JP2015227453A - Lubricant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lubricant composition comprising a dihydrocarbyldithiophosphate metal salt anti-wear agent and an ashless organic friction adjusting additive, exhibiting improved anticorrosion properties for engine components of non-ferrous metal, in particular, for the components containing copper and/or lead, or the alloy thereof.SOLUTION: A lubricant composition has a sulfated ash content of 1.2 mass% or less when determined by ASTM D874, and a phosphorus content of 0.12 mass% or less when determined by ASTM D5185. The lubricant composition comprises the following components: a large amount of oil with a lubricating viscosity; an oil-soluble or oil-dispersible polymer friction adjusting agent as a small amount of effective additive; and at least one oil-soluble or oil-dispersible dihydrocarbyldithiophosphate metal salt as a small amount of effective additive; or is made of a mixture of these components.

Description

FIELD OF THE INVENTION This invention relates to automotive lubricating oil compositions. More particularly, but not exclusively, the present invention relates to automotive crankcase lubricant compositions for use in gasoline (spark ignition) and diesel (compression ignition) internal combustion engines (the compositions are referred to as crankcase lubricants); And additions in the lubricating oil composition to improve the corrosion resistance performance characteristics of non-ferrous metal engine parts, particularly engine parts (eg bearings) containing copper and / or lead (ie to inhibit corrosion of non-ferrous metal engine parts) The use of the agent.

BACKGROUND OF THE INVENTION Crankcase lubricating oil is oil that is used for general lubrication of an internal combustion engine in which a sump is generally located under the crankshaft of the engine and circulating oil returns to it.
Antiwear agents are typically used as an additive to crankcase lubricants to reduce excessive wear on 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 that is always utilized in crankcase lubricants is metal dihydrocarbyl dithiophosphate.
It is also desirable to reduce engine energy and fuel consumption requirements, and therefore a crankcase lubricant that reduces the overall friction of the engine is also needed. Reduction of engine friction loss greatly contributes to improving engine fuel efficiency and fuel retention characteristics. Therefore, 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)) have long been used as an additive to crankcase lubricants. Is known to obtain improved friction characteristics and improved fuel efficiency.
Therefore, to provide a crankcase lubricant having the desired wear resistance and desired friction properties, lubricant formulators typically combine lubricant compositions with ashless organic friction modifier additives such as 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 GMO in lubricating oils typically results in significant amounts of lead and copper corrosion. In addition, the use of ashless organic friction modifying additives such as GMO in combination with dihydrocarbyl dithiophosphate metal salt antiwear additives typically further increases the amount of lead corrosion. The corrosivity of ashless organic friction modifiers such as GMO 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 lubricant formulators. For example, particularly when used in combination, the corrosive nature of the additive component may necessitate a reduction in the processing rate of the additive, thereby affecting the wear resistance and / or fuel economy performance of the lubricating oil; In order to counter the corrosivity of dihydrocarbyl dithiophosphate metal salts and ashless organic friction modifying additives, it may be necessary to include a relatively expensive anti-corrosion additive in the lubricating oil.

  Accordingly, dihydrocarbyl dithiophosphate metal salt antiwear and ashless organic friction modifier additives that exhibit improved corrosion resistance performance characteristics for non-ferrous metal engine parts, particularly those parts containing copper and / or lead, or alloys thereof. There is a need for lubricating oil compositions containing.

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 has the following components:
(A) a large amount of oil of lubricating viscosity;
(B) Oil-soluble or oil-dispersible polymeric friction modifier as an effective small amount of additive (this polymeric friction modifier is:
(i) functionalized polyolefin;
(ii) polyalkylene glycol;
(iii) a polyol; and
(iv) reaction product of polycarboxylic acid only);
as well as
(C) Provide a lubricating oil composition comprising or mixing these components with at least one oil-soluble or oil-dispersible dihydrocarbyl dithiophosphate metal salt as an effective minor amount of an additive.
Preferably, the lubricating oil composition of the present invention is a crankcase lubricating oil.

