JP6774940B2 - How to prevent or reduce slow pre-ignition - Google Patents

Description

(Field)
The present disclosure comprises at least one boron-containing compound, preferably at least one booxide dispersant, or a mixture of a boron-containing compound and a dispersant, present in the blended oil in a particular amount. It relates to a method of preventing or reducing low speed pre-ignition (LSPI) in an engine lubricated with this lubricating oil by using it as a lubricating oil. The lubricating oil of the present disclosure is useful as a passenger vehicle engine oil (PVEO) product.

(background)
Pre-ignition in a flame propagation (or "spark ignition") engine is the phenomenon in which the air / fuel mixture in a cylinder ignites before the spark plug ignites. Pre-ignition is initiated by non-spark sources such as hot parts of the combustion chamber, spark plugs that are overheated to apply, or carbonaceous deposits in the combustion chamber that have been heated to incandescence by previous engine combustion phenomena. Will be done.

Many passenger car manufacturers have observed intermittent pre-ignition in their turbocharged gasoline engines, especially at low speeds and moderate to high loads. At such high loads, pre-ignition usually results in severe engine knock, which can damage the engine. The cause of pre-ignition is not fully understood and is actually high temperature deposits in the combustion chamber, high concentration of lubricant vapor entering the PCV system, oil leaching from the turbo supercharger compressor seal, or It can be due to multiple phenomena such as automatic ignition of oil and / or fuel droplets between compression strokes.

Pre-ignition can cause the combustion chamber temperature to rise sharply, resulting in poor engine operation or poor performance. Conventional methods of eliminating pre-ignition include, for example, selection of the appropriate spark plugs, adjustment of the appropriate fuel / air mixture and regular cleaning of the combustion chamber. Hardware solutions such as cooled exhaust gas recirculation (EGR) are known, but they are costly to implement and can lead to packaging problems.

Low speed pre-ignition (LSPI) is a type of abnormal combustion that affects engines operating at high net mean effective pressure (BMEP) and low engine speed (RPM). This includes internal combustion engines that use a variety of fuels, including natural gas, gasoline, diesel, biofuels and the like. Reduced size and slowed turbocharged engines are most susceptible to operation under these engine conditions and are therefore most susceptible to LSPI. Concerns about LSPI continue to grow as the automotive industry continues to move towards further size reductions, slowdowns and increased turbocharging in order to increase vehicle fuel economy and reduce carbon dioxide emissions.

Further development of slowed down turbocharged gasoline engines is hampered by LSPI. A solution to this problem or mitigation of its occurrence will remove barriers to original equipment manufacturer (OEM) technology and efficiency improvements. Lubricant formulation solutions will allow product differentiation with respect to LSPI.

Pre-ignition problems can be solved or solved by optimizing internal engine components and by using new component technologies such as electronic control, but are used to lubricate such engines. Modification of the lubricating oil composition is desirable. For example, it would be desirable to develop new lubricating oil formulations that are particularly useful in internal combustion engines and that will prevent or minimize pre-ignition problems when used in internal combustion engines. It is desirable that the lubricating oil composition be useful in a spark ignition engine with a lubricating oil mixed gasoline fuel.

Despite advances in lubricant oil formulation technology, there is a need for engine oil lubricants that effectively prevent or reduce low speed pre-ignition, especially for reduced and slowed turbocharged engines.

(Summary)
The present disclosure relates, in part, to novel lubricating oil formulations that are particularly useful in internal combustion engines (or internal combustion engines) and that will prevent or minimize pre-ignition problems when used in internal combustion engines. The lubricating oil composition of the present disclosure is useful in a spark ignition engine using a lubricating oil mixed gasoline fuel. The chemistry of the lubricant formulations of the present disclosure may be used in engines already designed or commercially available, as well as in future engine technology to prevent or control the adverse effects of LSPI. it can. The chemistry of the lubricant formulations of the present disclosure removes barriers to OEM technology and efficiency improvements, and allows further development of slowed turbocharged gasoline engines currently hampered by LSPI. The solution with a lubricant formulation obtained by the present disclosure to prevent or reduce LSPI allows product differentiation with respect to LSPI.

The present disclosure also relates in part to methods of preventing or reducing low speed ligation in lubricating oil-lubricated engines by using formalized oil as lubricating oil. The compounded oil has a composition (product) containing a lubricating oil base stock as a main component (or major component) and at least one boron-containing compound as a sub component (or minor component). At least one boron-containing compound comprises at least one boron-containing dispersant, or a mixture of a boron-containing compound and a dispersant. The engine is achieved with the engine using at least one booxide dispersant, or a lubricating oil that does not contain a mixture of boron-containing compound and non-borated dispersant. Standardized engine operation at 25,000 engine cycles, revolutions per minute (RPM) and 18 bar net mean effective pressure (BMEP) when compared to slow pre-ignition performance. It indicates a reduction in slow pre-ignition greater than about 50% based on the number (or count) of low speed pre-ignition (LSPI).

Further, the present disclosure relates to a method for preventing or reducing low-speed pre-ignition in a lubricating oil-lubricated engine by using the above-mentioned compound oil further containing at least one cleaning agent as a lubricating oil. .. The cleaning agent contains an alkaline earth metal salt of at least one organic acid, and the alkaline earth metal salt of at least one organic acid contains a magnesium salt of at least one organic acid.

Further, the present disclosure lubricates the above compound oil, in which the auxiliary component further contains at least one detergent and at least one zinc-containing compound or at least one anti-wearing agent. Further relates to methods of preventing or reducing low speed regignation in lubricated engines by use as oils. The cleaning agent contains an alkaline earth metal salt of at least one organic acid, and the alkaline earth metal salt of at least one organic acid contains a magnesium salt of at least one organic acid. At least one anti-wear agent comprises at least one zinc dialkyl dithiophosphate compound (or zinc dialkyl dithiophosphate compound) derived from a secondary alcohol or partially derived from a secondary alcohol. ..

The present disclosure also relates to a lubricating engine oil having a composition (product) containing a lubricating oil base stock as a main component and at least one boron-containing compound as a sub component. The at least one boron-containing compound comprises at least one booxide dispersant and / or a mixture of the boron-containing compound and a non-boration dispersant. The engine is 25,000 compared to the low speed pre-ignition performance achieved by the engine using at least one booxide dispersant, or a lubricant that does not contain a mixture of boron-containing compounds and non-booxide dispersants. Low speed pres greater than about 50% based on standardized low speed pre-ignition (LSPI) numbers for engine cycles, engine operation at 2000 rpm (RPM) and net mean pressure (BMEP) of 18 bar. Indicates a reduction in ignition.

Further, the present disclosure relates to the above-mentioned lubricating engine oil, which further contains at least one cleaning agent as an auxiliary component. The cleaning agent contains an alkaline earth metal salt of at least one organic acid, and the alkaline earth metal salt of at least one organic acid contains a magnesium salt of at least one organic acid.

Furthermore, the present disclosure relates to the above-mentioned lubricating engine oil, which partially contains at least one cleaning agent and at least one zinc-containing compound or at least one anti-wearing agent. The cleaning agent contains an alkaline earth metal salt of at least one organic acid, and the alkaline earth metal salt of at least one organic acid contains a magnesium salt of at least one organic acid. The at least one anti-wear agent comprises at least one zinc dialkyl dithiophosphate compound derived from a secondary alcohol.

Surprisingly, according to the present disclosure, at least one boron-containing compound (eg, about 0.1 to about 20% by weight based on the total weight of the lubricating oil) present in the lubricating oil. (Succinimide booxide), preferably at least one booxide dispersant, or a blended oil containing a mixture of a boron-containing compound and a non-boroxide dispersant, was lubricated with this lubricant. It has been found that prevention or reduction of LSPI can be achieved in the engine. In particular, with respect to lubricant formulations containing at least one boron-containing compound, surprisingly, the engine comprises at least one booxide dispersant, or a mixture of boron-containing compound and non-borrowing dispersant. For low-speed pre-ignition performance achieved in the engine using no lubricating oil, engine operation at 25,000 engine cycles, 2000 rpm (RPM) and net mean effective pressure (BMEP) of 18 bar. Based on the standardized slow pre-ignition (LSPI) numbers, it was found to show a reduction in slow pre-ignition greater than about 50%. In addition, surprisingly, in accordance with the present disclosure, a blended oil having a particular basestock (eg, a gas-liquid basestock or an ester basestock) was lubricated with the lubricating oil. It has been found that a reduction in LSPI can be achieved in the engine.

Further, the present disclosure is a method for preventing or reducing low-speed regeneration in an engine lubricated with a lubricating oil by using a formed engine oil as a lubricating oil, wherein the compounded engine oil is 70. It has a composition (product) containing at least one kind of lubricating oil base stock of about 85% by weight and at least one kind of dispersant in an amount of providing 30 to 1500 ppm of boron in the compounded engine oil, and the above-mentioned at least one kind. Dispersant comprises at least one booxide dispersant, or a mixture of boron-containing compound and non-boration dispersant, and the engine comprises at least one booxide dispersant, or boron-containing compound and non-boration. Engine operation at 25,000 engine cycles, 2000 rpm (RPM) and net 18 bar when compared to the low speed ignition performance achieved in the engine using lubricating oil without mixture with dispersant. For average effective pressure (BMEP), it relates to a method that exhibits a reduction in slow play ignition greater than 50% based on a standardized number of slow play ignitions (LSPIs).

Other objects and benefits of this disclosure will become apparent from the detailed description below.

All concentrations shown in the drawings are quoted with respect to "when delivered".

Details of the various lubricating oil formulations detailed in Example A, in weight percent based on the total weight percent of the formulation, and test results for the various lubricating oil formulations are shown. The thermogravimetric analysis curves of the three different dispersants detailed in Example A are shown as a graph. Details of the various lubricating oil formulations detailed in Example B are shown in weight percent based on the total weight percent of the formulation. The test results of the various lubricant formulations shown in FIG. 3, detailed in Example B, are shown. Details of the various lubricating oil formulations detailed in Example C are shown in weight percent based on the total weight percent of the formulation. The test results of the various lubricant formulations shown in FIG. 5, detailed in Example C, are shown. The details of the formulation in weight percent based on the total weight percent of the formulation of the formulation embodiments of the present disclosure detailed in Example D are shown. The expected test results of the various lubricant formulations shown in FIG. 7, detailed in Example D, are shown. The details of the formulation in weight percent based on the total weight percent of the formulation of the formulation embodiments of the present disclosure detailed in Example E are shown. The expected test results for the various lubricant formulations of FIG. 9, detailed in Example E, are shown. The details of the formulation in weight percent based on the total weight percent of the formulation of the formulation embodiments of the present disclosure detailed in Example F are shown. Shown are the expected test results of the various lubricant formulations of FIG. 11, detailed in Example F. The results of engine performance mapping detailed in Example A are shown.

(Detailed explanation)
The detailed description of the specification and all figures within the scope of the claims are modified by "about" or "approximately" to the values shown, and experimental errors and variations that would be expected by those skilled in the art. Is considered.

At least one boron-containing compound (eg, succinimide booxide), preferably present in a particular amount (eg, about 0.1 to about 20% by weight based on the total weight of the lubricant) in the lubricant. Preventing or reducing LSPI in lubricating oil-lubricated engines by using at least one booxide dispersant, or a blended oil containing a mixture of boron-containing compounds and non-boroxide dispersants, as the lubricant. It has been found that it can be achieved. In addition, it has been found that a reduction in LSPI can be achieved in lubricant-lubricated engines by using a blended oil with a particular basestock as the lubricant. The blended oil has a composition containing a lubricating oil base stock as a main component and at least one boron-containing compound as a sub component. The at least one boron-containing compound comprises at least one booxide dispersant or a mixture of a boron-containing compound and a non-boration dispersant. The lubricating oils of the present disclosure are particularly convenient in internal combustion engines that use a variety of fuels, including natural gas, gasoline, diesel, biofuels, etc., as well as for a variety of applications, including passenger vehicle engine oils and natural gas engine oils. ..

The lubricants of the present disclosure will be particularly useful in internal combustion engines and will prevent or minimize pre-ignition problems when used in internal combustion engines. The lubricating oil composition of the present disclosure is useful in a spark ignition engine using a lubricating oil mixed gasoline fuel.

As described herein, the chemistry of the lubricant formulations of the present disclosure is to prevent or control the adverse effects of LSPI in engines already designed or commercially available, and in future engine technology. Can be used for. The chemistry of the lubricant formulations of the present disclosure removes barriers to OEM technology and efficiency improvements, and allows further development of slowed turbocharged gasoline engines currently hampered by LSPI. The solution with lubricant formulations obtained by the present disclosure to prevent or reduce LSPI allows product differentiation with respect to LSPI.

Lubricants Base Stock A wide range of lubricant base oils are known in the art. The lubricant base oils useful in the present disclosure are both natural and synthetic oils, and unconventional oils (or mixtures thereof) can also be used in unrefined, refined or rerefined states ( The latter is also known as recycled or retreated oil). Unrefined oils are obtained directly from natural or synthetic sources and are used without additional refining. These include shale oils obtained directly from carbonization operations, petroleum directly obtained from primary distillations, and ester oils obtained directly from ester formation processes. Refined oils are similar to the oils discussed for unrefined oils, except that they undergo one or more refining steps to improve at least one lubricating oil property. Those skilled in the art are familiar with many purification processes. These processes include solvent extraction, secondary distillation, acid extraction, base extraction, filtration and percolation. Rerefined oils are similar to refined oils, but use previously used oils as the feed stock.

Groups I, II, III, IV and V are a broad classification of base oil stocks developed and defined by the American Petroleum Institute (API Publication 1509; www.API.org) to develop guidelines for lubricant base oils. Is. Group I basestock has a viscosity index of about 80-120 and contains more than about 0.03% sulfur and / or less than about 90% saturation. Group II basestocks have a viscosity index of about 80-120 and contain about 0.03% or less sulfur and about 90% or more saturation. Group III stocks have a viscosity index higher than about 120 and contain less than about 0.03% sulfur and more than about 90% saturation. Group IV comprises polyalphaolefins (PAOs). Group V basestock includes basestock not included in groups I-IV. The table below summarizes the characteristics of each of these five groups.

Natural oils include animal oils, vegetable oils (eg castor oil and lard oil), and mineral oils. Animal and vegetable oils with favorable thermal oxidative stability can be used. Of the natural oils, mineral oil is preferred. Mineral oils vary widely depending on their crude oil origin, for example, whether they are paraffinic, naphthenic or mixed paraffin-naphthenic. Oils derived from coal or shale are also useful. Natural oils are either straight-dwelled, decomposed, hydrorefined, or solvent-extracted by the methods used for their production and purification, eg, by their distillation range. It also depends on whether or not it was used.

Group II and / or Group III hydrogenated or hydrocracked basestocks containing synthetic oils such as polyalphaolefins, alkylaromatics and synthetic esters are also well known basestock oils.

