CN102089415A - Liquid additives for the stabilization of lubricant compositions - Google Patents

Abstract

A lubricating oil composition comprising: (A) a base stock; and (B) a liquid additive package. The liquid additive package comprises: (i) an alkylated diphenylamine; (ii) at least 5% by weight, based on the weight of the additive package, of a phenylnaphthylamine; and (iii) a sulfur-containing phenol.

Description

Liquid additive for stabilizing lubricant compositions

Cross References to Related Applications

This application claims priority to U.S. Patent Application No. 12/476,423, filed June 2, 2009, which claims priority to U.S. Provisional Application No. 61/080,547, filed July 14, 2008 right. The entire content of each of these applications is incorporated herein by reference.

field of invention

This invention relates to lubricating oil compositions. More specifically, the present invention relates to lubricating oil compositions comprising an additive package for reducing oxidative deterioration.

Background of the invention

Lubricants, such as those used in various machines, are susceptible to oxidative deterioration during storage, transportation, and use, especially when such lubricants are exposed to high temperatures and iron-catalyzed environments that greatly promote lubricant oxidation. If not controlled, this oxidation promotes the formation of corrosive acid products, sludge, varnish deposits, resins and other oil insoluble products, and can lead to loss of the lubricant's specified physical and tribological properties. These oxidation products can lead to the formation of harmful deposits on critical engine components such as pistons, piston liners, valves and valve lifters.

Accordingly, it is common practice to include deposition control compounds and/or additives such as anti-oxidant additives in lubricants to prevent oxidation, at least to some extent, thereby prolonging the useful life of the lubricant. One of these antioxidant additives is alkylated diphenylamine (ADPA), which has been widely used due to its performance and low cost. However, in recent years, driven by increasing performance and environmental requirements, there has been a general trend in the industry to build machinery smaller but operate at higher speeds and higher operating temperatures. In this way, greater output and improved fuel economy are achieved. However, under such operating conditions, the thermal and oxidative stress of the lubricant becomes so severe that conventional ADPA antioxidants are insufficient to stabilize the lubricant.

Lubricant compositions containing various antioxidants are widely known in the art. As an example, U.S. Patent No. 6,326,336 to Gatto et al. (hereinafter "Gatto") discloses a turbine lubricating oil comprising: (A) an amine antioxidant selected from the group consisting of alkylated diphenyl Amines, phenylnaphthylamines, and mixtures thereof; (B) sulfur-containing additives selected from the group consisting of sulfurized olefins, sulfurized fatty acids, ashless dithiocarbamates, tetraalkylthiuram disulfides, and their mixture, and (C) base oil. According to Gatto, such compositions provide excellent oxidation protection and acceptable sludge control in turbine oils formulated with Group II or higher base stocks. An important criterion for selecting the concentration of sulfur-containing additives is the sulfur content of the additive package. According to Gatto, sulfur-containing additives should provide 0.005wt% - 0.07wt% sulfur to the finished turbine oil. However, Gatto utilizes only sulfurized olefins, sulfurized fatty acids, ashless dithiocarbamates, tetraalkylthiuram disulfides, and mixtures thereof. Gatto noted that there are a number of issues that can be associated with the use of hindered phenols. Gatto points out that hindered phenols can dealkylate at high temperatures and produce free phenols, and that water extractability of some water-soluble phenols is another potential concern. Therefore, Gatto noted, phenol-free formulations may be desirable.

U.S. Patent No. 5,091,099 discloses a phosphite-free lubricating oil composition comprising: a) a mineral oil or a synthetic oil or a mixture thereof; and b) comprising at least one aromatic amine of formula (I),

and at least one phenol of formula (II)

and said compound is present in said mixture in a ratio of 2 to 6 parts by weight of aromatic amine(s) of formula (I) to 1 part by weight of phenol(s) of formula II .

U.S. Patent No. 5,523,007 discloses a lubricating oil composition comprising diesel engine oil and a compound of formula I as an antioxidant

where X is

And R is a linear or branched alkyl group of formula _{CnH2n +1} , wherein n is an integer from 8 to 22. Such phenols may contain sulfur, but the weight percent and relationship to other components is not taught.

One potential antioxidant that can be used to achieve superior performance in antioxidant packages is phenylnaphthylamine (PNA). However, PNA is generally sold as a solid at room temperature, and as such does not readily mix into base oils.

Even with these known lubricant compositions in mind, there remains a need for cost effective antioxidant packages that provide improved antioxidant stability and are easily blendable with base stocks.

Detailed Description of the Preferred Embodiment

The present invention generally relates to lubricating oil compositions useful in high temperature environments. Typically, such high temperature environments promote oxidative deterioration of the lubricant. The lubricating oil compositions of the present invention are less prone to such oxidative deterioration, they are more stable, and thus provide improved physical and tribological properties at elevated temperatures.

In one embodiment of the invention, the composition comprises a liquid additive package having at least about 1 weight percent (wt%), such as at least about 3wt%, at least about 5wt%, at least about 7 wt%, at least about 10 wt%, or at least about 15 wt% phenylnaphthylamine (PNA), such as phenyl-alpha-naphthylamine. In terms of ranges, the PNA can be present at about 1 wt % to about 50 wt %, such as about 2 wt % to about 50 wt %, about 3 wt % to about 40 wt %, about 5 wt % to about 30 wt %, or about 5 wt % to about 30 wt % Quantities within the range exist. When combined with a suitable base stock, such an additive package reduces the amount of detrimental deposits produced by oxidation of the lubricating oil composition compared to an additive package having less than 5 wt% PNA.

Preferably, the liquid additive package, such as a liquid antioxidant additive package, comprises a diphenylamine such as alkylated diphenylamine (ADPA) and at least about 5 wt% PNA. Generally, PNA is solid at room temperature and is difficult to dissolve in liquids such as ADPA or base stocks. In a preferred embodiment of the invention, PNA is combined with ADPA, for example under heating, for example at about 150°C, about 100°C, about 65°C or about 50°C, and/or under nitrogen or similar inert atmosphere , until a homogeneous mixture is obtained. The mixture is a stable liquid at room temperature. ADPA and PNA can be mixed for about 10 to about 20 minutes, such as about 12 to about 18 minutes, or about 14 to about 16 minutes. It should be noted that the times listed above are exemplary only and times will vary with the amount of each material. In one embodiment, the resulting composition is dark red in color and has a viscosity measured at 25°C of less than about 50,000 cP, such as less than about 30,000 cP or less than about 20,000 cP. In terms of range, the composition has a viscosity in the range of about 100 to about 100.000 cP, such as in the range of about 100 to about 50,000 cP, or in the range of about 1,000 to about 25,000 cP, measured at 25°C .

In one embodiment of the present invention, the lubricating oil composition, when combined with a poly-alpha-olefin base stock at a base stock to additive package weight ratio of about 99:1, exhibits at least about 25 minutes, such as at least about An oxidation induction time (OIT) of 38 minutes, at least about 40 minutes, at least about 50 minutes, or at least about 75 minutes, measured under the pressurized differential scanning calorimeter (PDSC) conditions shown in Table 1. This is a significant improvement over a similar lubricating oil composition comprising the same poly-alpha-olefin base stock and pure ADPA which showed an oxidation time of 28.6 minutes in a similar test. It should be noted that the test parameters under which the PDSC was operated may affect the OIT of the samples. For example, a sample tested at 160°C may have a longer OIT than a similar sample tested at 185°C.

In another embodiment of the present invention, the additive package comprises ADPA, PNA and sulfur-containing phenols. Typically, the sulfur-containing phenols are solids at room temperature. However, it is also possible to use sulfur-containing phenols which are liquid at room temperature. In one embodiment, the combination of ADPA, PNA and sulfur-containing phenol forms a clear liquid. In another embodiment, the combination of ADPA, PNA, and sulfur-containing phenols results in an additive package that significantly improves oxidation stability and reduces medium-high temperature thermal oxidation engine oil simulation test (TEOST MHT, ASTM D7097) amount of sediment (see below). When such an additive package was blended (at about 1 wt. %) into a motor oil containing an API Group II basestock, it exhibited an OIT of about 40 minutes and exhibited 37 milligrams (mg) of deposits. In one embodiment of the invention, the lubricating oil composition has a TEOST MHT value of less than about 60 mg, such as less than about 50 mg, less than about 40 mg, or less than about 20 mg. It should be noted that the additive package of pure ADPA yielded a TEOST MHT value of about 55 mg, pure PNA yielded a TEOST MHT value of about 80 mg, and pure sulfur-containing phenols yielded a TEOST MHT value of about 63 mg. Therefore, a TEOSTMHT value of less than 55 mg for the lubricant composition is surprising and unexpected.

In a preferred embodiment of the invention, ADPA is present in an amount of at least about 50 wt%, such as at least about 60 wt%, or at least about 70 wt%, based on the weight of the additive package. In terms of ranges, preferably ADPA is present in an amount of from about 50 to about 99 wt%, such as from about 60 to about 99 wt%, from about 70 to about 95 wt%, or from about 70 to about 90 wt%, based on the weight of the additive package.

