JP6639482B2 - How to prevent or reduce slow pre-ignition - Google Patents

Description

(Field)
The present disclosure relates to at least one zinc-containing compound, or at least one antiwear agent, preferably at least one zinc derived at least in part from a secondary alcohol, present in a specific amount in the formulated oil. A method for preventing or reducing low speed pre-ignition (LSPI) in a lubricated oil-lubricated engine by using a compounded oil having a dialkyldithiophosphate compound as a lubricating oil. The lubricating oils of the present disclosure are useful as passenger vehicle engine oil (PVEO) products.

(background)
Preignition in a flame propagation (or "spark ignition") engine refers to the phenomenon in which the air / fuel mixture in a cylinder ignites before the spark plug ignites. Preignition is initiated by a non-spark ignition source, such as a hot section of the combustion chamber, a spark plug that has been overheated to apply, or carbonaceous deposits in the combustion chamber that have been heated to incandescence by previous engine combustion phenomena. Is 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 causes of preignition are not fully understood and, in practice, hot deposits in the combustion chamber, high concentrations of lubricant vapors entering the PCV system, oil leaching from turbocharger compressor seals, or It may be due to several phenomena, such as auto-ignition of oil and / or fuel droplets during the compression stroke.

  Preignition can cause the combustion chamber temperature to increase sharply, leading to poor engine operation or poor performance. Conventional methods of eliminating preignition include, for example, selection of a suitable spark plug, adjustment of a suitable fuel / air mixture, and periodic cleaning of the combustion chamber. Although hardware solutions such as cooled exhaust gas recirculation (EGR) are known, they are costly to implement and can lead to packaging problems.

  Low speed preignition (LSPI) is a type of abnormal combustion that affects engines operating at high net mean effective pressure (BMEP) and low engine speed (RPM). Turbocharged engines that have been reduced in size and slowed down 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 toward further size reductions, lower speeds and increased turbocharging to increase vehicle fuel economy and reduce carbon dioxide emissions.

  Further development of slowed turbocharged gasoline engines is hampered by LSPI. A solution to this problem, or mitigating its occurrence, would remove barriers to Original Equipment Manufacturer (OEM) technology and efficiency improvements. The lubricant formulation solution will allow product differentiation with respect to LSPI.

  The problem of preignition can or can be solved by optimizing internal engine components and by using new component technologies such as electronic control, but is 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 would be particularly useful in internal combustion engines and would prevent or minimize pre-ignition problems when used in internal combustion engines. It is desirable that the lubricating oil composition be useful in spark-ignition engines with lubricating oil-blended 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.

(Abstract)
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 preignition problems when used in internal combustion engines. The lubricating oil compositions of the present disclosure are useful in spark ignition engines with lubricating oil blended gasoline fuels. The chemistry of the lubricant formulations of the present disclosure can be used to prevent or control the detrimental effects of LSPI in engines that are already designed or commercially available, as well as future engine technologies. it can. The chemistry of the lubricant formulations of the present disclosure removes barriers to OEM technology and efficiency improvements, and allows for the further development of slowed turbocharged gasoline engines currently hampered by LSPI. The lubricant formulation solution provided by the present disclosure for preventing or reducing LSPI allows for product differentiation with respect to LSPI.

  The present disclosure also relates, in part, to a method of preventing or reducing low speed pre-ignition in an engine lubricated with a lubricating oil by using the formulated oil as a lubricating oil. The blended oil comprises a lubricating base stock as a major component (or major component) and at least one zinc-containing compound or at least one antiwear agent as a minor component (or minor component). )). The at least one antiwear agent comprises at least one zinc dialkyl dithiophosphate compound derived at least in part from a secondary alcohol. The engine has 25,000 engine cycles, 2000 revolutions per minute when compared to the low speed preignition performance achieved with the engine using at least one zinc-containing compound or a lubricant that does not contain antiwear agents. per minute (RPM) for engine operation and 18 bar net mean effective pressure (BMEP) based on standardized low speed pre-ignition (LSPI) numbers (or counts). Shows a reduction in slow pre-ignition greater than about 20%.

  In addition, the present disclosure provides for the use of the above blended oil, in which the minor component further comprises at least one boron-containing compound, as a lubricating oil, thereby reducing the low speed in an engine lubricated with the lubricating oil. A method for preventing or reducing preignition. The boron-containing compound comprises at least one borated dispersant and / or a mixture of a boron-containing compound and a non-borated dispersant.

  Further, the present disclosure provides a method for using a lubricating oil as described above, in which the auxiliary component further comprises at least one boron-containing compound and at least one detergent (or detergent). It further relates to a method of preventing or reducing low speed pre-ignition in a lubricated engine. The boron-containing compound comprises at least one borated dispersant or a mixture of a boron-containing compound and a non-borated dispersant. The detergent comprises at least one alkaline earth metal salt of an organic acid, and the at least one alkaline earth metal salt of an organic acid comprises at least one magnesium salt of an organic acid.

  The present disclosure also provides, in part, lubricating compositions having a lubricating oil base as a major component and at least one zinc-containing compound or at least one antiwear agent as a minor component. Related to lubricating engine oil. The at least one antiwear agent comprises at least one zinc dialkyldithiophosphate compound at least partially derived from a secondary alcohol. The engine has 25,000 engine cycles, 2000 revolutions per minute (RPM) when compared to the low speed pre-ignition performance achieved with the engine using at least one zinc-containing compound or lubricating oil without antiwear agents. 3) shows a reduction in slow pre-ignition of more than about 20% for engine operation and a net mean effective pressure (BMEP) of 18 bar, based on standardized low pre-ignition (LSPI) numbers.

  Further, the present disclosure relates in part to the above lubricating engine oil, wherein the minor component further comprises at least one boron-containing compound. The boron-containing compound comprises at least one borated dispersant and / or a mixture of a boron-containing compound and a non-borated dispersant.

  Still further, the disclosure relates in part to the above lubricating engine oil, wherein the minor components further comprise at least one boron-containing compound and at least one detergent. The boron-containing compound comprises at least one borated dispersant or a mixture of a boron-containing compound and a non-borated dispersant. The detergent comprises at least one alkaline earth metal salt of an organic acid, and the at least one alkaline earth metal salt of an organic acid comprises at least one magnesium salt of an organic acid.

  Surprisingly, in accordance with the present disclosure, at least one zinc-containing material present in a lubricating oil in a particular amount (eg, from about 0.1% to about 5.0% by weight based on the total weight of the lubricating oil). Lubricating with a lubricating oil by using as a lubricating oil a compound or a compounded oil comprising at least one antiwear agent, preferably at least one zinc dialkyldithiophosphate compound derived at least in part from a secondary alcohol It has been found that prevention or reduction of LSPI can be achieved in a given engine. In particular, with respect to lubricating oil formulations containing at least one zinc-containing compound or at least one anti-wear agent, surprisingly, the engine may comprise at least one zinc-containing compound or an auxiliary component other than the anti-wear agent. 25,000 engine cycles when compared to low speed pre-ignition performance achieved in engines using lubricating oils in amounts other than the amount of at least one zinc-containing compound or antiwear agent in the lubricating oil. , For engine operation at 2000 revolutions per minute (RPM) and a net mean effective pressure (BMEP) of 18 bar, based on standardized low speed preignition (LSPI) numbers, a reduction in low speed preignition of greater than about 20%. It was found to show. In addition, surprisingly, according to the present disclosure, a lubricating oil was lubricated by using a compounded oil having a specific base stock (eg, a gas-liquid base stock or an ester base stock) as the lubricating oil. It has been found that LSPI reduction can be achieved in the engine.

  The present disclosure also provides a method of preventing or reducing low speed pre-ignition in an engine lubricated with this lubricant by using a formulated engine oil as a lubricant, wherein the blended engine oil comprises: A composition comprising 70-85% by weight of a lubricating oil basestock and at least one zinc-containing compound or at least one antiwear agent in an amount providing from 400 ppm to about 2000 ppm phosphorus to the formulated engine oil. Wherein the at least one antiwear agent comprises at least one zinc dialkyl dithiophosphate compound at least partially derived from a secondary alcohol, and wherein the engine comprises at least one zinc-containing compound or at least one Low speed pre-ignition achieved in the engine using lubricants without antiwear agents Compared to Noh, based on a standardized low speed preignition (LSPI) number for 25,000 engine cycles, engine operation at 2000 revolutions per minute (RPM) and a net mean effective pressure (BMEP) of 18 bar A method that exhibits a reduction in slow preignition of greater than 50%.

  Other objects and advantages of the present disclosure will become apparent from the following detailed description.

  All concentrations shown in the figures are given on a "as delivered" basis.

1 shows the formulation details in weight percent based on the total weight percent of the formulation and the test results of the various lubricant formulations for the various lubricant formulations detailed in Example A. 3 shows formulation details of various lubricating oil formulations detailed in Example B in weight percent based on the total weight percent of the formulation. 3 shows the test results of various lubricating oil formulations shown in FIG. 2 and detailed in Example B. 9 shows formulation details of various lubricating oil formulations detailed in Example C in weight percent based on the total weight percent of the formulation. 5 shows the test results of various lubricating oil formulations shown in FIG. 4, detailed in Example C. 7 shows formulation details in weight percent, based on the total weight percent of the formulation, of the formulation embodiment of the present disclosure detailed in Example D. 7 shows the expected test results for the various lubricating oil formulations of FIG. 6, detailed in Example D. 9 shows formulation details in weight percent, based on the total weight percent of the formulation, of the formulation embodiments of the present disclosure detailed in Example E. 9 shows the expected test results for the various lubricating oil formulations of FIG. 8, as detailed in Example E. 9 shows formulation details of various lubricating oil formulations detailed in Example F in weight percent based on the total weight percent of the formulation. 11 shows the expected test results for the various lubricating oil formulations of FIG. 10 as detailed in Example F. 9 shows the results of the engine performance mapping detailed in Example A.

(Detailed description)
All numerical values within the detailed description and claims of this specification are modified by "about" or "approximately" to the values indicated, and experimental errors and variability that would be expected by one of ordinary skill in the art. Be considered.

  Here, at least one zinc-containing compound, or at least one zinc-containing compound, present in the lubricating oil in a specific amount (eg, from about 0.1% to about 5.0% by weight based on the total weight of the lubricating oil). Anti-wear agents, preferably a blended oil comprising at least one zinc dialkyldithiophosphate compound derived at least in part from a secondary alcohol, by means of a lubricating oil-lubricated engine. It has been found that prevention or reduction can be achieved. In addition, it has been found that by using a blended oil having a particular basestock as a lubricating oil, a reduction in LSPI can be achieved in a lubricated oil-lubricated engine. The compounding oil preferably has a composition comprising as a major component a lubricating oil basestock and as a minor component at least one zinc-containing compound or at least one antiwear agent. The at least one antiwear agent comprises at least one zinc dialkyldithiophosphate compound at least partially derived from a secondary alcohol. The lubricating oil of the present disclosure is particularly advantageous as a PVEO product.

  The lubricating oils of the present disclosure are particularly useful in internal combustion engines and will prevent or minimize pre-ignition problems when used in internal combustion engines. The lubricating oil compositions of the present disclosure are useful in spark ignition engines with lubricating oil blended gasoline fuels.

