Lubricating Oil Compositions with Improved Performance

The present invention is aimed at lubricating oil compositions with improved oxidative per¬ formance. WO 2000/22070 discloses a long life gas engine oil and additive system comprising a minor amount of phenolic antioxidants. U.S. Patent Specification No. 5,711,767 discloses stabilizer systems for the prevention of gum formation in gasoline comprising phenolic antioxidants. Titova, T. F. et al. in Zhurnal Organicheskoi Khimii 1984, 20(9), 1899-905 disclose the syn¬ thesis of dimethyl α-(3,5-di-tert-butyl-4-hydroxybenzyl)glutarate. It has surprisingly been found that lubricating oil compositions containing certain antioxidants display improved oxidative performance. The present invention relates to a lubricating oil composition with improved oxidative per¬ formance, said composition comprising a) At least one hindered phenolic antioxidant compound of formula (I),

Wherein Ri is alkyl of 1 to 4 carbon atoms; n is an integer from 1 to 4; R2 is H or has the meanings of R3; R3 is -(CH2)X-COOR4, where x is 1 to 10; R4 is straight or branched chain alkyl of 1 to 24 carbon atoms or the group of the par¬ tial formula E; When n is 1, E is straight or branched chain alkyl of 1 to 24 carbon atoms; When n is 2, E is straight or branched chain alkylene of 2 to 12 carbon atoms or said alkylene interrupted by one to five O or S atoms; When n is 3, E is a straight or branched chain alkanetriyl of 3 to 6 carbon atoms; and When n is 4, E is pentaerythrityl;

b) At least one additional antioxidant compound; and

c) A base fluid.

In the composition described above the percent by weight of component a) to the total weight of component a) plus component b) is about 0.001% to about 99.999%,

Alkyl is straight or branched chain and is for example methyl, ethyl, n-propyl, iso-propyl, n- butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, 3-heptyl, n-octyl, 2- ethylhexyl, n-nonyl, n-decyl, undecyl, n-dodecyl, tridecyl, n-tetradecyl, pentadecyl, n-hexade- cyl, n-octadecyl, n-icosyl, heptadecyl, 2-ethylbutyl, 1-methylpentyl, 1,3-dimethylbutyl, 1,1,3,3- tetramethylbutyl, 1 -methyl hexyl, isoheptyl, 1 -methyl heptyl, 1 ,1,3-trimethylhexyl, and 1-me- thylundecyl.

Specific compounds of component a) include hindered phenolic antioxidant compounds of the formula (I) selected from the group consisting of:

Dimethyl α-(3,5-di-tert-butyl-4-hydroxybenzyl)glutarate,

Diisooctyl α-(3,5-di-tert-butyl-4-hydroxybenzyl)glutarate, and

Monomethyl-monoisooctyl α-(3,5-di-tert-butyl-4-hydroxybenzyl)glutarate.

The antioxidant compounds of component b) in the compositions of the present invention are phenolic antioxidants.

Preferred phenolic antioxidants of component b) in the compositions of the present invention are selected from the group consisting of:

n-Octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate,

lsooctyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate,

Neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate),

1 ,3,5-tris(3,5-Di-tert-butyl-4-hydroxybenzyl)isocyanurate,

Thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),

1 ,3,5-Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) benzene,

3,6-Dioxaoctamethylene bis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),

2,6-Di-tert-butyl-p-cresol,

2,21-Ethylidene-bis(4,6-di-tert-butylphenol), 1 ,3,5-tris(2,6-Dinnethyl-4-tert-butyl-3-hydroxybenzyl)isocyan urate, 1 ,1 ,3-tris(2-Methyl-4-hydroxy-5-tert-butylphenyl)butane, 1 ,3,5-tris[2-(3,5-Di-tert-butyl-4-hydroxyhydrocinnannoyloxy)e thyl] isocyanurate, 3J5-Di-(3J5-di-tert-butyl-4-hydroxybenzyl)mesitolJ Hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1-(3,5-Di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-t riazine, N,N1-Hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinna nnannide), Calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), Ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], Octyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, bis(3,5-Di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, N,N1-bis[2-(3,5-Di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-et hyl]oxannide, 2,6-Di-tert-butylphenol, 2,4-Di-tert-butylphenol, Methyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, Pentaerythritol tris(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), Pentaerythritol di(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), tris(2,4-Di-tert-butylphenyl) phosphite, Di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, N,N-Di-(Ci4-C24alkyl)-N-nnethylannine oxide, N,N-Dialkylhydroxylamine, and N,N-Di(hydrogenated tallow)hydroxylamine. Particularly preferred phenolic antioxidants of component b) in the compositions of the pre¬ sent invention are selected from the group consisting of: n-Octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, lsooctyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, Neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnammate), Thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),

2,21-Ethylidene-bis(4,6-di-tert-butylphenol),

1 ,1 ,3-tris(2-Methyl-4-hydroxy-5-tert-butylphenyl)butane,

Hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),

N,N1-Hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydroci nnannannide),

Ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate],

bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide,

2,6-Di-tert-butylphenol,

2,4-Di-tert-butylphenol,

Methyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate,

Pentaerythritol tris(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),

Pentaerythritol di(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), and

tris(2,4-Di-tert-butylphenyl) phosphite.

Highly preferred phenolic antioxidants of component b) in the compositions of the present in- vention are selected from the group consisting of:

n-Octadecyl S.S-di-tert-butyl^-hydroxyhydrocinnamate,

lsooctyl a.S-di-tert-butyl^-hydroxyhydrocinnamate,

Neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate),

Thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),

2,6-Di-tert-butylphenol,

2,4-Di-tert-butylphenol,

Methyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate,

Pentaerythritol tris(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),

Pentaerythritol di(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), and

tris(2,4-Di-tert-butylphenyl) phosphite.

The base fluids in component c) in accordance with the invention utilize mineral oil based fluids (API Group I, Il and III), lubricating oil base stock, poly-alpha-olefins - PAOs (API Group IV), esters (API Group V), other synthetic fluids, natural oils that are animal or vegeta- ble in origin, and mixtures thereof. The base fluids are of suitable viscosity for utilization in engine oil applications.