In one embodiment of the invention, the PNA is at least about 1 wt%, such as at least about 3 wt%, at least about 5 wt%, at least about 7 wt%, at least about 10 wt%, at least about 15 wt%, at least about It is present in an amount of 20 wt%, at least about 25 wt%, or at least about 50 wt%. In terms of ranges, the PNA is from about 1 wt% to about 50 wt%, based on the weight of the additive package, such as from about 2 wt% to about 50 wt%, from about 5 wt% to about 50 wt%, from about 3 wt% to about 40 wt%, from about 5 wt% to about It is present in an amount of 30 wt % or about 5 wt % to about 30 wt %. Additive packages with the above amounts of PNA show Surprising and unexpected results.

In another embodiment of the present invention, the sulfur-containing phenol is at least about 1 wt%, based on the weight of the additive package, such as at least about 5 wt%, at least about 10 wt%, at least about 15 wt%, at least about 20 wt%, at least about It is present in an amount of 25 wt%, or at least about 50 wt%. In terms of ranges, the sulfur-containing phenol is in an amount of about 5 to about 50 wt%, such as about 10 wt% to about 25 wt%, about 10 wt% to about 20 wt%, or about 10 wt% to about 15 wt%, based on the weight of the additive package exist.

In one embodiment of the invention APDA is present in an amount of at least 50 wt%, such as at least 60 wt% or at least 70 wt%, PNA is present in an amount of at least 1 wt%, such as at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt% or at least 50 wt% is present, and the sulfur-containing phenol is present in an amount of at least 1 wt%, such as at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt% or at least 50 wt%, all wt % are based on the weight of the additive package.

In a preferred embodiment of the invention, ADPA is present in an amount of about 70 wt % +/- 10 wt %, for example +/- 5 wt %, +/- 3 wt % or +/- 1 wt %; PNA is present in an amount of about 15 wt % +/- 1 wt % -14 wt%, e.g. +/-10 wt%, +/-5 wt%, +/-3 wt% or +/-1 wt%; Amounts of 5 wt%, +/- 3 wt% or +/- 1 wt% were present; all wt% are based on the weight of the additive package. Additional preferred embodiments employ the wt% combinations of ADPA, PNA, and sulfur-containing phenols listed in Table 2. Each weight percent listed for these embodiments may vary by +/- 10 wt%, eg +/- 5 wt%, +/- 3 wt%, +/- 2 wt% or +/- 1 wt%.

In one embodiment of the invention, the weight ratio of ADPA to sulfur-containing phenol in the additive package is at least about 3:1, such as at least about 6:1 or at least about 10:1.

In another embodiment of the invention, the weight ratio of PNA to sulfur-containing phenol in the additive package is in the range of about 1:10 to about 10:1, for example in the range of about 1:8 to about 8:1 , in the range of about 1:5 to about 5:1, or in the range of about 1:3 to about 3:1.

In another embodiment of the invention, the weight ratio of the sum of ADPA and PNA to the sulfur-containing phenol is at least about 2:1, such as at least about 3:1, at least about 4:1, at least about 5:1 or at least about 10 : 1.

In another embodiment of the invention, the weight ratio of ADPA to PNA in the additive package is at least about 2:1, such as at least about 3:1, at least about 4:1, at least about 5:1 or at least about 10:1. 1. In terms of ranges, the weight ratio is in the range of about 3:1 to about 20:1, such as in the range of about 3:1 to about 15:1, or in the range of about 3:1 to about 10:1 Inside.

In one embodiment, the base stock is present in an amount of at least about 50 wt%, such as at least about 75 wt%, at least about 95 wt%, or at least about 99 wt%, based on the weight of the lubricating oil composition (including the additive package).

In one embodiment, the additive package is present in an amount of at least about 0.05 wt%, such as at least about 0.5 wt%, at least about 1 wt%, or at least about 10 wt%, based on the weight of the lubricating oil composition.

In terms of ranges, the ratio of base stock to additive package is in the range of about 50:50 to about 99.95:0.05, for example in the range of about 75:25 to about 99.9:0.1, in the range of about 90:10 to about 99:1 , or in the range of about 95:5 to about 99:1. In a preferred embodiment of the present invention, the lubricating oil composition comprises about 99 wt% base stock and about 1 wt% additive package, based on the total weight of the lubricating oil.

The additive package of the present invention is particularly useful as a component in combination with many possible base stocks. The additive package can be included in various oils of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof. As an example, the additive package is included in crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines. The additive package can also be used, for example, with gas engine lubricants, turbine lubricants, automatic transmission fluids, gear lubricants, compressor lubricants, metalworking lubricants, hydraulic fluids, and other lubricating oil and grease compositions. In one embodiment of the present invention, the additive package is used in the preparation of a lubricant which may have food contact, eg incidental food contact. More specifically, the additive package can be used with H1 food grade base stocks.

In one embodiment, the additive package is combined with a grease or combination of greases. Greases are often used in applications with high pressure and low speed. Such applications include, but are not limited to, continuous casting operations.

In one embodiment of the invention, the ADPA of the invention comprises ADPA of formula I:

Wherein R ₁ and R ₂ are independently selected from linear or branched C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₃ -C ₂₀ cycloalkyl.

In one embodiment of the present invention, _R1 and _R2 may be the same substituent. In one embodiment of the invention, neither _R1 nor _R2 is hydrogen.

Representative examples of alkyl groups for R _{and R} herein include, for example, straight or branched hydrocarbon chain groups containing 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, 1- Methylethyl (isopropyl), n-butyl, isobutenyl, n-pentyl, etc., mixtures and isomers thereof, and the like.

Representative examples of cycloalkyl groups for R _{and R} herein include, for example, substituted or unsubstituted rings containing from about 5 to about 20 carbon atoms, such as cyclopentyl, cyclohexyl, n-methylcyclohexyl , n-dimethylcyclohexyl, n-ethylcyclohexyl, cycloheptyl, cyclooctyl, etc., mixtures thereof, and the like.

In another embodiment of the present invention, said ADPA is further alkylated with more than two substituents. In another embodiment of the present invention, said ADPA is alkylated with only one substituent.

Preferred ADPAs useful in the practice of this invention include, for example, nonylated diphenylamines, octylated diphenylamines (such as di(octylphenyl)amine), styrylated diphenylamines , octylated styrenated diphenylamine, butylated octylated diphenylamine, diphenylamine, butyldiphenylamine, dibutyldiphenylamine, octyldiphenylamine Amine, dioctyldiphenylamine, nonyldiphenylamine, dinonyldiphenylamine, heptyldiphenylamine, diheptyldiphenylamine, methylstyryldiphenylamine, Mixed butyl/octyl alkylated diphenylamines, mixed butyl/styryl alkylated diphenylamines, mixed nonyl/ethyl alkylated diphenylamines, mixed octyl/ Styryl-alkylated diphenylamine, mixed ethyl/methyl-styryl-alkylated diphenylamine, tert-butyldiphenylamine, di-tert-butyldiphenylamine, monooctyl Diphenylamine, dodecyldiphenylamine, hexadecyldiphenylamine, eicosenyldiphenylamine, tetradecenyldiphenylamine, octadecenyl Diphenylamine, polyisobutyldiphenylamine and mixtures thereof.

和

得自Chemtura Corporation的NaugaAMS、

和

得自BFGoodrich Specialty Chemicals的

和可得自EthylCorporation的

抗氧剂和抗氧剂；得自R.T.Vanderbilt Company，Inc.的

DND、

NA、

和

和在本发明的一个实施方案中，所述添加剂包包含选自上面所指定的结构和化合物的两种或更多种ADPA的混合物。示例性的混合物是混合的单和二辛基二苯基胺(DPA)、混合的单和二壬基DPA、混合的单和二苯乙烯基DPA、混合的丁基/苯乙烯基烷基化的DPA、混合的辛基/苯乙烯基烷基化的DPA和混合的丁基/辛基烷基化的DPA。Preferred commercially produced ADPAs that can be used in the present invention include, for example, DPA from Ciba Specialty Chemicals

and

Nauga from Chemtura Corporation AMS,

and

Available from BFGoodrich Specialty Chemicals

and Available from Ethyl Corporation

Antioxidants and Antioxidant; available from RTVanderbilt Company, Inc.

DND,

NA,

and

and In one embodiment of the invention, the additive package comprises a mixture of two or more ADPAs selected from the structures and compounds specified above. Exemplary mixtures are mixed mono and dioctyldiphenylamine (DPA), mixed mono and dinonyl DPA, mixed mono and distyryl DPA, mixed butyl/styryl alkylated DPA, mixed octyl/styryl alkylated DPA and mixed butyl/octyl alkylated DPA.

In one embodiment of the invention, the PNA comprises phenyl-alpha-naphthylamine. In another embodiment of the present invention, the PNA comprises phenyl-beta-naphthylamine.

In one embodiment of the invention, the PNA comprises one or more PNAs of formula II:

In another embodiment of the invention, said PNA comprises one or more PNAs of formula III:

In another embodiment of the present invention, the PNA comprises a mixture of PNAs of the above two formulas.