Synthetic oils include hydrocarbon oils. Hydrocarbon oils include oils such as polymerized and copolymerized olefins (eg, polybutylene, polypropylene, propylene isobutylene copolymers, ethylene-olefin copolymers and ethylene-alphaolefin copolymers). Polyalphaolefin (PAO) oil-based stocks are commonly used synthetic hydrocarbon oils. As an example, PAOs derived from C ₆ , C ₈ , C ₁₀ , C ₁₂ , C ₁₄ or mixtures thereof may be utilized. See, for example, U.S. Pat. Nos. 4,965,122, 4,827,064 and 4,827,073.

The number average molecular weight of PAO, which is a known material and is generally available on a commercial scale from sources such as the Exxon Mobile Chemical Company, Chevron Phillips Chemical Company, BP and others, typically ranges from 250 to 3,000. However, PAO may be produced with viscosities up to about 150 cSt (100 ° C.). PAOs are typically composed of relatively low molecular weight hydrogenated polymers or oligomers of alpha olefins, including, but not limited to, C ₂ to about C ₃₂ alpha olefins, 1-hexene, 1-. C ₆ to about C ₁₆ alpha olefins such as octene, 1-decene, 1-dodecene, 1-tetradene are preferred. Preferred polyalphaolefins are poly-1-hexene, poly-1-octene, poly-1-decene and poly-1-dodecene and mixtures thereof and mixed olefin-derived polyolefins. However, higher olefin dimers in the range C _{14 to} C ₁₈ may be used to provide a low viscosity base stock with sufficiently low volatility. Depending on the viscosity grade and starting oligomer, the PAO may be primarily trimers and tetramers of starting olefins with small amounts of higher oligomers having a viscosity range of 1.5-12 cSt. PAO fluids for a particular application may include 3.0 cSt, 3.4 cSt and / or 3.6 cSt and combinations thereof. If desired, a bimodal mixture of PAO fluids with a viscosity range of 1.5-150 cSt may be used.

The PAO fluid is free containing, for example, aluminum trifluoride, boron trifluoride, or a complex of boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as acetate or ethyl propionate. It may be conveniently produced by polymerization of alpha olefins in the presence of a polymerization catalyst such as the Del-Crafts catalyst. For example, the methods disclosed in US Pat. Nos. 4,149,178 or 3,382,291 may be conveniently used herein. Other descriptions of PAO synthesis are described in US Pat. Nos. 3,742,082, 3,769,363, 3,876,720, 4,239,930. No. 4, No. 4,367,352, No. 4,413,156, No. 4,434,408, No. 4,910,355, No. It is found in 4,965,122 and 5,068,487. Dimers of C _14- C ₁₈ olefins are described in US Pat. No. 4,218,330.

Other useful lubricating oil base stocks include hydrogen isomerized waxy stocks (eg waxy stocks such as gas oils, slack waxes, fuel hydrocracking equipment residues), hydrogen isomerized Fisher-Tropsch wax, gases. -Liquid (GTL) base stocks and base oils, and other isomerized waxes Hydrogen isomerized base stocks and base oils, or isomerized wax base stocks and base oils comprising mixtures thereof. Fischer-Tropsch wax is a high boiling residue of Fischer-Tropsch synthesis and is a high paraffinic hydrocarbon with a very low sulfur content. In the hydrogenation treatment used for the production of such basestock, an amorphous hydrocracking / hydrogen isomerization catalyst, such as one of the special lubricating oil hydrocracking (LHDC) catalysts, or crystalline hydrogen. A chemical decomposition / hydrogen isomerization catalyst, preferably a zeolite-based catalyst, may be used. For example, one useful catalyst is ZSM-48, which is described in US Pat. No. 5,075,269, the disclosure of which is incorporated herein by reference in its entirety. Methods for producing the hydrocracking / hydrogen isomerized distillate and the hydrocracking / hydrogen isomerized wax are described in, for example, US Pat. Nos. 2,817,693, 4,975,177, and No. 4,921,594 and 4,897,178, and U.S. Pat. Nos. 1,429,494, 1,350,257, 1,440, It is described in the specification No. 230 and the same No. 1,390,359. Each of the above patents is incorporated herein by reference in its entirety. Particularly preferred methods are described in European Patent Application Publication Nos. 464,546 and 464,547, which are incorporated herein by reference. Methods of using the Fischer-Tropschwax feed material are described in US Pat. Nos. 4,594,172 and 4,943,672, the disclosure of which is incorporated herein by reference in its entirety. To.

Gas-liquid (GTL) base oils, Fisher-Tropsch wax-derived base oils, and other wax-induced hydrogen isomerization (isomerized wax) base oils can be conveniently used in the present disclosure and are from about 3 cSt to about 3 cSt at 100 ° C. Useful kinematic viscosities of 50 cSt, preferably about 3 cSt to about 30 cSt, more preferably about 3.5 cSt to about 25 cSt, for example, for GTL4, about 4.0 cST kinematic viscosity and about 4.0 cST at 100 ° C. It may have a viscosity index of 141. These gas-liquid (GTL) base oils, Fisher-Tropsch wax-derived base oils, and other wax-induced hydrogen isomerization base oils can have useful pour points of about -20 ° C or lower, and some. Under conditions, it may have a convenient pour point of about -25 ° C or less, but a useful pour point is about -30 ° C to about -40 ° C or less. Useful compositions of gas-liquid (GTL) base oils, Fisher-Tropsch wax-derived base oils, and wax-induced hydrogen isomerization base oils are incorporated herein by reference in their entirety, eg, US Pat. No. 6,080, It is described in the specification 301, the specification 6,090,989 and the specification 6,165,949.

A hydrocarbyl aromatic is any hydrocarbyl molecule that can be used as a base oil or a base oil component and contains at least about 5% of its weight derived from an aromatic moiety such as a benzenoid moiety or a naphthenoid moiety or a derivative thereof. It is also possible to be. These hydrocarbyl aromatics include alkylbenzene, alkylnaphthalene, alkyldiphenyl oxide, alkylnaphthol, alkyldiphenylsulfide, alkylated bisphenol A, alkylated thiodiphenol and the like. Fragrances can be monoalkylated, dialkylated, polyalkylated and the like. Aromatic can be monofunctionalized or polyfunctionalized. The hydrocarbyl group can also be composed of a mixture of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl and other related hydrocarbyl groups. Hydrocarbyl groups can range from about C ₆ to about C ₆₀ , but often ranges from about C ₈ to about C ₂₀ . Mixtures of hydrocarbyl groups are often preferred, and up to three such substituents may be present. The hydrocarbyl group may optionally contain sulfur, oxygen and / or nitrogen-containing substituents. Aromatic groups can also be derived from natural (petroleum) sources, provided that at least about 5% of the molecule is composed of aromatic moieties of the above type. With respect to the hydrocarbyl aromatic component, a viscosity of about 3 cSt to about 50 cSt at 100 ° C. is preferable, and a viscosity of about 3.4 cSt to about 20 cSt is more preferable. In one embodiment, alkylnaphthalene is used in which the alkyl group is mainly composed of 1-hexadecene. It is also possible that other aromatic chelates may be used to advantage. For example, naphthalene or methylnaphthalene can be alkylated with olefins such as octene, decene, dodecene, tetradecene or higher olefins, mixtures of similar olefins and the like. The useful concentration of hydrocarbyl fragrance in the lubricating oil composition can be from about 2 to about 25%, preferably from about 4% to about 20%, more preferably from about 4% to about 15%, depending on the application.

Alkylated aromatics such as the hydrocarbyl aromatics of the present disclosure may be produced by the well-known Friedel-Crafts alkylation method of aromatic compounds. Friedel-Crafts and Related Reactions, Olah, G. et al. A. (Ed.), Inter-science Publicers, New York, 1963. For example, aromatic compounds such as benzene or naphthalene are alkylated with olefins, alkyl halides or alcohols in the presence of Friedel-Crafts catalysts. Friedel-Crafts and Related Reactions, Vol. 2, part 1, chapters 14, 17 and 18, Olah, G.M. A. (Ed.), Inter-science Publicers, New York, 1964. Many homogeneous or heterogeneous solid catalysts are known to those of skill in the art. The choice of catalyst depends on the reactivity of the starting material and the required quality of the product. For example, strong acids such as AlCl ₃ , BF ₃ or HF may be used. In some cases, milder catalysts such as FeCl ₃ or SnCl ₄ are preferred. Newer alkylation techniques use zeolites or solid superacids.

Esters make up a useful base stock. Additional dissolution and seal compatibility characteristics can be ensured by the use of esters such as dibasic acid esters with monoalkanols and polyol esters of monocarboxylic acids. The former type of ester includes, for example, phthalic acid, succinic acid, alkylsuccinic acid, alkenylsuccinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid. , Alkylmalonic acid, alkenylmalonic acid and other dicarboxylic acids and various alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol and the like. Specific examples of these types of esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl sebacate, dioctyl sebacate, diisooctyl azelaate, diisodecyl azelaate, dioctyl phthalate, Includes dodecyl phthalate, diecosyl sebacate, etc.

Particularly useful synthetic esters are one or more polyhydric alcohols, preferably hindered polyols (neopentyl polyols such as neopentyl glycol, trimethylolethane, 2-methyl-2-propyl-1,3-propanediol. , Trimethylol propane, pentaerythritol and dipentaerythritol, etc.), an alkanoic acid containing at least about 4 carbon atoms, preferably capric acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, eikosan. By reacting with saturated linear fatty acids, including acids and behenic acids, or equivalent branched fatty acids, or unsaturated fatty acids such as oleic acid, or C _{5 to} C ₃₀ acids such as mixtures of any of these materials. It is what you get.

Suitable synthetic ester components include trimethylolpropane, trimethylolbutane, trimethylolethane, pentaerythritol and / or dipentaerythritol, and one or more monocarboxylic acids containing about 5 to about 10 or more carbon atoms. And ester is included. These esters are commercially available and are, for example, Mobil P-41 and P-51 esters from ExxonMobil Chemical Company.

Preferred synthetic esters useful in the present disclosure have kinematic viscosities at 100 ° C. of about 3 cSt to about 50 cSt, preferably about 3 cSt to about 30 cSt, more preferably about 3.5 cSt to about 25 cSt, and even more preferably about 2 cSt to about 8 cSt. Has. Group V-based oils useful in the present disclosure preferably constitute the ester at a concentration of about 2% to about 20%, preferably about 5% to about 15%.

Esters derived from renewable materials such as coconut, palm, rapeseed, soybeans and sunflower are also useful. These esters may be monoesters, diesters, polyol esters, composite esters or mixtures thereof. These esters are commercially available and are, for example, the Mobil P-51 esters of ExxonMobil Chemical Company.

Engine oil formulations containing renewable esters are included in this disclosure. For such formulations, the renewable content of the ester is typically greater than about 70 weight percent, preferably greater than about 80 weight percent, and most preferably greater than about 90 weight percent.

Other useful fluids with lubrication viscosities include non-conventional or non-conventional basestocks, preferably catalyzed or synthesized to provide high performance lubrication properties.

Non-conventional or non-conventional base stocks / base oils include mixtures of base stocks derived from one or more gas-liquid (GLT) materials, as well as natural waxes or waxy feed materials, mineral oils and / or non-mineral oils. Wax-like feed stocks, such as slack wax, natural wax, and wax-like stocks, such as gas oil, waxy fuel hydrocracking equipment residues, waxy raffinates, hydrocracking products, thermal cracking products or other 1 of mineral, mineral oil, or non-petroleum-derived waxy materials, such as waxy materials received from coal liquefaction or isomerized / iso-dewaxed basestocks derived from shale oil, and mixtures of such basestocks. Includes seeds and above.

GTL materials include gaseous carbon-containing compounds, hydrogen-containing compounds and as supply stocks such as hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propene, butyne, butyne and butyne. / Or a material induced by one or more synthesis, combination, conversion, rearrangement, and / or decomposition / deconstruction processes from an element. GTL base stocks and / or base oils are generally waxy synthetic hydrocarbons derived from hydrocarbons, such as gaseous carbon-containing compounds, hydrogen-containing compounds and / or other elements, which themselves are simpler as feed stocks. It is a GTL material with a lubricating viscosity derived from. The GTL base stock and / or base oil is an oil that boils in the lubricating oil boiling range, and is (1) separated / distilled from the synthesized GTL material by, for example, distillation, and then the flow point decreases. Those undergoing a final waxing step involving one or both of a catalytic dewaxing process or a solvent dewaxing process to produce a waxed / low flow point lubricant; (2) for example, hydrogen dewaxed or hydrogen isomerized. Synthetic wax containing a catalyst and / or waxy hydrocarbon; (3) Hydrogen dewaxed or hydrogen isomerized catalyst and / or solvent dewaxed Fisher-Tropsch (FT) material (ie, hydrocarbons, waxy hydrocarbons, waxes and possible similar oxygenates); preferably hydrogen dewaxed or hydrogen isomerized / subsequently catalytic and / or solvent dewaxed. FT waxy hydrocarbons, or hydrogen dewaxed or hydrogen isomerized / subsequently catalyst (or solvent) dewaxed FT wax, or mixtures thereof.

GTL basestock and / or base oils derived from GTL materials, in particular hydrogen dewaxed or hydrogen isomerized / subsequently catalytic and / or solvent dewaxed wax or waxy feed materials, preferably F- T-material derived base stocks and / or base oils are typically characterized by having kinematic viscosities at 100 ° C. of about 2 mm ² / sec to about 50 mm ² / sec (ASTM D445). They are typically further characterized by having a pour point of about 5 ° C to about 40 ° C or less (ASTM D97). They are also typically characterized by having a viscosity index of about 80 to about 140 or higher (ASTM D2270).

The term GLT basestock and / or base oil and / or wax isomer basestock and / or base oil refers to the individual fractions of such materials with a wide viscosity range recovered during the manufacturing process, 2 of such fractions. It is understood to include one or more mixtures, as well as one or more mixtures of low viscosity fractions for producing blends exhibiting the kinematic viscosity of the target and one or more of high viscosity fractions. To.

The GLT material from which the GLT base stock and / or base oil is derived is preferably an FT material (ie, a hydrocarbon, a waxy hydrocarbon, a wax).

In addition, GTL basestock and / or base oils are typically high paraffin (> 90% saturated) and contain a mixture of monocyclic and polycyclic paraffins in combination with acyclic isoparaffin. You may be doing it. The proportion of naphthenic (ie, cycloparaffin) content in such combinations will vary depending on the catalyst used and the temperature. In addition, GTL basestock and / or base oils, and hydrogen-dewaxed or hydrogen-isomerized / catalytic (and / or solvent) dewaxed basestocks and / or base oils are typically very It has a low sulfur and nitrogen content, and generally contains less than about 10 ppm, more typically less than about 5 ppm, of each of these elements. The sulfur and nitrogen content of GTL base stocks and / or base oils derived from FT materials, especially FT waxes, is essentially zero. In addition, the absence of phosphorus and aromatics makes this material particularly suitable for the formulation of low sulfur, sulfated ash and phosphorus (low SAP) products.

