KR20140111027A - Lubricating oil composition with reduced phosphorus levels - Google Patents

Abstract

The present invention relates generally to lubricants that are low in internal combustion engines, yet still provide good deposition control while still maintaining excellent viscosity control.

Description

LUBRICATING OIL COMPOSITION WITH REDUCED PHOSPHORUS LEVELS < RTI ID = 0.0 >

See related application

This application claims priority from U.S. Provisional Patent Application No. 60 / 665,961, filed March 29, 2005, the disclosure of which is incorporated herein by reference in its entirety.

Technical field

The present invention relates generally to lubricants that are low in internal combustion engines, yet still provide good deposition control while still maintaining excellent viscosity control.

Future engine oil lubricants will need to be low in phosphorus to protect the release system and will also be needed to provide extensive oxidation protection to the lubricant and to reduce wear and deposit in the engine. This is a difficult problem with conventional lubricants because the most effective abrasion resistance and antioxidant additive is phosphorus-containing zinc dialkyl dithiophosphate (ZDDP). In the past, high levels of ZDDP have been used because ZDDP is a low cost material and provides excellent wear and anti-oxidation performance. However, in the future, ZDDP will only be allowed at low levels. In 2004, some commercially available gasoline engine oil specifications allowed phosphorus up to 800 ppm from ZDDP. In future engine oil specifications, the level of phosphorus can fall below 500 ppm, possibly even further down. It is well known that when the level of ZDDP is reduced, the ashless antioxidant can replace some of the lost oxidation performance. However, it is known that higher levels of non-antioxidant do not always result in improved oxidation control. In fact, modern engine oils generally require the use of two or more asbestos antioxidant types to compensate for the loss of oxidative stability due to little use of ZDDP. In addition, the standard for deposition control is becoming more demanding. In many cases, modern and future lubricants will require a much higher level of the various non-aseptic antioxidants. The level of conventional ashless antioxidants in excess of 2.0% by weight may be unsuitable for adequately protecting lubricants and engines. These high levels of conventional ashless antioxidants are costly and can also lead to lubricant defects such as corrosion, rust, and seal incompatibility. There is a need for new low cost and low ash antioxidant systems that are effective in controlling lubricant oxidation and minimizing engine deposits.

In the present invention, the particular combinations and ratios of 4,4'-methylenebis (2,6-di-tert-butylphenol) and alkylated diphenylamines provide unexpectedly high levels of oxidation and deposition control ≪ / RTI > This allows the use of significantly lower treatment levels of aseptic antioxidants. The antioxidant system of the present invention is also effective in significantly reducing the formation of volatile organic molecules produced upon heating and oxidation of the lubricant. This effect has significant advantages for the environment because the reduction of volatile organic molecules will contribute to the reduction of emissions.

Summary of the Invention

One aspect of the present invention relates to a novel lubricating oil composition for internal combustion engines that still provides excellent deposition control while maintaining excellent viscosity control. Another aspect of the invention relates to the use of a novel lubricating oil composition for reducing the amount of deposition in an internal combustion engine. Yet another aspect of the present invention relates to the use of novel lubricant compositions for reducing the toxicity of catalysts in internal combustion engine systems.

A low engine oil as a composition of the present invention includes 4,4'-methylene bis (2,6-di-tert-butylphenol) and alkylated diphenylamine; Wherein the weight ratio of 4,4'-methylenebis (2,6-di-tert-butylphenol) to alkylated diphenylamine is greater than or equal to about 0.5 and the engine oil has a total solids content of less than 35 mg according to ASTM D7097 measurements .

Another composition of the present invention comprises:

(A) a lubricating viscosity oil selected from the group consisting of Group II, Group III, Group IV and synthetic ester base oils;

(B) 4,4'-methylenebis (2,6-di-tert-butylphenol);

(C) alkylated diphenylamine;

(D) at least one component selected from the group consisting of a dispersant and a detergent;

(E) zinc dialkyl dithiophosphate; Randomly

(F) a lipophilic organomolybdenum compound; And optionally

(G) hindered phenolic antioxidants (note that the hindered phenolic antioxidant is not 4,4'-methylenebis (2,6-di-tert-butylphenol));

Wherein the lubricating oil composition contains less than about 600 ppm phosphorus derived from zinc dialkyldithiophosphate;

(B) to (C) is about 0.5 or more.

Another composition of the present invention comprises:

(A) a lubricating viscosity oil selected from the group consisting of Group II, Group III, Group IV and synthetic ester base oils;

(B) 4,4'-methylenebis (2,6-di-tert-butylphenol);

(C) alkylated diphenylamine;

(E) zinc dialkyl dithiophosphate; And

(F) a lipophilic organomolybdenum compound; And optionally

(G) a hindered phenolic antioxidant, provided that the hindered phenolic antioxidant is not 4,4'-methylenebis (2,6-di-tert-butylphenol);

Wherein the weight ratio of (B) to (C) is at least about 0.5;

The composition produced less than about 35 mg of total deposits according to the ASTM D7097 measurement].

Still other compositions of the invention include:

(A) a lubricating viscosity oil selected from the group consisting of Group II, Group III, Group IV and synthetic ester base oils;

(B) 4,4'-methylenebis (2,6-di-tert-butylphenol);

(C) alkylated diphenylamine;

(D) at least one component selected from the group consisting of a dispersant and a detergent;

(E) zinc dialkyl dithiophosphate; And

(F) a lipophilic organomolybdenum compound; And optionally

(G) a hindered phenolic antioxidant, provided that the hindered phenolic antioxidant is not 4,4'-methylenebis (2,6-di-tert-butylphenol);

Wherein the lubricating oil composition comprises:

About 600 ppm or less derived from zinc dialkyldithiophosphate; And

Containing about 50 to 400 ppm molybdenum derived from a fat-soluble organomolybdenum compound.

Yet another composition of the present invention is an engine oil lubricant composition comprising:

(A) a lubricating viscosity oil selected from the group consisting of Group II, Group III, Group IV and synthetic ester base oils;

(B) 4,4'-methylenebis (2,6-di-tert-butylphenol);

(C) from 0.2 to 1.0% by weight alkylated diphenylamine;

(E) 200 to 600 ppm phosphorus derived from zinc dialkyldithiophosphate; And

(F) 50 to 400 ppm molybdenum derived from a fat-soluble organomolybdenum compound;

Wherein the weight ratio of (b) to (c) is at least 0.5.

Yet another composition of the present invention is an engine oil lubricant composition comprising:

(A) a lubricating viscosity oil selected from the group consisting of Group II, Group III, Group IV and synthetic ester base oils;

(B) 0.1 to 1.5% by weight of 4,4'-methylenebis (2,6-di-tert-butylphenol);

(C) alkylated diphenylamine;

(D) from 1.0 to 12.0% by weight of at least one compound selected from the group consisting of dispersants and detergents;

(E) 200 to 600 ppm phosphorus derived from zinc dialkyldithiophosphate; And

(F) 50 to 400 ppm molybdenum derived from a fat-soluble organomolybdenum compound;

Wherein the weight ratio of (b) to (c) is at least 0.5.

