JPH01502031A - Grease and gear lubricating compositions containing at least one metal-containing composition and at least one sulfurized organic compound - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] at least one metal-containing composition and at least one sulfurized organic compound Contain something. Grease lubricating compositions and gear lubricating compositions Lord's favor l ass Ω mamedate The present invention relates to grease lubricating compositions and gear lubricating compositions, and in particular to grease lubricating compositions and gear lubricating compositions. The present invention relates to additives for improving the extreme pressure properties of lubricating compositions and gear lubricating compositions. more special The present invention provides at least one metal-containing composition and at least one metal-containing composition. Contains sulfurized organic compounds. Regarding these lubricating compositions. It is Gri Additions that provide improved load-bearing properties to base or gear lubricating compositions. It is a combination of two components made up of a mixture.

Lid stop level Additives of the type of the invention are suitable for use in lubricants formulated for very specific applications, especially It has been found to be used as a lubricant in metalworking processes. Uses like this No. 4,505,830 and co-pending application filed by the same applicant. One of them is U.S. Patent Application No. 777.475 (filed September 18, 1985). Disclosed.

A mixture of zirconium salts of carboxylic acids, or carboxylic acids and at least one mixture of oil-soluble, sulfur-containing extreme pressure agents (this additive mixture is useful in lubricants). A similar type of additive containing It is shown.

Hydrogenated disulfide compounds useful as extreme pressure additives in lubricating oils are It is disclosed in Patent No. 4,228,021.

U.S. Pat. No. 4,283,294 describes Group IIA overbased d) Addition mixture of a metal salt and an overbased metal salt of group IA, which is.

may further contain an organic sulfur antioxidant compound) is disclosed. There is. This patent states that lubricating oil compositions containing such additive mixtures are It is disclosed that it is useful in diesel engines.

U.S. Pat. Nos. 4,394,276 and 4,394,277 include various Oxygen-containing alkanediols can be formulated as lubricating oils and reduce fuel consumption in internal combustion engines. It is disclosed that this can be effectively reduced.

U.S. Pat. No. 3,384,586 describes various non-Newtonian colloidal dispersions and and dispersed materials. This system and substance can be used in lubricating oils to improve It is useful for providing specific rheological properties.

Any of the above disclosures may be useful in grease or gear lubricant formulations. It does not teach mixtures and, more specifically, that these mixtures have extreme pressure properties. when evaluated.

It has been pointed out that it gives an unexpectedly high welding point.

Lord royal! hill In accordance with the present invention, a grease composition has been developed that provides improved extreme pressure properties.

Further in accordance with the present invention, a metallic tone composition (preferably.

a basic alkaline earth or alkali metal salt substance) and at least one sulfur Additive mixtures of chemically modified organic compounds can modify the extreme pressure properties of grease compositions in unpredictable ways. It has been discovered that the improvement is even greater.

A further nine inventive additive mixtures according to the invention are also available.

It has been discovered that it may be useful in gear lubricant compositions.

Further, according to one aspect of the present invention, a negative aspect of a grease lubricating composition and a gear lubricating composition is provided. A method of improving load-bearing properties is provided.

These and other aspects of the invention will become clear to you upon reading and understanding this specification. will be clear to those skilled in the art.

■Star n plate for the main lord The load-bearing properties of grease compositions and gear lubricants are determined by the It has been discovered that unforeseen improvements can be made by formulating with additive mixtures. It is. Specifically, the additive mixture contains the following ingredients; (A) a metal-containing component; a composition; and (B) at least one sulfurized organic compound.

Component (1) of this additive mixture is a Newtonian material or a non-Newtonian colloid. It can be made into a do-shaped dispersion system. This distributed system.

A solid metal-containing material predispersed in a dispersion medium of at least one inert organic liquid. colloidal particles, and organic compounds, which are substantially dissolved in this dispersion medium. a third component selected from the class consisting of This organicization The molecule of the compound (i.e. the third component) contains a polar substituent and a hydrophobic moiety within one molecule. It is characterized by having. Such a system is described in US Pat. No. 3.38 discussed above. No. 4.586, the contents of which are solely based on such disclosure. The metal-containing compositions of the present invention are preferably with alkaline earth metals or alkali metals.