The base oils for use in the formulated lubricants useful in the present disclosure are API Group I, Group II, Group III, Group IV due to their excellent volatility, stability, viscosity measurement and cleanliness properties. And Group V oils and mixtures thereof, preferably any of the various oils corresponding to API Group II, Group III, Group IV and Group V oils and mixtures thereof, more preferably Group III-Group V base oils. Is it? The base stock, when used in combination with the additive components disclosed in the present disclosure, has excellent LSPI performance, SAE 0W-8, SAE 0W-12, SAE 0W-16, SAE 0W-20, SAE 0W. It can be used to formulate -30, SAE 0W-40, SAE 5W-12, SAE 5W-16, SAE 5W-20, SAE 5W-30 and SAE 10W-40 products. These base stocks, when used in combination with the additive components disclosed in the present disclosure, have excellent LSPI performance, SAE 0W-8, SAE 0W-12, SAE 0W-16, SAE 0W-20, SAE. It is particularly effective when blending 0W-30, SAE 0W-40 and SAE 5W-30 oils.

The base oil constitutes the main component of the engine oil lubricating oil composition of the present disclosure, and is typically about 50 to about 99% by weight, preferably about 70 to about 95% by weight, based on the total weight of the composition. More preferably, it is present in an amount in the range of about 85 to about 95% by weight. The base oil may also be selected from either synthetic or natural oils typically used as crank chamber lubricants for spark ignition and compression ignition engines. Base oils, conveniently, in accordance with ASTM standard, about 2.5cSt~ about 12 cSt (or mm ² / s) at 100 ° C., preferably from about 2.5cSt~ about 9 cSt (or mm ² / s) at 100 ° C., more preferably, at 100 ° C. to about 3.5cSt~ about 7 cSt (or mm ² / s), in some applications, even more preferably, at 100 ° C. to about 3.5cSt~ about 5 cSt (or mm ² / sec) Has a kinematic viscosity of. If desired, a mixture of synthetic and natural base oils may be used. If desired, a mixture of groups III, IV and V may be preferably used.

Dispersant Oil-insoluble oxidation by-products are produced during engine operation. Dispersants facilitate the retention of these by-products in solution and thus reduce their deposition on metal surfaces. The dispersant used in the lubricating oil formulation may be essentially ash-free or ash-forming. Preferably, the dispersant is ashless. So-called ashless dispersants are organic materials that do not or do not form ash substantially during combustion. For example, non-metal-containing or booxidized metal-free dispersants appear to be ashless. In contrast, the metal-containing detergents mentioned above form ash when burned.

In the present disclosure, at least one boron-containing compound is useful. The boron-containing compound comprises at least one booxide dispersant, or a mixture of the boron-containing compound and a non-boration dispersant or booxide dispersant. The effective range of boron in formulations from booxide dispersants or other boron-containing additives is in the more preferred range of 30 ppm to 1500 ppm, or 60 ppm to 1000 ppm, or the most preferred range of 120 ppm to 600 ppm.

Preferably, the boron-containing compound includes, for example, borated succinimide, borated succinate ester, borated succinate ester amide, borated Mannich. base) and mixtures thereof are included.

Non-booxidant dispersants include, for example, hydrocarbyl succinic anhydride-induced succinimide or succinic acid ester with a coupling agent comprising a boron-containing compound.

Preferably, the boron is an organic or inorganic boron-containing compound and succinimide booxide, and / or a boron-containing compound and hydrocarbyl succinimide, and / or succinimide booxide, succinimide booxide, succinimide booxide esteramide, Mannig base ester. , Or a mixture of their mixtures provides the lubricating oil. The succinimide booxide is preferably monosuccinimide, bis-succinimide or a mixture thereof. Effective boron-containing compounds include those derived for hydrocarbyl sources having a number average molecular weight (Mn) of 50-5000 daltons, hydrocarbyl succinimide booxide, hydrocarbyl succinate booxide, hydrocarbyl booxide substituted Mannig base, Alcohol booxide, Alcohol booxide alkoxylated, Hydrocarbylborobooxide, Hydrocarbylamine booxide, Hydrocarbyldiamine borate, Hydrocarbyltriamine booxide, Hydrocarbylamine booxide, Hydrocarbylbooxide alkoxylated, Hydrocarbylbooxide-containing hydroxyl ester , Hydrocarbyl booxide substituted oxazoline, hydrocarbyl booxide substituted imidazolone, etc., and mixtures of organic borates are included. Borates of the -NH and / or -OH induced portions can also be used. These borates can be inorganic or organic partially derived borates. Borate can be prepared using boric acid, alcohol borate and the like. These borates, if desired, result in unexpected and surprising improvements in LSPI, such as 30-1500 ppm boron, 60-1200 ppm boron, 60-240 ppm boron, 240-1200 ppm boron in engine oil formulations. , 240-500 ppm boron, or 60-120 ppm boron can be used at concentrations providing.

The ratio of total zinc from zinc-containing compounds and anti-wear agents in lubricating oil plus total alkaline earth metals from detergents divided by total boron from boron-containing compounds and booxide dispersants is , Approximately 9.2-45, preferably 11-15.

Suitable dispersants typically contain polar groups attached to relatively high molecular weight hydrocarbon chains. Polar groups typically contain at least one element of nitrogen, oxygen or phosphorus. A typical hydrocarbon chain contains 50-400 carbon atoms. In some embodiments, the hydrocarbon chain can range from 6 to 50 carbon atoms.

Chemically, many dispersants may be characterized as phenates, sulfonates, sulphide phenates, salicylates, naphthenates, stearate, carbamate, thiocarbamate, phosphorus derivatives. A particularly useful class of dispersant is typically a long hydrocarbyl-substituted succinic acid compound, usually an alkylsuccinic acid derivative produced by the reaction of hydrocarbyl-substituted succinic anhydride with a polyhydroxy or polynet compound. The long-chain hydrocarbyl groups that make up the lipophilic portion of the molecule that provides solubility in oil are usually polyisobutylene groups. Many examples of this type of dispersant are well known commercially and in the literature. Representative US patents describing such dispersants are US Pat. Nos. 3,172,892, 3,214,707, 3,219,666, and the same. No. 3,316,177, No. 3,341,542, No. 3,444,170, No. 3,454,607, No. 3,541,012. No. 3, 630,904, No. 3,632,511, No. 3,787,374, and No. 4,234,435. Other types of dispersants include US Pat. Nos. 3,036,003, 3,200,107, 3,254,025, and 3,275,554. Specification, No. 3,438,757, No. 3,454,555, No. 3,565,804, No. 3,413,347, No. 3 , 697,574, 3,725,277, 3,725,480, 3,726,882, 4,454,059. No. 3,329,658, No. 3,449,250, No. 3,519,565, No. 3,666,730, No. 3, It is described in the specification of 687,849, the specification of No. 3,702,300, the specification of No. 4,100,082, and the specification of No. 5,705,458. Further descriptions of dispersants can be found, for example, in European Patent Application Publication No. 471 071 referenced for this purpose.

Hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic anhydride derivatives are useful dispersants. In particular, succinimide, succinate or succinate amides prepared by reaction of a hydrocarbon substituted succinic acid compound preferably having at least 50 carbon atoms during the hydrocarbon substitution phase with at least 1 equivalent of an alkylene amine. Although useful, in some cases it may be useful to have a hydrocarbon substituent having 20 to 50 carbon atoms.

Succinimide is formed by the condensation reaction of hydrocarbyl-substituted succinic anhydride with an amine. The molar ratio can vary depending on the polyamide. For example, the molar ratio of hydrocarbyl-substituted succinic anhydride to ethyleneamine (eg, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, hexaethyleneheptamine, heptaethyleneoctamine, etc.). Polyethyleneamine containing tetraethylenepentamine (TEPA) is often preferred. High molecular weight polyethyleneamine residues comprising hexaethylene heptamine and heptaethylene octaamine can also be used. The ratio of hydrocarbyl-substituted succinic anhydride polyethyleneamines can vary from about 1: 1 to about 5: 1. Representative examples are US Pat. Nos. No. 087,936, No. 3,172,892, No. 3,219,666, No. 3,272,746, U.S. Pat. It is shown in the specification No. 3,322,670, the specification No. 3,652,616, the specification No. 3,948,800, and the specification of Canadian Patent No. 1,094,044.

The succinic anhydride is formed by a condensation reaction of hydrocarbyl-substituted succinic anhydride with an alcohol or polyol. The molar ratio can vary depending on the alcohol or polyol used. For example, a condensate of hydrocarbyl-substituted succinic anhydride and pentaerythritol is a useful dispersant.

The succinic anhydride amide is formed by a condensation reaction of hydrocarbyl-substituted succinic anhydride and an alkanolamine. For example, suitable alkanolamines include polyalkenyl polyamines such as ethoxylated polyalkyl polyamines, propoxylated polyalkyl polyamines and polyethylene polyamines. One example is propoxylated hexamethylenediamine. Representative examples are shown in US Pat. No. 4,426,305.

The amount of branching of hydrocarbyl-substituted succinic anhydride used in all stages typically ranges from 800 to 2,500 daltons or more. The product can be subsequently reacted with various reagents such as carboxylic acids such as sulfur, oxygen, formaldehyde and oleic acid. The product is generally a boric acid, boric acid ester or highly borooxidized dispersion to form a boric acid dispersant with about 0.1 to about 5 moles of boron per mole of dispersant reaction product. It is also possible to subsequently react with a boron compound such as an agent.

The Mannich base dispersant is made from the reaction of alkylphenols, formaldehyde and amines. See U.S. Pat. No. 4,767,551, which is incorporated herein by reference. Process aids and catalysts such as oleic acid and sulfonic acid can also be part of the reaction mixture. The molecular weight of the alkylphenol is in the range of 800 to 2,500. Representative examples are U.S. Pat. Nos. 3,697,574, 3,703,536, 3,704,308, 3,751,365, and 3,751,365. It is shown in the specification of No. 3,756,953, the specification of No. 3,798,165 and the specification of No. 3,803,039.

Typical high molecular weight fatty acid modified Mannich condensation products useful in the present disclosure can be prepared from high molecular weight alkyl-substituted hydroxy aromatics or HN (R) _two- group-containing reactants.

Hydrocarbyl-substituted amine ashless dispersant additives are well known to those of skill in the art, for example, US Pat. Nos. 3,275,554, 3,438,757, 3,565,804. See, No. 3,755,433, No. 3,822,209 and No. 5,084,197.

Preferred dispersants include succinimide booxide, which comprises monosuccinimide, bissuccinimide and / or their derivatives from a mixture of mono and bissuccinimide, where hydrocarbylsuccinimide is from about 500 to about 5000 daltons, or from about 1000 to about 1000. Derived from a hydrocarbylene group such as polyisobutylene having a Mn of about 3000 daltons, or about 1000 to about 2000 daltons, or a mixture of such hydrocarbylene groups, which often have a high terminal vinyl group. Preferred dispersions useful in the present disclosure are characterized by having a Mn of about 800 to about 1700 daltons for low molecular weight and about 1700 to about 5000 dalton or more for high molecular weight. Other preferred dispersants include succinates and amides, alkylphenol-polyamine binding Mannich adducts, cap-forming derivatives thereof and other related compounds. Such additives may be used in an amount of about 0.1 to 20% by weight, preferably about 0.5 to 8% by weight, or more preferably 0.5 to 4% by weight. The hydrocarbon moiety of the dispersant atom can range from C _{60 to} C ₄₀₀ , or C _{70 to} C ₃₀₀ , or C _{70 to} C ₂₀₀ . These dispersants may contain neutral, basic nitrogen or a mixture of both. The ratio of basic nitrogen to non-basic nitrogen in the dispersion can be in the range of 1: 5-5: 1, or more preferably 1: 2-2: 1. The dispersant can be endcapped with borate and / or cyclic carbonate and / or any carboxylic acid such as hydrocarbylcarboxylic acid or hydrocarbylcarboxylic acid anhydride.

According to the present disclosure, an engine is achieved in an engine using a lubricant containing an accessory component other than at least one boron-containing compound in an amount other than the amount of at least one boron-containing compound in the lubricant. Low speed pre-ignition (LSPI) standardized for 25,000 engine cycles, engine operation at 2000 rpm (RPM) and 18 bar net mean effective pressure (BMEP) compared to slow pre-ignition performance. ) Shows a reduction in slow pre-ignition greater than about 50%, preferably greater than about 70%, more preferably greater than about 80%, based on numbers. Similar or greater reduction in slow pre-ignition can be achieved with at least one boron-containing compound and at least one of the cleaning agents described herein, preferably magnesium-containing cleaning agents, and / or at least one zinc. It can be achieved using a containing compound or a mixture with at least one anti-wear agent.

As used herein, the detergent concentration is shown relative to "when delivered." Typically, the active detergent is delivered with the process oil. The "on-delivery" cleaning agent typically contains about 20% to about 80% by weight, or about 40% to about 60% by weight, of the active cleaning agent in the "on-delivery" cleaning agent. Included in.

Cleaners Examples of exemplary cleansers useful in the present disclosure include, for example, alkaline earth metal cleansers or mixtures of alkaline earth metal cleansers. A typical alkaline earth metal detergent is an anionic material containing a long-chain hydrophobic portion of the molecule and a smaller anionic or oleophobic hydrophilic portion of the molecule. The anionic portion of the detergent is derived from sulfur acids, organic acids such as carboxylic acids, phosphorous acids, phenols or mixtures thereof. The counterion is an alkaline earth metal. Preferably, the cleaning agent comprises an alkaline earth metal salt of at least one organic acid, and the alkaline earth metal salt of at least one organic acid comprises a magnesium salt of at least one organic acid. Become.

Preferred detergents useful in the lubricating oils of the present disclosure consist of a group consisting of alkaline earth metal sulfonates, alkaline earth metal carboxylates (eg salicylates), alkaline earth metal phenates, alkaline earth metal phosphates and mixtures thereof. Be selected. Alkaline earth metal sulfonate, alkaline earth metal carboxylate, alkaline earth metal phenate, alkaline earth metal phosphate and their mixtures, and alkaline earth metal sulfonate, alkaline earth metal carboxylate, alkaline earth in lubricating oil. Amounts of metal phenates, alkaline earth metal phosphates and mixtures thereof include cleaning agents other than alkaline earth metal sulfonates, alkaline earth metal carboxylates, alkaline earth metal phenates, alkaline earth metal phosphates and mixtures thereof. Achieved in engines that use lubricating oils that are contained in lubricating oils in amounts other than alkaline earth metal sulfonates, alkaline earth metal carboxylates, alkaline earth metal phenates, alkaline earth metal phosphates and mixtures thereof. Compared to slow play ignition performance, the engine is sufficient to show a reduction in slow play ignition.

Alkaline earth metal detergents useful in the present disclosure can be prepared by methods known in the art.

A preferred type of cleaning agent is alkaline earth metal sulfonate. Sulfur acids useful for preparing alkaline earth metal sulfonates include sulfonic acid, thiosulfonic acid, sulfinic acid, sulfenic acid, partially esterified sulfuric acid, sulfite and thiosulfate. Sulfonic acid is preferred.

