM D5185). Suitably, the lubricating oil composition comprises at least 0.01% by weight based on the total weight of the composition, preferably at least 0.02% by weight, more preferably at least 0.03% by weight, even more preferably at least 0.05% by weight of phosphorus (ASTM D5185).
Typically, the lubricating oil compositions of the present invention may contain low levels of sulfur. Preferably, the lubricating oil composition contains sulfur in an amount of up to 0.4%, more preferably up to 0.3%, even more preferably up to 0.2% by weight sulfur (ASTM D2622) based on the total weight of the composition. I do.
Typically, the lubricating oil composition of the present invention has, based on the total weight of the composition, up to 0.30 wt%, more preferably up to 0.20 wt%, most preferably up to 0.15 wt% as measured according to ASTM method D5291. Contains nitrogen.
Suitably, the lubricating oil composition may have a total base number (TBN) of 4 to 15, preferably 5 to 12 mg KOH / g as measured according to ASTM D2896.

In this specification, where the following words and expressions are used, they have the meanings given below.
“Active ingredient” or “(ai)” refers to an additive that is not a diluent or solvent.
"Including" or any of its congeners identifies the presence of the stated feature, step, or integer or component, but excludes the presence or addition of one or more other features, steps, integers, components, or groups thereof. Do not hinder. The expression “consisting of” or “consisting essentially of” or homologous expressions is encompassed by “comprising” or congeners, wherein “consisting essentially of” refers to a substance that is substantially composed of Allow the inclusion of substances that do not have a significant effect.
“Hydrocarbyl” is a chemical group on a compound that contains a hydrogen atom and a carbon atom, and refers to a chemical group that is directly bonded to the remainder of the compound via a carbon atom. This group may contain one or more atoms other than carbon and hydrogen, provided that they do not affect the basic hydrocarbyl properties of the group. One skilled in the art would know suitable groups (eg, halo, especially chloro and fluoro, amino, alkoxyl, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.). Preferably, this group consists essentially of hydrogen and carbon unless otherwise specified. Preferably, the hydrocarbyl group comprises an aliphatic hydrocarbyl group. The term “hydrocarbyl” includes “alkyl”, “alkenyl”, “allyl” and “aryl” as defined herein.
"Alkylene" is synonymous with "alkanediyl", C ₂ -C ₂₀ derived from an alkane by removing a hydrogen atom from two different carbon atoms, preferably C ₂ -C _10, more preferably C ₂ means -C ₆ divalent saturated acyclic aliphatic hydrocarbon radical; it may be linear or branched. Representative examples of alkylene, ethylene (ethanediyl), propylene (propanediyl), butylene (butanediyl), isobutylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, 1-methylethylene, 1-ethylethylene, 1-ethyl 2-methylethylene, 1,1-dimethylethylene and 1-ethylpropylene.
"Poly (alkylene)" means a polymer containing suitable alkanediyl repeat groups. The polymer can be formed by polymerization of a suitable alkene (eg, polyisobutylene can be formed by polymerizing isobutene).
"Alkyl" means a C ₁ -C ₃₀ alkyl group linked through the remainder single carbon atom directly compounds. Unless otherwise specified, when there is a sufficient number of carbon atoms, the alkyl group may be straight-chain (i.e., unbranched) or branched and may be cyclic, acyclic or partially cyclic. / May be acyclic. Preferably, the alkyl group comprises a linear or branched acyclic alkyl group. Representative examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, heptyl, Octyl, dimethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl and triacontyl.
`` Alkynyl '' contains at least one carbon-carbon triple bond and is connected directly to the remainder of the compound by a single carbon atom, with C <sub>2</sub> -C <sub>30</sub> being otherwise as defined for `` alkyl '', preferably means C ₂ -C ₁₂ group.
"Aryl" includes any one or more alkyl groups, halo, hydroxyl, may be substituted by alkoxy and amino groups, are linked by the remainder single carbon atom directly the compounds C ₆ -C ₁₈ preferably means C ₆ -C ₁₀ aromatic group. Preferred aryl groups include phenyl and naphthyl groups and substituted derivatives thereof, especially phenyl and alkyl substituted derivatives thereof.
“Alkenyl” contains at least one carbon-carbon double bond and is connected directly to the remainder of the compound by a single carbon atom, with C ₂ -C ₃₀ being otherwise as defined for “alkyl”. preferably means C ₂ -C ₁₂ group.
`` Polyol '' refers to an alcohol containing two or more hydroxyl functional groups (i.e., a polyhydric alcohol), but is used to form an oil-soluble or oil-dispersible polymeric friction modifier (polyalkylene glycol) (constitution Exclude element B (ii)). More specifically, the term "polyol" embraces diols, triols, tetraols, and / or related dimers or chain-extended polymers of the compound. Still more particularly, the term "polyol" includes glycerol, neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, dipentaerythritol, tripentaerythritol and sorbitol.
"Polycarboxylic acid" means an organic acid containing two or more carboxylic acid functional groups, preferably hydrocarbylic acid, more preferably aliphatic hydrocarbylic acid. The term "polycarboxylic acid" includes dicarboxylic acids, tricarboxylic acids and tetracarboxylic acids.
"Halo" or "halogen" includes fluoro, chloro, bromo and iodo.
As used herein, `` oil-soluble '' or `` oil-dispersible '' or congenial terms necessarily mean that the compound or additive is soluble, soluble, miscible, or can be suspended in the oil in all proportions. Does not mean. However, these terms mean that the compounds or additives can be dissolved or stably dispersed in the oil to an extent sufficient to exert their intended effect, for example, in an environment utilizing the oil. I do. In addition, the incorporation of other additives, if desired, may allow for higher levels of incorporation of certain additives.
"Ashless" with respect to an additive means that the additive is free of metals.
"Ash-containing" with respect to an additive means that the additive comprises a metal.
"Major amount" is expressed in terms of the stated component, and means, in terms of the total weight of the composition, more than 50% by weight of the composition, calculated as the active ingredient of the component.
"Minor amount" is expressed in terms of the additives mentioned and means, based on the total weight of the composition, less than 50% by weight of the composition, calculated as active ingredient of said additives.
By "effective minor amount" with respect to an additive is meant a small amount of the additive in a lubricating oil composition such that the additive provides the desired technical effect.
"Non-ferrous metals" include metals such as lead, copper, tin, or alloys thereof, preferably metals of copper or lead, or alloys of such metals, especially copper or alloys thereof, including copper.
Non-ferrous metal corrosion (eg, copper and lead corrosion) is measured in a hot corrosion bench test according to ASTM D6594.
"Ppm" means parts per million by weight based on the total weight of the lubricating oil composition.
The "metal content" of the lubricating oil composition or additive component, for example, the molybdenum content or the total metal content of the lubricating oil composition (ie, the sum of all individual metal contents) is measured according to ASTM D5185.
"TBN" for the additive component or lubricating oil composition of the present invention means the total base number (mg KOH / g) as measured by ASTM D2896.
“KV ₁₀₀ ” means the kinematic viscosity at 100 ° C. as measured by ASTM D445.
"Phosphorus content" is measured by ASTM D5185.
"Sulfur content" is measured by ASTM D2622.
"Sulfated ash content" is measured by ASTM D874.
All percentages reported are by weight on an active ingredient basis, ie, without regard to carriers or diluent oils, unless otherwise specified.
It will also be appreciated that the various components used, not only essential, but also optimal and customary, may react under the conditions of formulation, storage or use, and the present invention contemplates any such reaction. The resulting or obtained product is also provided.
Furthermore, it should be understood that any upper and lower amount, range and ratio limits set forth herein may be independently combined. Accordingly, any upper or lower amount, range and ratio limits set forth herein in connection with a particular technical feature of the invention are not set forth herein in connection with other specific technical features of the invention. Any of the upper and lower amounts, ranges and ratio limits set forth above may be independently combined. Furthermore, any particular technical feature of the present invention, and all preferred variants thereof, may be independently combined with any other particular technical feature, and all preferred variants thereof.
Also, it should be understood that preferred features of each aspect of the invention are considered to be preferred features of any other aspect of the invention.