In another embodiment of the invention, said PNA is substituted with one or more substituents, eg alkylated. Possible substituents include, for example, the substituents mentioned above as alternatives for _R1 and _R2 . In one embodiment, the phenyl ring of formula II or formula III is substituted in the ortho, para or meta position.

L06。可用于本发明的优选的商业生产的PNA包括例如

PANA。Preferred PNAs useful in the present invention include, for example, octylalkylated phenyl-alpha-naphthylamines, decylphenyl-alpha-naphthylamines, and mixed alkylated phenyl-alpha-naphthylamines . Examples of commercially produced substituted PNAs are PANA and

L06. Preferred commercially produced PNAs useful in the present invention include, for example

Pana.

In one embodiment of the invention there is a composition comprising a mixture of two or more PNAs selected from the structures and compounds specified above.

In one embodiment of the invention, the sulfur-containing phenol comprises a sulfur-containing phenol of formula IV:

wherein _R is a sulfur-containing alkyl or aryl group, or a sulfur-containing alkene or carboxylic acid; and

wherein _R4 and _R5 are alkyl or aryl.

Preferred sulfur-containing phenols useful in the present invention include, for example, 2,2'-thiodiethylenebis(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,2'-thio Bis(4-methyl-6-tert-butylphenol), 4,4′-thiobis(2-tert-butyl-5-methylphenol) and (3,5-di-tert-butyl-4- Iso(C10-C14)alkyl hydroxyphenyl)methylthioacetate.

得自Ciba Specialty chemicals的

和在本发明的一个实施方案中，所述添加剂包通过将

与

和含硫酚混合而制备。混合在65℃和氮气保护下进行。混合可进行至少5分钟，例如至少10分钟，至少15分钟，至少25分钟或至少60分钟。本领域普通技术人员明白，混合时间将根据各种材料的量而变化。所得到的混合物在室温下为自由流动的液体，其在40℃下测量具有小于约100,000cP，例如小于约50,000cP，小于约40,000cP，小于约25,000cP或小于约10,000cP的粘度。在其它实施方案中，所得到的混合物颜色是暗红色的。Preferred commercially-produced sulfur-containing phenols useful in the present invention include, for example, Teflon® from Chemtura Corporation. and

from Ciba Specialty chemicals

and In one embodiment of the invention, the additive package is obtained by

and

Prepared by mixing with sulfur-containing phenol. Mixing was carried out at 65°C under nitrogen protection. Mixing may be performed for at least 5 minutes, such as at least 10 minutes, at least 15 minutes, at least 25 minutes or at least 60 minutes. Those of ordinary skill in the art will appreciate that mixing times will vary depending on the amounts of the various materials. The resulting mixture is a free-flowing liquid at room temperature that has a viscosity measured at 40°C of less than about 100,000 cP, such as less than about 50,000 cP, less than about 40,000 cP, less than about 25,000 cP, or less than about 10,000 cP. In other embodiments, the resulting mixture is dark red in color.

In a preferred embodiment of the present invention, the additive package comprises nonylated diphenylamine, octylphenyl-α-naphthylamine and 2,2'-thiodiethylenebis(3, 5-di-tert-butyl-4-hydroxyphenyl)propionate. In another preferred embodiment of the present invention, the additive package comprises butyl and octylated diphenylamines, octylalkylated phenyl-α-naphthylamines and 2,2'-thio Bis(4-methyl-6-tert-butylphenol). In another preferred embodiment of the present invention, the additive package comprises octyl and styrylated diphenylamines, mixed alkylated phenyl-α-naphthylamines and 2,2'-sulfur Diethylenebis(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

Additional embodiments employ the combinations of ADPA, PNA, and sulfur-containing phenols listed in Table 3. This list is not exhaustive of all preferred embodiments.

Exemplary ADPA, PNA and sulfur-containing phenol candidates are listed in Table 4. This list is not exclusive.

Further additives may be incorporated into the compositions of the invention in order to enable them to meet specific requirements. Examples of additives that may be included in lubricating oil compositions are dispersants, detergents, metal rust inhibitors, viscosity index improvers, corrosion inhibitors, oxidation inhibitors, friction modifiers, other dispersants, defoamers, Antiwear additive and pour point depressant. Some are discussed in more detail below.

The lubricating oil compositions of the present invention may further contain one or more ashless dispersants which, when added to lubricating oils, are effective in reducing deposit formation when used in gasoline and diesel engines. Ashless dispersants useful in the compositions of the present invention comprise an oil-soluble polymeric long-chain backbone having functional groups capable of associating with the particles to be dispersed. Typically, such dispersants contain amine, alcohol, amide or ester polar moieties attached to the polymer backbone (often through bridging groups). The ashless dispersant, for example, can be selected from oil-soluble salts, esters, amino esters, amides, imides and oxazolines of long-chain hydrocarbon-substituted mono- and polycarboxylic acids or their anhydrides; thiocarboxylic acids of long-chain hydrocarbons salt derivatives; long chain aliphatic hydrocarbons having a polyamine moiety directly attached thereto; and Mannich condensation products formed by condensing long chain substituted phenols with formaldehyde and polyalkylene polyamines.

Preferred dispersants include polyamine derivatized polyalphaolefin dispersants, especially ethylene/butylene alphaolefin and polyisobutylene based dispersants. Particularly preferred are those derived from polyvinylamines substituted with succinic anhydride groups such as polyethylene diamine, tetraethylene pentamine; or polyoxyalkylene polyamines such as polyoxypropylene diamine, trihydroxy Methylaminomethane; hydroxyl compounds such as pentaerythritol; and combinations thereof. Ashless dispersants for polyisobutylene. A particularly preferred combination of dispersants is the combination of: (A) polyisobutylene substituted with succinic anhydride groups and its combination with (B) hydroxyl compounds such as pentaerythritol; (C) polyoxyalkylene polyamines such as polyoxypropylenediamine Or (D) polyalkylene diamine such as polyethylene diamine and tetraethylene pentamine reaction, adopt about 0.3 to about 2 moles of (B), (C) and/or (D)/mole ( A). Another preferred dispersant combination comprises (A) polyisobutenyl succinic anhydride with (B) polyalkylene polyamines such as tetraethylenepentamine and (C) polyols or polyhydroxyl substituted primary aliphatic amines such as A combination of pentaerythritol or tris, as described in US Patent No. 3,632,511.

Another class of ashless dispersants comprises Mannich base condensation products. Typically, these products are produced by combining about one mole of an alkyl-substituted mono- or polyhydroxybenzene with about 1 to 2.5 moles of one or more carbonyl compounds (such as formaldehyde and paraformaldehyde) and about 0.5 to 2 moles of polyalkylene prepared by condensation of polyamine-based polyamines, as disclosed, for example, in US Pat. No. 3,442,808. Such Mannich base condensation products may include metallocene-catalyzed polymerized polymer products as substituents on phenyl groups, or may be combined with compounds containing such polymers substituted on succinic anhydride in a manner similar to that described in U.S. Patent React in the manner described in No. 3,442,808. Examples of functionalized and/or derivatized olefin polymers synthesized using metallocene catalyst systems are disclosed in the publications indicated above.

The dispersant can be further post-treated by various conventional post-treatments such as boration, as generally taught in US Pat. Nos. 3,087,936 and 3,254,025. Borylation of dispersants is accomplished by treating acyl nitrogen-containing dispersants with boron compounds such as boron oxides, boron halides, boric acids, and borate esters in an amount sufficient to provide a composition of boron per mole of acylated nitrogen in an atomic ratio of from about 0.1 to about 20. Easily done. Useful dispersants contain from about 0.05 to about 2.0 wt%, such as from about 0.05 to about 0.7 wt%, boron. Boron present in the product in the form of dehydrated boronic acid polymers (mainly (HBO ₂ ) ₃ ) is believed to be attached to the dispersant imide and imide as amine salts, such as metaborate of the imide. Boration can be carried out by adding about 0.5 to 4 wt%, such as about 1 to about 3 wt% (based on the mass of the acyl nitrogen compound), of a boron compound, preferably boric acid, usually in the form of a slurry, to the acyl nitrogen compound and stirring Heating at about 135°C to about 190°C, eg, 140°C to 170°C, for about 1 to about 5 hours, followed by nitrogen removal. Alternatively, the boron treatment can be performed by adding boric acid to a heated reaction mixture of dicarboxylic acid material and amine while removing water. Other post-reaction methods generally known in the art may also be used.

The dispersants can also be further worked up by reaction with so-called "blocking agents". Typically, nitrogen-containing dispersants have been "capped" to reduce the adverse effects of such dispersants on fluoroelastomer engine seals. Many capping agents and methods are known. Among the known "capping agents", those that convert the basic dispersant amino group into a non-basic moiety (eg amido or imido) are the most suitable. The reaction of nitrogen-containing dispersants and alkyl acetoacetates such as ethyl acetoacetate (EAA) is described, for example, in US Pat. Nos. 4,839,071, 4,839,072, and 4,579,675. The reaction of nitrogen-containing dispersants and formic acid is described, for example, in US Patent No. 3,185,704. Reaction products of nitrogen-containing dispersants and other suitable capping agents are described in U.S. Patent Nos. 4,663,064 (glycolic acid); such as ethylene carbonate); U.S. Patent No. 5,328,622 (monoepoxide); U.S. Patent No. 5,026,495; U.S. Patent No. 5,085,788; anhydride or succinic anhydride). The foregoing list is not exhaustive, and other methods of capping nitrogen-containing dispersants are known to those skilled in the art.

