JPH06200281A - Grease composition - Google Patents

Abstract

This invention relates to improved grease compositions comprising a major amount of an oil based simple metal soap thickened base grease and a minor amount of at least one phosphorus and boron containing composition, said phosphorus and boron containing composition prepared by reacting a combination of (A) at least one boron compound and (B) at least one phospholipid. In one embodiment, the phosphorus and boron containing composition is present in amounts sufficient to improve the extreme pressure, antiwear and lubricity properties of the base grease. In another embodiment the phosphorus and boron containing composition is present in amounts sufficient to increase the dropping point of the base grease, as determined by ASTM procedure D-2265, by at least 20 DEG C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a grease composition. More particularly, the invention relates to metal soap thickened base greases containing certain boron and phosphorus containing property improving additives.

[0002]

The need for humankind to reduce friction dates back to ancient times. In the early 1400 BC, both sheep fat and beef fat (tallow) were used to reduce axle friction in wagons.

By the mid 1800's, lubricants were still predominantly sheepskin and beef tallow, with some types of vegetable oils becoming more prevalent. However, in 1859, Colonel Drake dug the first well. Since this time, most lubricants, including grease, are based on petroleum (“mineral”) oils, but synthetic oil-based lubricants have also been used for special applications.

NLGI Lubricating Grease Guide , ^C 1987
(Nati of Kansas City, Missouri, USA
(available from onal Lubricating Grease Institute)
Describe in detail greases containing various types of thickeners. Such thickeners include metal soaps, complex metal salt-metal soaps and non-soaps.

Metal soap thickened greases provide typical performance. The performance of greases can be enhanced by mixing various types of additives. AC Wit
te) Lubrication (Volume 77, Issue 1, Texac
Inc.), White Plains, New York (1991),
(Pages 2-3), there is a discussion of additives for grease,
These additives include antioxidants, rust and corrosion inhibitors, EP (extreme pressure) additives, antiwear additives, lubricants, tackifiers and fillers.

Drop point is one measure of the thermal stability of grease. One way to increase the dropping point of base greases is to use simple metal soap greases with some acids (typically carboxylic acids such as acetic acid, α-ω dicarboxylic acids, and some aromatic acids). May be converted into a complex grease by mixing with. This additional step necessarily consumes a considerable amount of time, which results in reduced productivity.

Doner et al. In a series of US patents, particularly the following US patents, teach the use of certain boron-containing compounds to increase the thickening of metal salt thickened base greases. No .: No. 5,084,194 No. 5,068,045 No. 4,961,868
No. 4,828,734 No. 4,828,732 No. 4,781,850
No. 4,780,227 No. 4,743,386 No. 4,655,948
Other additives contemplated for use with boron-containing compounds by donors are phosphorus and sulfur-containing materials, especially zinc dithiophosphate.

[0008]

SUMMARY OF THE INVENTION The present invention is an improved grease composition containing a major amount of an oil-based simple metal soap thickening base grease and a minor amount of at least one phosphorus and boron containing composition. The phosphorus- and boron-containing composition comprises (A) at least one boron-containing compound,
(B) Prepared by reacting a formulation with at least one phospholipid. In one embodiment, the phosphorus and boron containing composition comprises the extreme pressure properties of the base grease,
Present in an amount sufficient to improve wear resistance and lubricity. In another embodiment, the phosphorus and boron containing composition is present in an amount sufficient to increase the dropping point of the base grease as determined by ASTM procedure D-2265 by at least 20 ° C.

The grease of the present invention is a mechanical element (for example,
It is useful for lubricating, sealing and protecting gears, axles, bearings, shafts, hinges, etc.). Such mechanical elements include automobiles, trucks, bicycles, steel mills, mining equipment, railroad equipment including vehicles, aircraft,
Found in boats, construction equipment, and many other types of industrial machinery and consumables.

To meet the requirements of these and other applications, greases provide, to varying degrees, lubricity, extreme pressure properties and wear resistance, and, depending on the application, a suitable thermal stability. Must be given the property (heat resistance).

[0011]

DETAILED DESCRIPTION OF THE INVENTION This application is a continuation-in-part application of Co-pending Application No. 07 / 687,271 filed April 18, 1991, the contents of which are hereby incorporated by reference in its entirety. .

The grease composition of the present invention is an improved grease composition containing a major amount of an oil-based simple metal soap thickening base grease and a minor amount of at least one phosphorus and boron containing composition. The phosphorus and boron containing composition is prepared by reacting a blend of (A) at least one boron containing compound and (B) at least one phospholipid.

In a preferred embodiment, the phosphorus- and boron-containing composition comprises a boron-containing compound (A), a phospholipid (B), an amine (C) and an acylated nitrogen-containing compound.
(D), carboxylic acid ester (E), Mannich reaction product
It is prepared by reacting with (F), the basic nitrogen-containing polymer (G) or a mixture of the organic acid with a neutral metal salt or a basic metal salt (H).

In a preferred embodiment, the phosphorus and boron containing composition is an acylation having a boron containing compound (A), an amine (C) and a substituent containing an average of up to about 40 carbon atoms. Nitrogen-containing compound (D), carboxylic acid ester (E), Mannich reaction product (F), basic nitrogen-containing polymer (G), or neutral or basic metal salt of organic acid (H) Reacting to form an intermediate, then
It is prepared by reacting the intermediate with a phospholipid (B).

The grease composition of the present invention also increases the dropping point of major amounts of oil-based simple metal soap thickened base greases and, in small amounts, base greases determined by ASTM method D-2265 by at least 20 ° C. Is an improved grease composition containing a sufficient amount of at least one phosphorus- and boron-containing composition, the phosphorus- and boron-containing composition comprising (A) at least one boron-containing compound; B) Prepared by reacting a formulation with at least one phospholipid.

The method of the present invention is a method of increasing the dropping point of an oil-based simple metal soap thickened base grease measured by ASTM method D-2265 by at least about 20 ° C., (A)
At least one boron-containing compound and (B) at least 1
A composition containing phosphorus and boron, prepared by reacting a formulation with a seed phospholipid, is added to a base grease in a small amount to achieve a dropping point of at least 20 of the base grease, based on the total weight of the grease composition. Adding in an amount sufficient to raise the temperature by ° C.

The extreme pressure capability of the grease allows it to function under high load conditions (especially critical conditions). Typically, base greases cannot provide adequate extreme pressure properties without additives that improve extreme pressure properties.

Lubricating greases likewise provide protection against unwanted wear of the lubricated parts. Chemical additives are often used to enhance the antiwear performance of base greases.

Oil-based greases inherently provide some degree of lubricity. The lubricity of the base grease is
It can be enhanced by admixing certain lubricity improving additives.

These characteristics are characterized by well-known tests, such as the Timken OK Load test (ASTM D-250).
9), Shell 4-Ball test (for example, AST
M D-2596) and other tests).

The heat resistance of grease is measured in a number of ways. One of the evaluation criteria of heat resistance is a dropping point. Greases typically do not have a well-defined melting point, but rather soften until they no longer function as a thickening lubricant. The American Society for Testing and Materials
(Race Street, Philadelphia, PA, 1916) presented an ASTM D-2265 test method that provides a means for measuring grease drop point.

Generally, the dropping point of grease is the temperature at which the grease changes from a semi-solid state to a liquid state under the test conditions. Drop point is the temperature at which the first drop of material falls from the test cup used in the container used in ASTM Method D-2265.

For many applications, simple metal soap thickened base greases are quite desirable. However, for some applications it is desirable to use simple metal soap thickened greases to obtain high heat resistance (as evidenced by the dropping point).

Although complex metal soap greases raise the dropping point, they have many serious drawbacks. The complex thickener contains a non-fatty acid component (eg, benzoic acid, organic dibasic acid, etc.) in addition to the fatty acid component. To form this complex grease,
Typically, an additional step of reacting the non-fatty acid with the simple metal soap is included, and long heating times are required,
Occasionally, it takes several times the time required to prepare a simple metal soap thickened grease. Therefore, it would be desirable to provide a means for preparing simple metal soap thickened grease compositions having drop points close to or higher than those of complex greases.

Therefore, it is one of the objects of the present invention to provide a novel grease composition.

A further object of the present invention is to provide a grease composition having beneficial properties.

Another object of the present invention is to provide a grease composition having improved extreme pressure properties, wear resistance and lubricity.

Yet another object of the present invention is ASTM Method D-22.
It is to provide a grease composition having improved thermal stability as indicated by the increase in dropping point measured by 65.

Yet another object of the present invention is to provide a grease composition having improved thermal stability without the need for additional processing steps.

Other objects will become apparent to those skilled in the art after reading this specification and the description of the invention.