Unexpectedly, the use of the polymeric friction modifier (B) defined according to the first aspect of the present invention as an effective small amount additive in a lubricating oil composition comprising a large amount of oil of lubricating viscosity is Corrosion of engine parts containing non-ferrous metals (for example, copper and / or lead) can be suppressed as compared with comparable lubricating oils that do not contain the friction modifier (B). In other words, the polymeric friction modifier (B) can function as a corrosion-resistant agent for non-ferrous metal-containing engine parts, particularly engine parts containing copper and / or lead or alloys containing the metal.
Further, in the lubricating oil composition comprising a large amount of oil of lubricating viscosity, the oil-soluble or oil-dispersible polymer friction modifier (B) defined in the first aspect of the present invention as an effective small amount of additive, The use in combination with the oil-soluble or oil-dispersible dihydrocarbyl dithiophosphate metal salt as defined in the first aspect of the invention as an effective minor additive is typically oil-soluble or as defined in the first aspect of the invention. Improved corrosion of engine parts containing non-ferrous metals (eg copper and / or lead) compared to comparable lubricating oils containing ashless organic friction modifiers such as GMO in combination with oil dispersible dihydrocarbyl dithiophosphate metal salts It has also been found to provide lubricating oils that exhibit greater prevention and / or reduction (ie, inhibit corrosion).
Still further, in the lubricating oil composition comprising a large amount of oil of lubricating viscosity, the oil-soluble or oil-dispersible polymeric friction modifier (B) defined in the first aspect of the present invention as an effective small amount of additive. The use in combination with the oil-soluble or oil-dispersible dihydrocarbyl dithiophosphate metal salt defined in the first aspect of the invention as an effective minor amount of additive typically comprises (i) a metal salt of dihydrocarbyl dithiophosphate. A comparable lubricant without the polymeric friction modifier (B); and (ii) a comparable lubricant without both the dihydrocarbyl dithiophosphate metal salt and the polymeric friction modifier (B), It has also been found to provide a lubricating oil that exhibits improved prevention and / or reduction of corrosion (ie, inhibits corrosion) of copper-containing metal engine components.
Thus, such non-ferrous metal corrosion level reduction (eg, copper and / or lead corrosion level reduction) associated with the use of polymeric friction modifiers (B) compared to ashless organic friction modifiers such as GMO is particularly dihydrocarbyl. When used in combination with a metal salt of dithiophosphate, it can allow an increase in the treat rate of the additive combination in the lubricating oil. Additionally or alternatively, such non-ferrous metal corrosion level reduction can reduce the need for the use of relatively expensive supplemental anti-corrosion additives. Therefore, the use of polymeric friction modifiers (B) in combination with dihydrocarbyl dithiophosphate metal salts typically results in severe wear resistance as specified 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 efficiency 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 large amount of lubricant to reduce and / or prevent (ie, inhibit corrosion) corrosion of non-ferrous metal-containing engine parts during engine operation in the lubrication of spark ignition or compression ignition internal combustion engines. There is provided the use of an oil-soluble or oil-dispersible polymeric friction modifier (B) as defined in the first aspect of the invention as an effective small amount of an 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 the metal.
Preferably, the lubricating oil composition as defined in the third aspect of the present invention further comprises a metal salt of dihydrocarbyl dithiophosphate as defined in the first aspect of the present invention as an effective small amount of additive.
According to a fourth aspect, the present invention provides a significant amount of lubrication for spark ignition or compression ignition internal combustion engines to reduce and / or prevent (ie, inhibit corrosion) corrosion of non-ferrous metal-containing engine components during engine operation. Addition of an effective small amount of the oil-soluble or oil-dispersible polymer friction modifier (B) 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 There is provided use in combination with an oil-soluble or oil-dispersible dihydrocarbyl dithiophosphate metal salt (C) as defined in the first aspect of the invention as an agent. Suitably, the non-ferrous metal-containing engine component comprises copper, lead or an alloy of said metal, in particular copper or an alloy thereof.
According to a fifth aspect, the present invention provides for reducing and / or preventing (ie, inhibiting corrosion) corrosion of non-ferrous metal-containing engine parts during engine operation in the lubrication of spark ignition or compression ignition internal combustion engines. Use of a lubricating oil composition according to the first aspect of the invention is provided. Suitably, the non-ferrous metal-containing engine component comprises copper, lead or an alloy of said metal, in particular copper or an alloy thereof.

According to a sixth aspect, the present invention provides a method for preventing and / or reducing corrosion of non-ferrous metal-containing engine parts of an engine (that is, inhibiting corrosion), comprising a large amount of oil of lubricating viscosity and an effective small amount of additive. There is provided a method comprising lubricating an engine with a lubricating oil composition comprising an oil-soluble or oil-dispersible polymeric friction modifier (B) as defined in the first aspect of the invention and operating the engine. Suitably, the non-ferrous metal containing part comprises copper, lead or an alloy of said metal. Preferably, the engine 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 provides a method for preventing and / or reducing corrosion of a nonferrous metal-containing engine part of an engine (that is, inhibiting corrosion), wherein the engine is treated with the lubricating oil composition of the first aspect of the present invention. A method is provided that includes the steps of lubricating and operating the engine. Suitably, the non-ferrous metal containing part comprises copper, lead or an alloy of said metal, in particular copper or an alloy thereof. Preferably, the engine 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 dihydrocarbyl dithiophosphate metal salt (C) is an oil-soluble or oil-dispersible zinc dihydrocarbyl dithiophosphate (i.e. zinc dihydrocarbyl dithiophosphate (ZDDP)), more preferably 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 defined in the second, third, fourth, fifth, sixth and seventh aspects of the present invention are additive components ( In addition to B) and (C), select from ashless dispersant, metal detergent, corrosion inhibitor, antioxidant, pour point depressant, antiwear agent, friction modifier, demulsifier, defoamer and viscosity modifier Further comprising an effective small 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 composition of the present invention contains low levels of phosphorus. The lubricating oil composition is 0.12% by weight or less, preferably up to 0.11% by weight, more preferably 0.10% by weight or less, still more preferably 0.09% by weight or less, still more preferably 0.08% by weight, based on the total weight of the composition. Hereinafter, phosphorus is most preferably contained in an amount of 0.06% by mass or less of phosphorus (ASTM D5185). Suitably, the lubricating oil composition comprises 0.01% by weight or more based on the total weight of the composition, preferably 0.02% by weight or more, more preferably 0.03% by weight or more, and even more preferably 0.05% by weight or more phosphorus (ASTM D5185) contains phosphorus.
Typically, the lubricating oil composition 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 wt%, more preferably up to 0.3 wt%, even more preferably up to 0.2 wt% sulfur (ASTM D2622), based on the total weight of the composition. To do.
Typically, the lubricating oil composition of the present invention is 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 4-15, preferably 5-12 mg KOH / g as measured according to ASTM D2896.