Another composition of the present invention is an engine oil lubricant composition comprising:

(A) a lubricating viscosity oil selected from the group consisting of Group II, Group III, Group IV and synthetic ester base oils;

(B) 4,4'-methylenebis (2,6-di-tert-butylphenol);

(C) from 0.2 to 1.0% by weight alkylated diphenylamine; And

(D) 300-600 ppm phosphorus derived from zinc dialkyldithiophosphate;

Wherein the weight ratio of (b) to (c) is at least 0.5.

Yet another composition of the present invention is an engine oil lubricant composition comprising:

(A) a lubricating viscosity oil selected from the group consisting of Group II, Group III, Group IV and synthetic ester base oils;

(B) 0.1 to 1.5% by weight of 4,4'-methylenebis (2,6-di-tert-butylphenol);

(C) alkylated diphenylamine;

(D) from 1.0 to 12.0% by weight of at least one compound selected from the group consisting of dispersants and detergents;

(E) 300-600 ppm phosphorus derived from zinc dialkyldithiophosphate;

Wherein the weight ratio of (b) to (c) is at least 0.5.

"High amount" means an amount of more than 50% by weight based on the total weight of the composition.

Figure 1 is a graph of the deposition results obtained from ASTM D7097 (TEOST MHT-4) in the absence of MoDTC (molybdenum bis (dialkyldithiocarbamate) containing 4.5 wt% molybdenum).
Figure 2 is a graph of the deposition results obtained from ASTM D7097 (TEOST MHT-4) in the presence of MoDTC.

DETAILED DESCRIPTION OF THE INVENTION

I. Definition

ASTM D7097 is a standard test method for the measurement of adequately hot piston deposits by heat-oxidation engine oil simulation test, approved in December 2004, which is hereby incorporated by reference in its entirety for any purpose. (Standard Test Method for Determination of Moderately High Temperature Piston Deposits by Thermo-Oxidation Engine Oil Simulation Tests). ASTM D7097 is a new standard lubricant industry test for the evaluation of oxidative and carbonaceous deposit-forming characteristics of engine oils. The test is designed to simulate the formation of high temperature deposits in the piston ring belt region of a modern engine. Details of test operations and specific conditions for the various protocols are further described in the following publications, all of which are incorporated by reference in their entirety for any purpose:

[Proceedings of 12th International Colloquium Tribology, TAE, Ostfildern, Germany, January 11-13, 2000, Supplement, pp. 55-62 [Selby and Florkowski, "Development of the TEOST Protocol MHT as a Bench Test of Engine Oil Piston Deposit Tendency" ].

SAE Technical Paper Series, 962039, from International Fall Fuels & Lubricants Meeting and Exposition, San Antonio, TX, October 14-17, 1996).

[Selby, "Recent Developments in Testing Lubricants" 6th International LFE Congress, Brussels, Belgium, June 2-4, 1999].

The test is also a useful tool for studying the formation of volatile organic molecules in the oxidation of engine oil. Generally, the formation of volatile organic molecules upon oxidation of the lubricant is considered harmful because it results in an increase in emissions and can further promote polymerization of the lubricant. Polymerization of the lubricant causes viscosity increase, which is also undesirable. The additive combination of the present invention is effective in controlling both the formation of volatile organic molecules and the deposition formation. Typically, polar, volatile organic molecules are formed by the decomposition of organic peroxides in the lubricant. This decomposition can react with another oil molecule to produce an alcohol, or it can decompose to produce an organic alkoxy radical that can form aldehydes and ketones. Decomposition of aldehydes and ketones generally reduces molecular weight and thus produces more volatile fragments, which are also active precursors of oligomers and polymers that are both contaminating and thickening lubricants. Therefore, it is more preferable to prevent or eliminate the formation of the polar, volatile organic molecules.

As used herein, "low engine oil" refers to an engine oil containing less than about 600 ppm phosphorus derived from zinc dialkyldithiophosphate.

As used herein, "hydrocarbyl" refers to any alkyl, alkenyl, or alkynyl group that may be linear, cyclic, or any combination thereof, wherein each group is optionally substituted. Such substituents may include reactive groups including, but not limited to, succinic groups.

The term "about" as used herein is intended to encompass a specified endpoint (s) and an excess of 20% or less. Accordingly, the above range is broad, and for example, "about 1" includes the range of 0.8 to 1.2.

The organic friction modifier is a molecule containing a non-polar hydrocarbon long chain having a polar end-group that has affinity for the metal engine surface. As used herein, "organic friction modifier" includes long chain organic fatty acids or carboxylic acids, esters, ethers, amines, imides, amides, sulfated fatty acids, metallo-organic compounds, high molecular weight organic phosphorus and phosphate esters But is not limited thereto. Examples of other conventional organic friction modifiers include those compounds which are incorporated by reference in their entirety for any purpose [R. Hoogendoorn and D. Kenbeek, "Friction Modifiers to the Rescue" in Lubes-n-Greases (2003), Vol. 9, Issue 11, pp. 14-20]. The organic friction modifier is typically used in an amount of 0 to 1.0 wt.% In fully formulated engine oil.

A "corrosion inhibitor" as used herein includes, but is not limited to, thiadiazole polysulfides containing 5 to 50 carbon atoms, derivatives thereof and polymers thereof. Typical corrosion inhibitors are described in [Hamblin, et al., "Ashless Antioxidants, Copper Deactivators and Corrosion Inhibitors: Their Use in Lubricating Oils", Lubrication Science (1990), 2 (4), pp. 287-318. A suitable corrosion inhibitor is a polysulfide derivative of 2,5-dimercapto-1,3,4-thiadiazole (1,3,4-thiadiazole polysulfide) having the formula: 4 < / RTI > thiadiazole derivatives:

Wherein x and y are from 0 to 8, x and y are independently selected from the group consisting of alkyl, aralkyl, aryl, and alkaryl radicals, wherein R ¹ and R ² are the same or different hydrocarbon radicals, Is 1 or more, and in some embodiments is 2 to 16; Methods of making such compounds are disclosed in U.S. Patent Nos. 2,719,125, 2,719,126, and 3,087,932, each of which is incorporated by reference in its entirety for any purpose. Other similar materials are disclosed in U.S. Patent No. 3,821,236; 3,904,537; 4,097,387; 4,107,059; 4,136,043; 4,188,299; And 4,193,882. Other corrosion inhibitors are thio and polythiosulfenamides of thiadiazoles such as those of the formula:

Wherein z is 2 to 5, R ³ is hydrogen, a hydrocarbyl group, another sulfenamide or thiosulfenamide group, R ⁴ and R ⁵ are hydrogen, or a hydrogen and a carbon-containing group, provided that R ⁴ and R < ⁵ > are not hydrogen), or R < ⁴ > and R < ⁵ > together with the nitrogen atom to which they are attached form a heterocyclic ring, as described in British Patent Specification 1,560,830. All referenced references are incorporated herein by reference in their entirety for any purpose. Benzotriazole derivatives also belong to the class of additives. Other examples of corrosion inhibitors are dodecenylsuccinic acid, esters, amides and mixed ester / amides, fatty amines, linear alkylamines, fatty acids, linear carboxylic acids, some branched alkylamines, some branched carboxylic acids, Some cleaning agents are included. Corrosion inhibitors are typically used in an amount of 0 to 0.5% by weight in fully formulated engine oil.