The compositions are useful in lubricating oils. The present lubricating oils are for example those employed in internal combustion engines. The present oils have necessary lubricating viscosity. The oils are for example mineral oils or are synthetic and mixtures thereof.

The lubricating oil base stock can be derived from natural lubricating oils, synthetic lubricat¬ ing oils or mixtures thereof. Suitable lubricating oil base stocks obtained by isomerization of synthetic wax and slack wax, as well as hydrocrackate base stocks produced by hydro- cracking (rather than solvent extracting) the aromatic and polar components of the crude oil.

Natural lubricating oils include animal oils, vegetable oils (for example, rapeseed oils, castor oils, and lard oil), petroleum oils, mineral oils, and oils derived from coal or shale.

Synthetic oils include hydrocarbon oils and halo-substituted hydrocarbon oils, such as po¬ lymerised and inter-polymerised olefins, alkyl benzenes, polyphenols, alkylated diphenyl ethers, alkylated diphenyl sulphides, as well as their derivatives, analogues and homologues thereof, and the like. Synthetic lubricating oils also include alkylene oxide polymers, inter- polymers, copolymers and derivatives thereof wherein the terminal hydroxy groups have been modified by esterification, etherification, etc. Another suitable class of synthetic lubri¬ cating oils comprises the esters of dicarboxylic acids with a variety of alcohols. Esters useful as synthetic oils also include those made from C5 to C12 monocarboxylic acids and polyols and polyol ethers.

Silicon-based oils, such as the polyalkyl-, polyaryl, polyalkoxy, or polyaryloxy-siloxane oils and silicate oils, comprise another useful class of synthetic lubricating oils. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids, polymeric tetrahydrofu- rans, polyalphaolefins, and the like.

The lubricating oil may be derived from unrefined, refined, rerefined oils, or mixtures thereof. Unrefined oils are obtained directly from a natural source or synthetic source (for example, coal, shale, or tar and bitumen) without further purification or treatment. Examples of unre¬ fined oils include a shale oil obtained directly from a retorting operation, petroleum oil ob¬ tained directly from distillation, or an ester oil obtained directly from an esterification process, each of which is then used without further treatment. Refined oils are similar to unrefined oils except that refined oils have been treated in one or more purification steps to improve one or more properties. Suitable purification techniques include distillation, hydro treating, dewax- ing, solvent extraction, acid or base extraction, filtration, and percolation, all of which are known to those skilled in the art. Rerefined oils are obtained by treating refined oils in proc- esses similar to those used to obtain refined oils. These rerefined oils are also known as re¬ claimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.

Lubricating oil base stocks derived from the hydroisomerization of wax may also be used, either alone or in combination with the aforesaid natural and/or synthetic base stocks. Such wax isomerised oil is produced by the hydroisomerization of natural or synthetic waxes or mixtures thereof over hydroisomerization catalyst.

Examples of natural waxes are the slack waxes recovered by the solvent dewaxing of min¬ eral oils; synthetic waxes are the wax produced by the Fischer-Tropsch process. The result- ing isomerised product is subjected to solvent dewaxing and fractionation to recover various fractions of specific viscosity indices, generally having a Vl of at least 130, preferably at least 135 and higher and following dewaxing, a pour point of about -200C and lower.

The production of wax isomerised oil meeting the requirements of the present invention is disclosed in U.S. Patent Specification Nos. 4,049,299 and 4,158,671.

Greases or other solid lubricants are also lubricating oils according to this invention.

The synthetic hydrocarbon oils include long chain alkanes, such as cetanes and olefin poly¬ mers, such as trimer and tetramers of octane and decane. These synthetic oils can be mixed with 1) ester oils, such as pentaerythritol esters of monocarboxylic acids having about 2 to 20 carbon atoms, 2) polyglycol ethers, 3) polyacetals and 4) siloxane fluids. Useful among the synthetic esters are those made from polycarboxylic acids and monohydric alcohols. For ex¬ ample, ester fluids made from pentaerythritol or mixtures thereof with di- and tri pentaerythri¬ tol, and an aliphatic monocarboxylic acid containing from 1 to 20 carbon atoms, or mixtures of such acids. Other examples are ester fluids made from trimethylolpropane and an aliphatic monocarboxylic acid containing from 1 to 20 carbon atoms, or mixtures of such acids.

The present lubricating oils are also for example crude oil, industrial lubrication oils, cutting oil, metal working fluids and greases.

Fuels are also a base fluid according to the invention, for example certain aviation fuels and the like, wherein lubrication properties are desired. The fuels are for example a hydrocarbo- naceous petroleum distillate, such as motor gasoline, diesel fuel or fuel oil. Liquid fuel com- positions comprising non-hydrocarbonaceous materials, such as alcohols, ethers, organo-ni- tro compounds and the like (e.g. methanol, ethanol, diethyl ether, methyl ethyl ether, nitro- methane) are also within the scope of this invention as are liquid fuels derived from vegeta¬ ble or mineral sources, such as corn, alfalfa, shale and coal. Fuels that are mixtures of one or more hydrocarbonaceous fuels and one or more non-hydrocarbonaceous materials are also contemplated. Examples of such mixtures are combinations of gasoline and ethanol and of diesel fuel and ether.

The present additives provide extreme pressure, antiwear and friction reducing properties to the oil, and upon combustion, are innocuous to conventional catalytic converters in automo- biles.

The percent by weight of component a) to the total weight of component a) plus component b) is for example from about 0.001 to about 99.999%. For instance the percent by weight of component a) to the total weight of a) plus b) is from about 0.05% to about 90.0%, from about 0.1% to about 50.0%, or from about 1.0% to about 10.0%.