To obtain adequate piston deposit control, the nitrogen-containing dispersant may be added in an amount to provide from about 0.03 wt% to about 0.15 wt%, preferably from about 0.07 to about 0.12 wt% nitrogen to the lubricating oil composition.

Metal-containing or ash-forming detergents act as detergents to reduce or remove deposits and act as acid neutralizers or rust inhibitors, reducing wear and corrosion and extending engine life. Detergents generally comprise a polar head with a long hydrophobic tail, wherein the polar head comprises a metal salt of an acidic organic compound. The salts may contain substantially stoichiometric amounts of metals, in which case they are generally described as normal or neutral salts, and will generally have a Total Base Number or TBN (measured by ASTM D2896 ). Large quantities of metal bases can be introduced by reacting an excess of a metal compound such as an oxide or hydroxide with an acid gas such as carbon dioxide. The resulting overbased detergent contains the neutralized detergent as the outer layer of the metal base (eg carbonate) micelles. Such overbased detergents may have a TBN of 150 or greater, and typically have a TBN of 250 to 450 or greater.

Detergents that may be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates of metals, especially alkali or alkaline earth metals such as sodium, potassium, lithium, calcium and magnesium , salicylate, naphthenate and other oil-soluble carboxylate. The most frequently used metals are calcium and magnesium (both can be present in detergents for lubricants) and mixtures of calcium and/or magnesium with sodium. Particularly convenient metal detergents are neutral and overbased calcium sulfonates having a TBN of 20 to 450 TBN, and neutral and overbased calcium phenates and sulfurized phenates having a TBN of 50 to 450. Combinations of detergents may be used, whether overbased or neutral or both.

Sulfonates can be prepared from sulfonic acids generally by sulfonation of alkyl-substituted aromatic hydrocarbons, such as those obtained from fractionation of petroleum or by alkylation of aromatic hydrocarbons get. Examples include those obtained by alkylation of benzene, toluene, xylene, naphthalene, biphenyl or their halogen derivatives such as chlorobenzene, chlorotoluene and chloronaphthalene. The alkylation may be performed with an alkylating agent having from about 3 to greater than 70 carbon atoms in the presence of a catalyst. The alkaryl sulfonates generally contain from about 9 to about 80 or more carbon atoms, preferably from about 16 to about 60 carbon atoms, per alkyl-substituted aromatic moiety.

The oil-soluble sulfonates or alkarylsulfonic acids can be used as oxides, hydroxides, alkoxides, carbonates, carboxylates, sulfides, hydrosulfides, nitrates, borates and metal ethers neutralize. The amount of metal compound is selected taking into account the desired TBN of the final product, but is generally about 100 to 220 wt% (preferably at least 125 wt%) of the stoichiometrically required amount.

Metal salts of phenols and sulfurized phenols are prepared by reaction with suitable metal compounds such as oxides or hydroxides, and neutral or overbased products can be obtained by methods well known in the art. Sulfurized phenols can be prepared by reacting phenols with sulfur or sulfur-containing compounds such as hydrogen sulfide, sulfur monohalides, or sulfur dihalides to form products which are usually mixtures of compounds in which two or more phenolic Bridged by a sulfur-containing bridging moiety.

Metal dihydrocarbyl dithiophosphates are often used as antiwear additives and antioxidants. The metal may be an alkali or alkaline earth metal, or aluminium, lead, tin, molybdenum, manganese, nickel or copper. Zinc salts are most often used in lubricating oils in amounts of 0.1 to 10 wt%, preferably 0.2 to 2 wt%, based on the total weight of the lubricating oil composition. They can be obtained by first forming dihydrocarbyl dithiophosphoric acid (DDPA) ₍ usually by reaction of one or more alcohols or phenols with _P2S5 ), and then neutralizing the formed DDPA with a zinc compound, according to known techniques to prepare. For example, dithiophosphoric acids can be prepared by reacting a mixture of primary and secondary alcohols. Alternatively, multiple dithiophosphoric acids can be prepared wherein the hydrocarbyl groups on one dithiophosphoric acid are entirely secondary in nature and the hydrocarbyl groups on the other are entirely primary in nature. For the preparation of the zinc salts, any basic or neutral zinc compound can be used, but oxides, hydroxides and carbonates are most commonly used. Commercial additives often contain excess zinc due to the use of excess basic zinc compound in the neutralization reaction.

The preferred zinc dihydrocarbyl dithiophosphates are oil soluble salts of dihydrocarbyl dithiophosphates and may contain zinc dialkyl dithiophosphates. When used in passenger car diesel engine lubricant compositions comprising a phosphorus content of from about 0.02 to about 0.12 wt%, such as from about 0.03 to about 0.10 wt% or from about 0.05 to about 0.08 wt%, based on the total mass of the composition and based on the total composition The present invention may be particularly useful in heavy duty diesel engine lubricant compositions comprising a phosphorus content of from about 0.02 to about 0.16 wt%, such as from about 0.05 to about 0.14 wt%, or from about 0.08 to about 0.12 wt%, by mass. In a preferred embodiment, the lubricating oil composition of the present invention comprises zinc dialkyldithiophosphate derived predominantly (eg, more than 50 mol%, such as more than 60 mol%) from secondary alcohols.

Oxidation inhibitors or antioxidants reduce the tendency of mineral oils to deteriorate in use. Oxidative deterioration can be manifested by sludge in the lubricant, lacquer-like deposits on metal surfaces, and viscosity growth. Such oxidation inhibitors include hindered phenols, alkaline earth metal salts of alkylphenol thioesters (which preferably have _C5 to _C12 alkyl side chains), calcium nonylphenol sulfide, oil-soluble phenates and sulfurized phenates. , phosphorus sulfurized or sulfurized hydrocarbons, phosphorus-containing esters, metal thiocarbamates, oil-soluble copper compounds (as described in US Patent No. 4,867,890), and molybdenum-containing compounds.

Typical oil soluble aromatic amines having at least two aryl groups attached directly to one amine nitrogen contain 6 to 16 carbon atoms. The amine may contain more than two aryl groups. having a total of at least three aryl groups, wherein two aryl groups are linked by covalent bonds or by atoms or groups (such as oxygen or sulfur atoms, or -CO-, _-SO2- or alkylene groups) and two aryl groups Compounds attached directly to an amine nitrogen are also considered aromatic amines having at least two aryl groups attached directly to the nitrogen. The aromatic ring is generally substituted with one or more substituents selected from alkyl, cycloalkyl, alkoxy, aryloxy, acyl, acylamino, hydroxy and nitro.

Preferably, lubricating oil compositions useful in the practice of the present invention, particularly lubricating oil compositions useful in the practice of the present invention, are required to contain no more than 1200 ppm phosphorus, at about 0.1 to about 5 wt %, preferably about 0.3 wt % to about 4 wt % %, more preferably in an amount from about 0.5 wt% to about 3 wt%, comprising an ashless antioxidant other than phenylenediamine. Where a lower phosphorus content is required, the amount of ashless antioxidant other than phenylenediamine is preferably increased accordingly.

Representative examples of suitable viscosity modifiers are polyisobutylene, copolymers of ethylene and propylene, polymethacrylates, copolymers of methacrylates, copolymers of unsaturated dicarboxylic acids and vinyl compounds, styrene and acrylic acid Copolymers of esters, and partially hydrogenated copolymers of styrene/isoprene, styrene/butadiene, and isoprene/butadiene, and partially hydrogenated homopolymers of butadiene and isoprene Polymer.

Viscosity Index Improver Dispersants function as viscosity index improvers as well as dispersants. Examples of viscosity index improver dispersants include the reaction products of amines, such as polyamines, with hydrocarbyl substituted mono- or dicarboxylic acids, wherein the hydrocarbyl substituent comprises a chain long enough to impart viscosity index improving properties to the compound. Generally, viscosity index improver dispersants can be, for example, _C4 to _C24 unsaturated esters of vinyl alcohol or _C3 to _C10 unsaturated monocarboxylic acids or _C4 to _C10 dicarboxylic acids with 4 to 20 carbons Atoms of unsaturated nitrogen-containing monomers; polymers of _C2 to _C20 olefins and unsaturated _C3 to _C10 mono- or dicarboxylic acids neutralized with amines, hydroxylamines or alcohols; or ethylene with _C3 to C ₂₀ polymers of olefins by grafting C ₄ to C ₂₀ unsaturated nitrogen-containing monomers onto them or by grafting unsaturated acids onto the polymer backbone and then making the carboxylic acid of the grafted acid The groups react further with amines, hydroxylamines or alcohols.