As used herein, "viscosity modifier" includes modifiers that serve to impart high temperature and low temperature operability to the lubricating oil. Such modifiers include copolymers of polyisobutylene, ethylene and propylene, and copolymers of higher alpha-olefins, polymethacrylates, polyalkyl methacrylates, methacrylate copolymers, unsaturated dicarboxylic acids and vinyl compounds, Partially hydrogenated copolymers of styrene / isoprene, styrene / butadiene, and isoprene / butadiene, as well as partially hydrogenated homopolymers of butadiene and isoprene and isoprene / divinylbenzene, It is not limited. A typical viscosity modifier is a polymer having a molecular weight in the range of 20,000 to 1,000,000. Typical viscosity modifiers include those described in [M. Mishra and R.G. Saxton, "Polymer Additives For Engine Oils" CHEMTECH, April 1995, pp. 35-41.

Pour point depressants are molecules added to oils that interfere with and modify the growth of wax crystals at low temperatures. A "pour point depressant " as used herein includes a depressant that acts to lower the minimum temperature at which the fluid can flow or pour. Such depressants include, but are not limited to, C ₈ to C ₁₈ dialkyl fumarate / vinyl acetate copolymers, polyalkyl methacrylates, and the like. Typical pour point depressants are described in [Mishra and Saxton, CHEMTECH, April 1995, pp. 35-41.

As used herein, "phosphorus-free abrasion resistant additive " refers to any phosphorus-free compound that reduces wear in engine, engine test, or bench wear tests when added to fully formulated engine oil. Examples of phosphorus-free abrasion resistant additives include sulfurized olefins, sulfurized fatty acids and oils, sulfurized fatty esters, sulfurized mixed fatty acid / fatty esters, sulfurized mixed fatty acids / olefins, sulfurized mixed fatty esters / fatty acids, organic sulfides, disulfides, And polysulfides, thiocarbamates, thioureasulfides, disulfides, triesulfides and polysulfides, molybdenum dithiocarbamates, zinc dithiocarbamates, molybdenum amine complexes, molybdenum alcohol complexes, mixed molybdenum Amine / molybdenum alcohol complex, and molybdenum carboxylate.

The "fully formulated engine oil" as used herein may contain further exemplary additives known to those skilled in the art and is used as engine oil on an as-received basis.

II. The component

Component (A)

Component (A) may be any combination of lubricating viscosity oils selected from the group consisting of Group II, Group III, Group IV and synthetic ester base oils. Component (A) may further comprise up to about 15% by weight of Group I base oil. A variety of base oil groups have been incorporated for reference in their entirety herein by reference [American Petroleum Institute (API) publication Engine Oil Licensing and Certification System, Industry Services Department, 14th Ed. (December 1996) Addendum 1 (December 1998)]. In one embodiment of the invention, the viscosity of the base oil is 3-12 mm ² / s (cSt) at 100 ° C; In another embodiment, the base oil has a viscosity of 4 to 10 mm ² / s (cSt) at 100 ° C; In yet another embodiment, the viscosity of the base oil is from 4.5 to 8 mm ² / s (cSt) at 100 ° C.

The Group II mineral oil base contains not less than 90% by weight of saturates and not more than 0.03% by weight of sulfur and a viscosity index of not less than 80 and less than 120, using the test method described in Table 1 below. In one embodiment, Group II base oils contain not less than 95 wt% saturates and not more than 0.01 wt% sulfur, and a viscosity index of greater than 100 and less than 120, using the test method described in Table 1 below.

The Group III mineral oil base contains not less than 90% by weight of saturates and not more than 0.03% by weight of sulfur and a viscosity index of not less than 120, using the test method described in Table 1 below. In one embodiment, the Group III base oil contains not less than 98% by weight of saturates and not more than 0.01% by weight of sulfur, and a viscosity index of 130 or more, using the test method described in Table 1 below.

Group IV base oils are poly-a-olefins.

Suitable ester base oils that may be used include dicarboxylic acids with various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoethers, propylene glycol, etc.) Such as phthalic acid, succinic acid, alkylsuccinic acid, alkenylsuccinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acid, ≪ / RTI > Specific examples of such esters include dibutyl adipate, bis (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, di-isooctyl azelate, di-isodecyl azelate, Ethylhexyl diester of linoleic acid dimer, complex ester formed by the reaction of 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid, and the like, .

Esters useful as base oils also include those prepared from C ₅ -C ₁₂ monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol and the like.

Analytical methods for base oil testing characteristic Test method Container ASTM D2007 Viscosity index ASTM D2270 sulfur ASTM D2622, D4292, D4927, or D3120

Component A comprises about 75 to 97 weight percent of the composition, based on the total weight of the composition. Most preferably, component A will comprise about 80 to 95% by weight.

Component (B)

The chemical structure of a hindered phenolic antioxidant which is 4,4'-methylenebis (2,6-di-tert-butylphenol) is shown below:

.

.

In one embodiment of the present invention, 4,4'-methylenebis (2,6-di-tert-butylphenol) is used in about 0.1 to about 1.5 weight percent in fully formulated engine oil.

Component (C)

The alkylated diphenylamine (component C) has the formula:

R _{a is} -NH-R _b

[Wherein R _a and R _b each independently represents a substituted or unsubstituted phenyl group]. The substituent on the phenyl ring may include, but is not limited to, an alkyl group having from 1 to 20 carbon atoms, an alkylaryl group, a hydroxy group, a carboxyl group and a nitro group. In one embodiment of the invention, one or two phenyl groups are substituted with alkyl. In yet another embodiment of the present invention, both of the phenyl groups are alkyl substituted.

Examples of alkylated diphenylamines that can be used in the present invention include 3-hydroxydiphenylamine, N-phenyl-1,2-phenylenediamine, N-phenyl- , Dibutyl diphenylamine, octyldiphenylamine, dioctyldiphenylamine, nonyldiphenylamine, dinonyldiphenylamine, heptyldiphenylamine, diheptyldiphenylamine, methylstyryldiphenylamine, mixed butyl / octylalkylated di Phenylethylamine, mixed butyl / styryl alkylated diphenylamine, mixed ethyl / nonyl alkylated diphenylamine, mixed octyl / styryl alkylated diphenylamine, mixed ethyl / methylstyryl alkylated diphenylamine, and petroleum industry Lt; RTI ID = 0.0 > purity. ≪ / RTI >

In one embodiment of the present invention, the nitrogen content of the alkylated diphenylamine ranges from about 2% to about 12% by weight of the alkylated diphenylamine. The concentration of the alkylated diphenylamine in the fully formulated oil may vary depending on the needs and applications of the customer and the desired level of antioxidant protection required for the particular composition of the present invention. In one embodiment of the invention, the alkylated diphenylamine is present in the composition of the present invention in an amount from about 0.05% to about 1.0% by weight of the composition; In another embodiment, is present in an amount from about 0.1% to about 0.75% by weight; In yet another embodiment, the alkylated diphenylamine is present in an amount from about 0.2 wt% to about 1.0 wt%.