In this specification, when the following words and expressions are used, they have the meanings given below.
“Active ingredient” or “(ai)” refers to an additive material that is not a diluent or solvent.
"Including" or any congener specifies the presence of a specified feature, process, or integer or component, but the presence or addition of one or more other features, steps, integers, components or groups thereof I do not disturb. The expression “consisting of” or “consisting essentially of” or a homologous expression is encompassed by “including” or a homologous term, “consisting essentially of” being substantially in the properties of the composition to which it applies. Include substances that do not affect
“Hydrocarbyl” is a chemical group of a compound containing a hydrogen atom and a carbon atom and means a chemical group bonded directly 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 nature of the group. The person skilled in the art will know suitable groups such as halo, in particular chloro and fluoro, amino, alkoxyl, mercapto, alkylmercapto, nitro, nitroso, sulphoxy and the like. Preferably, this group consists essentially of hydrogen and carbon atoms, 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 It means -C ₆ divalent saturated acyclic aliphatic hydrocarbon radical; it may be linear or branched. Representative examples of alkylene include ethylene (ethanediyl), propylene (propanediyl), butylene (butanediyl), isobutylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, 1-methylethylene, 1-ethylethylene, 1-ethyl Examples include 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 attached to the remainder of the compound directly by a single carbon atom. Unless otherwise specified, when there are a sufficient number of carbon atoms, the alkyl group may be linear (ie, unbranched) or branched and may be cyclic, acyclic or partially cyclic / It 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, Examples include 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 bonded directly to the remainder of the compound by a single carbon atom, with the rest being as defined for “alkyl” C ₂ -C ₃₀ , preferably means C ₂ -C ₁₂ group.
“Aryl” is optionally substituted with one or more alkyl groups, halo, hydroxyl, alkoxy and amino groups, and is C ₆ -C ₁₈ bonded directly to the remainder of the compound by a single carbon atom. preferably means C ₆ -C ₁₀ aromatic group. Preferred aryl groups include phenyl and naphthyl groups and substituted derivatives thereof, particularly phenyl and alkyl substituted derivatives thereof.
“Alkenyl” contains at least one carbon-carbon double bond, and is bonded directly to the remainder of the compound by a single carbon atom, otherwise defined as C ₂ -C _30. preferably means C ₂ -C ₁₂ group.
`` Polyol '' means an alcohol containing two or more hydroxyl functional groups (i.e., a polyhydric alcohol), but a `` polyalkylene glycol '' (constituent) used to form an oil soluble or oil dispersible polymeric friction modifier Exclude element B (ii)). More specifically, the term “polyol” includes diols, triols, tetraols, and / or related dimers or chain-extending polymers of the compounds. Still more particularly, the term “polyol” includes glycerol, neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, pentaerythritol, dipentaerythritol, tripentaerythritol and sorbitol.
“Polycarboxylic acid” means an organic acid containing two or more carboxylic acid functional groups, preferably hydrocarbyl acid, more preferably aliphatic hydrocarbyl 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 a cognate term, does not necessarily mean that the compound or additive is soluble, soluble, miscible or suspendable in oil in all proportions. I don't 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 that utilizes the oil. To do. Further, if necessary, further incorporation of other additives may allow higher levels of incorporation of certain additives.
“Ashless” with respect to an additive means that the additive does not contain a metal.
“Ash content” for an additive means that the additive contains a metal.
“Major amount” is expressed for the component referred to and means an amount greater than 50% by weight of the composition, calculated as the active ingredient of the component, relative to the total weight of the composition.
“Minor amount” is expressed for the additive mentioned and means an amount of less than 50% by weight of the composition, calculated as the active ingredient of the additive, relative to the total weight of the composition.
By “effective minor amount” for an additive is meant the minor amount of the additive in the lubricating oil composition such that the additive provides the desired technical effect.
“Non-ferrous metals” include metals or alloys thereof, including lead, copper, tin, or alloys thereof, preferably copper or lead metals, or alloys of the metals, particularly copper or alloys thereof.
Non-ferrous metal corrosion (eg, copper and lead corrosion) is measured in a high temperature 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, such as the molybdenum content or the total metal content of the lubricating oil composition (ie, the sum of all individual metal contents) is measured by 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 reported percentages are by weight, unless otherwise specified, based on the active ingredient base, i.e. not considering carrier or diluent oil.
It will also be appreciated that the various components, not only essential but also optimal and customary, that are used may react under the conditions of formulation, storage or use, and the present invention is not limited to any such reaction. The resulting or obtained product is also provided.
Further, it will be appreciated that any upper and lower amount, range and ratio limits set forth herein may be combined independently. Accordingly, any upper and lower amount, range and ratio limits set forth herein that are associated with a particular technical feature of the invention shall be considered herein in connection with the other particular technical features of the invention. Any upper and lower quantities, ranges and ratio limits described in may be combined independently. Further, any particular technical feature of the present invention, and all preferred variations thereof, may be independently combined with any other particular technical feature, and all preferred variations thereof.
It should also be understood that preferred features of each aspect of the invention are considered preferred features of any other aspect of the invention.

DETAILED DESCRIPTION OF THE INVENTION The features of the invention relating to each and every aspect of the invention are described in detail below, as appropriate.
Oil of lubricating viscosity (A)
Oil of lubricating viscosity (sometimes referred to as `` base stock '' or `` base oil '') is the main liquid component of a lubricant, in which additives and optionally other oils are blended, e.g. A final lubricant (or lubricant composition) is produced. Base oils serve to make concentrates and to make lubricating oil compositions therefrom, and can be selected from natural (plant, animal or mineral) lubricating oils and synthetic lubricating oils and mixtures thereof.
Basestock groups are 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 of preferably 3-12, more preferably 4-10, most preferably 4.5-8 mm ² / sec (cSt) at 100 ° C.
The definitions of base stock 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 stock contains less than 90 percent saturates and / or more than 0.03 percent sulfur and has a viscosity index of 80 to less than 120, using the test methods specified in Table E-1. .
b) Group II base stocks contain 90% or more of saturates and 0.03% or less of sulfur and have a viscosity index of 80 to less than 120 using the test methods specified in Table E-1.
c) Group III base stock contains 90% or more of saturates and 0.03% or less of sulfur and has a viscosity index of 120 or more using the test method specified in Table E-1.
d) Group IV base stock is poly alpha olefin (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 methods