DETAILED DESCRIPTION OF THE INVENTION The features of the present invention relating to each aspect and all aspects of the present invention will be described in detail below as necessary.
Oil of lubricating viscosity (A)
Oils of lubricating viscosity (sometimes referred to as `` basestocks '' or `` base oils '') are the main liquid constituents of lubricants, into which additives and optionally other oils are blended, e.g., A final lubricant (or lubricant composition) is produced. The base oil serves to make the concentrate as well as to make the lubricating oil composition therefrom, and may be selected from natural (vegetable, animal or mineral) lubricating oils and synthetic lubricating oils and mixtures thereof.
The basestock group is defined in the American Petroleum Institute (API) publication "Engine Oil Licensing and Certification System", Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998. Typically, the base stock will have a viscosity at 100 ° C. of preferably 3-12, more preferably 4-10, most preferably 4.5-8 mm ² / sec (cSt).
The definitions of basestock and base oil in the present invention are the same as those found in the American Petroleum Institute (API) publication "Engine Oil Licensing and Certification System", Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998. It is. The publication classifies the base stock as follows.
a) Group I base stocks contain less than 90 percent saturates and / or more than 0.03 percent sulfur and have a viscosity index greater than or equal to 80 and less than 120 using the test methods specified in Table E-1 .
b) Group II basestocks contain 90% or more saturates and 0.03% or less sulfur and have a viscosity index of 80 or more and less than 120 using the test methods specified in Table E-1.
c) Group III base stocks contain 90% or more saturates and 0.03% or less sulfur and have a viscosity index of 120 or more using the test methods specified in Table E-1.
d) Group IV base stock is polyalphaolefin (PAO).
e) Group V base stocks include all other base stocks not included in Group I, II, III, or IV.

Table E-1: Basestock analysis method

Other oils of lubricating viscosity that may be included in the lubricating oil composition are described in detail below.
Natural oils include animal and vegetable oils (eg, castor oil and lard oil), liquid petroleum, and hydrorefined, solvent-treated mineral lubricating oils of the paraffinic, naphthenic, and mixed paraffin-naphthenic types. 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 copolymer, chlorinated polybutylene, poly (1-hexene), poly (1-octene), poly (1-decene )); Alkylbenzenes (eg, dodecylbenzene, tetradecylbenzene, dinonylbenzene, di (2-ethylhexyl) benzene); polyphenols (eg, biphenyl, terphenyl, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenylsulfides, and the like. Derivatives, analogs and homologs.
Another suitable class of synthetic lubricating oils is dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acid and alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer). , Malonic acid, alkylmalonic acid, alkenylmalonic acid) and esters of various alcohols (eg, butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, sebacine Dieicosyl acid, 2-ethylhexyl diester of linoleic acid dimer, and complex esters formed by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid.
Included Esters useful as synthetic oils, C ₅ -C ₁₂ monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaerythritol, even those made from dipentaerythritol and tripentaerythritol, etc. It is.

Unrefined, refined and rerefined oils can be used in the compositions of the present invention. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, shale oil obtained directly from a carbonization operation, petroleum oil obtained directly from distillation, or ester oil obtained directly from an esterification process would be an unrefined oil if used without further processing. Refined oils are similar to the unrefined oils except that they have been further processed in one or more purification 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 percolation. Rerefined oils are obtained by applying a process similar to the one used to obtain a refined oil to a refined oil that has already been used. Such rerefined oils, also known as reclaimed or reprocessed oils, are often further processed with techniques to identify used additives and oil breakdown products.
Another example of a base oil is a gas to liquid ("GTL") base oil. That is, the base oil may be oil derived from Fischer-Tropsch synthesized hydrocarbons made using a Fischer-Tropsch catalyst from the synthesis gas containing H ₂ and CO. These hydrocarbons typically require further processing to serve as a base oil. For example, they can be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed by methods known in the art.

Although the composition of the base oil will depend on the particular application of the lubricating oil composition, the oil formulator will choose the base oil to achieve the desired performance characteristics at a reasonable cost, but the base oil of the lubricating oil composition of the present invention will not. The oil typically comprises up to 85% by weight of a Group IV base oil, the base oil may comprise up to 70% by weight of a Group IV base oil, and even up to 50% by weight of a Group IV base oil. The base oil of the lubricating oil composition of the present invention may comprise 0% by weight of a Group IV base oil. Alternatively, the base oil of the lubricating oil composition of the present invention may comprise at least 5%, at least 10% or at least 20% by weight of a Group IV base oil. The base oil of the lubricating oil composition of the present invention may comprise from 0 to 85% by weight, or from 5 to 85% by weight, alternatively from 10 to 85% by weight of a Group IV base oil.
Preferably, the volatility of the oil or oil blend of lubricating viscosity is 20% or less, preferably 16% or less, preferably 12% or less, more preferably 10% or less, as measured by the NOACK test (ASTM D5800). . Preferably, the viscosity index (VI) of the oil of lubricating viscosity is at least 95, preferably at least 110, more preferably up to 120, even more preferably at least 120, even more preferably at least 125, most preferably about 130-140. It is.

Lubricating by supplying a large amount of oil of lubricating viscosity together with a small amount of additive components (B) and (C) as defined herein, and, if necessary, one or more co-additives as described below Make up the oil composition. This preparation can be achieved by adding the additives directly to the oil or in the form of a concentrate of the additives to disperse or dissolve the additives in the oil. The additives may be added to the oil before, simultaneously with, or after the addition of the other additives by any method known to those skilled in the art.
Preferably, the oil of lubricating viscosity is present in an amount of more than 55%, more preferably more than 60%, even more preferably more than 65% by weight, based on the total weight of the lubricating oil composition. Preferably, the oil of lubricating viscosity is present in an amount of less than 98%, more preferably less than 95%, even more preferably less than 90% by weight, based on the total weight of the lubricating oil composition.
When making a lubricating oil composition using the concentrate, the concentrate can be diluted with an oil having a lubricating viscosity of, for example, 3 to 100, for example, 5 to 40 parts by weight per part by weight of the concentrate.
Preferably, the lubricating oil composition is a multigrade oil identified by the viscometric descriptor SAE 20WX, SAE 15WX, SAE 10WX, SAE 5WX or SAE 0WX. Where X represents any one of 20, 30, 40 and 50; the properties of the different viscometric grades can be found in the SAE J300 classification. In an embodiment of each aspect of the invention, independently of the other embodiments, the lubricating oil composition is in the form of SAE 10WX, SAE 5WX or SAE 0WX, preferably in the form of SAE 5WX or SAE 0WX, where X is 20, 30, 40 or 50). Preferably X is 20 or 30.

