JP2020526641A - Lubricating oil compositions containing sulfur phosphorus-free zinc compounds, and methods for preventing or reducing low-speed, premature ignition in direct-injection spark-ignition engines. - Google Patents

Abstract

Lubricating compositions for direct injection boost spark-ignition internal combustion engines are disclosed that include at least one sulfur phosphorus-free zinc compound. The disclosure also relates to methods of preventing or reducing low speed premature ignition in blended oil lubricated engines. The compounded oil has a composition containing at least one oil-soluble or oil-dispersible sulfur phosphorus-free zinc compound.

Description

The present disclosure relates to a lubricant composition for a directly injected spark-ignition internal combustion engine, comprising at least one sulfur phosphorus-free zinc compound. The disclosure also relates to methods of preventing or reducing low speed premature ignition in blended oil lubricated engines. The blended oil has a composition comprising at least one oil-soluble or oil-dispersible non-sulfur phosphorus-zinc compound.

One of the main theories surrounding the cause of low speed early ignition (LSPI) is, at least in part, by the automatic ignition of engine oil droplets flowing into the engine combustion chamber through the piston gap under high pressure, during which the engine Is operating at low speed and has the longest compression stroke time (Amann et al. SAE 2012-01-1140).

Some problems, such as engine knocking and premature ignition, can be solved by using new engine technologies such as electronic control and knock sensors, as well as optimizing engine operating conditions, but with lubricating oil compositions the above problems It has a role to reduce or prevent. We have found a solution to address the problem of LSPI by using non-sulfur phosphorus-zinc-containing additives.

In one aspect, the present disclosure is a method of preventing or reducing low-speed, premature ignition of a direct-injection boost spark-ignition engine to at least one sulfur phosphorus-free zinc compound relative to the total weight of the lubricating oil. Provided is a method comprising a step of lubricating an engine crankcase with a lubricating oil composition containing from about 200 to about 3000 ppm of zinc metal derived from it.

For example, sulfur phosphorus-free zinc compounds include zinc alkoxides or thiolate compounds, zinc aryloxides or aryl thiolate compounds, zinc oxide colloidal dispersions, stable colloidal zinc suspensions, zincamide compounds, zinc acetylacetone compounds (zinc). acetyllacetone compound), zinc carboxylate (zinc carbidelate), zinc alkylhydroxydroxybenzoate, zinc arylsulfonate, zinc sulfide complex, zinc dithiocarbamate complex, zinc dithiocarbamate complex. Zinc ester, zinc phosphinate, zinc phosphinate complex, zinc pyridyl complex, zinc polypyridyl complex, zinc quinolinolato complex, zinc succinimide.

In yet another aspect, the present disclosure is a direct injection boost spark ignition internal combustion engine containing from about 200 to about 3000 ppm zinc metal derived from at least one phosphorus sulfide-free zinc compound relative to the total weight of the lubricating oil. To provide a lubricating engine oil composition for.

Definitions The term "boost" is used throughout this specification. Boost refers to operating an engine with a higher intake pressure than a naturally aspirated engine. A boosted state can be reached by using a turbocharger (driven by exhaust) or a supercharger (driven by engine). By using smaller engines that provide higher power densities, engine manufacturers have been able to offer superior performance while reducing friction and pumping losses. This is achieved by using a turbocharger or mechanical supercharger to increase the boost pressure and decelerating the engine using the high gear ratios enabled by the high torque generation at low engine speeds. However, high torque at low engine speeds has been found to cause random premature ignition in low engine speeds. This is a phenomenon known as low speed early ignition, or LSPI, which results in very high cylinder peak pressures and can lead to catastrophic engine failure. Due to the potential of LSPI, engine manufacturers are unable to fully optimize engine torque at lower engine speeds with such small high power engines.

The term oil-soluble or oil-dispersible is used throughout the specification and claims. Oil-soluble or oil-dispersible means that the amount required to provide the desired level of activity or performance can be incorporated by dissolving, dispersing, or suspending in an oil of lubricating viscosity. Generally, this means that at least about 0.001% by weight of material can be incorporated into the lubricating oil composition. See US Pat. No. 4,320,019 for further discussion of oil solubility and oil dispersibility, in particular the term "stable dispersibility". This patent specification is expressly incorporated herein by reference with respect to relevant teachings in this regard.

As used herein, the term "sulfate ash" refers to nonflammable residues resulting from detergents and metal additives in lubricants. Sulfate ash content can be measured using ASTM Test D874.

As used herein, the term "Total Base Number" or "TBN" refers to the amount of base corresponding to KOH (milligrams) in 1 gram of sample. Therefore, the higher the TBN value, the more alkaline products there are, and therefore the higher the alkalinity. TBN was measured using the ASTM D 2896 test.

Unless otherwise stated, all percentages are weight percent.

Generally, the concentration of sulfur in the lubricating oil composition of the present invention is about 0.7% by weight or less based on the total weight of the lubricating oil composition, for example, the concentration of sulfur is about 0.01 weight by weight. % To about 0.70% by weight, 0.01 to 0.6% by weight, 0.01 to 0.5% by weight, 0.01 to 0.4% by weight, 0.01 to 0.3% by weight, 0 It is 0.01 to 0.2% by weight and 0.01% to 0.10% by weight. In one embodiment, the concentration of sulfur in the lubricating oil composition of the present invention is about 0.60% by weight or less, about 0.50% by weight or less, and about 0% based on the total weight of the lubricating oil composition. It is 40% by weight or less, about 0.30% by weight or less, about 0.20% by weight or less, and about 0.10% by weight or less.

In one embodiment, the concentration of phosphorus in the lubricating oil composition of the present invention is about 0.12% by weight or less based on the total weight of the lubricating oil composition, for example, the concentration of phosphorus is about 0.01. It is from% by weight to about 0.12% by weight. In one embodiment, the concentration of phosphorus in the lubricating oil composition of the present invention is about 0.11% by weight or less based on the total weight of the lubricating oil composition, for example, the concentration of phosphorus is about 0.01. It is from% by weight to about 0.11% by weight. In one embodiment, the concentration of phosphorus in the lubricating oil composition of the present invention is about 0.10% by weight or less based on the total weight of the lubricating oil composition, for example, the concentration of phosphorus is about 0.01. It is from% by weight to about 0.10% by weight. In one embodiment, the concentration of phosphorus in the lubricating oil composition of the present invention is about 0.09% by weight or less based on the total weight of the lubricating oil composition, for example, the concentration of phosphorus is about 0.01. It is from% by weight to about 0.09% by weight. In one embodiment, the concentration of phosphorus in the lubricating oil composition of the present invention is about 0.08% by weight or less based on the total weight of the lubricating oil composition, for example, the concentration of phosphorus is about 0.01. It is from% by weight to about 0.08% by weight. In one embodiment, the concentration of phosphorus in the lubricating oil composition of the present invention is about 0.07% by weight or less based on the total weight of the lubricating oil composition, for example, the concentration of phosphorus is about 0.01. It is from% by weight to about 0.07% by weight. In one embodiment, the concentration of phosphorus in the lubricating oil composition of the present invention is about 0.05% by weight or less based on the total weight of the lubricating oil composition, for example, the concentration of phosphorus is about 0.01. It is from% by weight to about 0.05% by weight.

In one embodiment, the concentration of sulfated ash produced by the lubricating oil composition of the present invention is about 1.60% by weight or less as measured by ASTM D 874, for example, the concentration of sulfated ash is ASTM. It is about 0.10 to about 1.60 wt% as measured by D 874. In one embodiment, the concentration of sulfated ash produced by the lubricating oil composition of the present invention is about 1.00% by weight or less as measured by ASTM D 874, for example, the concentration of sulfated ash is ASTM. It is about 0.10 to about 1.00 wt% as measured by D 874. In one embodiment, the concentration of sulfated ash produced by the lubricating oil composition of the present invention is about 0.80% by weight or less as measured by ASTM D 874, for example, the concentration of sulfated ash is ASTM. It is about 0.10 to about 0.80 wt% as measured by D 874. In one embodiment, the concentration of sulfated ash produced by the lubricating oil composition of the present invention is about 0.60% by weight or less as measured by ASTM D 874, for example, the concentration of sulfated ash is ASTM. It is about 0.10 to about 0.60 wt% as measured by D 874.

Suitably, the lubricating oil composition has a total base value (TBN) of 4 to 15 mg KOH / g (eg, 5 to 12 mg KOH / g, 6 to 12 mg KOH / g, or 8 to 12 mg KOH / g). Can have.

