Molybdenum, sulfur and boron containing lubricating oil...

Solid anti-friction devices – materials therefor – lubricant or se – Lubricants or separants for moving solid surfaces and... – Organic compound containing boron

Reexamination Certificate

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C508S230000, C508S363000, C508S364000, C508S365000, C508S371000, C508S375000

Reexamination Certificate

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06777378

ABSTRACT:

TECHNICAL FIELD
This invention relates to molybdenum, sulfur and boron containing lubricating oil compositions. More particularly, this invention relates to a lubricating oil composition containing a molybdenum and sulfur containing composition, a boron-containing compound, and optionally a phosphorus containing compound provided the amount of phosphorus does not exceed about 0.10% by weight.
BACKGROUND OF THE INVENTION
For more than 40 years, zinc dialkyl dithiophosphates (ZDDP) have been used as antiwear and antioxidant additives in engine lubricating oil compositions. During this period typical concentrations of phosphorus contributed to the lubricating oil compositions by these compounds exceeded 0.10% by weight. However, ILSAC GF-3 requirements limit the amount of phosphorus that can be used in a lubricating oil composition to a maximum concentration of 0.10% by weight, and it is believed that GF-4 may limit the amount of phosphorus to a maximum concentration of 0.05% by weight. The problem therefore is to provide for a reduction in the amount of phosphorus-containing additives used in these lubricating oil compositions and yet provide the lubricating oil with required antiwear and antioxidant properties.
The use of molybdenum and sulfur containing compositions in lubricating oil compositions as antiwear agents and antioxidants is known. U.S. Pat. No. 4,285,822 discloses lubricating oil compositions containing a molybdenum and sulfur containing composition prepared by (1) combining a polar solvent, an acidic molybdenum compound and an oil-soluble basic nitrogen compound to form a molybdenum-containing complex and (2) contacting the complex with carbon disulfide to form the molybdenum and sulfur containing composition.
The replacement of part of the ZDDP in a lubricating oil composition with a molybdenum and sulfur containing composition of the type described in the above-mentioned patent provides the advantage of restoring antiwear and antioxidant properties lost with the reduction in ZDDP. However, a problem with these compositions is that they fail to pass the required GF-3/GF-4 Sequence VIII Bearing Corrosion Engine Test. This problem has been overcome with the present invention.
SUMMARY OF THE INVENTION
This invention relates to a lubricating oil composition, comprising:
(A) a base oil;
(B) a molybdenum and sulfur containing composition derived from a basic nitrogen containing compound, a molybdenum compound and carbon disulfide;
(C) a boron-containing compound selected from the group consisting of:
(C-I) a borated ester represented by one or more of the formulae
 wherein in formulae (C-I-1), (C-I-2) and (C-I-3), each R is independently a hydrocarbon group and any two adjacent R groups may together form a cyclic group;
(C-II) at least one borated epoxide comprising the product made by reacting a boron reactant with one or more epoxides represented by the formula
 wherein in formula (C-II-1) each R is independently hydrogen or a hydrocarbon group and any two adjacent R groups may together form a cyclic group, with the proviso that when a single epoxide is used the total number of carbon atoms in the R groups does not exceed about 12, and when a mixture of epoxides is used the average on a mole basis for the total number of carbon atoms in the R groups for the mixture does not exceed about 12; and
(C-III) mixture of (C-I) and (C-II); and
(D) optionally a phosphorus containing compound provided the phosphorus content of the lubricating oil composition does not exceed about 0.10% by weight.
DETAILED DESCRIPTION OF THE INVENTION
The terms “hydrocarbon” and “hydrocarbyl” when referring to a group having a carbon atom directly attached to the remainder of a molecule denote a group having a hydrocarbon or predominantly hydrocarbon character within the context of this invention. These groups include the following:
(1) Purely hydrocarbon groups; that is, aliphatic, (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl or cycloalkenyl), aromatic, aliphatic- and alicyclic-substituted aromatic, aromatic-substituted aliphatic and alicyclic groups, and the like, as well as cyclic groups wherein the ring is completed through another portion of the molecule (that is, any two indicated substituents may together form an alicyclic group). Examples include methyl, ethyl, octyl, cyclohexyl, phenyl, etc.
(2) Substituted hydrocarbon groups; that is, groups containing non-hydrocarbon substituents which do not alter the predominantly hydrocarbon character of the group. Examples include hydroxy, nitro, cyano, alkoxy, acyl, etc.
(3) Hetero groups; that is, groups which, while predominantly hydrocarbon in character, contain atoms other than carbon in a chain or ring otherwise composed of carbon atoms. Suitable hetero atoms include, for example, nitrogen, oxygen and sulfur.
In general, no more than about three substituents or hetero atoms, and in one embodiment no more than one, will be present for each 10 carbon atoms in the hydrocarbyl group.
The term “lower” as used herein in conjunction with terms such as hydrocarbyl, alkyl, alkenyl, alkoxy, and the like, is intended to describe such groups which contain a total of up to 7 carbon atoms.
The term “oil-soluble” refers to a material that is soluble in mineral oil to the extent of at least about one gram per liter at 25° C.
The term “TBN” refers to total base number. This is the amount of acid (perchloric) needed to neutralize a material's basicity, expressed as milligrams of KOH per gram of sample.
The term “TAN” refers to total acid number. This is the amount of base (potassium hydroxide orsodium hydroxide) needed to neutralize a material's acidity, expressed as milligrams of KOH per gram of sample.
The Lubricating Oil Composition.
The inventive lubricating oil composition may be comprised of a major amount of base oil. The base oil may be present in an amount greater than about 50% by weight, and in one embodiment greater than about 60%, and in one embodiment greater than about 70%.
The inventive lubricating oil composition may have a viscosity of up to about 17 cSt at 10° C., and in one embodiment about 5 to about 17 cSt at 10° C., and in one embodiment about 6 to about 13 cSt at 100° C.
The inventive lubricating oil composition may have an SAE Viscosity Grade of 0W, 0W-20, 0W-30, 0W-40, 0W-50, 0W-60, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W-30, 10W-40, 10W-50, 10W-60, 15W-30, 15W-40, 15W-50, 20W, 20W-50, or 30W.
The inventive lubricating oil composition may have a molybdenum content of about 25 to about 800 parts per million (ppm), and in one embodiment about 50 to about 700 ppm, and in one embodiment about 100 to about 600 ppm.
The inventive lubricating oil composition may have a sulfur content of about 0.02 to about 1.3% by weight, and in one embodiment about 0.07 to about 0.8% by weight, and in one embodiment about 0.1 to about 0.5% by weight.
The inventive lubricating oil composition may have a boron content of about 30 to about 600 ppm, and in one embodiment about 35 to about 400 ppm, and in one embodiment about 40 to about 200 ppm.
The inventive lubricating oil composition may have a phosphorus content of up to about 0.10% by weight, and in one embodiment up to about 0.09% by weight, and in one embodiment up to about 0.08% by weight, and in one embodiment up to about 0.075% by weight, and in one embodiment up to about 0.07% by weight, and in one embodiment up to about 0.06% by weight, and in one embodiment up to about 0.05%.
The ash content of the inventive lubricating oil composition as determined by the procedures in ASTM D-874-96 may be in the range up to about 1.2% by weight, and in one embodiment up to about 1.1% by weight, and in one embodiment from about 0.3 to about 1.2% by weight, and in one embodiment about 0.3 to about 1.1% by weight, and in one embodiment about 0.3 to about 1.0% by weight, and in one embodiment about 0.5 to about 1.0% by weight.
The inventive lubricating oil composition may have a chlorine content of up to about 100 ppm, and in one embodiment up to about 80 ppm, and in o

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