Solid anti-friction devices – materials therefor – lubricant or se – Lubricants or separants for moving solid surfaces and... – Heterocyclic ring compound; a heterocyclic ring is one...
Reexamination Certificate
2002-07-12
2003-07-29
Howard, Jacqueline V. (Department: 1764)
Solid anti-friction devices, materials therefor, lubricant or se
Lubricants or separants for moving solid surfaces and...
Heterocyclic ring compound; a heterocyclic ring is one...
C508S322000, C508S331000
Reexamination Certificate
active
06599865
ABSTRACT:
TECHNICAL FIELD OF THE INVENTION
This invention relates to lubricating oil compositions, their method of preparation, and use. More specifically, this invention relates to lubricating oil compositions containing an alkylated diphenylamine, a sulfurized olefin/fatty oil and/or an ashless dialkyldithiocarbamate, and an alkylated phenothiazine. The lubricating oil compositions of this invention are particularly useful as crankcase lubricants.
BACKGROUND OF THE INVENTION
Lubricating oils as used in the internal combustion engines and transmissions of automobiles or trucks are subjected to a demanding environment during use. This environment results in the oil suffering oxidation which is catalyzed by the presence of impurities in the oil, such as iron compounds, and is also promoted by the elevated temperatures of the oil during use.
The oxidation of lubrication oils during use is usually controlled to some extent by the use of antioxidant additives which may extend the useful life of the lubricating oil, particularly by reducing or preventing unacceptable viscosity increases. Aminic antioxidants are antioxidants that contain one or more nitrogen atoms. An example of an aminic antioxidant is phenothiazine. The prior art discloses the many teachings on the synthesis and uses of phenothiazine. Phenothiazine antioxidants have been used as a stand alone additive, chemically modified or grafted onto the backbone of polymers.
A new trend in engine oils is a shift to lower and lower phosphorus levels. Thus, at some point the industry will require lubricant formulations for crankcase with significantly lower, zero or essentially zero phosphorus content.
Existing lubricants employing phenothiazine are taught in U.S. Pat. No. 5,614,124 and references cited therein, all of which are incorporated herein in their entirety by reference.
Existing lubricants employing alkylated diarylamine and a sulfurized compound are taught in U.S. Pat. Nos. 5,840,672, 6,174,842, 6,326,336, and references cited therein, all of which are incorporated herein in their entirety by reference.
U.S. Pat. No. 2,781,318 teaches the synthesis and use of dialkylphenothiazines as an oil soluble ashless detergent additive for mineral lubricating oils. The alkylation is on the aromatic ring and each alkyl group contains 4 to 16 carbons.
U.S. Pat. No. 3,536,706 teaches the use of branched mono-alkylated alkylphenothiazine as an antioxidant additive for synthetic lubricants. The alkyl groups contain 4 to 12 carbons.
U.S. Pat. No. 4,072,619 teaches the use of nitrogen substituted polyoxyalkylene phenothiazines for use in synthetic motor oils.
U.S. Pat. No. 5,073,278 teaches a lubricant composition containing an aromatic amine and a sterically hindered amine. The aromatic amine can be a ring-substituted alkylphenothiazine or nitrogen substituted alkylated phenothiazine.
U.S. Pat. No. 5,157,118 teaches the nitrogen substitution of a phenothiazine where the nitrogen substitutent contains an additional sulfur atom.
U.S. Pat. No. 5,200,100 teaches the grafting of a monomer onto the backbone of an E-P polymer. The monomer contains an aminoalkylphenothiazine moiety.
U.S. Pat. No. 5,503,759 teaches the alkylation of mixtures of diphenylamine, alkyldiphenylamines, phenothiazine and alkylphenothiazines with an olefin in the presence of an acid catalyst.
U.S. Pat. No. 5,167,844 teaches a lubricant formulation containing at lease three additives to guard against oxidative degradation. These three additives are: alkali metal dialkyl dithiophosphates, an aromatic amine such as an alkylphenothiazine and a compound from either a sterically hindered amine, acyclic sterically hindered amine or alkylphenols.
The aforementioned patents are hereby incorporated by reference.
SUMMARY OF THE INVENTION
In broadest terms, a lubricating composition of the present invention comprises a major amount of lubricating oil, and a minor amount of an oil soluble alkylated diarylamine, an oil soluble alkylated phenothiazine, and an oil soluble sulfurized compound. It is preferred that the sulfurized compound is selected from the group consisting of sulfurized olefins, and sulfurized fatty oils. A second lubricating composition of the present invention comprises a major amount of lubricating oil, and a minor amount of an oil soluble alkylated diarylamine, an oil soluble alkylated phenothiazine, and an oil soluble ashless dialkyldithiocarbamate.