Slow early ignition is most likely to occur with direct injection, boost (turbocharged or supercharged), spark-ignition (gasoline) internal combustion engines, which operate from about 1500 to about 2500 per minute during operation. At engine speeds of rotation (rpm), such as about 1500 to about 2000 rpm, a net mean effective pressure is generated above about 15 bar (peak torque), for example at least about 18 bar, especially at least about 20 bar. As used herein, net mean effective pressure (BMEP) is defined as the work achieved during a single engine cycle divided by the total engine displacement, and engine torque is engine displacement. Normalized by quantity. The word "brake" refers to the actual torque / power available on the engine flywheel as measured by a dynamometer. Therefore, BMEP is a measured value of the effective output of the engine.

In one embodiment of the invention, the engine is operated at speeds of 500 rpm to 3000 rpm, or 800 rpm to 2800 rpm, and even 1000 rpm to 2600 rpm. In addition, the engine can be operated with a net mean effective pressure of 10 bar to 30 bar, or 12 bar to 24 bar.

LSPI events, although relatively rare, can be catastrophic in nature. Therefore, a significant reduction or even elimination of LSPI events during normal or sustained operation of a direct fuel injection engine is desired. In one embodiment, the method of the invention is such that there are less than 15 LSPI events per 100,000 combustion events, or less than 10 LSPI events per 100,000 combustion events. In one embodiment, less than 5 LSPI events per 100,000 combustion events, less than 4 LSPI events per 100,000 combustion events, less than 3 LSPI events per 100,000 combustion events, less than 3 per 100,000 combustion events. LSPI events can be less than 2, LSPI events per 100,000 combustion events less than 1, or LSPI events per 100,000 combustion events can be zero.

Accordingly, in one aspect, the present disclosure is a method of preventing or reducing low speed premature ignition of a direct injection boost spark ignition internal combustion engine, wherein the engine is a lubricating oil composition comprising at least one phosphorus sulfide-free zinc compound. A method including a step of lubricating a crankcase of an internal combustion engine is provided. In one embodiment, the amount of zinc metal derived from at least one sulfur phosphorus-free zinc compound is about 200 to about 3000 ppm, or about 250 to about 3000 ppm, about 300 to about 3000 ppm, about 350 to about 3000 ppm, about 400 ppm. ~ About 3000ppm, about 500 ~ about 3000ppm, about 600 ~ about 3000ppm, about 700 ~ about 3000ppm, about 900 ~ about 3000ppm, about 950 ~ about 3000ppm, about 1000 ~ 3000ppm, about 1050 ~ about 3000ppm, about 1100 ~ about 3000ppm , About 1200 to about 3000 ppm, about 1300 to about 3000 ppm, about 1400 to about 3000 ppm, or about 1400 to 3000 ppm.

In one embodiment, the total amount of zinc in the formulation containing the metal derived from at least one phosphorus sulfide-free zinc compound is about 700 to about 4000 ppm, or about 800 to about 4000 ppm, about 900 to about 4000, about 950. ~ About 4000 ppm, about 1000-4000 ppm, about 1050 to about 4000 ppm, about 1100 to about 4000 ppm, about 1200 to about 4000 ppm, about 1300 to about 4000 ppm, about 1400 to about 4000 ppm, or about 1400 to 4000 ppm.

In one embodiment, the methods of the invention increase the number of LSPI events by at least 10 percent, or at least 20 percent, or at least 30 percent, or at least, as compared to oils that do not contain at least one phosphorus sulfide-free zinc compound. Reduce by 50 percent, or at least 60 percent, or at least 70 percent, or at least 80 percent, or at least 90 percent, or at least 95 percent.

In another aspect, the present disclosure is a method of reducing the severity of slow, premature ignition events of a direct injection boost spark ignition internal combustion engine, wherein the engine is a lubricating oil composition comprising at least one sulfur phosphorus free zinc compound. A method including a step of lubricating a crankcase of an internal combustion engine is provided. LSPI events are measured by monitoring the peak cylinder pressure (PP) and combustion mass ratio (MFB) of the fuel supply in the cylinder. If either or both meet the criteria, it can be said that an LSPI event has occurred. The peak cylinder pressure threshold varies from test to test, but typically exceeds the average cylinder pressure by 4-5 standard deviations. Similarly, the MFB threshold is typically 4-5 standard deviations faster than the average MFB (represented by crank angle). LSPI events can be reported as mean events per test, events per 100,000 combustion cycles, events per cycle, and / or combustion cycles per event. In one embodiment, if both the MFB02 and peak pressure (PP) requirements exceed a pressure of 90 bar, the number of LSPI events is less than 5 events, less than 4 events, less than 3 events, less than 2 events, or less than 1 event. is there. In one embodiment, the number of LSPI events above 90 bar is zero events, in other words, the number of LSPI events above 90 bar is completely suppressed. In one embodiment, if both the MFB02 and peak pressure (PP) requirements exceed a pressure of 100 bar, the number of LSPI events is less than 5 events, less than 4 events, less than 3 events, less than 2 events, or less than 1 event. is there. In one embodiment, the number of LSPI events above 100 bar is zero events, in other words, the number of LSPI events above 100 bar is completely suppressed. In one embodiment, if both the MFB02 and peak pressure (PP) requirements exceed a pressure of 110 bar, the number of LSPI events is less than 5 events, less than 4 events, less than 3 events, less than 2 events, or less than 1 event. is there. In one embodiment, the number of LSPI events above 110 bar is zero events, in other words, the number of LSPI events above 110 bar is completely suppressed. For example, if both the MFB02 and peak pressure (PP) requirements exceed a pressure of 120 bar, the number of LSPI events is less than 5 events, less than 4 events, less than 3 events, less than 2 events, or less than 1 event. In one embodiment, the number of LSPI events above 120 bar is zero events, in other words, very severe LSPI events (ie, events above 120 bar) are completely suppressed.

It has now been found that the generation of LSPI in engines susceptible to the generation of LSPI can be reduced by lubricating such engines with a lubricating oil composition containing a sulfur phosphorus-free zinc compound.

The present disclosure further provides the methods described herein fueling an engine with a liquid hydrocarbon fuel, a liquid non-hydrocarbon fuel, or a mixture thereof.

The disclosure further provides the methods described herein for fueling an engine with natural gas, liquefied petroleum gas (LPG), compressed natural gas (CNG), or a mixture thereof.

Lubricating oil compositions suitable for use as passenger car motor oils have traditionally included major amounts of lubricating viscosity oils and small amounts of performance-enhancing additives, including ash-containing compounds. Conveniently, zinc is introduced into the lubricating oil composition used in the practice of the present disclosure by one or more sulfur phosphorus-free zinc compounds.

Lubricating Viscosity Oils / Base Oil Components Lubricating viscosity oils used in the lubricating oil compositions of the present disclosure, also referred to as base oils, typically weigh 50 weight relative to a major amount, eg, the total weight of the composition. It is present in an amount of more than%, preferably more than about 70% by weight, more preferably about 80 to about 99.5% by weight, most preferably about 85 to about 98% by weight. As used herein, the term "base oil" refers to lubricating oil components manufactured by a single manufacturer with the same specifications (regardless of the source of supply or the location of the manufacturer), of the same manufacturer. It is understood to mean a blend of basestocks or basestocks, which are lubricating oil components that meet specifications and are lubricant components identified by a unique formula, product identification number, or both. The base oils used herein are used in any application, such as in the formulation of lubricating oil compositions for use in functional fluids such as engine oils, marine cylinder oils, hydraulic oils, gear oils, transmission fluids and the like. It can be an oil with a lubricating viscosity that is currently known or later discovered. In addition, the base oil used herein is optionally a viscosity index improver, eg, a polymeric alkyl methacrylate; an olefin copolymer, eg, an ethylene-propylene copolymer or a styrene-diene copolymer. Etc., and mixtures thereof.

The viscosity of the base oil depends on the application, as will be easily understood by those skilled in the art. Therefore, the viscosities of the base oils used herein are typically in the range of about 2 to about 2000 centimeters Stokes (cSt) at 100 ° C. (Celsius). Generally, the base oils used as engine oils individually have a kinematic viscosity range of about 2 cSt to about 30 cSt, preferably about 3 cSt to about 16 cSt, most preferably about 4 cSt to about 12 cSt at 100 ° C. Selected or blended according to the end application and additives in the finished oil, the desired grade of engine oil, eg SAE viscosity grades 0W, 0W-8, 0W-12, 0W-16, 0W-20, 0W -26, 0W-30, 0W-40, 0W-50, 0W-60, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W-30 A lubricating oil composition such as 10W-40, 10W-50, 15W, 15W-20, 15W-30, 15W-40, 30, 40 and the like is obtained.