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

Lubricating oil base stocks A wide range of lubricant base oils is known in the art. The lubricant base oils useful in this disclosure are both natural and synthetic oils, and unconventional oils (or mixtures thereof) can also be used in an unrefined, refined or rerefined state ( The latter is also known as recycled or reprocessed oil). Unrefined oils are those obtained directly from a natural or synthetic source and are used without further purification. These include shale oil obtained directly from the carbonization operation, petroleum oil obtained directly from primary distillation, and ester oil obtained directly from the ester formation process. Refined oils are similar to the oils discussed for the 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 a previously used oil as the feedstock.

  Groups I, II, III, IV and V are a broad base oil stock classification developed and defined by the American Petroleum Institute (API Publication 1509; www.API.org) to create guidelines for lubricant base oils. It is. Group I basestocks have a viscosity index of about 80-120 and contain 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 greater than about 120 and contain less than about 0.03% sulfur and greater than about 90% saturation. Group IV includes polyalphaolefins (PAO). Group V basestocks include basestocks not included in Groups I-IV. The following table summarizes the characteristics of each of these five groups.

  Natural oils include animal oils, vegetable oils (eg, castor oil and lard oil), and mineral oil. Animal and vegetable oils having favorable thermo-oxidative stability can be used. Of the natural oils, mineral oils are preferred. Mineral oils vary greatly depending on their crude origin, for example, whether they are paraffinic, naphthenic or mixed paraffin-naphthenic. Oils derived from coal or shale are also useful. Natural oils are extracted by the methods used for their production and refining, e.g., by their distillation range, and when they are straight run or cracked, hydrorefined, or solvent extracted. It depends on whether it is or not.

  Group II and / or Group III hydrotreated 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 copolymer, ethylene-olefin copolymer and ethylene-alpha olefin copolymer). Polyalphaolefin (PAO) oil basestocks 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. 4,956,122, 4,827,064 and 4,827,073.

The number average molecular weight of PAOs of known materials and generally available on a commercial scale from sources such as ExxonMobil Chemical Company, Chevron Phillips Chemical Company, BP, and others typically ranges from 250 to 3,000. However, PAOs may be manufactured with viscosities up to about 150 cSt (100 ° C.). PAO is typically composed of a relatively low molecular weight hydrogenated polymers or oligomers of alpha-olefins, these include, but are not limited to, include C 2 _~ about C ₃₂ alpha-olefins include 1-hexene, 1- octene, 1-decene, 1-dodecene, _{C 6} ~ about _{C 16} alpha olefins such as 1-tetradecene are preferred. Preferred polyalphaolefins are poly-1-hexene, poly-1-octene, poly-1-decene and poly-1-dodecene, 1-tetradecene, and mixtures and mixed olefin-derived polyolefins. However, dimers of more higher olefins in the range of C ₁₄ -C _18, may be used to provide low viscosity basestocks sufficiently low volatility. Depending on the viscosity grade and the starting oligomer, the PAO may be predominantly trimers and tetramers of the starting olefin with a modest amount of higher oligomers having a viscosity range of 1.5 to 12 cSt. PAO fluids for certain applications may include 3.0 cSt, 3.4 cSt and / or 3.6 cSt and combinations thereof. If desired, a bimodal mixture of PAO fluids having a viscosity range of 1.5 to 150 cSt may be used.

PAO fluids include, for example, aluminum trichloride, boron trifluoride, or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as acetates or ethyl propionate, and the like. It may be conveniently prepared by the polymerization of an alpha olefin in the presence of a polymerization catalyst such as a Del-Crafts catalyst. For example, the methods disclosed by US Pat. Nos. 4,149,178 or 3,382,291 may be conveniently used herein. Other descriptions of PAO synthesis are described in U.S. Patent Nos. 3,742,082, 3,769,363, 3,876,720, and 4,239,930. No. 4,367,352, No. 4,413,156, No. 4,434,408, No. 4,910,355, No. 4,956,122 and 5,068,487. Dimers of C ₁₄ -C ₁₈ olefins are described in U.S. Patent No. 4,218,330.

  Other useful lubricating oil basestocks include hydroisomerized waxy stocks (eg, waxy stocks such as gas oil, slack wax, fuel hydrocracker residue), hydroisomerized Fischer-Tropsch wax, gas -Liquid (GTL) base stocks and base oils, and isomerized wax hydroisomerized 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 highly paraffinic hydrocarbon with very low sulfur content. Hydrotreating processes used for the production of such basestocks include amorphous hydrocracking / hydroisomerization catalysts, such as one of special lubricating oil hydrocracking (LHDC) catalysts, or crystalline hydrogen A pyrolysis / hydroisomerization catalyst, preferably a zeolite-based catalyst, may be used. For example, one useful catalyst is ZSM-48, described in U.S. Pat. No. 5,075,269, the disclosure of which is incorporated herein by reference in its entirety. Methods for producing hydrocracking / hydroisomerized distillate and hydrocracking / hydroisomerized wax are described, for example, in US Pat. Nos. 2,817,693, 4,975,177, and Nos. 4,921,594 and 4,897,178, and British Patent Nos. 1,429,494, 1,350,257 and 1,440, No. 230 and No. 1,390,359. Each of the above patents is incorporated herein by reference in its entirety. Particularly preferred methods are described in EP-A-646,546 and EP-A-645,547, which are incorporated herein by reference. Methods of using Fischer-Tropsch wax feeds are described in U.S. Patent Nos. 4,594,172 and 4,943,672, the disclosure of which is incorporated herein by reference in its entirety. You.

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

Hydrocarbyl aromatic is any hydrocarbyl molecule that can be used as a base oil or base oil component and that contains at least about 5% of its weight derived from an aromatic moiety, such as a benzenoid moiety or a naphtenoid moiety or a derivative thereof. It is also possible that These hydrocarbyl aromatics include alkyl benzene, alkyl naphthalene, alkyl diphenyl oxide, alkyl naphthol, alkyl diphenyl sulfide, alkylated bisphenol A, alkylated thiodiphenol, and the like. Aromatics can be monoalkylated, dialkylated, polyalkylated, and the like. Aromatics can be monofunctionalized or polyfunctionalized. The hydrocarbyl group can also be comprised of a mixture of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl and other related hydrocarbyl groups. Hydrocarbyl groups, but may range from about _{C 6} ~ about _{C 60,} is often preferred range of from about _{C 8} ~ 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 a sulfur, oxygen and / or nitrogen containing substituent. Aromatic groups can also be derived from natural (petroleum) sources, provided that at least about 5% of the molecules are composed of aromatic moieties of the type described above. For the hydrocarbyl aromatic component, a viscosity at 100 ° C. of about 3 cSt to about 50 cSt is preferred, and a viscosity of about 3.4 cSt to about 20 cSt is more preferred. In one embodiment, an alkyl naphthalene in which the alkyl group is mainly composed of 1-hexadecene is used. It is also possible that other alkylates of aromatics are used advantageously. For example, naphthalene or methylnaphthalene may be alkylated with olefins, such as octene, decene, dodecene, tetradecene or higher olefins, mixtures of similar olefins, and the like. Useful concentrations of the hydrocarbyl aromatic 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 made by the well-known Friedel-Crafts alkylation method of aromatic compounds. Friedel-Crafts and Related Reactions, Olah, G .; A. (Ed.), Inter-science Publishers, New York, 1963. For example, aromatic compounds such as benzene or naphthalene are alkylated with olefins, alkyl halides or alcohols in the presence of a Friedel-Crafts catalyst. Friedel-Crafts and Related Reactions, Vol. 2, part 1, chapters 14, 17, and 18, Olah, G .; A. (Ed.), Inter-science Publishers, New York, 1964. Many homogeneous or heterogeneous solid catalysts are known to those skilled in the art. The choice of catalyst depends on the reactivity of the starting materials and the required quality of the product. For example, a strong acid such as AlCl ₃ , BF ₃ or HF may be used. In some cases, a milder catalyst such as FeCl ₃ or SnCl ₄ is preferred. Newer alkylation techniques use zeolites or solid superacids.

  Esters constitute a useful base stock. Additional dissolution and seal compatibility features can be ensured by the use of esters such as esters of dibasic acids with monoalkanols and polyol esters of monocarboxylic acids. Esters of the former type include, for example, phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid And esters of dicarboxylic acids such as alkylmalonic acid and alkenylmalonic acid with various alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol and 2-ethylhexyl alcohol. Specific examples of these types of esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, Didecyl phthalate, diicosyl sebacate and the like are included.

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). , Trimethylolpropane, pentaerythritol and dipentaerythritol, etc.) with alkanoic acids containing at least about 4 carbon atoms, preferably caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, eicosan saturated linear fatty acids containing acid and behenic acid, or corresponding branched chain fatty acids, or unsaturated fatty acids such as oleic acid or by reaction with C ₅ -C ₃₀ acids such as mixtures of any of these materials, It is obtained.

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

  Preferred synthetic esters useful in the present disclosure have a kinematic viscosity 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, even more preferably about 2 cSt to about 8 cSt. Having. Group V base oils useful in the present disclosure preferably comprise the ester at a concentration of about 2% to about 20%, preferably about 5% to about 15%.

  Also useful are esters derived from renewable materials such as coconut, coconut, rapeseed, soybean, sunflower and the like. These esters may be monoesters, diesters, polyol esters, complex esters or mixtures thereof. These esters are widely available commercially, for example, Mobil P-51 ester from 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 of lubricating viscosity include non-conventional or unconventional basestocks, preferably treated or synthesized with a catalyst to provide high performance lubricating 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 or waxy feeds, mineral and / or non-mineral oils Waxy feedstocks, such as slack wax, natural wax, and waxy stocks, such as gas oil, waxy fuel hydrocracker residue, waxy raffinate, hydrocracked products, pyrolysis products or other One of a mineral, mineral oil, or non-petroleum derived waxy material, for example, a waxy material received from coal liquefaction or an isomerized / isodewaxed basestock derived from shale oil, and mixtures of such basestocks More than species.

  GTL materials include gaseous carbon-containing compounds, hydrogen-containing compounds and hydrogen-containing compounds as feedstocks such as hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane, butylene and butyne. And / or materials derived from one or more synthesis, combination, transformation, rearrangement, and / or degradation / deconstruction processes from the element. GTL basestocks and / or base oils are generally hydrocarbon, for example, waxy synthetic hydrocarbons derived from simpler gaseous carbon-containing compounds, hydrogen-containing compounds and / or other components as feedstocks themselves. GTL material with lubricating viscosity derived from GTL basestocks and / or base oils are oils that boil in the lubricating oil boiling range and are (1) separated / fractionated from the synthesized GTL material, eg, by distillation, after which the pour point decreases. Undergoing a final waxing step that includes one or both of a catalytic dewaxing process or a solvent dewaxing process to produce a lubricating oil with reduced / pour point; (2) for example, hydrodewaxing or hydroisomerization (3) a hydrodewaxed or hydroisomerized catalyst and / or a solvent dewaxed Fischer-Tropsch, comprising a catalyst and / or a solvent dewaxed synthetic wax or a waxy hydrocarbon. (FT) materials (i.e., hydrocarbons, waxy hydrocarbons, waxes and possible similar oxygenates); Is a hydrodewaxed or hydroisomerized / subsequent catalyst and / or solvent dewaxed FT waxy hydrocarbon or a hydrodewaxed or hydroisomerized / subsequent catalyst (or solvent) Includes waxed FT wax, or mixtures thereof.