Polymer friction modifier (B)
The oil-soluble or oil-dispersible polymer friction modifier (B) is as follows:
(i) a functionalized polyolefin as defined herein;
(ii) polyalkylene glycol;
(iii) a polyol; and
(iv) a reaction product of only a polycarboxylic acid as defined herein.
By the term "only", we have defined that the oil-soluble or oil-dispersible polymeric friction modifier (B) as defined in each aspect of the present invention is a reaction of only functionalized polyolefins, polyalkylene glycols, polyols and polycarboxylic acids. (I.e., a copolymer that is a reaction product of only one or more functionalized polyolefins, one or more polyalkylene glycols, one or more polyols, and one or more polycarboxylic acids). means.

Functionalized polyolefin (B (i))
The one or more functionalized polyolefin is a polyalkylene that contains at least one diacid or anhydride functional group. The one or more functionalized polyolefins are preferably olefins having 2 to 6 carbon atoms, especially the polymerization and results of monoolefins such as ethene, propene, but-1-ene and isobutene (i.e. 2-methylpropene). Is derived by functionalization with a diacid or anhydride functional group. Preferably, one or more functionalized polyolefins are poly functionalized with diacid or anhydride functional groups (C ₂ -C ₆ alkylene). Still more preferably, the one or more functionalized polyolefins are derived from the polymerization of isobutene and the resulting polyisobutylene being functionalized with a diacid or anhydride functionality (i.e., the functionalized polyolefin is a functionalized polyisobutylene. is there).
One or more polyalkylene moiety of the functionalized polyolefin (e.g., poly (C ₂ -C ₆ alkylene)) is preferably from 15 to 500 (e.g. 35～500,40～500,50～500), preferably 50 Contains a carbon chain of 200 carbon atoms. Suitably, the polyalkylene moiety of the one or more functionalized polyolefins has a number average molecular weight (Mn) of 300 to 5000, preferably 500 to 1500, especially 800 to 1200 Dalton.

The functionalized polyolefin contains at least one diacid or anhydride function capable of reacting with the hydroxyl function of the polyalkylene glycol (B (ii)) or the hydroxyl group of the polyol (B (iii)). Thus, functionalized polyolefins can be formed by the reaction of a polyolefin (ie, a poly (alkylene)) with an unsaturated diacid or anhydride. Preferably, the functionalized polyolefin contains anhydride functionality. Preferably anhydride functionalized polyalkylene is derived from the reaction of polyalkylenes (for example, poly (C ₂ -C ₆ alkylene)) with an anhydride, maleic anhydride, especially forming a succinic anhydride functional group . Thus, the functionalized polyolefin contains anhydride functionality, especially succinic anhydride functionality.
Accordingly, polyalkylene preferred one or more functionalized polyolefins containing anhydride functional groups, more poly preferably comprising an anhydride functional group (C ₂ -C ₆ alkylene), still further preferably succinic anhydride functionality Poly (C ₂ -C ₆ alkylene), especially polyisobutylene (PIB) containing succinic anhydride functionality, ie, polyisobutylene succinic anhydride (PIBSA). Suitably, the polyisobutylene of PIBSA has a number average molecular weight (Mn) of 300-5000, preferably 500-1500, especially 800-1200 daltons. PIB is a commercially available compound, sold by BASF under the trade name Glissopal, which product can be reacted to give a functionalized polyolefin (B (i)).
Preferably, the functionalized polyolefin containing diacid or anhydride functionality, as defined herein (e.g., poly containing diacid or anhydride functional groups (C ₂ -C ₆ alkylene), even more preferably succinic anhydride poly including things functional group (C ₂ -C ₆ alkylene), especially polyisobutylene containing succinic anhydride functionality (PIB), i.e. polyisobutylene succinic anhydride (PIBSA)) is suitable unsaturated diacid or anhydride (e.g. maleic anhydride) and the polyolefin (e.g., poly (C ₂ -C ₆ alkylene), preferably polyisobutylene (PIB)) direct thermal condensation reaction between (i.e., thermal ene (ene) reaction) Formed by This process is known as the thermal ene reaction and is usually carried out at a temperature above 150 ° C. for 1 to 48 hours. The functionalized polyolefin formed in the thermal ene reaction is chemically distinct and has comparable functionalization formed in the chlorination process (i.e., reaction of the polyolefin with the appropriate diacid or anhydride after chlorination). It has different physical and chemical properties than polyolefins.

Polyalkylene glycol (B (ii))
Preferably, one or more polyalkylene glycols are poly (C ₂ -C ₂₀ alkylene) glycols, preferably poly (C ₂ -C ₁₀ alkylene) glycols, more preferably poly (C ₂ -C ₆ alkylene) glycol is there. Preferred one or more polyalkylene glycols are one or more polyethylene glycols or one or more polypropylene glycols or one or more mixed poly (ethylene-propylene) glycols, or mixtures thereof. The most preferred one or more polyalkylene glycols is one or more polyethylene glycol (PEG), especially water soluble PEG.
The polyalkylene glycol can basically form a polyolefin-polyalkylene glycol copolymer by reacting with the functional groups of the functionalized polyolefin (B (i)) and / or react with the polycarboxylic acid (B (iv)). By doing so, it contains essentially two hydroxyl groups that can form a polyolefin-polyalkylene glycol-carboxylic acid compound or a polyalkylene glycol-carboxylic acid compound. It is understood that the compounds may further react with functionalized polyolefins (B (i)), polyalkylene glycols (B (ii)), polyols (B (iii)) and / or polycarboxylic acids (B (iv)). Will be done.
Suitably, the polyalkylene glycol (eg PEG) has a number average molecular weight (Mn) of 300-5000, preferably 400-1000, especially 400-800 daltons. Thus, in a preferred embodiment, the polyalkylene glycol (B (ii)) is PEG ₄₀₀ , PEG ₆₀₀ or PEG ₁₀₀₀ . Preferably, PEG ₄₀₀ , PEG ₆₀₀ and PEG ₁₀₀₀ are commercially available from Croda International.

Polyol (B (iii))
The polyol reactant can react with the functionalized polyolefin, thereby providing a backbone moiety that connects the discrete blocks of the functionalized polyolefin. Suitably, when the functionalized polyolefin is functionalized with an anhydride or diacid functionality, the polyol provides a backbone that connects the discrete blocks of the polyolefin by ester linkages.
Suitably, the polyol reactant may also provide a polyol-carboxylic acid compound by reacting with a polycarboxylic acid, which compound may further comprise a functionalized polyolefin (B (i)) and / or a polyalkylene glycol (B ( ii)).
Polyols are alcohols containing two or more hydroxyl functional groups (i.e., polyhydric alcohols), but are used to form oil-soluble or oil-dispersible polymeric friction modifiers (polyalkylene glycols) (component B ( ii)) is excluded. Preferably, the polyol contains three or more hydroxyl functions. Thus, the polyol may be a diol, a triol, a tetraol, and / or a related dimer or chain extended polymer of the compound. Preferably, one or more polyols are C ₂ -C ₂₀ hydrocarbyl polyol, more preferably C ₂ -C ₂₀ aliphatic hydrocarbyl polyol, even more preferably a saturated C ₂ -C ₂₀ aliphatic hydrocarbyl polyol, even more preferably is a saturated C ₂ -C ₁₅ aliphatic hydrocarbyl polyol. Suitably, the polyol has a molecular weight (Mw) of 400 or less, preferably 350 or less, more preferably 300 or less, and most preferably 280 daltons or less. Examples of suitable polyols include glycerol, neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, dipentaerythritol, tripentaerythritol and sorbitol. A highly preferred polyol is glycerol.