Group I base oils generally have a saturated content of less than 90% by weight (as measured by ASTM D 2007) and / or by ASTM D 2622, ASTM D 4294, ASTM D 4297, or ASTM D 3120. Refers to petroleum-derived lubricating base oils with a total sulfur content greater than 300 ppm (measured) and a viscosity index (VI) of 80 or more and less than 120 (measured by ASTM D 2270).

Group II base oils generally have a total sulfur content (measured by ASTM D 2622, ASTM D 4294, ASTM D 4927 or ASTM D 3120) less than or equal to 300 million percent (ppm) and (ASTM D 2007). Refers to petroleum-derived lubricating base oils with a saturated content of 90% by weight or more (measured by ASTM D 2270) and a viscosity index (VI) of 80-120 (measured by ASTM D 2270).

Group III base oils generally refer to petroleum-derived lubricating base oils with less than 300 ppm sulfur, a saturated content of more than 90 weight percent, and a VI of 120 or more.

The base oil of Group IV is polyalphaolefin (PAO).

Group V base oils include all other base oils not included in Group I, II, III, or IV.

The lubricating oil composition can contain a small amount of other base oil components. For example, the lubricating oil composition can include a small amount of base oil derived from natural lubricating oils, synthetic lubricating oils or mixtures thereof. Suitable base oils include basestocks obtained by isomerization of synthetic waxes and slack waxes, as well as hydrocracking basestocks produced by hydrocracking (rather than solvent extraction) of aromatic and polar components of crude oil. Is done.

Suitable natural oils include mineral lubricating oils such as liquid petroleum, paraffinic, naphthenic or paraffinic naphthenic mixed type solvent or acid treated mineral lubricating oils, coal or shale derived oils, animal oils, vegetable oils (eg). , Rapeseed oil, paraffin oil and lard oil) and the like.

Suitable synthetic lubricating oils include, but are not limited to, hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and copolymerized olefins, specifically polybutylene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylene. Poly (1-hexene), poly (1-octene), poly (1-decene), etc., and mixtures thereof; alkylbenzenes such as dodecylbenzene, tetradecylbenzene, dinonylbenzene, di (2-ethylhexyl) -benzene, etc. Polyphenyls such as biphenyls, terphenyls, alkylated polyphenyls, etc .; include alkylated diphenyl ethers and alkylated diphenyl sulfides, and derivatives, analogs and homologues thereof.

Other synthetic lubricants include, but are not limited to, olefins having less than 5 carbon atoms, such as ethylene, propylene, butylene, isobutene, pentene, and oils produced by polymerizing mixtures thereof. .. Methods of preparing such polymerized oils are well known to those of skill in the art.

Further synthetic hydrocarbon oils include liquid polymers of alpha olefins with suitable viscosities. Particularly useful synthetic hydrocarbon oils are hydrogenated liquid oligomers of C _6- C ₁₂ alpha olefins, such as 1-decene trimers.

Another category of synthetic lubricants includes, but are not limited to, alkylene oxide polymers, namely homopolymers, copolymers, and derivatives of those in which the terminal hydroxyl groups have been modified, for example, by esterification or etherification. Be done. Examples of these oils are oils prepared by polymerization of ethylene oxide or propylene oxide, alkyl and phenyl ethers of these polyoxyalkylene polymers (eg, methylpolypropylene glycol ethers with an average molecular weight of 1,000, molecular weights from 500 to 500). diphenyl ether of 1000 polyethylene glycol, polypropylene such as diethyl ether glycol) or their mono- molecular weight 1,000 to 1,500 - and polycarboxylic esters thereof, for example, mixed _C 3 -C ₈ fatty acid esters or tetraethylene, there are _{C 13} oxo acid diester of glycol.

Yet another classification of synthetic lubricants is, but is not limited to, esters of dicarboxylic acids such as phthalic acid, succinic acid, alkylsuccinic acid, alkenylsuccinic acid, malonic acid, azelaic acid, suberic acid, sebacic acid, fumal. In addition to acids, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acid, alkenylmalonic acid, etc., various alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol Examples include monoether and propylene glycol. Specific examples of these esters include dibutyl adipate, di (2-ethylhexyl sebacate), di-n-hexyl sebacate, dioctyl sebacate, diisooctyl azelaate, diisodecyl azelaate, dioctyl phthalate, and didecyl phthalate. Examples thereof include diecosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, and composite ester formed by reacting 1 mol of sebacic acid with 2 mol of tetraethylene glycol and 2 mol of 2-ethylhexanoic acid. ..

Esters useful as synthetic oils include, but are not limited to, carboxylic acids having about 5 to about 12 carbon atoms and polyols and polyol ethers such as alcohols such as methanol and ethanol, such as neopentythritol and trimethylol. Examples include esters produced from propane, pentaerythritol, dipentaerythritol, tripentaerythritol and the like.

Silicone oils such as polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysiloxane oils and silicate oils constitute another useful classification of synthetic lubricating oils. Specific examples of these include, but are not limited to, tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra- (4-methyl-hexyl) silicate, and tetra-(p) silicate. -Tert-Butylphenyl), hexyl- (4-methyl-2-pentoxy) disiloxane, poly (methyl) siloxane, poly (methylphenyl) siloxane and the like. Still other useful synthetic lubricants include, but are not limited to, liquid esters of phosphorus-containing acids, such as high molecular weight tetrahydrofuran, such as tricresyl phosphate, trioctyl phosphate, diethyl ester of decanthophionic acid.

The lubricating oil can be derived from a mixture of two or more of the unrefined, refined and re-refined oils of natural oils, synthetic oils, or the types of lubricating oils disclosed above. Unrefined oils are oils obtained directly from natural or synthetic raw materials (eg, coal, shale, or tar sands bitumen) without further refining or treatment. Examples of unrefined oils include, but are not limited to, shale oils obtained directly from carbonization operations, petroleum directly obtained from distillation, or ester oils obtained directly from esterification steps, each of which is untreated. Used in. Refined oils are similar to unrefined oils, except that they have been further processed in one or more refinement steps to improve one or more properties. These purification techniques are well known to those skilled in the art and include, for example, solvent extraction, secondary distillation, acid or base extraction, filtration, leaching, hydrogenation, dewaxing and the like. The rerefined oil is obtained by treating the used oil in a process similar to the process used to obtain the refined oil. Such rerefined oils, also known as regenerated or reprocessed oils, are often further treated by techniques relating to the removal of used additives and oil decomposition products.

Lubricating oil base stocks obtained from hydrogen isomerization of waxes can also be used alone or in combination with the natural and / or synthetic base stocks described above. Such wax isomerized oils are produced by hydrogen isomerizing natural or synthetic waxes or mixtures thereof on a hydrogen isomerization catalyst.

Natural waxes are typically slack waxes recovered by solvent dewaxing of mineral oils, and synthetic waxes are typically waxes produced by the Fischer-Tropsch method.

Other useful lubrication viscosity fluids include non-conventional or original basestocks, preferably catalytically treated or synthesized to provide high performance lubrication properties.

Sulfur Phosphorus Free Zinc Compounds The lubricating oil compositions herein can contain one or more sulfur phosphorus free zinc compounds. Sulfur phosphorus-free zinc compounds indicate that the zinc additive does not contain both phosphorus and sulfur in the binding ligand, but may contain phosphorus or sulfur separately, or none of those atoms separately. Interpreted to mean. For those skilled in the art, suitable additives are Stahl, L; et al., "Zinc Organometallics" in Comprehensive Organometallic Chemistry III; 1st Edition; Mingos, D. et al. M. P. Crabtree, R.M. H. , Meyer, K. et al. Eds. It will be understood as described in Elsevier: Oxford, 2007, pp311-412. These documents are incorporated herein by reference. The zinc complexes described in the present disclosure are typically prepared by reacting a divalent or tetravalent zinc reactant with a suitable ligand using methods apparent to those skilled in the art. Although the zinc complexes described are represented by the simplest molecular formulas, it is understood in the art that aggregated, multinucleated and clustered complexes may also exist in chemical equilibrium with simplified molecular formulas. .. Zinc complexes are generally taken to mean the product between a zinc reactant and a suitable ligand. Commonly used zinc reactants include, but are not limited to, zinc oxide, zinc sulfide, zinc sulfate, zinc chloride, zinc chloride tetrahydrofuran complex, dichloro (N, N, N', N'-tetramethylethylenediamine. ) Zinc, zinc bromide, zinc iodide, zinc fluoride, zinc methoxydo, zinc phosphate, zinc stearate, zinc acetylacetoneate, zinc acetate, zinc carbonate hydroxide, zinc naphthenate, or similar zinc compounds. Be done. Some zinc reagents can be present as hydrated species. Any one of these zinc compounds described above can be used as the zinc compound of the present disclosure. Preferred zinc compounds are zinc oxide or zinc chloride. The zinc reaction product may be a zinc compound of the present disclosure as long as it does not contain both sulfur and phosphorus. The zinc complexes described herein are oil-soluble or oil-dispersible.

