BRPI0710256A2 - lubricating oil composition; concentrated composition of lubricating oil additive; motor oil composition; concentrated composition of motor oil additive; and method of increasing the concentration of at least one hindered phenolic antioxidant in a concentrated lubricating oil additive composition - Google Patents

Abstract

<B> LUBRICATING OIL COMPOSITION; CONCENTRATED COMPOSITION OF LUBRICATING OIL ADDITIVE, ENGINE OIL COMPOSITION; CONCENTRATED COMPOSITION OF ENGINE OIL ADDITIVE; AND METHOD OF INCREASING THE CONCENTRATION OF AT LEAST ONE PHENOLIC ANTIOXIDANT PREVENTED IN A CONCENTRATED LUBRICATING OIL ADDITIVE COMPOSITION. <D> A lubricating oil composition with synergistic oxidative stability is described, the composition comprising at least one phenolic antioxidant. at least one mono-boronated hindered phenolic antioxidant, at least one dorsoronated hindered phenolic antioxidant, at least one alkylated diphenylamine and at least one organomolybdenum compound. The present invention also provides a concentrated lubricating oil additive composition that provides synergistic oxidative stability to a lubricating oil with its addition, the concentrated composition comprising at least one hindered phenolic antioxidant, at least one mono-boronated hindered phenolic antioxidant, at least a di-boronated hindered phenolic antioxidant, at least one alkylated diphenylamine and at least one organomolybdenum compound. In addition, the concentrated composition of the present invention can also be prepared with a high concentration of hindered phenolic antioxidants without deleterious effects on viscosity or solubility of the lubricant.

Description

LUBRICANT OIL COMPOSITION; ADDITIVE LUBRICANT OIL COMPOSITION, DEMOTOR OIL COMPOSITION; CONCENTRATED ENGINE OIL ADDITIVE COMPOSITION AND METHOD OF INCREASING CONCENTRATION AT LEAST ONE PHENOLIC ANTIOXIDANT IMPEDED IN A CONCENTRATED LUBRICANT OIL ADDITIVE COMPOSITION ".

FIELD OF THE INVENTION The present invention relates to additive lubricating oil compositions and lubricating oil compositions containing them. More particularly, the present invention relates to combinations of hindered phenolic antioxidants, boronated hindered phenolic antioxidants, alkylated diphenylamines, and useful organomolybdenum compounds as lubricating oil compositions and additive to lubricating oil compositions. Hindered phenolics and boronated hindered phenolics are well known in the art. including large molecular phenolics incorporating the moiety, 2,6-di-tert-butylphenol, and the like. See, for example, the following U.S. and foreign patents: U.S. 4,927,553; U.S. 3,356,707; U.S. 3,509,054; U.S. 3,347,793; U.S. 3,014,061; U.S. 3,359,298; U.S. 2,813,830; U.S. 2,462,616; GB 864,840; U.S. 5,698,499; U.S. 5,252,237; U.S. RE 32,295; U.S. 4,547,302; U.S. 3,211,652; and U.S. 2,807,653. The use of alkylated diphenylamine as an antioxidant additive in

Lubricating oil formulations are also well known in the art. See, for example, the following U.S. patents: U.S. 5,620,948; U.S. 5,595,964; U.S. 5,569,644; U.S. 4,857,214; U.S. 4,455,243; and U.S. 5,759,965.

There are several examples in the patent literature showing the use of molybdenum killers as antioxidants, deposit control additives, anti-wear additives and friction modifiers. See, for example, U.S. and foreign patents below: U.S. 5,840,672; U.S. 5,814,587; U.S. 4,529,526; WO 95/07966; U.S. 5,650,381; U.S. 4,812,246; U.S. 5,458,807; WO 95/07964; U.S. 5,880,073; U.S.5,658,862; U.S. 5,696,065; WO 95/07963; U.S. 5,665,684; 4,360,438; U.S. 5,736,491; WO 95/27022; U.S. 5,786,307; U.S. 4,501,678; U.S. 5,688,748; EP 0 447916 A1; U.S. 5,807,813; U.S. 4,692,256; U.S. 5,605,880; WO 95/07962; U.S. 5,837,657; U.S. 4,832,867; U.S. 4,705,641; EP 0 768 366 A1; U.S. 6,103,674; U.S. 6,010,987; U.S. 6,110,878; EP 1 136 496 A1; U.S. 6,150,309; U.S. 6,232,276; U.S. 6,306,802; EP 1 136 497 A1; U.S. 5,888,945; U.S. 6,187,723; U.S. 6,117,826; U.S. 6,103,674; U.S. 6,063,741; U.S. 6,017,858; U.S. 5,994,277; and U.S. 6,174,842.

SUMMARY OF THIS INVENTION

The present invention generally provides an oil-lubricant composition having improved oxidative stability, the composition comprising at least one hindered phenolic antioxidant, at least one mono-boronated hindered phenolic antioxidant, at least one di-boronated hindered phenolic antioxidant, at least one alkylated diphenylamine, and at least one organomolybdenum compound. The present invention also provides a concentrated oil-lubricant additive composition which provides synergistic oxidative stability to a lubricating oil upon addition thereof, the concentrated composition comprising at least one hindered phenolic antioxidant, at least one mono-boronated hindered phenolic antioxidant, but at least one di-hindered phenolic antioxidant. boronate, at least one alkylated diphenylamine, and at least one organomolybdenum compound. In addition, the concentrated composition of the present invention may also be prepared with a high concentration of hindered phenolic antioxidants without deleterious effects on viscosity or lubricant solubility.