It is a salt with at least one acidic organic compound. These salt substances are known to those skilled in the art as Also, 'overbased'.

“superbased” and “hyperbased” (byperbased) a metal-containing substance that can be described by technical terms such as “salt” It is recognized that it is a composition. This term is.

In addition to the substances of the present invention, other classes of metal-containing substances (which may be used in lubricating oil compositions) (used as a cleaning agent and/or dispersant) being admired. These preparation methods are usually 2g overbased (overbasis). The term “metallic ratio” is also used to describe these salts. or used to define the amount of metal in a complex compared to the amount of organic anion. It is being This metal ratio is the anion (which is the compound in which it is included) relative to the number of equivalents of ) present in the normal salt based on the normal stoichiometry of number of metal equivalents For the purposes of this invention, defined as the ratio of 0 to 5 or higher Such metal-containing compositions are also described in US Pat. No. 4.5, discussed above. No. 05,830, and No. 4.230.586. Simply this The content of this disclosure as it relates to metal-containing compositions is hereby incorporated by reference. Ru.

The specific metal cation constituting this metal-containing composition is not particularly important in the present invention. do not have. However, zinc dialkyldithiophosphate and dialkyldithiocal Zinc salts such as zinc bamate and similar zinc salts are excluded from the scope of this invention. It is intended that In other respects, in fact, any other metal salt can be added to this Useful for preparing component (A) of mixtures. More specifically, one addition of the present invention The metal compounds useful in preparing the overbase materials for mixtures are usually 9 in the periodic table. basic metal salts of Groups I-A and II-A as well as 9 Group B elements of the periodic table. There are transition metals other than zinc. Such metals include Na, K, Mg, Includes Ca, Ba, Ti, Cr, Fe, Mo, Cu, etc.

Also, group IV-A and group V-A metals such as Pb, Sn and sb 9 may also be useful within the scope of the present invention.

Alkaline earth metals as basic alkaline earth metal salts.

Preferred for the present invention, primarily calcium.

Includes magnesium, barium and strontium.

Calcium salts are the most preferred and most useful because of their effectiveness and relatively low cost. Acidic organic compounds are carboxylic acids, sulfonic acids, organophosphoric acids and phenols. Ru.

Sulfonic acids are preferably used to prepare component A.

These are represented by the formula R' (SOJ), and (R''), T (SOJ). There is an acid that In these formulas, 11 is an aliphatic or aliphatic-substituted cycloaliphatic A hydrocarbon group or substantially a hydrocarbon group.

These groups have acetylenic unsaturation and have up to about 60 carbon atoms. If R1 is aliphatic, it is usually 9.

Contains at least about 15 carbon atoms. When R1 is an aliphatic W-substituted cycloaliphatic group , the aliphatic substituents usually have a total of at least about 12 carbon atoms. . Examples of R1 include an alkyl group.

There are alkenyl groups and alkoxyalkyl groups, and aliphatic substituents include alkyl, Alkenyl, alkoxy, alkoxyalkyl, carboxyalkyl, etc. . Generally, this cycloaliphatic nucleus is a cycloalkane or cycloalkene (e.g. cyclopenkune, cyclohexane, cyclohexene or cyclopentene) derived from. Specific examples of R1 include cetylcyclohexyl group, laurylcyclohexyl group, lohexyl, cetyloxyethyl, octadecenyl, and petroleum, saturated or or unsaturated paraffin waxes, and olefin polymers (which are monopolymerized monomer containing about 2 to 8 carbon atoms per monomer unit. (including olefins and diolefins), R1 is the carbon Other substituents may also be included so long as they do not substantially impair the hydrogenated properties. these Substituents include 1, for example, phenyl, cycloalkyl, hydroxy, mercapto, halogen. nitro, amino, nitroso, lower alkoxy, lower alkyl mercapto, carbon carboxy, carbalkoxy, oxo or thio, or interrupting groups (e.g. - NH-, -0- or -5-).