In one embodiment, the zinc compound can be a zinc alkoxide or a thiolate compound. For example, straight-zinc alkoxide or thiolate can be in the form of _{Zn (YR A) n L X} , in the formula, Y is an oxygen or sulfur atom, the _{R A} having from 1 to about 20 carbon atoms Chain, cyclic, or branched, saturated or unsaturated aliphatic hydrocarbon moieties, n is an integer of 0 to 2, L is a ligand that saturates the coordination sphere of zinc, and x is an integer of 0 to 4. is there. In certain embodiments, the ligand L is water, hydroxide, phosphine, phosphine, ammonia, amino, amide, alkylthiolate, halide, and as long as the zinc species does not contain both sulfur and phosphorus. It is selected from the group consisting of combinations thereof. For example, the zinc alkoxide can be zinc methoxide or the like.

In one embodiment, the zinc compound can be a zinc aryl oxide or an aryl thiolate compound. For example, zinc aryl oxide or aryl thiolate is described in Formula 1:

In expressed, wherein, R _B is a straight chain having a hydrogen atom or 1 to about 30 carbon atoms, cyclic, or branched, aliphatic hydrocarbon moiety, saturated or unsaturated, Y is an oxygen atom or A sulfur atom, n is an integer of 0 to 2, L is a ligand that saturates the coordination sphere of zinc, and x is an integer of 0 to 4. In certain embodiments, the ligand L is water, hydroxide, phosphine, phosphine, ammonia, amino, amide, alkylthiolate, halide, and as long as the zinc species does not contain both sulfur and phosphorus. It is selected from the group consisting of combinations thereof.

In one embodiment, the zinc compound can be a colloidal dispersion of zinc oxide. For example, zinc oxide has a net molecular formula ZnO, but can include repeating units of [Zn—O—Zn] _n . In certain embodiments, the zinc oxide colloidal dispersion has an average nanoparticle diameter of less than 100 nm as measured by microscopic techniques such as TEM. Solvents can be added to aid in the dispersion of colloidal particles. For example, U.S. Patent Application Publication No. 20160237373, incorporated herein by reference, teaches that it is possible to disperse the zinc oxide nanoparticles using C ₁ -C ₃ alcohol solvent in the oil. In general, the amount of zinc oxide colloidal dispersion can be from about 0.01% to about 5% by weight.

In another embodiment, the zinc compound can be a stable colloidal suspension. For example, US Pat. No. 7,884,058, incorporated herein by reference, discloses stable colloidal suspensions of various inorganic oxides. These can be prepared in the presence of an oil phase with a dispersant, the dispersant being polyalkylene succinic anhydride and group I and / or group II mono of polyalkylene succinic acid, polyalkylene succinic acid. Or a nitrogen-free polyalkylene succinic anhydride selected from the group consisting of di-salts, polyalkylene succinic anhydrides or polyalkylene succinic acid esters formed by the reaction of acid anhydrides with alcohols, and mixtures thereof. Derivatives, mixtures thereof and dilute oils are included and the stable colloidal suspension is substantially clear.

In one embodiment, the zinc compound can be a zinc amide compound. For example, zinc amide compound can be in the form of _{Zn (NR C) n L X} , R C is straight chain having a trimethylsilyl group or from 1 to about 20 carbon atoms, cyclic or branched, saturated or The unsaturated aliphatic hydrocarbon moiety, n is an integer of 0 to 2, L is a ligand that saturates the coordination sphere of zinc, and x is an integer of 0 to 4. In certain embodiments, the ligand L is water, hydroxide, phosphine, phosphine, ammonia, amino, amide, alkylthiolate, halide, and as long as the zinc species does not contain both sulfur and phosphorus. It is selected from the group consisting of combinations thereof.

In one embodiment, the zinc compound can be a zinc acetylacetoneate compound. For example, zinc acetylacetoneate has the following equation 2:

In the formula, _RD is a symmetric or asymmetric linear, cyclic, or branched, saturated or unsaturated aliphatic hydrocarbon moiety or aromatic moiety having 1 to about 20 carbon atoms. Obtained, n is an integer of 0 to 2, L is a ligand that saturates the coordination sphere of zinc, and x is an integer of 0 to 4. In certain embodiments, the ligand L is water, hydroxide, phosphine, phosphine, ammonia, amino, amide, alkylthiolate, halide, and as long as the zinc species does not contain both sulfur and phosphorus. It is selected from the group consisting of combinations thereof.

In one embodiment, the zinc compound can be zinc carboxylate. For example, zinc carboxylate has the following formula 3:

In expressed, wherein, R _E is a straight-chain having from 1 to about 50 carbon atoms, cyclic, or branched, aliphatic hydrocarbon moiety, saturated or unsaturated, or 1 to about 20 carbon atoms, a It can be an aromatic and alkyl aromatic ring with an alkyl group that can be a linear, cyclic, or branched, and saturated or unsaturated aliphatic hydrocarbon moiety, where n is an integer of 0-2 and L is zinc. It is a ligand that saturates the coordination zone, and x is an integer from 0 to 4. In certain embodiments, the zinc _carboxylate, it is possible to form a Zn _{3 (O 2} CR _E) in the form of 6 _{L x} small clusters. In certain _{embodiments, O} 2 CR _E may represent a naphthenic acid residue, which is generally understood to be a complex mixture of cycloaliphatic residue obtained by oxidation of naphtha. In certain embodiments, the ligand L is water, hydroxide, phosphine, phosphine, ammonia, amino, amide, alkylthiolate, halide, and as long as the zinc species does not contain both sulfur and phosphorus. It is selected from the group consisting of combinations thereof. For example, zinc carboxylate can be zinc stearate or another fatty acid. Zinc carboxylate can be, for example, zinc octanate or zinc 2-ethylhexanoate.

In one embodiment, the zinc compound can be zinc alkylhydroxybenzoate. For example, zinc salicylate has the following equation 4:

In expressed, wherein, R _F is a straight chain having a hydrogen atom, 1 to about 30 carbon atoms, cyclic or branched, an aliphatic hydrocarbon moiety, saturated or unsaturated, p is 1-2 An integer, n is an integer of 0 to 2, L is a ligand that saturates the coordination sphere of zinc, and x is an integer of 0 to 4. In particular, n is an integer from 0 to 2. In certain embodiments, the ligand L is water, hydroxide, phosphine, phosphine, ammonia, amino, amide, alkylthiolate, halide, and as long as the zinc species does not contain both sulfur and phosphorus. It is selected from the group consisting of combinations thereof. In one embodiment, the alkylhydroxybenzoate is salicylate. In some embodiments, alkaline earth metals such as magnesium, calcium, strontium, and barium may be added. Alkaline earth metals are typically basic salts including, but not limited to, metal oxides, metal alkoxides, metal carbonates, and metal bicarbonates.

In another embodiment, the zinc compound can be zinc aryl sulfonate. For example, zinc arylsphonate has the following formula 5:

In the formula, _RG is a hydrogen atom, a linear, cyclic, or branched, saturated or unsaturated aliphatic hydrocarbon moiety having 1 to about 30 carbon atoms, and p is 1 to 5. An integer, n is an integer of 0 to 2, L is a ligand that saturates the coordination sphere of zinc, and x is an integer of 0 to 4. In particular, n is an integer from 0 to 2. In particular, p is 1 or 2. In certain embodiments, the ligand L is water, hydroxide, phosphine, phosphine, ammonia, amino, amide, alkylthiolate, halide, and as long as the zinc species does not contain both sulfur and phosphorus. It is selected from the group consisting of combinations thereof. In some embodiments, alkaline earth metals such as magnesium, calcium, strontium, and barium may be added. Alkaline earth metals are typically basic salts including, but not limited to, metal oxides, metal alkoxides, metal carbonates, and metal bicarbonates.