The synergistic improvement of oxidative stability in lubricating oil compositions and concentrated lubricating oil additive compositions comprising at least one hindered phenolic antioxidant, at least one mono-boronated hindered phenolic antioxidant, at least one di-boronated hindered phenolic antioxidant, and at least one alkylated diphenylamine is described in the commonly assigned US provisional application, filed concurrently filed 60 / 758,754 filed January 13, 2006, and PCT application number PCT / US2007 / 060489 which claims priority over provisional application No. 60 / 758,754, both of which are incorporated herein by reference. in its entirety to the extent permitted by applicable law. The present invention is an improvement over US Provisional Application No. 60 / 758,754 such that lubricating oil compositions and concentrated lubricating oil additive compositions comprising at least one hindered phenolic antioxidant, at least one mono-boronated hindered phenolic antioxidant at least one di-boronated hindered phenolic antioxidant, at least one alkylated diphenylamine, and at least one organomolybdenum compound exhibit enhanced oxidative stability compared to conventional formulations.

In one aspect, a lubricating oil or concentrated lubricating oil additive composition comprising: (a) 4,4'-methylenobis (2,6-di-tert-butylphenol), (b) 4,4'-methylenobis (2,6) -di-tert-butylphenol) -mono- (di-alkyl orthoborate), (c) 4,4'-methylenobis (2,6-di-tert-butylphenol) -di- (di-alkyl orthoborate), (d) an alkylated diphenylamine, and (e) an organomolybdenum compound, is an effective antioxidant combination for use in lubricants.

In another aspect, a lubricating oil or deadly concentrated lubricating oil composition comprising: (a) a hindered phenolic antioxidant, (b) is a single or multiple ortho-borate ester, or combinations thereof derived from a hindered phenolic antioxidant , where boron is fixed to phenolic oxygen prevented, (c) a relieved diphenylamine, and (d) an organomolbdenum compound, is an effective antioxidant combination for use in lubricants.

BRIEF DESCRIPTION OF THE FIGURE

Figure 1 shows graphical results from Example A.

DETAILED DESCRIPTION OF THIS INVENTION

Suitable hindered phenolics for use in the compositions of the present invention include phenolics incorporating the 2,6-di-tert-butylphenol moiety. A suitable prevented phenolic, which is commercially sold by Albemarle Corporation ™ under the registered name Etanox® 702, is 4,4'methylenebis (2,6-di-tert-butylphenol), hereinafter referred to as MBDTBP, having the structure of Structure I below. :

Structure I <formula> formula see original document page 5 </formula>

Other suitable hindered phenolics include: 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, 6-tert-butyl-ortho-cresol, 2,6-diisopropylphenol, 2,4-di- sec-butylphenol, higher molecular weight hindered phenolic antioxidants synthetically derived from 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, 6-tert-butyl-ortho-cresol, 2,6- diisopropylphenol, or 2,4-di-sec-butylphenol, butylated hydroxy toluene (BHT), and the like.

The amount of hindered phenolics present in the compositions of the present invention ranges from about 1 to about 50 weight percent of the total concentration of hindered phenolics, boronated hindered phenolics, and alkylated diphenylamine. Further aspects The amount of phenolics present in the compositions of the present invention ranges from about 1 percent to about 40 percent by weight, from about 1 percent to about 30 percent by weight, from about 1 percent. percent to about 25 percent by weight, from about 1 percent to about 20 percent by weight, and about 1 percent to about 15 percent by weight of the total concentration of prevented phenolics, boronated hindered phenolics, and diphenylamine. alkylated.

Boronated hindered mono- and di-phenolics suitable for use in the compositions of the present invention are derived from hindered phenolics described above by reaction with tri-alkyl orthoborates. Said process is described in U.S. 4,927,553. In one aspect, suitable boronated hindered mono- and di-phenolics present the structures of Structures II and III below: Structure II

<formula> formula see original document page 6 </formula>

Structure III

<formula> formula see original document page 6 </formula>

where R1, R2, R3, and R4 are independently selected from the group consisting of straight or branched cyclic C1 to C6 alkyl groups. Examples of said groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, and the like. propyl, n-butyl, sec-butyl, iso-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, 2-methyl-2-butyl, 3-methyl-2-butyl, isopentyl, n-hexyl, cyclopentyl, cyclohexyl, 2-ethylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 3-methyl-3-pentyl, 3,3-dimethylbutyl, 3, 3-dimethyl-2-butyl, 2,3-dimethyl-2-butyl, 2-methyl-2-hexyl, 2,2-dimethyl-3-pentyl, 2-heptyl, 3-heptyl, 2-methyl-3 hexyl, 3-ethyl-3-pentyl, 2,3-dimethyl-3-pentyl, 2,4-dimethyl-3-pentyl, 5-methyl-2-hexyl, 4,4-dimethyl-2-pentyl, 5- methylhexyl, n-heptyl, n-octyl, isooctyl, 2-ethylhexyl, 2-propylpentyl, 2-octyl, 3-octyl, 2,44-trimethylpentyl, 4-methyl-3-heptyl and 6-methyl-2- heptyl.

Other boronated hindered mono- and di-phenolics may be derived from reaction of the specific hindered phenolics described above, or hindered-phenolic mixtures with tri-alkyl orthoborates.

The total combination of boronated hindered mono- and di-phenolics present in the compositions of the present invention range from about 10 to about 80 percent by weight of the total concentration of hindered phenolics, boron-hindered phenolics, and alkylated diphenylamine. The ratio of boronated hindered mono-phenolics to boronated hindered di-phenolics may range from about 0.01: 1 to about 1: 0.01. The amount of boronated hindered mono-phenolics may be approximately equal to or greater than boronated hindered di-phenolics.