GTL basestocks and / or base oils derived from GTL materials, in particular, hydrodewaxed or hydroisomerized / subsequent catalyst and / or solvent dewaxed waxes or waxy feeds, preferably F- T-material derived basestocks and / or base oils are typically characterized by having a kinematic viscosity at 100 ° C. of about 2 mm ² / sec to about 50 mm ² / sec (ASTM D445). They are further characterized by typically 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 from about 80 to about 140 or more (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 in a wide viscosity range recovered in the manufacturing process, two fractions of such fractions One or more mixtures as well as mixtures of one or more of the low viscosity fractions with one or more of the high viscosity fractions to produce a blend exhibiting the target kinematic viscosity. You.

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

  In addition, GTL basestocks and / or base oils are typically high paraffins (> 90% saturation) and contain a mixture of monocyclic and polycyclic paraffins in combination with acyclic isoparaffins. It may be. The ratio of naphthenic (ie, cycloparaffin) content in such combinations will vary with the catalyst and temperature used. In addition, GTL basestocks and / or base oils and hydrodewaxed or hydroisomerized / catalyst (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 each of these elements, more typically less than about 5 ppm. The sulfur and nitrogen content of GTL basestocks 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 formulating low sulfur, sulfated ash and phosphorus (low SAP) products.

  Base oils for use in compounded lubricating oils useful in the present disclosure are based on 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 API Group II, Group III, Group IV and Group V oils and mixtures thereof, more preferably Group III to Group V base oils and mixtures thereof One of the various oils you want. When used in combination with the additive components disclosed in the present disclosure, the base stock has excellent LSPI performance, SAE 0W-8, SAE 0W-12, SAE 0W-16, SAE 0W-20, SAE 0W. -30, SAE 0W-40, SAE 5W-12, SAE 5W-16, SAE 5W-20, SAE 5W-30 and SAE 10W-40 products. These basestocks, when used in combination with the additive components disclosed in this disclosure, have excellent LSPI performance, SAE 0W-8, SAE 0W-12, SAE 0W-16, SAE 0W-20, SAE 0W-20. It is particularly effective when blending 0W-30, SAE 0W-40 and SAE 5W-30 oils.

The base oil constitutes a major component of the engine oil lubricating oil composition of the present disclosure, and typically comprises 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 ranging from about 85 to about 95% by weight. The base oil may be selected from any of the synthetic or natural oils typically used as crankcase 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) Having a kinematic viscosity of If desired, mixtures of synthetic and natural base oils may be used. If desired, mixtures of groups III, IV and V may preferably be used.

Anti-wear agent Metal alkylthiophosphate (or metal alkylthiophosphate), particularly metal dialkyldithiophosphate (or metal dialkyldithiophosphate) in which the metal component is zinc, or zinc dialkyldithiophosphate (or zinc dialkyldithiophosphate) (zinc dialkyldithiophosphate: ZDDP) Is a useful component of the lubricating oil of the present disclosure. ZDDP can be derived from primary alcohols, secondary alcohols, or mixtures thereof. Preferred ZDDP compounds generally have the formula:
Zn [SP (S) (OR ¹ ) (OR ² )] ₂
Wherein R ¹ and R ² are independently primary and / or secondary C ₁ -C ₈ alkyl groups.
Represented by Mixtures of primary alcohol (1 °) derived ZDDP and secondary alcohol (2 °) derived ZDDP can be used. The R ¹ and R ² substituents can independently be a C ₁ -C ₁₈ alkyl group, preferably a C ₂ -C ₁₂ alkyl group. Preferably, ^{R 1} and ^{R 2} are independently the a primary and / or secondary _C 1 -C ₈ alkyl group (provided that at least one of ^{R 1} and ^{R 2} is secondary _C 1 ~ A C ₈ alkyl group). Mixtures of primary and secondary alcohol-derived ZDDPs where R ¹ and R ² are C ₁ -C ₈ alkyl groups can be used. These alkyl groups may be straight-chain or branched. Alkylaryl groups may be used.

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

Preferably, primary or secondary _C 1 -C ₈ alkyl group zinc dialkyldithiophosphate compound, some 2-propanol (C3), 1-butanol (n-C4), 1-isobutanol (1 -I-C4), 2-butanol (2-C4), 1-pentanol (primary C-5), 3-methyl-1-butanol (primary C-5), 2-pentanol (C5 ), 3-pentanol (C5), 3-methyl-2-butanol (C5), 1-hexanol (primary C6), 4-methyl-1-pentanol (primary C6), 4-methyl- It is derived from an alcohol selected from the group consisting of 2- (C6) and 2-ethyl-1-hexanol (primary C8) and mixtures thereof. In some cases, ZDDPs derived from alcohols having an average carbon number of 5 or less are desirable. In some cases, ZDDPs derived from alcohols having an average carbon number greater than 5 are desirable. Table 1 shows the alcohol mixtures used to produce ZDDP that can be conveniently used in the present disclosure.

The amount of zinc dialkyldithiophosphate compound having 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 dialkyldithiophosphate compound Compare the low preignition performance achieved in engines using lubricating oils containing minor components other than the specific zinc dialkyldithiophosphate compound in amounts other than the specific zinc dialkyldithiophosphate compound in the lubricating oil. Thus, the engine is sufficient to exhibit reduced slow pre-ignition.

  Generally, ZDDP is about 0.4% to about 1.2%, preferably about 0.5% to about 1.0%, more preferably about 0% to about 1.2% by weight, based on the total weight of the lubricating oil. While amounts of from 0.6% to about 0.8% by weight can be used, higher or lower amounts can often be used to advantage. Preferably, the ZDDP is a primary, secondary or mixed ZDDP, and is present in an amount of about 0.6 to 1.0 weight percent of the total weight of the lubricating oil.

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

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

Preferably, zinc dialkyl dithiophosphate compound is derived from C ₃ -C ₈ secondary alcohol or mixtures thereof. Likewise, preferably, derived zinc dialkyldithiophosphate compound is from C ₁ -C ₈ mixtures of primary alcohols and C ₁ -C ₈ secondary alcohol.

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

  The ratio of zinc to phosphorus in the lubricating oil ranges from about 1.0 to about 2.0, preferably from about 1.1 to about 1.9.

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

  Exemplary zinc-containing compounds useful in the present disclosure include, for example, zinc carboxylates, zinc sulfonates, zinc acetates, zinc napthenates, zinc alkenyl succinates Nitrate (zinc alkenyl succinates), zinc acid phosphate salts (zinc acid phosphate salts), zinc phenates (zinc phenates), zinc salicylates (zinc salicylates) and the like are included.

  According to the present disclosure, an engine may include a lubricating oil containing at least one zinc-containing compound or at least one accessory component other than an antiwear agent in the lubricating oil with at least one zinc-containing compound or at least one zinc-containing compound. 25,000 engine cycles, engine operation at 2000 revolutions per minute (rpm) and a net average of 18 bar compared to the low speed pre-ignition performance achieved with the engine using amounts other than the amount of antiwear agent. Based on the number of low speed pre-ignitions (LSPI) normalized to effective pressure (BMEP), a reduction in low speed pre-ignition of greater than about 20%, preferably greater than about 25%, more preferably greater than about 30% Show. A similar or even greater reduction in slow preignition may be at least one zinc containing compound or at least one antiwear agent, at least one boron containing compound described herein, and / or at least one Can be achieved using a mixture with a detergent.

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. Zinc dialkyl dithiophosphate compounds having R ¹ and R ² primary or secondary alkyl groups, derived from tanol (n-C5), are present in an amount of about 0.1% to about 0.1% by weight, based on the total weight of the lubricating oil. 5.0% by weight, preferably from about 0.1% to about 1.2% by weight, more preferably from about 0.2% to about 0.8% by weight.

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

Dispersants During engine operation, oil-insoluble oxidation by-products form. Dispersants help keep these by-products in solution, thus reducing their deposition on metal surfaces. The dispersant used in the lubricating oil formulation may be essentially ashless or ash forming. Preferably, the dispersant is ashless. So-called ashless dispersants are organic materials that do not or only slightly form ash on combustion. For example, non-metal-containing or borated metal-free dispersants may be ashless. In contrast, the above metal-containing detergents form ash on combustion.

  In the present disclosure, at least one boron-containing compound is useful. The boron-containing compound comprises at least one borated dispersant or a mixture of a boron-containing compound and a non-borated dispersant. Effective ranges for boron in formulations from borated dispersants or other boron-containing additives are 30 ppm to 1500 ppm, or a more preferred range of 60 ppm to 1000 ppm, or a 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, and borated Mannich base. base) and mixtures thereof.

  Non-borated dispersants include, for example, hydrocarbyl succinic anhydride-derived succinimides or succinates with a coupling agent comprising a boron-containing compound.

  Preferably, the boron is provided to the lubricating oil by a mixture of an organic or inorganic boron-containing compound and borated succinimide, borated succinate, borated succinamide, Mannich base ester, or mixtures thereof. The borated succinimide is preferably monosuccinimide, bis-succinimide or a mixture thereof. Useful boron-containing compounds include borated hydrocarbyl succinimides, borated hydrocarbyl succinates, borated hydrocarbyl substituted Mannich bases, including those derived with respect to hydrocarbyl sources having a number average molecular weight (Mn) of 50-5000 daltons, Borated alcohol, borated alkoxylated alcohol, borated hydrocarbyl diol, borated hydrocarbyl amine, borated hydrocarbyl diamine, borated hydrocarbyl triamine, borated alkoxylated hydrocarbyl amine, borated alkoxylated hydrocarbyl amide, borated hydrocarbyl containing hydroxyl ester , Borated hydrocarbyl-substituted oxazolines, borated hydrocarbyl-substituted imidazolones and the like Compounds are included. Borates of -N-H and / or -OH derived moieties can also be used. These borates can be inorganic or organic partially derived borates. Borates can be prepared using boric acid, borated alcohols and the like. These borates, if necessary, can provide unexpected and surprising improvements in LSPI, such as 60-1200 ppm boron, 60-240 ppm boron, 240-1200 ppm boron, 240-500 ppm boron in engine oil formulations. , Or at a concentration that provides between 60 and 120 ppm of boron.

  The ratio of the total zinc from the zinc-containing compound and antiwear agent in the lubricating oil plus the total alkaline earth metal from the detergent and divided by the total boron from the boron-containing compound and the borated dispersant is , About 9.2-45, preferably 11-15.

  Suitable dispersants typically contain a polar group attached to a relatively high molecular weight hydrocarbon chain. The polar group typically contains at least one element of nitrogen, oxygen or phosphorus. Typical hydrocarbon chains contain 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, sulfurized phenates, salicylates, naphthenates, stearates, carbamates, thiocarbamates, phosphorus derivatives. A particularly useful class of dispersants are typically the long chain hydrocarbyl-substituted succinic compounds, typically alkyl succinic acid derivatives prepared by the reaction of hydrocarbyl-substituted succinic anhydrides with polyhydroxy or poly-netted compounds. The long-chain hydrocarbyl groups that make up the lipophilic portion of the molecule that confer solubility in oil are usually polyisobutylene groups. Many examples of this type of dispersant are well known commercially and in the literature. Representative U.S. Patents describing such dispersants are U.S. Patent Nos. 3,172,892, 3,2145,707, 3,219,666; Nos. 3,316,177, 3,341,542, 3,444,170, 3,454,607, and 3,541,012 No. 3,630,904, No. 3,632,511, No. 3,787,374 and No. 4,234,435. Other types of dispersants are disclosed in U.S. Pat. Nos. 3,036,003, 3,200,107, 3,254,025, and 3,275,554. Specification, 3,438,757, 3,454,555, 3,565,804, 3,413,347, and 3 , 697,574, 3,725,277, 3,725,480, 3,726,882, and 4,454,059. No. 3,329,658, No. 3,449,250, No. 3,519,565, No. 3,666,730, No. 3, 687,849, 3,702,300, 4,100,082, It is described in US Specification No. 5,705,458. Further descriptions of dispersants can be found, for example, in EP-A-4717101, referenced for this purpose.