In one embodiment, the grease composition of the present invention exhibits improved extreme pressure properties when compared to the base grease. In another embodiment, the grease composition exhibits improved wear resistance, and in yet another embodiment, improved lubricity.

The grease composition of the present invention may also exhibit a drop point that is at least 20 ° C. higher than the drop point of the corresponding oil-based simple metal soap thickened base grease. This advantage is found in simple metal soap thickened base greases, as per ASTM Method D-
It is obtained by mixing sufficient amounts of certain of the above boron and phosphorus containing compositions to raise the drop point of the corresponding base grease measured by 2265 by at least about 20 ° C.

Frequently, the base grease is mixed with the boron- and phosphorus-containing compositions described herein to improve two or more of the above properties.

Greases are often exposed to water. Therefore, it is desirable for general purpose greases to be substantially free of components that are easily adversely affected by water.

Many boron-containing compounds are water-sensitive and are water soluble or leach from grease into water?
It is either easily hydrolyzed to give an undesired hydrolysis product, or is sensitive to hydrolysis products that readily leach into water. Surprisingly, the phosphorus- and boron-containing compositions used in the grease compositions of the present invention do not exhibit undesired water sensitivity.

Greases are typically prepared by thickening an oil basestock. The grease in the present invention is an oil base. That is, the grease contains oil thickened with a metal soap thickener.

The grease composition of the present invention uses an oil having a lubricating viscosity. Oils of lubricating viscosity include natural or synthetic lubricating oils and mixtures thereof. Natural oils include animal oils, vegetable oils, mineral oils, solvent-treated or acid-treated mineral oils, and oils derived from coal or shale. For synthetic lubricants,
Hydrocarbon oils, halo-substituted hydrocarbon oils, alkylene oxide polymers, esters of carboxylic acids and polyols, esters of polycarboxylic acids and alcohols, esters of phosphorus-containing acids, polymeric tetrahydrofurans, silicone base oils and mixtures thereof. Included.

Specific examples of oils of lubricating viscosity are described in US Pat. No. 4,326,972 and EP 107,282, the contents of both patents being incorporated herein by reference for their disclosure regarding lubricating oils. Incorporated. A basic and concise description of lubricant base oils is given in an article by DV Brock (Brock) , "Lubricant Base Oils", Lubricant Engineering , 4th.
Volume 3, p.184-185 (March 1987)).
The content of this paper is incorporated herein by reference for disclosure regarding lubricating oils. A description of oils of lubricating viscosity can be found in US Pat. No. 4,582,618 (Davies
s)) (column 2, line 37 to column 3, line 63, inclusive), the contents of which are incorporated herein by reference for disclosure of oils of lubricating viscosity. Has been done.

Other sources of information on the oils used to prepare lubricating greases include NLGI Lubricating Grease
Guide (National Lubricating Grease Institute, Kansas City, Missouri, 1987)
P.1.06-1.09, and AC Witte Lubrica
tion there is (77 Vol, No. 1, Texaco, White Plains, New York (1991), page 2), the contents of both of which are expressly indicated by reference herein.

The simple metal soap thickeners used in the grease compositions of this invention are well known in the art. These metal soaps are typically about 1% to about 30% by weight of the base grease composition, often about 1% to about 15%.
It is mixed in a weight percent amount with a base oil, typically an oil of lubricating viscosity. Often, the amount of metal soap used to thicken the base oil comprises from about 5% to about 25% by weight of the total weight of the base grease. In other cases, the base grease will have from about 2% to about 15% metal soap present.

The particular amount of metal soap required is often
Depends on the metal soap used. The type and amount of metal soap used is often dictated by the desired properties of the grease.

The type and amount of metal soap used is also governed by the desired consistency, which is a measure of how much the grease resists deformation under the application of stress. Viscosity is usually measured by the ASTM cone penetration test (Cone penetr
cation test), ASTM D-217 or ASTM D-1403.

The type and amount of simple metal soap thickener used is well known to those skilled in the grease art. These are substantially neutral metal salts of fatty group-containing acids, as defined herein. NLGI Lubricating Grease Guid
e . p. 1.09-1.11 and above by Wit, Lubri.
Pages 1-2 of cation , pages 3-4 and 7 describe simple metal soap thickeners. The contents of these textbooks are incorporated herein by reference for their disclosure of simple metal soap grease thickeners.

As indicated above, the grease composition of the present invention is oil-based, which includes natural and synthetic oils. Greases can be prepared by adding a thickener or by forming a thickener there.
Manufactured from these oils. Thickeners useful in the greases of this invention include simple metal soaps. By simple metal soap is meant a substantially stoichiometrically neutral metal salt of a fatty acid. Substantially stoichiometrically neutral means that the metal salt is about 90% to about 110%, preferably about 95% to about 100% metal required to prepare the stoichiometrically neutral salt. It is meant to contain about 105%, more preferably about 99% to about 101%.
In a preferred embodiment, the simple metal soap is a fatty carboxylic acid salt.

Fatty acids, as used herein, range from about 8 to.
Defined as a carboxylic acid containing about 24 carbon atoms, preferably about 12 to about 18 carbon atoms. This fatty acid is usually a monocarboxylic acid. Examples of useful fatty acids include capric acid, palmitic acid, stearic acid, and oleic acid. Mixtures of acids are useful. The preferred carboxylic acid is linear. That is, it is substantially free of hydrocarbon branches. Substantially free of hydrocarbon branches means that no more than one hydrocarbon substituent (eg, methyl, ethyl, etc.) is present for each 6 carbon atoms in the linear chain. It means to exist.

Particularly useful acids are hydroxy-substituted fatty acids,
For example, hydroxystearic acid in which one or more hydroxyl groups are located inside the carbon chain, for example, 12-
Examples include hydroxystearic acid and 14-hydroxystearic acid.

Although this soap is a fatty acid salt, it need not be prepared directly from fatty acids, and often is not. Typical grease making methods include fats, which are glycerides or other esters (eg,
Saponification of fatty acid methyl or ethyl esters, preferably methyl esters), which is generally carried out in situ in the base oil from which the grease is produced.

Whether the metal soap, whether fatty acid or ester (eg fat), is prepared, the grease is usually prepared in a grease kettle,
A mixture of base oil, fat, ester or fatty acid and metal-containing reaction components is formed, whereupon soap is formed. Continuous processes are also available. The additives used in this grease are present or may be added during base grease manufacture, but are often added after the base grease is formed.

The metals of the metallic soap are typically alkali metals, alkaline earth metals and aluminum. In a preferred embodiment, the metal soap is an alkali metal soap. In a preferred embodiment, the metal soap is alkaline earth metal soap. For reasons of cost and ease of process, the metal is combined with the fat, ester or fatty acid and basic metal-containing reaction components such as oxides, hydroxides, carbonates and alkoxides (typically , A lower alkoxide, that is, one containing 1 to 7 carbon atoms in the alkoxy group)), to be mixed with the thickener. The soap can also be prepared from the metal itself, but many metals are either too reactive or not fully reactive with fats, esters or fatty acids to successfully carry out the process.

Preferred metals include lithium, sodium, calcium, magnesium, barium and aluminum. Lithium, sodium and calcium are particularly preferred, especially lithium.

Preferred fatty acids include stearic acid, palmitic acid, oleic acid and their corresponding esters, including glycerides (fats). Hydroxy-substituted acids and corresponding esters, including fats, are especially preferred.

These and other thickeners are described in US Pat. Nos. 2,197,263; 2,564,561 and 2,999,066.
And NLGI Lubricating Grease Guide, supra, and Wit's reference, Lubrication , supra, the entire contents of which are incorporated herein by reference for related disclosures of grease thickeners.

Complex greases, such as those containing a metal soap-salt complex (eg, metal soap-acetate, metal soap-dicarboxylate, etc.), are simple metal soap thickening greases as defined herein. Absent.

The phosphorus- and boron-containing composition used in the grease composition of the present invention comprises (A) a boron-containing compound and (B)
It is prepared by reacting a formulation with a phospholipid. The formulation also includes (C) amine, (D) acylated nitrogen compound, (E) carboxylic acid ester, (F) Mannich reaction product, (G) basic nitrogen-containing polymer, or (H) organic acid. Basic metal salts or neutral metal salts of. However, when the acylated nitrogen compound (D) has a substituent having at least 40 carbon atoms on average, the boron-containing compound (A) reacts with the phospholipid (B) to form an intermediate. And the intermediate reacts with (D). These reaction products are useful as additives for oil-based lubricants, including greases. These materials act as antiwear agents, extreme pressure agents and friction modifiers. In simple metal soap thickened oil base greases, these products also raise the dropping point of this base grease when used in sufficient amounts in the grease.