The amount of MBDTBP in conventional oil lubricant additive concentrate compositions was limited by its solubility to about 10% by weight of the total additive concentration. However, the present invention provides a method for increasing the concentration of hindered phenolic antioxidant in the lubricating deadly concentrated composition to be increased as much as about 50% by weight by including boronated hindered phenolic antioxidants in the concentrated lubricating oil additive composition.

Alkylated diphenylamines suitable for use in the compositions of the present invention are prepared from diphenylamine by reaction with olefins. A particularly useful method of preparing alkylated diphenylamines is described in US Patent Publication US-2006-0276677-A1 (which relates to US 11/442856 filed May 30, 2006, which claims priority in the US Patent Application 60 / 687,182 filed in June 2, 2005, and Interim Patent Application US 60/717322 filed September 14, 2005), the US Patent Application of which is incorporated herein by reference in its entirety to the extent permitted by applicable law. Both alkylated mono- and di-diphenylamines may be employed, either alone or in combination, and have the structures shown in Structures IV and V below:

Structure IV

<formula> formula see original document page 8 </formula>

Structure V

<formula> formula see original document page 8 </formula>

wherein R1, R2 and R3 are independently selected from the group consisting of cyclic, linear and branched C4 to C32 alkyl groups. Examples of such groups include, but are not limited to, alkyl groups derived from delineating alpha olefins, isomerized alpha olefins, polymerized alpha olefins, low molecular weight depropylene oligomers, and low molecular weight isobutylene oligomers. Specific examples include but are not limited to butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, dipropyl, tripropyl, tetrapropyl, pentapropyl, hexapropyl, heptapropyl, octapropyl, diisobutyl, triisobutyl, tetobutyl, tetobutyl, , and heptaisobutyl.

The total combination of alkylated mono- and di-diphenylamine present in the compositions of the present invention ranges from about 10 percent to about 80 percent by weight of the total concentration of hindered phenolics, boron-hindered phenolics, and alkylated diphenylamine. The ratio of mono- to di-diphenylamine alkyl may vary from about 0.01: 1 to about 1: 0.01.

Examples of suitable alkylated diphenylamines are nonylated diphenylamines (NDPA), octylated diphenylamines, octylated / styrenic mixed diphenylamines (such as Durad® AX55), and mixed butylated / octylated diphenylamines (such as Vanlube® 961). be in the range of about 2.0 to about 6.0% by weight. Lower nitrogen levels dilute the effectiveness of alkylated diphenylamines while higher nitrogen levels may adversely affect the compatibility of alkylated diphenylamines in the lubricant and lubricity of the lubricant. Alkylated diphenylamines may be a low melting liquid or solid.

Organomolybdenum compounds suitable for use in the present invention include sulfur free compounds, phosphorus free compounds, and sulfur containing compounds. The molybdenum content of organomolybdenum compounds may range from about 1 wt% to about 15 wt%. The concentration of the organomolybdenum compound may range from about 1 wt.% To about 40 wt.% Of the total concentration of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine, and organomolybdenum compound.

The amount of organomolybdenum compound used in the compositions of the present invention is such that the weight ratio of molybdenum to boron ranges from about 0.01: 1 to about 10: 1. The molybdenum content of a lubricating oil may range from about 50 to about 1000 ppm and the boron content may range from about 50 to about 500 ppm. The molybdenum content of a lubricating oil may range from about 100 to about 400 ppm and the boron content may range from about 100 to about 400 ppm.

Sulfur-free and phosphorus-free organomolybdenum compounds can be prepared by reacting a source of phosphorus-free sulfur-molybdenum with an organic compound containing amino and / or alcohol groups. Examples of sulfur-free and phosphorus-free molybdenum include molybdenum trioxide, ammonium molybdate, sodium molybdate and potassium molybdate. Amino groups may be monoamines, diamines, or polyamines. The alcohol groups may be mono-substituted alcohols, diol or bis-alcohols, or polyalcohols. As an example, the reaction of fatty oil diamines produces a product containing both amino and alcohol groups that can react with the sulfur free and phosphorus free molybdenum source.

Suitable phosphorus for use in the present invention include the following: compounds prepared by reacting certain basic nitrogen compounds with a demolibdenum source as defined in U.S. Pat. 4,259,195 and 4,261,843; compounds prepared by reacting a hydrocarbyl substituted alkyl hydroxy amine with a molybdenum source as defined in U.S. Patent Nos. 4,164,473; compounds prepared by reacting a phenol aldehyde condensation product, a monoalkylated alkylene diamine, and a molybdenum source as defined in US Patent No. 4,266,945; compounds prepared by reacting a fatty oil, diethanolamine, and a molybdenum source as defined in US Patent No. 4,889,647; compounds prepared by reacting an oleograx or acid with 2- (2-aminoethyl) aminoethanol, and a molybdenum source as defined in U.S. Patent No. 5,137,647; compounds prepared by reacting a secondary amine with a molybdenum source as defined in U.S. Patent No. 5,692,256; compounds prepared by reacting a diol, diamino, or amino alcohol compound with a demolibdenum source as defined in U.S. Patent No. 5,412,130; compounds prepared by reacting a fatty oil, monoalkylated alkylene diamine, and a molybdenum source as defined in European Patent Application EP 1 136 496 A1; and compounds prepared to contain a fatty acid, monoalkylated alkylene diamine, glycerides, and a demolibdenum source as defined in European Patent Application EP 1 136 497 A1.