  Hydrocarbyl-substituted succinic acids and hydrocarbyl-substituted succinic anhydride derivatives are useful dispersants. In particular, succinimides, succinates or succinate amides prepared by reacting a hydrocarbon-substituted succinic compound preferably having at least 50 carbon atoms during the hydrocarbon-substitution phase with at least one equivalent of an alkyleneamine are especially While useful, in some cases it can be useful to have a hydrocarbon substituent having from 20 to 50 carbon atoms.

  Succinimide is formed by the condensation reaction of a 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, heptaethyleneoctaamine, etc.). Polyethylene amines containing tetraethylene pentaamine (TEPA) are often preferred. High molecular weight polyethyleneamine residues comprising hexaethyleneheptamine and heptaethyleneoctamine can also be used. The ratio of hydrocarbyl substituted succinic anhydride polyethyleneamine can vary from about 1: 1 to about 5: 1. Representative examples are described in U.S. Patent Nos. 087,936, 3,172,892, 3,219,666, 3,272,746, Nos. 3,322,670 and 3,652,616, 3,948,800, and Canadian Patent 1,094,044.

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

  Succinic amides are formed by the condensation reaction of hydrocarbyl-substituted succinic anhydrides with alkanolamines. 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 U.S. Pat. No. 4,426,305.

  The molecular weight of the hydrocarbyl-substituted succinic anhydride used in the preceding paragraph typically ranges from 800 to 2,500 daltons or more. The product can be subsequently reacted with various reagents such as sulfur, oxygen, formaldehyde, and carboxylic acids such as oleic acid. The product is typically boric acid, borate ester or highly borated dispersion to form a borated dispersant having from 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.

  Mannich base dispersants are made from the reaction of alkylphenols, formaldehyde and amines. See U.S. Patent No. 4,767,551, which is incorporated herein by reference. Process aids and catalysts such as oleic and sulfonic acids can also be part of the reaction mixture. The molecular weight of the alkyl phenol ranges from 800 to 2,500. Representative examples are U.S. Pat. Nos. 3,697,574, 3,703,536, 3,704,308, 3,751,365, Nos. 3,756,953, 3,798,165 and 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 aromatic or HN (R) ₂ group containing reactants.

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

Preferred dispersants include borated succinimides, including monosuccinimide, bissuccinimide, and / or their derivatives from a mixture of mono and bissuccinimide, wherein the hydrocarbyl succinimide has about 500 to about 5000 daltons, or about 1000 daltons. Derived from hydrocarbylene groups, such as polyisobutylene, having a Mn of from about 3000 to about 3000 daltons, or from about 1000 to about 2000 daltons, or a mixture of such hydrocarbylene groups, which often have high terminal vinyl groups. Preferred dispersions useful in the present disclosure are characterized by having a Mn of about 800 to about 1700 daltons for low molecular weights and about 1700 to about 5000 daltons or more for high molecular weights. Other preferred dispersants include succinic esters and amides, alkylphenol-polyamine linked Mannich adducts, their cap-forming derivatives and other related compounds. Such additives may be used in an amount of about 0.1-20%, preferably about 0.5-8%, or more preferably 0.5-4% by weight. Hydrocarbon moiety of the dispersant atoms _may be in the range of C _{60 -C 400} or _C 70 _{-C 300,} or _{C70~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 range from 1: 5 to 5: 1, or more preferably, from 1: 2 to 2: 1. The dispersant can be end-capped with borates and / or cyclic carbonates, and / or any carboxylic acid such as hydrocarbyl carboxylic acid or hydrocarbyl carboxylic anhydride.

  For lubricating oil formulations containing at least one boron-containing compound and at least one zinc-containing compound or an antiwear agent according to the present disclosure, the engine may comprise at least one boron-containing compound and at least one zinc-containing compound or Engines using lubricating oils containing minor components other than antiwear agents in amounts other than the amount of at least one boron containing compound and at least one zinc containing compound or antiwear agent in the lubricating oil. Standardized low speed preignition (LSPI) for 25,000 engine cycles, engine operation at 2000 revolutions per minute (rpm) and a net mean effective pressure (BMEP) of 18 bar compared to low speed preignition performance ) Based on the number, greater than about 20%, preferably greater than about 25%, Ri preferably represents a reduction of about 30% greater than the low speed pre-ignition.

  As used herein, detergent concentrations are given on a "as delivered" basis. Typically, the active detergent is delivered with the process oil. The "as delivered" detergent typically comprises from about 20% to about 80%, or from about 40% to about 60%, by weight of the active detergent in the "as delivered" detergent. Included.

Detergents Exemplary detergents useful in the present disclosure include, for example, alkaline earth metal detergents or mixtures of alkaline earth metal detergents. Typical alkaline earth metal detergents are anionic materials that include a long chain hydrophobic portion of the molecule and a smaller anionic or oleophobic hydrophilic portion of the molecule. The anionic part of the detergent is derived from sulfur acids, organic acids, such as carboxylic acids, phosphorous acids, phenols or mixtures thereof. The counter ion is an alkaline earth metal. Preferably, the detergent comprises at least one alkaline earth metal salt of an organic acid, and the at least one alkaline earth metal salt of an organic acid comprises at least one magnesium salt of an organic acid. Become.

  Preferred detergents useful in the lubricating oils of the present disclosure are from the group consisting of alkaline earth metal sulfonates, alkaline earth metal carboxylates (eg, salicylates), alkaline earth metal phenates, alkaline earth metal phosphates, and mixtures thereof. Selected. Alkaline earth metal sulfonates, alkaline earth metal carboxylates, alkaline earth metal phenates, alkaline earth metal phosphates and mixtures thereof, and alkaline earth metal sulfonates, alkaline earth metal carboxylates, alkaline earths in lubricating oils The amount of metal phenate, alkaline earth metal phosphate and mixtures thereof may include detergents other than alkaline earth metal sulfonates, alkaline earth metal carboxylate, alkaline earth metal phenates, alkaline earth metal phosphates and mixtures thereof, Engines that use lubricating oils 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 low speed pre-ignition performance achieved, the engine is sufficient to show a reduction in low speed pre-ignition.

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

  A preferred type of detergent is an alkaline earth metal sulfonate. Sulfuric acids useful for preparing alkaline earth metal sulfonates include sulfonic, thiosulfonic, sulfinic, sulfenic, partially esterified sulfuric, sulfurous and thiosulfuric acids. Sulfonic acid is preferred.

  The sulfonic acids are generally petroleum sulfonic acids or alkaryl sulfonic acids prepared by synthesis. Among the petroleum sulfonic acids, the most useful products are those prepared by sulfonation of the appropriate petroleum fraction, followed by removal and purification of the acid sludge. Synthetically prepared alkaryl sulfonic acids are usually prepared from alkylated benzenes, such as the 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 to illustrate such alkaline earth metal salts of sulfonic acids. In other words, for all sulfonic acids listed, it is intended to be understood that their corresponding basic alkaline earth metal salts are also described.

  Such sulfonic acids include mahogany sulfonic acid, bright stock sulfonic acid, petrolatum sulfonic acid, mono- and polywax-substituted naphthalene sulfonic acids, cetyl chlorobenzene sulfonic acid, cetyl phenol sulfonic acid, cetyl phenol disulfide sulfonic acid, cetoxycapryl benzene. Sulfonic acid, dicetylthianthrenesulfonic acid, dilauryl beta-naphtholsulfonic acid, dicaprylnitronaphthalenesulfonic acid, saturated paraffin wax sulfonic acid, unsaturated paraffin wax sulfonic acid, hydroxy-substituted paraffin wax sulfonic acid, tetra-isobutylenesulfonic acid, Tetra-amylene sulfonic acid, chloro-substituted paraffin wax sulfonic acid, nitroso-substituted paraffin wax sulfonic acid, petroleum naphthenesul Phosphate, cetyl cyclopentyl sulfonic acids, lauryl cyclohexyl sulfonic acids, mono- and poly-wax-substituted cyclohexyl sulfonic acids, dodecylbenzene sulfonic acids, and the like "dimer alkylate" sulfonic acids.

Alkyl-substituted benzene sulfonic acids where the alkyl group contains at least 8 carbon atoms are useful in the present disclosure, including dodecylbenzene "residue" sulfonic acid. 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, mainly mixtures of mono- and didodecylbenzene, are available from household detergent manufacturers as by-products.

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

A useful class of detergents is alkaline earth phenates. 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 sulfurized alkylphenols. It can be manufactured by performing Useful alkyl groups include straight or branched chain C ₁ -C ₃₀ alkyl groups, preferably C ₄ -C ₂₀ or mixtures thereof. Examples of suitable phenols include isobutyl phenol, 2-ethylhexyl phenol, nonyl phenol, dodecyl phenol, and the like. It should be noted that the starting alkylphenol may contain two or more alkyl substituents, each of which is independently linear or branched, and that 0.5 to 6% by weight may be used. is there. If a non-sulfurized alkyl phenol is used, the sulphided product may be obtained by methods well known in the art. These methods include heating a mixture of an alkylphenol and a sulfurizing agent (including elemental sulfur, sulfur halides such as sulfur dichloride, etc.), and then reacting the sulfurized phenol with an alkaline earth metal base.

  Preferred phenate compounds include, for example, magnesium phenate, calcium phenate, overbased phenate compounds, sulfurized / carbonated calcium phenate compounds and mixtures thereof.

  Alkaline earth metal salts of carboxylic acids are also useful as detergents. 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 overbased 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。 Detergents made from salicylic acid are a preferred class of detergents derived from carboxylic acids. Useful salicylates include long chain alkyl salicylates. One useful family of compositions is of the formula:

Wherein R is an alkyl group having from 1 to about 30 carbon atoms, n is an integer from 1 to 4, and M is an alkaline earth metal.
It is. Preferred R groups are alkyl chains of at least C ₁₁ , preferably C ₁₃ or higher. R may be optionally substituted by 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 acids can be prepared from phenol by the Kolbe reaction (see US Pat. No. 3,595,791). Alkaline earth metal salts of hydrocarbyl-substituted salicylic acids can be prepared by metathesis of alkaline earth metal salts in a polar solvent such as water or alcohol.

  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 a substantially stoichiometric amount of alkaline earth metal are described as neutral salts and have a total base number (TBN, measured by ASTM D2896) of 0-100. Many compositions are overbased and contain large amounts of metal bases achieved by reacting an excess of an alkaline earth metal compound with an acidic gas (such as carbon dioxide). Useful detergents can be neutral, slightly overbased, or highly overbased. These detergents can be used in neutral, overbased, highly overbased magnesium salicylates, sulfonates, phenates and / or calcium salicylates, mixtures of sulfonates and phenates. The TBN range may vary from a low value of 0 to a high value of 600, with a low TBN of about 0-100, a medium TBN of about 100-200, and a high TBN of about 200-600. A mixture of low, medium, high TBN can be used with calcium and magnesium metal based detergents including sulfonates, phenates, salicylates 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 with a metal ratio of 1 can be used in combination with a detergent with a metal ratio of 2 and a detergent with a metal ratio of 5 or 10 or 15. Borated detergents can also be used.