Component (D)

The composition further comprises any dispersant and / or detergent (component D) used in engine oils and known in the art. In one embodiment of the present invention, a detergent or dispersant is present in the fully formulated engine oil formulation. In another embodiment, both the detergent and the dispersant are present in a fully formulated engine oil formulation. The dispersant or detergent may be boronized, or boron-injected.

Dispersants are well known in the lubricant art and do not normally contribute to any ash-forming metal when the dispersant does not contain ash-forming metal (before being mixed in the lubricant composition) and is added to the lubricant, "Including what is essentially a dispersant.

The dispersant is typically a non-metallic additive containing a nitrogen or oxygen polar group bonded to a high molecular weight hydrocarbon chain. The hydrocarbon chain provides solubility in the hydrocarbon base oil. The dispersant serves to maintain the oil degradation product suspended in the oil. Examples of suitable dispersing agents are polymethacrylates, styrene-maleic acid ester copolymers, substituted succinimides (e.g., PIBSA (polyisobutylene succinic anhydride)), polyamine succinimides, polyhydroxy succinic esters, Mannich bases, and substituted triazoles.

The dispersant may be boron-injected. Boron-implanted dispersants are well-known materials and can be prepared by treatment with a boronating agent such as boric acid. Typical conditions include heating the dispersant with boric acid at about 100 to < RTI ID = 0.0 > 150 C. < / RTI > The dispersant may also be treated by reaction with maleic anhydride; For example, succinimide dispersants can also be prepared by reacting an amount of an alpha, beta -unsaturated acid, such as maleic anhydride, or an equivalent thereof, with the amount of a hydrocarbyl-substituted acylating agent, Characterized in that there is present at least 1.3 succinic groups relative to the weight of the equivalents, wherein the reaction of the acid is carried out in accordance with WO 00/26327, filed October 13, 1999, the entirety of which is hereby incorporated by reference for any purpose May occur simultaneously or subsequent to the reaction of the amine with the hydrocarbyl-substituted acylating agent, as described.

In one embodiment of the invention, the amount of dispersant in the composition of the present invention ranges from about 0.5% to about 10% by weight based on the total composition weight. In another embodiment of the present invention, the amount of dispersant in the composition of the present invention ranges from about 1.0 wt% to about 12.0 wt%; In yet another embodiment, the amount ranges from about 1.0 wt% to about 8.0 wt%. In another embodiment of the present invention, the amount of dispersant in the composition of the present invention ranges from about 3.0 wt% to about 7.0 wt%. The concentration of the dispersant in the concentrate will correspondingly be increased, for example, from about 5% to about 90% by weight.

Detergents are generally salts of organic acids that are often over-chlorinated. Metal perchlorinated salts of organic acids are widely known to those skilled in the art and generally include metal salts in which the amount of metal present exceeds the stoichiometric amount. The detergent is typically a metallic additive containing a metal ion and a polar group, such as a sulfonate or carboxylate, together with an aliphatic, cycloaliphatic or alkylaromatic chain. The detergent acts by lifting deposits from various surfaces of the engine. Suitable detergents include neutral and perchlorinated alkali and alkaline earth metal sulfonates, neutral and perchlorinated alkali and alkaline earth metal phenates, sulfated phenates, and perchlorinated alkaline earth metal salicylates. Patents describing techniques for the manufacture of detergents generally include those described in U. S. Patent Nos. 2,501, 731, incorporated herein by reference for any purpose; 2,616,905; 2,616,911; 2,616,925; 2,777,874; 3,256,186; 3,384,585; 3,365,396; 3,320,162; 3,318,809; 3,488,284; 3,629,109.

The cleaning agent can generally be boron implanted by treatment with a boronating agent such as boric acid. Typical conditions include heating the detergent with boric acid at about 100 to 150 ° C, and the number of the boric acid equivalents generally corresponds to the number of equivalents of the metal in the salt. U.S. Pat. No. 3,929,650 discloses the use of boric acid in an oleophilic liquid reaction medium with alkali metal carbonates, perchlorinated metal sulfonates (prepared by over-chlorinating neutral alkaline or alkaline earth metal sulfonates with alkali metal carbonates) Disclose boron implanted composites prepared by contact, and are incorporated herein by reference in their entirety for any purpose.

In one embodiment of the invention, the amount of detergent in the compositions of the present invention ranges from about 0.5 wt% to about 5 wt%, based on the total weight of the composition. In another embodiment of the present invention, the amount of detergent in the compositions of the present invention ranges from about 1.0 wt% to about 6.0 wt%; In yet another embodiment, the amount ranges from about 1.0 wt% to about 4.0 wt%. In another embodiment of the present invention, the amount of detergent in the compositions of the present invention ranges from about 1.0 wt% to about 3.0 wt%, based on the total weight of the composition. The concentration of the detergent in the concentrate will be correspondingly increased, for example, from about 5% to about 70% by weight.

Component (E)

Zinc dialkyl dithiophosphate (ZDDP) (component E) in the oil composition is prepared by reaction of an alcohol or a phenol with an imidazole compound (P ₂ S ₅ ) to produce a dialkyl dithiophosphate derivative (DDPA) Can be any ZDDP derived from neutralization using a basic zinc compound.

A zinc salt of the formula (M = Zn):

Wherein R ⁸ and R ⁹ are independently a hydrocarbyl group containing 3 to 30 carbon atoms, can be prepared by reacting (P ₂ S ₅ ) with an alcohol or phenol:

.

.

The reaction involves mixing 4 moles of alcohol or phenol with 1 mole of the phosphorus pentasulfide at a temperature of 20 < 0 > C to 200 < 0 > C. The hydrogen sulfide is liberated in this reaction. Next, the acid reacts with the basic zinc compound to form a salt. In one embodiment of the invention, the basic zinc compound is zinc oxide (ZnO), and the resulting zinc compound is represented by the formula:

.

.

The R ⁸ and R ⁹ groups are independently, in one embodiment of the invention, a hydrocarbyl group free of acetylenic unsaturation. In yet another embodiment, R ⁸ and R ⁹ are free of ethylenic unsaturation, and in still other embodiments, R ⁸ and R ⁹ are free of both acetylenic and ethylenic unsaturation. In one embodiment, R ⁸ and R ⁹ are alkyl, cycloalkyl, aralkyl or alkaryl groups and have from 3 to 20 carbon atoms; In yet another embodiment, R ⁸ and R ⁹ have from 3 to 16 carbon atoms, and in yet other embodiments, no more than 13 carbon atoms, for example, from 3 to 13 carbon atoms. The alcohol that reacts to provide the R ⁸ and R ⁹ groups may be one or more primary alcohols, one or more secondary alcohols, or a mixture of secondary alcohols and primary alcohols. Mixtures of two secondary alcohols such as isopropanol and 4-methyl-2-pentanol may also be used.

Such materials are often referred to as zinc dialkyl dithiophosphates or simply zinc dithiophosphates. Such materials are well known and readily available to those skilled in the art of lubricant formulations.