In one embodiment, the zinc compound can be a zinc sulfide phenate. For example, zinc sulfide phenate has the following formula 6:

In the formula, _RH is a hydrogen atom, a linear, cyclic, or branched, saturated or unsaturated aliphatic hydrocarbon moiety having 1 to about 30 carbon atoms, and x'is 1 to zinc. An integer of 8 is an integer of 1 to about 15, L is a ligand that saturates the coordination sphere of zinc, and x is an integer of 0 to 4. In particular, n is an integer of 1 to about 5. In certain embodiments, the ligand L is water, hydroxide, phosphine, phosphine, ammonia, amino, amide, alkylthiolate, halide, and as long as the zinc species does not contain both sulfur and phosphorus. It is selected from the group consisting of combinations thereof. In some embodiments, alkaline earth metals such as magnesium, calcium, strontium, and barium may be added. Alkaline earth metals are typically basic salts including, but not limited to, metal oxides, metal alkoxides, metal carbonates, and metal bicarbonates.

In one embodiment, the zinc compound can be a zinc dithiocarbamato complex. For example, zinc dithiocarbamate has the formula 7:

In the formula, each _RI is independently a linear, cyclic, or branched, saturated or unsaturated aliphatic hydrocarbon moiety having 1 to about 10 carbon atoms, where n is 0 to 0. The integer of 2 and L are ligands that saturate the coordination sphere of zinc, and x is an integer of 0-4. In certain embodiments, the ligand L is selected from the group consisting of water, hydroxides, ammonia, aminos, amides, alkylthiolates, halides, and combinations thereof.

In one embodiment, the zinc compound can be a salen complex. For example, zinc salen has the formula 8:

In the equation, each _RJ is an independently hydrogen atom, or a linear, cyclic, or branched, saturated or unsaturated hydrocarbon moiety having 1 to about 8 carbon atoms, and each Y is Independently -C ( _{RJ "} ) _z , where each _RJ" is a straight-chain, cyclic, or branched, saturated or unsaturated fat with a hydrogen atom, 1 to about 8 carbon atoms. a family hydrocarbon moiety or an aromatic ring,, z, when N is imide or amino, 1 or 2, each R _{J 'is} independently hydrogen or from 1 to about 8 carbons, 5-, 6-, or 7-membered rings (5-, 6-, or 7-membered rings that are linear, cyclic, or branched, saturated or unsaturated aliphatic chain hydrocarbon moieties with atoms, or together with the atoms to which they are attached. It forms aromatics, fully saturated, or can contain varying levels of unsaturated), where n is an integer of 0-2, L is a ligand that saturates the coordination zone of zinc, and x is 0-4. Is an integer of. In certain embodiments, the ligand L is water, hydroxide, phosphine, phosphine, ammonia, amino, amide, alkylthiolate, halide, and as long as the zinc species does not contain both sulfur and phosphorus. It is selected from the group consisting of combinations thereof.

In one embodiment, the zinc compound can be a dimetalzinc complex. For example, the dimetalzinc complex has the formula 9:

In the formula, each _RK is a linear, cyclic, or branched, saturated or unsaturated hydrocarbon moiety having an independent hydrogen atom or 1 to about 30 carbon atoms, and each _{RK is represented by. "is} independently a hydrogen atom, a straight chain having from 1 to about 8 carbon atoms, cyclic, or branched, aliphatic hydrocarbon moiety, saturated or unsaturated or aromatic ring, each R _{K 'is} Independently with hydrogen atoms, or straight-chain, cyclic, or branched, saturated or unsaturated aliphatic chain hydrocarbon moieties with 1 to about 8 carbon atoms, or atoms to which they are attached. Together they form a 5-, 6-, or 7-membered ring (which can contain fully saturated or varying levels of unsaturated), where L is a ligand that saturates the coordination zone of zinc, x. Is an integer from 0 to 4. In certain embodiments, the ligand L is water, hydroxide, phosphine, phosfit, ammonia, amino, unless the zinc species contains both sulfur and phosphorus. It is selected from the group consisting of amides, alkylthiolates, halides, and combinations thereof.

In one embodiment, the zinc compound can be a phosphate ester, phosphinate, or phosphinite complex. For example, zinc phosphate ester, phosfit, phosphinate, or phosphinite can be expressed in the formula 10:

In the formula, when the phosphorus atom is in the oxidized state of +5 or +3, respectively, W is an oxo or unbound electron pair, and each _RL independently has 1 to about 10 carbon atoms. A linear, cyclic, or branched, saturated or unsaturated aliphatic hydrocarbon moiety, aromatic ring or alkoxide moiety, where n is an integer of 0 to 2 and L is a ligand that saturates the coordination zone of zirconium. Yes, x is an integer from 0 to 4. In some embodiments, the zinc phosphate ester, phosfit, phosphinate, and phosphinite structures are dimers with cross-linking ligand groups. In certain embodiments, the ligand L is selected from the group consisting of water, hydroxides, phosphines, phosphines, ammonia, aminos, amides, halides, and combinations thereof.

In one embodiment, the zinc compound can be pyridyl, polypyridyl, and quinolinolato complexes. For example, the pyridyl, polypyridyl, and quinolinolato complexes of zinc have the following formula 11:

In the formula, each _RM is independently a hydrogen atom, or a linear, cyclic, or branched, saturated or unsaturated aliphatic hydrocarbon moiety having 1 to about 10 carbon atoms, non-functional. A pyridyl ring typically substituted at the 2-position, which can be transformed or linked to another functionalized pyridyl ring to form a fused ring system commonly referred to as 8-hydroxyquinolin, quinoline, or phenanthroline. n is an integer of 0 to 2, L is a ligand that saturates the coordination sphere of zinc, and x is an integer of 0 to 4. In certain embodiments, the ligand L is water, hydroxide, phosphine, phosphine, ammonia, amino, amide, alkylthiolate, halide, and as long as the zinc species does not contain both sulfur and phosphorus. It is selected from the group consisting of combinations thereof.

In one embodiment, the zinc reactant can be complexed with the basic nitrogen dispersant succinimide. The basic nitrogen succinimide used to prepare the zinc complex has at least one basic nitrogen and is preferably oil-soluble. The succinimide composition can be post-treated with, for example, boron using procedures well known in the art, as long as the composition continues to contain basic nitrogen. The mono and porris succinimides that can be used to prepare the zinc complexes described herein are disclosed in numerous references and are well known in the art. Certain basic types of succinimide and related materials within the term "succinimide" in the art are described in US Pat. Nos. 3,219,666, 3,172,892 and 3,272,746. It has been taught and their disclosure is incorporated herein by reference. The term "succinimide" is understood in the art to include many of the amide, imide, and amidine species that may also be formed. However, the major product is succinimide, the term generally taken to mean the product of the reaction of an alkenyl-substituted succinic acid or anhydride with a nitrogen-containing compound. Preferred succinimides are succinimides prepared from hydrocarbyl succinic anhydride due to their commercial availability, hydrocarbyl groups contain from about 24-about 350 carbon atoms and ethyleneamines, and ethyleneamines are ethylenediamine, diethylenetriamine. , Triethylene tetraamine, tetraethylene pentaamine, in particular. Particularly preferred are polyisobutenyl succinic anhydrides of 70-128 carbon atoms and succinimides prepared from tetraethylenepentamine or triethylenetetraamine or mixtures thereof. The term "succinimide" also includes co-oligomers of hydrocarbyl succinic acid or anhydrides, and poly-secondary amines containing at least one tertiary amino nitrogen in addition to two or more secondary amino groups. Generally, the average molecular weight of this composition is 1,500 to 50,000. A typical compound would be a compound prepared by reacting polyisobutenyl succinic anhydride with ethylenedipiperazine.

Succinimides with an average molecular weight of 1000 or 1300 or 2300 and mixtures thereof are most preferred.

Generally, the amount of sulfur phosphorus-free zinc compound is about 0.001% to about 25% by weight, about 0.05% to about 20% by weight, or about 20% by weight, based on the total weight of the lubricating oil composition. It can be from 0.1% to about 15% by weight, or from about 0.5% to about 5% by weight, from about 1.0% to about 4.0% by weight.