Sulfonic acids are generally petroleum sulfonic acids or synthetically prepared alkaline reel sulfonic acids. Of the petroleum sulfonic acids, the most useful products are those prepared by the appropriate sulfonated petroleum distillate, followed by the removal and purification of acid sludge. Alkyral sulfonic acids prepared by synthesis are usually prepared from alkylated benzenes such as Friedel-Crafts reaction products of polymers such as benzene and tetrapropylene. The following are specific examples of sulfonic acids useful for preparing alkaline earth metal sulfonate detergents useful in the present disclosure. It is understood that such examples are also useful in explaining alkaline earth metal salts of such sulfonic acids. In other words, it is intended to be understood that for all the listed sulfonic acids, their corresponding basic alkaline earth metal salts are also explained.

Such sulfonic acids include mahogany sulfonic acid, brightstock sulfonic acid, petrolatum sulfonic acid, mono and polywax substituted naphthalene sulfonic acid, cetylchlorobenzene sulfonic acid, cetylphenol sulfonic acid, cetylphenol disulfide sulfonic acid, setoxycapril benzene. Sulfonic Acid, Disetyl Thiantrene Sulfonic Acid, Dilauryl Beta-naphthol Sulfonic Acid, Dicapril Nitronaphthalene Sulfonic Acid, Saturated Paraffin Wax Sulfonic Acid, Unsaturated Paraffin Wax Sulfonic Acid, Hydroxy Substituted Paraffin Wax Sulfonic Acid, Tetra-Isobutylene Sulfonic Acid Tetra-amylene sulfonic acid, chloro-substituted paraffin wax sulfonic acid, nitroso-substituted paraffin wax sulfonic acid, petroleum naphthenic sulfonic acid, cetylcyclopentylsulfonic acid, laurylcyclohexylsulfonic acid, mono- and polywax-substituted cyclohexylsulfonic acid, dodecylbenzenesulfonic acid, "Dimer Alchelate" sulfonic acid and the like are included.

Alkyl-substituted benzene sulfonic acids containing at least 8 carbon atoms in the alkyl group are useful in the present disclosure, including dodecylbenzene "residue" sulfonic acids. The latter are acids derived from alkylated benzenes by propylene terpolymer or isobutene trimers to introduce 1, 2, 3 or more branched C ₁₂ substituents on the benzene ring. Dodecylbenzene residues, predominantly mono and mixtures of dodecylbenzene, are available as by-products from household detergent manufacturers.

Preferred alkaline earth metal sulfonates include magnesium sulfonate, calcium sulfonate and mixtures thereof.

A useful type of cleaning agent is alkaline earth phenate. These detergents react alkaline earth metal hydroxides or oxides (eg, CaO, Ca (OH) ₂ , BaO, Ba (OH) ₂ , MgO, Mg (OH) ₂ ) with alkylphenols or alkylphenol sulfides. It can be manufactured by letting it. Useful alkyl groups include straight or branched C _{1 to} C ₃₀ alkyl groups, preferably C _{4 to} C ₂₀ or mixtures thereof. Examples of suitable phenols include isobutylphenol, 2-ethylhexylphenol, nonylphenol, dodecylphenol and the like. It should be noted that the starting alkylphenol may contain two or more alkyl substituents, each independently linear or branched, and 0.5-6% by weight may be used. is there. When non-sulfurized alkylphenols are used, the sulfurized products may be obtained by methods well known in the art. These methods include heating a mixture of alkylphenols and sulfides (including sulfur elements, sulfur halides such as sulfur dichloride) and then reacting the phenol sulfides with alkaline earth metal bases.

Preferred phenate compounds include, for example, magnesium phenates, calcium phenates, hyperbasic phenate compounds, sulfide / carbonated calcium phenate compounds and mixtures thereof.

Alkaline earth metal salts of carboxylic acids are also useful as cleaning agents. These carboxylic acid detergents can be prepared by reacting a basic alkaline earth metal compound with at least one carboxylic acid and removing water from the reaction product. These compounds may be hyperbasic to produce the desired TBN levels.

［式中、Ｒは、１〜約３０個の炭素原子を有するアルキル基であり、ｎは１〜４の整数であり、かつＭはアルカリ土類金属である］
である。好ましいＲ基は、少なくともＣ_１１、好ましくはＣ_１３以上のアルキル鎖である。Ｒは、清浄剤の機能を妨害しない置換基によって任意選択的に置換されていてもよい。Ｍは、好ましくは、カルシウム、マグネシウムまたはバリウムである。より好ましくは、Ｍはカルシウムまたはマグネシウムである。 A cleaning agent made from salicylic acid is a preferred type of cleaning agent derived from a carboxylic acid. Useful salicylates include long-chain alkyl salicylates. One of the useful lineages of the composition is the formula:

[In the formula, R is an alkyl group having 1 to about 30 carbon atoms, n is an integer of 1 to 4, and M is an alkaline earth metal].
Is. A preferred R group is an alkyl chain of at least C ₁₁ , preferably C ₁₃ or higher. R may be optionally substituted with a substituent that does not interfere with the function of the detergent. M is preferably calcium, magnesium or barium. More preferably, M is calcium or magnesium.

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

Preferred carboxylate compounds include non-carbonated magnesium salicylate (carboxylate), carbonated magnesium salicylate (carboxylate), non-carbonated calcium salicylate (carboxylate), carbonated calcium salicylate (carboxylate) and mixtures thereof. Become.

Salts containing substantially stoichiometric amounts of alkaline earth metals are described as neutral salts and have a total base number (TBN, measured by ASTM D2896) from 0 to 100. Many compositions are hyperbasic and contain large amounts of metal bases achieved by reacting excess amounts of alkaline earth metal compounds with acidic gases (such as carbon dioxide). Useful detergents can be neutral, slightly hyperbasic, or highly hyperbasic. These detergents can be used in neutral, hyperbasic, highly hyperbasic magnesium salicylate, sulfonate, phenate and / or a mixture of calcium salicylate, sulfonate and phenate. The range of TBN can vary from low TBN of about 0 to 100, moderate TBN of about 100 to 200 and high TBN of about 200 to 600. Mixtures of low, medium and high TBN can be used with calcium and magnesium metal-based detergents containing sulfonate, phenate, salicylate and carboxylate. Further examples of mixed TBN detergents can be found as described in US Pat. No. 7,704,930, which is incorporated herein by reference. A detergent mixture having a metal ratio of 1 can be used in combination with a cleaning agent having a metal ratio of 2 and a cleaning agent having a metal ratio of 5 or 10 or 15. Oxidation cleaning agents can also be used.

Alkaline earth metal phosphates may also be used as detergents, which are known in the art.

The cleaning agent may be known as a single cleaning agent or a hybrid or composite cleaning agent. The latter cleaning agent can provide the properties of two types of cleaning agents without the need to blend separate materials. See U.S. Pat. No. 6,034,039.

Suitable cleaning agents include magnesium sulfonate (or magnesium sulfonate), calcium sulfonate (or calcium sulfonate), calcium phenate, magnesium phenate, calcium salicylate (or calcium salicylate), magnesium salicylate (or magnesium salicylate) and others. Includes related components (including magnesium detergents) and mixtures thereof. Preferred cleaning agents include magnesium sulfonate (or magnesium sulfonate), calcium sulfonate (or calcium sulfonate), magnesium phenate, calcium phenate, magnesium salicylate (or magnesium salicylate), calcium salicylate (or calcium salicylate) and theirs. Contains a mixture.

Other exemplary cleaning agents that can be used with alkaline earth metal cleaning agents include, for example, alkali metal cleaning agents or mixtures of alkali metal cleaning agents.

In a cleaning agent containing a mixture of a magnesium salt of an organic acid and a calcium salt of an organic acid, the cleaning agent ratio of magnesium metal to calcium metal is about 1: 0 to 1:10, preferably about 1: 0 to about 1. The range is 1: 4.

Magnesium and alkaline earth metals provided by the detergent are present in the lubricating oil in an amount of about 500 ppm to about 5000 ppm, preferably about 1000 ppm to about 2500 ppm. Magnesium provided by the cleaning agent is present in the lubricant in an amount of about 100 ppm to about 3000 ppm, preferably about 300 ppm to about 2500 ppm, more preferably about 750 ppm to about 2000 ppm.

The total alkalinization (TBN) provided by the detergent, as measured by ASTM D2896, ranges from about 2 mg KOH / g to about 17 mg KOH / g, preferably from about 4 mg KOH / g to about 14 mg KOH / g. .. The TBN provided by the magnesium detergent is about 2 mg KOH / g to about 17 mg KOH / g, preferably about 3 mg KOH / g to about 14 mg KOH / g, more preferably about 5 mg KOH / g to about 10 mg KOH / g. Is the range of.

The sulfated ash content provided by the cleaning agent is from about 0.4 to about 1.7% by weight, preferably from about 0.5 to about 1.6% by weight, more preferably from about 0.6 to about 1.0% by weight. Is the range of. The sulfated ash content provided by the magnesium detergent is from about 0.3 to about 1.8% by weight, preferably from about 0.4 to about 1.6% by weight, more preferably from about 0.6 to about 1.0% by weight. It is in the range of%. The lubricating engine oils of the present disclosure preferably contain less than about 1.6% by weight of sulfated ash and / or more preferably less than about 4000 ppm magnesium. Greater reductions in LSPI numbers than 95% are achieved at engine oil sulphate ash content higher than 1.2% ash content (due to the use of magnesium detergent). At a sulfate ash level <1.2% with the use of magnesium detergent, LSPI can be completely eliminated.

For lubricant formulations containing at least one boron-containing compound and at least one cleaning agent according to the present disclosure, the engine contains at least one boron-containing compound and sub-ingredients other than at least one cleaning agent. 25,000 times the lubricating oil is compared to the low speed pre-ignition performance achieved in the engine using an amount other than the amount of at least one boron-containing compound and at least one cleaning agent in the lubricating oil. Greater than about 50%, preferably about, based on engine cycle, engine running at 2000 rpm (RPM) and standardized low speed pre-ignition (LSPI) numbers for 18 bar net mean pressure (BMEP). It exhibits a reduction in slow pre-ignition greater than 75%, more preferably greater than about 95%.

The concentration of the cleaning agent in the lubricating oil of the present disclosure is about 1.0 to about 6.0% by weight, preferably about 2.0 to about 5.0% by weight, more preferably based on the total weight of the lubricating oil. It can range from about 2.0 to about 4.0% by weight. In the lubricating oils of the present disclosure, the amount of alkaline earth metal sulfonate is preferably from about 0.5 to about 2.5% by weight, preferably from about 0.5 to about 2.0, based on the total weight of the lubricating oil. It can be in the range of% by weight, more preferably about 0.5 to about 1.5% by weight. In the lubricating oils of the present disclosure, the amount of alkaline earth metal phenate is preferably from about 0.5 to about 2.5% by weight, preferably from about 0.5 to about 2.0, based on the total weight of the lubricating oil. It can be in the range of% by weight, more preferably about 0.5 to about 1.5% by weight. In the lubricating oils of the present disclosure, the amount of alkaline earth metal carboxylate is about 1.0 to about 4.0% by weight, preferably about 1.0 to about 3.0% by weight, based on the total weight of the lubricating oil. , More preferably in the range of about 1.5 to about 2.5% by weight. In the lubricating oils of the present disclosure, the amount of alkaline earth metal phosphate is about 1.0 to about 4.0% by weight, preferably about 1.0 to about 3.0% by weight, based on the total weight of the lubricating oil. More preferably, it may be in the range of about 1.5 to about 2.5% by weight.

As used herein, the detergent concentration is shown relative to "when delivered." Typically, the active detergent is delivered with the process oil. The "on-delivery" cleaning agent typically contains about 20% to about 80% by weight, or about 40% to about 60% by weight, of the active cleaning agent in the "on-delivery" cleaning agent. Included in.

Anti-wearing agents Metal alkyl thiophosphate (or metal alkyl thiophosphate), especially metal dialkyl dithiophosphate (or metal dialkyl dithiophosphate) whose metal component is zinc, or zinc dialkyl dithiophosphate (or zinc dialkyl dithiophosphate) (zinc) dialkyl dithiophosphate (ZDDP) is a useful component of the lubricating oils of the present disclosure. ZDDP can be derived from primary alcohols, secondary alcohols, or mixtures thereof. Preferred ZDDP compounds are generally of the formula:
Zn [SP (S) (OR ¹ ) (OR ² )] ₂
[In the formula, R ¹ and R ² are independently primary or secondary C _{1 to} C ₈ alkyl groups]
Represented by. A mixture of primary alcohol (1 °) -induced ZDDP and secondary alcohol (2 °) -induced ZDDP can be used. The R ¹ and R ² substituents can independently be C _{1 to} C ₁₈ alkyl groups, preferably C _{2 to} C ₁₂ alkyl groups. Preferably, R ¹ and R ² are independently primary or secondary C _{1 to} C ₈ alkyl groups (where at least one of R ¹ and R ² is secondary C _{1 to} C _8). It is an alkyl group). Mixtures of primary alcohol-derived ZDDP and secondary alcohol-derived ZDDP in which R ¹ and R ² are C _{1 to} C ₈ alkyl groups can be used. These alkyl groups may be straight chain or branched chain. Alkylaryl groups may be used.

Preferred commercially available zinc dithiophosphates (or zinc dithiophosphates) include, for example, the trade names "LZ 677A", "LZ 1095", "LZ 1389" and "LZ 1371" from The Lubrizol Corporation, eg, Includes the brand name "OLOA 262" from Chevron Oronite, eg, the brand name "HITEC 7169" from Afton Chemical, and secondary zinc dithiophosphates, such as those available from Infinium under the brand names Infinium C9417 and Infinium C9414. ..

Preferably, primary or secondary _C 1 -C ₈ alkyl group of the zinc dialkyl dithiophosphate compounds, some 2-propanol (C3), 1-butanol (n-C4), 1-iso-butanol ( 1-i-C4), 2-butanol (2-C4), 1-pentanol (primary C-5), 3-methyl-1-butanol (primary C-5), 2-pentanol (primary C-5) i-C5), 3-pentanol (C5), 3-methyl-2-butanol (C5), 1-hexanol (primary C6), 4-methyl-1-pentanol (primary C6), 4 It is derived from an alcohol selected from the group consisting of -methyl-2-pentanol (i-C6) and 2-ethyl-1-hexanol (primary C8) and mixtures thereof. In some cases, ZDDP derived from alcohols with an average carbon number of 5 or less is desirable. In some cases, ZDDP derived from alcohols with an average carbon number greater than 5 is desirable. Table 1 shows the alcohol mixtures used to make ZDDP that can be conveniently used in the present invention.

Zinc dialkyl dithiophosphate compounds with R ¹ and R ² primary or secondary alkyl group, and R ¹ and R ² primary or secondary alkyl groups in the lubricating oil of the zinc dialkyl dithiophosphate compound The amount is the low speed regeneration achieved in engines using lubricating oils containing sub-ingredients other than the specific zinc dialkyl dithiophosphate compound in an amount other than the amount of the specific zinc dialkyl dithiophosphate compound in the lubricating oil. Compared to performance, the engine is sufficient to show a reduction in slow play ignition.