The additive mixture of this invention, the combination of component a) and component b), are present in the oil composition in a total amount of fer example about 0.01% to about 20.0% by weight of the total composition. For instance, the antioxidant compositions are pre¬ sent from about 0.05% to about 15.0%, from about 0.1% to about 10.0%, from about 0.2% to about 5.0% by weight, based on the weight of the entire composition. For example, the anti- oxidant compositions are present from about 0.1 % to about 20.0%, from about 0.1% to about 15.0% or from about 0.1% to about 5.0% by weight, based on the weight of the entire com¬ position.

In lubricating compositions operated under extremely adverse conditions, such as lubricating compositions for marine diesel engines, the additives of this invention may be present in amounts of up to about 30.0% by weight, or more, of the total weight of the lubricating com¬ position.

The additives of this invention are present in the fuel compositions at a level of from about 1 ppm to about 50 000 ppm based on the fuel. For example the additives are present from about 4 ppm to about 5 000 ppm based on the fuel by weight.

Another object of the invention is the antioxidant mixture based on the combination of com¬ ponent a) and component b).

Thus, also disclosed are antioxidant compositions, which comprise a mixture of

a) At least one hindered phenolic antioxidant compound of formula (I), wherein R1, R2, R3, R4 and E are as defined above; and

b) At least one additional antioxidant compound.

The present invention also relates to the above-defined composition additionally comprising e) At least one organic material subject to the deleterious effects of oxidative, thermal, or light-induced degradation.

The invention furthermore relates to compositions comprising an organic material in compo¬ nent e) which is sensitive to oxidative, thermal, or light-induced degradation and at least one compounds listed in component a) formula (I) and at least one antioxidant compound listed in component b).

The invention also relates to a process for stabilizing an organic material in component e) which is sensitive to oxidative, thermal, or light-induced degradation, which comprises add¬ ing, to this material, at least one compound listed in component a) formula (I) and at least one antioxidant compound listed in component b).

Organic materials in component e), which would benefit from the incorporation of the antioxi¬ dants are polymers, for example synthetic polymers, in particular thermoplastic polymers. Particularly preferred organic materials in component e) are polyolefins and styrene copoly¬ mers, for example those mentioned in U.S. Patent Specification No. 5,478,875 under items 1 to 3 and items 6 and 7. Especially preferred organic materials in component e) are for exam¬ ple polyethylene, polypropylene, ABS, and styrene/butadiene copolymers. The invention therefore preferably relates to compositions in which the organic material in component e) is a synthetic organic polymer or a mixture of such polymers, in particular a polyolefin or a styrene copolymer.

The invention also relates to a method of improving oxidative performance in a lubricating oil composition comprising

b) At least one antioxidant compound according to component b), as defined above; and

c) A base fluid,

which method comprises incorporating into said lubricating oil composition at least one com- pound of component a) formula (I) as defined above.

The lubricating oils stabilized in accordance with the invention may additionally or optionally include other additives, component d), which are added in order to improve still further the basic properties of these formulations; such additives include other antioxidants, metal pas- sivators, rust inhibitors, corrosion inhibitors, viscosity index improvers, extreme pressure agents, pour point depressants, solid lubricants, dispersants, detergents, antifoams, colour stabilizers, further extreme pressure additives, demulsifiers, friction modifiers, and, antiwear additives. Such additives are added in the customary amounts in each case in the range from in each case about 0.01% to 10.0% by weight, based on the lubricating oil. The text below gives examples of such additional additives:

Examples of antioxidants are:

1) Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-di- methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert- butyl-4-iso-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2-(α-methyl-cyclohexyl)-4,6- dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclo-hexylphenol, 2,6-di-tert- butyl-4-methoxymethyl phenol, linear or side chain-branched nonylphenols, for example 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1 '-methyl-undec-1 '-yl)phenol, 2,4-dimethyl- 6-(1 '-methyl heptadec-1 '-yl)phenol, 2,4-dimethyl-6-(1 '-methyltridec-1 '-yl)phenol or mixtures thereof;

2) Alkylthiomethylphenols, for example 2,4-di-octylthiomethyl-6-tert-butylphenol, 2,4-di-octyl- thiomethyl-6-methylphenol, 2,4-di-octylthiomethyl-6-ethylphenol or 2,6-di-dodecylthiome- thyl-4-nonylphenol;

3) Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxyphe- nol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade- cyloxyphenol, 2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di- tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate or bis(3,5-di-tert- butyl-4-hydroxyphenyl) adipate;

4) Tocopherols, for example α-, β-, γ- or δ-tocopherol or mixtures thereof (vitamin E);

5) Hydroxylated thiodiphenyl ethers, for example 2,21-thiobis(6-tert-butyl-4-methylphenol), 2J21-thiobis(4-octylphenol)J 4J41-thiobis(6-tert-butyl-3-methylphenol)J 4,41-thiobis-(6-tert- butyl-2-methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol) or 4,4'-bis(2,6-dimethyl-4-hy- droxyphenyl) disulphide;

6) Alkylidenebisphenols, for example 2,21-methylenebis(6-tert-butyl-4-methylphenol), 2,2'- methylenebis(6-tert-butyl-4-ethylphenol), 2,21-methylenebis(4-methyl-6-(α -methylcyclo- hexyl)-phenol), 2,2'-methylenebis(4-methyl-6-cyclohexyl phenol), 2,2'-methylenebis(6- nonyl-4-methylphenol), 2,21-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6- di-tert-butylphenol), 2,21-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis(6- (α-methylbenzyl)-4-nonylphenol), 2,21-methylene-bis(6-(α,α-dimethylbenzyl)-4-nonylphe- nol)J 4J41-methylenebis(2J6-di-tert-butylphenol)J 4,41-methylenebis(6-tert-butyl-2-methyl- phenol), 1 , 1 -bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-me- thyl-2-hydroxybenzyl)-4-methylphenol, 1 , 1 ,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)- butane, 1 , 1 -bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmerca ptobutane, ethylene glycol bis(3,3-bis(31-tert-butyl-41-hydroxyphenyl)butyrate), bis(3-tert-butyl-4- hydroxy-5-methylphenyl)dicyclo-pentadiene, bis(2-(31-tert-butyl-21-hydroxy-51-methyl- benzyl)-6-tert-butyl-4-methylphen yl)terephthalate, 1 ,1 -bis(3,5-dimethyl-2-hydroxy- phenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tert-butyl-4- hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane or 1 , 1 ,5,5-tetra(5-tert-butyl-4-hy- droxy-2-methylphenyl)-pentane;