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

  The detergent may be a single detergent or what is known as a hybrid or complex detergent. The latter detergent can provide the properties of two detergents without the need to blend separate materials. See U.S. Patent No. 6,034,039.

  Suitable detergents include magnesium sulfonate, calcium sulfonate, calcium phenate, magnesium phenate, calcium salicylate, magnesium salicylate and other related components (including borated detergents) and mixtures thereof. Preferred detergents include magnesium sulfonate, calcium sulfonate, magnesium phenate, calcium phenate, magnesium salicylate, calcium salicylate and mixtures thereof.

  Other exemplary detergents that can be used with the alkaline earth metal detergent include, for example, an alkali metal detergent or a mixture of alkali metal detergents.

  In detergents comprising a mixture of a magnesium salt of an organic acid and a calcium salt of an organic acid, the detergent ratio of magnesium metal to calcium metal is from about 1: 0 to 1:10, preferably from about 1: 0 to about 1:10. The range is 1: 4.

  The magnesium and alkaline earth metals provided by the detergent are present in the lubricating oil in an amount from about 500 ppm to about 5000 ppm, preferably from about 1000 ppm to about 2500 ppm. The magnesium provided by the detergent is present in the lubricating oil 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 ranges from about 2 mg KOH / g to about 17 mg KOH / g, preferably from about 3 mg KOH / g to about 14 mg KOH / g.

  The sulfated ash provided by the detergent may comprise 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. Range. The sulfated ash provided by the magnesium detergent may be about 0.3 to about 1.8% by weight, preferably about 0.4 to about 1.6% by weight, more preferably about 0.6 to about 1.0% by weight. % Range. The lubricating engine oil of the present disclosure preferably contains less than about 1.6% by weight sulfated ash and / or more preferably contains less than about 4000 ppm magnesium. At higher engine oil sulphated ash contents of 1.2% or more ash (due to the use of magnesium detergents), a reduction of LSPI numbers of more than 95% is achieved. At sulfated ash levels <1.2% due to the use of magnesium detergent, LSPI can be completely eliminated.

  For lubricating oil formulations containing at least one zinc-containing compound or antiwear agent and at least one detergent according to the present disclosure, the engine may comprise at least one zinc-containing compound or antiwear agent and at least one detergent. A low speed press achieved in an engine using a lubricating oil containing ancillary components other than the detergent in an amount other than the amount of at least one zinc-containing compound or antiwear and at least one detergent in the lubricating oil. Compared to ignition performance, standardized low preignition (LSPI) numbers for 25,000 engine cycles, engine operation at 2000 revolutions per minute (RPM) and a net mean effective pressure (BMEP) of 18 bar On the basis of more than about 50%, preferably more than about 75%, more preferably more than about 95% Exhibit reduced low speed pre-ignition.

  Also, with respect to a lubricating oil formulation containing at least one zinc-containing compound or antiwear agent, at least one boron-containing compound and at least one detergent according to the present disclosure, the engine may comprise at least one zinc-containing compound. Alternatively, a lubricating oil containing an antiwear agent, at least one boron-containing compound and at least one auxiliary component other than a detergent is mixed in the lubricating oil with at least one zinc-containing compound or at least one antiwear agent. Engine at 25,000 engine cycles, 2000 revolutions per minute (RPM) compared to the low speed pre-ignition performance achieved with the engine using amounts other than the amount of the boron-containing compound and at least one detergent. Low speed pre-ignition standardized for operation and 18 bar net mean effective pressure (BMEP) (LSPI) based on the number, greater than about 50%, preferably greater than about 75% and more preferably reduced to about 95% greater than the low speed pre-ignition.

  The concentration of the detergent in the lubricating oils of the present disclosure is from about 1.0 to about 6.0% by weight, preferably from about 2.0 to about 5.0% by weight, more preferably about 2.0 to about 5.0% by weight, 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, based on the total weight of the lubricating oil, preferably from about 0.5 to about 2.0. %, More preferably from 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. %, More preferably from 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 from about 1.0 to about 4.0% by weight, preferably from 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 from about 1.0 to about 4.0% by weight, preferably from about 1.0 to about 3.0% by weight, based on the total weight of the lubricating oil. More preferably, it can range from about 1.5 to about 2.5% by weight.

  As used herein, detergent concentrations are given on a "as delivered" basis. Typically, the active detergent is delivered with the process oil. The "as delivered" detergent typically comprises from about 20% to about 80%, or from about 40% to about 60%, by weight of the active detergent in the "as delivered" detergent. Included.

Other Additives Useful lubricants useful in this disclosure include, but are not limited to, other antiwear 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-staining agents, color formers, defoamers, demulsifiers, It may additionally contain one or more other commonly used lubricating oil performance additives, including emulsifiers, densifiers, wetting agents, gelling agents, tackifiers, colorants and others. For a number of commonly used additives, see Klamann's Lubricants and Related Products, Verlag Chemie, Deerfield Beach, FL; ISBN 0 89573 177. M. Noyes Data Corporation of Parkridge, NJ (1973). W. See also "Lubricant Additives" by Ranney and U.S. Patent No. 7,704,930, which is incorporated herein by reference in its entirety. These additives are generally delivered with varying amounts of diluent oil, which can range from 5% to 50% by weight.

  The type and amount of performance additive used in combination with the present disclosure in the lubricant composition is not limited by the embodiments set forth herein by way of example.

Viscosity Index Improvers The lubricant compositions of the present disclosure may include viscosity index improvers (also known as VI improvers, viscosity modifiers and viscosity improvers).

  Viscosity index improvers provide high and low temperature running performance to lubricants. 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 function as both viscosity index improvers and dispersants. Typical molecular weights of these polymers are between about 10,000 and 1,500,000, more typically between 20,000 and 1,200,000, and even more typically between 50,000 and 1,000,000. is there.

  Examples of suitable viscosity index improvers are linear or star polymers and copolymers of methacrylate, butadiene, olefin or alkylated styrene. Polyisobutylene is a commonly used viscosity index improver. Another suitable viscosity index improver is polymethacrylate (eg, a copolymer of alkyl methacrylates of various chain lengths), and some of their blends also function 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 a molecular weight of 50,000 to 200,000.

  Olefin copolymers are available from Chevron Oronite Company LLC under the trade name “PARATONE®” (eg, “PARATONE® 8921” and “PARATONE® 8941”), and the trade name “HiTEC®” from Afton Chemical Corporation. Trademark) "(e.g.," HiTEC (R) 5850B "), commercially available from The Lubrizol Corporation under the tradename" Lubrizol (R) 7067C ". Polyisoprene polymers are commercially available from Infineum International Limited, for example, under the trade name "SV200", and diene-styrene copolymers are commercially available from Infineum International Limited, for example, under the trade name "SV 260". 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 less than about 0.1% by weight, based on the total weight of the formulated oil or lubricating engine oil. It may be used in amounts less than 5% by weight. The viscosity improver is typically added as a concentrate in a bulk diluent oil.

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

Antioxidants Antioxidants inhibit oxidative degradation of the base oil during use. Such decomposition can result in deposition on metal surfaces, 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 oxidation inhibitors useful in lubricating oil compositions. See, for example, the above-mentioned Klamann's Lubricants and Related Products, and U.S. Patent 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 hindered hydroxyl groups, including dihydroxy aryl compounds in which the hydroxyl groups are ortho or para to one another. Derivatives are included. Typical phenolic antioxidants include hindered phenols substituted by C6 or higher alkyl groups, and alkylene-linked derivatives of these hindered phenols. Examples of this type of phenolic material are: 2-tert-butyl-4-heptylphenol; 2-tert-butyl-4-octylphenol; 2-tert-butyl-4-dodecylphenol; 2,6-di-tert-phenol. Butyl-4-heptylphenol; 2,6-di-tert-butyl-4-dodecylphenol; 2-methyl-6-tert-butyl-4-heptylphenol; and 2-methyl-6-tert-butyl-4- Dodecylphenol. Other useful hindered monophenolic antioxidants may include, for example, 2,6-di-alkyl-phenol propionic acid ester derivatives. Bis-phenolic antioxidants may also be advantageously used in combination with the present disclosure. Examples of ortho-linked phenols include 2,2'-bis (4-heptyl-6-tert-butyl-phenol); 2,2'-bis (4-octyl-6-tert-butyl-phenol); , 2'-bis (4-dodecyl-6-t-butyl-phenol). 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 comprises 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. Or a combination of both b) and c). Catalytic oxidation inhibitors are more fully described in U.S. Patent 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 such or in combination with phenol. Typical examples of non-phenolic antioxidants include those of the formula R ⁸ R ⁹ R ¹⁰ N, where R ⁸ is an aliphatic, aromatic or substituted aromatic group, and R ⁹ is an aromatic or substituted aromatic group. And R ¹⁰ is H, alkyl, aryl or R ¹¹ S (O) XR ¹² , R ¹¹ is an alkylene, an alkylene group linked to or present in an alkene, and R ¹² is a higher alkyl group Or an alkenyl, aryl or alkaryl group, and x is 0, 1 or 2), including alkylated or non-alkylated aromatic amines. Aliphatic group R ⁸ may also contain 1 to 20 carbon atoms, preferably containing from 6 to 12 carbon atoms. An aliphatic group is a saturated aliphatic group. Preferably, R ⁸ and R ⁹ are both aromatic or aromatic groups, and the aromatic groups may be fused ring aromatic groups such as naphthyl. The aromatic groups R ⁸ and R ⁹ may be bonded together with another group such as S.

  Typical aromatic amine antioxidants have an alkyl substituent having at least 6 carbon atoms. Examples of the aliphatic group include hexyl, heptyl, octyl, nonyl, and decyl. Generally, an aliphatic group will not contain more than 14 carbon atoms. Common classes of amine antioxidants useful in the present compositions include diphenylamine, phenylnaphthylamine, phenothiazine, imidodibenzyl and biphenylphenylenediamine. Mixtures of two or more aromatic amines are also useful. Polymeric amine 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.

  Sulfurized alkyl phenols and their alkali or alkaline earth metal salts are also useful antioxidants.

  Preferred antioxidants include hindered phenols and arylamines. These antioxidants may be used individually by type or in combination with one another. Such additives are used in an amount of 0.01 to 5%, preferably 0.01 to 2%, more preferably 0 to about 1.5%, more preferably 0 to less than 1% by weight. May be.

Pour point depressant (PPD)
If desired, conventional pour point depressants (also known as lube oil flow improvers) 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 lower the minimum temperature at which the fluid will be able to flow or be able to flow out. Examples of suitable pour point depressants include polymethacrylates, polyacrylates, polyarylamides, haloparaffin waxes and condensation products of aromatic compounds, vinyl carboxylate polymers, and dialkyl fumarate, vinyl esters of fatty acids and allyl vinyl ether. Of terpolymers. U.S. Pat. Nos. 1,815,022, 2,015,748, 2,191,498, 2,387,501, and 2,655 No. 2,479,479, 2,666,746, 2,721,877, 2,721,878 and 3,250,715. Describe 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 Compatible Agents Seal compatible agents facilitate inflating an elastomeric seal by effecting a chemical reaction in the fluid or a physical change in the elastomer. Suitable seal compatibility agents for lubricating oils include organic phosphates, alkoxysulfolane, aromatic esters, aromatic hydrocarbons, esters (eg, butylbenzyl phthalate) and polybutenyl succinic anhydride. Such additives may be used in amounts of about 0.01 to 3% by weight, preferably about 0.01 to 2% by weight.