In general, ZDDP is about 0.4% to about 1.2% by weight, preferably about 0.5% to about 1.0% by weight, more preferably about 0%, based on the total weight of the lubricating oil. It can be used in an amount of 6.6% to about 0.8% by weight, but more or less can often be used advantageously. Preferably, the ZDDP is a mixture of primary alcohol-derived ZDDP and secondary alcohol-derived ZDDP, or ZDDP derived from primary and secondary alcohols, and about the total weight of the lubricating oil. It is present in an amount of 0.6-1.0 weight percent.

Preferably, the R ¹ and R ² primary or secondary alkyl groups are derived from 2-ethyl-1-hexanol (primary C8), the R ¹ and R ² primary or secondary alkyls. The group-containing zinc dialkyldithiophosphate compound is from about 0.1% to about 5.0% by weight, preferably from about 0.1% to about 1.2% by weight, based on the total weight of the lubricating oil. More preferably, it is present in an amount of about 0.2% by weight to about 0.8% by weight.

Preferably, the R ¹ and R ² primary or secondary alkyl groups are derived from 4-methyl-2-pentanol (C6), the R ¹ and R ² primary or secondary alkyl groups. The zinc dialkyldithiophosphate compound having is about 0.1% by weight to about 5.0% by weight, preferably about 0.1% by weight to about 1.2% by weight, more preferably, based on the total weight of the lubricating oil. Is present in an amount of about 0.2% by weight to about 0.8% by weight.

Preferably, the zinc dialkyldithiophosphate compound is derived from a C _{3 to} C ₈ secondary alcohol or a mixture thereof. Similarly, preferably, the zinc dialkyldithiophosphate compound is derived from a mixture of C _1- C ₈ primary alcohols and C _1- C ₈ secondary alcohols.

The zinc content provided by the zinc-containing compound or anti-wear agent in the lubricant ranges from about 500 ppm to about 2000 ppm, preferably from about 600 ppm to about 900 ppm.

The phosphorus content provided by the zinc-containing compound or anti-wear agent in the lubricant ranges from about 400 ppm to about 2000 ppm, preferably from about 500 ppm to about 900 ppm. Phosphorus derived from secondary ZDDP is preferably 0 to 900 ppm, more preferably 400 to 900 ppm.

The zinc to phosphorus ratio in the lubricating oil is in the range of about 1.0 to about 2.0, preferably about 1.05 to about 1.9.

The ratio of total metal to zinc-containing compound provided by the cleaning agent and total metal provided by the anti-wear agent is from about 0.8 to 4.8, preferably from about 1.4 to 4.0, more preferably from about. It is 1.5 to 3.7.

Illustrative zinc-containing compounds useful in the present disclosure include, for example, zinc sulfonate (or zinc sulfonate), zinc carboxylates (or zinc carboxylate), zinc acetates (or zinc acetates). Or zinc acetate), zinc napthenates (or zinc naphthate), zinc alkenyl succinates (or zinc alkenyl succinates), zinc acid phosphate salts (or zinc). Acid phosphate), zinc phenates (or zinc phenates), zinc salicylates (or zinc salicylate) and the like.

With respect to the lubricating oil formulations containing at least one boron-containing compound and at least one zinc-containing compound or anti-wearing agent according to the present disclosure, the engine may include at least one boron-containing compound and at least one zinc-containing compound or Achieved in engines using lubricating oils containing sub-ingredients other than anti-wear agents in amounts other than at least one boron-containing compound and at least one zinc-containing compound or anti-wear agent in the lubricating oil. Standardized low-speed generation (LSPI) for 25,000 engine cycles, engine operation at 2000 rpm (RPM) and 18 bar net average effective pressure (BMEP) compared to low-speed compounding performance. ) Based on the number, it indicates a reduction in slow play ignition greater than about 20%, preferably greater than about 25%, more preferably greater than about 30%.

Also, with respect to the lubricating oil formulation containing at least one boron-containing compound, at least one cleaning agent and at least one zinc-containing compound or anti-wearing agent according to the present disclosure, the engine will also include at least one boron-containing compound. , At least one cleaning agent and at least one zinc-containing compound or a lubricating oil containing an auxiliary component other than an anti-wearing agent, at least one boron-containing compound in the lubricating oil, at least one cleaning agent and at least. Engine at 25,000 engine cycles, 2000 rpm (RPM) compared to the low speed regeneration performance achieved by the engine when used in amounts other than the amount of one zinc-containing compound or anti-wear agent Greater than about 50%, preferably greater than about 75%, more preferably greater than about 95%, based on standardized low speed compound (LSPI) numbers for driving and a net average effective pressure (BMEP) of 18 bar. Shows a large reduction in slow play ignition.

Preferably, the R ¹ and R ² primary or secondary alkyl groups are 2-propanol (C3), 2-butanol (2-C4), 1-isobutanol (1-i-C4) or n-pen. Zincdialkyl dithiophosphate compounds having R ¹ and R ² primary or secondary alkyl groups derived from tanol (n-C5) are from about 0.1% by weight based on the total weight of the lubricating oil. It is present in an amount of about 5.0% by weight, preferably about 0.1% by weight to about 1.2% by weight, more preferably about 0.2% by weight to about 0.8% by weight.

The concentration of the zinc-containing compound or anti-wearing agent in the lubricating oil of the present disclosure is from about 0.1% by weight to about 5.0% by weight, preferably from about 0.2% by weight, based on the total weight of the lubricating oil. It can be in the range of about 2.0% by weight, more preferably about 0.2% by weight to about 1.0% by weight. In the presence of magnesium detergents and boron-containing additives, only small amounts of ZDDP are required to result in very low LSPI numbers. In the presence of such magnesium and boron-containing compounds, low ZDDP of about 0.1% to 1.0% (phosphorus in compounded engine oil is 100 ppm to 1000 ppm) can result in unexpected improvements in LSPI performance. There will be. At higher ash and higher TBN concentrations, a ZDDP concentration of 1.1-4.0% can result in unexpected improvements in LSPI performance. For SAE xW-40 and xW-50 oils (x = 0, 5, 10, 15), ZDDP concentrations of 1.1-4.0% are particularly useful to bring about unexpected improvements in LSPI performance. ..

Other Additives The blended lubricants useful in the present disclosure are, but are not limited to, other anti-wear agents, other dispersants, other detergents, corrosion inhibitors, rust inhibitors, metal deactivators, extreme pressures. Additives, anti-seizure agents, wax modifiers, viscosity index improvers, viscosity modifiers, dehydration additives, seal compatibility agents, friction modifiers, lubricants, anti-stainers, color formers, defoaming agents, demulsifiers, It may additionally contain one or more other commonly used lubricating oil performance additives, including emulsifiers, densifying agents, wetting agents, gelling agents, tackants, colorants and others. For many commonly used additives, see Klamann's Lubricants and Related Products, Verlag Chemie, Deerfield Beach, FL; ISBN 0 89573 1770. Noyes Data Corporation of Park Ridge, published by NJ (1973). W. See also Lubricant Additives by Ranney, as well as US Pat. No. 7,704,930, which is incorporated herein in its entirety. These additives are generally delivered with varying amounts of diluent oil, which may range from 5% to 50% by weight.

The types and amounts of performance additives used in the lubricant composition in combination with the present disclosure are not limited by the embodiments shown herein by way of example.

Viscosity Index Improver The lubricant composition of the present disclosure may include a viscosity index improver (also known as a VI improver, a viscosity modifier and a viscosity improver).

The viscosity index improver provides the lubricant with high and low temperature operating performance. These additives provide shear stability at high temperatures and acceptable viscosity at low temperatures.

Suitable viscosity index improvers include high molecular weight hydrocarbons, polyesters, and viscosity index improver dispersants that act as both viscosity index improvers and dispersants. Typical molecular weights of these polymers range from about 10,000 to 1,500,000, more typically 20,000 to 1,200,000, and even more typically 50,000 to 1,000,000. is there.

Examples of suitable viscosity index improvers are straight or star polymers and copolymers of methacrylate, butadiene, olefins or alkylated styrenes. Polyisobutylene is a commonly used viscosity index improver. Another suitable viscosity index improver is polymethacrylate (eg, copolymers of alkyl methacrylates of various chain lengths), some of which also serve as pour point depressants. Other suitable viscosity index improvers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (eg, copolymers of acrylates of various chain lengths). Specific examples include styrene-isoprene or styrene-butadiene-based polymers with molecular weights of 50,000 to 200,000.

Olefin copolymers are traded under the brand name "PARATONE®" (eg, "PARATONE® 8921" and "PARATONE® 8941") from Chevron Origin Company LLC, and under the trade name "HiTEC" from Afton Chemical Corporation. Trademark) ”(eg,“ HiTEC® 5850B ”), commercially available from The Lubrizol Corporation under the trade name“ Lubrizol® 7067C ”. Polyisoprene polymers are commercially available from Infinium International Limited, for example under the trade name "SV200", and diene-styrene copolymers are commercially available from Infinium International Limited, for example under the trade name "SV260". It is possible.

In one embodiment of the present disclosure, the viscosity index improver is less than about 2.0% by weight, preferably less than about 1.0% by weight, more preferably about 0% by weight, based on the total weight of the blended oil or lubricating engine oil. It may be used in an amount less than 5% by weight. The viscosity improver is typically added as a concentrate in a large amount of diluent oil.

In another embodiment of the present disclosure, the viscosity index improver is 0.25 to about 2.0% by weight, preferably 0.15 to about 1.0% by weight, based on the total weight of the blended oil or lubricating engine oil. , More preferably in an amount of 0.05 to about 0.5% by weight.

Antioxidants Antioxidants inhibit the oxidative decomposition of the base oil during use. Such decomposition can result in deposits on the metal surface, the presence of sludge, or an increase in the viscosity of the lubricant. Those skilled in the art are aware of a wide variety of antioxidants that are useful in lubricating oil compositions. See, for example, Kramann's Lubricants and Related Products, and US Pat. Nos. 4,798,684 and 5,084,197.

Useful antioxidants include hindered phenols. These phenolic antioxidants may be ashless (metal-free) phenolic compounds, or neutral or basic metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are hindered phenols, which are phenols containing sterically impaired hydroxyl groups, which are dihydroxylaryl compounds in which the hydroxyl groups are in the ortho or para position with respect to each other. Derivatives are included. Typical phenolic antioxidants include hindered phenols substituted with alkyl groups of C6 and above, and alkylene bond derivatives of these hindered phenols. Examples of this type of phenolic material are 2-t-butyl-4-heptylphenol; 2-t-butyl-4-octylphenol; 2-t-butyl-4-dodecylphenol; 2,6-di-t-. Butyl-4-heptylphenol; 2,6-di-t-butyl-4-dodecylphenol; 2-methyl-6-t-butyl-4-heptylphenol; and 2-methyl-6-t-butyl-4- Dodecylphenol. Other useful hindered monophenolic antioxidants may include, for example, 2,6-di-alkyl-phenol propionic acid ester derivatives. Bis-phenol antioxidants can also be used advantageously in combination with the present disclosure. Examples of ortho-linked phenols are 2,2'-bis (4-heptyl-6-t-butyl-phenol); 2,2'-bis (4-octyl-6-t-butyl-phenol); and 2 , 2'-Bis (4-dodecyl-6-t-butyl-phenol) is included. Para-bonded bisphenols include, for example, 4,4'-bis (2,6-di-t-butylphenol) and 4,4'-methylenebis (2,6-di-t-butylphenol).

An effective amount of one or more catalytic antioxidants may also be used. The catalytic antioxidant is an effective amount of a) one or more oil-soluble polymetal organic compounds; and an effective amount of b) one or more substituted N, N'-diaryl-o-phenylenediamine compounds or c) one or more. Hindered phenolic compounds; or combinations of both b) and c). The catalytic oxidation inhibitor is fully described by US Pat. No. 8,048,833, which is incorporated herein by reference in its entirety.

Non-phenolic antioxidants that may be used include aromatic amine antioxidants, which may be used as is or in combination with phenol. A typical example of a non-phenolic antioxidant is the formula R ⁸ R ⁹ R ¹⁰ N (in the formula, R ⁸ is an aliphatic, aromatic or substituted aromatic group and R ⁹ is an aromatic or substituted aromatic group. A group group, and R ¹⁰ is an H, alkyl, aryl or R ¹¹ S (O) XR ¹² , R ¹¹ is an alkylene group linked to or in an alkylene, an arche, and R ¹² is a higher alkyl group. , Or an alkylated or non-alkylated aromatic amine such as an aromatic monoamine (which is an alkenyl, aryl or phenolic group, and x is 0, 1 or 2). The aliphatic group R ⁸ may contain 1 to 20 carbon atoms, preferably 6 to 12 carbon atoms. Aliphatic groups are saturated aliphatic groups. Preferably, both R ⁸ and R ⁹ are aromatic or aromatic groups, and the aromatic group may be a fused ring aromatic group such as naphthyl. The aromatic groups R ⁸ and R ⁹ may be attached together with other groups such as S.

A typical aromatic amine antioxidant has an alkyl substituent having at least 6 carbon atoms. Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl and decyl. In general, aliphatic groups will not contain more than 14 carbon atoms. Common types of amine antioxidants useful in the composition include diphenylamine, phenylnaphthylamine, phenothiazine, imidedibenzyl and biphenylphenylenediamine. Mixtures of two or more aromatic amines are also useful. Polymeramine antioxidants can also be used. Specific examples of aromatic amine antioxidants useful in the present disclosure include p, p'-dioctyldiphenylamine; t-octylphenyl-alpha-naphthylamine; phenyl-alphanaphthylamine; and p-octylphenyl-alpha-naphthylamine. included.

Alkyl sulfide phenols and their alkaline or alkaline earth metal salts are also useful antioxidants.

Preferred antioxidants include hindered phenols, arylamines. These antioxidants may be used individually by type or in combination with each other. Such additives are used in an amount of 0.01-5% by weight, preferably 0.01-2% by weight, more preferably 0-1.5% by weight, more preferably less than 0-1% by weight. You can.

Pour point depressant (PPD)
If necessary, a conventional pour point lowering agent (also known as a lubricating oil fluidity improver) may be added to the compositions of the present disclosure. These pour point depressants may be added to the lubricating compositions of the present disclosure to reduce the minimum temperature at which the fluid can flow or flow out. Examples of suitable pour point depressants are polymethacrylates, polyacrylates, polyarylamides, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, and dialkyl fumarate, vinyl esters of fatty acids and allyl vinyl ethers. Includes terpolymer. U.S. Pat. Nos. 1,815,022, 2,015,748, 2,191,498, 2,387,501, 2,655 , No. 479, No. 2,666,746, No. 2,721,877, No. 2,721,878 and No. 3,250,715. Describes useful pour point depressants and / or their preparation. Such additives may be used in an amount of about 0.01-5% by weight, preferably about 0.01-1.5% by weight.

Seal Compatibility Agents Seal compatibility agents promote the expansion of elastomeric seals by causing chemical reactions in fluids or physical changes in elastomers. Suitable seal compatibility agents for lubricants include organic phosphates, alkoxysulfolanes, aromatic esters, aromatic hydrocarbons, esters (eg, butylbenzylphthalate) and polybutenyl succinic anhydride. Such additives may be used in an amount of about 0.01-3% by weight, preferably about 0.01-2% by weight.