7) O-, N- and S-Benzyl compounds, for example S.S.S'.S'-tetra-tert-butyl^^'-dihydroxydi- benzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl 4- hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl)amine, bis(4-tert- butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxy- benzyl) sulphide or isooctyl S.S-di-tert-butyl^-hydroxy-benzylmercaptoacetate;

8) Hydroxybenzylated malonates, for example-dioctadecyl 2,2-bis(3,5-di-tert-butyl-2-hydro- xybenzyl)malonate, dioctadecyl 2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate, di- dodecyl mercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-mal onate or di(4- (1 ,1,3,3-tetramethylbutyl)phenyl)2,2-bis(3,5-di-tert-butyl-4-h ydroxybenzyl)malonate;

9) Aromatic hydroxybenzyl compounds, for example 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6- tetramethyl benzene or 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol;

10)Triazine compounds, for example 2,4-bisoctylmercapto-6-(3,5-di-tert-butyl-4-hydroxyani- lino)-1 ,3,5-triazine, 2-octylmercapto-4J6-bis(3,5-di-tert-butyl-4-hydroxyanilino)- 1 ,3,5-triaz- ine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)- 1 ,3,5-triazine, 2,4,6- tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,2,3-triazine, 1 ,3,5-tris(3,5-di-tert-butyl-4-hy- droxybenzyl)-isocyanurate, 1 ,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) iso- cyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1 ,3,5-triazine, 1 ,3,5-tris(3,5- di-tert-butyl-4-hydroxyphenylpropionyl)hexahydro-1 ,3,5-triazine or 1 ,3,5-tris(3,5-dicyclo- hexyl-4-hydroxybenzyl)-isocyanurate;

11) Benzyl phosphonates, for example dimethyl 2,5-di-tert-butyl-4-hydroxybenzyl-phospho- nate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert-butyl-4- hydroxybenzylphosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzylphospho- nate or the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphos- phonic acid;

12) Acylaminophenols, for example 4-hydroxyauranilide, 4-hydroxystearanilide or octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl)carbamate; 13) Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, β-(5-tert-butyl-4-hydroxy-3- methylphenyl)propionic acid, β-(3,5-dicyclohexyl-4-hydroxyphenyl)-propionic acid, 3,5-di- tert-butyl-4-hydroxyphenylacetic acid or β-(5-tert-butyl-4-hydroxyphenyl)-3-thiabutyric acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hy- droxyethyl) isocyanurate, N,N1-bis(hydroxyethyl)oxalamide, 3-thiaundecanol, 3-thiapenta- decanol, trimethyl-hexanediol, trimethylol propane, 4-hydroxymethyl-1-phospha-2,6,7-tri- oxabicyclo(2.2.2)octane, glycerol or transesterification products based on natural trigly- cerides of, for example, coconut oil, rape seed oil, sunflower oil or colza oil;

14) Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, e.g. N,N1-bis(3,5-di-tert-bu- tyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N1-bis(3,5-di-tert-butyl-4-hydroxy- phenylpropionyl)trimethylenediamine or N,N1-bis(3,5-di-tert-butyl-4-hydroxyphenylprop- ionyl) hydrazine;

The previous list of items 1) through 14) contains examples of phenolic antioxidants which are well known in the prior art; and

15) Ascorbic acid (vitamin C);

16)Amine-type antioxidants, for example N.N'-diisopropyl-p-phenylenediamine, N,N'-di-sec- butyl-p-phenylenediamine, N,Nl-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1- ethyl-3-methyl-pentyl)-p-phenylenediamine, N,Nl-bis(1-methyl-heptyl)-p-phenylendiamine, N.N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di- (naphth-2-yl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3- dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenyl- enediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluenesulphonamido)di- phenylamine, N, N'-dimethyl-N.N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N- allyldiphenylamine, 4-isopropoxy-diphenylamine, N-phenyl-1-naphthylamine, N-(4-tert- octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, e.g. p.p'-di-tert-octyidiphenyl-amine, 4-n-butylaminophenol, 4-butyrylamino-phenol, 4-nona- noylamino-phenol, 4-dodecanoylaminophenol, 4-octadecanoylamino-phenol, di-(4-meth- oxyphenyl)-amine, 2,6-di-tert-butyl-4-dimethylamino-methyl-phenol, 2,4'-diamino-diphen- ylmethane, 4,41-diamino-diphenylmethane, N.N.N'.N'-tetramethyl^^'-diamino-diphen- ylmethane, 1 ,2-di-((2-methyl-phenyl)-amino)-ethane, 1,2-di-(phenylamino)propane, (o- tolyl)biguanide, di(4-(1l,3l-dimethyl-butyl)-phenyl)amine, tert-octylated N-phenyl-1-naph- thylamine, a mixture of mono- and dialkylated tert-butyl/tert-octyidiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dial- kylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/iso- hexyldiphenylamines, mixtures of mono- and dialkylated tert-butyidiphenylamines, 2,3- dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl/tert-octyl-phenothiazines, a mixture of mono- and dialkylated tert- octyl-phenothiazines, N-allylphenothiazine, N.N.N'.N'-tetraphenyl-i ,4-diaminobut-2-ene, N,N-bis-(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediam ine, bis-(2,2,6,6-tetrame- thylpiperidin-4-yl) sebacate, 2,2J6,6-tetramethylpiperidin-4-one or 2,2,6,6-tetrame- thylpiperidin-4-ol; and

17) Aliphatic or aromatic phosphites, esters of thiodipropionic acid or of thiodiacetic acid, or salts of dithiocarbamic or dithiophosphoric acid, 2,2, 12,12-tetramethyl-5,9-dihydroxy- 3,7,1 -trithiatridecane or 2,2,15,15-tetramethyl-5,12-dihydroxy-3,7,10,14-tetrathiahexa - decane.