Antifoaming agents Antifoaming agents may advantageously be added to the lubricant composition. These drugs inhibit the formation of stable bubbles. Silicones and organic polymers are typical defoamers. For example, silicone oils or polysiloxanes such as polydimethylsiloxane provide antifoam properties. Defoamers are commercially available and may be used in small amounts conventionally together with other additives, such as demulsifiers, and usually the amount of these combined additives is less than 1% by weight And often less than 0.1% by weight.

Inhibitors and Anti-Rust Additives Anti-rust additives (or corrosion inhibitors) are additives that protect lubricated metal surfaces against 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 protects a metal surface with a wet, oily 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 bonds to create a non-reactive surface. Examples of suitable additives include zinc dithiophosphate, 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 modifier A friction modifier is any material that can modify the coefficient of friction of a surface lubricated by any lubricant or fluid containing such a material. Friction reducers, or lubricants or oily agents, and also such base agents, compounded lubricant compositions or other such agents that modify the ability of functional fluids to modify the coefficient of friction of a lubricated surface Known friction modifiers may be effectively used, if desired, with the base oil or lubricant compositions of the present disclosure. Friction modifiers that reduce the coefficient of friction are particularly advantageous 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 organometallic 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 tungstate, molybdenum dithiocarbamate, molybdenum dithiophosphate, molybdenum Includes amine complexes, molybdenum carboxylate, and the like, 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, borated glycerol fatty acid esters, fatty alcohol ethers, and mixtures thereof. included.

  Exemplary alkylated fatty acid esters include, for example, polyoxyethylene stearate, 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, diethyl alkanolamide laurate, diethylalkanolamide palmitate, and the like. These can include diethyl alkanolamide oleate, diethyl alkanolamide stearate, diethyl alkanolamide oleate, polyethoxylated hydrocarbylamide, polypropoxylated hydrocarbylamide, and the like.

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

  Exemplary borated glycerol fatty acid esters include, for example, borated glycerol monooleate, borated saturated mono-, di- and triglyceride esters, borated glycerol 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 the corresponding glycerol monopalmitate, glycerol dipalmitate and glycerol tripalmitate and Each may be an isostearate, a linoleate. In some cases, glycerol esters, as well as mixtures containing any of these, may be preferred. Ethoxylation, propoxylation, butoxylated fatty acid esters of the polyols may be preferred, especially using glycerol as the underlying polyol.

Exemplary fatty alcohol ethers include, for example, stearyl ether, myristyl ether, and the like. Alcohols including those having carbon numbers of C ₃ -C ₅₀ include ethoxylated, and propoxylated or butoxylated, it is possible to form the corresponding fatty acid alkyl ethers. The basic alcohol moiety, preferably, stearyl, _myristyl, C 11 _{-C 13} hydrocarbons, oleyl, can isostearyl are like.

  Useful concentrations of the friction modifier are from 0.01% to 5%, or from about 0.1% to about 2.5%, or from about 0.1% to about 1.5%, or It may range from about 0.1% to about 1% by weight. Molybdenum-containing material concentrations are often stated in terms of Mo metal concentration. Convenient concentrations of Mo may range from 25 ppm to 700 ppm or more, and often the preferred range is 50-200 ppm. All types of friction modifiers may be used alone or in mixtures with the present disclosure. Often, a mixture of two or more friction modifiers, or a mixture of a friction modifier with another surface activating material, is also desirable.

  If the lubricating oil composition contains one or more of the above-mentioned additives, the additives are blended into the composition in an amount sufficient to cause 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 a concentrate containing one or more additives together with a particular amount of base oil diluent. Thus, the weights in the table below, as well as other amounts described herein, relate to the amount of active ingredient (which is the non-diluent portion of the ingredient). The weight percentages (wt%) given below are based on the total weight of the lubricating oil composition.

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

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

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

  Engines that are very susceptible to low pre-ignition (LSPI) are those 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 various fuels, including natural gas, gasoline, diesel, biofuels, and the like. Reduced size, slowed supercharged (eg, turbocharged) engines are most susceptible to operation under these engine conditions, and are therefore susceptible to LSPI. Non-limiting examples of engines having these features include the GM Ecotec, Ford EcoBoost family of engines, and other high BMEP (> 10 bar capable) engines with displacements ranging from about 1 L to about 6 L. , And 2-10 in geometric arrangements including series, horizontally opposed (or flat) (Boxer) and "V" (e.g., "V8", "straight 3", "straight 4", "flat 4", etc.). An engine having a single combustion cylinder is included. Further, engine calibration and operational setpoints can significantly affect both the frequency and severity of LSPI events.

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

Example A
The formulation was prepared as described in FIG. All components used herein are commercially available. Group III, IV and V basestocks were used in the formulation.

  The antiwear agents used in the formulations were ZDDP derived from secondary alcohols (containing 10% by weight of phosphorus and prepared from mixed C3 and C6 secondary alcohols) and primary alcohols ZDDP (containing 7% by weight of phosphorus and prepared from C8 primary alcohol). In addition, zinc-only and phosphorus-only antiwear agents were used in the formulation.

  The remaining components used in the formulation include viscosity index improvers, antioxidants, dispersants, antiwear agents, pour point depressants, corrosion inhibitors, metal deactivators, seal compatibility additives, defoamers Agents, inhibitors, rust additives and friction modifiers.

  Tests were performed on the formulation described in FIG. The results are shown in FIG. The sulfated ash test was determined based on ASTM D874. Zinc and phosphorus contents were determined based on ASTM D6443.

  It is described that various engine hardware and control schemes can significantly affect the emergence of LSPI. For example, U.S. Patent Application Publication Nos. 2012/1866225 and 2003/0908070, and SAE 2012-02-1148, SAE 2011-01-0340 and SAE 2011, all of which are incorporated herein by reference. See -01-0343. FIG. 12 shows drive cycle data obtained from a taxi cab field test. Two different 2.0L L4 TGDI engine types from different original equipment manufacturers were operated on a typical taxi cab 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 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 maps of these engines bounded by these operating conditions is potentially LSPI prone. Based on the measured data of the OBD-II data logger, it can be shown that engines with different calibrations may exhibit different LSPI behavior based on the way they are adjusted. FIG. 12 shows approximately 1.2 million data points summarizing the operation of two different engine types in a typical taxi cab city drive cycle over two weeks. Multiple taxi cabs using each engine type were observed in this manner. Both engines were 2.0-liter inline 4-cylinder TGDI engines, whereas engine type 1 used 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 cabcity drive cycle. Furthermore, engine type 2 showed zero defects in the LSPI related field, while engine type 1 showed multiple defects associated with LSPI. This further illustrates the different responsiveness 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 LSPI testing. A six segment test procedure was used to determine the number of LSPI phenomena that occurred at two different specified engine load and speed conditions. Each segment of the test procedure consisted of 25,000 engine cycles, one cycle corresponding to 720 degrees of crankshaft rotation. The first set of conditions is a BMEP of 2000 rpm and 18 bar, hereinafter referred to as "high load". The second set of conditions is 1500 rpm and 12.5 bar BMEP, 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. Before starting the test procedure, a 30 minute warm-up was also performed at 2000 rpm and 4 bar BMEP. This test procedure was repeated four times for each of the lubricants tested. The number of LSPI events was counted only during high load segments, using pressure transducers located in each of the four cylinders to monitor peak cylinder pressure. Peak pressures in cylinders 4.7 standard deviations above or 4.7 standard deviations below the average peak cylinder pressure were counted as LSPI phenomena. The results of such an LSPI test are shown in FIG.

  This test evaluated the effect of ZDDP on LSPI. As shown in FIG. 1, using secondary alcohol-derived ZDDP is preferred over using primary alcohol-derived ZDDP to reduce LSPI numbers. Example 1 shows that about 27 phenomena of LSPI can be obtained using secondary ZDDP, while Comparative Example 1 shows that with equal zinc and phosphorus content, primary ZDDP is 25, 9 shows that it has an unexpectedly high LSPI number of 34 counts per 000 engine cycles. Thus, formulations with secondary alcohol-derived ZDDP show an unexpected 20% LSPI reduction. This new finding of reducing LSPI numbers by using secondary ZDDP, or almost secondary ZDDP, can be very beneficial for lubricant formulations. Example 2 represents the case where the ZDDP processing rate is performed to a very high level, and this can reduce and almost eliminate the LSPI number by increasing the amount of ZDDP in the formulation Indicates that Finally, Comparative Examples 2 and 3 further explore the benefits of ZDDP by testing the effects of zinc and phosphorus separately. In Comparative Example 2, a zinc-only antiwear agent was used at a processing rate equivalent to that of Example 1 and Comparative Example 1, and an LSPI number of 36 was obtained. On the other hand, in Comparative Example 3, an LSPI phenomenon of 55 was obtained by using an antiwear agent consisting of only phosphorus at a processing rate equivalent to that of Example 1 and Comparative Example 1. Comparison of Comparative Example 2 with Comparative Example 3 clearly shows the unique benefit of zinc compounds in controlling LSPI numbers. At the same time, the detrimental effects of using phosphorus-only antiwear agents can be seen.

Example B
The formulation was prepared as described in FIG. All components used herein are commercially available. Group III, IV and V basestocks were used in the formulation.

  The antiwear agents used in the formulation were ZDDP derived from secondary alcohols and ZDDP derived from primary alcohols.

  Dispersants used in the formulations include borated succinimide (comprising borated polyisobutenyl succinimide with a B / N ratio equal to about 0.5), high molecular weight succinimide (about 1% total nitrogen High MW succinimide dispersant 1) comprising ethylene carbonate-capped bispolyisobutenyl succinimide dispersant having a high molecular weight and a high molecular weight succinimide (bispolyisobutenyl succinimide having a total nitrogen content of about 1.2%). A high MW succinimide dispersant 2).

  The remaining components used in the formulation include viscosity index improvers, antioxidants, dispersants, antiwear agents, pour point depressants, corrosion inhibitors, metal deactivators, seal compatibility additives, defoamers Agents, inhibitors, rust additives and friction modifiers.

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

  This test evaluated the effect of ZDDP derived from borated dispersants and secondary alcohols on LSPI. As shown in FIG. 3, the use of a borated dispersant and secondary ZDDP is unexpectedly beneficial for LSPI performance. Example 1, Comparative Example 4, Comparative Example 5 and Example 3 all use a secondary ZDDP antiwear agent at the same processing rate, but the dispersant is changed. As the boron content increases, the LSPI number unexpectedly decreases, as indicated by the boron content in these blends. In particular, Example 3 having only about 507 ppm of boron causes only 24 LSPI phenomena, while Comparative Examples 4 and 5 without boron have 46 and 43 LSPI phenomena, respectively. When increasing from 0 to 240 ppm boron and 507 ppm boron, the LSPI number decreases from 46 to 27 and 24 respectively. This is a 40% reduction with about 240 ppm boron and a 48% reduction with about 507 ppm boron. As the boron concentration increases, LSPI reduction is expected to continue. The benefits of using a borated dispersant with secondary ZDDP are clearly seen. By showing the disadvantages of borated dispersants and primary ZDDP, Comparative Example 1 further demonstrates the unique and unexpected benefits of borated dispersants and secondary ZDDP. Compared to Example 1 with the same concentration of boron as Comparative Example 1, Comparative Example 1 shows an increase in LSPI number from 27 to 34 when secondary ZDDP is exchanged for primary ZDDP.