Phospholipids, sometimes called phosphatides or phospholipins, are lipids containing phosphoric acid or its derivatives. Glycerophospholipids, called phosphatides and phosphoglycerides, are glycerophosphoric acids or their derivatives with one or two acyl, alkenyl or alkyl groups attached to glycerol residues. These materials can be prepared synthetically or can be derived from natural sources. Natural sources that produce phospholipids are typically seed and animal products (eg,
Egg).

As used herein, the term "hydrocarbyl" or "hydrocarbyl group", in the context of this invention, is a group having a carbon atom directly attached to the remainder of the molecule and having a predominantly hydrocarbon character. Represents a group having properties. Therefore, the term "hydrocarbyl" includes hydrocarbon groups as well as substantial hydrocarbon groups. Substantially hydrocarbon group refers to groups containing non-hydrocarbon substituents or non-carbon atoms in the ring or chain which do not alter the predominantly hydrocarbon character of the group.

The hydrocarbyl group may be in a ring or chain,
It may contain up to 3, preferably up to 2, more preferably up to 1 non-hydrocarbon substituents or non-carbon heteroatoms for each 10 carbon atoms. However, the non-hydrocarbon substituent or non-carbon heteroatom does not substantially change the predominantly hydrocarbon character of the group. Such heteroatoms (eg oxygen, sulfur, phosphorus and nitrogen) or substituents (eg hydroxyl, halo (especially chloro and fluoro), alkoxyl, alkylmercapto, alkylsulfoxy and the like. )
Are known to those skilled in the art.

Examples of hydrocarbyl groups include, but are not necessarily limited to:

(1) Hydrocarbon group, that is, aliphatic group (eg, alkyl or alkenyl), alicyclic group (eg, cycloalkyl, cycloalkenyl), aromatic group (eg, phenyl, naphthyl), aromatic Substituted aromatic groups, aliphatic substituted aromatic groups, alicyclic substituted aromatic groups, and the like, and cyclic groups. Where this ring is
It is completed by the other parts of the molecule (ie, for example, any two designated groups may together form an alicyclic group).

(2) Substituted hydrocarbon groups, ie these groups contain non-hydrocarbon containing substituents or atoms other than carbon bonded to the hydrocarbon group. This non-hydrocarbon containing substituent does not significantly alter the major hydrocarbon character within the context of the present invention; such groups (eg halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, Alkyl mercapto, nitro, nitroso, sulfoxy, etc.) are known to those skilled in the art.

(3) a heteroatom-containing group, that is, within the context of the present invention, while having a predominantly hydrocarbon character,
Groups having heteroatoms present in the ring or chain, but otherwise composed of carbon atoms. Suitable heteroatoms will be apparent to those skilled in the art and include, for example, sulfur, oxygen,
Includes nitrogen and phosphorus. Such groups (eg, pyridyl, furyl, thienyl, imidazolyl, etc.) are representative of heteroatom-containing cyclic groups.

Typically, the hydrocarbyl group will be
For each 10 carbon atoms, there will be no more than about 2, and preferably no more than 1, non-hydrocarbon substituents or heteroatoms in the chain or ring. However, typically the hydrocarbyl group is a pure hydrocarbon and is substantially free of such non-hydrocarbon groups, substituents or heteroatoms.

Unless otherwise indicated, hydrocarbyl groups can be saturated or unsaturated. The saturated group includes a substantially saturated group. Substantially saturated means that each of the
It is meant to contain no more than one carbon-carbon unsaturated bond, ie olefinic unsaturation, for every ten carbon-carbon bonds. Often, these are 50 each
It does not contain more than one carbon-carbon non-aromatic unsaturated bond for each carbon-carbon bond. Often, the hydrocarbyl groups are substantially free of carbon-carbon unsaturation. It should be understood that in the context of the present invention aromatic unsaturation is not normally considered to be olefinic unsaturation. That is, aromatic groups are not considered to have carbon-carbon unsaturated bonds.

(A) Boron-Containing Compound The grease composition of the present invention comprises (A) a boron-containing compound and (B)
It contains a composition prepared by reacting a formulation with a phospholipid. This boron-containing compound includes boron oxide, boron oxide hydrate, boron trioxide, boron trifluoride, boron tribromide, boron trichloride, a boron-containing acid (for example, boronic acid (i.e., alkyl-B (OH ) ₂ or aryl-B (OH) ₂ ; this includes methylboronic acid, phenylboronic acid, cyclohexylboronic acid, p-heptylphenylboronic acid and dodecylboronic acid), boric acid (ie H ₃ BO ₃ ), tetraboric acid (ie, H ₂ B ₄ O ₇ ), metaboric acid (ie, HBO ₂ )),
Included are boron-containing anhydrides, boron-containing amides, and various esters of such boron-containing acids. In a preferred embodiment, the boron-containing compound (A) is
Boric acid. Using a complex of an ether, an organic acid, an inorganic acid or a hydrocarbon with a boron trihalide is
It is a convenient means of introducing the boron-containing reaction component into the reaction mixture. Such complexes are well known and include boron trifluoride-triethyl orthoester complex, boron trifluoride-phosphate complex, boron trichloride-chloroacetic acid complex, boron tribromide-dioxane complex, and boron trifluoride. -Methylethyl ether complex.

Esters of boron-containing acids include in particular mono-organic, di-organic and tri-organic esters of boric acid with alcohols or phenols such as: methanol, ethanol, propanol, 1- Octanol, benzyl alcohol, ethylene glycol, glycerol, cellosolve and phenol. Lower alcohols, 1,2-glycols and 1,3-glycols, ie, those having less than about 8 carbon atoms, are particularly useful for preparing borate esters for the purposes of this invention. Methods for preparing esters of boron-containing acids are well known and disclosed in the art (see, eg, "Chemical Reviews" p.959-1064, p.
Volume 6).

(B) Phospholipid The phospholipid (B) of the present invention is a lipid containing a phosphorus-containing derivative (eg, phosphoric acid or its ester), such as lecithin or cephalin, preferably lecithin or its derivative. obtain. In a preferred embodiment,
The phospholipid (B) is at least one type of lecithin. Examples of phospholipids are phosphatidylcholine, phosphatidylserine, phosphatidylinositol, phosphatidylethanolamine, phosphotidic acid.
dic acid) and mixtures thereof. Preferably, the phospholipid is a glycerophospholipid, more preferably a glycero derivative of the phospholipids listed above.
Typically, the glycerophospholipid has one or two acyl, alkyl or alkenyl groups on the glycerol residue. In a preferred embodiment,
The phospholipid (B) is a monoacyl glycerophospholipid or a diacyl glycerophospholipid. These alkyl or alkenyl groups generally contain about 8 to about 30 carbon atoms, preferably 8 to about 25 carbon atoms, and more preferably 12 to about 24 carbon atoms. Examples of these groups include octyl, dodecyl, hexadecyl, octadecyl, docosanyl, octenyl, dodecenyl, hexadecenyl and octadecenyl. In a preferred embodiment, the phospholipid (B) is monoacyl or diacylphosphatidylcholine, phosphatidylethanol, phosphatidylserine, phosphatidylinositol, phosphatidic acid or mixtures thereof.

The acyl groups on this glycerophospholipid are generally derived from fatty acids. About 8 to about 30 fatty acids
Carbon atoms, preferably about 12 to about 24 carbon atoms,
More preferred are acids having from about 12 to about 18 carbon atoms. Examples of fatty acids are myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, arachidonic acid or mixtures thereof,
Preferably stearic acid, oleic acid, linoleic acid and linolenic acid or mixtures thereof are included.

Derivatives of phospholipids may also be used in the present invention. Derivatives of phospholipids can be acylated phospholipids or hydroxylated phospholipids. For example, lecithin, and acylated and hydroxylated lecithin can be used in the present invention. Acylated lecithin can be prepared by reacting an acylating agent with lecithin. The acylating agent includes acetic acid. An example of an acylated lecithin is Los Androw (R
oss & Rowe, Inc.) (Decatur, Illinois), Thermolec 200 acylated soya lecithin. Hydroxylated lecithin can also be used. Hydroxylated lecithin
It can be prepared by acidic hydrolysis or enzymatic hydrolysis.
An example of a hydroxylated lecithin is Thermorec 1018 hydroxylated lecithin available from Ross and Law.