Friction modifiers and fuel economy agents that are compatible with the other components of the final oil may also be included. Examples of such materials include: monoglycerides of higher fatty acids, such as glycerol monooleate; esters of long-chain polycarboxylic acids and diols, such as butanediol esters of dimeric unsaturated fatty acids; oxazoline compounds; and Alkoxylated alkyl-substituted monoamines, diamines and alkyl ether amines, such as ethoxylated tallow amines and ethoxylated tallow ether amines.

Other known friction modifiers include oil-soluble organomolybdenum compounds. Such organomolybdenum friction modifiers also provide antioxidant and antiwear benefits to lubricating oil compositions. Examples of such oil-soluble organic molybdenum compounds include dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, etc. and their mixture. Particularly preferred are molybdenum dithiocarbamates, dialkyldithiophosphates, alkylxanthates and alkylthioxanthates.

In addition, the molybdenum compound may be an acidic molybdenum compound. These compounds will react with basic nitrogen compounds (measured by ASTM test D-664 or D-2896 titration procedures) and are generally hexavalent. Included are molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate and other alkali metal molybdates and other molybdenum salts, such as sodium bimolybdate, MoOCl ₄ , MoO ₂ Br ₂ , Mo ₂ O ₃ Cl ₆ , Molybdenum trioxide or similar acidic molybdenum compounds.

Another class of organomolybdenum compounds useful in the lubricating compositions of the present invention are trinuclear molybdenum compounds, particularly those of the formula Mo ₃ S _k L _n Q _z and mixtures thereof, wherein L is independently selected to have sufficient The number of carbon atoms is such that the compound is soluble or dispersible in the ligand of the organic group in the oil, n is 1 to 4, k is 4 to 7, Q is selected from neutral electron donating compounds such as water, amines, alcohols, Phosphines and ethers, and z is from 0 to 5 inclusive of non-stoichiometric values. There should be a total of at least 21 carbon atoms, eg at least 25 carbon atoms, at least 30 carbon atoms or at least 35 carbon atoms present in all ligand organic groups.

Pour point depressants, also known as lubricating oil flow improvers (LOFIs), lower the minimum temperature at which a fluid can flow or be poured. Such additives are well known. Typical additives to improve the low temperature fluidity of fluids are _C8 to _C18 dialkyl fumarate/vinyl acetate copolymers and polymethacrylates. Foam control can be provided by silicone type antifoam agents such as silicone oil or dimethicone.

Some of the above additives can provide multiple effects; thus, for example, one additive can function as a dispersant-oxidation inhibitor. Such methods are well known and need not be explained further here.

In the present invention, it may be necessary to include additives to maintain the stability of the viscosity of the formulation. Thus, although additives containing polar groups achieve suitably low viscosities during the pre-blending stage, some compositions have been observed to increase in viscosity when stored for extended periods of time. Additives effective in controlling this viscosity increase include long chain hydrocarbons functionalized by reaction with the mono- or dicarboxylic acids or anhydrides used to prepare the ashless dispersants as disclosed above.

When the lubricating composition contains one or more of the additives described above, each additive is typically blended into the base stock in an amount such that the additive can provide its desired function. Representative effective amounts of such additives when used in crankcase lubricants are listed in Table 5 below. All values listed are exemplary and are given in % by weight active ingredient.

The fully formulated passenger car diesel engine oil (PCDO) compositions of the present invention preferably have a sulfur content of less than about 0.4 wt%, such as less than about 0.35 wt%, more preferably less than about 0.03 wt%, such as A sulfur content of less than about 0.15 wt%. Preferably, the Noack volatility of the fully formulated PCDO (oil of lubricating viscosity plus all additives) will be no greater than 13, such as no greater than 12, preferably no greater than 10. The fully formulated PCDO of the present invention preferably has no greater than 1200 ppm phosphorous, such as no greater than 1000 ppm phosphorous or no greater than 800 ppm phosphorous. The fully formulated PCDO of the present invention preferably has a sulfated ash (SASH) content of about 1.0 wt% or less.

The fully formulated heavy duty diesel (HDD) lubricating oil compositions of the present invention preferably have a sulfur content of less than about 1.0 wt%, such as less than about 0.6 wt%, more preferably less than about 0.4 wt%, such as less than Sulfur content of about 0.15 wt%. Preferably, the Noack volatility of the fully formulated HDD lubricating oil composition (oil of lubricating viscosity plus all additives) will be no greater than 20, such as no greater than 15, preferably no greater than 12. The fully formulated HDD lubricating oil compositions of the present invention preferably have no greater than 1600 ppm phosphorus, such as no greater than 1400 ppm phosphorus or no greater than 1200 ppm phosphorus. The fully formulated HDD lubricating oil compositions of the present invention preferably have a sulfated ash (SASH) content of about 1.0 wt% or less.

Examples of phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6 -Di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclo Amyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4, 6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, o-tert-butylphenol, 2,6-di-tert-butyl-4-methoxyphenol, 2,5 -Di-tert-butyl hydroquinone, 2,5-di-tert-amyl hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,2'-thiobis(6 -tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 2,2'-methylenebis(6-tert-butyl-4-methylphenol) , 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol ], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2' -Methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylenebis(4,6-di-tert-butylphenol), 2,2'-ethylenebis(6- tert-butyl-4-isobutylphenol or -5-isobutylphenol, 2,2'-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2, 2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol, 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylene-bis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2 -methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3 -tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-5-methylbenzyl)-6- tert-butyl-4-methylphenyl]terephthalate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-tri Methylbenzene, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) disulfide Alcohol terephthalate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(4-tert-butyl -3-hydroxy-2,6-dimethylbenzyl) isocyanurate, -3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid bis(octadecyl)ester, 3 , 5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester calcium salt, 4-hydroxylauranilide, 4-hydroxystearanilide, 2,4-bisoctylmercapto-6-( 3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine, N-(3,5-di-tert-butyl-4-hydroxyphenyl)octyl carbamate, β-(3,5 -Di-tert-butyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols (such as methanol, triethylene glycol, stearyl alcohol, trihydroxyethyl isocyanurate, 1,6-hexanediol, bis Esters of hydroxyethyl oxalic acid diamide, neopentyl glycol, diethylene glycol) and/or β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols (e.g. Methanol, triethylene glycol, stearyl alcohol, trihydroxyethyl isocyanurate, 1,6-hexanediol, bishydroxyethyl oxalic acid diamide, neopentyl glycol, diethylene glycol) esters, β- Amides of (3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, such as N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-1,6 -Hexamethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-1,3-propanediamine, N,N'-bis(3,5-di tert-Butyl-4-hydroxyphenylpropionyl)hydrazine.

Examples of amine antioxidants include N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethyl Amylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)- p-Phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-di(2-naphthyl)-p-phenylenediamine, 4-(p-toluenesulfonylamino)diphenylamine , N, N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-deca Dialkanoylaminophenol, 4-octadecanoylaminophenol, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-di Aminodiphenylmethane, N, N, N', N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1 , 2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine, 2,3-dihydro-3,3 -Dimethyl-4H-1,4-benzothiazine, phenothiazine, N-allylphenothiazine.

Examples of additional antioxidants include esters of thiodipropionic acid or thiodiacetic acid, and salts of dithiocarbamide acid or dithiophosphoric acid.

Examples of metal deactivators include triazoles, benzotriazoles and their derivatives, tolutriazole and their derivatives, 2-mercaptobenzothiazole, 2-mercaptobenzotriazole, 2, 5-dimercaptobenzotriazole, 2,5-dimercaptobenzothiadiazole, 5,5'-methylenebisbenzotriazole, 4,5,6,7-tetrahydrobenzotriazole, o-Hydroxybenzylidenepropylenediamine, salicylaminoguanidine and their salts.

Examples of rust inhibitors include: a) organic acids and their esters, metal salts and anhydrides such as N-oleoyl sarcosine, sorbitan monooleate, lead naphthenate, alkenyl succinic anhydrides such as lauryl Carbenylsuccinic anhydrides, half-esters and half-amides of alkenylsuccinic acids, and 4-nonylphenoxyacetic acid; b) nitrogen-containing compounds such as primary, secondary or tertiary aliphatic or cycloaliphatic amines and organic and inorganic Amine salts of acids such as oil-soluble alkylammonium carboxylates; heterocyclic compounds such as substituted imidazolines and oxazolines; c) phosphorus compounds such as amine salts of partial esters of phosphoric acid or phosphonic acids, di zinc alkyl dithiophosphates; d) sulfur compounds such as barium dinonyl naphthalene sulfonate, calcium petroleum sulfonate.

Examples of viscosity index improvers include polyacrylates, polymethacrylates, vinylpyrrolidone/methacrylate copolymers, polyvinylpyrrolidone, polybutenes, olefin copolymers, styrene/acrylic acid copolymers , Polyether.

Examples of pour point depressants include polymethacrylates and alkylated naphthalene derivatives.

Examples of dispersants/surfactants include polybutenyl succinamides or imides, polybutenyl phosphonic acid derivatives, basic magnesium, calcium and barium sulfonates, and phenates.