While any conventional or non-conventional lubricating oil may be used in the present invention, it is preferred that the lubricating oil is selected from the group consisting of paraffinic oils, naphthenic oils, aromatic oils, and synthetic oils and mixtures thereof.
The concentration of the alkylated diarylamine may range from about 0.001 to 10 wt % in the lubricating composition, however, it is preferred that the concentration range from about 0.05 to 2.5 wt % in the lubricating composition.
It is preferred that the alkylated diarylamine is selected from the group consisting of: diphenylamine, alkylated diphenylamine, 3-hydroxydiphenylamine, N-phenyl-1,2-phenylenediamine, N-phenyl-1,4-phenylenediamine, monobutyldiphenylamine, dibutyldiphenylamine, monooctyldiphenylamine, dioctyldiphenylamine, monononyldiphenylamine, dinonyldiphenylamine, monotetradecyldiphenylamine, ditetradecyldiphenylamine, phenyl-alpha-naphthylamine, monooctyl phenyl-alpha-naphthylamine, phenyl-beta-naphthylamine, monoheptyldiphenylamine, diheptyldiphenylamine, p-oriented styrenated diphenylamine, mixed butyloctyidiphenylamine, and mixed octylstryryldiphenylamine.
The concentration of the alkylated phenothiazine may range from about 0.001 to 10 wt % in the lubricating composition, however, it is preferred that the concentration range from about 0.05 to 2.5 wt % in the lubricating composition.
It is further preferred that the alkylated phenothiazine have the chemical formula:
wherein R1 is a linear or branched C4-C24 alkyl, aryl, heteroalkyl or alkylaryl group and R2 is hydrogen or a linear or branched C4-C24 alkyl, aryl, heteroalkyl, or alkylaryl group.
It is even more preferred that the alkylated phenothiazine is selected from the group consisting of monotetradecylphenothiazine, ditetradecylphenothiazine, monodecylphenothiazine, didecylphenothiazine, monononylphenothiazine, dinonylphenothiazine, monoctylphenothiazine, dioctylphenothiazine, monobutylphenothiazine, dibutylphenothiazine, monostyrylphenothiazine, distyrylphenothiazine, butyloctylphenothiazine, and styryloctylphenothiazine.
While the sulfurized compound may be present in sufficient concentration so as to provide from about 25 to 5000 ppm of sulfur in the lubricating composition, it is preferred that the sulfurized compound be present in a concentration sufficient to provide from about 150 to 2500 ppm of sulfur in the lubricating composition.
It is preferred that the sulfurized olefin is selected from the group consisting of sulfurized C4-C24 alpha-olefins, sulfurized isomerized C4-C24 alpha-olefins, sulfurized branched C4-C24 olefins, sulfurized cyclic C4-C24 olefins, HITEC® 7084, HITEC® 7188, HITEC® 312, ADDITIN RC 2540-A, and combinations thereof. HiTEC® is a registered trademark of Ethyl Corporation.
It is preferred that the sulfurized fatty oil is selected from the group consisting of sulfurized corn oil, sulfurized canola oil, sulfurized cottonseed oil, sulfurized grapeseed oil, sulfurized olive oil, sulfurized palm oil, sulfurized peanut oil, sulfurized coconut oil, sulfurized rapeseed oil, sulfurized sesame seed oil, sulfurized soybean oil, sulfurized sunflower seed oil, sulfurized tallow, sulfurized fish oil including herring oil and sardine oil, ADDITIN R 4410, ADDITIN R 4412-F, ADDITIN R 4417, ADDITIN RC 2515, ADDITIN RC 2526, ADDITIN RC 2810-A, ADDITIN RC 2814-A, ADDITIN RC 2818-A, and combinations thereof. ADDITIN® is a registered trademark of Rhein Chemie Corporation.
It is preferred that the ashless dialkyldithiocarbamate have a concentration sufficient to provide from about 150 to 2500 ppm of sulfur in the lubricating composition. It is further preferred that the ashless d
Esche, Jr. Carl K.
Gatto Vincent J.
Lam William Y.
Ethyl Corporation
Howard Jacqueline V.
Rainear Dennis H.
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