Polycarboxylic acid (B (iv))
The polycarboxylic acid reactant can provide a skeletal moiety that connects the separate blocks of the polyalkylene glycol via an ester linkage by reacting with the hydroxyl groups of the polyalkylene glycol (B (ii)).
Suitably, the polycarboxylic acid may also react with the polyol (B (iii)) to give a polyol-carboxylic acid compound, which compound may further comprise a functionalized polyolefin (B (i)) and / or a polyalkylene. It can react with glycol (B (ii)).
Polycarboxylic acids are organic acids having two or more carboxylic acid groups. The polycarboxylic acids may be dicarboxylic acids, tricarboxylic acids and tetracarboxylic acids; dicarboxylic acids are preferred. Preferably, one or more polycarboxylic acids C ₂ -C ₃₀ hydrocarbyl poly carboxylic acids, preferably C ₂ -C ₂₀ hydrocarbyl poly carboxylic acids, even more preferably C ₂ -C ₃₀ hydrocarbyl bilge carboxylic acid, even more preferably Is a C ₂ -C ₂₀ hydrocarbyl dicarboxylic acid, even more preferably a C ₂ -C ₂₀ aliphatic hydrocarbyl dicarboxylic acid. Even more preferably, one or more polycarboxylic acids are acyclic C ₂ -C ₃₀ aliphatic hydrocarbyl bilge carboxylic acid, even more preferably acyclic C ₂ -C ₂₀ aliphatic hydrocarbyl bilge carboxylic acid. Linear polycarboxylic acids are preferred over branched polycarboxylic acids. Saturated polycarboxylic acids are preferred over unsaturated polycarboxylic acids such as maleic acid.
Thus, one or more preferred polycarboxylic acids, C ₂ -C ₃₀ hydrocarbyl poly carboxylic acids, such as saturated C ₂ -C ₃₀ hydrocarbyl poly carboxylic acids (e.g., saturated C ₂ -C ₃₀ hydrocarbyl bilge carboxylic acid), more preferably C ₂ -C ₃₀ aliphatic hydrocarbyl poly carboxylic acids, such as saturated C ₂ -C ₃₀ aliphatic hydrocarbyl poly carboxylic acids (e.g., saturated C ₂ -C ₃₀ aliphatic hydrocarbyl bilge carboxylic acid), more preferably C ₂ -C ₂₀ aliphatic hydrocarbyl polycarboxylic acids, such as saturated C ₂ -C ₂₀ aliphatic hydrocarbyl poly carboxylic acids (e.g., saturated C ₂ -C ₂₀ aliphatic hydrocarbyl bilge carboxylic acid), even more preferably C ₆ -C ₂₀ aliphatic hydrocarbyl poly carboxylic acids, such as saturated C ₆ -C ₂₀ aliphatic hydrocarbyl poly carboxylic acids (e.g., saturated C ₆ -C ₂₀ aliphatic hydrocarbyl bilge carboxylic acid), Contact more preferably C ₈ -C ₂₀ aliphatic hydrocarbyl poly carboxylic acids, such as saturated C ₈ -C ₂₀ aliphatic hydrocarbyl poly carboxylic acids (e.g., saturated C ₈ -C ₂₀ aliphatic hydrocarbyl bilge carboxylic acid, in particular sebacic acid).
Suitable polycarboxylic acids include oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and sebacic acids. The most preferred polycarboxylic acid is sebacic acid.

Thus, according to a highly preferred embodiment, the oil-soluble or oil-dispersible polymeric friction modifier (B) comprises:
(i) PIBSA as defined herein;
(ii) polyethylene glycol as defined herein;
(iii) a polyol, preferably glycerol; and
(iv) A reaction product of only a polycarboxylic acid, preferably sebacic acid.
Preferably, during the formation of the polymeric friction modifier, the functionalized polyolefin (B (i)), polyalkylene glycol (B (ii)), polyol (B (iii)) and polycarboxylic acid (B (iv) ) May occur. For example, a functionalized polyolefin reacts with a polyalkylene glycol, such that the polyolefin is directly attached to the polyalkylene glycol (eg, by an ester bond), and the resulting polymer is functionalized with the functionalized polyolefin, polyalkylene glycol, polyol and / or polycarboxylic acid. A subsequent reaction with the acid can take place. Alternatively or additionally, the polyalkylene glycol reacts with the polycarboxylic acid to form a block of polyalkylene glycol linked by the esterified polycarboxylic acid, and the resulting block of polyalkylene glycol and the functionalized polyolefin and / or functionalized A subsequent reaction can take place with the functionalized polyolefin block. Still further, the functionalized polyolefin reacts with the polyol to form a block of functionalized polyolefin linked by the polyol (typically by an ester linkage), and the resulting block of functionalized polyolefin is combined with a polyalkylene glycol and / or polyalkylene glycol. A subsequent reaction with the alkylene glycol block can take place.

Thus, the functionalized polyolefin, polyalkylene glycol, polyol and polycarboxylic acid may react to form a block copolymer. When present, the number of block copolymer units in the organic friction modifier additive typically ranges from 2 to 20, preferably 2 to 15, and more preferably 2 to 10 units.
As with all polymers, polymeric friction modifiers will typically comprise a mixture of molecules of various sizes. The polymeric friction modifier (B) suitably has a number average molecular weight of 1,000 to 30,000, preferably 1,500 to 25,000, more preferably 2,000 to 20,000 daltons.
The polymeric friction modifier (B) suitably has an acid number of less than 20, preferably less than 15, more preferably less than 10 mg KOH / g (ASTM D974). The polymeric friction modifier (B) suitably has an acid number greater than 1, preferably greater than 1.5 mg KOH / g. In a preferred embodiment, the polymeric friction modifier (B) has an acid number in the range from 1.5 to 9.
The polymeric friction modifier (B) can be prepared by techniques well known to those skilled in the art, as described in US patent application Ser. No. 13 / 582,589. Typically, the functionalized polyolefin, polyalkylene glycol, polyol, and polycarboxylic acid are heated at 100-250 ° C in the presence of a catalyst (eg, tetrabutyl titanate) to remove water.
In a preferred embodiment, the polymeric friction modifier (B) is the reaction product of maleated polyisobutylene (PIBSA), PEG, glycerol and sebacic acid, wherein the maleated polyisobutylene (PIBSA) polyisobutylene is about PIBSA has a number average molecular weight of 950 daltons, PIBSA has an approximate saponification number of 98 mg KOH / g, and PEG has a number average molecular weight of about 600 daltons and a hydroxyl number of 190 mg KOH / g. Suitable additives are 158.4 g (0.128 mol) of PIBSA, 101 g (0.168 mol) of PEG ₆₀₀ , 10.4 g in a glass round bottom flask equipped with a nitrogen purge, mechanical stirrer, isomantle heater and distillation arm. (0.0514 mol) sebacic acid and 7.7 g (0.0835 mol) glycerol. The reaction takes place in the presence of 0.5 ml of the esterification catalyst tetrabutyl titanate at 180-230 ° C. with removal of water to a final acid number of 1.7 mg / KOH / g. Therefore, the alternative polymer friction modifier (B) can be prepared by a similar synthetic method.
The polymeric friction modifier (B) is suitably present in the lubricating oil composition of the present invention in an amount of at least 0.1, preferably at least 0.2% by weight, based on the active compound, based on the total weight of the lubricating oil composition. I do. The polymeric friction modifier of the present invention is suitably in the lubricating oil composition, on an active substance basis, based on the total weight of the lubricating oil composition, 5 or less, preferably 3 or less, more preferably 1.5% by weight. Present in the following amounts:

Dihydrocarbyl dithiophosphate metal salt (C)
The lubricating oil composition of the present invention may utilize any suitable oil-soluble or oil-dispersible metal dihydrocarbyl dithiophosphate having antiwear properties in the lubricating oil composition. Of note is a metal dihydrocarbyl dithiophosphate wherein the metal can be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel, copper, or preferably zinc. Accordingly, preferred dihydrocarbyl dithiophosphate metal salts are zinc dihydrocarbyl dithiophosphates (ZDDP), more preferably a zinc dialkyl dithiophosphate, especially di (C ₂ -C ₈ alkyl) dithiophosphate, the di (C ₂ -C ₈ alkyl) C ₂ -C ₈ alkyl radical zinc dithiophosphate may be the same or different.
Dihydrocarbyl dithiophosphate metal salts by known techniques, usually after forming the first dihydrocarbyl dithiophosphate by reacting one or more alcohols or phenols with P ₂ S ₅ (DDPA), resulting DDPA with a metal compound It can be prepared by neutralization. For example, dithiophosphoric acid can be made by reacting a mixture of primary and secondary alcohols. Alternatively, multiple dithiophosphoric acids can be prepared in which one hydrocarbyl group is entirely secondary in nature and the other hydrocarbyl group is entirely primary in nature. Although any basic or neutral metal compound can be used to make the metal salt, oxides, hydroxides and carbonates are most commonly utilized. Commercial additives often contain excess metal due to the use of excess basic metal compound in the neutralization reaction.
Preferred zinc dihydrocarbyl dithiophosphate (ZDDP) is an oil-soluble salt of dihydrocarbyl dithiophosphate and can be represented by the following formula.

Wherein R and R ′ may be the same or different hydrocarbyl groups containing 1 to 18, preferably 2 to 12, carbon atoms, and include alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic. And the like. Particularly preferred as R and R 'groups are alkyl groups of 2 to 8 carbon atoms. Thus, this group is, for example, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, It can be 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl. To obtain oil solubility, the total number of carbon atoms in the dithiophosphoric acid (ie, R and R ') will generally be about 5 or greater. Thus, the zinc dihydrocarbyl dithiophosphate can include a zinc dialkyldithiophosphate.
Based on the total weight of the lubricating oil composition, and sufficient to provide the lubricating oil with no more than 1200 ppm, preferably no more than 1000 ppm, more preferably no more than 900 ppm, and most preferably no more than 850 ppm of phosphorus by weight as measured according to ASTM D5185. A metal dihydrocarbyl dithiophosphate such as ZDDP is added to the lubricating oil composition in an amount. Suitably, the ZDDP is in an amount sufficient to provide the lubricating oil with at least 100 ppm, preferably at least 350 ppm, and more preferably at least 500 ppm phosphorus by weight based on the total weight of the lubricating oil composition and as measured according to ASTM D5185. A metal salt of a dihydrocarbyl dithiophosphate is added to the lubricating oil composition.
Suitably, the metal salt of dihydrocarbyl dithiophosphate such as ZDDP is present in an amount of at least 0.1% by weight, preferably at least 0.25% by weight, more preferably at least 0.5% by weight, based on the total weight of the lubricating oil composition. . Suitably, the metal salt of dihydrocarbyl dithiophosphate such as ZDDP is present in an amount of 10% by mass or less, preferably 5.0% by mass or less, more preferably 3.0% by mass or less, based on the total mass of the lubricating oil composition. .

Engine The lubricating oil composition of the invention is added to a mechanical engine component, in particular an internal combustion engine, for example a spark-ignition or compression-ignition internal combustion engine, in particular an engine component of a spark-ignition or compression-ignition two- or four-stroke reciprocating engine. The engine component can be lubricated using an object. The engine may be a conventional gasoline or diesel engine designed to be powered by gasoline or petroleum diesel, respectively; or the engine is specifically modified to be powered by alcohol-based fuel or biodiesel fuel It may be.

Co-additives Co-additives that may be present, different from additive components (B) and (C), are listed below along with their typical effective amounts. All values listed provide the active ingredient in a fully formulated lubricating oil as a percentage by weight.
Additive mass% mass%
(Wide range) (Preferable range)
Ashless dispersant 0.1-20 1-8
Metal detergent 0.1-15 0.2-9
Friction modifier 0-5 0-1.5
Corrosion inhibitor 0-5 0-1.5
Metal dihydrocarbyl dithiophosphate 0 to 100 to 4
Antioxidant 0-5 0.01-3
Pour point depressant 0.01-5 0.01-1.5
Antifoaming agent 0-5 0.001-0.15
Auxiliary antiwear agent 0-5 0-2
Viscosity modifier (1) 0-10 0.01-4
Mineral or synthetic base oil Residue Residual
(1) Use viscosity modifiers only for multi-grade oils.

The final lubricating oil composition typically made by blending each additive into a base oil may contain 5-25, preferably 5-18, typically 7-15% by weight of a co-additive. Yes, the rest is oil of lubricating viscosity.
Preferably, the lubricating oil composition comprises, in addition to the additive components (B) and (C), an ashless dispersant, a metal detergent, a corrosion inhibitor, an antioxidant, a pour point depressant, an antiwear agent, friction It contains one or more minor co-additives selected from modifiers, demulsifiers, defoamers and viscosity modifiers.
The co-additives are discussed in further detail below; as is well known in the art, some additives can provide a variety of effects, for example, a single additive can serve as a dispersant and as an antioxidant. May work.
Metal detergents function both as detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life. Detergents generally comprise a polar head and a long hydrophobic tail, the polar head comprising a metal salt of an acidic organic compound. The salts may contain substantially stoichiometric amounts of metal, in which case they are usually described as normal or neutral salts, typically with a total base number of 0-80 mg KOH / g or TBN ( (As measured by ASTM D2896). Large amounts of metal bases can be incorporated by reacting excess metal compounds (eg, oxides or hydroxides) with acidic gases (eg, carbon dioxide). The resulting overbased detergent includes a neutralizing detergent as the outer layer of a metal base (eg, carbonate) micelle. The overbased detergent will have a TBN of 150 mg KOH / g or more, and will typically have a TBN of 250-450 mg KOH / g or more. In the presence of a compound of Formula I, the amount of overbased detergent can be reduced, or a detergent with reduced overbased levels (e.g., a detergent having a TBN of 100-200 mg KOH / g), or Neutral detergents can be utilized, resulting in a corresponding reduction in the SASH content of the lubricating oil composition without compromising its performance.
Detergents which can be used include oil-soluble neutral and overbased sulphonates of metals, in particular alkali or alkaline earth metals, such as sodium, potassium, lithium, calcium and magnesium, phenates, phenates sulfide, thiophosphones Acid salts, salicylates, and naphthenates and other oil-soluble carboxylate salts. The most commonly used metals are calcium and magnesium, both of which may be present in detergents used in lubricating oils, and may be present in a mixture of calcium and / or magnesium and sodium. Combinations of detergents, whether overbased or neutral or both, may be used.
In one embodiment of the invention, the lubricating oil composition comprises neutral or overbased calcium sulfonate having a TBN of 20-450 mg KOH / g, and neutral and overbased having a TBN of 50-450 mg KOH / g. Metal sulphate and metal sulphate phenates and mixtures thereof.
Sulfonates can typically be prepared from petroleum fractionation or from sulfonic acids obtained by sulfonation of alkyl-substituted aromatic hydrocarbons, such as those obtained by alkylation of aromatic hydrocarbons. Examples include benzene, toluene, xylene, naphthalene, diphenyl or their halogen derivatives, such as those obtained by alkylating chlorobenzene, chlorotoluene and chloronaphthalene. Alkylation can be carried out with an alkylating agent having about 3 to more than 70 carbon atoms in the presence of a catalyst. Alkaryl sulfonates generally contain from about 9 to about 80 or more carbon atoms, preferably from about 16 to about 60 carbon atoms per alkyl-substituted aromatic moiety. Oil-soluble sulfonates or alkaryl sulfonic acids can be neutralized with metal oxides, hydroxides, alkoxides, carbonates, carboxylates, sulfides, hydrosulfides, nitrates, borates and ethers. The amount of metal compound is selected in view of the desired TBN of the final product, but typically ranges from about 100-220% (preferably at least 125%) by weight of the stoichiometrically required amount. .
Metal salts of phenols and sulfurized phenols are prepared by reaction with a suitable metal compound, such as an oxide or hydroxide, to give neutral or overbased products in a manner well known in the art. The product of the reaction of phenol with sulfur or a sulfur-containing compound, for example hydrogen sulfide, sulfur monohalide or sulfur dihalide, generally a mixture of two or more phenols cross-linked by a sulfur-containing bridge To form a sulfurized phenol.
In another embodiment of the invention, the lubricating oil composition comprises a neutral or overbased alkali metal or alkaline earth metal having a TBN of 50-450 mg KOH / g, preferably 50-250 mg KOH / g. Includes metal detergents that are salicylates or mixtures thereof. Highly preferred salicylate detergents include salicylates of alkaline earth metals, especially magnesium and calcium salicylates, especially calcium salicylate. In one embodiment of the present invention, the alkali metal or alkaline earth metal salicylate detergent is the only metal-containing detergent in the lubricating oil composition.

