KR20070116049A - Lubricating oil composition with reduced phosphorus levels - Google Patents

Abstract

This invention is generally related to a low phosphorus lubricant for an internal combustion engine that provides superior deposit control while still retaining excellent viscosity control.

Description

Lubricant composition with reduced phosphorus level {LUBRICATING OIL COMPOSITION WITH REDUCED PHOSPHORUS LEVELS}

See related applications

This application claims priority to US Provisional Patent Application 60 / 665,961, filed March 29, 2005, the entirety of which is hereby incorporated by reference herein.

Technical field

The present invention generally relates to low phosphorus lubricants for internal combustion engines, which still provide excellent deposition control while still maintaining good viscosity control.

Future engine oil lubricants will need to have a low phosphorus level to protect the release system, and will also be needed to provide the lubricant with extensive oxidative protection and to reduce wear and deposition in the engine. This is a difficult problem with conventional lubricants because the most effective wear and antioxidant additives are phosphorus-containing zinc dialkyldithiophosphates (ZDDP). In the past, high levels of ZDDP were used because ZDDP was a low cost material and provided excellent wear resistance and anti-oxidation performance. In the future, however, ZDDP will only be allowed at low levels. In 2004, some commercial gasoline engine oil specifications allowed up to 800 ppm of phosphorus from ZDDP. In future engine oil specifications, the level of phosphorus may drop to less than 500 ppm, possibly even further. It is well known that ashless antioxidants can replace some of the lost oxidation performance when the level of ZDDP is reduced. However, it is known that higher levels of ashless antioxidants do not always result in improved oxidation control. In fact, modern engine oils generally require the use of two or more ashless antioxidant types in order to compensate for the loss of oxidative stability due to the low use of ZDDP. In addition, specifications for deposition control are becoming more demanding. In many cases, modern and future lubricants will require even higher levels of the various ashless antioxidants. Conventional ashless antioxidant levels in excess of 2.0% by weight may be inadequate for adequate protection of lubricants and engines. These high levels of conventional ashless antioxidants are expensive and can also lead to lubricant defects such as corrosion, rust, and sealing 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, special combinations and ratios of 4,4'-methylenebis (2,6-di-tert-butylphenol) and alkylated diphenylamines provide unexpectedly superior levels of oxidation and deposition control in low phosphorus engine oils. Was found. This allows the use of significantly lower levels of ashless 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 lubricants. This effect has a significant advantage for the environment, since the reduction of volatile organic molecules will contribute to the reduction of emissions.

Summary of the Invention

One aspect of the present invention is directed to a novel lubricating oil composition for an internal combustion engine that provides excellent deposition control while still maintaining good 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 the novel lubricating oil composition for reducing the toxicity of the catalyst in internal combustion engine systems.

Low phosphorus engine oils of one composition of the present invention include 4,4'-methylenebis (2,6-di-tert-butylphenol) and alkylated diphenylamines; Wherein the weight ratio of 4,4'-methylenebis (2,6-di-tert-butylphenol) to alkylated diphenylamine is at least about 0.5 and the engine oil is at most 353 mg of total deposits according to ASTM D7097 measurements. Create

Another composition of the invention comprises:

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

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

(C) alkylated diphenylamines;

(D) at least one component selected from the group consisting of dispersants and cleaners;

(E) zinc dialkyldithiophosphate; Randomly

(F) fat-soluble organomolybdenum compounds; And optionally

(G) hindered phenolic antioxidants, provided the hindered phenolic antioxidants are not 4,4'-methylenebis (2,6-di-tert-butylphenol);

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

The weight ratio of (B) to (C) is at least about 0.5].

Another composition of the invention comprises:

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

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

(C) alkylated diphenylamines;

(E) zinc dialkyldithiophosphate; And

(F) fat-soluble organomolybdenum compounds; And optionally

(G) hindered phenolic antioxidants, provided the hindered phenolic antioxidants are 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 produces up to about 35 mg of total deposits according to ASTM D7097 measurements.

Still another composition of the present invention includes:

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

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

(C) alkylated diphenylamines;

(D) at least one component selected from the group consisting of dispersants and cleaners;

(E) zinc dialkyldithiophosphate; And

(F) fat-soluble organomolybdenum compounds; And optionally

(G) hindered phenolic antioxidants, provided the hindered phenolic antioxidants are not 4,4'-methylenebis (2,6-di-tert-butylphenol);

[Where the lubricating oil composition is:

About 600 ppm or less of phosphorus derived from zinc dialkyldithiophosphate; And

About 50-400 ppm molybdenum derived from a fat-soluble organomolybdenum compound.

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

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

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

(C) 0.2-1.0 wt% alkylated diphenylamine;

(E) 200 to 600 ppm of 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 lubricating composition comprising:

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

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

(C) alkylated diphenylamines;

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

(E) 200 to 600 ppm of 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 invention is an engine oil lubricating composition comprising:

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

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

(C) 0.2-1.0 wt% alkylated diphenylamine; And

(D) 300 to 600 ppm of 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 lubricating composition comprising:

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

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

(C) alkylated diphenylamines;

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

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

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

"A large amount" means an amount greater than 50% by weight based on the total weight of the composition.

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).