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 paraffinic, naphthenic and mixed paraffin-naphthenic hydrotreated refined solvent-treated mineral lubricating oils. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
Synthetic lubricating oils include hydrocarbon oils such as polymerized and copolymerized olefins (e.g. polybutylene, polypropylene, propylene-isobutylene 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 diphenyl sulfides and their Derivatives, analogs and homologues are mentioned.
Another suitable class of synthetic lubricants 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 (for example, 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, sebacin Examples include dieicosyl acid, 2-ethylhexyl diester of linoleic acid dimer, and complex esters formed by reacting 1 mol of sebacic acid with 2 mol of tetraethylene glycol and 2 mol 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 natural or synthetic sources without further purification. 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 treatment. Refined oils are similar to 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. The re-refined oil is obtained by applying a process similar to that used to obtain the refined oil to the refined oil already used. Such rerefined oils, also known as reclaimed or reprocessed oils, are often further processed with techniques to recognize 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 can be an oil derived from a Fischer-Tropsch synthesized hydrocarbon made from a synthesis gas containing H ₂ and CO using a Fischer-Tropsch catalyst. These hydrocarbons typically require further processing to serve as base oils. For example, they can be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed by methods known in the art.

The composition of the base oil will depend on the specific application of the lubricating oil composition, and the oil formulator will select the base oil to achieve the desired performance characteristics at a reasonable cost, but the base of the lubricating oil composition of the present invention The oil typically comprises no more than 85% by weight Group IV base oil, and the base oil may comprise no more than 70% by weight Group IV base oil, and even no more than 50% by weight Group IV base oil. The base oil of the lubricating oil composition of the present invention may comprise 0% by weight Group IV base oil. Alternatively, the base oil of the lubricating oil composition of the present invention may comprise at least 5 wt%, at least 10 wt% or at least 20 wt% Group IV base oil. The base oil of the lubricating oil composition of the present invention may comprise 0 to 85%, or 5 to 85%, or 10 to 85% by weight of 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.

Lubricate a large amount of oil of lubricating viscosity with a small amount of additive components (B) and (C) as defined here, and optionally one or more co-additives as described below. An oil composition is constituted. This preparation can be accomplished by adding the additive directly to the oil or in the form of a concentrate of the additive to disperse or dissolve the additive in the oil. Additives may be added to the oil by any method known to those skilled in the art before, simultaneously with, or after the addition of other additives.
Preferably, the oil of lubricating viscosity is present in an amount greater than 55 wt%, more preferably greater than 60 wt%, and even more preferably greater than 65 wt%, 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%, and 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 a viscosity measurement 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 different viscometric grades can be found in the SAE J300 classification. In embodiments 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 SAE 5WX or SAE 0WX (where X is 20, 30, Represents one of 40 and 50). Preferably X is 20 or 30.

Polymer friction modifier (B)
The oil-soluble or oil-dispersible polymer friction modifier (B) is:
(i) a functionalized polyolefin as defined herein;
(ii) polyalkylene glycol;
(iii) a polyol; and
(iv) A reaction product of only polycarboxylic acid as defined herein.
By the term “only” we mean 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. A copolymer derived from (i.e., a copolymer that is the 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 polyolefins are polyalkylenes containing at least one diacid or anhydride functional group. One or more functionalized polyolefins are preferably polymerized and the result of olefins having 2-6 carbon atoms, especially monoolefins such as ethene, propene, but-1-ene and isobutene (ie 2-methylpropene). The resulting polyolefin is derived by functionalization with diacid or anhydride functional groups. Preferably, the one or more functionalized polyolefins are poly (C ₂ -C ₆ alkylene) functionalized with diacid or anhydride functional groups. Even more preferably, the one or more functionalized polyolefins are derived from the polymerization of isobutene and the resulting polyisobutylene is functionalized with diacid or anhydride functional groups (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 portion 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 daltons.

The functionalized polyolefin contains at least one diacid or anhydride functional group capable of reacting with the hydroxyl functionality of the polyalkylene glycol (B (ii)) or the hydroxyl functionality of the polyol (B (iii)). Thus, a functionalized polyolefin can be formed by reaction of a polyolefin (ie, poly (alkylene)) with an unsaturated diacid or anhydride. Preferably, the functionalized polyolefin contains anhydride functional groups. 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 . Accordingly, the functionalized polyolefin contains anhydride functional groups, particularly succinic anhydride functional groups.
Accordingly, preferred one or more functionalized polyolefins are polyalkylenes containing anhydride functional groups, more preferably poly (C ₂ -C ₆ alkylene) containing anhydride functional groups, and even more preferably succinic anhydride functional groups. Poly (C ₂ -C ₆ alkylene) containing, 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 to 5000, preferably 500 to 1500, in particular 800 to 1200 daltons. PIB is a commercially available compound, sold by BASF under the trade name Glissopal, which 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 (C ₂ -C ₆ alkylene) containing product functional groups, in particular polyisobutylene (PIB) containing succinic anhydride functional groups, i.e. polyisobutylene succinic anhydride (PIBSA)) are suitable unsaturated diacids 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 temperatures above 150 ° C. for 1-48 hours. The functionalized polyolefin formed by the thermal ene reaction is chemically distinct and is a comparable functionalization formed by a chlorination process (i.e. reaction with a suitable diacid or anhydride after chlorination of the polyolefin). Has different physical and chemical properties than polyolefins.