Auxiliary antiwear agents other than metal dihydrocarbyl dithiophosphate (additive component (c)) that may be included in the lubricating oil composition include 1,2,3-triazole, benzotriazole, sulfurized fatty acid esters, and dithiocarbamic acid. Including derivatives.
Ashless dispersants include an oil-soluble polymeric hydrocarbon skeleton having a functional group that can bind to the particles to be dispersed. Typically, the dispersant comprises an amine, alcohol, amide, or ester polar moiety, often attached to the polymer backbone through a cross-linking group. Ashless dispersants include, for example, oil-soluble salts, esters, amino-esters, amides, imides, and oxazolines of long-chain hydrocarbon-substituted mono- and dicarboxylic acids or their anhydrides; thiocarboxylic acid derivatives of long-chain hydrocarbons; Directly attached long chain aliphatic hydrocarbons; and Mannich condensation products formed by the condensation of long chain substituted phenols with formaldehyde and polyalkylene polyamines.
Examples of the friction modifier include glycerol monoesters of higher fatty acids such as glycerol monooleate (GMO); esters of long-chain polycarboxylic acids and diols such as butanediol esters of dimerized unsaturated fatty acids; oxazoline compounds; And alkoxylated alkyl-substituted monoamines, diamines and alkyl ether amines, such as ethoxylated tallow amine and ethoxylated tallow ether amine.
Typically, the total amount of additional organic ashless friction modifier in the lubricating oil of the present invention does not exceed 5% by weight, preferably does not exceed 2% by weight, based on the total weight of the lubricating oil composition; More preferably, it does not exceed 0.5% by mass. In embodiments of the present invention, the lubricating oil composition does not contain an additional organic ashless friction modifier.
Other known friction modifiers include oil-soluble organomolybdenum compounds. The organomolybdenum friction modifier also provides the lubricating oil composition with antioxidant and antiwear properties. Suitable oil-soluble organomolybdenum compounds have a molybdenum-sulfur core. Examples include dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and mixtures thereof. Molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum alkylxanthate and molybdenum alkylthioxanthate are particularly preferred. Molybdenum compounds are dinuclear or trinuclear.
Preferred organic molybdenum compounds useful a class in all aspects of the present invention have the formula Mo ₃ S _k L _n Q trinuclear organo-molybdenum compounds and mixtures thereof _z (wherein, L is soluble compounds in oil Or an independently selected ligand having an organic group of sufficient number of carbon atoms to render it dispersible, wherein n is 1-4, k varies from 4-7, and Q is Selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, ethers, etc., wherein z ranges from 0 to 5 and includes non-stoichiometric values). There should be at least 21 total carbon atoms in the organic groups of all ligands, for example, at least 25, at least 30, or at least 35 carbon atoms.
The molybdenum compound may be present in the lubricating oil composition at a concentration that gives a molybdenum atom in the range of 0.1-wt%, or at least 10, for example 50-2,000 wtppm.
Preferably, the molybdenum from the molybdenum compound is present in an amount of from 10 to 1500, such as from 20 to 1000, more preferably from 30 to 750 ppm, based on the total weight of the lubricating oil composition. In some applications, molybdenum is present in an amount greater than 500 ppm.

The viscosity modifier (VM) functions to provide high and low temperature operability to the lubricating oil. The VM used may have the sole function or may be multifunctional. Multifunctional viscosity modifiers that also function as dispersants are also known. Suitable viscosity modifiers are polyisobutylene, copolymers of ethylene and propylene with higher alpha-olefins, polymethacrylates, polyalkylmethacrylates, methacrylate copolymers, copolymers of unsaturated dicarboxylic acids and vinyl compounds, interpolymers of styrene and acrylic esters. And partially halogenated copolymers of styrene / isoprene, styrene / butadiene, and isoprene / butadiene, and partially halogenated homopolymers of butadiene and isoprene and isoprene / divinylbenzene.
Antioxidants which may also be referred to as antioxidants, enhance the resistance to oxidation of the composition, and compounds with a peroxide, or detoxify them by modifying or decomposing a peroxide, or It can work by deactivating the oxidation catalyst. Oxidative alteration can be manifested by sludge in the lubricating oil, varnish-like deposits on metal surfaces, and increased viscosity.
Examples of suitable antioxidants are selected from copper containing antioxidants, sulfur containing antioxidants, aromatic amine containing antioxidants, hindered phenolic antioxidants, dithiophosphoric acid derivatives, and metal thiocarbamates . Preferred antioxidants are aromatic amine containing antioxidants, hindered phenolic antioxidants and mixtures thereof. In a preferred embodiment, an antioxidant is present in the lubricating oil composition of the present invention.
A rust inhibitor selected from the group consisting of nonionic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, and anionic alkyl sulfonic acids may be used.
Although copper and lead bearing corrosion inhibitors may be used, they are not typically required in the formulations of the present invention. Typically, the compounds are thiadiazole polysulfides containing 5 to 50 carbon atoms, their derivatives and their polymers. Derivatives of 1,3,4-thiadiazole, such as those described in US Pat. Nos. 2,719,125; 2,719,126; and 3,087,932 are typical. Other similar materials are described in U.S. Patent Nos. 3,821,236; 3,904,537; 4,097,387; 4,107,059; 4,136,043; 4,188,299; and 4,193,882. Other additives are the thio and polythiosulfenamides of thiadiazole, such as those described in GB 1,560,830. Benzotriazole derivatives also fall into this category of additives. When these compounds are included in a lubricating oil composition, they are preferably present in an amount of active ingredient not exceeding 0.2 wt.%.
Small amounts of demulsifying components may be used. Preferred demulsifying components are described in EP 330522. It is obtained by reacting an alkylene oxide with an adduct obtained by reacting a bisepoxide with a polyhydric alcohol. Demulsifiers should be used at a level of active ingredient not exceeding 0.1% by weight. A processing rate of 0.001-0.05% by weight of active ingredient is convenient.
Pour point depressants, also known as lube oil flow improvers, lower the minimum temperature at which the fluid flows or can be poured. Such additives are well known. Typical such additives that improve the low temperature fluidity of the fluid are, C ₈ -C ₁₈ dialkyl fumarate / vinyl acetate copolymers, polyalkyl methacrylates, and the like.
Foam control can be achieved with a number of compounds including polysiloxane-type defoamers , for example, silicone oil or polydimethylsiloxane.