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 moderately high temperature piston deposition by a thermal-oxidation engine oil simulation test, approved in December 2004, which is hereby incorporated by reference in its entirety. (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 oxidation and carbonaceous deposition-forming characteristics of engine oils. The test is designed to simulate high temperature deposition formation in the piston ring belt region of a modern engine. Details of the test operations and specific conditions for the various protocols are further documented in the following publications, all of which are incorporated by reference in their entirety for any purpose:

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

Selby, Richardson and Florkowski, "Engine Oil Deposits and the TEOST-Protocol 33 and Beyond" 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 upon oxidation of engine oils. In general, the formation of volatile organic molecules upon oxidation of the lubricant is considered detrimental because it results in increased release and can further promote the polymerization of the lubricant. Polymerization of the lubricant leads to an increase in viscosity, which is also undesirable. The additive combinations of the present invention are effective in controlling both the formation and deposition formation of volatile organic molecules. Typically, polar volatile organic molecules are formed by decomposition of organic peroxides in a lubricant. This decomposition produces organic alkoxy radicals that can react with another oil molecule to produce an alcohol, or can degrade to form aldehydes and ketones. Degradation of aldehydes and ketones generally reduces molecular weight and thus produces more volatile fragments, which are both contaminants and active precursors of oligomers and polymers that thicken lubricants. Therefore, it is more preferable to prevent or eliminate the formation of the polar volatile organic molecules.

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

As used herein, “hydrocarbyl” refers to any alkyl, alkenyl, or alkynyl group, which 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 succin groups.

The term "about" as used herein is meant to include the specified end point (s) and greater than 20%. Thus, the range is broad and for example "about 1" includes the range of 0.8 to 1.2.

Organic friction modifiers are molecules containing non-polar hydrocarbon long chains with polar end-groups having affinity for the metal engine surface. "Organic friction modifiers" as used herein include long chain organic fatty acids or carboxylic acids, esters, ethers, amines, imides, amides, sulfurized fatty acids, metallo-organic compounds, high molecular weight organic phosphorus and phosphate esters This is not restrictive. Examples of other conventional organic friction modifiers are described in R. R. Hoogendoorn and D. Kenbeek, "Friction Modifiers to the Rescue" in Lubes-n-Greases (2003), Vol. 9, Issue 11, pp. 14-20. Organic friction modifiers are typically used at 0 to 1.0% by weight in fully formulated engine oils.

"Corrosion inhibitors" as used herein include, but are not limited to, thiadiazole polysulfides containing 5 to 50 carbon atoms, derivatives thereof and polymers thereof. Typical corrosion inhibitors are described in Hamlin, et al., "Ashless Antioxidants, Copper Deactivators and Corrosion Inhibitors: their Use in Lubricating Oils" Lubrication Science (1990), 2 (4), pp. 287-318. Suitable corrosion inhibitors include 1,3, such as polysulfide derivatives of 2,5-dimercapto-1,3,4-thiadiazole (1,3,4-thiadiazole polysulfide) having the formula: 4 derivatives of thiadiazole include:

[Wherein R ¹ and R ² are the same or different hydrocarbon radicals and may be aliphatic or aromatic, including alkyl, aralkyl, aryl and alkaryl radicals, x and y are 0 to 8 and x and y Sum is at least 1, and in some embodiments is 2-16. Methods of preparing such compounds are disclosed in US Pat. 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 described in US Pat. No. 3,821,236; 3,904,537; 4,076,384; No. 4,097,387; No. 4,107,059; No. 4,136,043; No. 4,188,299; And 4,193,882. Other corrosion inhibitors are thio and polythio sulfenamides of thiadiazoles, such as those of the formula:

[Wherein z is 2 to 5, R ³ is hydrogen, hydrocarbyl group, another sulfenamide or thiosulfenamide group, and R ⁴ and R ⁵ are hydrogen or a hydrogen and carbon containing group (where R Both 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 No. 1,560,830. All referenced references are incorporated herein by reference in their entirety for any purpose. Benzotriazole derivatives also belong to this class of additives. Other examples of corrosion inhibitors include dodecenyl succinic acid, esters, amides, and mixed esters / amides, fatty amines, linear alkyl amines, fatty acids, linear carboxylic acids, some branched alkyl amines, some branched carboxylic acids, sulfur and phosphorus compounds, and Some detergents. Corrosion inhibitors are typically used at 0 to 0.5% by weight in fully formulated engine oils.

As used herein, "viscosity modifier" includes modifiers that act to impart high and low temperature operability to the lubricant. Such modifiers include copolymers of polyisobutylene, ethylene and propylene, and copolymers of higher alpha-olefins, polymethacrylates, polyalkylmethacrylates, methacrylate copolymers, unsaturated dicarboxylic acids and vinyl compounds, Internal polymers of styrene and acrylic esters, and 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. Typical viscosity modifiers are polymers having a molecular weight ranging from 20,000 to 1,000,000. Typical viscosity modifiers are described in M.K. Mishra and R.G. Saxton, "Polymer Additives For Engine Oils" CHEMTECH, April 1995, pp. 35-41.

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

As used herein, "phosphorus-free wear resistant additive" refers to any phosphorus-free compound that, when added to a fully formulated engine oil, reduces wear in an engine, engine test, or bench wear test. Examples of phosphorus-free antiwear additives include sulfided olefins, sulfided fatty acids and oils, sulfided fatty esters, sulfided mixed fatty acids / fatty esters, sulfided mixed fatty acids / olefins, sulfided mixed fatty esters / fatty acids, organic sulfides, disulfides, trisulfides And polysulfide, thiocarbamate, thiuram sulfide, disulfide, trisulfide and polysulfide, molybdenum dithiocarbamate, zinc dithiocarbamate, molybdenum amine complex, molybdenum alcohol complex, mixed molybdenum Amine / molybdenum alcohol complexes, and molybdenum carboxylates.

"Fully formulated engine oil" as used herein may contain additional typical additives known to those skilled in the art and are used as engine oil on an as-received basis.