Defoaming agent The defoaming agent may be advantageously added to the lubricant composition. These agents inhibit the formation of stable bubbles. Silicones and organic polymers are typical defoamers. For example, silicone oil or polysiloxane, such as polydimethylsiloxane, provides antifoaming properties. Defoamers are commercially available and may still be used in small amounts with other additives such as deemulsifiers, usually in the amount of these combined additives less than 1% by weight. Often less than 0.1% by weight.

Inhibitors and Anti-Rust Additives Anti-rust additives (or corrosion inhibitors) are additives that protect a lubricated metal surface from chemical attack by water or other contaminants. A wide variety of these are commercially available.

One type of anti-rust additive is a polar compound that preferentially moistens the metal surface and protects it with an oil film. Another type of anti-rust additive absorbs water by incorporating it into a water-in-oil emulsion such that only the oil contacts the metal surface. Yet another type of anti-rust additive chemically binds to give a non-reactive surface. Examples of suitable additives include zinc dithiophosphates, metal phenolates, basic metal sulfonates, fatty acids and amines. Such additives may be used in an amount of about 0.01-5% by weight, preferably about 0.01-1.5% by weight.

Friction denaturant A friction denaturant is any material that can change the coefficient of friction of any lubricant or fluid-lubricated surface that contains such a material. As a friction reducer, or lubricant or oily agent, and other such agents that alter the ability of the base oil, blended lubricant composition or functional fluid to modify the coefficient of friction of the lubricated surface. Known friction modifiers may be effectively used in conjunction with the base oils or lubricant compositions of the present disclosure, if desired. Friction modifiers that reduce the coefficient of friction are particularly convenient in combination with the base oil and lubricating oil compositions of the present disclosure.

Exemplary friction modifiers may include, for example, organometallic compounds or materials, or mixtures thereof. Exemplary organic metal friction modifiers useful in the lubricating engine oil formulations of the present disclosure include, for example, molybdenum amine, molybdenum diamine, molybdenum amine, molybdenum diamine, organic tongue stenate, molybdenum dithiocarbamate, molybdenum dithiophosphate, molybdenum. Includes amine complexes, molybdenum carboxylates, etc., and mixtures thereof. Similar tungsten-based compounds may be preferred.

Other exemplary friction modifiers useful in the lubricating engine oil formulations of the present disclosure include, for example, alkylated fatty acid esters, alkanolamides, polyol fatty acid esters, booxide glycerol fatty acid esters, fatty alcohol ethers and mixtures thereof. included.

Exemplary alkylated fatty acid esters include, for example, polyoxyethylene stearates, fatty acid polyglycol esters and the like. These can include polyoxypropylene stearate, polyoxybutylene stearate, polyoxyethylene isostearate, polyoxypropylene isostearate, polyoxyethylene palmitate and the like.

Exemplary alkanolamides include, for example, lauric acid diethyl alkanol amide, palmitic acid diethyl alkanol amide and the like. These can include oleic acid diethyl alkanolamide, stearic acid diethyl alkanol amide, oleic acid diethyl alkanol amide, polyethoxylated hydrocarbyl amide, polypropoxylated hydrocarbyl amide and the like.

Exemplary polyol fatty acid esters include, for example, glycerol monooleates, saturated mono-, di- and triglyceride esters, glycerol monostearate and the like. These can include polyol esters, hydroxyl-containing polyol esters, and the like.

Exemplary glycerol booxide fatty acid esters include, for example, glycerol booxide monooleates, saturated monoborides, di- and triglyceride esters, glycerol booxide monostearate and the like. In addition to glycerol polyols, these can include trimethylolpropane, pentaerythritol, sorbitan and the like. These esters can be polyol monocarboxylate esters, polyol dicarboxylic acid esters, and optionally polyol tricarboxylate esters. Preferably, glycerol monooleate, glycerol dioleate, glycerol trioleate, glycerol monostearate, glycerol distearate, and glycerol tristearate and corresponding glycerol monopalmitates, glycerol dipalmitates and glycerol tripalmitates and It can be an isoste alert and a linoleate, respectively. In some cases, glycerol esters, as well as mixtures containing any of these, may be preferred. With particular use of glycerol as the root polyol, ethoxylated, propoxylated, butoxylated fatty acid esters of the polyol may be preferred.

Exemplary fatty alcohol ethers include, for example, stearyl ethers, myristyl ethers and the like. Alcohols containing those having C _{3 to} C ₅₀ carbon atoms can be ethoxylated, propoxylated or butoxylated to form the corresponding fatty acid alkyl ethers. The basic alcohol moiety can preferably be stearyl, myristyl, C _11- C ₁₃ hydrocarbons, oleyl, isostearyl and the like.

Useful concentrations of friction modifiers are 0.01% to 5% by weight, or about 0.1% to about 2.5% by weight, or about 0.1% to about 1.5% by weight, or It may be in the range of about 0.1% by weight to about 1% by weight. The concentration of molybdenum-containing material is often described with respect to the Mo metal concentration. A convenient concentration of Mo may be in the range of 25 ppm to 700 ppm or more, and often a preferred range is 50 to 200 ppm. All types of friction modifiers may be used alone or in admixture with those of the present disclosure. Often, a mixture of two or more friction modifiers, or a mixture of friction modifiers with another surface activating material, is also desirable.

If the lubricating oil composition contains one or more of the above additives, the additives are blended into the composition in an amount sufficient for it to perform its intended function. Typical amounts of such additives useful in the present disclosure are shown in Table 1 below.

It is noted that many additives are shipped from additive manufacturers as concentrates containing one or more additives together with a particular amount of base oil diluent. Therefore, the weights in the table below, as well as the other amounts described herein, relate to the amount of active ingredient (which is the non-diluent portion of the ingredient). The% by weight (wt%) shown below is based on the total weight of the lubricating oil composition.

All of the above additives are commercially available materials. These additives may be added independently, but are usually pre-combined in a package available from the supplier of the lubricant additive. Additive packages with various ingredients, properties and characteristics are available, and the selection of the appropriate package will take into account the required use of the underlying composition.

The compounded engine oils of the present disclosure exhibit a substantial elimination of LSPI. Substantial elimination of LSPI means engine operation at 25,000 engine cycles, 2000 rpm (rpm) and standardized slow pre-ignition (LSPI) for 18 bar net mean pressure (BMEP). Based on the number, it means a reduction in slow pre-ignition greater than about 95%, or greater than about 97%, or greater than about 99%.

Formulated engine oils with higher ash concentrations of 1.2-1.6% or higher can significantly reduce the number of LSPI phenomena to 96% or higher in combination with the other components disclosed in the present disclosure. Formulated engine oils with lower ash concentrations of 0.2-1.2% can be combined with the other components disclosed in the present disclosure to completely reduce the number of LSPI phenomena.

Engines that are highly sensitive to low speed pre-ignition (LSPI) are engines that operate at high net mean effective pressure (BMEP) and low engine speed (RPM). This includes internal combustion engines (or internal combustion engines) that use a variety of fuels, including natural gas, gasoline, diesel, biofuels and the like. Reduced size and slowed down supercharged (eg, turbocharged) engines are most susceptible to operation under these engine conditions and are therefore more susceptible to LSPI. Non-limiting examples of engines with these characteristics include GM Ecotec, Ford EcoBoost lineage engines, and other high BMEP (> 10 bar possible) engines with displacements ranging from about 1L to about 6L. , And 2-10 in geometric arrangements including in-line, horizontally opposed (or boxer) and "V" (eg, "V8", "straight 3", "straight 4", "flat 4", etc.) Includes engines with a number of combustion cylinders. In addition, engine calibration and operational set values can significantly affect both the frequency and severity of the LSPI phenomenon.

The following non-limiting examples are provided to illustrate the disclosure.

Example A
The formulation was prepared as described in FIG. All ingredients used herein are commercially available. Group III, IV and V base stocks were used in the formulations. The dispersants used in the formulation are succinimide booxide (consisting of polyisobutenyl succinimide booxide having a B / N ratio equal to about 0.5), high molecular weight succinimide (about 1% total nitrogen). High MW succinimide dispersant 1) and high molecular weight succinimide (bispolyisobutenyl succinimide with a total molecular weight of about 1.2%) comprising an amount of ethylene carbonate capped bispolyisobutenyl succinimide dispersant. It was a high MW succinimide dispersant 2).

The remaining ingredients used in the formulation are viscosity index improvers, antioxidants, dispersants, anti-friction agents, pour point depressants, corrosion inhibitors, metal deactivators, seal compatible additives, defoamers. It was one or more of agents, inhibitors, anti-rust additives and friction modifiers.

The formulations shown in FIG. 1 were tested. The results are shown in FIG. The sulfate ash test was determined based on ASTM D874. The boron content was determined based on ASTM D6443. Nitrogen content was determined based on ASTM D3228.

Various engine hardware and control schemes can significantly influence the emergence of LSPI. For example, US Patent Application Publication Nos. 2012/1866225 and 2003/09008070, all incorporated herein by reference, and SAE 2012-02-1148, SAE 2011-01-0340 and SAE 2011. Please refer to -01-0343. In addition, FIG. 13 shows drive cycle data obtained from a taxi cab field test. Two different 2.0L L4 TGDI engine types from different destination brand manufacturers were driven in a typical taxi cab city drive cycle for two weeks. Engine performance data was collected using the vehicle's OBD-II data port and mapped onto the published engine torque map for each engine. As published in SAE 2011-01-0339, engines are particularly prone to LSPI when they are operated in the region of BMEP above 10 bar and engine speed below 3000 rpm. As such, any region of the torque map of these engines demarcated by these operating conditions is potentially prone to LSPI. Based on the measurement data of the OBD-II data logger, it can be shown that engines with different calibrations may exhibit different LSPI behaviors based on how they are tuned. FIG. 13 shows about 1.2 million data points summarizing the operation of two different engine types in a typical taxi cab city drive cycle over a two week period. Multiple taxi cabs using each engine type were observed in this way. Both engines were 2.0L in-line 4-cylinder TGDI engines, with engine type 1 using an average of 1.67% of its operating time in the LSPI "danger zone", while engine type 2 averaged 0. Only .17% is used in a typical taxi cab city drive cycle. Further, the engine type 2 was shown to have zero defects in the LSPI-related field, while the engine type 1 showed a plurality of defects related to the LSPI. This further illustrates the different reactivity of different engine platforms to LSPI.

For the purposes of this disclosure, a 2.0 L 4-cylinder TGDI GM Ecotec engine was used for the LSPI test. A 6-segment test procedure was used to determine the number of LSPI phenomena occurring under two different specified engine loads and speed conditions. Each segment of the test procedure consisted of 25,000 engine cycles, one cycle corresponding to 720 degree crankshaft rotational movement. The first set of conditions is BMEP at 2000 rpm and 18 bar, hereinafter referred to as "high load". The second set of conditions is BMEP at 1500 rpm and 12.5 bar, hereinafter referred to as "low load". The test procedure consisted of two segments of high load, followed by two segments of low load, followed by two segments of high load. A 30 minute warm-up was also performed at 2000 rpm and 4 bar BMEP prior to starting the test procedure. This test procedure was repeated 4 times for each of the lubricants tested. The number of LSPI events was counted only during the high load segment using pressure transducers located on each of the four cylinders to monitor peak cylinder pressure. The peak pressure in the cylinder, which is 4.7 standard deviation higher than the average peak cylinder pressure or 4.7 standard deviation lower than the average peak cylinder pressure, was counted as the LSPI phenomenon. The results of such an LSPI test are shown in FIG.

This test evaluated the effect of dispersant chemistry on LSPI. As shown in FIG. 1, the amount of boron in the formulation has a strong correlation with the total number of LSPIs in the oil. In particular, as the ppm of boron increases from 0 to 241 to 507, the number of LSPIs surprisingly decreases from about 43 to 27 to 24. This is a 40% reduction with only about 241 ppm boron and a 48% reduction with about 507 ppm boron. The relative change in the number of LSPIs from 0 ppm to 241 ppm is greater than the relative change in the number of LSPI numbers from 241 ppm to 507 ppm boron, but the unexpected advantage of boron directional is still preserved. Even an increase in boron of about 240 ppm unexpectedly reduced the LSPI number by 40%. Therefore, a boron source that supplies 0 to about 1000 ppm, more preferably 0 to about 500 ppm of boron is beneficial in reducing LSPI. Moreover, by comparing Comparative Example 5 with Example 2 and Example 11, the usefulness of the booxide dispersant in reducing the adverse effects of other dispersant types is further demonstrated. Comparative Example 5 and Example 2 showed approximately the same number of LSPI phenomena of 22 and 24 phenomena, respectively, but Example 2 contained only a succinimide booxide dispersant and Comparative Example 5 did not contain a dispersant. .. Moreover, comparing Examples 1 and 11 with Comparative Examples 1 and 2, booxide dispersants are observed with respect to lubricants containing non-booxide dispersants alone, even at very high concentrations of dispersant-induced nitrogen. It was shown to significantly reduce the number of LSPI phenomena.

The dispersants used in this test were further evaluated using thermogravimetric analysis (TGA). An ATA device Q5000 TGA equipped with a platinum reference pan was used. Nitrogen gas was passed over the sample at 60.0 ml / min. Approximately 15 mg of sample dispersant was used for the analysis, and the next temperature rise program: balancing at 50 ° C, followed by temperature rise to 650 ° C over about 1 minute, balancing at 650 ° C, and so on. Then, it was subjected to isothermal permeation at 650 ° C. for about 15 seconds. The gas was then exchanged for oxygen, flushed at 60.0 ml / min, and further subjected to further isothermal permeation at 650 ° C. for 45 seconds. Finally, the temperature was raised from 650 ° C to 750 ° C in about 30 seconds and isothermally infiltrated at 750 ° C for an additional 30 seconds.

The results are shown in FIG. This indicates that the number of LSPIs decreases as the temperature at which 20% and / or 50% weight loss is achieved in TGA measurements increases. The three traces on the TGA plot represent the three dispersant types used in this analysis. In particular, the dispersant 1 represents a high MW succinimide dispersant 1, the dispersant 2 represents a high MW succinimide dispersant 2, and the dispersant 3 represents a booxide succinimide dispersant. The temperatures at which 20% weight loss is achieved are about 355 ° C, 344 ° C and 328 ° C, respectively, for these dispersants. The temperatures at which 50% weight loss was achieved are approximately 406 ° C, 400 ° C and 377 ° C for these dispersants, respectively. Surprisingly, the succinimide booxide dispersants with lower LSPI numbers gave higher TGA temperatures at 20% and 50% weight loss than the non-succinimide dispersants with higher LSPI numbers.

Example B
The formulation was prepared as shown in FIG. All ingredients used herein are commercially available. Group III, IV and V base stocks were used in the formulations.