In one embodiment of the invention, the level of ZDDP delivers less than about 600 ppm phosphorus to the composition of the present invention; In one embodiment, about 200 to about 600 ppm of phosphorus is delivered; In yet another embodiment, about 300 to about 600 ppm of phosphorus is delivered. "ppm" is based on the total weight of the composition. In another embodiment, the level of ZDDP delivers less than about 550 ppm phosphorus to the composition of the present invention. For example, ZDDP containing 8.5% by weight of phosphorus will be used at a level of less than 0.65% by weight in the composition of the present invention. In yet another embodiment, the level of ZDDP delivers less than about 500 ppm phosphorus to the composition of the present invention.

Component (F)

Any lipophilic organomolybdenum compound (Component F) may be used as an optional ingredient in the lubricating composition of the present invention. The amount of molybdenum delivered to the composition of the present invention will vary depending on the needs and applications of the customer and the desired level of antioxidant protection required for the particular composition of the present invention. Any concentration of liposoluble organomolybdenum may be used, but in one embodiment, the level is less than about 600 ppm. In another embodiment, the level is less than about 500 ppm. In yet another embodiment, the level is about 50 to 400 ppm. In another embodiment, the molybdenum level is about 100 to 250 ppm. In yet another embodiment, the level of molybdenum metal is about 250 to 400 ppm. "ppm" is based on the total weight of the composition.

In general, molybdenum is an effective antioxidant in lubricating oil compositions; The use of molybdenum in the compositions of the present invention needs to be balanced against the cost of lipophilic organomolybdenum compounds as compared to other antioxidants such as ZDDP.

Examples of some oil soluble organomolybdenum compounds that may be used in the present invention include molybdenum dithiocarbamate, oxymolybdenum sulfide dithiocarbamate, molybdenum dithioxane tongue, oxymolybdenum sulfide dithioxane tongue, molybdenum organo Molybdenum carboxylate, molybdenum amine complex, molybdenum alcohol complex, molybdenum amide complex, mixed molybdenum amine / alcohol / amide complex, and combinations thereof. The molybdenum amine / alcohol / amide complex may be used alone or in combination. In one embodiment of the invention, the molybdenum compound is a sulfur containing and phosphorus free compound.

Component (G)

Component (G) can be any hindered phenolic antioxidant other than 4,4'-methylenebis (2,6-di-tert-butylphenol). Component (G) is, for example: 2,6-di-tert-butylphenol; 2,6-di-tert-butyl-4-methylphenol; 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, isooctyl ester; 3,5-di -tert- butyl-4-hydroxy cinnamic acid hydrochloride, C ₇ -C ₉ - branched alkyl ester; 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, n-octadecyl ester; 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, n-butyl ester; 2,4,6-tri-tert-butylphenol; 2,4-di-tert-butylphenol; 4,4'-thiobis (2,6-di-tert-butylphenol); 4,4'-dithiobis (2,6-di-tert-butylphenol); 4,4'-polythiobis (2,6-di-tert-butylphenol); 2,2'-thiobis (4,6-di-tert-butylphenol); 2,2'-dithiobis (4,6-di-tert-butylphenol); 2,2'-polythiobis (4,6-di-tert-butylphenol); 4,4'-ethylidenebis (2,6-di-tert-butylphenol); 4,4'-butylidenebis (2,6-di-tert-butylphenol); 2,2'-methylenebis (4,6-di-tert-butylphenol); 2,2'-ethylidenebis (4,6-di-tert-butylphenol); 2,2'-butylidenebis (4,6-di-tert-butylphenol); 4,4'-thiobis (2-methyl-6-tert-butylphenol); 4,4'-dithiobis (2-methyl-6-tert-butylphenol); 4,4'-polythiobis (2-methyl-6-tert-butylphenol); 2,2'-thiobis (4-methyl-6-tert-butylphenol); 2,2'-dithiobis (4-methyl-6-tert-butylphenol); 2,2'-polythiobis (4-methyl-6-tert-butylphenol); 4,4'-ethylidenebis (2-methyl-6-tert-butylphenol); 4,4'-butylidenebis (2-methyl-6-tert-butylphenol); 2,2'-methylenebis (4-methyl-6-tert-butylphenol); 2,2'-ethylidenebis (4-methyl-6-tert-butylphenol); 2,2'-butylidenebis (4-methyl-6-tert-butylphenol); 4,4'-methylenebis (2-methyl-6-tert-butylphenol); Octylphenol; Nonylphenol; Dodecylphenol; Thiobis (octylphenol); Thiobis (nonylphenol); Thiobis (dodecylphenol); Dithiobis (octylphenol); Dithiobis (nonylphenol); Dithiovis (dodecylphenol); Polythiobis (octylphenol); Polythiobis (nonylphenol); Polythiobis (dodecyl phenol); Methylene bis (octylphenol); Methylene bis (nonylphenol); Methylene bis (dodecyl phenol); Ethylidene bis (octylphenol); Ethylidene bis (nonylphenol); Ethylidene bis (dodecyl phenol); Butyrylidene bis (octylphenol); Butyrylidene bis (nonylphenol); Butyrylidene bis (dodecylphenol); α, α'-thiobis (2,6-di-tert-butyl-p-cresol); α, α'-thiobis (2-methyl-6-tert-butyl-p-cresol); 2,6-di-tert-butyl-4-ethylphenol; 2,6-di-tert-butyl-4-butylphenol; 2,6-di-tert-butyl-4-octylphenol 2,6-di-tert-butyl-4-isoheptylphenol; 2,6-di-tert-butyl-4-isooctylphenol; 2,6-di-tert-butyl-4- (2-ethylhexyl) phenol; 2,6-di-tert-butyl-4-isononyl phenol; 2,6-di-tert-butyl-4-nonylphenol 2,6-di-tert-butyl-4-isodecylphenol; 2,6-di-tert-butyl-4-isododecylphenol; 2,6-di-tert-butyl-4-dodecylphenol; 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, isoheptyl ester; 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, isononyl ester; 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, isodecyl ester; 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, isododecyl ester; Or non-volatile multi-ring (or methylene bridged) tert-butyl phenolic as defined below:

Wherein R may be hydrogen, or tert-butyl, as defined in any one of U.S. Patent No. 3,211,652, or alternatively, And as described in U.S. Patent Application 2002/0142923 and U.S. Patent No. 2,807,653, for example, R may be hydrogen or a hydrocarbon having up to about 9 carbon atoms May be radicals]. Each of the referenced references is incorporated herein by reference in its entirety for any purpose.

In one embodiment of the present invention, the hindered phenolic antioxidant contains sulfur. In another embodiment of the present invention, the hindered phenolic antioxidant is free of sulfur.

In one embodiment of the invention, the amount of hindered phenolic antioxidant other than 4,4'-methylenebis (2,6-di-tert-butylphenol) is in the range of about 0.1% to about 0.75% % ≪ / RTI > In another embodiment, it is present in an amount from about 0.1% to about 0.5% by weight, all percentages by weight being based on the total weight of the composition.

III. Other Embodiments of the Invention

The present invention provides a lubricating oil composition that can provide improved conditioning control to an internal combustion engine.