II. Component of the Invention

Ingredient (A)

Component (A) can be any combination of a lubricating viscosity oil and a synthetic ester base oil selected from the group consisting of Group II, III, IV. Component (A) may further comprise up to about 15 weight percent of Group I base oil. Various base oil classes are described in the American Petroleum Institute (API) publication Engine Oil Licensing and Certification System, Industry Services Department, 14th Ed. (December 1996) Addendum 1 (December 1998)] chemically and physically. 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 viscosity of the base oil is 4-10 mm ² / s (cSt) at 100 ° C; In yet another embodiment, the viscosity of the base oil is 4.5-8 mm ² / s (cSt) at 100 ° C.

Group II mineral oil base oils contain at least 90% by weight of saturates and up to 0.03% by weight of sulfur using the test methods described in Table 1 below, and have a viscosity index of at least 80 and less than 120. In one embodiment, Group II base oils contain at least 95% by weight saturates and up to 0.01% by weight sulfur using the test methods described in Table 1 below, and the viscosity index is at least 100 and less than 120.

Group III mineral oil base oils contain at least 90% by weight saturates and up to 0.03% by weight sulfur using the test methods described in Table 1 below, and the viscosity index is at least 120. In one embodiment, Group III base oils contain at least 98% by weight saturates and up to 0.01% by weight sulfur using the test methods described in Table 1 below, and the viscosity index is at least 130.

Group IV base oils are poly-α-olefins.

Suitable ester base oils that may be used are dicarboxylic acids (eg, butyl alcohol, hexyl alcohol, dodecyl alcohol 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.) Phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc.) Ester. Specific examples of such esters are dibutyl adipate, bis (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, di-isooctyl azelate, di-isodecyl azelate, dioctyl Phthalates, didecyl phthalates, diecosyl sebacates, 2-ethylhexyl diesters of linoleic acid dimers, complex esters formed by the reaction of 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid; Include.

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

Analytical Methods for Base Oil Testing characteristic Test method Saturated Water ASTM D2007 Viscosity index ASTM D2270 sulfur ASTM D2622, D4292, D4927, or D3120

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

Ingredient (B)

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

.

.

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

Ingredient (C)

Alkylated diphenylamine (component C) has the formula:

R _a -NH-R _b

[Wherein, R _a and R _b each independently represent a substituted or unsubstituted phenyl group.]. Substituents on the phenyl ring may include, but are not limited to, alkyl groups, alkylaryl groups, hydroxy groups, carboxyl groups and nitro groups having 1 to 20 carbon atoms. In one embodiment of the invention, one or two phenyl groups are substituted with alkyl. In yet another embodiment of the invention, both 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-1,4-phenylenediamine, butyldiphenylamine Dibutyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine, nonyldiphenylamine, dinonyldiphenylamine, heptyldiphenylamine, diheptyldiphenylamine, methylstyryldiphenylamine, mixed butyl / octyl alkylated di Phenylamine, mixed butyl / styryl alkylated diphenylamine, mixed ethyl / nonyl alkylated diphenylamine, mixed octyl / styryl alkylated diphenylamine, mixed ethyl / methylstyryl alkylated diphenylamine, and petroleum industry It includes combinations of the above with varying degrees of purity commonly used in the art.

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

Ingredient (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 invention, the detergent or dispersant is present in the fully formulated engine oil formulation. In another embodiment, both detergents and dispersants are present in the fully formulated engine oil formulation. Dispersants or cleaners may be boronated or boron infused.

Dispersants are well known in the lubricant art and do not contain ash-forming metals (before mixing in the lubricating composition) and do not normally contribute to any ash-forming metals when added to the lubricant, often being "ashless. "Includes dispersants inherently.

Dispersants are typically nonmetallic additives containing nitrogen or oxygen polar groups bonded to high molecular weight hydrocarbon chains. Hydrocarbon chains provide solubility to hydrocarbon base oils. Dispersants serve to maintain oil decomposition products suspended in oil. Examples of suitable dispersants include polymethacrylates, styrene-maleic ester copolymers, substituted succinimides (eg, PIBSA (polyisobutylene succinic anhydride)), polyamine succinimides, polyhydroxy succinic esters, substituted Mannich bases, and substituted triazoles.

The dispersant may be boron injected. Boron-infused 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 100-150 ° C. Dispersants can also be treated by reaction with maleic anhydride; For example, succinimide dispersants may also be prepared by reacting an amount of an α, β-unsaturated acid such as maleic anhydride or an equivalent thereof with an amount of hydrocarbyl-substituted acylating agent, which is characterized by Characterized by the presence of at least 1.3 succinic groups relative to the weight of the equivalent, wherein the reaction of the acid in WO 00/26327, filed October 13, 1999, incorporated herein by reference in its entirety for any purpose. As described, this may occur simultaneously or subsequently with the reaction of the amine with the hydrocarbyl-substituted acylating agent.

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

Detergents are generally often salts of organic salts that have been overchlorideed. Metal oversalated 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. Detergents are typically metallic additives containing polar groups and metal ions such as sulfonates or carboxylates, together with aliphatic, cycloaliphatic or alkylaromatic chains. The cleaning agent works by lifting deposits from various surfaces of the engine. Suitable detergents include neutral and perchlorated alkali and alkaline earth metal sulfonates, neutral and perchlorated alkali and alkaline earth metal phenates, sulfide phenates, and perchlorated alkaline earth metal salicylates. Patents describing techniques for preparing detergents generally include US Pat. No. 2,501,731, incorporated herein by reference for any purpose; 2,616,905; 2,616,905; 2,616,911; 2,616,911; 2,616,925; 2,616,925; 2,777,874; 2,777,874; 3,256,186; 3,256,186; 3,384,585; 3,384,585; 3,365,396; 3,365,396; 3,320,162; 3,320,162; 3,318,809; 3,318,809; 3,488,284; 3,629,109.