Polyalkylene glycol (B (ii))
Suitably, the 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) glycols. 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 are one or more polyethylene glycols (PEG), especially water-soluble PEG.
Polyalkylene glycols can basically form polyolefin-polyalkylene glycol copolymers by reacting with functional groups of functionalized polyolefins (B (i)) and / or react with polycarboxylic acids (B (iv)) In principle, it contains 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 compound may further react with a functionalized polyolefin (B (i)), polyalkylene glycol (B (ii)), polyol (B (iii)) and / or polycarboxylic acid (B (iv)). Will be done.
Suitably the polyalkylene glycol (eg PEG) has a number average molecular weight (Mn) of from 300 to 5000, preferably from 400 to 1000, in particular from 400 to 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 bonds separate blocks of the functionalized polyolefin. Preferably, when the functionalized polyolefin is functionalized with an anhydride or diacid functional group, the polyol provides a backbone portion that connects separate blocks of the polyolefin through ester linkages.
Suitably, the polyol reactant may also provide a polyol-carboxylic acid compound by reacting with a polycarboxylic acid, which further comprises a functionalized polyolefin (B (i)) and / or a polyalkylene glycol (B ( Can react with ii)).
Polyols are alcohols that contain two or more hydroxyl functional groups (i.e., polyhydric alcohols), but are `` polyalkylene glycols '' (component B ( Excluding ii)). Preferably, the polyol contains 3 or more hydroxyl functional groups. Thus, the polyol can be a diol, triol, tetraol, and / or a related dimer or chain-extending 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 it 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, trimethylol ethane, trimethylol propane, trimethylol butane, pentaerythritol, dipentaerythritol, tripentaerythritol and sorbitol. A highly preferred polyol is glycerol.

Polycarboxylic acid (B (iv))
The polycarboxylic acid reactant can react with the hydroxyl group of the polyalkylene glycol (B (ii)) to provide a backbone moiety that connects separate blocks of the polyalkylene glycol via an ester linkage.
Suitably, the polycarboxylic acid can also be reacted with a polyol (B (iii)) to give a polyol-carboxylic acid compound, which further comprises a functionalized polyolefin (B (i)) and / or a polyalkylene. Can react with glycol (B (ii)).
A polycarboxylic acid is an organic acid 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 the C ₂ -C ₂₀ hydrocarbyl bilge carboxylic acid, even more preferably a C ₂ -C ₂₀ aliphatic hydrocarbyl bilge carboxylic 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. A linear polycarboxylic acid is preferred to a branched polycarboxylic acid. 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 acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. 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) is:
(i) PIBSA as defined herein;
(ii) polyethylene glycol as defined herein;
(iii) a polyol, preferably glycerol; and
(iv) A reaction product of only 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)) ) Multiple reactions can occur. For example, a functionalized polyolefin and a polyalkylene glycol react so that the polyolefin binds directly to the polyalkylene glycol (eg, through an ester linkage) and the resulting polymer and functionalized polyolefin, polyalkylene glycol, polyol, and / or polycarboxylic acid. A subsequent reaction can occur with the acid. 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 functionalized polyolefin and / or functional A subsequent reaction can occur with the modified polyolefin block. Still further, the functionalized polyolefin reacts with the polyol to form a functionalized polyolefin block bonded by the polyol (typically by an ester bond), and the resulting functionalized polyolefin block and the polyalkylene glycol and / or polyalkylene glycol. A subsequent reaction can occur with the alkylene glycol block.

Thus, functionalized polyolefins, polyalkylene glycols, polyols and polycarboxylic acids can react to form block copolymers. When present, the number of block copolymer units in the organic friction modifying additive typically ranges from 2-20, preferably 2-15, more preferably 2-10 units.
As with all polymers, polymeric friction modifiers will typically contain 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 of 1.5-9.
The polymeric friction modifier (B) can be prepared by techniques well known to those skilled in the art, such 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 a reaction product of maleated polyisobutylene (PIBSA), PEG, glycerol and sebacic acid, wherein the polyisobutylene of maleated polyisobutylene (PIBSA) is about It 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) PIBSA, 101 g (0.168 mol) PEG ₆₀₀ , 10.4 g in a glass round bottom flask equipped with a nitrogen purge, mechanical stirrer, isomantle heater and distillation arm. It can be made by packing (0.0514 mol) sebacic acid and 7.7 g (0.0835 mol) glycerol. The reaction takes place to a final acid value of 1.7 mg / KOH / g while removing water at 180-230 ° C. in the presence of 0.5 ml of the esterification catalyst tetrabutyl titanate. Therefore, the alternative polymer friction modifier (B) can be prepared by a similar synthesis method.
The polymeric friction modifier (B) is suitably present in the lubricating oil composition of the present invention on an active substance basis in an amount of at least 0.1, preferably at least 0.2% by weight, based on the total weight of the lubricating oil composition. To do. The polymeric friction modifier of the present invention is suitably based on the active substance in the lubricating oil composition, 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)
Any suitable oil-soluble or oil-dispersible dihydrocarbyl dithiophosphate metal salt that has antiwear properties in the lubricating oil composition may be utilized in the lubricating oil composition of the present invention. Of note are dihydrocarbyl dithiophosphate metal salts where the metal can be an alkali metal 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 zinc dialkyl dithiophosphates, especially zinc di (C ₂ -C ₈ alkyl) dithiophosphates, which di (C ₂ -C ₈ alkyl) C ₂ -C ₈ alkyl radical zinc dithiophosphate may be the same or different.
Dihydrocarbyl dithiophosphate metal salts are formed by known techniques, usually by first forming dihydrocarbyl dithiophosphate (DDPA) by reaction of one or more alcohols or phenols with P ₂ S ₅ and then converting the 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. Any basic or neutral metal compound can be used to make the metal salt, but oxides, hydroxides and carbonates are most commonly utilized. Commercially available additives often contain excess metal because an excess of the basic metal compound is used in the neutralization reaction.
A preferred zinc dihydrocarbyl dithiophosphate (ZDDP) is an oil-soluble salt of dihydrocarbyl dithiophosphate and can be represented by the following formula:

In which R and R ′ may be the same or different hydrocarbyl groups containing 1 to 18, preferably 2 to 12 carbon atoms, alkyl, alkenyl, aryl, arylalkyl, alkaryl and alicyclic. Groups such as groups. 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 (ie R and R ′) in the dithiophosphoric acid will generally be about 5 or greater. Accordingly, the zinc dihydrocarbyl dithiophosphate can comprise a zinc dialkyldithiophosphate.
Sufficient to provide the lubricating oil with phosphorus of 1200 ppm or less, preferably 1000 ppm or less, more preferably 900 ppm or less, and most preferably 850 ppm or less based on the total weight of the lubricating oil composition and measured according to ASTM D5185. A dihydrocarbyl dithiophosphate metal salt such as ZDDP is added to the lubricating oil composition in an amount. ZDDP is preferably based on the total weight of the lubricating oil composition and in an amount sufficient to provide the lubricating oil with phosphorus of at least 100 ppm, preferably at least 350 ppm, more preferably at least 500 ppm by weight as measured according to ASTM D5185. A dihydrocarbyl dithiophosphate metal salt such as is added to the lubricating oil composition.
Suitably, the dihydrocarbyl dithiophosphate metal salt such as ZDDP is present in an amount of 0.1% by weight or more, preferably 0.25% by weight or more, more preferably 0.5% by weight or more, based on the total weight of the lubricating oil composition. . Suitably, the dihydrocarbyl dithiophosphate metal salt such as ZDDP is present in an amount of 10% by weight or less, preferably 5.0% by weight or less, more preferably 3.0% by weight or less, based on the total weight of the lubricating oil composition. .

Engine The composition of the present invention is obtained by adding the lubricating oil composition of the present invention to mechanical engine parts, particularly engine parts of internal combustion engines such as spark ignition or compression ignition internal combustion engines, particularly spark ignition or compression ignition 2 or 4 stroke reciprocating engines. The engine parts can be lubricated with objects. The engine may be a normal gasoline engine 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 May be.

Coadditives Coadditives that may be present, different from additive components (B) and (C), are listed below along with their typical effective amounts. All the values listed present the active ingredient in the fully formulated lubricating oil as a percentage by weight.
Additive mass% mass%
(Wide range) (Preferred 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 0-10 0-4
Antioxidant 0 ~ 5 0.01 ~ 3
Pour point depressant 0.01-5 0.01-1.5
Antifoam 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 Residue
(1) Viscosity modifiers are used only for multigrade oils.

The final lubricating oil composition, typically made by blending each additive into the base oil, should contain 5-25, preferably 5-18, typically 7-15% by weight co-additive. 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, a friction agent. Contains one or more minor co-additives selected from regulators, demulsifiers, defoamers and viscosity modifiers.
The co-additives are discussed in further detail below; as is well known in the art, several additives can provide a variety of effects, for example, a single additive 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. The detergent generally includes a polar head and a long hydrophobic tail, which includes a metal salt of an acidic organic compound. The salts can contain substantially stoichiometric amounts of metals, in which case they are usually described as normal or neutral salts, typically 0-80 mg KOH / g total base number 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 acid gases (eg, carbon dioxide). The resulting overbased detergent includes a neutralized 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 higher, and typically will have a TBN of 250-450 mg KOH / g or higher. In the presence of a compound of formula I, the amount of overbased detergent can be reduced, or a detergent with a reduced overbasing level (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 degrading its performance.
Usable detergents include oil-soluble neutral and overbased sulfonates of metals, especially alkali metals or alkaline earth metals such as sodium, potassium, lithium, calcium, and magnesium, phenates, sulfide phenates, thiophosphones. Acid salts, salicylates, and naphthenates and other oil-soluble carboxylates. The most commonly used metals are calcium and magnesium, both may be present in detergents used in lubricating oils, and may be present in calcium and / or a mixture of magnesium and sodium. A combination of detergents, whether overbased or neutral or both, may be used.
In one embodiment of the present invention, the lubricating oil composition comprises a neutral or overbased calcium sulfonate having a TBN of 20 to 450 mg KOH / g and a neutral and overbased having a TBN of 50 to 450 mg KOH / g. Metal detergents selected from basic calcium phenate and sulfurized phenate, and mixtures thereof.
Sulfonates are typically prepared from sulfonic acids obtained from the fractionation of petroleum or from sulfonation of alkyl-substituted aromatic hydrocarbons such as those obtained by alkylation of aromatic hydrocarbons. Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl or their halogen derivatives such as chlorobenzene, chlorotoluene and chloronaphthalene. Alkylation can be performed using an alkylating agent having about 3 to more than 70 carbon atoms in the presence of a catalyst. Alkaryl sulfonates generally contain about 9 to about 80 or more carbon atoms, preferably 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 to 220% by weight (preferably at least 125% by weight) of the stoichiometrically required amount. .
The metal salts of phenol and sulfurized phenol are prepared by reaction with a suitable metal compound, such as an oxide or hydroxide, and neutral or overbased products can be obtained by methods well known in the art. A product that is a mixture of a compound in which two or more phenols are generally crosslinked by a sulfur-containing bridge by reacting phenol with sulfur or a sulfur-containing compound, such as hydrogen sulfide, sulfur monohalide or sulfur dihalide. Sulfurized phenols can be prepared by forming
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 to 450 mg KOH / g, preferably 50 to 250 mg KOH / g TBN. It includes a metal detergent which is a salicylate or a mixture thereof. Highly preferred salicylate detergents include alkaline earth metal salicylates, especially magnesium salicylate and calcium salicylate, especially calcium salicylate. In one embodiment of the present invention, an alkali metal or alkaline earth metal salicylate detergent is the only metal-containing detergent in the lubricating oil composition.