Phospholipids can be synthetically prepared or derived from natural sources. Synthetic phospholipids can be prepared by methods well known to those skilled in the art. Naturally derived phospholipids are extracted by methods well known to those skilled in the art. Phospholipids can be derived from animal or plant sources.
Animal sources include fish, fish oil, shellfish, bovine brain, or any type of egg, preferably chicken egg. For plant raw materials,
Rapeseed, sunflower seeds, peanuts, palm nuts, gourd seeds, wheat, barley, rice, olives, mangoes, avocados, palash, papaya, jungle (jangl)
i), bodani, carrot, soybean, corn and cottonseed, more preferably soybean, corn, sunflower seed and cottonseed. Phospholipids can be derived from microorganisms. The microorganisms include blue-green algae, green algae, bacteria that grow on methanol or methane, and yeasts that grow on alkanes. In a preferred embodiment, the phospholipid (B) is soybean, cottonseed, corn, rapeseed, sunflower seed, peanut, coconut, gourd seed, wheat, barley, rice, olive, mango, avocado, papaya and It is a lecithin derived from at least one carrot.

Useful phospholipids are derived from sunflower seeds. The phospholipid is typically about 35% to about 60% phosphatidylcholine, about 20% to about 35% phosphatidylinositol, about 1% to about 25% phosphatidic acid and about 10% to about 25%. Contains phosphatidylethanolamine, where the percentages are by weight based on total phospholipids. This fatty acid content is typically about 20
-30 wt% palmitic acid, about 2-10 wt% stearic acid, about 15-25 wt% oleic acid, and about 40-55 wt% linoleic acid. In one embodiment, the phospholipid is derived from a sunflower seed with a high oleic acid content.
These species typically produce phospholipids having an oleic acid content of greater than about 75%, preferably greater than about 80%, and more preferably greater than about 85%. The fatty acid content of phospholipids derived from high oleic sunflower seeds is generally about 3.5-4.5% palmitic acid, about 3.0-.
It ranges from 5.5% stearic acid, about 75-95% oleic acid and about 5-15% linoleic acid. Generally, this phospholipid is derived from flour produced from sunflower seeds with high oleic acid content. This powder is SVO Enterprise (SV
O Enterprises) (35585-B Curtis Boulevard (Curtis
Boulevard), East Lake, Ohio 44095) under the trade name TRISUN® high oleic sunflower flour.

In one embodiment, the phospholipids encompassed by the present invention are represented by one of the formulas below or mixtures thereof:

[0072]

[Chemical 1]

Where each R ₁ is independently a hydrocarbyl group, and each R ₂ is independently —CH ₂ CH ₂ N ⁺ (C
_{H 3) 3, -CH 2 CH} 2 N + H 3, is selected from ^{_{-CH 2 CH (N + H 3}} ) COOH or mixtures thereof, and each R ₃ is independently, -C ₆
H ₆ (OH) ₆ , hydrogen or a mixture thereof. Preferably, each R is independently an alkyl, alkenyl or acyl group as described above.

Phospholipids and lecithin are available from Encyclopedia of Chemical Technology.
f Chemical Technology) (Kirk and Osmer
and Othmer), 3rd edition, "Fats and Fat Oils" (9th.
Vol. 795-831), and "Lecithin" (Vol. 14, 250).
~ Page 269). The above disclosures of phospholipids and lecithin are incorporated herein by reference.

In one embodiment, the formulation used to prepare the compositions of the present invention further comprises (C) at least 1
Included are amines, (D) acylated nitrogen-containing compounds, (E) carboxylic acid esters, (F) Mannich reaction products, or (G) neutral or basic metal salts of organic acids. However, when the acylated nitrogen compound (D) has a substituent having an average of at least 40 carbon atoms, the boron-containing compound (A) reacts with the phospholipid (B) to form an intermediate. , This intermediate is
Reacts with (D).

[0076] in (C) an amine amine, ammonia, monoamines or polyamines. This monoamine is generally 1 to about 24
It contains 1 carbon atom, preferably 1 to about 12 carbon atoms, more preferably 1 to about 6 carbon atoms. Examples of monoamines useful in the present invention include substantially hydrocarbon-based amines which can be primary amines, secondary amines and tertiary amines.

In another embodiment, the monoamine may be hydroxyhydrocarbylamine. Typically,
The hydroxyamine is a primary, secondary or tertiary alkanolamine or mixtures thereof. Such amines can be represented by the formula:

[0078]

[Chemical 2]

Wherein each R ₄ is independently a hydrocarbyl group having 1 to about 8 carbon atoms, or 2 to about 8 carbon atoms, preferably 1 to about 4 carbon atoms. A hydroxyhydrocarbyl group having an atom, and R '
Is about 2 to about 18 carbon atoms, preferably 2 to about 4.
It is a divalent hydrocarbyl group having 4 carbon atoms.
The -R'-OH group in these formulas represents a hydroxyhydrocarbyl group. R'can be an acyclic group, an alicyclic group or an aromatic group. Typically, R'is an acyclic straight or branched chain alkylene group. When two R ₄ groups are present in the same molecule, they are linked by a direct carbon-carbon bond or via a heteroatom (eg oxygen, nitrogen or sulfur) and a 5-membered heterocyclic structure, A 6-membered heterocyclic structure, a 7-membered heterocyclic structure or an 8-membered heterocyclic structure can be formed. However, typically, each R group is independently a methyl group,
It is an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group.

The hydroxyhydrocarbylamine can also be an ether-N- (hydroxyhydrocarbyl) amine. These are hydroxypoly (hydrocarbyloxy) analogs of the above hydroxyamines (these analogs also include hydroxyl-substituted oxyalkylene analogs). Such N- (hydroxyhydrocarbyl) amines can be conveniently prepared by the reaction of epoxides with the above amines and can be represented by the formula:

[0081]

[Chemical 3]

Where x is a number from about 2 to about 15, and R ₄ and R ′ are as described above. R ₄ can also be a hydroxypoly (hydrocarbyloxy) group.

The amine can also be a polyamine. The polyamine can be aliphatic, cycloaliphatic, heterocyclic or aromatic. Examples of these polyamines include alkylene polyamines, hydroxy containing polyamines, aryl polyamines and heterocyclic polyamines.

The alkylene polyamine is represented by the formula:

[0085]

[Chemical 4]

Where n is an average value between about 1 and about 10,
Preferably an average value of about 2 to about 7, more preferably about 2
Has an average value of from about 5 to about 5, and the "alkylene" group has from 1 to about 10 carbon atoms, preferably from about 2 to about 6.
It has 1 carbon atom, more preferably about 2 to about 4 carbon atoms. R ₅ is independently preferably hydrogen; or an aliphatic or hydroxy-substituted aliphatic group having up to about 30 carbon atoms. Preferably R ₅ is defined similarly to R ₄ .

The higher homologues obtained by the condensation of two or more alkylene amines are useful, as are mixtures of two or more polyamines.

Ethylene polyamines such as any of those mentioned above are useful. Such a polyamine is referred to as ethyleneamine under the name Kirk Ozmer.
thmer) "Encyclopedia of Chemical Technology" (2nd edition, Volume 7, p.22-37, Interscience Publishers),
New York (1965)). Such polyamines are most conveniently prepared by the reaction of ethylene dichloride with ammonia, or by the reaction of ethyleneimine with a ring opening reagent (eg, water, ammonia, etc.). As a result of such a reaction, a complex mixture of polyalkylene polyamines including a cyclic condensation product (for example, piperazine described above) is formed. Ethylene polyamine mixtures are useful.

Other useful types of polyamine mixtures are those obtained by stripping the above polyamine mixtures, leaving a residue often referred to as "polyamine bottoms". Generally, the alkylene polyamine bottoms can be characterized as containing less than 2% by weight, usually less than 1% by weight, of substances that boil below about 200 ° C. A typical sample of such ethylene polyamine bottoms obtained from the Dow Chemical Company (Freeport, Tex.) (Designated “E-100”) had a temperature of 1.0168 at 15.6 ° C. It has a specific gravity, a nitrogen content of 33.15% by weight, and a viscosity of 121 centistokes at 40 ° C. Gas chromatographic analysis of such a sample showed that it contained about 0.93% by weight "light end" (probably diethylenetriamine), 0.72% by weight triethylenetetramine, 21.74% by weight tetraethylenepentamine, and 76.61% by weight. % And higher pentaethylenehexamine. These alkylene polyamine bottoms include cyclic condensation products (eg, piperazine) and higher homologues such as diethylenetriamine and triethylenetetramine.

Other useful polyamines are condensation reaction components between at least one hydroxy compound and at least one polyamine reactant containing at least one primary amino group or secondary amino group. Is. The hydroxy compound is preferably a polyhydric alcohol and an amine. Polyamine reaction components that react with polyhydric alcohols or amines to form condensation products or condensed amines are described above. Preferably the hydroxy compound is a polyamine.

This amine condensate and its production method are
It is described in US Pat. No. 5,053,152, the contents of which are hereby incorporated by reference for the disclosure of this condensate and its method of preparation.