Examples of metal passivators, for example for copper, are:

1 ) Benzotriazoles and their derivatives, for example 4- or 5-alkylbenzotriazoles (e.g. tolutria- zole) and derivatives thereof, 4,5,6,7-tetrahydrobenzotriazole, S.δ'-methylenebisbenzotri- azole; Mannich bases of benzotriazole or tolutriazole, such as 1-(di(2-ethylhexyl)amino- methyl)tolutriazole and 1-(di(2-ethylhexyl)aminomethyl)-benzotriazole; alkoxyalkylbenzo- triazoles, such as 1-(nonyloxymethyl)-benzotriazole, 1-(1-butoxyethyl)-benzotriazole and 1 -(1 -cyclohexyloxybutyl)-tolutriazole;

2) 1 ,2,4-Triazoles and derivatives thereof, for example 3-alkyl(or aryl)-1 ,2,4-triazoles, Man¬ nich bases of 1 ,2,4-triazoles, such as1-(di(2-ethylhexyl)aminomethyl)-1,2,4-triazole; alkoxyalkyl-1 ,2,4-triazoles, such as1-(1-butoxyethyl)-1 ,2,4-triazole; acylated 3-amino- 1 ,2,4-triazoles;

3) Imidazole derivatives, for example 4,41-methylenebis(2-undecyl-5-methyl-imidazole), bis((N-methyl)imidazol-2-yl)carbinol octyl ether;

4) Sulphur-containing heterocyclic compounds, for example 2-mercaptobenzothiazole, 2,5- dimercapto-1 ,3,4-thiadiazole, 2,5-dimercaptobenzothiadiazole and derivatives thereof; 3,5-bis(di(2-ethylhexyl)aminomethyl)-1 ,3,4-thiadiazolin-2-one; and

5) Amino compounds, for example salicylidenepropylenediamine, salicylaminoguanidine and salts thereof. Examples of rust inhibitors are:

1 ) Organic acids, their esters, metal salts, amine salts and anhydrides, for example alkyl- and alkenylsuccinic acids and the partial esters thereof with alcohols, diols or hydroxy- carboxylic acids, partial amides of alkyl- and alkenylsuccinic acids, 4-nonylphenoxyacetic acid, alkoxy- and alkoxyethoxycarboxylic acids, such as dodecyloxyacetic acid, dodecy- loxy(ethoxy)acetic acid and the amine salts thereof, and also N-oleoylsarcosine, sorbitan monooleate, lead naphthenate, alkenylsuccinic anhydrides, for example dodecenylsuc- cinic anhydride, 2-(2-carboxyethyl)-1-dodecyl-3-methylglycerol and its salts, especially sodium and triethanolamine salts;

2) Nitrogen-containing compounds, for example:

i) Primary, secondary or tertiary aliphatic or cycloaliphatic amines and amine salts of organic and inorganic acids, for example oil-soluble alkylammonium carboxylates, and also 1-(N,N-bis(2-hydroxyethyl)amino)-3-(4-nonyl- phenoxy)propan-2-ol;

ii) Heterocyclic compounds, for example: substituted imidazolines and oxazoli- nes, 2-heptadecenyl-1 -(2-hydroxyethyl)-imidazoline;

3) Phosphorus-containing compounds, for example Amine salts of phosphoric acid partial esters or phosphonic acid partial esters, zinc dialkyldithiophosphates;

4) Sulphur-containing compounds, for example: barium dinonylnaphthalene-sulphonates, calcium petroleumsulphonates, alkylthio-substituted aliphatic carboxylic acids, esters of aliphatic 2-sulphocarboxylic acids and salts thereof; and

5) Glycerol derivatives, for example: glycerol monooleate, 1-(alkylphenoxy)-3-(2-hy- droxyethyl)glycerols, 1 -(alkylphenoxy)-3-(2,3-dihydroxypropyl)glycerols, 2-carboxyalkyl- 1 ,3-dialkylglycerols.

Useful viscosity index improvers include any of the polymers which impact enhanced viscos¬ ity properties to the finished oil. They are generally hydrocarbon-based polymers having a molecular weight, Mw, in the range of between about 2 000 to 1 000 000, preferably about 50 000 to 200 000. Viscosity index improver polymers include olefin copolymers, for exam- pie, ethylene-propylene copolymers, ethylene-(iso)-butylene copolymers, propylene-(iso)- butylene copolymers, ethylene-polyalphaolefin copolymers, polymethacrylates; styrene-diene block copolymers, for example, styrene-isoprene copolymers, and star copolymers; poly- acrylates, vinylpyrrolidone/methacrylate copolymers, polyvinylpyrrolidones, polybutenes, sty- rene/acrylate copolymers, and polyethers. Viscosity index improvers may be monofunctional or multifunctional, such as those bearing substituents that provide a secondary lubricant per¬ formance feature, such as dispersancy, pour point depression, etc.

Examples of pour point depressants are: Polymethacrγlates or alkylated naphthalene deriva- tives;

Examples of dispersants/surfactants are: Polybutenylsuccinamides or -imides, polybutenyl- phosphonic acid derivatives, and basic magnesium, calcium and barium sulphonates, phe- nolates and salicylates;

Examples of antifoams are: Silicone oils and polymethacrylen;

The demulsifiers are, for example, selected from polyetherpolyols and dinonylnaphthalene- sulphonates;

The friction modifiers are, for example, selected from: fatty acids and their derivatives (i.e. natural esters of fatty acids, such as glycerol monooleate), amides, imides and amines (i.e. oleylamine), sulphur containing organo molybdenum dithiocarbamates, sulphur-phosphorus containing organo molybdenum dithiophosphates, sulphur-nitrogen containing organo mo¬ lybdenum compounds based on dispersants, molybdenum carboxylate salts, molybdenum- amine complexes, molybdenum amine/alcohol/amid complexes and molybdenum cluster compounds, Teflon™ and molybdenum disulphide;

Examples of antiwear additives are:

Sulphur- and/or phosphorus- and/or halogen-containing compounds, such as sulphurised olefins and vegetable oils, zinc dialkyldithiophosphates, tritolyl phosphate, tricresyl phos¬ phate, chlorinated paraffins, alkyl and aryl di- and trisulphides, amine salts of mono- and dialkyl phosphates, amine salts of methylphosphonic acid, diethanolaminomethyltolyl tria- zole, di-(2-ethylhexyl)-aminomethyltolyl triazole, derivatives of 2,5-dimercapto-1,3,4-thiadia- zole, ethyl(bisisopropyloxyphosphinothioyl)thiopropionate, triphenyl thiophosphate (triphenyl phosphorothioate), tris(alkylphenyl) phosphorothioates and mixtures thereof, for example tris(isononylphenyl) phosphorothioate, diphenylmonononylphenyl phosphorothioate, isobu- tylphenyl diphenyl phosphorothioate, the dodecylamine salt of 3-hydroxy-1,3-thiaphosphetan 3-oxide, trithiophosphoric acid 5,5,5-tris-isooctyl 2-acetate, derivatives of 2-mercaptoben- zothiazole, such as 1-N,N-bis(2-ethylhexyl)aminomethyl-2-mercapto-1 H-1,3-benzothiazole, and ethoxycarbonyl 5-octyldithiocarbamate; Dihydrocarbyl dithiophosphate metal salts where the metal is aluminum, lead, tin manga¬ nese, cobalt, nickel, zinc or copper, but most often zinc. The zinc salt (zinc dialkyl dithio¬ phosphate) is represented as

R1O'

where R and R' are independently of one another CrC2oalkyl, C3-C2oalkenyl, C5-Ci2cyclo- alkyl, C7-Ci3aralkyl or C6-Ci0aryl, for example R and R' are independently d-Ci2alkyl;

Suitable antiwear additives are described in U.S. Patent Specification Nos. 4,584,021; 5,798,321; 5,750,478; 5,801,130; 4,191,666; 4,720,288; 4,025,288; 4,025,583 and WO 095/20592, amines for example polyalkylene amines, such as ethylene diamine, diethylene triamine, triethylene tetraamine, tetraethylene pentamine, pentaethylene hexamine, nonaethylene decylamine and aryl amines as described in United States Patent Specification No. 4,267,063, salts of amine phosphates comprising specialty amines and mixed mono- and di-acid phosphates; the mono- and di-acid phosphate amines have the structural formulae:

O O H H I l I + I + R28O-P-O - O-P-0 R29 ^ R31 R29 ^ R31 OR27 OR27 R R 30 30 and

Wherein R27 is hydrogen, CrC25 linear or branched chain alkyl, which is unsubstituted or substituted by at least one d-C6alkoxy groups, a saturated acyclic or alicyclic group, or aryl

R28 is CrC25 linear or branched chain alkyl, which is unsubstituted or substituted by at least one CrC6alkoxy groups, a saturated acyclic or alicyclic group, or aryl;

R29 is hydrogen, CrC25 linear or branched chain alkyl, a saturated or unsaturated acyclic or alicyclic group, or aryl; and are hydrogen or CrCi2 linear or branched chain alkyl; and

R30 and R3i are, each independently of the other, CrC25 linear or branched chain alkyl, a saturated or unsaturated acyclic or alicyclic group, or aryl. Preferably, R27 and R28 are linear or branched CrCi2 alkyl; and R29, R30 and R3i are linear or branched CrCi8 alkyl;

Irgalube® 349 (Ciba Specialty Chemicals) has been found to be very useful, particularly by enhancing the wear performance of the base oil such that it meets stringent military perform¬ ance specifications; IRGALUBE 349 corresponds to the formula O (R33O)x P N (OH)y - (HN(R34)^

Wherein R33 is n-hexyl, R34 is Cn-Ci4 branched alkyl, and when x=1 then y=2; when x=2 then y=1.

Other conventional antiwear additives are compounds of the formula

in which R1 and R2 independently of one another are C3-Ci8alkyl, C5-Ci2cycloalkyl, C5- C6cycloalkyl methyl, Cg-dobicycloalkylmethyl, C9-Ci Otricycloalkyl methyl, phenyl or C7- C24alkyl phenyl or together are (CH3)2C(CH2)2 and R3 is hydrogen or methyl.

A representative compound is Irgalube® 353 (Ciba Specialty Chemicals), a dialkyl dithio- phosphate ester, CAS Reg. No. 268567-32-4.

The lubricating oil compositions can contain, in addition to the antioxidant additives, other known additives. These include antiknocking agents, such as tetralkyl lead compounds, lead scavengers, such as haloalkanes (e.g., ethylene dichloride and ethylene dibromide), deposit preventers or modifiers, such as triaryl phosphates, dyes, cetane improvers, antioxidants, such as 2,6-di-tert-butyl-4-methylphenol, rust inhibitors, such as alkylated succinic acids and anhydrides, bacteriostatic agents, gum inhibitors, metal deactivators, demulsifiers, upper cylinder lubricants and anti-icing agents.

The present antioxidant compositions can be introduced into the lubricating oil in manners known per se. The compounds are readily soluble in oils. They may be added directly to the lubricating oil or they can be diluted with a substantially inert, normally liquid organic diluent, such as naphtha, benzene, toluene, xylene or a normally liquid oil or fuel to form an additive concentrate or master batch. These concentrates generally contain from about 10% to about 90% by weight additive and may contain at least one other additional additives. The present antioxidant compositions may be introduced as part of an additive package.