In one aspect of the present invention, the low engine oil composition comprises: 4,4'-methylene bis (2,6-di-tert-butylphenol) and alkylated diphenylamine; Wherein the weight ratio of 4,4'-methylenebis (2,6-di-tert-butylphenol) to alkylated diphenylamine is greater than or equal to about 0.5 and the engine oil has a total solids content of less than 35 mg according to ASTM D7097 measurements . In one embodiment, the composition further comprises zinc dialkyl dithiophosphate; Here, the engine oil contains about 600 ppm or less phosphorus derived from zinc dialkyldithiophosphate. In another embodiment, the composition further comprises a lipid soluble organomolybdenum compound. Engine oils include formulated oils used in gasoline, diesel, natural gas and railroad engines.

In one aspect of the present invention, the engine oil comprises:

(A) a lubricating viscosity oil selected from the group consisting of Group II, Group III, Group IV and synthetic ester base oils;

(B) 4,4'-methylenebis (2,6-di-tert-butylphenol);

(C) alkylated diphenylamine;

(D) at least one component selected from the group consisting of a dispersant and a detergent; And

(E) zinc dialkyldithiophosphate (ZDDP);

Wherein the composition comprises less than about 600 ppm phosphorus (ZDDP) derived from zinc dialkyldithiophosphate; (B) to (C) is about 0.5 or more.

In another embodiment of the present invention, the composition further comprises a lipid soluble organomolybdenum compound. In yet another embodiment, the liposoluble organomolybdenum compound comprises sulfur and is free of phosphorus. In one embodiment of the present invention, the weight ratio of phosphorus to molybdenum in the composition is at least 1.0. In another embodiment, the weight ratio of phosphorus to molybdenum is greater than 0.0 and less than 1.0. In yet another embodiment of the present invention, the weight ratio of phosphorus to molybdenum is less than or equal to 1.0. In another embodiment of the invention, the composition may contain a hindered phenolic antioxidant (G), provided that the hindered phenolic antioxidant is 4,4'-methylenebis (2,6-di- tert-butylphenol). In yet another embodiment of the invention, the sum of (B), (C) and (G) is less than or equal to about 1.5% by weight of the composition. In another embodiment of the present invention, the lubricating viscosity oil (component (A)) comprises up to about 15% by weight of Group I base oil (based on the weight of Component A). A further embodiment is the lubricating oil composition described above, wherein the composition produces less than about 35 mg of total deposits according to ASTM D7097 measurements; In yet another embodiment, the composition produces less than about 25 mg total deposit according to the ASTM D7097 measurement; In yet another embodiment, the composition produces less than about 15 mg total deposits.

In another aspect of the present invention, the engine oil comprises:

(A) a lubricating viscosity oil selected from the group consisting of Group II, Group III, Group IV and synthetic ester base oils;

(B) 4,4'-methylenebis (2,6-di-tert-butylphenol); And

(C) alkylated diphenylamine;

(E) zinc dialkyl dithiophosphate; And

(F) a lipophilic organomolybdenum compound;

Wherein the weight ratio of (B) to (C) is at least about 0.5; The composition produces less than about 35 mg total deposits according to ASTM D7097 measurements.

In one embodiment of the invention, the liposoluble organomolybdenum compound contains sulfur and no phosphorus. In one embodiment, the weight ratio of phosphorus to molybdenum is at least 1.0; In another embodiment, the weight ratio is greater than 0.0 and less than 1.0. In yet another embodiment of the present invention, the weight ratio of phosphorus to molybdenum is less than or equal to 1.0. In another embodiment of the present invention, the composition further comprises at least one component selected from the group consisting of a dispersant and a detergent. In another embodiment of the present invention, the engine oil further comprises (G) a hindered phenolic antioxidant, wherein the hindered phenolic antioxidant is 4,4'-methylenebis (2,6-di- tert-butylphenol). In yet another embodiment, the sum of (B), (C) and (G) is less than or equal to about 1.5% by weight of the composition. In a further embodiment of the invention, such a composition produces less than about 25 mg of total deposits in accordance with the ASTM D7097 measurement. In yet another embodiment of the present invention, the engine oil further comprises (G) at least one component selected from the group consisting of (D) a dispersant and a detergent, and (G) a hindered phenolic antioxidant, provided that the hindered phenol The sex antioxidant is not 4,4'-methylene bis (2,6-di-tert-butylphenol). In yet another embodiment, the sum of (B), (C) and (G) is less than or equal to about 1.5 weight percent of engine oil. In a further embodiment of the present invention, such engine oil produces less than about 25 mg total deposits in accordance with ASTM D7097 measurements. A further embodiment is the engine oil described above, wherein the engine oil produces less than 15 mg total deposits in accordance with ASTM D7097 measurements.

In yet another aspect of the present invention, engine oil comprises:

(A) a lubricating viscosity oil selected from the group consisting of Group II, Group III, Group IV and synthetic ester base oils;

(B) 4,4'-methylenebis (2,6-di-tert-butylphenol); And

(C) alkylated diphenylamine;

(D) zinc dialkyl dithiophosphate;

(E) a liposoluble organomolybdenum compound;

(F) at least one component selected from the group consisting of a dispersant and a detergent; And

(G) a hindered phenolic antioxidant, provided that the hindered phenolic antioxidant is not 4,4'-methylenebis (2,6-di-tert-butylphenol);

Wherein the composition comprises: up to about 600 ppm phosphorus derived from zinc dialkyldithiophosphate, and

Containing about 50 to 400 ppm molybdenum derived from a fat-soluble organomolybdenum compound.

In one embodiment of the invention, the liposoluble organomolybdenum compound contains sulfur and no phosphorus. In one embodiment, the weight ratio of phosphorus to molybdenum is at least 1.0; In another embodiment, the weight ratio is greater than 0.0 and less than 1.0. In yet another embodiment of the present invention, the weight ratio of phosphorus to molybdenum is less than or equal to 1.0. In another embodiment of the present invention, the engine oil contains less than about 550 ppm phosphorus derived from zinc dialkyldithiophosphate. In another embodiment of the present invention, the engine oil contains less than about 500 ppm phosphorus derived from zinc dialkyldithiophosphate. In yet another embodiment of the present invention, the composition comprises less than about 400 ppm of phosphorus derived from zinc dialkyldithiophosphate. In yet another embodiment, the engine oil comprises less than about 300 ppm of phosphorus derived from zinc dialkyl dithiophosphate. In another embodiment of the present invention, the engine oil comprises about 100 to 250 ppm of molybdenum derived from the oil-soluble organomolybdenum compound. In yet another embodiment of the present invention, the engine oil comprises about 250 to 400 ppm of molybdenum derived from the oil-soluble organomolybdenum compound. In yet another embodiment of the present invention, the engine oil comprises about 300 to 400 ppm of molybdenum derived from the oil-soluble organomolybdenum compound. In yet another embodiment of the present invention, the composition comprises about 50 to 150 ppm of molybdenum derived from a liposoluble organomolybdenum compound. In this paragraph, all parts per million (ppm) are based on the total weight of engine oil.

Yet another aspect of the present invention is an engine oil comprising:

(A) a lubricating viscosity oil selected from the group consisting of Group II, Group III, Group IV and synthetic ester base oils;

(B) 4,4'-methylenebis (2,6-di-tert-butylphenol);

(C) from 0.2 to 1.0% by weight alkylated diphenylamine;

(E) 200 to 600 ppm phosphorus derived from zinc dialkyldithiophosphate; And

(F) 50 to 400 ppm molybdenum derived from a fat-soluble organomolybdenum compound;

Wherein the weight ratio of (B) to (C) is at least 0.5.