R2 is generally a hydrocarbon group or a substantially hydrocarbon group; Free of tyrenic unsaturation and having about 4 to about 60 aliphatic carbon atoms. child These groups are preferably aliphatic hydrocarbon groups such as alkyl and alkenyl. Ru.

However, pt may include substituents or interrupting groups such as those listed above. provided that it retains its hydrocarbon character.

May contain. - Any non-carbon atoms present in R1 or R2 in the melon However, it is inconceivable that it exceeds 10% of its total weight.

The group T is an aromatic hydrocarbon (eg benzene, naphthalene).

anthracene or biphenyl), or heterocyclic compounds (e.g. pyridine, iridium) isoindole or isoindole). Usually, T is The aromatic hydrocarbon nucleus 9 is particularly a benzene nucleus or a naphthalene nucleus.

The subscript X is at least 1, and generally 1-3.

The subscripts r and y have an average value of about 1 to 4 per molecule.

And in general, it is still 1.

Exemplary sulfonic acids useful in preparing component A include mahogany sulfonic acid, persulfonic acid, Trolatam, sulfonic acid, mono- and polywax-substituted naphthalene sulfones acid, cetylchlorobenzenesulfonic acid, cetylphenolsulfonic acid, cetylf phenolic disulfide sulfonic acid, cetoxycabrylbenzene sulfonic acid, disulfide Dicetylthianthrene sulfonic acid, zira uryl-β-naphthol sulfonic acid, capril nitronaphthalene sulfonic acid, Saturated paraffin wax sulfonic acid, unsaturated paraffin wax sulfonic acid, Droxy-substituted paraffin wax sulfonic acid, tetraisobutylene sulfonic acid, Tetra-amylene sulfonic acid, chloro-substituted paraffin wax sulfonic acid, nitrate Roso-substituted paraffin wax sulfonic acid 9 Petroleum naphthenesulfonic acid, cetyl sulfonic acid Clopentylsulfonic acid, laurylcyclohexylsulfonic acid.

Mono- or polywax substituted cyclohexyl sulfonic acid.

Post-dodecylbenzene sulfonic acid, sulfonic acid “dimer alkyl ester” These sulfonic acids are known in the art and are further described herein. There's no need to argue.

Suitable carboxylic acids include aliphatic carboxylic acids, cycloaliphatic carboxylic acids, and aromatic carboxylic acids. Aromatic monobasic and polybasic carboxylic acids (these have acetylenic unsaturation) ) are included. The carboxylic acids include naphthenic acid, alkyl or Kenyl-substituted cyclopenconic acid, alkyl- or alkenyl-substituted cyclohexa and alkyl- or alkenyl-substituted aromatic carboxylic acids. child The aliphatic acids generally have about 8 to about 50 carbon atoms, preferably about 12 to about It has 25 carbon atoms. Cycloaliphatic carboxylic acids and aliphatic carboxylic acids Preferably they may be saturated or unsaturated. Specific examples include 2-ethyl Hexanoic acid, lylunic acid.

Maleic acid, behenic acid substituted with propylene tetramer.

Isostearic acid, pelargonic acid, capric acid, palmitic acid leic) acids, linoleic acid, lauric acid, oleic acid.

Ricinoleic acid, undecylic acid, dioctylcyclopentanecarboxylic acid, myristi dilauryldehydronaphthalenecarboxylic acid, stearyl-octa-hydro Indene carboxylic acid.

palmitic acid, alkyl and alkenyl succinic acid, petrolatum or hydrocarbon Acid formed by oxidation of base wax.

and commercially available mixtures of two or more carboxylic acids (e.g., tall oil acid, dinic acid), etc.

Pentavalent phosphorus-containing acids useful in preparing component A can be represented by the following formula: Here, each of R2 and R4 is hydrogen or a hydrocarbon group.

or a substantially hydrocarbon group, which preferably has from about 4 to about 25 carbon atoms. ), and at least one of R3 and R' is a hydrocarbon group or is essentially a hydrocarbon group;

Each of xZ, X3 and X4 is oxygen or sulfur; and a and b each is 0 or 1. Therefore, this phosphorus-containing acid is an organic phosphoric acid, a phosphorus Acids or phosphinic acids, or thio analogs of either of them, may be Appropriate.