Commercially available examples of sulfur-free and phosphorus-free oil-soluble molybdenum are Sakura-Lube 700 offered by Asahi Denka, and Molyvan856B and Molyvan 855 offered by RT Vanderbilt Company, Inc.diethanolamine, and a molybdenum source as defined in US Patent 4,889 .647 are sometimes illustrated as having one or both of the following structures,

Molybdenum compounds prepared by reacting a fatty oil, where R is an alkyl grease chain. The exact chemical structure of said materials is not completely known and may in fact be multi-compound mixtures of many organomolybdenum compounds.

Sulfur-containing organomolybdenum compounds can be prepared by a variety of methods. One method involves reacting a source of phosphorus free sulfur and molybdenum with an amino group and one or more sulfur sources. Sulfur sources include carbon disulfide, hydrogen sulfide, sodium sulfide and elemental sulfur. Alternatively, the sulfur-containing molybdenum compound may be prepared by reacting a sulfur-containing molybdenum source with an amino group or thiourama group and optionally a second sulfur source. Examples of sulfur-free and phosphorus-free demolibdenum sources include molybdenum trioxide, ammonium molybdate, sodium molybdate, potassium molybdate, and molybdenum halides. The amino groups may be monoamines, diamines, or polyamines. As an example, the reaction of molybdenum dioxide with a secondary amine and carbon disulfide produces molybdenum dithiocarbamates. Alternatively, the reaction of (NH4) 2Mo3Sii3.n (H2O) onden ranges from 0 to 2 with the tetralkylthiourama disulfide, yielding a trinuclear sulfur-containing demolibdenum dithiocarbamate.

Examples of sulfur-containing organomolybdenum compounds suitable for use in the present invention include the following: compounds prepared by reacting molybdenum reactive trioxide with a secondary amine and carbon disulfide as defined in U.S. Pat. 3,509,051 and 3,356,702; compounds prepared by reacting a sulfur free molybdenum source with a secondary amine, carbon disulfide, and an additional sulfur source as defined in U.S. Patent No. 4,098,705; compounds prepared by reacting a molybdenum halide with a secondary amine and decarbon disulfide as defined in U.S. Patent No. 4,178,258; compounds prepared by reacting a molybdenum source with a basic nitrogen compound and a sulfur source as defined in U.S. Pat. Nos. 4,263,152, 4,265,773, 4,272,387, 4,285,822,4,369,119, and 4,395,343: compounds prepared by reacting common ammonium tetrathiomolybdate basic nitrogen compound as defined in US Patent No. 4,283,295; reacting an olefin, sulfur, an amine and a demolbdenum source as defined in US Patent No. 4,362,633; compounds prepared by ammonium reacting tetrathiomolybdate with a basic nitrogen compound and an organic sulfur source as defined in U.S. Patent No. 4,402,840; compounds prepared to provide a phenolic compound, an amine and a molybdenum source with a sulfur source as defined in U.S. Patent No. 4,466,901; compounds prepared by reacting a triglyceride, a basic nitrogen compound, a molybdenum source, and a sulfur source as defined in U.S. Patent No. 4,765,918; compounds prepared by reacting alkali metal alkylthioxanthate salts with molybdenum halides as defined in U.S. Patent. No. 4,966,719; compounds prepared by reacting a tetralkylthiourama disulfide with molybdenum hexacarbonyl as defined in U.S. Patent No. 4,978,464; compounds prepared by reacting an alkyl dixantogen with hexacarbonyl demolbdenum as defined in U.S. Patent No. 4,990,271; compounds prepared by reacting alkali metal alkylxanthate with dimolbdenum tetraacetate as defined in U.S. Patent No. 4,995,996; compounds prepared by reacting (NH4) 2Mo3 Si3.2 (H2 O) with an alkali metal dialkyl dithiocarbamate or tetraalkyl thiourama disulfide as defined in U.S. Patent No. 6,232,276; compounds prepared by reacting an ester or acid with a diamine, a source of molybdenum and carbon disulfide as defined in U.S. Patent No. 6,103,674; and compounds prepared by reacting an alkali metal dialkyl dithiocarbamate with 3-chloropropionic acid, followed by molybdenum trioxide as defined in U.S. Patent No. 6,117,826.

Examples of commercial sulfur-containing soluble molybdenum compounds are Sakura-Lube® 100, Sakura-Lube® 155, Sakura-Lube® 165, and Sakura-Lube® 180 offered by Asahi Denka Kogyo KK, Molyvan® A, Molyvan® 807 eMolyvan ® 822 offered by RT Vanderbilt Company, and Naugalube® MolyFM offered by Crompton Corporation.

Molybdenum dithiocarbamates are suitable organomolybdenum compounds and have the following structure: <formula> formula see original document page 13 </formula>

where R is independently selected from hydrogen or an alkyl group containing from 4 to 18 carbons, and X is independently selected from oxygen or sulfur.

The lubricating oil may be any base stock or base oil (characterized as Group I, Group II, Group III, Group IV or Group V as defined by the API base stock classification system), or lubricant composed predominantly of aromatics, naphthenes, paraffin, poly-alpha-olefin and / or synthetic ester. In addition, the lubricant may also contain additional additives to make the system acceptable for use in a variety of applications. Such additives include dispersants, detergents, viscosity index enhancers, pour point inhibitors, anti-wear additives, extreme pressure additives, friction modifiers, corrosion inhibitors, rust inhibitors, emulsifiers, demulsifiers, defoamers, colorants, seal swelling, and additional antioxidants.