Yet another aspect of the present invention is an engine oil lubricant composition comprising:

(A) a lubricating viscosity oil selected from the group consisting of Group II, Group III, Group IV and synthetic ester base oils;

(B) 0.1 to 1.5% by weight of 4,4'-methylenebis (2,6-di-tert-butylphenol);

(C) alkylated diphenylamine;

(D) from 1.0 to 12.0% by weight of at least one compound selected from the group consisting of dispersants and detergents;

(E) 200 to 600 ppm phosphorus derived from zinc dialkyldithiophosphate; And

(F) 50 to 400 ppm molybdenum derived from a fat-soluble organomolybdenum compound;

Wherein the weight ratio of (B) to (C) is at least 0.5.

In one embodiment of the invention, the engine oil comprises from 0.1 to 0.5% by weight of any ester derived from 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid.

Another aspect of the present invention is an engine oil comprising:

(A) a lubricating viscosity oil selected from the group consisting of Group II, Group III, Group IV and synthetic ester base oils;

(B) 4,4'-methylenebis (2,6-di-tert-butylphenol);

(C) 0.2 to 1.0 wt% alkylated diphenylamine, and

(E) 300-600 ppm phosphorus derived from zinc dialkyldithiophosphate;

Wherein the weight ratio of (B) to (C) is at least 0.5.

In one embodiment of the present invention, the engine oil further comprises 0.1 to 0.5 wt% of any ester derived from 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid.

Another aspect of the present invention is an engine oil comprising:

(A) a lubricating viscosity oil selected from the group consisting of Group II, Group III, Group IV and synthetic ester base oils;

(B) 0.1 to 1.5% by weight of 4,4'-methylenebis (2,6-di-tert-butylphenol);

(C) alkylated diphenylamine;

(D) from 1.0 to 12.0% by weight of at least one compound selected from the group consisting of dispersants and detergents; And

(E) 300-600 ppm phosphorus derived from zinc dialkyldithiophosphate;

Wherein the weight ratio of (B) to (C) is at least 0.5.

All percentages by weight (% by weight) given above for the engine oil of the present invention are based on the total weight of the engine oil. By "large amount" is meant an amount of greater than 50% by weight based on the total weight of the engine oil.

A further embodiment of the present invention is any composition or engine as described above, further comprising at least one component selected from the group consisting of an organic friction modifier, a corrosion inhibitor, a viscosity modifier, a pour point depressant, and a phosphorus- It is oil.

A further aspect of the present invention relates to the use of the total volatile organic compounds produced by the internal combustion engine during heating and oxidation of engine oil, including lubrication of the engine with any composition or engine oil described herein, Both of the polarity).

Yet another aspect of the present invention is a method of reducing the amount of deposits in an internal combustion engine, including lubricating the engine with any composition or engine oil described herein.

A further aspect of the present invention is a method of reducing the toxicity of a catalyst in an internal combustion engine emission system, comprising lubrication of the engine with any composition or engine oil described herein.

The following combinations are examples of embodiments of the invention wherein the sum of (B), (C) and (G) is less than or equal to about 1.5% by weight of the composition.

TEOST MHT equipment will have to proceed according to ASTM D7097 method and manufacturer's specifications. The test involves passing a thin film of test engine oil over a heated wire-bending depositor bar with an aide of a precision pump. The test rod was heated at 285 DEG C and the test was allowed to proceed for 24 hours. The thin film of oil moves uniformly down the bar and is collected at the flow out point of the test assembly equipment. The recovered oil is circulated back to the depositing bar via a tube peristaltic pump. During a 24 hour test period, the volatiles are generated to flash off from the hot rod surface and condense on the glass layer of the test assembly device. These volatiles are recovered from the volatiles outside the port of the test assembly and collected in a glass vial. Upon completion of the test, the deposits are measured by increasing the deposition rod weight and recorded in milligrams (mg). Accumulate the weight of the volatiles collected and record in grams (g).

The method requires many independent corrections, including, for example, correcting the convection rate, oil pump speed, thermostat setting, and regulating thermocouple. The method also requires that the certification standard oil be run periodically to determine the severity of the test. For example, an authentic media deposition standard oil will typically produce 40 to 60 mg of deposits while an authentic high deposition standard oil will generate approximately 70 to 90 mg of deposits. Strict test conditions will usually produce heavier deposits and higher levels of volatiles. On the other hand, moderate test conditions will usually produce lighter deposits and much lower levels of volatiles. Under stringent test conditions, engine oil that performs well with low deposition and low volatility is expected to perform much better under moderate test conditions. However, engine oils that perform well under moderate test conditions are expected to perform poorly under stringent test conditions. The additive combination of the present invention results in excellent deposition control and reduced volatilization, under both stringent and moderate conditions. Under both rigorous and moderate conditions, the robust performance of the novel additive combination is another advantage of the present invention.

III. Example

Measurement of deposits and volatiles in TEOST-MHT

A fully formulated oil (8.4 g) and an organometallic catalyst (about 0.1 g) were added to a flask equipped with a Teflon stir bar and stirred for 20-60 minutes without heating. The deposition rod, sample flask, oil inlet, air inlet, and volatile material collection vials were fitted to TEOST equipment according to the manufacturer's specifications. The pump was started at a high flow rate and progressed until the test oil reached the connection of the pump and the oil supply tube (when the pump flow returned to zero). With the heater switch on and the calender bar thermostat at 200-210 ° C, the pump speed is increased to allow the sample to be delivered at a rate of 0.25 ± 0.02 g / min so that the oil flows below the depositor bar and is not leaked Respectively. The temperature was allowed to stabilize at 285 +/- 2 DEG C and the test was allowed to proceed for 24 hours under these conditions.

Three test tubes were prepared for oil extraction from the deposition rod using cyclohexane or another suitable hydrocarbon solvent. The test equipment was disassembled as instructed by the manufacturer, the deposition rod was transferred to a gravimetric boat and held under the cover. In each of the three test tubes made using the hydrocarbon solvent, the deposition bar was continuously placed for 10 minutes each. The rod was placed in a tared weight boat and left for 10 minutes to allow the hydrocarbon solvent to evaporate. Rods and boats were weighed to confirm that a certain mass was achieved. The contents of the three test tubes along the lower end cap deposits and the glass layer deposits were washed in a conventional container and then filtered using a glass funnel equipped with a filter cartridge. After the filtration was completed, the filter cartridge was dried under vacuum and weighed until a constant mass was achieved. Next, the total mass of deposits and filter deposits from the deposition rod was measured.

During the test period of 24 hours, the volatile compounds in the formulated oil, either originally formed or during the test, were flash-off from the deposition bar. These volatiles were condensed on the glass layer and collected on a continuous basis in a small, heavy weight vial. The vials and volatiles were measured at the completion of the 24 hour test period and the amount of volatiles was calculated by subtracting the original weight of the vial.

Example A

The pre-dentate was prepared by blending the following materials:

150 N II group base oil, 92.1 wt%;

4.92 wt% ashless dispersant concentrate;

1.85% by weight of a perchlorinated detergent concentrate containing calcium;

0.51% by weight of a neutral detergent concentrate containing calcium; And

Secondary zinc dialkyldithiophosphate, 0.62 wt%.