The detergents used in the formulation are medium calcium TBN alkyl salicylate (calcium salicylate 1 containing 7.3% Ca and having about 200 TBN), low TBN alkyl calcium salicylate (2.3%). Calcium salicylate 2) containing Ca and having about 65 TBN, high TBN alkyl sulfonate calcium (calcium sulfonate 1 containing 11.6% Ca and having about 300 TBN), low TBN Calcium alkyl sulfonate (calcium sulfonate 2 containing 2.0% Ca and having about 8 TBN) and high TBN magnesium alkyl sulfonate (containing 9.1% Mg and about 400 TBN) It was magnesium sulfonate 1). The range of TBN is defined as low TBN as high as about 0-100, medium TBN as high as about 100-200, and high TBN as high as about 200-600.

The dispersants used in the formulation were succinimide booxide, high molecular weight succinimide (high MW succinimide dispersant 1) and high molecular weight succinimide (high MW succinimide dispersant 2).

The remaining ingredients used in the formulation are viscosity index improvers, antioxidants, dispersants, anti-friction agents, pour point depressants, corrosion inhibitors, metal deactivators, seal compatible additives, defoamers. It was one or more of agents, inhibitors, anti-rust additives and friction modifiers.

Tests were performed on the formulations shown in FIG. The results are shown in FIG. The sulfate ash test was determined based on ASTM D874. Boron, calcium and magnesium contents were determined based on ASTM D6443. Nitrogen content was determined based on ASTM D3228. The LSPI test on the formulation was performed using a 2.0 L, 4-cylinder TGDI GM Ecotec engine according to the procedure described in Example 1.

This test evaluated the effects of magnesium detergents and booxide dispersants on LSPI. As shown in FIG. 4, the use of booxide dispersant with magnesium sulfonate detergent is found to be unexpectedly beneficial in terms of LSPI performance. Comparative Examples 1 and 2 and Example 2 reproduce the new findings identified in Example A with respect to the benefits of using a boron source to significantly reduce or reduce LSPI. Examples 4 and 5, both formulated using a magnesium sulfonate detergent and a boron source, show excellent LSPI performance at different concentrations of sulfated ash. Although it is known that sulfated ash is harmful to LSPI performance, doubling the sulfated ash content from 0.8% by weight to 1.6% by weight increases the number of LSPIs from 0 to 2 by a small amount. The fact that is led unexpectedly reproduces the new findings represented by these blends, even at extremely high ash concentrations. Examples 4 and 5 show 100% and 95% LSPI reduction, respectively.

Example C
The formulation was prepared as shown in FIG. All ingredients used herein are commercially available. Group III, IV and V base stocks were used in the formulations.

The detergents used in the formulation are medium calcium TBN alkyl salicylate (calcium salicylate 1 containing 7.3% Ca and having about 200 TBN), low TBN alkyl calcium salicylate (2.3%). Calcium salicylate 2) containing Ca and having about 65 TBN, high TBN alkyl sulfonate calcium (calcium sulfonate 1 containing 11.6% Ca and having about 300 TBN), low TBN Calcium alkyl sulfonate (calcium sulfonate 2 containing 2.0% Ca and having about 8 TBN), moderate TBN calcium alkylphenate (containing 5.5% Ca and about 150) Calcium phenate 1) with TBN and high TBN alkyl sulfonate magnesium (magnesium sulfonate 1) containing 9.1% Mg and having about 400 TBN. The range of TBN is defined as low TBN as high as about 0-100, medium TBN as high as about 100-200, and high TBN as high as about 200-600.

The dispersants used in the formulation were succinimide booxide and high molecular weight succinimide. The anti-wearing agents used in the formulation are derived from ZDDP (containing 10 wt% phosphorus, prepared from mixed C3 and C6 secondary alcohols) and primary alcohols derived from secondary alcohols. ZDDP (containing 7% by weight phosphorus, prepared from C8 primary alcohol).

The remaining ingredients used in the formulation are viscosity index improvers, antioxidants, dispersants, anti-friction agents, pour point depressants, corrosion inhibitors, metal deactivators, seal compatible additives, defoamers. It was one or more of agents, inhibitors, anti-rust additives and friction modifiers.

Tests were performed on the formulations shown in FIG. The results are shown in FIG. The sulfate ash test was determined based on ASTM D874. The calcium, magnesium, boron, zinc and phosphorus contents were determined based on ASTM D6443. Nitrogen content was determined based on ASTM D3228. The LSPI test on the formulation was performed using a 2.0 L, 4-cylinder TGDI GM Ecotec engine according to the procedure described in Example 1. This test evaluated the effect of three additive systems (ie, detergents, dispersants and anti-wear agents) on LSPI. As shown in FIG. 6, when the LSPI of a formulation containing a non-boration dispersant and a formulation containing a mixture of a non-boration dispersant and a booxide dispersant is measured, the booxide succinimide dispersant is used. The use has a unique LSPI benefit over the high molecular weight succinimide dispersant. Comparative Example 3, Example 6 and Example 10 show the effect of increasing boron content on LSPI performance. When the boron content increases from 0 to 240 ppm and from 507 ppm, the LSPI number decreases from 46 to 27 and from 24. The benefit of boron in reducing LSPI frequency represents the significant and unexpected findings shown in FIGS. 5 and 6. Examples 8 and 9 show a unique combination of a double dispersant system and a magnesium sulfonate detergent with a secondary alcohol-induced ZDDP. The double dispersant system contains a boron source. The uniqueness of this combination is demonstrated by using different calcium salicylate-based detergent systems and comparing with Comparative Example 3 having the highest LSPI number. The use of magnesium sulfonate detergents with secondary alcohol-induced ZDDP and booxide dispersants has been shown to significantly reduce LSPI, if not eliminate. The desired ratio of the total concentration of ([Mg] + [Ca] + [Zn] + [P]) / ([B] + [N] _dispersant ) is about 2.5 to 7, more preferably. It is about 3.3 to 5. By comparing Example 6 with Example 12, the effectiveness of this method of incorporating a booxide dispersant in combination with a secondary alcohol-induced ZDDP and a combination of magnesium sulfonate detergent and calcium salicylate detergent is further demonstrated. Shown. Example 12 shows a 98% reduction in LSPI as compared to Comparative Example 3.

Example D
The lubricating engine oil formulations of FIGS. 7 and 8 are a combination of additives and basestock and have a kinematic viscosity of about 7.5-8.5 cSt at 100 ° C and about 2.5-2.9 cP at 150 ° C. It has high temperature and high shear ( ^10-6 seconds- ¹ ) viscosity. Lubricating engine oil formulations of Examples P1, P2, P3 are expected to have boron to dispersant nitrogen ratios of 0.05, 0.15 and 0.51, respectively. The total boron content in these formulations is expected to be in the range of 50 ppm to 800 ppm. The (Mg + Ca) / (B + N dispersant) ratio is expected to range from 1.28 for Example P3 to 2.91 for Example P1. Similarly, the ([Zn] + [P]) / ([B] + [N] _dispersant ) ratio is expected to range from 0.71 for Example P3 to 1.62 for Example P1. To. Finally, the ratio of ([Mg] + [Ca] + [Zn] + [P]) / ([B] + [N] _dispersant ) of Examples P1, P2 and P3 is 1.99 to 4.53. Is expected to be. The lubricating engine oil formulations of Examples P4 and P5 are expected to have a magnesium content of 300 ppm to 600 ppm. Similarly, the lubricating engine oil formulations of Examples P6, P7 and P8 have a magnesium content of 300 ppm to 900 ppm and a magnesium to calcium ratio of about 0.12 for Example P6 to 1.21 for Example P8. Is expected. At the same time, the TBN of these examples varies from 6.8 for Example P8 to P9 for Example P6. Similarly, the sulfated ash content of Examples P4, P5 and P6 varies from 0.3% by weight to 1.2% by weight. Other ratios identified in FIGS. 7 and 8 also vary as shown herein. Lubricating engine oil formulations of Examples P9 and P10 are expected to have magnesium to calcium ratios of about 0.06 and 3, respectively, at a constant TBN. Lubricating engine oil formulations of Examples P11, P12 and P13 are expected to have a zinc content in the range of about 96 ppm for Example P13 to about 635 ppm for Example P11. Lubricating engine oil formulations of Examples P11, P12 and P13 are expected to have a phosphorus content in the range of about 87 ppm for Example P13 to about 570 ppm for Example P11. The ([Mg] + [Ca]) / ([Zn] + [P]) ratio ranges from about 2.5 for Example P11 to 16.5 for Example P13. The ([Zn] + [P]) / ([B] + [N] _dispersant ) ratio is in the range of about 1 for Example P11 to 0.15 for Example P13. The ([Mg] + [Ca] + [Zn] + [P]) / ([B] + [N] _dispersant ) ratio ranges from about 3.4 for Example P11 to 2.6 for Example P13. Is.

Example E
The lubricating engine oil formulations of FIGS. 9 and 10 are a combination of additives and basestock and have a kinematic viscosity of about 5.5-7.5 cSt at 100 ° C and a high temperature of about 2-2.5 cP at 150 ° C. Has shear ( ^10-6 seconds- ¹ ) viscosity. Lubricating engine oil formulations of Examples P14, P15 and P16 are expected to have boron to dispersant nitrogen ratios of 0.05, 0.15 and 0.51, respectively. The total boron content in these formulations is expected to be in the range of 50 ppm to 800 ppm. The ([Mg] + [Ca]) / ([B] + [N] _dispersant ) ratio is expected to range from 1.28 for Example P16 to 2.91 for Example P14. Similarly, the ([Zn] + [P]) / ([B] + [N] _dispersant ) ratio is expected to range from 0.71 for Example P16 to 1.62 for Example P14. To. Finally, the ([Mg] + [Ca] + [Zn] + [P]) / ([B] + [N] _dispersant ) ratios of Examples P14, P15 and P16 are 1.99 to 4.53. Is expected to be. The lubricating engine oil formulations of Examples P17 and P18 are expected to have a magnesium content of 300 ppm to 600 ppm. Similarly, the lubricating engine oil formulations of Examples P19, P20 and P21 shall have a magnesium content of 300 ppm to 900 ppm and a magnesium to calcium ratio of about 0.12 for Example P19 to 1.21 for Example P21. Is expected. At the same time, the TBN of these examples varies from 6.8 for Example P21 to 9 for Example P19. Similarly, the sulfated ash content of Examples P17, P18 and P19 varies from 0.3% by weight to 1.2% by weight. Other ratios identified in FIGS. 9 and 10 also vary as shown herein. The lubricating engine oil formulations of Examples P22 and P23 are expected to have magnesium to calcium ratios of about 0.06 and 3, respectively, at a constant TBN. Lubricating engine oil formulations of Examples P24, P25 and P26 are expected to have a zinc content in the range of about 96 ppm for Example P26 to about 635 ppm for Example P24. Lubricating engine oil formulations of Examples P24, P25 and P26 are expected to have a phosphorus content in the range of about 87 ppm for Example P26 to about 570 ppm for Example P24. The ([Mg] + [Ca]) / ([Zn] + [P]) ratio ranges from about 2.5 for Example P24 to 16.5 for Example P26. The ([Zn] + [P]) / ([B] + [N] _dispersant ) ratio is in the range of about 1 for Example P24 and 0.15 for Example P26. The ([Mg] + [Ca] + [Zn] + [P]) / ([B] + [N] _dispersant ) ratio ranges from about 3.4 for Example P24 to 2.6 for Example P26. Is.

Example F
The lubricating engine oil formulations of FIGS. 11 and 12 are a combination of additives and basestock and have a kinematic viscosity of about 9-11 cSt at 100 ° C and a high temperature high shear of about 2.9-3.4 cP at 150 ° C. ^10-6 seconds- ¹ ) It has viscosity. Lubricating engine oil formulations of Examples P27, P28 and P29 are expected to have boron to dispersant nitrogen ratios of 0.05, 0.15 and 0.51, respectively. The total boron content in these formulations is expected to be in the range of 50 ppm to 800 ppm. The ([Mg] + [Ca]) / ([B] + [N] _dispersant ) ratio is expected to range from 1.28 for Example P29 to 2.91 for Example P27. Similarly, the ([Zn] + [P]) / ([B] + [N] dispersant) ratio is expected to range from 0.71 for Example P29 to 1.62 for Example P27. To. Finally, the ([Mg] + [Ca] + [Zn] + [P]) / ([B] + [N] _dispersant ) ratios of Examples P27, P28 and P29 are 1.99 to 4.53. Is expected to be. The lubricating engine oil formulations of Examples P30 and P31 are expected to have a magnesium content of 300 ppm to 600 ppm. Similarly, the lubricating engine oil formulations of Examples P32, P33 and P34 have a magnesium content of 300 ppm to 900 ppm and a magnesium to calcium ratio of about 0.12 for Example P32 to 1.21 for Example P34. Is expected. At the same time, the TBN of these examples varies from 6.8 for Example P34 to 9 for Example P32. Similarly, the sulfated ash content of Examples P30, P31 and P32 varies from 0.3% by weight to 1.2% by weight. Other ratios identified in FIGS. 11 and 12 also vary as shown herein. Lubricating engine oil formulations of Examples P35 and P36 are expected to have magnesium to calcium ratios of about 0.06 and 3, respectively, at a constant TBN. Lubricating engine oil formulations of Examples P37, P38 and P39 are expected to have a zinc content ranging from about 96 ppm for Example P39 to about 635 ppm for Example P37. Lubricating engine oil formulations of Examples P37, P38 and P39 are expected to have a phosphorus content in the range of about 87 ppm for Example P39 to about 570 ppm for Example P37. The ([Mg] + [Ca]) / ([Zn] + [P]) ratio ranges from about 2.5 for Example P37 to 16.5 for Example P39. The ([Zn] + [P]) / ([B] + [N] _dispersant ) ratio ranges from about 1 for Example P37 to 0.15 for Example P39. The ([Mg] + [Ca] + [Zn] + [P]) / ([B] + [N] _dispersant ) ratio ranges from about 3.4 for Example P37 to 2.6 for Example P39. Is. The concentration of metal used in the above examples is in units of total% by weight in the final lubricant. [N] _Dispersant means the nitrogen concentration provided to the final lubricant by the dispersant alone.

All patents and patent applications, test procedures (ASTM, UL, etc.) and other literature cited herein are tolerated as long as such disclosure is consistent with this disclosure, and such incorporation is acceptable. All permissions are fully incorporated by reference.

When numerical lower limits and numerical upper limits are described herein, the range from any lower limit to any upper limit is considered. Although exemplary embodiments of the present disclosure are described in detail, various other modifications are apparent to those skilled in the art and readily available to those skilled in the art without departing from the spirit and scope of the present disclosure. It will be understood that it can be done. Therefore, the appended claims are not intended to be limited to the examples and descriptions set forth herein, but rather the claims are equal by those skilled in the art to which this disclosure relates. It is construed to include all features of patentable novelty present in the present disclosure, including all features that will be treated as objects.