The present invention may be useful in passenger car engine oils, heavy duty diesel oils, medium speed diesel oils, degraded oils, marine engine oils, natural gas engine oils, 2-cycle engine oils, steam turbine oils, gas turbine oils, cyclocombined turbine oils, R&O oils, industrial gear oils, automotive gear oils, compressor oils, manual transmission fluids, automatic transmission fluids, track oils, quenching oils , rinse oils and hydraulic fluids. Suitable applications are in motor oils. A suitable application is a low phosphorus demotor oil characterized by a phosphorus content of less than 1000ppm. The concentrated lubricating oil additive may or may not contain an oil diluent. If a diluent oil is used, the diluent oil is typically present between 1% and 80% by weight of the concentrate.

Typically, the total amount of hindered phenolics, boron-hindered phenolics, alkylated diphenylamine, and organomolybdenum compound that are added to fully formulated oils depends on the end use application. For example, in a turbine oil the total amount of hindered phenolics, boronated hindered phenolics, alkylated diphenylamine, and organomolybdenum compound added to the oil ranges from about 0.05% to about 1.0% by weight. Differently, in a motor oil the total amount of impeded phenolics, boronated, diphenylamine alkylated and phenomolibdenum compound phenol added to the oil ranges from about 0.2% to about 3.0% by weight. In ultra-low phosphorus motor oils the total amount of hindered phenolics, boronated hindered phenolics, and alkylated diphenylamine may be about 5.0% by weight or more,

An example of a concentrated lubricating oil additive according to the present invention is as follows:

(a) 4,4-methylenebis (2,6-di-tert-butylphenol) @ 10 wt%;

(b) 4,4'-methylenebis (2,6-di-tert-butylphenol) mono- (di-sec-butylortoborate) and 4,4'-methylenobis (2,6-di-tert-butylphenol) di- ( di-sec-butyl orthoborate)> 40 wt%;

(c) dinonyl diphenylamine and monononyldiphenylamine> 10 wt%;

(d) a molybdenum dithiocarbamate containing 4.5 wt.% molybdenum @ 20 wt.%; and

(e) paraffinic diluent oil> 20 wt%.

An example of low phosphorus motor oil according to the present invention is as follows:

(a) 4,4-methylenebis (2,6-di-tert-butylphenol)> 0.5 wt%;

(b) 4,4'-methylenebis (2,6-di-tert-butylphenol) mono- (di-sec-butyl orthobo-rat) and 4,4'-methylenobis (2,6-di-tert-butylphenol) di- (di-sec-butyl orthoborate) 1.0 wt% (c) dinonyldiphenylamine and monononyldiphenylamine 0.75 wt%;

(d) a molybdenum dithiocarbamate containing 4.5 wt.% molybdenum @ 0.2 wt.%

(e) a concentrated dispersant> 4.8 wt%;

(f) a calcium detergent concentrated on base> 1.8 wt%;

(g) a neutral concentrated calcium detergent> 0.5 wt%;

(h) zinc dialkyl dithiophosphate> 0.6 wt%;

(i) a pour point inhibitor 0.1 wt%;

(j) a concentrated viscosity index enhancer> 8.0 wt%;

(k) an organic friction modifier> 0.5 wt%; and

(1) Paraffinic lubricating oil> 81.25 wt%.

Example A: Thickening and Oxidation of Oil at High Temperatures

A premixed passenger car engine oil was prepared according to the present invention by mixing the following materials:

(a) 5,000% by weight of an ashless dispersant;

(b) 1.875% by weight of a calcium-containing base detergent;

(c) 0.521% by weight of neutral detergent containing calcium;

(d) 0.625% by weight of secondary zinc dialkyl dithiophosphate; and

(e) 91.979 wt% 150N Group II base oil.

To said premixed motor oil was added the components indicated in Table 1.

Table 1. Components of Examples A.1 - A.6.

<table> table see original document page 15 </column> </row> <table> <table> table see original document page 16 </column> </row> <table>

MoDTC = molybdenum dithiocarbamate containing 4.5% by weight molybdenumBMBDTBP = a sample composed of: 15.6% by weight of 4,4-methylenobis (2,6-di-tert-butylphenol, 38.6% by weight of 4,4'-methylenobis ( 2,6-di-tert-butylphenol) -mono- (di-sec-butylortoborate), 17.4% by weight of 4,4'-methylenobis (2,6-di-tert-butylphenol) -di- (di-sec butyl orthoborate) (values calculated on the basis of HPLC analysis), 1.0% by weight of an ashless dispersant, and 29.0% by weight of a naphthenic 500N diluent oil .The sample has a boron content of 1.23% by weight as determined by ICP.HPE = 3,5-di-tert-butylhydroxyhydrocinamic acid, branched C7-alkyl alkyl estersNDPA = nonylated diphenylamine G2BO = 150N base oil Group II

The oxidative stability of said finished motor oils was evaluated in an oil volume oxidation test. Each oil (300 mL) was treated with an iron naphthenate oxidation catalyst to send 110 ppm iron to the finished oil. The oils were heated in a block heater to 150 ° C, while 10 liters / hour of dry oxygen was bubbled through the oil. Samples of the oxidized oils were removed at 24, 48, 72, 96, 120, 144, 168 and 192 hours. The kinetic viscosities of each sample were determined at 400 ° C. The percent increase in viscosity of oxidized oil relative to fresh oil was calculated. The results of percent viscosity increase are shown in Table 2.

Table 2. Percent increase in viscosity of A.l -

A.6 in the oil volume oxidation test.