Detergents can generally be boron infused by treatment with a boron agent such as boric acid. Typical conditions include heating the detergent with boric acid at about 100 to 150 ° C., and the number of equivalents of boric acid generally corresponds to the number of equivalents of metal in the salt. U.S. Patent No. 3,929,650 discloses boric acid in an lipophilic liquid reaction medium, with an alkali metal carbonate perchlorated metal sulfonate (prepared by oversalting a neutral alkali or alkaline earth metal sulfonate with an alkali metal carbonate) and A boron infused composite prepared by contact is disclosed, the entirety of which is incorporated herein by reference for any purpose.

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

Ingredient (E)

Zinc dialkyldithiophosphate (ZDDP) (component E) in the oil composition is the reaction of an alcohol or phenol with phosphorous pentasulphide (P ₂ S ₅ ) to produce a dialkyldithiophosphate derivative (DDPA), and then Can be any ZDDP derived from neutralization with a basic zinc compound.

Zinc salts of the formula (M = Zn):

[Wherein, R ⁸ and R ⁹ are independently a hydrocarbyl group containing 3 to 30 carbon atoms], for forming 0,0-dihydrocarbyl phosphorodithioic acid of the formula: ₂ S ₅₎ and it can be easily obtained by the reaction of alcohols or phenols:

.

.

The reaction comprises mixing 4 moles of alcohol or phenol with 1 mole of phosphorus pentasulphide at a temperature of 20 ° C. to 200 ° C. Hydrogen sulfide is liberated in the reaction. The acid then 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:

.

.

R ⁸ and R ⁹ groups are independently, in one embodiment of the invention, hydrocarbyl groups free of acetylenic unsaturation. In another embodiment, R ⁸ and R ⁹ are free of ethylenic unsaturation, and in yet another embodiment, R ⁸ and R ⁹ are free of both acetylenic and ethylenically unsaturated. In one embodiment, R ⁸ and R ⁹ are alkyl, cycloalkyl, aralkyl or alkaryl groups and have 3 to 20 carbon atoms; In another embodiment, R ⁸ and R ⁹ have 3 to 16 carbon atoms, and in yet another embodiment have up to 13, for example 3 to 13 carbon atoms. The alcohol that reacts to provide groups R ⁸ and R ⁹ 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 can also be used.

Such materials are often referred to as zinc dialkyldithiophosphates 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 invention; In one embodiment, from about 200 to about 600 ppm phosphorus; In yet another embodiment, it delivers about 300 to about 600 ppm phosphorus. "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 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 in the composition of the present invention.

Ingredient (F)

Any fat-soluble organomolybdenum compound (component F) can be used as an optional component 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 application of the customer and the desired level of antioxidant protection required for the particular composition of the present invention. Any concentration of fat soluble organomolybdenum can 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 50-400 ppm. In another embodiment, the molybdenum level is about 100-250 ppm. In yet another embodiment, the level of molybdenum metal is about 250-400 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 fat-soluble organomolybdenum compounds compared to other antioxidants such as ZDDP.

Examples of some fat-soluble organomolybdenum compounds that can be used in the present invention include molybdenum dithiocarbamate, oxymolybdenum sulfide dithiocarbamate, molybdenum dithioxanthogenate, oxymolybdenum sulfide dithioxanthogenate, molybdenum organophospho Sporodithioates, oxymolybdenum sulfide organophosphorodithioates, molybdenum carboxylates, molybdenum amine complexes, molybdenum alcohol complexes, molybdenum amide complexes, mixed molybdenum amine / alcohol / amide complexes, and combinations thereof. In one embodiment of the invention, the molybdenum compound is a compound containing sulfur and free of phosphorus.

Ingredient (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-methyl phenol; 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, isooctyl ester; 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, 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); Dithiobis (dodecylphenol); Polythiobis (octylphenol); Polythiobis (nonylphenol); Polythiobis (dodecylphenol); Methylenebis (octylphenol); Methylenebis (nonylphenol); Methylenebis (dodecylphenol); Ethylidenebis (octylphenol); Ethylidenebis (nonylphenol); Ethylidenebis (dodecylphenol); Butylidenebis (octylphenol); Butylidenebis (nonylphenol); Butylidenebis (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-ethyl phenol; 2, 6- di-tert- butyl- 4-butyl phenol; 2,6-di-tert-butyl-4-octylphenol 2,6-di-tert-butyl-4-isoheptylphenol; 2, 6- di-tert- butyl- 4-isooctyl phenol; 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-isododecyl phenol; 2, 6- di-tert- butyl- 4-dodecyl phenol; 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 crosslinked) tert-butylphenolic as defined below:

[Wherein X may vary from 1 to 5, R is hydrogen, or tert-butyl, or as defined in any one of US Pat. No. 3,211,652, for example, R is hydrogen, or 4 Alkyl groups having from 9 to 9 carbon atoms, and as described in US Patent Application 2002/0142923, and US Pat. No. 2,807,653, for example, R is hydrogen, or a hydrocarbon having up to about 9 carbon atoms May be a radical]. Each of the referenced references is incorporated herein by reference in its entirety for any purpose.

In one embodiment of the invention, the hindered phenolic antioxidant contains sulfur. In another embodiment of the 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 from about 0.1% to about 0.75% by weight in the composition of the present invention. Present in an amount of%; In another embodiment, it is present in an amount from about 0.1% to about 0.5% by weight, all weight percent based on the total weight of the composition.

III. Other embodiments of the invention

The present invention provides a lubricating oil composition capable of providing improved deposition control to an internal combustion engine.