  Comparative Example 8 shows an example where no dispersant was used and had an LSPI number of 22. This is substantially similar to the blend containing the borated dispersant, but further demonstrates the utility of the borated dispersant in reducing the LSPI of oils used in commercial applications. Typically, dispersants are required to be used to disperse sludge and other particulate matter that may be generated during normal operation. Comparing Comparative Example 4 with Comparative Example 4, the non-borated dispersant can cause an increase in LSPI number by almost 100%, but the borated dispersant alone or other non-borated dispersants The use in combination with a dispersant is shown to reduce the LSPI number.

Example C
The formulation was prepared as described in FIG. All components used herein are commercially available. Group III, IV and V basestocks were used in the formulation.

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

  The dispersants used in the formulation were borated succinimide and high molecular weight succinimide.

  The antiwear agents used in the formulation were ZDDP derived from secondary alcohols and ZDDP derived from primary alcohols.

  The remaining components used in the formulation include viscosity index improvers, antioxidants, dispersants, antiwear agents, pour point depressants, corrosion inhibitors, metal deactivators, seal compatibility additives, defoamers Agents, inhibitors, rust additives and friction modifiers.

  Tests were performed on the formulation described in FIG. FIG. 5 shows the results. The sulfated ash test was determined based on ASTM D874. 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 according to the procedure described in Example 1 using a 2.0 L, 4 cylinder TGDI GM Ecotec engine.

This test evaluated the effect of three additive systems (ie, detergent, dispersant, and antiwear agent) on LSPI. As shown in FIG. 5, when the LSPI of a formulation containing a non-borated dispersant and a formulation containing a mixture of a non-borated dispersant and a borated dispersant is measured, the borated succinimide dispersant is The use has unique LSPI benefits over high molecular weight succinimide dispersants. Comparative Example 6, Example 4 and Example 8 show the effect of increasing boron content on LSPI performance. When the boron content increases from 0 to 240 ppm, 507 ppm, the LSPI number decreases from 46 to 27,24. The benefit of boron in reducing LSPI frequency represents a significant and unexpected finding shown in FIGS. Examples 6 and 7 show the unique combination of magnesium sulfonate detergent with dual dispersant system and secondary alcohol derived ZDDP. The bidispersant system contains a boron source. The uniqueness of this combination is demonstrated by using different calcium salicylate based detergent systems and comparing to Comparative Example 6 which has the worst LSPI number. The use of magnesium sulfonate detergents with secondary alcohol derived ZDDP and borated dispersants has been shown to unexpectedly and significantly reduce, if not eliminate, LSPI. The desired ratio of the total concentration of ([Mg] + [Ca] + [Zn] + [P]) / ([B] + [N] _dispersant ) is about 2.5-7, more preferably It is about 3.3-5. Comparing Example 4 with Example 10 further demonstrates the effectiveness of this method of incorporating a borated dispersant with a secondary alcohol derived ZDDP and a combination of magnesium sulfonate and calcium salicylate detergents. Show. Example 10 shows a 98% reduction in LSPI as compared to Comparative Example 6.

Example D
The lubricating engine oil formulations of FIGS. 6 and 7 are a combination of an additive and a 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 a high temperature high shear (10 ^-6 sec ^-1 ) viscosity. The 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 range from 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. You. 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. 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 and 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 ash. Other ratios identified in FIGS. 6 and 7 also vary as shown herein. The lubricating engine oil formulations of Examples P9 and P10 are expected to have a magnesium to calcium ratio of about 0.06 and 3 at a constant TBN, respectively. The lubricating engine oil formulations of Examples P11, P12 and P13 are expected to have a zinc content ranging from about 96 ppm for Example P13 to about 635 ppm for Example P11. The lubricating engine oil formulations of Examples P11, P12 and P13 are expected to have a phosphorus content ranging from about 87 ppm for Example P13 to about 570 ppm for Example P11. The ratio ([Mg] + [Ca]) / ([Zn] + [P]) ranges from about 2.5 for example P11 to 16.5 for example P13. The ratio of ([Zn] + [P]) / ([B] + [N] _dispersant ) ranges from about 1 for example P11 to 0.15 for example P13. The ratio of ([Mg] + [Ca] + [Zn] + [P]) / ([B] + [N] _dispersant ) ranges from about 3.4 for Example P11 to 2.6 for Example P13. It is.

Example E
The lubricating engine oil formulations of FIGS. 8 and 9 are a combination of an additive and a basestock and have a kinematic viscosity at 100 ° C. of about 5.5-7.5 cSt and a high temperature It has a shear (10 ⁻⁶ sec ⁻¹ ) viscosity. The 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 range from 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 be in the range of 0.71 for Example P16 to 1.62 for Example P14. You. Finally, the ratio of ([Mg] + [Ca] + [Zn] + [P]) / ([B] + [N] _dispersant ) of Examples P14, P15 and P16 is 1.99 to 4.53. Is expected. 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 have a magnesium content of 300 ppm to 900 ppm and a magnesium to calcium ratio of about 0.12 for Example P19 and 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 ash. Other ratios identified in FIGS. 8 and 9 also vary as shown herein. The lubricating engine oil formulations of Examples P22 and P23 are expected to have a magnesium to calcium ratio of about 0.06 and 3 at a constant TBN, respectively. The lubricating engine oil formulations of Examples P24, P25 and P26 are expected to have a zinc content ranging from about 96 ppm for Example P26 to about 635 ppm for Example P24. The lubricating engine oil formulations of Examples P24, P25 and P26 are expected to have a phosphorus content ranging from about 87 ppm for Example P26 to about 570 ppm for Example P24. The ratio ([Mg] + [Ca]) / ([Zn] + [P]) ranges from about 2.5 for example P24 to 16.5 for example P26. The ratio of ([Zn] + [P]) / ([B] + [N] _dispersant ) ranges from about 1 for Example P24 to 0.15 for Example P26. The ratio ([Mg] + [Ca] + [Zn] + [P]) / ([B] + [N] _dispersant ) ranges from about 3.4 for Example P24 to 2.6 for Example P26. It is.

Example F
The lubricating engine oil formulations of FIGS. 10 and 11 are a combination of an additive and a 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 a viscosity. The 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 range from 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 be in the range of 0.71 for Example P29 to 1.62 for Example P27. You. Finally, the ratio of ([Mg] + [Ca] + [Zn] + [P]) / ([B] + [N] _dispersant ) of Examples P27, P28 and P29 is 1.99 to 4.53. Is expected. 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 and 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 ash. Other ratios identified in FIGS. 10 and 11 also vary as shown herein. The lubricating engine oil formulations of Examples P35 and P36 are expected to have a magnesium to calcium ratio of about 0.06 and 3 at a constant TBN, respectively. The 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. The lubricating engine oil formulations of Examples P37, P38 and P39 are expected to have a phosphorus content ranging from about 87 ppm for Example P39 to about 570 ppm for Example P37. The ratio ([Mg] + [Ca]) / ([Zn] + [P]) ranges from about 2.5 for example P37 to 16.5 for example P39. The ratio of ([Zn] + [P]) / ([B] + [N] _dispersant ) ranges from about 1 for Example P37 to 0.15 for Example P39.

  All patents and patent applications, test procedures (ASTM methods, UL methods, etc.) and other references cited herein are not allowed, as long as such disclosure is consistent with the present disclosure, and such incorporation is acceptable. All rights are fully incorporated by reference.

  Where numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated. While exemplary embodiments of the present disclosure have been described in detail, various other modifications will be apparent to and readily made by those skilled in the art without departing from the spirit and scope of the present disclosure. It will be appreciated that this can be done. Accordingly, the appended claims are not intended to be limited to the embodiments and description set forth herein, but rather, the claims will be interpreted by those skilled in the art to which this disclosure pertains. It is to be understood that it encompasses all features of patentable novelty that exist in this disclosure, including any features that may be treated as such.