In another embodiment, the amine is a polyalkene substituted amine. These polyalkene-substituted amines are well known to those skilled in the art. These amines are described in U.S. Pat. Nos. 3,275,554; 3,438,757; 3,454,555;
No. 3,565,804; 3,755,433; and 3,822,289. The contents of these patents are incorporated herein by reference for their disclosure of hydrocarbyl amines and methods for their preparation.

(D) Acylated Nitrogen-Containing Compound This formulation may also contain an acylated nitrogen-containing compound. The acylated nitrogen-containing compound includes the reaction product of a hydrocarbyl-substituted carboxylic acylating agent (eg, a substituted carboxylic acid or derivative thereof). These compounds include imides, amides, amidic acid or salts thereof, heterocyclic compounds (imidazoline, oxazoline, etc.), and mixtures thereof. In one embodiment, these compounds are useful as dispersants in lubricating compositions and are referred to as nitrogen-containing carboxylic dispersants.

The conditions under which the acidic reaction components are reacted with the polyalkene, ie temperature, stirring, solvent etc. are well known to those skilled in the art. Examples of patents describing various methods of preparing useful acylating agents include US Pat. Nos. 3,215,707 (Rense); 3,219,666 (Norman).
No. 3,231,587 (Rense); 3,912,764
No. (Palmer); No. 4,110,349 (Coen
hen)); and No. 4,234,435 (Main Holt (Meinha
rdt) et al.); and British Patent No. 1,440,219. The disclosures of these patents are incorporated herein by reference.

(E) Carboxylic Acid Esters In other embodiments, the formulations that make up the compositions used in the grease compositions of the present invention may also contain carboxylic acid esters. These compounds are prepared by reacting at least one of the above hydrocarbyl-substituted carboxylic acylating agents with at least one organic hydroxy compound. In another embodiment, the ester dispersant is prepared by reacting the acylating agent with the hydroxyamine. The carboxylic acid ester may be further reacted with any of the above amines.

The preparation of useful carboxylic ester dispersants is described in US Pat. Nos. 3,522,179 and 4,234,435.

The carboxylic acid esters may be further reacted with at least one of the above amines, and preferably of at least one of the above polyamines. These nitrogen-containing carboxylic ester dispersant compositions are well known in the art and the preparation of numerous derivatives thereof is described, for example, in U.S. Pat.Nos. 3,957,854 and 4,234,435, the contents of which are: It is used as a reference before this.

This carboxylic acid ester and its method of preparation are well known in the art and are described in US Pat. No. 3,219,66.
No. 6; No. 3,381,022; No. 3,522,179 and No. 4,234,435
No. 6,096,096, the contents of which are incorporated herein by reference for their disclosure of the preparation of carboxylic ester dispersants.

(F) Mannich Reaction Product This formulation may also contain a Mannich product. The Mannich product is formed by the reaction of at least one aldehyde, at least one amine as described above, and at least one hydroxyaromatic compound. This reaction is carried out at room temperature to 225 ° C, usually 50 ° C to about 200 ° C (75 ° C to 125 ° C).
C. is most preferred) and the amount of this reagent is such that the molar ratio of hydroxyaromatic compound to aldehyde to amine is in the range of about (1: 1: 1) to about (1: 3: 3). It is such an amount.

Mannich products are described in the following patents: US Pat. No. 3,980,569; US Pat. No. 3,877,89.
9; and U.S. Pat. No. 4,454,059 (the contents of these patents are incorporated herein by reference for their disclosure of Mannich products).

(G) Basic Nitrogen-Containing Polymer The reaction product may also contain a basic nitrogen-containing polymer. These polymers include polymer backbones that have been functionalized by reaction with an amine source. True or regular block copolymers, or random block copolymers, or blends of both are used.

Often, these block copolymers are
For reasons of oxidative stability, it contains less than about 5% residual olefinic unsaturation, preferably less than about 0.5% residual olefinic unsaturation, based on the total number of carbon-carbon covalent bonds in the average molecule. . Such unsaturation can be measured by numerous methods well known to those skilled in the art, such as infrared, NMR and the like. Most preferably, these copolymers are
It contains no discernible unsaturation as determined by the above analytical methods.

The amine source can be an unsaturated amine compound or unsaturated carboxylic acid reagent capable of reacting with an amine. The unsaturated carboxylic acid reagent and amine have been described above.

Examples of basic nitrogen-containing polymers are given in the following references: European Patent No. 171,167 No. 3,687,905 No. 3,687,849 No. 4,670,173 No. 3,756,954 No. 4,320,012 No. 4,320,019 (these contents) Are incorporated herein by reference for their disclosure of basic nitrogen-containing polymers).

(H) Neutral or Basic Metal Salts The formulations may also contain neutral or basic metal salts. Preferably, these salts include alkali metal salts,
Alkaline earth metal salts or transition metal salts are mentioned. Examples of metals for these salts include sodium, potassium, magnesium, calcium, barium, titanium, manganese,
Mention may be made of cobalt, nickel, copper, zinc, preferably sodium, potassium, calcium, magnesium, copper and zinc, more preferably zinc or magnesium cations, most preferably zinc.

In one embodiment, these salts are generally
It is formed from a metal compound that is a basic metal salt. In general, these metal compounds are oxides, hydroxides, chlorides, carbonates, phosphorus-containing acid (phosphonic or phosphoric acid) salts and sulfur-containing acid (sulfuric acid or sulfonic acid) salts of the metal cations mentioned above. Is.

The neutral salt is a salt having substantially the same number of equivalents of metal and acidic compound. Substantially the same means that the amount of metal present is in the range of about 0.9 to about 1.1 equivalents of metal per equivalent of acid, preferably about 0.95 to about 1.
It is meant that there is a range of 05 equivalents of metal, more preferably a range of about 0.99 to about 1.01 equivalents of metal per equivalent of acid.

In another embodiment, these salts are basic salts, commonly referred to as overbased salts. Overbased materials are single phase, homogeneous Newtonian systems characterized by a metal content in excess of that which would be present according to the stoichiometry of the metal and the particular acidic organic compound that reacts with that metal.

The excess amount of metal is usually expressed as a metal ratio. The term "metal ratio" is the ratio of total equivalents of metal to equivalents of acidic organic compound. Neutral metal salts have a metal ratio of 1. A salt that has 4.5 times the metal present in the normal salt has a 3.5 equivalent excess metal, ie, a metal ratio of 4.5. The basic salts of the present invention have a metal ratio of greater than about 1.1, preferably a metal ratio of about 1.5, more preferably a metal ratio of 3 up to about 40, preferably about a metal ratio.
It has a metal ratio of up to 30, more preferably up to about 20.

Methods for preparing this overbased material, and an extremely different group of overbased materials, are well known in the prior art and are disclosed, for example, in the following US patents: 2,616,904; 2,616,905. ; 2,616,
No. 906; No. 3,242,080; No. 3,250,710; No. 3,256,186
No .; 3,274,135; 3,492,231; and 4,230,58.
No. 6. These patents disclose suitable overbased metal bases, promoters and acidic materials, and a variety of specific overbased products useful in making the dispersions of the present invention, and , These disclosures are
Incorporated herein by reference.

The above (D) acylated nitrogen compound, (E) carboxylic acid ester, (F) Mannich product and (G) basic nitrogen-containing polymer are one or more selected from the group consisting of: It may be post-treated with the following post-treatment reagents: boron-containing compound (as described above), carbon disulfide, hydrogen sulfide, sulfur, sulfur chloride, alkenyl cyanide, carboxylic acylating agent, aldehyde, ketone, urea, Thiourea, guanidine, dicyanodiamide, hydrocarbyl phosphate, hydrocarbyl phosphite, hydrocarbyl thiophosphate, hydrocarbyl thiophosphite, phosphorus sulfide, phosphorus oxide, phosphoric acid, hydrocarbyl thiocyanate, hydrocarbyl isocyanate, hydrocarbyl isothiocyanate, epoxide, episulfide, Formaldehyde or formaldehyde-forming compound Phenol, and sulfur and phenol.

The contents of the following US patents are expressly incorporated herein by reference for their disclosure of post-treatment methods and reagents that can be utilized in the carboxylic acid derivative compositions of the present invention: US Patents No. 3,087,936; No. 3,254,025
No. 3,256,185; 3,278,550; 3,282,955;
No. 3,284,410; No. 3,338,832; No. 3,533,945; No. 3,6
No. 39,242; No. 3,708,522; No. 3,859,318; No. 3,865,81
No. 3 etc. British Patent Nos. 1,085,903 and 1,162,436 also describe such methods.

In one embodiment, (D) to (G) are post-treated with at least one boron containing compound as described above.
The reaction of this compound with the boron-containing compound can occur by simply mixing the reaction components at the desired temperature, preferably between about 50 ° C and about 250 ° C. In some cases, this temperature may be 25 ° C or lower. The upper limit of this temperature is the decomposition point of the particular reaction mixture and / or product.