<table> table see original document page 16 </column> </row> <table>

An increased viscosity percentage is a measure of increased oxidation and degradation of the lubricant. These results clearly show that the oxidant combination of the present invention in Examples A.3 to A.6 provides superior oxidation protection compared to the other Examples (A.1 - A.2). Antioxidant systems that do not contain the combination of 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenobis (2,6-di-tert-butylphenol) boronate, nonylated diphenylamine and organomolbdenum compound poor oxidation control while systems containing BMBDTBP, NDPA and MoDTC have superior oxidation control. These results are shown graphically in Figure 1.

Example B - Pressurized Differential Reading Calorimetry (PDSC)

The oxidative stability of finished engine oils prepared in Example A was assessed using pressurized differential reading calorimetry following standard ASTM D 6186 test method and using the following operating conditions: isothermal temperature = 180 ° C, oxygen gas @ 500 psig with a flow coefficient of 100 mL / min, approximately 3 mg sample size, in open aluminum pans. Each oil was treated with an iron naphthenate oxidation catalyst to send 55 ppm iron to the finished oil. Oxidation induction times (OIT) were determined according to the ASTM method. Each oil was tested in duplicate and the results averaged. The ILO results are shown in Table 3.

Table 3. Oxidation induction times in minutes for fresh oil

A.l - A.6 tested using PDSC.

<table> table see original document page 17 </column> </row> <table>

A longer induction time is a measure of higher lubricant oxidation stability. These results clearly show that the antioxidant combination of the present invention in Examples A.4 to A.6 provides superior oxidation protection compared to Examples not of the invention (A.1 - A.2). Antioxidant systems that do not contain the combination of 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenobis (2,6-di-tert-butylphenol) boronate, nonylated diphenylamine and molybdenum have a poor oxidation control while systems containing BMDTBP, NDPA and MoDTC have superior oxidative control. Also, considerably less, i.e. 25% less antioxidant is used in the oil of the present invention A.3 compared to the oil not of the present invention A.2 so the same level of performance in PDSC (112.12 minutes and 110.77 minutes statistically equivalent).

Although the compositions and methods of the present invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the art that variations may be applied to the compositions, methods and / or processes and steps or in sequence of the methods steps described herein without departing from the above. concept and scope of the present invention. More specifically, it will be apparent that certain agents that are both chemically and physiologically related may be substituted by the agents described herein provided that the same or similar results are achieved. All such similar substituents and modifications apparent to those of skill in the art are considered to be within the scope and concept of the present invention.

Claims (52)

