Low ash lubricant compositions containing multiple overbased...

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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C508S293000, C508S398000, C508S460000, C508S542000, C508S563000, C508S584000, C508S585000, C508S435000

Reexamination Certificate

active

06596672

ABSTRACT:

BACKGROUND OF THE INVENTION
The present invention relates to lubricating oil compositions and concentrates therefore which provide low sulfated ash while maintaining high performance standards.
There is continuous need for improving the performance characteristics of gasoline and diesel engines, stationary gas engines, and the lubricating oils used therein. For example, modern diesel engines are sometimes fitted with a particulate trap to minimize the amount of particulates which are emitted to the atmosphere as pollution. Such particulates may include soot from incomplete combustion but also include ash of various types, much of which is non-volatile metal compounds originating from metal-containing additives in the fuel or, especially, in the lubricant. Excessive ash buildup in particulate traps is a concern because certain types of metal-containing ash are not readily removed from the trap, thus making the regeneration and reuse of such traps difficult if not impossible. Likewise, stationary gas engines (typically large, heavy duty, stationary engines designed to run on natural gas and other like fuels) are facing changes. Trends in such engines include the development of smaller four-cycle, lean burning engines, for which low ash, high performance lubricants are important.
Despite the drawbacks from the use of metal compounds in lubricants, additives, including metal-containing additives, have been used for many years and will likely continue to be used for many years in the future. This is because metal-containing additives perform essential functions in motor oils and other lubricants. Certain metal salts are detergents, which serve to neutralize acidic combustion products which make their way into motor oil. Others are dispersants or antiwear agents. To simply reduce or eliminate the amount of metal-containing additives from a motor oil would lead to failure of the oil in many industry-mandated performance tests.
There are industrial performance criteria which must be met for a variety of lubricant applications. Among the most important are those for diesel engines, gasoline engines, stationary gas engines, and marine diesel engines. A useful lubricating oil will be able to pass the tests for one or more types of engines.
There has been a great deal of research reported on various lubricant formulations to solve specific problems. For example, U.S. Pat. No. 5,259,967, Ripple, Nov. 9, 1993, discloses a lubricating oil composition providing less than 1% sulfated ash, comprising an additive package of a carboxylic dispersant, a rust inhibiting mixture, a hydrocarbyl substituted phenol, and a neutralized acid or phenol.
U.S. Pat. Nos. 5,102,566 and 5,320,765, Fetterman, Jr., et al., Apr. 7, 1992 and Jun. 14, 1994, disclose low sulfated ash lubricating oil compositions for, e.g., natural gas fueled engines. The additives include at least about 2 wt. % of at least one ashless nitrogen- or ester-containing dispersant, an antioxidant, and at least one oil soluble dihydrocarbyl dithiophosphate antiwear material. Other materials which can be present include metal detergent inhibitors such as mixtures of Ca and Mg salts of one or more organic sulfonic acids. The antioxidant can be a variety of materials including 4,4′-methylenebis(2,6-di-tert-butylphenol). Examples include compositions of PIBSA-PAM dispersant, sulfurized nonyl phenol, zinc dialkyl dithiophosphate, overbased Mg sulfonate detergent inhibitor, VI improver, and base oil, ash being about 0.5.
U.S. Pat. No. 5,326,485, Cervenka et al., Jul. 5, 1994, discloses low ash lubricating oil compositions, employing certain specified types of zinc dialkyl dithiophosphates in combination with certain types of auxiliary additive components, including an oil-soluble hindered phenolic antioxidant or an aromatic secondary amine or a combination of them, and an overbased alkaline earth metal sulfurized alkyl phenate or alkyl aromatic sulfonate or a combination of them. Ca, Mg, Sr, or Ba materials can be used.
U.S. Pat. No. 4,528,108, Grover, Jul. 9, 1985, discloses a coolant fluid composition comprising a lubricating oil and one or more basic metal salts of organic acids, one or more phosphorus-containing metal salts, and one or more phenol antioxidants. Salts containing a mixture of ions of two or more metals can be used.
U.S. Pat. No. 5,164,102, Everett et al., Nov. 17, 1992, discloses motor oil containing a combination of (i) an overbased alkaline earth metal sulfonate, (ii) a zinc dihydrocarbyl dithiophosphate and other components. The composition can contain an ashless dispersant selected from polyolefin-substituted succinamides or imides of polyethylene polyamines and certain boronated materials.
U.S. Pat. No. 4,647,287, Muir, Mar. 3, 1987, discloses a lubricating oil containing a succinic anhydride promoter reaction product for an overbased magnesium sulfonate. Copromoters such as a salicylic acid may be employed.
U.S. Pat. No. 4,617,135, Muir, Oct. 14, 1986, discloses a process for the preparation of overbased magnesium sulfonates which includes the use of a sulfonic acid or salt thereof and e.g. a hydroxyaromatic carboxylic acid.
U.S. Pat. No. 3,385,791, Colyer et al., May 28, 1968, discloses a lubricant oil composition containing oil-soluble nitrogen- and boron-containing dispersant detergent, oil soluble calcium or magnesium sulfonate of high alkalinity, and oil-soluble zinc dialkyldithiophosphates. Sulfated ash of the compositions in the examples is 1.0%.
U.S. Pat. No. 4,981,603, Demange, Jan. 1, 1991, discloses a method for preparing lubricating oil additive concentrates in which dispersant and overbased detergent have improved compatibility. The detergent is a basic magnesium-containing detergent. Dispersants are selected from, nitrogen containing ashless dispersants such as succinimide dispersants. The succinimide can be post treated with boron.
U.S. Pat. No. 3,254,025, Le Suer, May 31, 1966, discloses lubricating compositions containing boron-containing acylated amines. Other additives include ash-containing detergents.
U.S. Pat. No. 2,944,970, Peterson, Jul. 12, 1960, discloses grease compositions containing salicylic acid derivatives.
U.S. Pat. No. 4,088,587, Lowe, May 9, 1978, discloses lubricating oil additive compositions including an antioxidant selected from oil-soluble sterically hindered phenols or thio phenols, succinimide dispersants, etc. Lubricants can be used in a natural gas engine.
There has now been found a lubricating oil composition which is significantly reduced in ash-forming additives but which still meets demanding performance requirements for a variety of engines, and, in particular, stationary gas engines.
SUMMARY OF THE INVENTION
The present invention provides a composition comprising: (a) a major amount of an oil of lubricating viscosity; (b) a calcium, barium, or strontium overbased acidic material in an amount to contribute 0.01 to 0.79 percent sulfated ash; (c) a magnesium or sodium overbased acidic material in an amount to contribute 0.01 to 0.79 percent sulfated ash; (d) about 0.1 to about 1.5 percent by weight of an alkylene-coupled hindered phenol antioxidant; (e) about 0.1 to about 6 percent by weight of at least one antioxidant other than an alkylene-coupled hindered phenol antioxidant; provided that components (d) and (e) together comprise at least about 0.5 percent by weight of the composition; and (f) at least about 0.2 percent by weight of a dispersant; further provided that the composition has a total sulfated ash content of about 0.1 percent to about 0.8 percent.
The invention further provides a composition comprising (a) a concentrate-forming amount of an oil of lubricating viscosity; (b) a calcium, barium, or strontium overbased acidic material; (c) a magnesium or sodium overbased acidic material; (d) about 1 to about 15 parts by weight of an alkylene-coupled hindered phenol antioxidant; (e) about 1 to about 60 parts by weight of at least one antioxidant other than an alkylene-coupled hindered phenol antioxidant; provided that components (d) and (e) together comprise at

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