The amount of the boron-containing compound used in the post-treatment of (D) to (G) is about 0.1 to about 0.1 to about (D) to (G) (for example, the atomic ratio of nitrogen or hydroxyl group) of each equivalent. Sufficient to provide 10 atomic percent boron. The preferred amount of reaction component is about 0.5 to about each equivalent of nitrogen or hydroxyl group.
The amount is such that it provides about 2 atomic percent boron. For illustration, used with 1 mole of acylated nitrogen compound having 5 nitrogen atoms per molecule, 1 per molecule
The amount of boron-containing compound having boron atoms is about 0.
Within the range of 1 mol to about 50 mol, preferably about 0.5 mol to about
Within the range of 10 moles.

The phosphorus- and boron-containing composition used in the grease composition of the present invention comprises (A) a boron-containing compound and (B)
It can be prepared by reacting with a phospholipid. Furthermore, this composition comprises (A) a boron-containing compound, (B) a phospholipid, the above (C) amine, (D) an acylated nitrogen compound, and (E).
It can be prepared by reacting with a mixture of a carboxylic ester, (F) Mannich reaction product, and (G) a basic nitrogen-containing polymer or one of its derivatives. The mixture may simply be a mixture of these components or a salt or partial salt of these components. In another embodiment, the boron- and phosphorus-containing composition may be prepared by reacting (A) a boron-containing compound with (B) a phospholipid to form an intermediate reaction product. This intermediate product is then reacted with one of (C) to (G) above.

The boron- and phosphorus-containing composition of the present invention comprises
It can be prepared by reacting the (A) boron-containing compound with one of the above (C) to (G) to form an intermediate. This intermediate is then reacted with (B) phospholipids, provided that the acylated nitrogen compound (D) is at least 40 on average.
When it has a substituent having carbon atoms, the boron-containing compound (A) reacts with the phospholipid (B) to form an intermediate,
This intermediate reacts with (D). When the acylated nitrogen-containing compound contains a substituent having an average of about 40 or less carbon atoms, the acylated nitrogen-containing compound need not have a substituent having an average number of carbon atoms. It should be understood that not. The substituent may have a particular individual number of carbon atoms, for example 18 carbon atoms. In one embodiment, the substituents on the acylated nitrogen compound have, on average, no more than about 30 carbon atoms. The average number of carbon atoms is based on the number average molecular weight.

This reaction usually occurs at a temperature of about 60 ° C to about 200 ° C, preferably about 90 ° C to 150 ° C. This reaction is typically about 0.5 to about 10 hours, preferably about 2
Is completed in about 6 hours, more preferably 4 hours. An inert organic diluent such as benzene, toluene, xylene or mineral oil can be used.

Boron-containing compound (A) and phospholipid (B)
Has an atomic ratio of boron to phosphorus of about (1: 1) to about (6: 1), preferably about (2: 1) to about (4: 1), more preferably about (3: 1). ) Reacts.

The boron-containing compound (A) is a phospholipid (B),
The mixture of one or more of (C) to (H) and the atomic ratio of boron to the equivalent weight of the mixture is from about (1: 1) to about (6: 1), preferably about (2: 1). ) To about (4: 1), more preferably about (3: 1). The equivalent weight of this mixture is based on the equivalent weight of the phosphorus-based phospholipid (B) and the equivalents of (C) to (H) combined. The equivalent weight of (C) to (G) is determined by the number of nitrogen atoms or hydroxyl groups. The equivalent weight of (H) is based on base number. Base number is represented by the equivalent milligram amount of potassium hydroxide per gram of sample required to titrate the sample to the desired endpoint. This base number is converted to equivalent weight by the following equation: equivalent weight = (56100 / base number).

The phospholipid (B) reacts with the post-treatment products of (C)-(H), with the phospholipid having an equivalent weight of about (1: 1) to about (6: 1). The post-treated product is reacted in a ratio, preferably an equivalence ratio of about (2: 1) to about (4: 1), more preferably an equivalence ratio of about (3: 1). The equivalent weight of this post-treatment product is based on boron atoms.

The following examples illustrate the preparation of reaction products of boron containing compounds with phospholipids. In the following examples and claims and specification, parts are parts by weight, temperature is degrees Celsius, and pressure is atmospheric pressure, unless otherwise indicated.

[0122]

【Example】

Example 1 A reaction vessel was loaded with lecithin (Central Soya Company, Fort Wayne, IN) from Centrophase (C
mixed phospholipid products marketed under the trade name of entrophase (typical analysis values:% P = 1.97,% N = 0.75)) 21
95 parts (1.40 equivalents), 100 neutral mineral oils 396 parts, and boric acid 26
Charge 0 parts (4.20 moles). The mixture is heated to 90 ° C and this temperature is maintained at 90-95 ° C for 0.75 hours. Reduce the pressure and maintain at 160 mmHg for 2.25 hours. During this time, the reaction temperature rises from 95 ° C to 120 ° C and distillate is collected. This is decompressed to 50 mmHg and the reaction temperature is 120-125 ° C.
Hold an additional 1.25 hours at (total reaction time equals 3.5 hours). During this period, 151 parts of distillate are collected. To this residue is added 100 neutral mineral oil (10 parts), the residue is cooled to 55 ° C. and filtered through a cloth. The filtrate has 1.52% phosphorus, 0.53% nitrogen, 1.78% boron and 15% oil.

Example 2 A reaction vessel is filled with a mixture of 2600 parts (1.66 equivalents) of lecithin and 600 parts of toluene. In a nitrogen atmosphere at 40 ℃ ~ 60 ℃ for 0.5 hours,
To this mixture is added boric acid (307 parts, 4.97 mol).
The reaction mixture is heated to reflux (130 ° C.) while removing 180 parts of water over 4 hours. Reduce the pressure (20mmH
g), and removing the toluene solvent while raising the reaction temperature to 110 ° C. The residue is filtered through diatomaceous earth. This filtrate contains 1.78% P (theoretical value is 1.88%), 0.71% N.
(Theoretical value is 0.72%) and 2.05% B (Theoretical value is 2.10)
%).

Example 3 In a reaction vessel, maize lecithin (ADM Ross and Row
(e) available as Corn Goodness UB) 800 parts (0.5 eq), 150 parts toluene, and a mixture of 141 parts 100 neutral mineral oil. To this mixture is added boric acid (104 parts (1.68 moles)) at 40-60 ° C over 0.5 hour. The reaction mixture was charged with distillate 63
Heat to reflux (125 ° C.-127 ° C.) for 4 hours while removing parts.

While increasing the temperature to 120 ° C, reduce the pressure (20 m
mHg) Remove the toluene solvent. The residue is filtered through diatomaceous earth. The filtrate is 1.55% P, 0.62% N,
Contains 1.1% B and 15% oil.

EXAMPLE 4 1562 parts of lecithin of Example 1 (1 equivalent), 200 parts of toluene, and a 40% oil solution of succinimide (2.5% nitrogen and 65 total bases) were placed in a reaction vessel. Having a valency, prepared by reacting a polyamine and a polyalkene succinic anhydride, wherein:
This polyalkene charges 560 parts (having a number average molecular weight of approximately 1000) (1 equivalent). 1 sc of this mixture
Heat to 50 ° C. with bubbling nitrogen at a rate of fh, whereupon 247 parts (4 moles) boric acid are added to the mixture over 0.25 hour. Heat the mixture to 120 ° C,
There, 25 parts of water are removed over a period of 1.5 hours. The reaction is maintained at 120 ° C to 125 ° C for 4.5 hours. During this period, 115 ml of distillate are obtained. The product is a clear, bright deep red color. Add this mixture to 80 ° C and 25 mm
Vacuum strip to Hg. This residue is 1.3%
Phosphorus (theoretical value is 1.37%), 1.07% nitrogen (theoretical value is 1.
14%), 1.86% boron (theoretical value is 1.95%), and 15
Product with 100% neutral mineral oil.

Example 5 A reaction vessel is filled with 1568 parts (1 equivalent) of lecithin of Example 1 and 200 parts of fiber spirits. The mixture was heated to 60 ° C., whereupon it was admixed with borated sodium sulfonate 525.
Parts (3 equivalents) are added. This borated sodium sulfonate is an overbased sodium alkylbenzene sulfonate (which has a metal ratio of 20 and a 36% diluent (this includes 100 neutral mineral oil and unreacted alkylbenzene sulfonate). It is prepared by reacting 1 equivalent (containing a salt) and 1 equivalent of boron. The reaction temperature is maintained at 60-70 ° C for 3 hours. The reaction mixture is vacuum stripped to 80 ° C. and 25 mm Hg. This product contains 1.47% phosphorus (theoretical value is 1.49%),
It contains 3.51% sodium (theoretical 2.87%), 1.52% boron (theoretical 1.57%) and has a specific gravity of 1.04.