In one aspect, the present disclosure provides a lubricating engine oil composition for a direct injection boost spark ignition internal combustion engine, comprising at least one sulfur phosphorus free zinc compound. In one embodiment, the amount of metal derived from at least one sulfur phosphorus-free zinc compound is from about 200 to about 3000 ppm, or from about 250 to about 3000 ppm, from about 300 to about 3000 ppm, from about 350 to about 3000 ppm, from about 400 ppm to. About 3000 ppm, about 500 to about 3000 ppm, about 600 to about 3000 ppm, about 700 to about 3000 ppm, about 900 to about 3000, about 950 to about 3000 ppm, about 1000 to 3000 ppm, about 1050 to about 3000 ppm, about 1100 to about 3000 ppm, It is about 1200 to about 3000 ppm, about 1300 to about 3000 ppm, about 1400 to about 3000 ppm, or about 1400 to 3000 ppm.

In one aspect, the present disclosure provides a lubricating engine oil composition for a direct injection boost spark ignition internal combustion engine, comprising at least one sulfur phosphorus free zinc compound and ZnDTP. In one embodiment, the amount of at least one sulfur phosphorus-free zinc compound and the metal derived from ZnDTP is about 700 to about 4000 ppm, or about 800 to about 4000 ppm, about 900 to about 4000, about 950 to about 4000 ppm, about. It is 1000-4000 ppm, about 1050 to about 4000 ppm, about 1100 to about 4000 ppm, about 1200 to about 4000 ppm, about 1300 to about 4000 ppm, about 1400 to about 4000 ppm, or about 1400 to 4000 ppm.

In one aspect, the present disclosure is a method of preventing or reducing low-speed, premature ignition of a direct-injection boost spark-ignition engine, while at the same time improving sediment control performance, at least one phosphorus sulfide-free zinc. Provided is a method comprising a step of lubricating an engine crankcase with a lubricating oil composition containing a compound. In one embodiment, the zinc compound does not contain sulfur or phosphorus. In one embodiment, the zinc compound is the zinc carboxylate described herein.

Generally, the amount of sulfur phosphorus-free zinc compound is about 0.001% to about 25% by weight, about 0.05% to about 20% by weight, or about 20% by weight, based on the total weight of the lubricating oil composition. It can be from 0.1% to about 15% by weight, or from about 0.1% to about 5% by weight, from about 0.1% to about 4.0% by weight.

In one embodiment, the sulfur phosphorus-free zinc compound can be combined with conventional lubricant cleaner additives containing magnesium and / or calcium. In one embodiment, the calcium detergent is 0 to about 2400 ppm metallic calcium, 0 to about 2200 ppm calcium metal, 100 to about 2000 ppm calcium metal, 200 to about 1800 ppm calcium metal, or about 100 in the lubricating oil composition. Approximately 1800 ppm, or about 200 to about 1500 ppm, or about 300 to about 1400 ppm, or about 400 to about 1400 ppm of calcium metal can be added in an amount sufficient to provide the lubricating oil composition. In one embodiment, the magnesium detergent lubricates about 100 to about 1000 ppm of magnesium metal in the lubricating oil composition, or about 100 to about 600 ppm, or about 100 to about 500 ppm, or about 200 to about 500 ppm of magnesium metal. It can be added in an amount sufficient to provide in the composition.

In one embodiment, the sulfur phosphorus-free zinc compound can be combined with conventional lubricant detergent additives containing lithium. In one embodiment, the lithium detergent is 0 to about 2400 ppm lithium metal, 0 to about 2200 ppm lithium metal, 100 to about 2000 ppm lithium metal, 200 to about 1800 ppm lithium metal, or about 100 in the lubricating oil composition. ~ About 1800 ppm, or about 200 to about 1500 ppm, or about 300 to about 1400 ppm, or about 400 to about 1400 ppm of lithium metal can be added in an amount sufficient to provide the lubricating oil composition.

In one embodiment, the sulfur phosphorus-free zinc compound can be combined with conventional lubricant cleaner additives containing sodium. In one embodiment, the sodium detergent is 0 to about 2400 ppm sodium metal, 0 to about 2200 ppm sodium metal, 100 to about 2000 ppm sodium metal, 200 to about 1800 ppm sodium metal, or about 100 in the lubricating oil composition. ~ About 1800 ppm, or about 200 to about 1500 ppm, or about 300 to about 1400 ppm, or about 400 to about 1400 ppm of sodium metal can be added in an amount sufficient to provide the lubricating oil composition.

In one embodiment, the sulfur phosphorus-free zinc compound can be combined with conventional lubricant cleaner additives containing potassium. In one embodiment, the potassium detergent is 0 to about 2400 ppm potassium metal, 0 to about 2200 ppm potassium metal, 100 to about 2000 ppm potassium metal, 200 to about 1800 ppm potassium metal, or about 100 in the lubricating oil composition. ~ About 1800 ppm, or about 200 to about 1500 ppm, or about 300 to about 1400 ppm, or about 400 to about 1400 ppm of potassium metal can be added in an amount sufficient to provide the lubricating oil composition.

In one embodiment, the present disclosure provides a lubricating engine oil composition comprising a lubricating oil basestock as a major component and at least one sulfur phosphorus free zinc compound as a trace component, at least one sulfur phosphorus free zinc. Compared to the slow early ignition performance achieved with engines using compound-free lubricants, the engine is 50% relative to the normalized slow early ignition (LSPI) number per 100,000 engine cycle. It shows a reduction of low speed early ignition, engine operation at 500-3,000 rpm, and net mean effective pressure (BMEP) of 10-30 bar.

In one aspect, the present disclosure provides a lubricating engine oil composition for use in a small boost engine containing a lubricating oil basestock as a major component and at least one sulfur phosphorus-free zinc compound as a trace component. , About 0.5 to about 3.6 liters, about 0.5 to about 3.0 liters, about 0.8 to about 3.0 liters, about 0.5 to about 2.0 liters, or about 1.0 It is in the range of ~ about 2.0 liters. The engine may have 2, 3, 4, 5, or 6 cylinders.

In one aspect, the present disclosure provides the use of at least one sulfur phosphorus-free zinc compound to prevent or reduce slow premature ignition in a direct injection boost spark ignition internal combustion engine.

Lubricating Oil Additives In addition to the zinc compounds described herein, lubricating oil compositions can include additional lubricating oil additives.

The lubricating oil compositions of the present disclosure may contain other conventional additives capable of imparting or improving any desired property of the lubricating oil composition in which these additives are dispersed or dissolved. Any additive well known to those of skill in the art can be used in the lubricating oil compositions disclosed herein. Some suitable additives are Mortar et al., "Chemistry and Technology of Lubricants", 2nd Edition, London, Springer, (1996), and Leslie R. et al. It is described in Radnik, "Lubricant Ads: Chemistry and Applications", New York, Marcel Dekker (2003), both of which are incorporated herein by reference. For example, lubricating oil compositions include antioxidants, abrasion resistant agents, metal cleaners, rust inhibitors, dehaze agents, anti-emulsifiers, metal inactivating agents, antiwear additives, flow point depressants, defoamers, etc. It can be blended with co-lubricants, corrosion inhibitors, ashless dispersants, multifunctional agents, dyes, extreme pressure agents and the like and mixtures thereof. Various additives are known and commercially available. These additives or similar compounds thereof can be used in the preparation of the lubricating oil compositions of the present disclosure by conventional blending procedures.

The lubricating oil composition of the present invention can contain one or more cleaning agents. Metal-containing or ash-forming cleaners act as cleaners to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life. Detergents generally have a polar head with a long hydrophobic tail. The polar head contains a metal salt of an acidic organic compound. Salts may contain substantially stoichiometric amounts of metal, in which case they are usually described as positive or neutral salts. Large amounts of metal bases can be incorporated by reacting excess metal compounds (eg, oxides or hydroxides) with acid gases (eg, carbon dioxide).

Cleaners that can be used include oil-soluble neutral and hyperbasic sulfonates, phenates, sulfide phenates, thiophosphonates, salicylates, and naphthenates, as well as metals, especially alkaline or alkaline earth metals such as barium, sodium, potassium, lithium. , Calcium, and other oil-soluble carboxylates of magnesium. The most commonly used metals are calcium and magnesium, and a mixture of calcium and / or magnesium and sodium, both of which can be present in the detergent used in the lubricant.