Auxiliary antiwear agents other than dihydrocarbyl dithiophosphate metal salts (additive component (c)) that may be included in the lubricating oil composition are 1,2,3-triazole, benzotriazole, sulfurized fatty acid esters, and dithiocarbamic acid. Including derivatives.
The ashless dispersant includes an oil-soluble polymer hydrocarbon skeleton having a functional group capable of binding to the particles to be dispersed. Typically, the dispersant comprises an amine, alcohol, amide, or ester polar moiety that is often attached to the polymer backbone via a bridging 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 condensation of long chain substituted phenols with formaldehyde and polyalkylene polyamines.
Friction modifiers 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 wt%, preferably does not exceed 2 wt%, based on the total weight of the lubricating oil composition, More preferably, it does not exceed 0.5% by mass. In an embodiment 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 antioxidant and antiwear capabilities to the lubricating oil composition. Suitable oil-soluble organomolybdenum compounds have a molybdenum-sulfur core. Examples include dithiocarbamate, dithiophosphate, dithiophosphinate, xanthate, thioxanthate, sulfide, and mixtures thereof. Molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum alkylxanthate and molybdenum alkylthioxanthate are particularly preferred. Molybdenum compounds are binuclear or trinuclear.
One class of preferred organomolybdenum compounds useful in all aspects of the present invention are trinuclear organomolybdenum compounds of the formula Mo ₃ S _k L _n Q _z and mixtures thereof (wherein L is a compound soluble in oil) Or independently selected ligands having an organic group of carbon atoms sufficient to be dispersible, n is 1 to 4, k varies from 4 to 7, and Q is A group of neutral electron donating compounds such as water, amines, alcohols, phosphines, ethers, etc., z ranging from 0 to 5 and including non-stoichiometric values). There should be at least 21 total carbon atoms, such as at least 25, at least 30, or at least 35 carbon atoms in the organic group of all ligands.
Molybdenum compounds may be present in the lubricating oil composition in concentrations ranging from 0.1 to mass percent, or at least 10, for example 50 to 2,000 mass ppm molybdenum atoms.
Preferably, the molybdenum from the molybdenum compound is present in an amount of 10 to 1500, such as 20 to 1000, more preferably 30 to 750 ppm, based on the total weight of the lubricating oil composition. For 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 this unique function or may be multifunctional. Multifunctional viscosity modifiers that also function as dispersants are also known. Suitable viscosity modifiers include polyisobutylene, copolymers of ethylene and propylene and higher alpha olefins, polymethacrylates, polyalkyl methacrylates, methacrylate copolymers, copolymers of unsaturated dicarboxylic acids and vinyl compounds, interpolymers of styrene and acrylate 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 evident from sludge in the lubricating oil, varnish-like deposits on the metal surface, and increased viscosity.
Examples of suitable antioxidants are selected from copper-containing antioxidants, sulfur-containing antioxidants, aromatic amine-containing antioxidants, hindered phenolic antioxidants, dithiophosphate 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.
Rust inhibitors 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 containing corrosion inhibitors may be used, they are typically not required in the formulations of the present invention. Typically the compounds are thiadiazole polysulfides containing 5 to 50 carbon atoms, their derivatives and polymers thereof. Derivatives of 1,3,4-thiadiazole are typical, such as those described in US Pat. Nos. 2,719,125; 2,719,126; and 3,087,932. Other similar materials are described in US Pat. 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 thiadiazole thio and polythiosulfenamides, such as those described in British Patent Specification 1,560,830. Benzotriazole derivatives also fall into this category of additives. When these compounds are included in the 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. A preferred demulsifying component is described in EP 330522. It is obtained by reacting an alkylene oxide with an adduct obtained by reacting a bisepoxide with a polyhydric alcohol. The demulsifier should be used at a level of active ingredient not exceeding 0.1% by weight. A treatment rate of 0.001 to 0.05 mass% active ingredient is convenient.
Pour point depressants, also known as lube oil flow improvers, lower the minimum temperature at which the fluid will flow 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 many compounds including polysiloxane type antifoams such as silicone oil or polydimethylsiloxane.

Individual additives can be incorporated into the base stock by any convenient means. Thus, each component can be added directly to the base stock or base oil blend by dispersing or dissolving each component in the base stock or base oil blend at a desired level of concentration. The blending can occur at ambient or elevated temperatures.
Preferably, all the additives except the viscosity modifier and 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 complete the finished lubricant. make. The concentrate will typically be formulated to contain additives in an amount suitable to give the desired concentration in the final formulation when the concentrate is combined with a predetermined amount of base lubricant.
The concentrate is preferably made by the method described in US 4,938,880. The patent describes making a premix of ashless dispersant and metal detergent that is pre-blended at a temperature of at least about 100 ° C. The premix is then 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, The lubricating oil composition of the invention has a total base number (TBN) of 4-15, preferably 5-12, as measured by ASTM D2896. In an embodiment of the 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 is from 9.05 to 9.27 as measured by ASTM D2896. Does not have a total base number (TBN).
The final crankcase lubricant formulation can utilize a 2-20, preferably 4-18, most preferably 5-17 wt% 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 0.2-0.25 wt% sulfur as measured according to ASTM method D4927.
In an embodiment of the invention, the lubricating oil composition of the first aspect of the invention does not contain 0.08 to 0.11 mass% nitrogen as measured according to ASTM method D5291.