In one aspect of the invention, the low phosphorus engine oil composition comprises: 4,4'-methylenebis (2,6-di-tert-butylphenol) and alkylated diphenylamines; Wherein the weight ratio of 4,4'-methylenebis (2,6-di-tert-butylphenol) to alkylated diphenylamine is at least about 0.5 and the engine oil is at most 35 mg total deposit according to ASTM D7097 measurements. To create. In one embodiment, the composition further comprises zinc dialkyldithiophosphate; Here, the engine oil contains about 600 ppm or less of phosphorus derived from zinc dialkyldithiophosphate. In another embodiment, the composition further comprises a fat soluble organomolybdenum compound. Engine oils include formulated oils used in gasoline, diesel, natural gas and rail engines.

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

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

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

(C) alkylated diphenylamines;

(D) at least one component selected from the group consisting of dispersants and cleaners; And

(E) zinc dialkyldithiophosphate (ZDDP);

[Where the composition comprises about 600 ppm or less of phosphorus (ZDDP) derived from zinc dialkyldithiophosphate; The weight ratio of (B) to (C) is at least about 0.5].

In another embodiment of the invention, the composition further comprises a fat soluble organomolybdenum compound. In yet another embodiment, the fat soluble organomolybdenum compound comprises sulfur and is free of phosphorus. In one embodiment of the 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 invention, the weight ratio of phosphorus to molybdenum is 1.0 or less. In another embodiment of the invention, the composition may contain (G) a hindered phenolic antioxidant, provided that the hindered phenolic antioxidant is 4,4'-methylenebis (2,6-di- tert-butylphenol). In another embodiment of the invention, the sum of (B), (C) and (G) is up to about 1.5% by weight of the composition. In another embodiment of the 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 up to about 35 mg of total deposit according to ASTM D7097 measurements; In another embodiment, the composition produces up to about 25 mg of total deposits according to ASTM D7097 measurements; In yet another embodiment, the composition produces up to about 15 mg of total deposits.

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

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

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

(C) alkylated diphenylamines;

(E) zinc dialkyldithiophosphate; And

(F) fat-soluble organomolybdenum compounds;

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

In one embodiment of the invention, the fat soluble organomolybdenum compound comprises sulfur and is free of 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 invention, the weight ratio of phosphorus to molybdenum is 1.0 or less. In another embodiment of the invention, the composition further comprises one or more components selected from the group consisting of dispersants and detergents. In another embodiment of the invention, the engine oil further comprises (G) a hindered phenolic antioxidant, provided that 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 up to about 1.5% by weight of the composition. In a further embodiment of the invention, such compositions produce up to about 25 mg of total deposits according to ASTM D7097 measurements. In yet another embodiment of the present invention, the engine oil further comprises (D) at least one component selected from the group consisting of dispersants and detergents, and (G) hindered phenolic antioxidants, provided that hindered phenols The antioxidant is not 4,4'-methylenebis (2,6-di-tert-butylphenol). In yet another embodiment, the sum of (B), (C) and (G) is about 1.5% by weight or less of the engine oil. In a further embodiment of the invention, such engine oil produces up to about 25 mg of total deposits according to ASTM D7097 measurements. A further embodiment is the engine oil described above, wherein the engine oil produces up to 15 mg of total deposits according to ASTM D7097 measurements.

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

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

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

(C) alkylated diphenylamines;

(D) zinc dialkyldithiophosphate;

(E) fat-soluble organomolybdenum compound;

(F) at least one component selected from the group consisting of dispersants and cleaners; And

(G) hindered phenolic antioxidants, provided the hindered phenolic antioxidants are not 4,4'-methylenebis (2,6-di-tert-butylphenol);

Wherein the composition comprises: about 600 ppm or less of phosphorus derived from zinc dialkyldithiophosphate, and

About 50-400 ppm molybdenum derived from a fat-soluble organomolybdenum compound.

In one embodiment of the invention, the fat soluble organomolybdenum compound comprises sulfur and is free of 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 invention, the weight ratio of phosphorus to molybdenum is 1.0 or less. In another embodiment of the invention, the engine oil comprises up to about 550 ppm of phosphorus derived from zinc dialkyldithiophosphate. In another embodiment of the invention, the engine oil comprises up to about 500 ppm of phosphorus derived from zinc dialkyldithiophosphate. In yet another embodiment of the invention, the composition comprises about 400 ppm or less of phosphorus derived from zinc dialkyldithiophosphate. In yet another embodiment, the engine oil contains about 300 ppm or less of phosphorus derived from zinc dialkyldithiophosphate. In another embodiment of the present invention, the engine oil comprises about 100-250 ppm of molybdenum derived from a fat-soluble organomolybdenum compound. In yet another embodiment of the present invention, the engine oil comprises about 250-400 ppm of molybdenum derived from a fat-soluble organomolybdenum compound. In yet another embodiment of the present invention, the engine oil comprises about 300-400 ppm molybdenum derived from a fat-soluble organomolybdenum compound. In yet another embodiment of the invention, the composition comprises about 50-150 ppm molybdenum derived from a fat-soluble organomolybdenum compound. All parts per million (ppm) in this paragraph are based on the total weight of the engine oil.

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

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

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

(C) 0.2-1.0 wt% alkylated diphenylamine;

(E) 200 to 600 ppm of 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 0.5 or more].

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

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

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

(C) alkylated diphenylamines;

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

(E) 200 to 600 ppm of 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 0.5 or more].

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

Another aspect of the invention is an engine oil comprising:

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

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

(C) 0.2 to 1.0 weight percent of alkylated diphenylamine, and

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

[Wherein the weight ratio of (B) to (C) is 0.5 or more].