The lubricating oil composition of the present invention can contain one or more wear resistant agents that can reduce friction and excessive wear. Any wear resistant agent well known to those skilled in the art can be used in the lubricating oil composition. Non-limiting examples of suitable abrasion resistant agents include zinc dithiophosphate, metal dithiophosphate (eg, Pb, Sb, Mo, etc.) salts, metal dithiocarbamate (eg, Zn, Pb, Sb, Mo, etc.) salts. , Metal (eg Zn, Pb, Sb, etc.) salts of fatty acids, boron compounds, phosphate esters, phosphite esters, phosphate esters or amine salts of thiophosphate esters, reaction products of dicyclopentadiene with thiophosphate. , And combinations thereof. The amount of abrasion resistant agent is about 0.01% by weight to about 5% by weight, about 0.05% by weight to about 3% by weight, or about 0.1% by weight based on the total weight of the lubricating oil composition. Can vary by ~ about 1% by weight.

In certain embodiments, the abrasion resistant agent is or comprises a dihydrocarbyl dithiophosphate metal salt, such as a dialkylzinc dithiophosphate compound. The metal of the dihydrocarbyl dithiophosphate metal salt can be an alkaline or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. In some embodiments, the metal is zinc. In other embodiments, the alkyl group of the dihydrocarbyl dithiophosphate metal salt has about 3 to about 22 carbon atoms, about 3 to about 18 carbon atoms, about 3 to about 12 carbon atoms, or about 3 carbon atoms. It has about 8 carbon atoms. In a further embodiment, the alkyl group is a straight chain or a branched chain.

The amount of dithiophosphate dihydrocarbyl metal salt containing dithiophosphate dialkyl zinc salt in the lubricating oil composition disclosed herein is determined by its phosphorus content. In some embodiments, the phosphorus content of the lubricating oil composition disclosed herein is from about 0.01% to about 0.14% by weight based on the total weight of the lubricating oil composition. is there.

The lubricating oil composition of the present invention can contain one or more friction modifiers that can reduce friction between moving parts. Any friction modifier well known to those skilled in the art can be used in the lubricating oil composition. Non-limiting examples of suitable friction modifiers are aliphatic carboxylic acids; derivatives of aliphatic carboxylic acids (eg, alcohols, esters, booxide esters, amides, metal salts, etc.); mono, di or trialkyl substituted phosphoric acids. Or phosphonic acid; mono, di or trialkyl substituted phosphoric acid or derivatives of phosphonic acid (eg, esters, amides, metal salts, etc.); mono, di or trialkyl substituted amines; mono or dialkyl substituted amides and combinations thereof. Be done. In some embodiments, examples of friction modifiers include, but are not limited to, alkoxylated fatty amines; booxide fatty epoxides; fatty phosfits, fatty epoxides, fatty amines, booxide alkoxylated fatty amines, fatty acids. metal salts, fatty acid amides, glycerol esters, borated glycerol esters; fatty imidazolines its contents are disclosed in U.S. Pat. No. 6,372,696, incorporated herein by _reference; C 4 _{-C 75} or C, _{6 to} C ₂₄ , or C _{6 to} C ₂₀ , friction modifiers obtained from reaction products of fatty acid esters with nitrogen-containing compounds selected from the group consisting of ammonia, alkanolamines and the like, and mixtures thereof. .. The amount of the friction modifier is about 0.01% by weight to about 10% by weight, about 0.05% by weight to about 5% by weight, or about 0.1% by weight based on the total weight of the lubricating oil composition. Can vary from ~ about 3% by weight.

The lubricating oil composition of the present disclosure may contain a molybdenum-containing friction modifier. The molybdenum-containing friction modifier can be either a known molybdenum-containing friction modifier or a known molybdenum-containing friction modifier composition.

Preferred molybdenum-containing friction modifiers are, for example, oxymolybdenum sulfide dithiocarbamate, oxymolybdenum sulfide dithiophosphate, amine-molybdenum complex compounds, oxymolybdenum diethylateamide, and oxymolybdenum monoglyceride. Most preferred is a molybdenum dithiocarbamate friction modifier.

The lubricating oil composition of the present invention generally contains a molybdenum-containing friction modifier in an amount of 0.01 to 0.15% by weight with respect to the molybdenum content.

The lubricating oil composition of the present invention preferably contains an organic antioxidant in an amount of 0.01 to 5% by weight, preferably 0.1 to 3% by weight. The antioxidant can be a hindered phenolic antioxidant or a diallylamine antioxidant. Diarylamine antioxidants are advantageous in giving a base value derived from the nitrogen atom. Hindered phenol antioxidants are advantageous in that they do not produce NOx gas.

Examples of hindered phenol antioxidants are 2,6-di-t-butyl-p-cresol, 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol). 6-t-butyl-o-cresol), 4,4'-isopropyridenebis (2,6-di-t-butylphenol), 4,4'-bis (2,6-di-t-butylphenol), 2 , 2'-Methylenebis (4-methyl-6-t-butylphenol), 4,4'-thiobis (2-methyl-6-t-butylphenol), 2,2-thio-diethylenebis [3- (3,5) -Di-t-butyl-4-hydroxyphenyl) propionate], octyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, octadecyl 3- (3,5-di-t-butyl- 4-Hydroxyphenyl) propionate, and, but not limited to, octyl 3- (3,54-butyl-4-hydroxy-3-methylphenyl) propionate, and IrganoxL135 (registered trademark in any country) (BASF). , Naugarube 531 (registered trademark in any country) (manufactured by Methylura), Ethanox376 (registered trademark in any country) (manufactured by SI Group) and the like.

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

Hindered phenol antioxidants and diarylamine antioxidants can be used alone or in combination, respectively. If necessary, other oil-soluble antioxidants can be used in combination with the above antioxidants.

The lubricating oil composition of the present invention may further contain a succinimide oxymolybdenum complex, particularly a succinimide sulfur-containing oxymolybdenum complex. The sulfur-containing oxymolybdenum complex of succinimide can enhance the antioxidant effect when used in combination with the above-mentioned phenol or amine-based antioxidant.

In the preparation of lubricating oil formulations, it is common practice to introduce additives in the form of 10-80% by weight active ingredient concentrates in hydrocarbon oils such as mineral lubricants or other suitable solvents. ..

Generally, these concentrates can be diluted with a finished lubricant, eg, 3-100 parts by weight of the additive package, eg 5-40 parts by weight, in forming the crankcase motor oil. .. The purpose of the concentrate is, of course, to reduce the difficulty and awkwardness of handling various materials and to facilitate dissolution or dispersion in the final blend.

Procedure for Preparing Lubricating Oil Composition The lubricating oil composition disclosed herein can be prepared by any method well known to those skilled in the art for producing lubricating oils. In some embodiments, the base oil can be blended or mixed with the sulfur phosphorus-free zinc compounds described herein. Optionally, in addition to the sulfur phosphorus-free zinc compound, one or more other additives can be added. Phosphorus sulfide-free zinc compounds and any additives can be added to the base oil individually or simultaneously. In some embodiments, the phosphorus sulfide-free zinc compound and any additive are added individually to the base oil in the case of one or more additions, the additions may be in any order. In other embodiments, the sulfur phosphorus-free zinc compound and the additive are optionally added simultaneously to the base oil in the form of an additive concentrate. In some embodiments, solubilization of the phosphorus sulfide-free zinc compound or any solid additive in the base oil makes the mixture about 25 ° C to about 200 ° C, about 50 ° C to about 150 ° C or about 75 ° C. It can be helped by heating to a temperature of about 125 ° C.

Any mixing or dispersing device known to those of skill in the art can be used for blending, mixing or solubilizing the ingredients. Blending, mixing, or solubilizing can be done in blenders, stirrers, dispersers, mixers (eg planetary mixers and double planetary mixers), homogenizers (eg Gaulin homogenizers and Rannie homogenizers), mills (eg colloid mills, ball mills). And sand mills) or other mixing or dispersing devices known in the art can be used.

Applications of Lubricating Oil Compositions Lubricating oil compositions disclosed herein are used as motor oils (ie, engine oils or crankcase oils) for spark-ignition internal combustion engines, especially direct injection boost engines that are prone to low speed and early ignition. May be suitable for use.

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

Examples The following examples are for illustration purposes only and do not limit the scope of the invention.

Baseline Formulation The baseline formulation is a mixture of primary and secondary dialkyl zinc dithiophosphates in an amount that gives 770 ppm phosphorus and 890 ppm Zn to the Group 3 base oil, lubricant composition, (booxide and ethylene carbonate post-treatment). A mixture of polyisobutenyl succinimide dispersants, a molybdenum succinimide complex in an amount that gives 180 ppm of molybdenum to the lubricating oil composition, an alkylated diphenylamine antioxidant, a booxide friction modifier, a foam suppressant, a flow point lowering agent, and It contained an olefin copolymer viscosity index improver.