The present disclosure has been described above with reference to a number of embodiments and individual examples. Taking into account the detailed description above, one of ordinary skill in the art will propose many variants. All such obvious variants are within all intended scope of the appended claims.
Disclosures of the present specification may include the following aspects.
(Aspect 1)
A method of preventing or reducing low-speed regignation in an engine lubricated with the lubricating oil by using the compounding oil as a lubricating oil, wherein the compounding oil is a lubricating oil base stock as a main component and a subcomponent. It has a composition containing at least one boron-containing compound, and the at least one boron-containing compound contains at least one booxide dispersant or a mixture of a boron-containing compound and a non-boroxide dispersant.
25, when compared to the low speed pre-ignition performance achieved by the engine using at least one booxide dispersant, or a lubricant that does not contain a mixture of boron-containing compounds and non-booxide dispersants. Low speed pre-ignition greater than 50% based on standardized slow pre-ignition (LSPI) numbers for 000 engine cycles, engine operation at 2000 rpm (RPM) and 18 bar net mean pressure (BMEP) Shows a reduction in
Method.
(Aspect 2)
The sub-ingredient further comprises at least one cleaning agent, the cleaning agent contains an alkaline earth metal salt of at least one organic acid, and the alkaline earth metal salt of at least one organic acid. The method of aspect 1, wherein the method comprises a magnesium salt of at least one organic acid.
(Aspect 3)
The sub-ingredient further comprises at least one cleaning agent and at least one zinc-containing compound or at least one anti-wearing agent, wherein the cleaning agent is an alkaline earth metal salt of at least one organic acid. The alkaline earth metal salt of the at least one organic acid contains the magnesium salt of the at least one organic acid, and the at least one anti-wearing agent is at least one derived from a secondary alcohol. The method according to aspect 1, comprising a zinc dialkyldithiophosphate compound.
(Aspect 4)
The lubricating oil base stock contains a group I, group II, group III, group IV or group V base oil, and the group V base oil contains an ester base oil at a concentration of 2% to 20%, 100. The method according to any one of aspects 1 to 3, wherein the group III base oil has a kinematic viscosity of 2 cSt to 8 cSt at ° C. and contains a GTL base oil.
(Aspect 5)
The boron-containing compound or booxide dispersant is selected from the group consisting of succinimide booxide, succinic anhydride ester, succinic anhydride ester amide, Mannig booxide base and mixtures thereof, and the non-booxide dispersant is The method according to any one of aspects 1 to 4, which comprises a succinic anhydride-induced succinimide or a succinic acid ester together with a coupling agent containing a boron-containing compound.
(Aspect 6)
Boron is provided in the lubricating oil by a mixture of an organic or inorganic boron-containing compound with a succinimide booxide, a succinimide booxide ester, a succinimide booxide ester amide, a Mannig base ester or a mixture thereof, and the succinimide booxide is provided in the lubricating oil. The method according to any one of aspects 1 to 5, wherein is monosuccinimide, bis-succinimide or a mixture thereof.
(Aspect 7)
The total zinc from the zinc-containing compound and the anti-wearing agent in the lubricating oil and the total alkali earth metal from the cleaning agent are added to obtain total boron from the boron-containing compound and the booxide dispersant. The method according to any one of aspects 3 to 6, wherein the divided ratio is 9.2 to 45.
(Aspect 8)
The alkaline earth metal salt of the organic acid is selected from the group consisting of alkaline earth metal sulfonates, alkaline earth metal carboxylates, alkaline earth metal phenates, alkaline earth metal phosphates and mixtures thereof. The method according to any one of 7.
(Aspect 9)
The cleaning agent
(I) At least one of magnesium sulfonate, magnesium phenate and magnesium salicylate and a mixture thereof, optionally at least one of calcium sulfonate, calcium phenate and calcium salicylate and a mixture thereof.
(Ii) At least one magnesium salt of an organic acid, selected from magnesium sulfonate, magnesium carboxylate, magnesium phenate, magnesium phosphate and mixtures thereof, or
(Iii) A mixture of magnesium sulfonate, magnesium sulfonate and magnesium salicylate, a mixture of magnesium sulfonate and magnesium phenate, or a mixture of magnesium sulfonate and magnesium carboxylate.
The method according to any one of aspects 2 to 8, wherein the method comprises.
(Aspect 10)
(I) Whether the magnesium and alkaline earth metals provided by the cleaning agent are present in the lubricating oil in an amount of 500 ppm to 5000 ppm.
(Ii) The total alkalinity (TBN) provided by the cleaning agent, as measured by ASTM D2896, is in the range of 2 mg KOH / g to 17 mg KOH / g, or
(Iii) The sulfated ash content provided by the cleaning agent is in the range of 0.4 to 1.7% by weight.
The method according to any one of aspects 2 to 9.
(Aspect 11)
Aspects 3-10, wherein the zinc-containing compound is selected from the group consisting of zinc carboxylate, zinc sulfonate, zinc acetate, zinc naphthenate, zinc alkenyl succinate, zinc acid phosphate salt, zinc phenate and zinc salicylate. The method according to any one item.
(Aspect 12)
The zinc dialkyldithiophosphate compound has the formula:
Zn [SP (S) (OR ¹ ) (OR ² )] ₂
[In the formula, R ¹ and R ² are independently primary or secondary C _{1 to} C ₈ alkyl groups ( where at least one of R ¹ and R ² is secondary C _{1 to} C). ₈ alkyl group)]
The method according to any one of aspects 3 to 11, represented by.
(Aspect 13)
A lubricating engine oil having a composition containing a lubricating oil base stock as a main component and at least one boron-containing compound as an auxiliary component, wherein the at least one boron-containing compound is at least one booxide dispersant. , Or a mixture of a boron-containing compound and a non-boroxidizing dispersant,
25,000 compared to the slow pre-ignition performance achieved by an engine using at least one booxide dispersant, or a lubricant that does not contain a mixture of boron-containing compounds and non-booxide dispersants. For low speed pre-ignition greater than 50% based on standardized low speed pre-ignition (LSPI) numbers for engine cycles, engine operation at 2000 rpm (RPM) and net mean effective pressure (BMEP) of 18 bar. Lubricating engine oil showing reduction.
(Aspect 14)
The sub-ingredient further comprises at least one cleaning agent, the cleaning agent contains an alkaline earth metal salt of at least one organic acid, and the alkaline earth metal salt of at least one organic acid. The lubricating engine oil according to aspect 13, which comprises a magnesium salt of at least one organic acid.
(Aspect 15)
The sub-ingredient further comprises at least one cleaning agent and at least one zinc-containing compound or at least one anti-wearing agent, wherein the cleaning agent is an alkaline earth metal salt of at least one organic acid. The alkaline earth metal salt of the at least one organic acid contains the magnesium salt of the at least one organic acid, and the at least one anti-wearing agent is at least one derived from a secondary alcohol. The lubricating engine oil according to aspect 13, which comprises a zinc dialkyldithiophosphate compound.
(Aspect 16)
A method for preventing or reducing low-speed ligation in an engine lubricated with the lubricating oil by using the compounded engine oil as a lubricating oil, wherein the compounded engine oil is at least one kind in an amount of 70 to 85% by weight. It has a composition containing a lubricating oil base stock and at least one dispersant in an amount that provides 30 to 1500 ppm of boron in the compounded engine oil, wherein the at least one dispersant is at least one booxide. Containing a dispersant or a mixture of a boron-containing compound and a non-booxidant dispersant
25, compared to the low speed pre-ignition performance achieved by the engine using at least one booxide dispersant, or a lubricant that does not contain a mixture of boron-containing compounds and non-booxide dispersants. Low speed pre-ignition greater than 50% based on standardized slow pre-ignition (LSPI) numbers for 000 engine cycles, engine operation at 2000 rpm (RPM) and 18 bar net mean pressure (BMEP) Shows a reduction in
Method.

Claims (14)

A method of preventing or reducing low-speed regignation in an engine lubricated with the lubricating oil by using the compounding oil as a lubricating oil, wherein the compounding oil is a lubricating oil base stock as a main component and a subcomponent. It has a composition containing at least one zinc-containing compound that gives zinc of 884 ppm or less and at least one boron-containing dispersant as an accessory component, and the at least one boron-containing dispersant is at least one hobo. Contains oxidative dispersants, or mixtures of boron-containing compounds with non-booxide dispersants
For the at least one boron-containing dispersant , the boron / nitrogen ratio is 0.26 or less.
25, when compared to the low speed pre-ignition performance achieved by the engine using at least one booxide dispersant, or a lubricant that does not contain a mixture of boron-containing compounds and non-booxide dispersants. Low speed pre-ignition greater than 50% based on standardized slow pre-ignition (LSPI) numbers for 000 engine cycles, engine operation at 2000 rpm (RPM) and 18 bar net mean pressure (BMEP) Shows a reduction in
The engine is a supercharged gasoline engine .
The lubricating oil is a lubricating oil for a supercharged gasoline engine.
As an accessory component, at least one cleaning agent is further contained, the cleaning agent contains an alkaline earth metal salt of at least one organic acid, and the alkaline earth metal salt of at least one organic acid is at least. Contains a magnesium salt of one organic acid,
Method. The method of claim 1, wherein the at least one zinc-containing compound comprises at least one zinc dialkyldithiophosphate compound derived from a secondary alcohol. The lubricating oil base stock comprises a group I, group II, group III, group IV or group V base oil, and the group V base oil is 2 weights based on the total weight of the group V base oils. 1 or claim 1, wherein the ester-based oil contains an ester-based oil at a concentration of% to 20% by weight, the ester-based oil has a kinematic viscosity of 2 cSt to 8 cSt at 100 ° C., and the group III base oil contains a GTL-based oil. The method according to 2 . The boron-containing compound or a borated dispersant, borated succinimide, borated succinic acid esters, borated succinic acid ester amides are selected from the group consisting of borated Mannich bases, and mixtures thereof, of claim 1 to 3 The method according to any one item. Boron is provided in the lubricating oil by a mixture of an organic or inorganic boron-containing compound with a succinimide booxide, a succinimide booxide ester, a succinimide booxide ester amide, a Mannig base ester or a mixture thereof, and the succinimide booxide is provided in the lubricating oil. The method according to any one of claims 1 to 4 , wherein the method is monosuccinimide, bis-succinimide, or a mixture thereof. The ratio of total zinc from the zinc-containing compound and total alkaline earth metal from the cleaning agent in the lubricating oil added and divided by total boron from the boron-containing compound and booxide dispersant. The method according to any one of claims 2 to 5 , which is 9.2 to 45. The alkaline earth metal salts of organic acids, alkaline earth metal sulfonates, alkaline earth metal carboxylates, alkaline earth metal phenate, is selected from the group consisting of alkaline earth metal phosphates and mixtures thereof, according to claim 1 The method according to any one of Items ~ 6 . The cleaning agent
(I) At least one of magnesium sulfonate, magnesium phenate and magnesium salicylate and a mixture thereof, optionally at least one of calcium sulfonate, calcium phenate and calcium salicylate and a mixture thereof.
(Iii) At least one magnesium salt of an organic acid selected from magnesium sulfonate, magnesium carboxylate, magnesium phenate, magnesium phosphate and mixtures thereof, or (iii) a mixture of magnesium sulfonate, magnesium sulfonate and magnesium salicylate, magnesium. The method according to any one of claims 1 to 7 , which comprises a mixture of sulfonate and magnesium phenate, or a mixture of magnesium sulfonate and magnesium carboxylate. (I) Whether the magnesium and alkaline earth metals provided by the cleaning agent are present in the lubricating oil in an amount of 500 ppm to 5000 ppm.
(Ii) The total alkalinity (TBN) provided by the cleaning agent is in the range of 2 mg KOH / g to 17 mg KOH / g, as measured by ASTM D2896, or (iii) provided by the cleaning agent. The sulfated ash content to be produced is in the range of 0.4 to 1.7% by weight.
The method according to any one of claims 1 to 8 . Claims 2-9 , wherein the zinc-containing compound is selected from the group consisting of zinc carboxylate, zinc sulfonate, zinc acetate, zinc naphthenate, zinc alkenyl succinate, zinc acid phosphate salt, zinc phenate and zinc salicylate. The method according to any one of the above. The zinc dialkyldithiophosphate compound has the formula:
Zn [SP (S) (OR ¹ ) (OR ² )] ₂
[In the formula, R ¹ and R ² are independently primary or secondary C _{1 to} C ₈ alkyl groups (where at least one of R ¹ and R ² is secondary C _{1 to} C). ₈ alkyl group)]
The method according to any one of claims 2 to 10 , represented by. A lubricating engine oil having a composition containing a lubricating oil base stock as a main component, at least one zinc-containing compound that imparts zinc of 884 ppm or less as a sub component, and at least one boron-containing dispersant as a sub component. , The at least one boron-containing dispersant comprises at least one booxide dispersant, or a mixture of a boron-containing compound and a non-boration dispersant.
For the at least one boron-containing dispersant , the boron / nitrogen ratio is 0.26 or less.
25,000 compared to the low speed pre-ignition performance achieved by an engine using at least one booxide dispersant, or a lubricant that does not contain a mixture of boron-containing compounds and non-booxide dispersants. For low speed pre-ignition greater than 50% based on standardized low speed pre-ignition (LSPI) numbers for engine cycles, engine operation at 2000 rpm (RPM) and net mean effective pressure (BMEP) of 18 bar. Shows reduction,
The engine is a supercharged gasoline engine .
The lubricating oil is a lubricating oil for a supercharged gasoline engine.
As an accessory component, at least one cleaning agent is further contained, the cleaning agent contains an alkaline earth metal salt of at least one organic acid, and the alkaline earth metal salt of at least one organic acid is at least. Contains a magnesium salt of one organic acid,
Lubricating engine oil for supercharged gasoline engines . The lubricating engine oil according to claim 12 , wherein the at least one zinc-containing compound contains at least one zinc dialkyldithiophosphate compound derived from a secondary alcohol. A method of preventing or reducing low-speed ligation in an engine lubricated with the lubricating oil by using the compounded engine oil as a lubricating oil, wherein the compounded engine oil is at least one of 70 to 85% by weight. It contains a lubricating oil base stock, at least one zinc-containing compound that provides 884 ppm or less of zinc as an accessory component, and at least one boron-containing dispersant in an amount that provides 30 to 1500 ppm of boron in the compounded engine oil. The composition of the at least one boron-containing dispersant comprises at least one booxide dispersant, or a mixture of a boron-containing compound and a non-boration dispersant.
For the at least one boron-containing dispersant , the boron / nitrogen ratio is 0.26 or less.
25, when compared to the low speed pre-ignition performance achieved by the engine using at least one booxide dispersant, or a lubricant that does not contain a mixture of boron-containing compounds and non-booxide dispersants. Low speed pre-ignition greater than 50% based on standardized slow pre-ignition (LSPI) numbers for 000 engine cycles, engine operation at 2000 rpm (RPM) and 18 bar net mean pressure (BMEP) Shows a reduction in
The engine is a supercharged gasoline engine .
The lubricating oil is a lubricating oil for a supercharged gasoline engine.
As an accessory component, at least one cleaning agent is further contained, the cleaning agent contains an alkaline earth metal salt of at least one organic acid, and the alkaline earth metal salt of at least one organic acid is at least. Contains a magnesium salt of one organic acid,
Method.

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