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

Another aspect of the invention is an engine oil comprising:

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

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

(C) alkylated diphenylamines;

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

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

[Wherein the weight ratio of (B) to (C) is 0.5 or more].

All weight percentages (% by weight) given above for the engine oil of the present invention are based on the total weight of the engine oil. "A large amount" means more than 50% by weight based on the total weight of the engine oil.

Additional embodiments or engines of any of the above described further comprising one or more components selected from the group consisting of organic friction modifiers, corrosion inhibitors, viscosity modifiers, pour point depressants, and phosphorus-free antiwear additives. Oil.

A further aspect of the invention is the total volatile organics (naturally polar and non-natural) produced by the internal combustion engine upon heating and oxidation of engine oil, comprising lubricating the engine with any of the compositions or engine oils described herein. Both polarity).

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

A further aspect of the present invention is a method of reducing the toxicity of a catalyst in an internal combustion engine release system comprising lubricating the engine with any of the compositions or engine oils described herein.

The following combination is an example of an embodiment of the invention, wherein the sum of (B), (C) and (G) is up to about 1.5% by weight of the composition.

Combination I ingredient weight% B 4,4'-methylenebis (2,6-di-tert-butylphenol) 0.7 C Nonylated Diphenylamine 0.4 G 2,6-di-tert-butylphenol 0.3

Combination II ingredient weight% B 4,4'-methylenebis (2,6-di-tert-butylphenol) 0.6 C Nonylated Diphenylamine 0.4 G 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, isooctyl ester 0.4

TEOST MHT equipment should be run in accordance with ASTM D7097 methodology and manufacturer specifications. Testing includes passing a thin film of test engine oil over a heated wire-bent depositor rod with an aide of a precision pump. The test rod was heated at 285 ° C. and the test was run for 24 hours. A thin film of oil moves uniformly under the rod and collects at the flow out point of the test assembly equipment. The recovered oil is circulated back to the depositor rod via a tube pump. During the 24 hour test period, volatiles are flashed off the hot rod surface and created to condense on the glass layer of the test assembly device. These volatiles are recovered from the volatiles outside the ports of the test assembly and collected in glass vials. At the completion of the test, the deposit is measured by increasing the depositor bar weight and reported in milligrams (mg). Accurately weigh the collected volatiles and record in grams (g).

The method requires many independent calibrations, including, for example, calibrating convection speed, oil pump speed, thermostat settings, and regulating thermocouples. The method also requires running a certified standard oil over time to determine the stringency of the test. For example, certified medium deposition standard oils should produce approximately 40-60 mg of deposits, while certified high deposition standard oils would produce approximately 70-90 mg of deposits. Stringent test conditions will usually produce heavier deposits and higher levels of volatiles. In contrast, mild test conditions will usually produce lighter deposits and much lower levels of volatiles. Under stringent test conditions, engine oils that perform well with low deposition and low volatility are 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 combinations of the present invention result in good deposition control and reduced volatile formation, under both stringent and moderate conditions. Under both stringent and moderate conditions, the firm performance of the novel additive combinations is another advantage of the present invention.

III. Example

TEOST - At MHT Deposit  And volatiles

Fully formulated oil (8.4 g) and organometallic catalyst (about 0.1 g) were added to the flask equipped with a Teflon stir bar and stirred for 20-60 minutes without heating. The depositor rods, sample flasks, oil inlets, air inlets, and volatile collection vials were fitted to TEOST equipment according to manufacturer's specifications. The pump was started at high flow rate and run until the test oil reached the connection of the pump and the oil feed tube (when the pump flow returned to zero). Turn on the heater and when the depositor rod thermostat is between 200 and 210 ° C, increase the pump speed so that the sample is delivered at a rate of 0.25 ± 0.02 g / min so that the oil flows down the depositor bar and does not leak It was confirmed. The temperature was allowed to stabilize at 285 ± 2 ° C. and the test was run for 24 hours under the above conditions.

Three test tubes were prepared using cyclohexane or another suitable hydrocarbon solvent for oil extraction from the depositor rods. The test equipment was disassembled as instructed by the manufacturer, the depositor rods were transferred to the weight boat and kept under the cover. In each of the three test tubes made with a hydrocarbon solvent, the depositor rods were each placed continuously for 10 minutes. The rod was placed in a tared weight boat and left for 10 minutes to allow the hydrocarbon solvent to evaporate. The 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 common 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 depositor rods was measured.

During the 24 hour test period, the volatile compounds in the formulated oils, either originally or formed during the test, were flashed off in the depositor rods. These volatiles condensed on the glass layer and collected on a continuous basis in small, weighty vials. 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

Pre-mixtures were prepared by blending the following materials:

150 N II group base oil, 92.1 wt%;

Ashless dispersant concentrate, 4.92 wt%;

Oversalted detergent concentrate containing calcium, 1.85 wt%;

Neutral detergent concentrate containing calcium, 0.51 wt%; And

Secondary zinc dialkyldithiophosphate, 0.62% by weight.

To this premix, the following components as indicated in Table 2 below in the preparation of various engine oils were added. The finished engine oil contained the following (calculated value): calcium 2400 ppm; 470 ppm phosphorus; 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. Certification Medium Deposition Standard oil produced 60.6 mg of deposit in a calibration experiment. Certified high deposition standard oil produced 96.8 mg of deposit in calibration experiments; These results indicate 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. In the present invention, it was also clear that the combination of MBDBP and NDPA without MoDTC resulted in low levels of deposits (14 mg) and volatiles (2.3 g) in TEOST MHT using ASTM D7097.