1. Lubricating oil composition, characterized in that it comprises at least one hindered phenolic antioxidant, at least one boronated hindered phenolic antioxidant, at least one alkylated diphenylamine, and at least one organomolybdenum compound. Lubricating oil composition according to claim 1, characterized in that at least one hindered phenolic antioxidant is derived from at least one hindered phenolic antioxidant. Lubricating oil composition according to claim 2, characterized in that the at least one hindered-phenolic antioxidant comprises mono- and di-boronated hindered phenolic antioxidants. Lubricating oil composition according to claim 3, characterized in that the hindered phenolic antioxidant is 4,4'-methylenobis (2,6-di-tert-butylphenol). Lubricating oil composition according to claim 4, characterized in that the boronated hindered phenolic mono-antioxidant is provided with the structure <formula> formula see original document page 19 </formula> and the hindered phenolic antioxidant is provided with the structure <formula> formula see original document page 20 </formula> where R 1, R 2, R 3, and R 4 are independently selected from the group consisting of linear C 1 to C 6 alkyl groups, branched C 1 to C 6 alkyl groups and alkyl groups C3 to Ce cyclic. Lubricating oil composition according to claim 5, characterized in that at least one alkylated diphenylamine comprises alkylated di-diphenylamine. Lubricating oil composition according to claim 6, characterized in that the alkylated mono-diphenylamine is provided with the structure <formula> formula see original document page 20 </formula> and the alkylated diphenylamine is provided with <formula> formula see original document page 20 </formula> where R1, R2 and R3 are independently selected from the group consisting of cyclic, linear and branched C4 to C32 alkyl groups. Lubricating oil composition according to claim 7, characterized in that the alkylated mono- and di-diphenylamine is selected from the group consisting of nonylated diphenylamines, octylated diphenylamines, octylated / styrenic mixed diphenylamines, and butylated diphenylamines. / mixed octiladas. Lubricating oil composition according to claim 3, characterized in that the organomolybdenum compound is selected from the group consisting of sulfur-free organomolybdenum compounds, phosphorus-free organomolybdenum compounds, and sulfur-containing organomolybdenum compounds. Lubricating oil composition according to claim 9, characterized in that the organomolybdenum compound is a molybdenum dithiocarbamate having the structure where R is independently selected from hydrogen or an alkyl group containing from 4 to 18 carbons, and X is independently selected from oxygen or sulfur. Lubricating oil composition according to claim 10, characterized in that the concentration of the organomolybdenum compound varies from about 1 wt.% To about 40 wt.% Of the total concentration of the prevented phenolic, boronated prevented phenolic, alkylated diphenylamine and organomolybdenum compound. Lubricating oil composition according to claim 11, characterized in that the weight ratio of molybdenum to boron ranges from about 0.01: 1 to about 10: 1. Lubricating oil composition according to claim 12, characterized in that the molybdenum content ranges from about 50 ppm to about 1000 ppm and the boron content ranges from about 50 ppm to about 500 ppm. Lubricating oil composition according to claim 13, characterized in that the molybdenum content ranges from about 100 ppm to about 400 ppm and the boron content ranges from about 100 ppm to about 400 ppm. Lubricating oil composition according to claim 4, characterized in that the concentration of 4,4'-methylenobis (2,6-di-tert-butylphenol) is from about 1 to about 50 percent. by weight of the total concentration hindered phenolic, boronated hindered phenolic, alkylated diphenylamine and organomolybdenum. Lubricating oil composition according to claim 15, characterized in that the concentration of mono- and di-phenolic boron-doped phenols is between about 10 to about 80 percent by weight of the total concentration of phenolic-biased phenolic phenolic phenol. boronates, alkylated diphenylamine and organomolybdenum compound. Lubricating oil composition according to claim 16, characterized in that the ratio of boronated hindered mono-phenolics to boronated hindered di-phenolics is from about 1: 1 to about 1: 0.01. Lubricating oil composition according to claim 17, characterized in that the concentration of alkylated diphenylamine is about 10 percent to about 80 percent by weight of the total concentration of impeded boronated phenolic, phenolic hindered phenolic, alkylated diphenylamine concentration. , and organomolybdenum compound. 19. Concentrated lubricating oil additive composition, characterized in that it comprises at least one prevented phenolic antioxidant, at least one boronated hindered phenolic antioxidant, at least one alkylated diphenylamine, and at least one organomolybdenum compound. Concentrated lubricating oil additive composition according to claim 19, characterized in that at least one boronated hindered phenolic antioxidant is derived from at least one impeded phenolic antioxidant. Concentrated lubricating oil additive composition according to claim 20, characterized in that at least one boronated hindered phenolic antioxidant comprises mono- and di-boronated hindered phenolic antioxidant. Concentrated lubricating oil additive composition according to claim 21, characterized in that the phenolic-prevented antioxidant is 4,4'-methylenobis (2,6-di-tert-butylphenol). Concentrated lubricating oil additive composition according to claim 22, characterized by the fact that the boronated prevented phenolic mono-antioxidant has the structure <formula> formula see original document page 23 </formula> and the prevented phenolic antioxidant di -boronate is provided with the structure <formula> formula see original document page 23 </formula> where R1, R2, R3, and R4 are independently selected from the group consisting of linear C1 to Cs alkyl groups, branched C1 to Cs alkyl groups cyclic C3 to C6 alkyl groups. Concentrated lubricating oil additive composition according to claim 23, characterized in that at least one alkylated diphenylamine comprises alkylated mono- and di-diphenylamine. Concentrated lubricating oil additive composition according to claim 24, characterized in that the alkylated mono-diphenylamine is provided with the formula and the alowylated and endowed diphenylamine of the <formula> formula see original document page 24 </formula> where R1, R2 and R3 are independently selected from the group consisting of cyclic, linear and branched C4 to C32 alkyl groups. Concentrated lubricating oil additive composition according to claim 25, characterized in that the alkylated mono- and di-diphenylamine is selected from the group consisting of nonylated diphenylamines, octylated diphenylamines, octylated / styrenic mixed diphenylamines, and mixed butylated / octylated diphenylamines. Lubricating oil composition according to Claim 21, characterized in that the organomolybdenum compound is selected from and alkylated di-diphenylamine is provided with the group consisting of sulfur-free organomolybdenum compounds, phosphorus-free organomolybdenum compounds. , and sulfur-containing organomolybdenum compounds. Lubricating oil composition according to claim 27, characterized in that the organomolybdenum compound is molybdenum dithiocarbamate having the structure where R is independently selected from hydrogen or an alkyl group containing from 4 to 18 carbons, and X is independently selected from oxygen or sulfur. Lubricating oil composition according to claim 28, characterized in that the concentration of the organomolybdenum compound ranges from about 1 wt.% To about 40 wt.