Examples of antiwear additives include sulfur and/or phosphorus and/or halogen containing compounds such as sulfurized vegetable oils, zinc dialkyl dithiophosphates, tricresyl phosphates, chlorinated paraffins, alkyl sulfides, aryl disulfides and aryl trisulfides, triphenylphosphorothionate (triphenylphosphorothionate) and diethanolaminomethyltolyltriazole, bis(2-ethylhexyl)aminomethyltolyltriazole.

The lubricating oil compositions of the present invention improve the oxidation stability of materials susceptible to oxidative, thermal and/or light-induced degradation. These organic materials can be natural or synthetic. These organic materials can include "functional fluids", lubricating oils, greases and fuels, as well as automatic and manual transmission fluids, power steering fluids, hydraulic fluids, gas turbine oils, compressor lubricants, automotive and industrial gear lubricants and heat transfer Oil.

并且所述基础油料是这样的H1食品级基础油料。In one embodiment, an H1 food grade lubricant is used as the base stock. Such base stocks are those for which incidental food contact is likely. These base stocks are sometimes referred to as "above the line" lubricants. Such oils may be used on food processing equipment as a protective anti-rust film, as a barrier agent on gaskets or seals in tank closures, and as machinery in locations where lubricated parts may be exposed to food Lubricants for components and equipment. In one embodiment of the invention, the amount used is the minimum required to achieve the desired technical effect on the device. In a preferred embodiment of the present invention, said ADPA is

And the base oil is such H1 food grade base oil.

和和得自TOTALLubricants USA，Inc.的

润滑剂。Preferred commercially produced H1 food grade lubricants that can be used in the present invention include Krylon® from Krylon Products Group.

and and from TOTALLubricants USA, Inc.

lubricant.

In one embodiment of the present invention, base stocks useful in lubricating viscosities within the range of the present invention are selected from natural lubricating oils, synthetic lubricating oils and mixtures thereof. The lubricating oils may range in viscosity from light distillate mineral oils to heavy lubricating oils, such as gasoline engine oils, mineral lubricating oils, and heavy duty diesel engine oils. Typically, the viscosity of the oil is in the range of about 2 centistokes to about 40 centistokes, especially in the range of about 4 centistokes to about 20 centistokes, measured at 100°C.

In one embodiment of the invention the diesel is a petroleum based fuel oil, especially a middle distillate fuel oil. Such distillate fuel oils typically boil in the range of 110°C to 500°C, eg 150°C to 400°C. The fuel oil may comprise atmospheric or vacuum distillates, cracked gas oils, or mixtures in any proportion of straight run products and thermal and/or refinery streams such as catalytically cracked and hydrocracked fractions.

Other examples of base stocks include Fischer-Tropsch fuels. Fischer-Tropsch fuels (also known as FT fuels) include those fuels described as gas-to-liquid (GTL) fuels, biomass-to-liquid (BTL) fuels, and coal-switched fuels. To produce such fuels, synthesis gas (CO+H ₂ ) is first produced and then converted into n-paraffins by the Fischer-Tropsch process. The normal paraffins can then be modified by processes such as catalytic cracking/reforming or isomerization, hydrocracking and hydroisomerization to produce various hydrocarbons such as isoparaffins, Naphthenes and aromatic compounds. The resulting FT fuel can be used as such or in combination with other fuel components and fuel types. Diesel oils derived from vegetable or animal sources are also suitable. These fuels can be used alone or in combination with other types of fuels.

Oils and fats derived from vegetable or animal materials are increasingly finding use as fuels, especially as partial or complete replacements for petroleum-derived middle distillate fuels such as diesel. Typically, such fuels are referred to as "biofuels" or "biodiesel". Biofuels can be derived from many sources. The most common include the alkyl (often methyl) esters of fatty acids extracted from plants such as rapeseed, sunflower, and the like. These types of fuels are often referred to as FAMEs (fatty acid methyl esters).

Base stocks may include: natural oils including animal and vegetable oils such as lard, castor oil, liquid petroleum lubricating oils and hydrorefined, solvent treated or acid treated paraffinic, naphthenic and mixed paraffinic-cyclic Alkane-type mineral oils. Oils of lubricating viscosity derived from coal or shale may also serve as useful base oils. Other examples of oils and fats derived from animal or plant materials are canola oil, coriander oil, soybean oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, corn oil, almond oil, canola oil , jojoba oil, palm kernel oil, coconut oil, mustard oil, jatropha oil, tallow and fish oil. Additional examples include oils derived from cereals, jute, sesame, shea nut, peanut and linseed oils, and can be derived therefrom by methods known in the art. Rapeseed oil, which is a mixture of fatty acids partially esterified with glycerol, is available in large quantities and can be obtained in a simple manner by pressing rapeseed. Recycled oils such as used kitchen oils are also suitable.

Useful base stocks are, for example, alkyl esters of fatty acids including commercial mixtures of ethyl, propyl, butyl and especially methyl esters of fatty acids having 12 to 22 carbon atoms. For example, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselinic acid, ricinoleic acid, clacostearic acid, linoleic acid, linolenic acid, arachidic acid, cod liver oil Acids, behenic acid or erucic acid are useful and have an iodine value of 50 to 150, especially 90 to 125. Mixtures with particularly advantageous properties are those containing predominantly (ie at least 50% by weight) methyl esters of fatty acids having 16 to 22 carbon atoms and 1, 2 or 3 double bonds. Preferred lower alkyl esters of fatty acids are the methyl esters of oleic, linoleic, linolenic and erucic acids.

Commercial mixtures of said type are obtained, for example, by their cleavage and esterification of animal and vegetable fats and oils by transesterification with lower aliphatic alcohols. For the production of alkyl esters of fatty acids, it is advantageous to start from fats and oils containing low levels of saturated acids of less than 20% and having an iodine value of less than 130. Mixtures of the following esters or oils are suitable: for example, rapeseed, sunflower, coriander, castor, soybean, peanut, cottonseed, tallow, and the like. Preference is given to alkyl esters of fatty acids based on various rapeseed oils, wherein the fatty acid component comprises more than 80% by weight of unsaturated fatty acids having 18 carbon atoms.

Particularly preferred base stocks are oils which can be used as biofuels. Biofuels, ie fuels derived from animal or plant material, are considered less environmentally damaging after combustion and are obtained from renewable sources. It has been reported that equivalent quantities of petroleum distillate fuels such as diesel form less carbon dioxide and form very little sulfur dioxide after combustion. Certain derivatives of vegetable oils, such as those obtained by saponification and re-esterification with monohydric alkyl alcohols, can be used as diesel substitutes.

Preferred biofuels are vegetable oil derivatives, wherein particularly preferred biofuels are alkyl ester derivatives of rapeseed oil, cottonseed oil, soybean oil, sunflower oil, olive oil or palm oil, alone or in admixture with other vegetable oil derivatives Rapeseed oil methyl ester, for example a mixture of rapeseed oil methyl ester and palm oil methyl ester in any proportion is particularly preferred.

Currently, biofuels are most often used in combination with petroleum-derived oils. The invention is applicable to mixtures of biofuels and petroleum derived fuels in any proportion. For example, at least 5%, preferably at least 25%, more preferably at least 50%, most preferably at least 95% by weight of the oil may be derived from vegetable or animal sources.

Synthetic base oils include hydrocarbon oils and halogenated hydrocarbon oils, such as polymerized and interpolymerized olefins (e.g., polybutene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutene, poly(1-hexene), poly(1-octene), poly(1-decene)); alkylbenzenes (e.g. dodecylbenzene, tetradecylbenzene, dinonylbenzene, bis(2-ethylhexyl)benzene); polyphenylenes (eg, biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides, and their derivatives, analogs, and homologues. Also useful are synthetic oils derived from the gas-to-liquid process of Fischer-Tropsch synthesis of hydrocarbons, often referred to as gas-to-liquid or "GTL" base oils.

Alkylene oxide polymers and interpolymers, and their derivatives, in which the terminal hydroxyl groups have been modified by esterification, etherification, etc., constitute another class of known synthetic lubricating oils. Examples of these synthetic lubricating oils are polyoxyalkylene polymers and alkyl and aryl ethers of polyoxyalkylene polymers (e.g. methyl-polyisoisocyanurate having a molecular weight of 1000) prepared by the polymerization of ethylene oxide or propylene oxide. Propyl glycol ether (methyl-polyisopropylene glycol ether or diphenyl ether of polyethylene glycol with a molecular weight of 1000 to 1500) and their mono- and polycarboxylates, such as tetraethylene glycol acetate, mixed C ₃ -C ₈ fatty acid esters and C ₁₃ oxyacid diesters.

Another class of suitable synthetic base oils includes dicarboxylic acids such as phthalic, succinic, alkyl and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, Fumaric acid, adipic acid, dimer linoleic acid, malonic acid, alkylmalonic acid, alkenylmalonic acid) and various alcohols (such as butanol, hexanol, lauryl alcohol, 2-ethyl Hexanol, Ethylene Glycol, Diethylene Glycol Monoether, Propylene Glycol). Specific examples of such esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, Diisodecyl dioate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, 2-ethylhexyl diester of dimer linoleic acid, and by adding A complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.