A graph of the deposition results in the presence of MoDTC is shown in FIG. 1.

A graph of the deposition results in the absence of MoDTC is shown in FIG. 2.

Example B -Oil Thickening and Oxidation at Elevated Temperatures

Premixes were prepared by admixing the following materials:

Ashless dispersant concentrate 4.92 wt%;

1.85% by weight of oversalted detergent concentrate containing calcium;

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

0.62% by weight of secondary zinc dialkyldithiophosphate; And

92.10% by weight of 150 N II group base oil.

To the engine oil premix, the components indicated in Table 3 were added.

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

The oxidation stability of the finished engine oil was evaluated in the 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 at 160 ° C. in a block heater while 10 liters / hour of dry oxygen was bubbled through the oil. Oxidized oil samples were removed at 24, 48, 72 and 96 hours. The kinematic viscosity of each sample was measured at 40 ° C. The% viscosity increase of oxidized oil to fresh oil was calculated. The results of% viscosity increase are shown in Table 4.

Higher% viscosity increase is a measure of increased oxidation and degradation of the lubricant. Designated as TVTM indicates serious disassembly of lubricant. These results clearly show that the antioxidant of the present invention in combination with Example B.6 provides superior oxidative 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) are hindered phenols. Better than systems containing castle HPE (B.3).

Example C -Oil Thickening and Oxidation

Oils A.2, A.3, A.7, A.9, A.11, A.13, A.15, A.16, and A.17 (Table 2) are described in Bulk B. Evaluated in oxidation test. In this study, 10 liters / hour of dry oxygen was bubbled through the oil while the oil was heated in a heating block at 150 ° C. Oxidized oil samples were removed at 24, 48, 72 and 96 hours. The kinematic viscosity of each sample was measured at 40 ° C. The% viscosity increase of oxidized oil to 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 control and volatility over all oils, as described in Example A. Thus, oil A.11 of the present invention is a better performing engine oil as a whole and provides excellent viscosity control, deposition control, and control of volatile organic compounds. The ability of the oil A.11 of the invention to show advantages 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 foregoing embodiments are not limiting, but merely illustrative of various aspects and embodiments of the invention. All documents mentioned herein are indicative of the level of skill in the art to which this invention pertains and are incorporated herein by reference in their entirety for any purpose. However, nothing is admitted to be prior art.

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

The invention described by way of example herein may be suitably carried out without any element or elements, limitations or limitations not specifically disclosed herein. The terms and expressions used are for the purpose of description and not of limitation, and have no intention in the use of such terms and expressions except for any equivalent of the features shown and described. It will be appreciated that various modifications are possible within the scope of the invention as claimed. Thus, although the 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 the details and the appended claims. It is to be understood that it is believed to be within the scope of the present invention as defined by.

Claims (44)

