Combination of a sulfur compound and specific phosphorus...

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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C508S291000, C508S433000, C508S435000, C508S441000, C508S569000, C568S021000

Reexamination Certificate

active

06489271

ABSTRACT:

TECHNICAL FIELD OF THE INVENTION
This invention relates to the combination of a sulfur compound and specific phosphorus compounds. The invention also relates to lubricating compositions, concentrates and grease containing the combination.
BACKGROUND OF THE INVENTION
Lubricating compositions are used to prevent damage to machinery under operating conditions. Especially under boundary lubrication conditions, a lubricant must act to minimize harmful metal-to-metal contact. Often additives are useful at providing protection under boundary lubricating condition but sometimes these additive adversely affect other performance characteristics. For instance, a lubricant must still provide protection under high speed, shock loading condition, while not be corrosive to copper and other soft metals.
It is desirable to have a combination of additives which provide extreme pressure protection with out sacrificing other performance characteristics. A combination of additives is desired which will provide good extreme pressure properties to lubricants, which maintain the other parameters required of industry standards, such as API GL-5 and MIL-L2105D gear lubricant requirements.
SUMMARY OF THE INVENTION
This invention relates to a lubricating composition comprising a major amount of an oil of lubricating viscosity and (a) a extreme pressure improving amount of at least one sulfur compound, and an antiwear or an extreme pressure improving amount of the combination of (b) at least one ammonium salt of a phosphoric acid ester, (c) at least one phosphite, and (d) at least one thiophosphate or at least one reaction product of a phosphite and sulfur or a source of sulfur. The invention also relates to concentrates and greases containing the combination of the sulfur compound and the specific phosphorus compounds.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The term “hydrocarbyl” includes hydrocarbon as well as substantially hydrocarbon groups. Substantially hydrocarbon describes groups which contain heteroatom substituents that do not alter the predominantly hydrocarbon nature of the substituent. Examples of hydrocarbyl groups include the following:
(1) hydrocarbon substituents, i.e., aliphatic (e.g., alkyl or alkenyl) and 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 which, 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 which 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, for example, 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 heteroatom substituent will be present for every ten carbon atoms in the hydrocarbyl group. Typically, there will be no such heteroatom substituents in the hydrocarbyl group. Therefore, the hydrocarbyl group is hydrocarbon.
As described above the lubricating compositions, concentrates, and grease contain a combination of (a) at least one sulfur compound and at least one mixture comprising (b) an ammonium salt of a phosphoric acid ester, (c) a phosphite, and (d) a thiophosphate or a reaction product of a phosphite and sulfur or a source of sulfur. In one embodiment, the sulfur compound (a) is present at concentrations in the range from about 0.1% to about 10% by weight, or preferably from about 0.2% up to about 8%, or more preferably from about 0.3% up to about 7%, more preferably from about 0.5% to about 5% by weight. Here, as well as elsewhere in the specification and claims, the range and ratio limits may be combined.
Sulfur Compounds
The sulfur compounds include mono- or polysulfide compositions, or mixtures thereof. The sulfur compounds are generally characterized as having sulfide linkages containing an average from 1 up to about 10, or from about 2 up to about 8, or from about 3 up to about 4 sulfur atoms. In one embodiment, the sulfur compound is a mixture of di-, tri- or tetrasulfide materials, preferably having a majority of trisulfide. Materials having at least 70% trisulfide are preferred, with materials containing greater than 80% trisulfide more preferred.
In one embodiment, the sulfur compound is prepared by sulfurizing unsaturated compounds. Materials which may be sulfurized include oils, unsaturated fatty acids, unsaturated fatty esters, olefins, terpenes, or Diels-Alder adducts. Oils which may be sulfurized are natural or synthetic oils, including mineral oils, lard oil, carboxylic acid esters derived from aliphatic alcohols and fatty acids or aliphatic carboxylic acids (e.g., myristyl oleate and oleyl oleate), and synthetic sperm whale oil substitutes and synthetic unsaturated esters or glycerides.
The unsaturated fatty acids generally contain from about 8 to about 30, or from about 12 to about 24 carbon atoms. Examples of unsaturated fatty acids include palmitoleic acid, oleic, linoleic, linolenic, erucic acid, lard oil acid, soybean oil acid, tall oil and rosin acid.
The unsaturated fatty esters include fatty oils, that is, naturally occurring or synthetic esters of glycerol and one or more of the above fatty acids. Examples of fatty esters include animal fats, such as Neat's-foot oil, lard oil, depot fat, beef tallow, and vegetable oils, including cottonseed oil, corn oil, safflower oil, sesame oil, soybean oil, and sunflower seed oil. The unsaturated fatty esters also may be prepared by esterifying alcohols and polyols with a fatty acid. The alcohols include the above described mono- and polyhydric alcohols, such as methanol, ethanol, propanol, butanol, ethylene glycol, neopentyl glycol, and glycerol.
The olefins, which may be sulfurized, contain at least one olefinic double bond, which is defined as a non-aromatic double bond. In its broadest sense, the olefin may be defined by the formula R
*1
R
*2
C═CR
*3
R
*4
, wherein each of R*l, R*, R*
3
, and R*
4
is hydrogen, or an hydrocarbyl group. In general, the R* groups in the above formula which are not hydrogen may be represented by —(CH
2
)
n
—A, wherein n is a number from 0 to about 10 and A is represented by —C(R
*5
)
3
, —COOR
*5
, —CON(R
*5
)
2
, —COON(R
*5
)
4
, —COOM, —CN, —X, —YR
*5
or —Ar, wherein: each R
*5
is independently hydrogen, or a hydrocarbyl group, with the proviso that any two R
*5
groups may be connected to form a ring of up to about 12 carbon atoms; M is one equivalent of a metal cation (preferably Group I or II, e.g., sodium, potassium, barium, or calcium); X is halogen (e.g., chloro, bromo, or iodo); Y is oxygen or divalent sulfur; Ar is an aromatic group of up to about 12 carbon atoms.
The olefinic compound is usually one in which each R group which is not hydrogen is independently alkyl, alkenyl or aryl group, preferably an alkyl group. In one embodiment, R
*3
and R
*4
are hydrogen and R
*1
and R
*2
are alkyl or aryl, especially alkyl, having from 1 up to about 30, or from 1 up to about 16, or from 1 up to about 8 carbon atoms. Olefins having from 2 up to about 30, or from about 3 up to about 16 (most often less than about 9) carbon atoms are particularly useful. Olefins having from 2 up to about 8, or from 2 up to about 4 carbon atoms are particularly useful. Isobutene, propylene and their dimers, trimers and tetramers, and mixtures thereof are esp

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