The individual additives can be incorporated into the base stock by any convenient means. Thus, each component can be added directly to the basestock or base oil blend by dispersing or dissolving the components at the desired level in the basestock or base oil blend. The blending can occur at ambient or elevated temperatures.
Preferably, all additives except the viscosity modifier and the pour point depressant are blended into the concentrate or additive package described herein, and the additive package is subsequently blended into the base stock to provide the finished lubricating oil. make. The concentrate will typically be formulated to contain the additives in an amount suitable to provide the desired concentration in the final formulation when the concentrate is combined with a predetermined amount of base lubricating oil.
The concentrate is preferably made by the method described in US 4,938,880. The patent describes making an ashless dispersant and metal detergent premix that is preblended at a temperature of at least about 100 ° C. Thereafter, the premix is cooled to at least 85 ° C and additional components are added.
Typically, the additive package used to formulate the lubricating oil composition of the present invention has a total base number (TBN) of 25-100, preferably 45-80, as measured by ASTM D2896, and The inventive lubricating oil composition has a total base number (TBN) of 4 to 15, preferably 5 to 12, as measured by ASTM D2896. In embodiments of the present invention, the additive package does not have a total base number (TBN) of 62-63.5 as measured by ASTM D2896, and the lubricating oil composition has a total base number of 9.05-9.27 as measured by ASTM D2896. Does not have total base number (TBN).
The final crankcase lubricating oil formulation can utilize a 2 to 20, preferably 4 to 18, most preferably 5 to 17% by weight concentrate or additive package with the remainder being base stock.
In an embodiment of the present invention, the lubricating oil composition of the first aspect of the present invention does not contain from 0.2 to 0.25% by weight of sulfur as measured according to ASTM method D4927.
In an embodiment of the present invention, the lubricating oil composition of the first aspect of the present invention is free from 0.08 to 0.11% by weight of nitrogen as measured according to ASTM method D5291.

Examples The following examples illustrate the present invention without limiting the scope of the claims of the present invention.
Unless otherwise specified, all additives described in the examples are available from lubricating oil additive companies such as Infineum UK Ltd, Lubrizol Corporation and Afton Chemical Corporation as standard additives.
Example 1 Preparation of Polymer Friction Modifier (B) A 500 cm ³ five-necked round bottom flask equipped with a nitrogen purge, a stirrer and a hermetic stirrer bearing, a temperature probe and a distillation arm attached to an outlet bubbler, was charged with PIBSA ( 158.4 g, 0.128 mol), PEG ₆₀₀ (101.0 g, 0.168 mol), sebacic acid (10.4 g, 0.0514 mol) and glycerol (7.7 g, 0.0835 mol) were added, and the mixture was heated at 180 ° C. for 1 hour with stirring. . The reaction mixture was heated to a temperature of 230 ° C. for 1 hour, then tetrabutyl titanate (0.5 ml) was added to the mixture, and heating and stirring were continued at a temperature of 230 ° C. and a reduced pressure of 50-150 mbar for 2 hours. The reaction mixture was cooled below 100 ° C. and the polymeric friction modifier (B) was poured from the round bottom flask. The polymeric friction modifier (B) had an acid value of 1.7 mg KOH / g.

Example 2 Corrosion resistance performance
Six lubricating oil compositions (designated base lubricating oil and oils 1-5) were prepared. The base lubricating oil and oils 1-5 each contained the same Group II base stock and equal amounts of the same additives: Overbased calcium sulfonate detergent (TBN 300 mg KOH / g); Dispersant; Antioxidant Agents; molybdenum friction modifiers; and viscosity modifiers. Oils 1-5 contained additional additives, also on an active ingredient basis, as detailed in Table 1. The oil containing ZDDP (ie, oils 3-5) had a phosphorus content of 880 ppm as measured by ASTM D5185. Oil 5 corresponds to the lubricating oil composition of the present invention.

¹高分子摩擦調整剤は実施例1の化合物だった。 table 1

^{1 The} polymer friction modifier was the compound of Example 1.

Tests and results
Measure corrosion control using the Hot Corrosion Bench Test (HTCBT) according to ASTM D6594-06. This test method simulates the corrosion of non-ferrous metals such as copper and lead found on cam followers and bearings in lubricating oils. The corrosion process under investigation is triggered by the chemistry of the lubricating oil rather than the decomposition or contamination of the lubricating oil.
Immerse four metal specimens of copper, lead, tin and phosphor bronze in a measured amount of test lubricant (100 ml) in a sample tube. The sample tube is immersed in a heated oil bath to heat the temperature of the test lubricant to 135 ° C. The test lubricating oil is heated at 135 ° C. for 168 hours, during which time dry air is blown into the heated oil at a rate of 5 liters per hour. Thereafter, the test lubricating oil is cooled and the metal test specimen is removed and examined for corrosion. The concentrations of copper, tin and lead in the test lubricating oil composition and a reference sample of the lubricating oil composition are then determined according to ASTM D5185. The difference between the concentration of each metal contaminant in the test lubricating oil composition and that of the reference sample lubricating oil composition gives a value for the change in various metal concentrations before and after the test. Industry standard limits for meeting the requirements of API CJ-4 are up to 20 ppm for copper and up to 120 ppm for lead. The results for the base lubricant and oils 1-5 are presented in Table 2.

Table 2

The results in Table 2 show that the base lubricant without ZDDP, ashless organic friction modifier or polymeric friction modifier (B) causes 23 ppm lead corrosion and 33 ppm copper corrosion. Comparison of the results of oil 1 equivalent to the base lubricating oil containing the polymer friction modifier (B) and the result of the base lubricating oil shows that the polymer friction modifier (B) contained in oil 1 contains copper (29 ppm vs. 33 ppm). ) And lead (13ppm vs 23ppm) are demonstrated to prevent corrosion. In contrast, the inclusion of an ashless organic friction modifier (GMO) in the base lubricant (Oil 2) significantly increases both lead (403 ppm vs. 23 ppm) and copper (49 ppm vs. 33 ppm) corrosion.
As can be seen by comparing the results for Oil 3 with the results for the base lubricant, including ZDDP in the base lubricant increases lead corrosion (63 ppm vs. 23 ppm) but shows a slight improvement in copper corrosion (27 ppm vs. 33 ppm) . As can be seen from a comparison of the results for Oil 4 and the base lubricant, including both ZDDP and ashless organic friction modifier (GMO) in the base lubricant (Oil 4) significantly increases lead corrosion (420 ppm vs. 420 ppm). 23 ppm), resulting in improved copper corrosion (22 ppm vs. 33 ppm). From the comparison of the result of Oil 5 (the lubricating oil of the present invention containing ZDDP and the polymer friction modifier (B)) with the result of Oil 4, the polymer friction modifier (B) was found to be an ashless organic compound present in Oil 4. It should be noted that polymeric friction modifiers significantly reduce lead corrosion (108 ppm vs. 420 ppm) over friction modifiers and are much superior to ashless organic friction modifiers (9 ppm vs. 22 ppm) in preventing copper corrosion. Furthermore, a comparison of the results for Oil 5 and the base lubricant clearly demonstrates that the presence of both ZDDP and the polymeric friction modifier results in a significant reduction in copper corrosion (9 ppm vs. 33 ppm).