The lubricating oil composition was blended with a 5W-30 viscosity grade oil.

Zinc compound A
Zinc compound A is a low hyperbasic Zn salicylate (Zn 3.8%) with a TBN of 66 based on an additive concentrate (35% diluted oil) prepared from C _14- C ₁₈ alkylphenols containing CO ₂ and Zn O. Was formed.

Zinc compound B
Zinc compound B is zinc dithiocarbamate (ie, (bis ((dibutylcarbamochi oil) thio) zinc)) (Zn 13.79%).

Zinc compound C
The zinc compound C is zinc 2-ethylhexanoate (Zn 17.86%).

Example 1
Lubricating oil compositions were prepared by adding 1809 ppm zinc compound A 1809 ppm and 2177 ppm calcium from a combination of perbasic Ca sulfonate and phenate detergent to the baseline formulation.

Example 2
The lubricating oil composition was prepared by adding 1798 ppm of zinc compound B and 2320 ppm of calcium from a combination of a hyperbasic Ca sulfonate and a phenate detergent to the baseline formulation.

Example 3
The lubricating oil composition was prepared by adding 1616 ppm of zinc compound C 1616 ppm and 2177 ppm of calcium from a combination of a perbasic Ca sulfonate and a phenate detergent to the baseline formulation.

Example 4
The lubricating oil composition was prepared by adding 774 ppm of zinc compound C 774 ppm and 1860 ppm of calcium from a combination of a hyperbasic Ca sulfonate and a phenate detergent to the baseline formulation.

Example 5
The lubricating oil composition was prepared by adding 1626 ppm of zinc compound C 1626 ppm and 1935 ppm of calcium from a combination of a hyperbasic Ca sulfonate and a phenate detergent to the baseline formulation.

Example 6
The lubricating oil composition was prepared by adding 2488 ppm zinc compound C 2488 ppm and 2150 ppm calcium from a combination of hyperbasic Ca sulfonate and phenate detergent to the baseline formulation.

Comparative Example 1
Lubricating oil compositions were prepared by adding 2148 ppm calcium from a combination of superbasic Ca sulfonate phenate detergents to the baseline formulation.

Comparative Example 2
Lubricating oil compositions were prepared by adding 1858 ppm calcium from the combination of superbasic Ca sulfonate phenate detergents to the baseline formulation.

LSPI Test Slow and early ignition events were measured with a Ford 2.0L EcoBoost engine. This engine is a turbocharged gasoline direct injection (GDI) engine.

The Ford LSPI test is repeated 4 times for 4 hours. The engine operates at 1750 rpm and 1.7 MPa net mean effective pressure (BMEP), with a reservoir temperature of 95 ° C. The engine is operated in each stage 175,000 combustion cycle.

LSPI events are measured by monitoring the peak cylinder pressure (PP) and combustion mass ratio (MFB) of the fuel supply in the cylinder. If either or both meet the criteria, it can be said that an LSPI event has occurred. The peak cylinder pressure threshold varies from test to test, but typically exceeds the average cylinder pressure by 4-5 standard deviations. Similarly, the MFB threshold is typically 4-5 standard deviations faster than the average MFB (represented by crank angle). LSPI events can be reported as mean events per test, events per 100,000 combustion cycles, events per cycle, and / or combustion cycles per event. The results of this test are shown below.

In addition, a GM 2.0L LHU 4-cylinder gasoline turbocharged direct injection engine was used for the LSPI test. Each cylinder was equipped with a combustion pressure sensor.

The data show that the applicant's invention with the non-phosphorus sulfide-zinc compound is far more significant in terms of LSPI events as well as the number of events than the baseline example without the phosphorus sulfide-free zinc compound in the Ford engine. It shows that it provided excellent LSPI performance.

Claims (20)

Direct Injection Boost A method of preventing or reducing low-speed, premature ignition of a spark-ignition internal combustion engine, in which a zinc metal derived from at least one phosphorus sulfide-free zinc compound is used relative to the total weight of the lubricating oil composition. A method comprising the step of lubricating the crankcase of an engine with a lubricating oil composition containing 200 to about 3000 ppm. The method of claim 1, wherein the engine is operated under load with net mean effective pressure (BMEP) of about 12 to about 30 bar. The method of claim 1, wherein the engine is operated at a speed of 500 to 3,000 rpm. The sulfur phosphorus-free zinc compound includes zinc alkoxide or thiolate compound, zinc aryloxide or aryl thiolate compound, a colloidal dispersion of zinc oxide, a stable colloidal zinc suspension, a zinc amide compound, a zinc acetylacetone compound, and a carboxylic acid. Zinc, Zinc Alkylhydroxybenzoate, Zinc aryl sulfonate, Zinc sulfide phenate, Zinc dithiocarbamato complex, Zinc salen complex, Dimetalzic zinc complex, Zinc phosphate ester, Zinc phosphinate, Zinc phosphite complex, Zinc pyridyl complex, Zinc The method according to claim 1, which is a polypyridyl complex, a zinc quinolinolato complex, or a zinc succinimide. The method of claim 1, wherein the lubricating oil composition further comprises a cleaning agent selected from a calcium cleaning agent, a magnesium cleaning agent, a sodium cleaning agent, a lithium cleaning agent, and a potassium cleaning agent. The method of claim 5, wherein the cleaning agent is a carboxylate, salicylate, phenate, or sulfonate cleaning agent. The method of claim 1, wherein the lubricating oil further comprises a molybdenum-containing compound. Claimed that the lubricating oil composition further comprises at least one other additive selected from ashless dispersants, ashless antioxidants, phosphorus-containing wear resistant additives, friction modifiers, and polymer viscosity modifiers. The method according to 1. A lubricating engine oil composition for a direct injection boost spark ignition internal combustion engine containing about 200 to about 3000 ppm of zinc metal derived from at least one sulfur phosphorus-free zinc compound based on the total weight of the lubricating oil. The sulfur phosphorus-free zinc compound includes zinc alkoxide or thiolate compound, zinc aryloxide or aryl thiolate compound, colloidal dispersion of zinc oxide, stable colloidal zinc suspension, zinc amide compound, zinc acetylacetoneate compound, and carboxylic acid. Zinc, Zinc Alkylhydroxybenzoate, Zinc arylsulfonate, Zinc sulfide phenate, Zinc dithiocarbamato complex, Zinc salen complex, Dimetalzic zinc complex, Zinc phosphate ester, Zinc phosphinate, Zinc phosphinate complex, Zinc pyridyl complex, Zinc The lubricating engine oil composition according to claim 9, which is a polypyridyl complex, a zinc quinolinolato complex, or a zinc succinimide. The lubricating engine oil composition according to claim 9, wherein the lubricating oil composition further comprises a cleaning agent selected from a calcium cleaning agent, a magnesium cleaning agent, a sodium cleaning agent, a lithium cleaning agent, and a potassium cleaning agent. The lubricating engine oil composition according to claim 11, wherein the cleaning agent is a cleaning agent of carboxylate, salicylate, phenate, or sulfonate. The lubricating engine oil composition according to claim 9, wherein the lubricating oil composition further contains a molybdenum-containing compound. Claimed that the lubricating oil composition further comprises at least one other additive selected from ashless dispersants, ashless antioxidants, phosphorus-containing wear resistant additives, friction modifiers, and polymer viscosity modifiers. 9. The lubricating engine oil composition according to 9. Use of at least one sulfur phosphorus-free zinc compound in a lubricating engine oil composition to prevent or reduce slow premature ignition in a direct injection boost spark ignition internal combustion engine. 15. The at least one sulfur phosphorus-free zinc compound is present in about 200 to about 3000 ppm of a metal derived from at least one sulfur phosphorus free zinc compound, based on the total weight of the lubricating oil composition. Use as described in. Direct Injection Boost Spark Ignition A method of preventing or reducing low-speed, premature ignition of an internal combustion engine while at the same time improving sediment control performance, with a lubricating oil composition containing at least one phosphorus sulfide-free zinc compound. , A method comprising the step of lubricating the crankcase of the engine. 17. The method of claim 17, wherein the zinc compound does not contain sulfur or phosphorus. The method of claim 18, wherein the zinc compound is zinc carboxylate. The use of a lubricating engine oil composition in a small boost engine, wherein the lubricating engine oil composition contains a lubricating oil basestock as a major component and at least one sulfur phosphorus-free zinc compound as a trace component, said small engine. The range of is 0.5 liters to 3.6 liters, use.