% Of the total concentration of defenolated, boronated hindered phenolics, alkylated diphenylamine and organomolybdenum compound. Concentrated lubricating oil additive composition according to claim 22, characterized in that the concentration of 4,4'-methylenobis (2,6-di-tert-butylphenol) is from about 1 to about 50 weight percent of the total concentration of hindered phenolics, boronated hindered phenolics, alkylated diphenylamine and organomolybdenum compound. Concentrated lubricating oil additive composition according to claim 30, characterized in that the concentration of boronated hindered mono- and di-phenolics is from about 10 percent to about 80 percent by weight of the total concentration of hindered phenolics, boronated hindered phenolics, alkylated diphenylamine and organomolybdenum compound. Concentrated lubricating oil additive composition according to claim 31, characterized in that the ratio of boronated to disrupted boronated mono-phenolics is from about 1: 1 to about 1: 0.01. Concentrated lubricating oil additive composition according to claim 32, characterized in that the concentration of alkylated diphenylamine is from about 10 percent to about 80 percent by weight of the total concentration of hindered phenolics, boronated hindered phenolics, alkylated diphenylamine and organomolybdenum compound. Concentrated lubricating oil additive composition according to claim 33, characterized in that it further comprises an oil diluent. Concentrated lubricating oil additive composition according to claim 34, characterized in that the concentration of the diluent oil is from about 1% to about 80% by weight. 36. Motor oil composition, characterized in that it comprises at least one hindered phenolic antioxidant, at least one boronated hindered phenolic antioxidant, at least one alkylated diphenylamine and at least one organomolybdenum compound. Motor oil composition according to claim 36, characterized in that the hindered phenolic antioxidant is 4,4'-methylenobis (2,6-di-tert-butylphenol). Motor oil composition according to claim 37, characterized in that at least one hindered phenolic antioxidant comprises a boronated hindered phenolic mono-antioxidant having the structure <formula> formula see original document page 27 </formula> and a di-boronated hindered phenolic antioxidant having the structure <formula> formula see original document page 27 </formula> where R1, R2, R3, and R4 are independently selected from the group consisting of linear C1 to C6 alkyl groups, alkyl groups Branched C1 to C8 and cyclic C3 to C8 alkyl groups. Motor oil composition according to claim 38, characterized in that at least one alkylated diphenylamine comprises an alkylated mono-diphenylamine having the structure <formula> formula and original diurne page 28 </formula> alkylated diphenylamine having the structure <formula> formula see original document page 28 </formula> where R1, R2 and R3 are independently selected from the group consisting of cyclic, linear and branched C4 to C32 alkyl groups. Motor oil composition according to claim 39, characterized in that the alkylated mono- and di-diphenylamine is selected from the group consisting of nonylated diphenylamines, octylated diphenylamines, octylated / styrenic mixed diphenylamines, and diphenylamines. butylated / octylated. 41. An engine oil composition according to claim 40, characterized in that the organomolybdenum compound is molybdenum dithiocarbamate having the structure where R is independently selected from hydrogen or an alkyl group containing from 4 to 18 carbons, and X is independently selected from oxygen or sulfur. Motor oil composition according to claim 41, characterized in that the concentration of 4,4'-methylenobis (2,6-di-tert-butylphenol) is from about 1 to about 50%. percent by weight of the total concentration of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine and organomolbdenum compound, the concentration of boronated hindered mono- and di-phenolics is about 10 percent to about 80 percent by weight of the total concentration of phenolic, hindered phenolic boronated hindered, alkylated diphenylamine and organomolybdenum compound, the ratio of boronated hindered to boronated di-phenolics impeded is between about 1: 1 to about 1: 0.01, the alkylated diphenylamine concentration is between about 10 percent to about 80 weight percent of the total concentration of hindered phenolics, boronated hindered phenolics, alkylated diphenylamine and organomolybdenum compound, and the concentration of Organomolybdenum is from about 1 percent to about 40 percent by weight of the total concentration of hindered phenolic, boronated hindered phenolic, alkylated diphenylamine, and organomolybdenum compound. Engine oil composition according to claim 42, characterized in that the engine oil is used to lubricate an engine 15 selected from the group consisting of a gasoline engine, a heavy duty diesel engine, a natural gas engine, a marine engine and a railroad engine. 44. Concentrated motor oil additive composition, characterized in that it comprises at least one hindered phenolic antioxidant, at least one boronated hindered phenolic antioxidant, at least one alkylated diphenylamine and at least one organomolybdenum compound. 45. Concentrated motor oil additive composition according to claim 44, characterized in that the prevented phenolic antioxidant is 4,4'-methylenebis (2,6-di-tert-butylphenol). 46. Concentrated motor oil additive composition according to claim 45, characterized in that at least one boronated hindered phenolic antioxidant comprises a hindered phenolic mono-antioxidant having the structure <formula> formula see original document page 30 </ formula > and a di-boronated hindered phenolic antioxidant having the structure <formula> formula see original document page 30 </formula> where R1, R2, R3, and R4 are independently selected from the group consisting of linear C1 to C8 alkyl groups, branched C1 to C8 alkyl groups and cyclic C3 to C8 alkyl groups. 47. Concentrated motor oil additive composition according to claim 46, characterized in that at least one alkylated diphenylamine comprises an alkylated mono-diphenylamine having the structure <formula> formula see original document page 31 </formula> alkylated di-diphenylamine having the structure <formula> formula see original document page 31 </formula> where R1, R2 and R3 are independently selected from the group consisting of cyclic, linear and branched C4 to C32 alkyl groups. 48. Concentrated motor oil additive composition according to claim 47, characterized in that the alkylated mono- and di-diphenylamine is selected from the group consisting of nonylated diphenylamines, octylated diphenylamines, octylated / styrenic mixed diphenylamines, and mixed butylated / octylated diphenylamines. 49. Concentrated motor oil additive composition according to claim 48, CHARACTERIZED by the fact that the organomolybdenum compound is molybdenum adithiocarbamate having the structure where R is independently selected. from hydrogen or an alkyl group containing from 4 to 18 carbons, and X is independently selected from oxygen or sulfur. 50. Concentrated composition of motor oil additive according to claim 49, CHARACTERIZED by the fact that the concentration of 4,4'-methylenobis (2,6-di-tert-butylphenol) is between about 1 per cent to About 50 percent by weight of the total concentration of hindered phenolics, boronated hindered phenolics, alkylated diphenylamine, and organomolybdenum compound, the concentration of boronated hindered mono- and di-phenolics is between about 10 percent to about 80 percent by weight. total of hindered phenolics, boronated hindered phenolics, alkylated diphenylamine and organomolybdenum compound, the ratio of boronated mono-phenolics to boronated hindered phenolics is between about 1: 1 to about 1: 0.01, the concentration of alkylated diphenylamine is between about 10 percent to about 80 weight percent of the total concentration of hindered phenolics, boronated hindered phenolics, alkylated diphenylamine and organomolibd NiO and aconcentração organo-molybdenum compound is from about 1 percent to about 40por weight percent of the total concentration of hindered phenolic, impedidosboronados phenolic, alkylated diphenylamine and organo compound. 51. Concentrated composition of engine oil additive according to claim 50, CHARACTERIZED by the fact that engine oil is used to lubricate an engine selected from the group consisting of gasoline engine, a heavy-duty diesel engine, a natural gas engine, a marine engine and a railroad engine. 52. A method of increasing the concentration of at least one hindered phenolic antioxidant in a concentrated lubricating oil additive composition, the method comprising the step of adding at least one boronated hindered phenolic antioxidant to the concentrated lubricating oil additive.