The invention will now be illustrated by the following examples which are not intended to limit the scope of the claims of the invention.
Unless otherwise specified, all additives described in the examples are available as standard additives from lubricant additive companies such as Infineum UK Ltd, Lubrizol Corporation and Afton Chemical Corporation.
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 airtight stirrer bearing, a temperature probe and a distillation arm attached to an outlet bubbler was added to a 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. with stirring for 1 hour. . 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 for 2 hours at a temperature of 230 ° C. and a reduced pressure of 50-150 mbar. The reaction mixture was cooled to 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
Six lubricating oil compositions (referred to as base lubricating oil and oil 1-5) were prepared. Base lubricant 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 also contained additional additives on an active ingredient basis as detailed in Table 1. The oil containing ZDDP (ie oil 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} polymeric friction modifier was the compound of Example 1.

Test and results
Measure corrosion control using high temperature corrosion bench test (HTCBT) according to ASTM D6594-06. This test method simulates corrosion of non-ferrous metals such as copper and lead found in cam followers and bearings in lubricating oil. The corrosion process under investigation is triggered by the chemistry of the lubricant rather than by the degradation or contamination of the lubricant.
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 test lubricant to 135 ° C. The test lubricant is heated at 135 ° C. for 168 hours, during which dry air is blown into the heated oil at a rate of 5 liters per hour. After this, the test lubricant is cooled and a metal specimen is removed and examined for corrosion. The copper, tin, and lead concentrations in the test lubricant composition and the reference sample of the lubricant composition are then determined according to ASTM D5185. The difference between the concentration of each metal contaminant in the test lubricant composition and that of the reference sample lubricant composition gives a value for the change in the various metal concentrations before and after the test. Industry standard limits to meet API CJ-4 requirements are up to 20ppm for copper and 120ppm for lead. The results for base lubricants and oils 1-5 are presented in Table 2.

Table 2

From the results in Table 2, it can be seen 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 base oil with oil 1 equivalent to base lubricant containing polymer friction modifier (B) shows that the polymer friction modifier (B) contained in oil 1 is copper (29 ppm vs. 33 ppm) ) And lead (13 ppm vs. 23 ppm) corrosion prevention is demonstrated. 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 and the base lubricant, inclusion of 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, inclusion of both ZDDP and ashless organic friction modifier (GMO) in the base lubricant (oil 4) leads to a significant increase in lead corrosion (420 ppm vs. 420 ppm). 23ppm), resulting in improved copper corrosion (22ppm vs. 33ppm). From the comparison between the results of oil 5 (the lubricating oil of the present invention containing ZDDP and the polymer friction modifier (B)) and the results of oil 4, the polymer friction modifier (B) is an ashless organic compound present in oil 4. It should be noted that lead corrosion is significantly reduced (108 ppm vs. 420 ppm) over friction modifiers, and that polymeric friction modifiers are far superior to ashless organic friction modifiers (9 ppm vs. 22 ppm) in preventing copper corrosion. Furthermore, a comparison of the oil 5 results with the base lubricant results clearly demonstrates that the presence of both ZDDP and polymeric friction modifier results in a significant reduction in copper corrosion (9 ppm vs. 33 ppm).

Claims (16)

A lubricating oil composition having a sulfated ash content of 1.2% by weight or less as determined by ASTM D874 and a phosphorus content of 0.12% by weight or less as determined by ASTM D5185, wherein the lubricating oil composition comprises the following components: :
(A) a large amount of oil of lubricating viscosity;
(B) Oil-soluble or oil-dispersible polymeric friction modifier as an effective small amount of additive, wherein the polymeric friction modifier is:
(i) one or more functionalized polyolefins that are poly (alkylene) functionalized with at least one diacid or anhydride functional group (the poly (alkylene) of said functionalized polyolefin is of 50 to 500 carbon atoms) Having a carbon chain length);
(ii) one or more polyalkylene glycols;
(iii) one or more polyols; and
(iv) a C ₂ -C ₃₀ hydrocarbyl reaction product of only one or more polycarboxylic acids polycarboxylic acids;
as well as
(C) A lubricating oil composition comprising or mixing these components comprising at least one oil-soluble or oil-dispersible dihydrocarbyl dithiophosphate metal salt as an effective minor amount of an additive. The one or more functionalized polyolefins are poly (C ₂ -C ₆ alkylene) functionalized with at least one diacid or anhydride functional group, and 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.   The composition according to claim 1 or 2, wherein the one or more functionalized polyolefins (B (i)) are polyisobutylenes functionalized with at least one diacid or anhydride functional group.   The composition of any one of claims 1 to 3, wherein the one or more functionalized polyolefins (B (i)) are functionalized with succinic anhydride functional groups.   The composition of claim 1, wherein the one or more functionalized polyolefin (B (i)) is polyisobutylene succinic anhydride (PIBSA). The composition according to any one of claims 1 to 5, wherein the one or more polyalkylene glycols (B (ii)) are poly (C ₂ -C ₆ alkylene) glycols.   The composition of claim 6, wherein the one or more polyalkylene glycols are polyethylene glycol (PEG). It said one or more polyols (B (iii)) is C ₂ -C ₂₀ aliphatic hydrocarbyl polyols, any one composition according to claims 1-7. 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 ₂ -C ₂₀ aliphatic hydrocarbyl bilge carboxylic acid, any one composition according to claims 1-9. Wherein the one or more saturated C ₂ -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 salt of 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 one of claims 1-12.   In lubricating a spark ignition or compression ignition internal combustion engine, in 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 the engine. Use of the oil-soluble or oil-dispersible polymeric friction modifier (B) as defined in any one of claims 1 to 12 as an effective small amount of additive.   15. Use according to claim 14, wherein the non-ferrous metal containing engine component comprises copper, lead or an alloy of the metal.   The lubricating oil composition further comprises an oil-soluble or oil-dispersible dihydrocarbyl dithiophosphate metal salt (C) as defined in any one of claims 1 to 12 as an effective small amount of an additive. 15. Use according to 15.