The present invention is further illustrated by the following Examples: Example 1 : Octyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate Examples 2-13: Antioxidant Compositions Examples 14-18: Application Examples Example 1 : Octyl 3.5-di-tert-butyl-4-hvdroxyhvdrocinnamate

Methyl S.S-di-tert-butyM-hydroxyhydrocinnannate (256.0 g, 0.88 mol) and isooctanol (133.0 g, 0.91 mol) are added to a laboratory reactor equipped with the necessary auxiliary equipment. The mixture is heated to 85°C under a reduced pressure of 0.04 bar. After fifteen minutes, the reduced pressure is released and aluminum isopropoxide (1.77 g, 0.0087 mol, Rhone-Poulenc, Manalox® 130) is added. The reaction mass is heated to 1300C, while under a reduced pressure of 0.1 bar. After two hours, the reaction mass is heated to 165°C while under a reduced pressure of 0.04 bar for one hour. The excess isooctanol is removed by reduced pressure distillation at 165°C. The title compound (331.0 g, 97% yield) is obtained as a light yellow oil whose assay is 97% as judged by calibrated gas chromatography.

Example 2: Antioxidant Compositions

Phenolic antioxidants and phosphites are crystallized from organic solvents; for example, methanol and isopropanol. These solvent streams are blended together and the solvents are recovered by distillation. The residue that remains after solvent distillation contains (as ana¬ lysed by calibrated gas chromatography): 2,6-di-tert-butylphenol: 5.4 wt%; 2,4-di-tert-butyl- phenol: 0.35 wt%; methyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate: 21.2 wt%; Compound A: 29.0 wt%; thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate): 3.7 wt%; neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate): 2.2 wt%; pentaery- thritol tris(3,5-di-tert-butyl-4-hydroxyhydrocinnamate): 5.9%; pentaerythritol di(3,5-di-tert-bu- tyl-4-hydroxyhydrocinnamate): 4.3 wt%; n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinna- mate: 4.2 wt%; and, tris(2,4-di-tert-butylphenyl) phosphite: 0.3 wt%.

Compound A is . Dimethyl α-(3,5-di-tert-butyl-4-hydroxyben- zyl)glutarate.

Example 3: Antioxidant Compositions

Phenolic antioxidants are purified by distillation during their manufacture. The distillation residue that remains contains (as analysed by calibrated gas chromatography): 2,6-di-tert- butylphenol: 42.3 wt%; 2,4-di-tert-butylphenol: 0.85 wt%; methyl 3,5-di-tert-butyl-4-hydroxy- hydrocinnamate: 29.0 wt%; and, Compound A (structural formula in Ex. 2): 27.9 wt%.

Example 4: Antioxidant Compositions

The composition as obtained according to Example 1 (80.0 g, 0.21 mol), Example 2 (20.0 g), and methanol (2.8 g, 0.088 mol) are added to a flask and stirred until homogeneity. The so¬ lution is then heated under reduced pressure to remove any moisture and methanol. Distilla¬ tion is continued until a constant weight is received. The antioxidant composition is received (99.0 g) as a light amber oil.

Example 5: Antioxidant Compositions

The compositions according to Examples 1 (90.0 g, 0.23 mol), Example 2 (10.0 g), and me¬ thanol (1.4 g, 0.044 mol) are added to a flask and stirred until homogeneity. The solution is then heated under reduced pressure to remove any moisture and methanol. Distillation is continued until a constant weight is received. The title antioxidant composition is received (98.0 g) as a light amber oil.

Example 6: Antioxidant Compositions

The compositions according to Example 1 (95.0 g, 0.24 mol), Example 2 (5.0 g), and metha¬ nol (0.7 g, 0.022 mol) are added to a flask and stirred until homogeneity. The solution is hea¬ ted under reduced pressure to remove any moisture and methanol. Distillation is continued until a constant weight is received. The antioxidant composition is received (99.0 g) as a light amber oil.

Example 7: Antioxidant Compositions

Methyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate (254.0 g, 0.87 mol), isooctanol (142.5 g, 1.09 mol, Exxal 8 from Exxon), and the composition according to Example 2 (51.0 g) are added to a reaction flask and heated to 85°C under reduced pressure. The reduced pressure is released and aluminum isopropoxide (5.0 g, 0.025 mol, Rhone Poulenc, MANALOX 130) is added portion wise. Reduced pressure is applied while heating to 1300C. After seven hours, the temperature is increased to 165°C for three hours. The excess isooctanol is re¬ moved by distillation under reduced pressure. The antioxidant composition is received (380.2 g) as a light amber oil and contains 87.6 wt% of isooctyl esters (as a mixture) by cali- brated gas chromatography. Example 8: Antioxidant Compositions

Methyl S.S-di-tert-butyl^-hydroxyhydrocinnannate (125.0 g, 0.43 mol), isooctanol (75.0 g, 0.58 nnol, Exxal 8 from Exxon), and the composition according to Example 3 (30.3 g) are added to a reaction flask and heated to 87°C under reduced pressure. The reduced pressure is released and aluminum isopropoxide (0.78 g, 0.004 mol, Rhone Poulenc, MANALOX 130) is added. A reduced pressure of 0.13 bar is applied while heating to 1500C. After two and one-half hours, the excess isooctanol is removed by distillation under reduced pressure. The antioxidant composition is received (187.3 g) as a light amber oil and contains 88.2 wt% of isooctyl esters (as a mixture) by calibrated gas chromatography.

Example 9: Antioxidant Compositions

Methyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate (10.224 g, 34.97 mol), isooctanol (6002.0 g, 46.1 mol, Exxal 8 from Exxon), and the composition according to Example 3 (1139.0 g) are added to a reaction flask and heated to 1000C under reduced pressure. The reduced pressure is released and aluminum isopropoxide (244.2 g, 1.25 mol, Rhone Poulenc, MANALOX 130) is added. A reduced pressure is applied while heating to 1500C. After one hour, the temperature is increased to 165°C for three hours. The excess isooctanol is removed by distillation under reduced pressure. The antioxidant composition is received (15.164 g) as a light amber oil and contains 90.8 wt% of isooctyl esters (as a mixture) by calibrated gas chromatography.

