Lubricating compositions with good thermal stability and...

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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C508S272000, C508S282000, C508S435000, C508S436000, C508S569000

Reexamination Certificate

active

06573223

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to lubricating compositions that are useful as industrial or automotive gear lubricants. These compositions provide antiwear/extreme-pressure protection, thermally stability, and have good demulsifying properties.
BACKGROUND OF THE INVENTION
For gear assemblies in the automotive and industrial gear areas, one major problem for lubricating compositions is providing antiwear and extreme-pressure protection. Each of these different type gear assemblies pose a different wear problem for lubricants. When a single lubricant provides protection for both these areas, it is known as a Universal gear oil. It is difficult to provide a lubricating composition that can provide protection to both the automotive gear assembly, with it high shearing and shock loading wear problems, and industrial gear assemblies that have rolling wear from it spur gears.
In addition to antiwear and extreme pressure protection as well as stability, including oxidation and thermal stability issues, lubricating compositions in the universal gear oils such as those used in the automotive and industrial gear oil areas must provide protection for the soft metal components of the gears. These soft metal components are typically copper and brass related components of the equipment. Traditionally copper deactivators have been added to prevent adverse effects of the lubricating composition, especially the organic polysulfides on the copper and soft metal components. Triazoles have been used as one of these additives. However, triazoles adversely effect the lubricating composition's ability to provide protection under shock-loading conditions such as those measured in the SAE L-42 test.
Cleanliness is a measure of the stability of the lubricant and is measured as results in the SAE L-60-1 test. At automotive gear oil treatment levels, the lubricant must provide a level of cleanliness acceptable in these tests. One approach for controlling cleanliness in an engine is to provide a dispersant to the lubricating compositions. The dispersant acts to suspense sludge and soot particles and emulsify the lubricating compositions.
It is difficult for lubricant formulators to provide an additive combination that is effective as a universal lubricant in both automotive and industrial gears. Additionally, it is difficult to provide additive combinations that provide the antiwear and extreme-pressure protection and have thermal stability without adversely effecting demulsibility properties of the lubricants. Further, it is difficult to provide protection for copper and soft metal components without adversely effecting the lubricant's ability to provide shock-loading protection. It is desirable to find a combination of additives that can provide performance under these various conditions.
SUMMARY OF THE INVENTION
The invention relates to a lubricating composition comprising: (a) at least one sulfur-free hydrocarbyl phosphoric acid ester or salt, (b) at least one sulfur-containing hydrocarbyl phosphoric acid or salt, (c) an organic polysulfide, (d) at least one dispersant, and (e) at least one triazole metal deactivator. The composition may also include a thiadiazole derivative. This additive combination provides good antiwear and thermal stability properties, even under severe thermal conditions. These compositions also have good demulsibility properties.
The above combination of additives provides the antiwear and extreme-pressure protection necessary for automotive and industrial gear applications. These additives additionally provide this protection without adversely effecting demulsibility properties of the lubricant.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The term “hydrocarbyl” includes hydrocarbon as well as substantially hydrocarbon groups. Substantially hydrocarbon describes groups that contain heteroatom substituents that do not alter the predominantly hydrocarbon nature of the group. Examples of hydrocarbyl groups include the following:
(1) hydrocarbon substituents, i.e., aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, aromatic-, aliphatic- and alicyclic-substituted aromatic substituents and the like as well as cyclic substituents wherein the ring is completed through another portion of the molecule (that is, for example, any two indicated substituents may together form an alicyclic radical);
(2) substituted hydrocarbon substituents, i.e., those substituents containing non-hydrocarbon groups that, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent; those skilled in the art will be aware of such groups (e.g., halo (especially chloro and fluoro), hydroxy, mercapto, nitro, nitroso, sulfoxy, etc.);
(3) heteroatom substituents, i.e., substituents that will, while having a predominantly hydrocarbon character within the context of this invention, contain an atom other than carbon present in a ring or chain otherwise composed of carbon atoms (e.g., alkoxy or alkylthio). Suitable heteroatoms will be apparent to those of ordinary skill in the art and include, e.g., sulfur, oxygen, nitrogen and such substituents as, e.g., pyridyl, furyl, thienyl, imidazolyl, etc.
In general, no more than about 2, preferably no more than one, hetero substituent will be present for every 10 carbon atoms in the hydrocarbyl group. Typically, there will be no such heteroatom substituents in the hydrocarbyl group. Therefore, the hydrocarbyl group is purely hydrocarbon.
In the specification and appended claims, the term “lubricating composition” refers to the combination of an oil of lubricating viscosity plus additives. The percentages of components are by weight are based on the total amount of the additive and the oil of lubricating viscosity. If not specifically stated, the oil of lubricating viscosity makes up the balance of the lubricating composition.
The lubricating compositions have two phosphorus antiwear agents. The antiwear and/or extreme pressure properties are provided by the combination of the sulfur-free and sulfur-containing phosphoric acid esters. The phosphoric acid esters are each independently present in an amount from about 0.05% to about 5%, or from about 0.08% to about 3%, or from about 0.1% to about 1% by weight. In one embodiment, the lubricating composition is an automotive gear oil. In this embodiment the phosphoric acid ester are each independently present in an amount from about 0.05% to about 5%, or from about 0.07% to about 3%, or from about 0.1% to about 1% by weight. In another embodiment, the lubricating composition is an industrial gear oil. In this embodiment, the phosphoric acid esters are each independently present in an amount from about 0.01% to about 1%, or from about 0.05% to about 0.7%, or from about 0.8% to about 0.5% by weight. Here and elsewhere in the specification and claims, range and ratio limits may be combined. In one embodiment, the phosphorus esters are present in a weight ratio from about 0.5 to about 2, or from about 0.75 to about 1.5 or from about 1 part sulfur-free phosphoric acid ester to 1 part of sulfur-containing phosphoric acid ester.
Sulfur-free Phosphoric Acid Esters
The sulfur-free phosphoric acid esters are those lacking a sulfur phosphorus bond. These esters are, in one embodiment, free of sulfur atoms. These esters at present at an amount to provide antiwear and/or extreme pressure properties to the lubricating composition.
The sulfur-free phosphoric acid ester may be prepared by reacting one or more sulfur-free phosphorus acids or anhydrides with one or more alcohols containing from 1 to about 30, or from 2 to about 24, or from about 3 to about 12 carbon atoms. The phosphorus acid or anhydride is generally an inorganic phosphorus reagent, such as phosphorus pentoxide, phosphorus trioxide, phosphorus tetroxide, phosphorous acid, phosphoric acid, phosphorus halide, or one or more C1-7 phosphorus esters. The alcohols generally contain from one to about 30, or from two to about 24, or from about 3 to about 12, or up to about 8 carb

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