Esters useful as synthetic oils also include those prepared from _C5 to _C12 monocarboxylic acids and polyols and polyol esters such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol. Silicone-based oils such as polyalkylsiloxane oils, polyarylsiloxane oils, polyalkoxysiloxane oils or polyaryloxysiloxane oils and silicate oils constitute another class of useful Synthetic lubricant. Other synthetic lubricating oils include liquid esters containing phosphoric acid, polytetrahydrofuran, polyalphaolefins, and the like.

Silicone-based oils such as polyalkylsiloxane oils, polyarylsiloxane oils, polyalkoxysiloxane oils or polyaryloxysiloxane oils and silicate oils constitute another class of useful synthetic bases lubricant. Such oils include tetraethyl silicate, tetraisopropyl silicate, tetra(2-ethylhexyl) silicate, tetra(4-methyl-2-ethylhexyl) silicate, tetra( p-tert-butylphenyl) ester, hexa(4-methyl-2-ethylhexyl)disiloxane, poly(methyl)siloxane and poly(methylphenyl)siloxane. Other synthetic lubricating oils include liquid esters of phosphoric acid (eg tris(cresyl) phosphate, trioctyl phosphate, diethyl decylphosphonic acid) and polytetrahydrofuran.

The lubricating oil may be derived from unrefined oils, refined oils, re-refined oils, or mixtures thereof. Unrefined oils are obtained directly from natural or synthetic sources such as coal, shale or tar and bitumen without further purification or treatment. Examples of unrefined oils include shale oils obtained directly from dry distillation operations, petroleum lubricating oils obtained directly from distillation, or ester oils obtained directly from esterification processes, each of which is then used without further treatment. Refined oils are similar to unrefined oils, except that the refined oil has been treated in one or more purification steps to improve one or more properties. Suitable purification techniques include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration, percolation, and the like, all of which are well known to those skilled in the art. Rerefined oils are obtained by treating refined oils in methods similar to those used to obtain refined oils. These re-refined oils are also known as regenerated or reprocessed oils and are often additionally processed by techniques for removing spent additives and oil breakdown products.

Lubricant base stocks derived from the hydroisomerization of waxes may also be used alone or in combination with the natural and/or synthetic base stocks described above. Such wax isomer oils are produced by hydroisomerization of natural or synthetic waxes or mixtures thereof in the presence of a hydroisomerization catalyst. Natural waxes are generally slack waxes recovered by solvent dewaxing of mineral oils; synthetic waxes are generally waxes produced by the Fischer-Tropsch process. The resulting isomerized product is typically solvent dewaxed and fractionated to recover various fractions having specific viscosity ranges. Wax isomers are also characterized as having a very high viscosity index, typically having a viscosity index of at least 130, preferably at least 135 or higher, and having a pour point of about -20°C or lower after dewaxing.

The base stock of lubricating viscosity may comprise a Group I, Group II, or Group III base stock, or a base oil blend of the foregoing base stocks. Preferably, the oil of lubricating viscosity is a Group II or Group III base stock or a mixture thereof, or a mixture of a Group I base stock and one or more of a Group II and Group III base stock. Preferably, a major amount of the oil of lubricating viscosity is a Group II, Group III, Group IV or Group V base stock or mixtures thereof. The base stock or base stock blend preferably has a saturate content of at least 65%, such as at least 75% or at least 85%. Most preferably, the base stock or base stock blend has a saturate content of greater than 90%.

Preferably, the oil or oil blend has a volatility of less than or equal to 30%, preferably less than or equal to 25%, more preferably less than or equal to 20%, most preferably less than or equal to 16%. Preferably, the oil or oil blend has a viscosity index (VI) of at least 85, preferably at least 100, most preferably from about 105 to 140.

The definitions of base stock and base oil in the present invention are the same as American Petroleum Institute (API) publication "Engine Oil Licensing and Certification System", IndustryServices Department (14th edition, December 1996), Appendix 1, in December 1998 The same definitions as those given. This publication classifies base stocks as follows.

(a) Group I base stocks contain less than 90% saturates (as determined by ASTM D 2007) and/or greater than 0.03% sulfur (as determined by ASTM D 2622, ASTM D 4294, ASTM D 4927, and ASTM D 3120) and have Viscosity index greater than or equal to 80 and less than 120 (measured by ASTM D 2270).

(b) Group II base stocks contain greater than or equal to 90 percent saturates (as determined by ASTM D 2007) and less than or equal to 0.03 percent sulfur (as determined by ASTM D 2622, ASTM D4294, ASTM D 4927, and ASTM D 3120), and Have a viscosity index (measured by ASTM D 2270) of greater than or equal to 80 and less than 120.

(c) Group III base stocks contain greater than or equal to 90 percent saturates (as determined by ASTM D 2007) and less than or equal to 0.03 percent sulfur (as determined by ASTM D 2622, ASTM D4294, ASTM D 4927, and ASTM D 3120), and Have a viscosity index greater than or equal to 120 (measured by ASTM D 2270).

(d) Group IV base stocks are polyalphaolefins (PAO).

(e) Group V base stocks include all other base stocks not included in Groups I, II, III or IV.

In one embodiment of the present invention, the additive package is added to the base stock in the form of an additive package concentrate. The total amount of additive components in the concentrate typically ranges from 20 to 95% by weight or more, with the balance being diluent oil. The diluent oil may be a base stock of the invention as defined above or a hydrocarbon solvent (preferably an aromatic solvent) or a mixture thereof. The concentrate may contain other additives listed below. Generally, the additive package concentrate is added to the base stock in an amount sufficient to provide the appropriate weight % of ADPA, PNA and/or sulfur-containing phenols to the finished lubricating oil composition.

Embodiments of the invention will become clearer with reference to the following non-limiting examples.

Medium and high temperature thermal oxidation engine oil simulation test (TEOST MHT)

ASTM D7097 is "Standard Test Method for Determination of Moderately High Temperature Piston Deposits by Thermo-oxidation Engine Oil Simulation Tests" approved December 2004, the entire contents of which are incorporated herein by reference for any purpose. ASTM D7097 is the new standard lubricant industry test for evaluating the oxidation and carbonaceous deposit formation characteristics of engine oils. The test is designed to simulate high temperature deposit formation in the piston ring region of modern engines.

The test is also a useful tool to study the formation of volatile organic molecules during engine oil oxidation. It is generally believed that the formation of volatile organic molecules during lubricant oxidation is detrimental as they lead to increased emissions and may also promote further polymerization of the lubricant. Polymerization of the lubricant leads to an increase in viscosity, which is also undesirable. The additive combination of the present invention is effective in controlling deposit formation and formation of volatile organic molecules. Typically, polar volatile organic molecules are formed by the decomposition of organic peroxides in lubricants. This decomposition produces organic alkoxy groups, which can react with another oil molecule to produce an alcohol, or which can degrade to form aldehydes and ketones. Degradation to aldehydes and ketones generally reduces molecular weight and thus produces more volatile fragments that are contaminants and active precursors to oligomers and polymers that thicken the lubricant. Therefore, preventing or eliminating the formation of these polar volatile organic molecules is highly desirable.

The TEOST MHT measures the mass of deposits formed on specially constructed, pre-weighed steel depositor rods. The fully formulated lubricant (8.4 g) and organometallic catalyst (ca. 0.1 g) were added to a flask equipped with a Teflon stir bar and stirred without heating for 20-60 minutes. The precipitator rod, sample flask, oil inlet, gas inlet, and volatile collection vial were assembled to the TEOST apparatus according to the manufacturer's instructions. Start the pump at high flow and run until the test oil reaches the connection between the pump and the oil feed line, at which point turn the pump flow to zero. Turn on the heater switch and when the depositor rod temperature controller is between 200-210°C, increase the pump speed to achieve a sample delivery of 0.25 ± 0.02g/min, ensuring that the oil flows down the depositor rod and does not leak out . The temperature was allowed to stabilize at 285±2°C, and the test was run at these conditions for 24 hours.

Prepare three test tubes with cyclohexane or another suitable hydrocarbon solvent for oil extraction from the sedimentor rods. The test apparatus was disassembled according to the manufacturer's instructions, and the settler rod was transferred to a weighing boat and kept under cover. The precipitator rods were placed sequentially for 10 minutes in each of the three test tubes prepared with the hydrocarbon solvent. The rods were placed in a tared weighing boat and left for 10 minutes to ensure evaporation of the hydrocarbon solvent. The rod and boat were weighed to confirm that constant weight had been reached. The contents of the three test tubes were washed into a common container along with the lower cap sediment and the glass jacket sediment, which was then filtered through a glass funnel fitted with a filter cartridge. After the filtration is complete, the filter cartridges are dried under vacuum and weighed until a constant weight is reached. The total mass of sediment from the settler rods and filter sediment is then determined.

Volatile compounds that were originally in the formulated oil or formed during the test were flashed off the precipitator rod over the 24 hour period of the test. These volatiles condense on the glass jacket and are collected continuously in small weighed vials. The vial and volatile material were measured at the end of the 24 hour test period and the amount of volatile material was calculated by subtracting the original weight of the vial.