Example 10: Antioxidant Compositions

Methyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate (8640 g, 29.5 mol), isooctanol (5339.0 g, 41 mol, Exxal 8 from Exxon), and the composition according to Example 2 (2229.0 g) are added to a reaction flask and heated to 1000C under reduced pressure. The reduced pressure is released and aluminum isopropoxide (120.0 g, 0.62 mol, Rhone Poulenc, MANALOX 130) is added. A reduced pressure is applied while heating to 150°C. After two and one-half hours, the excess isooctanol is removed by distillation under reduced pressure. The antioxidant composition is received (13,497 g) as a light amber oil and contains 88.1 wt% of isooctyl esters (as a mixture) by calibrated gas chromatography.

Example 11 : Antioxidant Compositions

Methyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate (8909.0 g, 30.5 mol), isooctanol (4999.0 g, 38.4 mol, Exxal 8 from Exxon), and the composition according to Example 2 (1815.0 g) are added to a reaction flask and heated to 1000C under reduced pressure. The reduced pres- sure is released and aluminum isopropoxide (174.0 g, 0.89 mol, Rhone Poulenc, MANALOX 130) is added portion wise. A reduced pressure is applied while heating to 1300C. After seven hours, the temperature is increased to 165°C for three hours. The excess isooctanol is removed by distillation under reduced pressure. The antioxidant composition is received (13,834 g) as a light amber oil and contains 89.0 wt% of isooctyl esters (as a mixture) by calibrated gas chromatography.

Example 12: Antioxidant Compositions

Methyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate (100 kg), isooctanol (62.9 kg Exxal 8 from Exxon), and the composition according to Example 3 (30.7 kg) are added to a reactor and heated to 1000C under reduced pressure. The reduced pressure is released and aluminum isopropoxide (650.0 g, 3.3 mol, Rhone Poulenc, MANALOX 130) is added. A reduced pres¬ sure of 0.2 bar is applied while heating to 1500C. After two and one-half hours, the excess isooctanol is removed by distillation under reduced pressure. The antioxidant composition is received (356.9 lbs.) as a light amber oil and contains 85.9 wt% of isooctyl esters (as a mix- ture) by calibrated gas chromatography.

Example 13: Antioxidant Compositions

Methyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, isooctanol, and the composition according to Example 3 are added to a reactor and heated to 100°C under reduced pressure. The re¬ duced pressure is released and MANALOX 130 is added. A reduced pressure of 0.2 bar is applied while heating to 150°C. After two and one-half hours, the excess isooctanol is re¬ moved by distillation under reduced pressure. Under these reaction conditions, dimethyl α- (3,5-di-tert-butyl-4-hydroxybenzyl)glutarate, diisooctyl α-(3,5-di-tert-butyl-4-hydroxyben- zyl)glutarate, and monomethyl-monoisooctyl α-(3,5-di-tert-butyl-4-hydroxybenzyl)glutarate are produced.

Example 14: Flash Point Test

A flash point test is performed on the examples to ensure no volatile, flammable components are present. The samples are tested using an Erdco Rapid Tester Model RT-1 at 22.2°C, 60.6 C, and 92.8°C. The results are summarized below: Example Flash Point [0C]

4 >199

5 >199

6 >199

8 >199

The results indicate that the compositions do not contain volatile, flammable components.

Example 15: TGA Analysis

A thermogravimetric analysis (TGA) is performed with the composition according to some representative Examples to evaluate their volatility at elevated temperatures. The weight loss of samples as temperature is increased is monitored and the temperatures at which a 10% and 50% weight loss occur are noted. The results are summarized below:

Example Temperature 1 [at 10% loss] Temperature 2 [at 50% loss]

1 216 260

9 224 271

11 228 275

10 230 276

The data show that the compositions are less volatile than the compound according to Exam¬ ple 1, a compound known in the prior art.

Example 16: High Temperature Deposit Test

The compositions are evaluated for their ability to reduce deposit formation in lubricants, such as passenger car motor oil and diesel engine oil formulations. Thin films of oil on steel cups are heated at 23O0C in the Alcor Micro Carbon Residue Tester for increasing periods of time. After each time interval the cups are washed with hexane and the amount of residue left behind is determined. The difference in percent deposits formed by a base formulation for a set time interval is compared with those formed by the base formulation plus stabilizers. The magnitude of a beneficial decrease in deposit formation is rated as a ratio that is designated the performance index (Pl). The higher the Pl, the better the sample is at controlling deposit formation. Each formulation contains 1.5% by weight of stabilizer in a fully formulated SAE 5W-30 passenger car motor oil, GF-4 type formulation with 0.05 % phosphorus by weight.

Example Performance Index [Pl]

1 6

11 24

10 34

12 45

9 67

Example 17: Hot Tube Test

The compositions are evaluated in a test that measures the deposit forming tendencies of an oil sample. In the test, oil droplets are pushed upward by compressed air inside a glass cap¬ illary tube that is heated to 248°C. Test oil percolates upward through the tube for 16 hours forming a lacquer on the inner wall of the tube. At the conclusion of the test, the tube is washed, dried and rated for cleanliness on a 0-10 scale (0: dirty, 10: clean).

Each formulation contains 1.5% by weight of stabilizer in a fully formulated SAE 5W-30 pas¬ senger car motor oil, GF-4 type formulation with 0.05 % phosphorus by weight. The data are summarized below and represent the average of two tests.

Example Cleanliness

1 4.5

9 4.7

10 4.8

11 5.0

Example 18: HPDSC Test

High pressure differential scanning calorimetry (HPDSC) is an analytical technique that evaluates oxidative performance of additives in various substrates. A TA Instruments Model 2920 is used for the evaluations. The test is run under pressure to prevent volatilization of the material to be evaluated. In this evaluation, the samples, in aluminum pans, are heated isothermally at 21O0C in a cell pressurized to 0.519 bar with air. The time until an exothermic reaction occurs (oxidation induction time) is measured. The longer the oxidation induction pe¬ riod, the more stable the sample.

Each formulation contains 1.5% by weight of stabilizer in a fully formulated SAE 5W-30 pas¬ senger car motor oil, GF-4 type formulation with 0.05 % phosphorus by weight. The data are summarized below and represent the average of two tests.

Example Oxidation Induction Time [minutes]

1 94

9 95

11 95

12 105