Low phosphorus engine oils, including: 4,4'-methylenebis (2,6-di-tert-butylphenol) and Alkylated diphenylamine; Wherein the weight ratio of 4,4'-methylenebis (2,6-di-tert-butylphenol) to the alkylated diphenylamine is at least about 0.5; The engine oil produced less than 35 mg of total deposits according to ASTM D7097 measurements. The compound of claim 1, further comprising zinc dialkyldithiophosphate; Wherein the engine oil comprises about 600 ppm or less of phosphorus derived from the zinc dialkyldithiophosphate. 3. The engine oil of claim 2, further comprising a fat soluble organomolybdenum compound. Compositions comprising: (a) large amounts of lubricating viscosity oils and synthetic ester base oils selected from the group consisting of Group II, III, IV; (b) 4,4'-methylenebis (2,6-di-tert-butylphenol); (c) alkylated diphenylamines; (d) at least one component selected from the group consisting of dispersants and cleaners; And (e) zinc dialkyldithiophosphate; Wherein the composition comprises about 600 ppm or less of phosphorus derived from the zinc dialkyldithiophosphate; the weight ratio of (b) to (c) is at least about 0.5. The composition of claim 4 further comprising: (f) fat-soluble organomolybdenum compounds. 6. The composition of claim 5, wherein said fat soluble organomolybdenum compound comprises sulfur and is free of phosphorus. The composition of claim 6 wherein the weight ratio of phosphorus to molybdenum is at least 1.0. The composition of claim 6 wherein the weight ratio of phosphorus to molybdenum is greater than 0.0 and less than 1.0. The composition of claim 6, wherein the weight ratio of phosphorus to molybdenum is 1.0 or less. The composition of claim 4 further comprising: (g) hindered phenolic antioxidants, provided the hindered phenolic antioxidants are not 4,4'-methylenebis (2,6-di-tert-butylphenol). The composition of claim 10, wherein the sum of (b), (c) and (g) is about 1.5% by weight or less of the composition. The composition of claim 6 further comprising: (g) Hindered phenolic antioxidants, provided the hindered phenolic antioxidants are not 4,4'-methylenebis (2,6-di-tert-butylphenol). 13. The composition of claim 12, wherein the sum of (b), (c) and (g) is about 1.5% by weight or less of the composition. The composition of claim 4, wherein the lubricating viscosity oil comprises about 15% or less by weight of Group I base oil. Compositions comprising: (a) large amounts of lubricating viscosity oils and synthetic ester base oils selected from the group consisting of Group II, III, IV; (b) 4,4'-methylenebis (2,6-di-tert-butylphenol); (c) alkylated diphenylamines; (e) zinc dialkyldithiophosphate; And (f) fat-soluble organomolybdenum compounds; Wherein the weight ratio of (b) to (c) is at least about 0.5; The composition produced up to about 35 mg of total deposits according to ASTM D7097 measurements. 16. The composition of claim 15, wherein said fat soluble organomolybdenum compound comprises sulfur and is free of phosphorus. The composition of claim 15 wherein the weight ratio of phosphorus to molybdenum is at least 1.0. The composition of claim 15 wherein the weight ratio of phosphorus to molybdenum is greater than 0.0 and less than 1.0. The composition of claim 15 wherein the weight ratio of phosphorus to molybdenum is 1.0 or less. The composition of claim 15 further comprising: (d) at least one component selected from the group consisting of dispersants and cleaners. The composition of claim 15 further comprising: (g) Hindered phenolic antioxidants, provided the hindered phenolic antioxidants are not 4,4'-methylenebis (2,6-di-tert-butylphenol). The composition of claim 21, wherein the sum of (b), (c) and (g) is about 1.5% by weight or less of the composition. The composition of claim 21, wherein the composition produces up to about 25 mg of total deposits according to ASTM D7097 measurements. The composition of claim 20 further comprising: (g) Hindered phenolic antioxidants, provided the hindered phenolic antioxidants are not 4,4'-methylenebis (2,6-di-tert-butylphenol). The composition of claim 24, wherein the sum of (b), (c) and (g) is about 1.5% by weight or less of the composition. The composition of claim 24, wherein the composition produces up to about 25 mg of total deposits according to ASTM D7097 measurements. Compositions comprising: (a) large amounts of lubricating viscosity oils and synthetic ester base oils selected from the group consisting of Group II, III, IV; (b) 4,4'-methylenebis (2,6-di-tert-butylphenol); And (c) alkylated diphenylamines; (d) at least one component selected from the group consisting of dispersants and cleaners; (e) zinc dialkyldithiophosphate; (f) fat-soluble organomolybdenum compounds; And (g) hindered phenolic antioxidants, provided the hindered phenolic antioxidants are not 4,4'-methylenebis (2,6-di-tert-butylphenol); Wherein the composition is: About 600 ppm or less of phosphorus derived from said zinc dialkyldithiophosphate; And And about 50-400 ppm molybdenum derived from said fat-soluble organomolybdenum compound. 28. The composition of claim 27, wherein said fat soluble organomolybdenum compound comprises sulfur and is free of phosphorus. The composition of claim 27 wherein the weight ratio of phosphorus to molybdenum is at least 1.0. The composition of claim 27 wherein the weight ratio of phosphorus to molybdenum is greater than 0.0 and less than 1.0. The composition of claim 27 wherein the weight ratio of phosphorus to molybdenum is 1.0 or less. 28. The composition of claim 27, wherein said composition comprises up to about 550 ppm of phosphorus derived from said zinc dialkyldithiophosphate. 28. The composition of claim 27, wherein said composition comprises about 100 to 250 ppm molybdenum derived from said fat soluble organomolybdenum compound. 28. The composition of claim 27, wherein said composition comprises up to about 500 ppm of phosphorus derived from said zinc dialkyldithiophosphate. 28. The composition of claim 27, wherein said composition comprises from about 250 to 400 ppm molybdenum derived from said fat soluble organomolybdenum compound. Engine oils including: (a) large amounts of lubricating viscosity oils and synthetic ester base oils selected from the group consisting of Group II, III, IV; (b) 4,4'-methylenebis (2,6-di-tert-butylphenol); (c) 0.2 to 1.0 weight percent of alkylated diphenylamine; (d) 1.0 to 12.0 wt% of at least one compound selected from the group consisting of dispersants and cleaners; (e) 200 to 600 ppm of 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. Engine oils including: (a) large amounts of lubricating viscosity oils and synthetic ester base oils selected from the group consisting of Group II, III, IV; (b) 0.1 to 1.5% by weight of 4,4'-methylenebis (2,6-di-tert-butylphenol); (c) alkylated diphenylamines; (d) 1.0 to 12.0 wt% of at least one compound selected from the group consisting of dispersants and cleaners; (e) 200 to 600 ppm of 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. 38. The engine oil of claim 37 further comprising: (g) 0.1 to 0.5% by weight of any ester derived from 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid. Engine oils including: (a) large amounts of lubricating viscosity oils and synthetic ester base oils selected from the group consisting of Group II, III, IV; (b) 4,4'-methylenebis (2,6-di-tert-butylphenol); (c) 0.2 to 1.0 weight percent of alkylated diphenylamine; And (d) 1.0 to 12.0 wt% of at least one compound selected from the group consisting of dispersants and cleaners; And (e) 300 to 600 ppm of phosphorus derived from zinc dialkyldithiophosphate; Wherein the weight ratio of (b) to (c) is at least 0.5. 40. The engine oil of claim 39 further comprising: (g) 0.1 to 0.5% by weight of any ester derived from 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid. Engine oils including: (a) large amounts of lubricating viscosity oils and synthetic ester base oils selected from the group consisting of Group II, III, IV; (b) 0.1 to 1.5% by weight of 4,4'-methylenebis (2,6-di-tert-butylphenol); (c) alkylated diphenylamines; (d) 1.0 to 12.0 wt% of at least one compound selected from the group consisting of dispersants and cleaners; And (e) 300 to 600 ppm of phosphorus derived from zinc dialkyldithiophosphate; Wherein the weight ratio of (b) to (c) is at least 0.5. A method for reducing the total amount of volatile organics produced by an internal combustion engine upon heating and oxidation of engine oil, comprising lubricating the engine with the composition according to claim 1. A method of reducing the amount of deposits in an internal combustion engine comprising lubricating the engine with the composition according to claim 1. A method of reducing poisoning of a catalyst in an internal combustion engine exhaust system comprising lubricating the engine with the composition according to claim 1.

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