To the prehomes were added the following ingredients as indicated in Table 2 below in the preparation of various engine oils. The finished engine oil contained (calculated): Calcium 2400 ppm; 470 ppm; Zinc 520 ppm; And had a total base number of 7.5 mg KOH / g (oil).

The finished oil was tested in TEOST MHT according to ASTM D7097. Certified Media Deposition Standard oil produced 60.6 mg of deposits in calibration experiments. The certified high-deposition standard oil produced 96.8 mg of the deposit in the calibration experiment; These results indicate the stringent conditions for TEOST MHT equipment. The results of the analysis under stringent conditions are reported in Table 2.

Table 2 clearly shows that the combination of MBDTBP, NDPA and MoDTC in the present invention results in low levels of deposits (12 and 10 mg) and volatiles (2.2 and 1.9 g) in TEOST MHT using ASTM D7097. It was also clear in the present invention that the combination of MBDTBP and NDPA without MoDTC resulted in low levels of deposit (14 mg) and volatiles (2.3 g) in TEOST MHT using ASTM D7097.

A graph of deposition results in the presence of MoDTC is shown in FIG.

A graph of deposition results in the absence of MoDTC is shown in FIG.

Example B - Oil vaporization and oxidation at elevated temperatures

The prehomogenate was prepared by blending the following materials:

4.92 wt% ashless dispersant concentrate;

1.85 wt% of a perchlorinated detergent concentrate containing calcium;

0.51% by weight of a neutral detergent concentrate containing calcium;

0.62 wt% of secondary zinc dialkyl dithiophosphate; And

150 N II group base oil 92.10% by weight.

To the engine oil pre-mixed, the components indicated in Table 3 were added.

The finished engine oil contained the following elements and physical properties (calculated values): B.1, B.3, B.4, B.5, and B.6: 2400 ppm of calcium; 470 ppm; Zinc 520 ppm; And total base number (TBN) of 8.6 mg KOH / g (oil). For example, B.2: calcium 2400 ppm; 690 ppm; Zinc 765 ppm; And a total base number of 8.6 mg KOH / g (oil).

The oxidation stability of the finished engine oil was evaluated in a bulk oil oxidation test. Each oil (300 mL) was treated with an iron naphthenate oxidation catalyst to deliver 110 ppm of iron to the finished oil. The oil was heated in a block heater at 160 DEG C while 10 liters / hour of dry oxygen was bubbled through the oil. The oxidized oil samples were removed at 24, 48, 72 and 96 hours. The kinematic viscosity of each sample was measured at 40 占 폚. The% viscosity increase of oxidized oil versus fresh oil was calculated. The% viscosity increase results are shown in Table 4.

The higher% viscosity increase is a measure of increased oxidation and degradation of the lubricant. The designation TVTM indicates a severe degradation of the lubricant. These results clearly show that the antioxidants of the present invention in combination with Example B.6 provide excellent oxidation protection compared to the other Examples (B.1-B.5). Antioxidant systems that do not contain organomolybdenum components (B.1, B.2, and B.4) exhibit poor oxidation control, while systems containing hindered phenolic MBDTBP (B.6) (B.3). ≪ / RTI >

Example C - Oil Deposition and Oxidation

A.2, A.3, A.7, A.9, A.11, A.13, A.15, A.16, and A.17 (Table 2) And evaluated in an oxidation test. In this study, 10 liters / hour of dry oxygen was bubbled through the oil while heating the oil in a heating block at 150 占 폚. The oxidized oil samples were removed at 24, 48, 72 and 96 hours. The kinematic viscosity of each sample was measured at 40 占 폚. The% viscosity increase of oxidized oil versus fresh oil was calculated. The% viscosity increase is shown in Table 5.

The results show that oil A.11 corresponds to oils A.2 and A.9 and is significantly better than oils A.3 and A.7. However, oil A.11 also shows a significant improvement in terms of deposition conditioning and volatility compared to all oils, as described in Example A. Thus, the oil A.11 of the present invention is an engine oil of better overall performance and provides excellent viscosity control, deposition control, and control of volatile organic compounds. The ability of the oil A.11 of the present invention to demonstrate its benefits in all these variables is valuable. Antioxidant systems containing organomolybdenum compounds (A.13, A.15, A.16 and A.17) show excellent viscosity control.

The above-described embodiments are not limiting, but merely illustrative of various aspects and implementations of the present invention. All documents referred to herein are indicative of the level of the art to which this invention pertains and are incorporated herein by reference in their entirety for any purpose. However, nothing is recognized as prior art.

Those skilled in the art will readily appreciate that the present invention is well adapted to carry out the subject matter mentioned and to achieve the objects and advantages, as well as those inherent therein. The methods and compositions described to illustrate various embodiments are illustrative and are not intended to limit the scope of the invention. Certain modifications and other uses will occur to those skilled in the art and such modifications and uses are intended to be included within the spirit of the invention as defined by the scope of the claims.

The invention illustratively described herein may suitably be practiced without any element or elements, limitations or limitations not specifically disclosed herein. The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention in the use of the above terms and expressions to exclude any corresponding items of the features shown and described. It will be appreciated that various modifications are possible within the scope of the claimed invention. Thus, although the present invention has been specifically disclosed by the described embodiments, any features, modifications and variations of the concepts disclosed herein may be reclassified by those skilled in the art, and such modifications and variations are possible in light of the detailed description and the appended claims Quot; is considered to be within the scope of the present invention as defined by < / RTI >

Claims (3)

A low phosphorus engine oil, comprising:
4,4'-methylenebis (2,6-di-tert-butylphenol);
Alkylated diphenylamine;
A liposoluble organomolybdenum compound; And
Zinc dialkyl dithiophosphate;
Wherein the engine oil comprises less than about 600 ppm phosphorus derived from the zinc dialkyl dithiophosphate;
The weight ratio of 4,4'-methylenebis (2,6-di-tert-butylphenol) to the alkylated diphenylamine is about 0.5 or more. A composition comprising:
(a) a lubricating viscosity oil selected from the group consisting of Group II, Group III, Group IV and synthetic ester base oil;
(b) 4,4'-methylenebis (2,6-di-tert-butylphenol);
(c) alkylated diphenylamine;
(d) at least one component selected from the group consisting of a dispersant and a detergent;
(e) zinc dialkyl dithiophosphate; And
(f) a lipophilic organomolybdenum compound;
Wherein the composition comprises less than about 600 ppm phosphorus derived from the zinc dialkyl dithiophosphate;
(b) to (c) is about 0.5 or more. A composition comprising:
(a) a lubricating viscosity oil selected from the group consisting of Group II, Group III, Group IV and synthetic ester base oil;
(b) 4,4'-methylenebis (2,6-di-tert-butylphenol);
(c) alkylated diphenylamine;
(e) zinc dialkyl dithiophosphate; And
(f) a lipophilic organomolybdenum compound;
Wherein the composition comprises less than about 600 ppm phosphorus derived from the zinc dialkyl dithiophosphate;
(b) to (c) is about 0.5 or more.

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