Example 6 In a reaction vessel, 784 parts (0.5 equivalents) of lecithin of Example 1, 124 parts (2.1 equivalents) boric acid, and tall oil fatty acid overbased with calcium (which has a metal ratio of 2) are used. , Neutralizing 58% of 100 neutral mineral oil and having a base number of 125), 449 parts (1 equivalent). The mixture is heated to 90 ° C and held for 1 hour. The reaction mixture is heated to 120 ° C. at 140 mmHg and the reaction system is maintained at 120 ° C. for 1 hour. The reaction mixture is cooled to 60 ° C. and vacuum stripped at 60 ° C. and 40 mm Hg. This residue contained 1.12% phosphorus (theoretical 1.19).
%), 1.63% calcium (theoretical value is 1.60%), 1.97%
Boron (theoretical value is 1.79%) and has a specific gravity of 1.02.

Example 7 (A) In a reaction vessel, sulfur-coupled tetrapropenylphenol (this was
With 5% sulfur and 42% mineral oil as diluent) 389
Parts (1 equivalent), 200 parts toluene and 20 parts 50% aqueous sodium hydroxide solution (0.25 equivalents) are charged. The mixture was stirred and heated to 80 ° C. whereupon the reaction vessel was charged with 33 parts (1.0 part) of paraformaldehyde over 2 minutes.
Equivalent) and hold for 1/4 hour. (B) Then,
A reaction vessel is charged with 1569 parts (1 equivalent) of lecithin of Example 1 and 200 parts of toluene. The mixture is warmed to 40 ° C. whereupon 185 parts boric acid (3 equivalents) are added over 1/2 hour with stirring to the vessel. Reaction temperature 100
Raise to ° C and hold for 3/4 hour. This product is
0.63% sulfur (theoretical value is 0.67%), 1.31% phosphorus (theoretical value is 1.37%), 1.34% boron (theoretical value is 1.45%),
And 10% 100 neutral mineral oil.

Lubricants As indicated above, the reaction products of the above boron-containing compounds with phospholipids are useful as additives for lubricants, including greases. In this lubricant, these additives may primarily function as antiwear agents, extreme pressure agents and / or friction modifiers. Moreover, when used in sufficient amounts, they raise the dropping point of oil-based simple metal soap thickened base greases. They can be used in these greases based on a wide variety of oils of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof.

The borated phospholipids can be mixed directly into the base grease, or as a component of an additive concentrate, by itself or in other known oil-based simple metal soap thickening base greases. It can be mixed in combination with additives. These additives include, but are not limited to, antioxidants, antiwear agents, extreme pressure agents, friction modifiers, rust inhibitors, corrosion inhibitors and dyes.

Antioxidants, corrosion inhibitors, extreme pressure agents and antiwear agents include metal salts of phosphorus-containing acids, metal salts of thiophosphorus or dithiophosphorus acids; organic sulfides and polysulfides; chlorinated aliphatics. Hydrocarbons; phosphorus-containing esters including dihydrocarbyl phosphite and trihydrocarbyl; and molybdenum-containing compounds include, but are not limited to.

Viscosity improvers and pour point depressants are sometimes used to improve the properties of the oil from which the base grease is derived.

Viscosity improvers include, but are not limited to: polyisobutene, polymethacrylic acid esters, polyacrylic acid esters, diene polymers,
Polyalkylstyrene, alkenylaryl conjugated diene copolymers, polyolefins and multifunctional viscosity improvers.

For extreme low temperature applications, the pour point of the oil component of this base grease is an important requirement. Pour point depressants are sometimes included in the lubricating oils described herein. For example, CV Smalheer and R. Kennedy Smith's “Lubricant Additive”
s "(Lezius-Hiles Company Publishers, Cleveland, Ohio, 1967), page 8.

These and other additives are described in great detail in US Pat. No. 4,582,618 (col. 14, line 52 to col. 17, line 16, inclusive of these lines),
The contents of which are incorporated herein by reference for disclosure of other additives that may be used with the present invention.

The additive concentrate may contain from 0.01% to 90% by weight of the phosphorus and boron containing composition used in the grease composition of the present invention. The boron and phosphorus containing composition is present in the grease composition of the present invention in an amount effective to provide extreme pressure properties or wear resistance or lubricity, preferably from about 0.1% to about 20% by weight. It can be present in an amount in the range, more preferably in the range of about 0.25% to about 10% by weight, most preferably in the range of about 0.5% to about 5% by weight. When the compositions of the present invention are used to raise the dropping point of base greases, they are most preferred in small amounts, preferably in amounts ranging from about 0.25% to about 10% by weight of the total grease composition. Is used in amounts ranging from about 0.5% to about 5% by weight.

As mentioned above, the boron- and phosphorus-containing compounds that raise the dropping point of the metal soap thickened grease are:
Used in small amounts effective to raise the dropping point of this base grease by at least 20 ° C.

The preferred minimum amount of boron- and phosphorus-containing compounds used depends, to some extent, on the additive; for example, certain high molecular weight compounds require slightly higher amounts to achieve the desired effect.

Generally, it is not necessary to use more than about 10% by weight boron and phosphorus containing compounds. Further use is usually ineffective, and often above this level of treatment, performance degradation is observed with respect to grease drop point or other properties. In many cases,
Up to about 5% and often up to about 2% boron and phosphorus containing compounds are used. Often 1% by weight is sufficient to raise the dropping point by 20 ° C.

Therefore, a minimum amount of boron- and phosphorus-containing additives suitable for obtaining the desired effect (eg extreme pressure properties, abrasion resistance, etc., or increase of dropping point of at least 20 ° C.) should be used. Is preferred.

The boron- and phosphorus-containing composition can be present in forming the grease, ie in forming the soap thickener in oils of lubricating viscosity, or after the base grease has been prepared. , Can be added. In many cases, it is preferable to add the boron and phosphorus containing composition to a preformed base grease.

Other additives may be incorporated into the base grease to improve the grease's performance as a lubricant. Such other additives are well known, including corrosion inhibitors, antioxidants, extreme pressure additives, and other additives that are useful in improving certain performance characteristics of base greases. It is easily recalled by the trader.

The following examples illustrate the grease compositions of this invention. It should be understood that these examples are intended to illustrate the invention and not to limit it in any way. Drop point was determined using ASTM method D-2265. All amounts are oil-free bases and are by weight unless otherwise indicated.

Example A Lithium 12-hydroxystearate thickened base grease shows a dropping point of 206 ° C. This is a typical simple lithium salt thickened base grease.

(Example B) Base grease 92 of Example A
A base grease is prepared by mixing 1 part with 8 parts of mineral oil having a kinematic viscosity of 800 Saybolt universal seconds (172.6 centistokes) measured at 100 ° F (37.8 ° C). The dropping point of this grease is 204 ° C.

Example C 4% by weight of the product of Example 1
By mixing with the base grease of Example B,
Prepare a grease composition. This grease has a dropping point of 277 ° C.

Example D 2% by weight of the product of Example 1
Is mixed with the base grease of Example B to prepare a grease composition. This grease composition is 267 ° C
Has a dropping point of.

Example E 1% by weight of the composition prepared according to the method of Example 1 on the base grease of Example B,
And a grease composition is prepared by adding 1% by weight of the following product: This product is prepared by reacting about 4 moles of methyl amyl alcohol with 1 mole of P ₂ S ₅ O, O. 1000 parts of '-(di) methylamyldithiophosphoric acid are reacted with 183 parts of propylene oxide, the product thus obtained is reacted with 144 parts of P ₂ O ₅ and the acidic product thus obtained is Tertiary alkyl primary amines having 11 to 14 carbon atoms in the primary alkyl group (Primene
(Primene) 81-R, Rohm and Has
s) company) and obtained by neutralizing with 584 parts. This grease composition has a dropping point of 272 ° C.

Example F A grease composition was prepared by adding 1% by weight of sulfurized isobutylene containing about 45% by weight of sulfur and 2% by weight of the product of Example 1 to the base grease of Example B. To prepare. The dropping point of this grease composition is 228.5 ° C.

Example G The grease composition of Example F was combined with Reomet 39 (this was Ciba-Geigy).
0.1% by weight (an oil-soluble benzotriazole derivative sold by the company Ciba-Geigy). The dropping point of this grease composition is 231 ° C.

Examples HM are comparative examples using a phosphorus-free additive containing no boron.