Pressurized Differential Scanning Calorimeter (PDSC) Test

The PDSC test can be used to measure the oxidation induction time (OIT) of a material. The samples discussed in this application were tested according to the parameters listed in Table 1 (shown above). In addition, the PDSC instrument used was Mettler DSC27HP manufactured by Mettler-Toledo, Inc. The PDSC method uses a steel cell under constant oxygen pressure throughout each experiment. For an OIT of 200 minutes, the instrument has a typical repeatability of ±5.0 minutes with a 95% confidence level. At the beginning of the PDSC experiment, the PDSC steel pool was pressurized with oxygen and heated to the isothermal temperature listed in Table 1 at a rate of 40 °C/min. The induction time is measured by the time for the sample to reach its isothermal temperature until an enthalpy change is observed. The longer the oxidation induction time, the better the oxidative stability of the oil, ie a longer OIT indicates a more stable composition. For every 50 grams of test oil prepared, 40 μL of oil-soluble iron naphthenate (6 wt % in mineral oil) was added prior to PDSC testing to promote 50 ppm iron in the oil.

The antioxidant effect of the present invention can preferably be demonstrated in, for example, low phosphorus SAE 5W20 fully formulated motor oils. Such motor oils were used in the PDSC tests discussed herein. The SAE 5W20 motor oil formulations were preconditioned with the components shown in Table 6, which are all commercially available. An antioxidant package was then added to the pre-blended motor oil. PDSC tests were performed at 185°C.

Example

Additive package mixes 1-6 and A-C were prepared according to the ratios shown in Table 7.

Table 7

Each of Additive Packages 1-6 and A-C was mixed with a base stock at a base stock to additive package weight ratio of about 99:1 to produce a lubricating oil composition. Example Mixtures 1-6 are representative embodiments of the invention. Example Mixtures A-C are comparative. The lubricating oil compositions were tested for OIT and TEOST MHT. The results are shown in Table 7.

As indicated above, Comparative Examples A, B and C represent pure ADPA, PNA and sulfur-containing phenol, respectively. These blends showed OIT values of 37.0, 52.0 and 3.8 minutes, respectively, and TEOST MHT values of 55.0, 63.7 and 63 grams of sediment, respectively. The expected OIT of the additive package can be calculated by adding the OITs of pure ADPA, PNA and sulfur-containing phenols in the appropriate weight percents of the respective mixtures. The expected TEOST MHT value for the additive package can be calculated in a similar manner. Expected OIT and expected TEOST MHT values are also listed in Table 7.

Surprisingly and unexpectedly, Lubricant Blend 1, which is representative of the present invention, exhibited a TEOST MHT value below 40. Additionally, additive packages of embodiments of the present invention exhibit OIT values greater than 38 minutes when tested according to the parameters described above.

Furthermore, additive packages of embodiments of the present invention surprisingly and unexpectedly exhibited superior OIT compared to expected values - in most cases, an increase of over 13%. Also, it was surprising and unexpected that these additive packages showed superior TEOST MHT values compared to expected values - in most cases, a drop of more than 20%.

Any feature described or claimed in relation to any disclosed embodiment may be combined in any combination with any one or more other features described or claimed in relation to any other disclosed embodiment or embodiments, up to the There is no technically necessary degree of contradiction, and all such combinations are within the scope of the present invention. Moreover, the following appended claims present some non-limiting combinations of features within the scope of the invention, but all possible combinations of the subject matter of any two or more claims, in any possible combination, are also considered to be within the scope of the invention. Within the scope of the present invention, as long as the combination is not necessarily technically contradictory.

Claims (15)

1. A liquid additive package comprising: (A) alkylated diphenylamine; (B) at least 5% by weight phenylnaphthylamine based on the weight of the additive package; and (C) Sulfur-containing phenols. 2. The additive package of claim 1 comprising said alkylated diphenylamine in an amount ranging from 50 to 99 wt%, preferably in an amount ranging from 70 to 90 wt%, based on the weight of said additive package. 3. The additive package of claim 1 comprising said phenylnaphthylamine in an amount in the range of 1 to 50% by weight, preferably in an amount in the range of 10 to 20% by weight, based on the weight of the additive package. 4. The additive package of claim 1 comprising said sulfur-containing phenol in an amount in the range of 5 to 50% by weight, preferably in an amount in the range of 10 to 20% by weight, based on the weight of the additive package. 5. The additive package of claim 1, comprising said alkylated diphenylamine in an amount of at least 50 wt%, preferably at least 70 wt%, based on the weight of said additive package, and said alkylated diphenylamine is based on the weight of said additive package The sulfur-containing phenol is contained in an amount of at least 1 wt%, preferably at least 5 wt%. 6. The additive package of claim 1 having a viscosity in the range of 100 to 50,000 cP at 25°C, preferably in the range of 1,000 to 25,000 cP at 25°C. 7. The additive package of claim 1, wherein said alkylated diphenylamine is selected from the group consisting of diphenylamine, monoalkylated diphenylamine, dialkylated diphenylamine, Trialkylated diphenylamine, 3-hydroxydiphenylamine, 4-hydroxydiphenylamine, mono- and/or di-tert-butyldiphenylamine, mono- and/or di-diheptyldiphenylamine Diphenylamine, mono- and/or dioctyldiphenylamine, dioctyldiphenylamine, mono- and/or dinonyldiphenylamine, mono- and/or didodecyldiphenylamine, Hexaalkyldiphenylamine, eicosenyldiphenylamine, tetradecenyldiphenylamine, octadecenyldiphenylamine, polyisobutyldiphenylamine, mono and /or bis(alpha-methylstyryl)diphenylamine, mono- and/or distyryldiphenylamine, 4-(p-toluenesulfonylamino)diphenylamine, 4-isopropoxy Diphenylamine, tert-octylated N-phenyl-1-naphthylamine, mixtures of mono- and dialkylated tert-butyl-tert-octyldiphenylamine and mixtures thereof. 8. The additive package of claim 1, wherein said sulfur-containing phenol is represented by formula I

wherein _R is a sulfur-containing alkyl group, a sulfur-containing aryl group, a sulfur-containing alkene, or a sulfur-containing carboxylic acid; and wherein _R2 and _R3 are alkyl, aryl or hydrogen. 9. A lubricating oil composition comprising: (A) base stocks; and (B) liquid additive package, Wherein said additive package comprises: (i) alkylated diphenylamines; (ii) at least 5% by weight phenylnaphthylamine based on the weight of the additive package; and (iii) Sulfur-containing phenols. 10. The composition of claim 9, comprising said base stock in an amount of at least about 50% by weight based on the weight of said lubricating oil composition, preferably at least 90% by weight, and based on said lubricating oil composition The additive package is included in an amount of at least 0.1% by weight, preferably at least 0.5% by weight. 11. The composition of claim 9, wherein said base stock is selected from the group consisting of natural lubricating oil, synthetic lubricating oil, lard, vegetable oil, oleic soybean oil, high oleic soybean oil, rapeseed oil, palm oil, Jojoba oil, canola oil, castor oil, sunflower oil, petroleum lubricating oils, mineral oils and oils derived from coal and shale, oils obtained by synthetic waxes and isomerization of waxes, white oils, by Hydrocracked product oils produced by hydrocracking the aromatic and polar components of crude oil, polymerized and interpolymerized olefins, alkylbenzenes, polyphenylenes, alkylated diphenyl ethers, alkylated diphenyl Thioethers, polymers, interpolymers, copolymers, and derivatives of alkylene oxides, esters of carboxylic acids, silicone-based oils, liquid esters containing phosphoric acid, polytetrahydrofuran, polyalphaolefins, food-grade lubricants, and their mixture. 12. The composition of claim 9, wherein said composition exhibits a pressurized differential scanning calorimeter oxidation induction time of at least 25 minutes, preferably at least 40 minutes and/or a thermal oxidation of less than 50 mg, preferably less than 40 mg Engine oil simulation test value. 13. The composition of claim 9, wherein said composition comprises: (A) 99% by weight of the base stock based on the weight of the lubricating oil composition; and (B) 1% by weight of the additive package based on the weight of the lubricating oil composition, Wherein said additive package comprises: (i) 70% by weight of alkylated diphenylamine based on the weight of the additive package; (ii) 15% by weight of phenyl-alpha-naphthylamine based on the weight of the additive package; and (iii) 15% by weight sulfur-containing phenol based on the weight of the additive package. 14. A method of producing a liquid additive package, the method comprising combining (i) alkylated diphenylamines; (ii) at least 5% by weight phenylnaphthylamine based on the weight of the additive package; and (iii) sulfur-containing phenols, Wherein said combining is optionally carried out under nitrogen. 15. A method of producing a lubricating oil composition, the method comprising: (A) providing a base stock; and (B) mixing said base stock with a liquid additive package comprising: (i) alkylated diphenylamines; (ii) at least 5% by weight phenylnaphthylamine based on the weight of the additive package; and (iii) Sulfur-containing phenols.