The present disclosure has been described above with reference to a number of embodiments and individual examples. In view of the above detailed description, those skilled in the art will suggest many variations. All such obvious variations are within the full intended scope of the appended claims.
The disclosure of the present specification may include the following aspects.
(Aspect 1)
A method for preventing or reducing low-speed pre-ignition in an engine lubricated with the lubricating oil by using the lubricating oil as a lubricating oil, wherein the lubricating oil is a lubricating oil base stock as a main component, and a A composition comprising at least one zinc-containing compound or at least one antiwear agent, wherein the at least one antiwear agent comprises at least one zinc dialkyldithiophosphate compound derived from a secondary alcohol. ,
The engine has 25,000 engine cycles, 2000 revolutions per minute (2,000 revolutions per minute) when compared to the low speed preignition performance achieved with the engine using at least one zinc-containing compound or a lubricant free of antiwear agents. Showing a reduction in low speed pre-ignition by more than 20% based on the low speed pre-ignition (LSPI) number standardized for engine operation at 18 RPM and a net mean effective pressure (BMEP) of 18 bar,
Method.
(Aspect 2)
The embodiment 1, wherein the minor component further comprises at least one boron-containing compound, wherein the boron-containing compound comprises at least one borated dispersant, or a mixture of a boron-containing compound and a non-borated dispersant. The described method.
(Aspect 3)
The sub-component further comprises at least one boron-containing compound and at least one detergent, wherein the boron-containing compound comprises at least one borated dispersant, or a mixture of a boron-containing compound and a non-borated dispersant. A mixture, wherein the detergent comprises at least one alkaline earth metal salt of an organic acid, and wherein the at least one alkaline earth metal salt of an organic acid comprises at least one magnesium salt of an organic acid. The method according to aspect 1.
(Aspect 4)
The lubricating oil base stock comprises a Group I, Group II, Group III, Group IV or Group V base oil, wherein the Group V base oil comprises an ester base oil at a concentration of 2% to 20%; 4. The method according to any of aspects 1 to 3, having a kinematic viscosity at 2O <0> C of 2 cSt to 8 cSt, wherein the Group III base oil comprises a GTL base oil.
(Aspect 5)
The method according to any one of aspects 1 to 4, wherein the zinc-containing compound is selected from the group consisting of zinc sulfonate, zinc acetate, zinc naphthenate, zinc alkenyl succinate, zinc acid phosphate salt, zinc phenate and zinc salicylate. The method described in.
(Aspect 6)
The zinc dialkyldithiophosphate compound has the formula:
Zn [SP (S) (OR ¹ ) (OR ² )] ₂
Wherein R ¹ and R ² are independently a primary or secondary C ₁ -C ₈ alkyl group (provided that at least one of R ¹ and R ^{2 is} a secondary C ₁ -C 8 ₈ alkyl groups)]
The method according to any one of aspects 1 to 5, represented by:
(Aspect 7)
The zinc dialkyldithiophosphate compound,
_(I) C 3 ~C ₈ secondary alcohol or mixtures thereof, or
(Ii) Mixtures of C ₁ -C ₈ primary alcohols and C ₁ -C ₈ secondary alcohols
7. The method according to any one of aspects 1 to 6, wherein the method is derived from
(Aspect 8)
The boron-containing compound or borated dispersant is selected from the group consisting of borated succinimide, borated succinate, borated succinate amide, borated Mannich base and mixtures thereof, wherein the non-borated dispersant is 8. The method according to any one of aspects 2 to 7, comprising succinic anhydride-derived succinimide or succinic ester together with a coupling agent comprising a boron-containing compound.
(Aspect 9)
In the lubricating oil, add the total zinc from the zinc-containing compound and the anti-wear agent and the total alkaline earth metal from the detergent to obtain the total boron from the boron-containing compound and the borated dispersant. The method according to any one of aspects 3 to 8, wherein the divided ratio is between 9.2 and 45.
(Aspect 10)
Embodiments 3 to 3, wherein the alkaline earth metal salt of the organic acid is selected from the group consisting of alkaline earth metal sulfonates, alkaline earth metal carboxylate, alkaline earth metal phenates, alkaline earth metal phosphates, and mixtures thereof. 10. The method according to any one of items 9 to 9.
(Aspect 11)
The detergent,
(I) at least one of magnesium sulfonate, magnesium phenate and magnesium salicylate and mixtures thereof, optionally at least one of calcium sulfonate, calcium phenate and calcium salicylate and mixtures thereof;
(Ii) a magnesium salt of at least one organic acid selected from magnesium sulfonate, magnesium carboxylate, magnesium phenate, magnesium phosphate and mixtures thereof, or
(Iii) magnesium sulfonate, a mixture of magnesium sulfonate and magnesium salicylate, a mixture of magnesium sulfonate and magnesium phenate, or a mixture of magnesium sulfonate and magnesium carboxylate
11. The method according to any one of aspects 3 to 10, comprising:
(Aspect 12)
(I) whether the magnesium and alkaline earth metal provided by the detergent are present in the lubricating oil in an amount from 500 ppm to 5000 ppm;
(Ii) the total alkali number (TBN) provided by the detergent ranges from 2 mg KOH / g to 17 mg KOH / g, as measured by ASTM D2896, or
(Iii) The sulfated ash content provided by the detergent is in the range of 0.4 to 1.7% by weight.
The method according to any one of aspects 3 to 11, wherein
(Aspect 13)
A lubricating engine oil having a composition comprising a lubricating oil basestock as a main component and at least one zinc-containing compound or at least one antiwear agent as a secondary component, wherein the at least one antiwear agent comprises: At least one zinc dialkyldithiophosphate compound derived from a secondary alcohol,
The engine has 25,000 engine cycles, 2000 revolutions per minute (RPM) when compared to the low speed preignition performance achieved with the engine using at least one zinc-containing compound or a lubricant that does not contain an antiwear agent. ) Shows a reduction in low speed preignition of more than 20%, based on the low speed preignition (LSPI) number standardized for engine operation and 18 bar net mean effective pressure (BMEP),
Lubricating engine oil.
(Aspect 14)
Aspect 13. In embodiment 13, wherein the minor component further comprises at least one boron-containing compound, wherein the boron-containing compound comprises at least one borated dispersant, or a mixture of a boron-containing compound and a non-borated dispersant. The described lubricating engine oil.
(Aspect 15)
The sub-component further comprises at least one boron-containing compound and at least one detergent, wherein the boron-containing compound comprises at least one borated dispersant, or a mixture of a boron-containing compound and a non-borated dispersant. A mixture, wherein the detergent comprises at least one alkaline earth metal salt of an organic acid, and wherein the at least one alkaline earth metal salt of an organic acid comprises at least one magnesium salt of an organic acid. 14. A lubricating engine oil according to aspect 13.
(Aspect 16)
A method of preventing or reducing low speed pre-ignition in an engine lubricated with said lubricating oil by using the compounded engine oil as a lubricating oil, wherein said compounded engine oil comprises 70-85% by weight of a lubricating oil base stock. And at least one zinc-containing compound or at least one antiwear agent in an amount that provides 400 ppm to about 2000 ppm of phosphorus to the formulated engine oil, wherein the at least one antiwear agent is Comprises at least a portion of at least one zinc dialkyldithiophosphate compound derived from a secondary alcohol,
The engine has 25,000 engine cycles, 2,000 2,000 engine cycles when compared to the low speed preignition performance achieved with the engine using at least one zinc-containing compound or at least one antiwear-free lubricant. Shows a reduction in low speed preignition of greater than 50% based on low speed preignition (LSPI) numbers standardized for engine operation and 18 bar net mean effective pressure (BMEP) at revolutions per minute (RPM),
Method.

Claims (10)

A method for preventing or reducing low-speed pre-ignition in an engine lubricated with the lubricating oil by using the lubricating oil as a lubricating oil, wherein the lubricating oil is a lubricating oil base stock as a main component, and a A composition comprising at least one antiwear agent, wherein the at least one antiwear agent comprises at least one zinc dialkyldithiophosphate compound derived from a secondary alcohol;
The zinc dialkyldithiophosphate compound gives 884 ppm or less of zinc to the lubricating oil,
As an auxiliary component, further comprise at least one boron-containing compound and at least one detergent, wherein the boron-containing compound comprises at least one borated dispersing agent, the cleaning agent is at least one organic acid Wherein the alkaline earth metal salt of at least one organic acid comprises a magnesium salt of at least one organic acid,
In the lubricating oil, the ratio of the total zinc from the anti-wear agent and the total alkaline earth metal from the detergent added and divided by the total boron from the boron-containing compound and the borated dispersant is 9.2-45,
The at least one boron-containing compound has a boron / nitrogen ratio of 0.26 or less;
The engine has 25,000 engine cycles, 2000 revolutions per minute (2,000 revolutions per minute) when compared to the low speed preignition performance achieved with the engine using at least one zinc-containing compound or a lubricant free of antiwear agents. Showing a reduction in low speed pre-ignition by more than 20% based on the low speed pre-ignition (LSPI) number standardized for engine operation at 18 RPM and a net mean effective pressure (BMEP) of 18 bar,
Method.   The lubricating base stock comprises a Group I, Group II, Group III, Group IV or Group V base oil, wherein the Group V base oil has a weight of 2% based on the total weight of the Group V base oil. 2. The composition of claim 1, comprising an ester base oil at a concentration of from about 20% to about 20% by weight, wherein the ester base oil has a kinematic viscosity at 100 ° C. of 2 cSt to 8 cSt, and wherein the Group III base oil comprises a GTL base oil. The described method. The zinc dialkyldithiophosphate compound has the formula:
Zn [SP (S) (OR ¹ ) (OR ² )] ₂
Wherein R ¹ and R ² are independently a primary or secondary C ₁ -C ₈ alkyl group (provided that at least one of R ¹ and R ^{2 is} a secondary C ₁ -C 8 ₈ alkyl groups)]
The method according to claim 1, wherein the method is represented by: The zinc dialkyldithiophosphate compound,
_(I) C 3 ~C ₈ are derived from a secondary alcohol or mixtures thereof, or _(ii) C 1 ~C ₈ mixtures of primary alcohols and _C 1 -C ₈ secondary alcohol, claim 1 The method according to any one of claims 1 to 3. 5. The method of claim 1, wherein the boron-containing compound or borated dispersant is selected from the group consisting of borated succinimide, borated succinate, borated succinamide, borated Mannich base and mixtures thereof. 6. A method according to any one of the preceding claims.   The alkaline earth metal salt of an organic acid is selected from the group consisting of alkaline earth metal sulfonates, alkaline earth metal carboxylate, alkaline earth metal phenates, alkaline earth metal phosphates and mixtures thereof. The method according to any one of claims 1 to 5. The detergent,
(I) at least one of magnesium sulfonate, magnesium phenate and magnesium salicylate and mixtures thereof, optionally at least one of calcium sulfonate, calcium phenate and calcium salicylate and mixtures thereof;
(Ii) magnesium salt of at least one organic acid selected from magnesium sulfonate, magnesium carboxylate, magnesium phenate, magnesium phosphate and mixtures thereof, or (iii) magnesium sulfonate, a mixture of magnesium sulfonate and magnesium salicylate, magnesium The method according to any one of claims 1 to 6, comprising a mixture of a sulfonate and magnesium phenate, or a mixture of magnesium sulfonate and magnesium carboxylate. (I) whether the magnesium and alkaline earth metal provided by the detergent are present in the lubricating oil in an amount from 500 ppm to 5000 ppm;
(Ii) the total alkali number (TBN) provided by the detergent ranges from 2 mg KOH / g to 17 mg KOH / g as measured by ASTM D2896, or (iii) provided by the detergent. The process according to any of the preceding claims, wherein the sulfated ash content is in the range of 0.4-1.7% by weight. A lubricating engine oil having a composition comprising a lubricating oil basestock as a main component and at least one antiwear agent as a secondary component, wherein said at least one antiwear agent comprises at least one anti-wear agent derived from a secondary alcohol. A zinc dialkyldithiophosphate compound,
The zinc dialkyldithiophosphate compound provides 884 ppm or less of zinc to the lubricating engine oil,
As an auxiliary component, further comprise at least one boron-containing compound and at least one detergent, wherein the boron-containing compound comprises at least one borated dispersing agent, the cleaning agent is at least one organic acid Wherein the alkaline earth metal salt of at least one organic acid comprises a magnesium salt of at least one organic acid,
In the lubricating engine oil, the ratio of the total zinc from the antiwear agent and the total alkaline earth metal from the detergent added and divided by the total boron from the boron containing compound and borated dispersant. Is 9.2 to 45,
The at least one boron-containing compound has a boron / nitrogen ratio of 0.26 or less;
The engine has 25,000 engine cycles, 2000 revolutions per minute (RPM) when compared to the low speed preignition performance achieved with the engine using at least one zinc-containing compound or a lubricant that does not contain an antiwear agent. ) Shows a reduction in low speed preignition of more than 20%, based on the low speed preignition (LSPI) number standardized for engine operation and 18 bar net mean effective pressure (BMEP),
Lubricating engine oil. A method of preventing or reducing low speed pre-ignition in an engine lubricated with said lubricating oil by using the compounded engine oil as a lubricating oil, wherein said compounded engine oil comprises 70-85% by weight of a lubricating oil base stock. And at least one antiwear agent in an amount providing from 400 ppm to 2000 ppm of phosphorus to the formulated engine oil, wherein the at least one antiwear agent comprises at least a portion of a secondary alcohol. At least one zinc dialkyldithiophosphate compound from
The zinc dialkyldithiophosphate compound gives 884 ppm or less of zinc to the lubricating oil,
As an auxiliary component, further comprise at least one boron-containing compound and at least one detergent, wherein the boron-containing compound comprises at least one borated dispersing agent, the cleaning agent is at least one organic acid Wherein the alkaline earth metal salt of at least one organic acid comprises a magnesium salt of at least one organic acid,
In the lubricating oil, the ratio of the total zinc from the anti-wear agent and the total alkaline earth metal from the detergent added and divided by the total boron from the boron-containing compound and the borated dispersant is 9.2-45,
The at least one boron-containing compound has a boron / nitrogen ratio of 0.26 or less;
The engine has 25,000 engine cycles, 2,000 2,000 engine cycles when compared to the low speed preignition performance achieved with the engine using at least one zinc-containing compound or at least one antiwear-free lubricant. Shows a reduction in low speed preignition of greater than 50% based on low speed preignition (LSPI) numbers standardized for engine operation and 18 bar net mean effective pressure (BMEP) at revolutions per minute (RPM),
Method.

Images