Examples H-I 12-having a dropping point of 207 ° C.
By blending lithium hydroxystearate-based grease with the mixed phosphate in the proportions shown below,
Prepare a grease composition: This mixed phosphate is CO14
3 moles of 18 alcohol (primary alcohol containing a mixture of C ₁₄ , C ₁₆ and C ₁₈ carbon chains) (based on OH)
And 1 mol of P ₂ O ₅ are reacted with each other, and the obtained acidic product is treated with 1.13 equivalents of Primene 81-R per equivalent of a strong acid.
It was prepared by reacting with.

[0154]

[Table 1]

(Examples J to L) Grease compositions are prepared by blending lithium 12-hydroxystearate with dibutyl hydrogen phosphite ((butyl-O) ₂ PH0) in the proportions shown below.

[0156]

[Table 2]

Example M A grease composition is prepared by blending the grease of Example B with 4% by weight of lecithin as described in Example 1. The dropping point of this grease composition is
194 ° C.

Examples N to R Examples C to G are repeated except that the lithium 12-hydroxystearate base grease is replaced with the corresponding calcium soap thickened base grease.

(Examples S to T) A lithium 12-hydroxystearate-based grease was added to sodium tallow (sodiu).
Example C and G are repeated, except that the m tallowate) thickening base grease is replaced.

From the previous examples, the use of certain boron- and phosphorus-containing compositions at low levels resulted in a heat treatment as shown by the increased drop point compared to the base grease without additives. It is clear that the stability is enhanced. It is also apparent that phosphorus-containing compounds that are substantially free of boron do not raise the dropping point significantly.

Although the present invention has been described in relation to its preferred embodiments, it should be understood that various modifications thereof will be apparent to those skilled in the art upon reading this specification. Therefore, it should be understood that the invention disclosed herein is intended to include such modifications as fall within the scope of the appended claims.

[0162]

INDUSTRIAL APPLICABILITY According to the present invention, a grease composition useful for lubricating, sealing and protecting mechanical elements (eg gears, axles, bearings, shafts, hinges, etc.) can be provided. .

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location (C10M 159/12 125: 26 137: 04 159: 16 133: 04 129: 68 149: 22 133: 16 129: 93 159: 24) C10N 10:02 10:04 30:06 40:02 40:04 50:10 60:14 (72) Inventor Side Kurab Abas Lizbi United States Ohio 44060, Mentor, APT. G4, Mentor Avenue 7950 (72) Inventor Carmen Vincent Luciani United States Ohio 44092, Wicliffe, Bridle Pass Trail 30383

Claims (36)

[Claims] 1. An improved grease composition containing a major amount of an oil-based simple metal soap thickening base grease and a minor amount of at least one phosphorus and boron containing composition. The composition is
A grease composition prepared by reacting a blend of (A) at least one boron-containing compound and (B) at least one phospholipid. 2. The grease composition according to claim 1, wherein the simple metal soap is a fatty acid carboxylate. 3. The simple metal soap is an alkali metal soap,
The grease composition according to claim 1, which is an alkaline earth metal soap or an aluminum metal soap. 4. The grease composition according to claim 3, wherein the simple metal soap is an alkali metal soap. 5. The grease composition according to claim 3, wherein the simple metal soap is an alkaline earth metal soap. 6. The grease composition according to claim 4, wherein the simple metal soap is a lithium salt. 7. The fatty acid is hydroxy-substituted,
The grease composition according to claim 2. 8. The grease composition according to claim 7, wherein the simple metal soap is 12-hydroxystearate. 9. The grease composition according to claim 1, wherein the phospholipid (B) is a monoacylglycerophospholipid or a diacylglycerophospholipid. 10. The grease composition according to claim 1, wherein the phospholipid (B) is monoacyl or diacylphosphatidylcholine, phosphatidylethanol, phosphatidylserine, phosphatidylinositol, phosphatidic acid or a mixture thereof. 11. The method of claim 9, wherein each acyl group is independently myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, arachidonic acid or mixtures thereof. Grease composition. 12. The grease composition according to claim 1, wherein the phospholipid (B) is at least one type of lecithin. 13. The phospholipid (B) is soybean, cottonseed, corn, rapeseed, sunflower seed, peanut, coconut,
At least one of gourd seeds, wheat, barley, rice, olives, mangos, avocados, papayas and carrots
13. The grease composition of claim 12, which is a seed-derived lecithin. 14. The grease composition according to claim 1, wherein the phospholipid (B) is a synthetic phospholipid. 15. The phosphorus- and boron-containing composition comprises a boron-containing compound (A), a phospholipid (B), an amine (C), an acylated nitrogen-containing compound (D), a carboxylic acid ester (E), The Mannich reaction product (F), the basic nitrogen-containing polymer (G) or the organic acid prepared by reacting with a mixture of a neutral metal salt or a basic metal salt (H) of the organic acid. Grease composition. 16. The phosphorus- and boron-containing composition comprises a boron-containing compound (A), an amine (C), and an acylated nitrogen-containing compound having a substituent containing an average of about 40 or less carbon atoms ( D), a carboxylic acid ester (E), a Mannich reaction product (F), a basic nitrogen-containing polymer (G), or a neutral or basic metal salt of an organic acid (H) is reacted, The grease composition according to claim 1, which is prepared by forming an intermediate and then reacting the intermediate with a phospholipid (B). 17. A major amount of an oil-based simple metal soap thickened base grease, and at least an amount sufficient to increase the dropping point of the base grease as determined by ASTM method D-2265 by at least 20 ° C. What is claimed is: 1. An improved grease composition containing one phosphorus and boron containing composition, wherein the phosphorus and boron containing composition comprises (A) at least one boron containing compound and (B) at least one A grease composition prepared by reacting a formulation with a phospholipid. 18. The grease composition according to claim 17, wherein the simple metal soap is a fatty carboxylic acid salt. 19. The grease composition according to claim 17, wherein the simple metal soap is an alkali metal soap, an alkaline earth metal soap or an aluminum metal soap. 20. The grease composition according to claim 19, wherein the simple metal soap is an alkali metal soap. 21. The grease composition according to claim 19, wherein the simple metal soap is an alkaline earth metal soap. 22. The grease composition according to claim 20, wherein the simple metal soap is sodium soap or lithium soap. 23. The grease composition according to claim 21, wherein the simple metal soap is calcium soap or magnesium soap. 24. The grease composition according to claim 18, wherein the fatty acid is a C _{8 to} C ₂₄ monocarboxylic acid. 25. The grease composition according to claim 18, wherein the fatty acid is hydroxy-substituted. 26. The grease composition according to claim 25, wherein the simple metal soap is 12-hydroxystearate. 27. The grease composition according to claim 17, wherein the phospholipid (B) is a monoacylglycerophospholipid or a diacylglycerophospholipid. 28. The grease composition according to claim 17, wherein the phospholipid (B) is a monoacyl or diacylphosphatidylcholine, phosphatidylethanol, phosphatidylserine, phosphatidylinositol, phosphatidic acid or a mixture thereof. 29. The method of claim 27, wherein each acyl group is independently myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, arachidonic acid or mixtures thereof. Grease composition. 30. The grease composition according to claim 17, wherein the phospholipid (B) is at least one lecithin. 31. The phospholipid (B) is soybean, cottonseed, corn, rapeseed, sunflower seed, peanut, coconut,
At least one of gourd seeds, wheat, barley, rice, olives, mangos, avocados, papayas and carrots
31. The grease composition of claim 30, which is a seed-derived lecithin. 32. The grease composition according to claim 17, wherein the phospholipid (B) is a synthetic phospholipid. 33. The grease composition according to claim 17, wherein the boron-containing compound (A) is boric acid. 34. The phosphorus- and boron-containing composition comprises a boron-containing compound (A), a phospholipid (B), an amine (C), an acylated nitrogen-containing compound (D), a carboxylic acid ester (E), 18. The preparation according to claim 17, prepared by reacting with a Mannich reaction product (F), a basic nitrogen-containing polymer (G) or a mixture of an organic acid with a neutral metal salt or a basic metal salt (H). Grease composition. 35. The phosphorus- and boron-containing composition comprises a boron-containing compound (A), an amine (C), and an acylated nitrogen-containing compound having a substituent containing an average of about 40 or less carbon atoms ( D), a carboxylic acid ester (E), a Mannich reaction product (F), a basic nitrogen-containing polymer (G), or a neutral or basic metal salt of an organic acid (H) is reacted, The grease composition according to claim 17, which is prepared by forming an intermediate and then reacting the intermediate with a phospholipid (B). 36. A method of increasing the dropping point of an oil-based simple metal soap thickened base grease measured by ASTM method D-2265 by at least about 20 ° C., wherein (A) at least 1
A phosphorus- and boron-containing composition prepared by reacting a blend of one boron-containing compound with (B) at least one phospholipid, in the base grease, based on the total weight of the grease composition. And adding in a small amount sufficient to raise the dropping point of the base grease by at least 20 ° C.