Claims (24)

A lubricating oil composition having a sulfated ash content of no more than 1.2 wt% as determined by ASTM D874 and a phosphorus content of no more than 0.12 wt% as determined by ASTM D5185, wherein the lubricating oil composition comprises the following components: :
(A) an oil having a large lubricating viscosity exceeding 50% by mass of the lubricating oil composition ;
(B) an oil-soluble or oil-dispersible polymeric friction modifier as an effective minor additive of at least 0.1% by weight based on the total weight of the lubricating oil composition , wherein the polymeric friction modifier is:
(i) at least one functionalized polyolefin that is a poly (alkylene) functionalized with at least one diacid or anhydride functional group, wherein the poly (alkylene) of the functionalized polyolefin has 50 to 500 carbon atoms; Having a carbon chain length);
(ii) one or more polyalkylene glycols;
(iii) 1 or more C ₂ -C ₂₀ aliphatic hydrocarbyl polyol; and
(iv) a C ₂ -C ₃₀ hydrocarbyl reaction product of only one or more polycarboxylic acids polycarboxylic acids;
as well as
(C) at least one oil-soluble or oil-dispersible metal salt of dihydrocarbyl dithiophosphate as an effective small amount of an additive that gives the lubricating oil composition at least 100 ppm by mass of phosphorus based on the total mass of the lubricating oil composition. A lubricating oil composition comprising or made by mixing these components. The one or more functionalized polyolefin, at least one diacid or anhydride functional groups in functionalized poly (C ₂ -C ₆ alkylene), of the functionalized polyolefin poly (C ₂ -C ₆ alkylene The composition of claim 1 wherein the moiety has a carbon chain length of 50 to 500 carbon atoms.   3. The composition according to claim 1, wherein the one or more functionalized polyolefins (B (i)) are polyisobutylenes functionalized with at least one diacid or anhydride function.   The composition according to any one of claims 1 to 3, wherein the one or more functionalized polyolefins (B (i)) are functionalized with succinic anhydride functional groups. The one or more functionalized polyolefin (B (i)) is a polyisobutylene succinic anhydride (PIBSA), according to claim 1 Symbol placement of the composition. The composition according to claim 1, wherein the one or more polyalkylene glycols (B (ii)) are poly (C ₂ -C ₆ alkylene) glycols.   The composition of claim 6, wherein said one or more polyalkylene glycols is polyethylene glycol (PEG). The one or more C ₂ -C ₂₀ aliphatic hydrocarbyl polyol (B (iii)) is selected from the group consisting of glycerol, neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, pentaerythritol, dipentaerythritol, tripentaerythritol The composition according to any one of claims 1 to 7, wherein the composition is selected from sorbitol and sorbitol . The one or more C ₂ -C ₂₀ aliphatic hydrocarbyl polyol is glycerol composition of claim 8. The one or more polycarboxylic acid (B (iv)) is a saturated C ₆ -C ₂₀ aliphatic hydrocarbyl bilge carboxylic acid, any one composition according to claims 1-9. Wherein the one or more saturated C ₆ -C ₂₀ aliphatic hydrocarbyl bilge carboxylic acids are sebacic acid, The composition of claim 10.   The composition according to any one of claims 1 to 11, wherein the oil-soluble or oil-dispersible metal dihydrocarbyl dithiophosphate is zinc dihydrocarbyl dithiophosphate.   A method of lubricating a spark-ignition or compression-ignition internal combustion engine, comprising the step of lubricating the engine with a lubricating oil composition according to any of the preceding claims. In lubricating a spark-ignition or compression-ignition internal combustion engine, a lubricating oil composition comprising a large amount of oil of lubricating viscosity to reduce and / or prevent corrosion of non-ferrous metal-containing engine parts during operation of said engine. Use of an oil- soluble or oil-dispersible polymeric friction modifier (B) as an effective small amount of an additive , wherein the lubricating oil composition has a sulfated ash content of 1.2% by weight or less as determined by ASTM D874. Having a phosphorus content of 0.12% by weight or less as determined by ASTM D5185, wherein the lubricating oil composition provides the lubricating oil composition with at least 100 ppm by weight of phosphorus based on the total weight of the lubricating oil composition. An effective small amount of an oil-soluble or oil-dispersible metal salt of dihydrocarbyl dithiophosphate (C) as an additive, wherein the friction modifier (B) is as follows:
(i) at least one functionalized polyolefin that is a poly (alkylene) functionalized with at least one diacid or anhydride functional group, wherein the poly (alkylene) of the functionalized polyolefin has 50 to 500 carbon atoms; Having a carbon chain length);
(ii) one or more polyalkylene glycols;
(iii) 1 or more C ₂ -C ₂₀ aliphatic hydrocarbyl polyol; and
(iv) C ₂ ~C ₃₀ 1 or more polycarboxylic acids is hydrocarbyl poly carboxylic acid
Use, which is the only reaction product . 15. Use according to claim 14, wherein the one or more functionalized polyolefins (B (i)) are polyisobutylene succinic anhydrides (PIBSA). The one or more polyalkylene glycols (B (ii)) are poly (C _Two ~ C ₆ 16. Use according to claim 14 or 15, which is an (alkylene) glycol. 17. The use according to claim 16, wherein said one or more polyalkylene glycols is polyethylene glycol (PEG). The one or more C _Two ~ C ₂₀ The aliphatic hydrocarbyl polyol (B (iii)) is selected from glycerol, neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, dipentaerythritol, tripentaerythritol and sorbitol. 18. Use according to any one of claims 17 to 17. The one or more C _Two ~ C ₂₀ 19. Use according to claim 18, wherein the aliphatic hydrocarbyl polyol is glycerol. The one or more polycarboxylic acids (B (iv)) are saturated C ₆ ~ C ₂₀ 20. Use according to any one of claims 14 to 19, which is an aliphatic hydrocarbyl dicarboxylic acid. The one or more saturated C ₆ ~ C ₂₀ 21. Use according to claim 20, wherein the aliphatic hydrocarbyl dicarboxylic acid is sebacic acid. The use according to any one of claims 14 to 21, wherein the oil-soluble or oil-dispersible metal dihydrocarbyl dithiophosphate is zinc dihydrocarbyl dithiophosphate. 23. Use according to any one of claims 14 to 22, wherein the non-ferrous metal containing engine component comprises copper, lead or an alloy of the metal. 13. The lubricating oil composition according to any one of claims 1 to 12, for lubricating a spark ignition or compression ignition internal combustion engine to reduce and / or prevent corrosion of non-ferrous metal containing engine parts during operation of the engine. use.