Typically, this phosphorus-containing acid is a first-order acid: where p2 represents up to 18 carbon atoms. is a phenyl group or (preferably) an alkyl group having an elementary atom, and R' is hydrogen.

or similar phenyl or alkyl groups. Mixtures of phosphorus-containing acids such as Polymer is preferred because it is easy to prepare.

Component A is a phenol (i.e., a compound containing a hydroxyl group directly bonded to an aromatic ring). can be prepared from The term “phenol” as used here is Compounds with more than one hydroxyl group attached to an aromatic ring (eg, catechol).

resorcinol and hydroquinone). It also requires creso Alkylphenols, such as alcohol and ethylphenol, and alkenylphenols, such as Nols are included.

at least one atom containing about 3 to 100 carbon atoms, and especially about 6 to 50 carbon atoms. Phenols with alkyl substituents are preferred. One example of these phenols For example, heptylphenol.

Octylphenol, dodecylphenol, tetrapropene alkylated phenol octadecylphenol and polybutenylphenol. more than one Also phenols with an alkyl substituent. may be used, but monoalkylphin Enols are preferred because they are useful and easy to manufacture.

The above phenol and at least one lower aldehyde (herein referred to as "lower") The term refers to aldehydes with not more than 7 carbon atoms). , is also useful.

Suitable aldehydes include formaldehyde, acetaldehyde, propional Includes dehyde, butyraldehyde, valeraldehyde and benzaldehyde. It will be done. Also, reagents obtained from aldehydes (e.g., paraformaldehyde, Rioxane, methylol, methylformcel (1'1ethyl Formce) l) and valaldehyde) are also suitable. formaldehyde and formal Reagents derived from dehydes are particularly preferred.

The equivalent weight of an acidic organic compound is the molecular weight of an acidic organic compound. In other words, the value divided by the number of sulfonic acid groups, carboxy groups, or acidic hydroxy groups) be.

Basic alkaline earth metal salts, which range from about 4 to about 40, preferably from about 6 to about 30 ．． in particular having a metal ratio of about 8 to about 25).

Particularly preferred for use as component A. This salt is determined by the solidification temperature of the reaction mixture. at a temperature between the decomposition temperature of Prepared by bringing reagents (A-1) and (A-2) into sufficient contact: (A-1) Carbon dioxide 2g selected from the group consisting of hydrogen hydride and sulfur dioxide At least one acidic gaseous substance.

(^-2) Reaction mixture containing the following components: (A-2-a) Overbased At least one oil-soluble sulfonic acid or its derivative capable of; (A-2-b ) at least one alkaline earth metal or basic alkaline earth metal compound ; (A-2-c) at least one lower aliphatic alcohol; and.

(A-2-d) One type of oil-soluble carboxylic acid or a functional derivative thereof.

Reagent A-1 may be carbon dioxide, hydrogen sulfide or sulfur dioxide. at least is also an acidic gaseous substance, and also mixtures of these gases. Useful.

Carbon dioxide is relatively inexpensive, useful, easy to use, and performs well. Therefore, it is preferable.

Reagent A-2 is a mixture containing at least four components. Of these, the ingredients A-2-a is at least one oil-soluble sulfonic acid, as defined above; is its derivative (this is.

mixtures of sulfonic acids and/or their derivatives, which can be overbased Things too. can be used. Sulfonic acid derivatives that can be overbased include These metal salts, especially.

Alkaline earth salts, copper salts, manganese salts, iron salts and lead salts; ammonium salts and salts (e.g., ethylamine salts, butylamine salts, and ethylene polyamine salts) salts); and esters (e.g. butylamine and ethylene polyamine salts): and esters (e.g. ethyl esters, butyl esters and glycerol esters).

Component A-2-b is at least one alkaline earth metal or a basic compound thereof It is. Examples of basic alkaline earth metal compounds include hydroxides and alkoxides. (Typically, the alkoxy group has up to 10 carbon atoms, preferably 7 or carbon atoms), hydrides and amides. Therefore, useful bases Chemical alkaline earth metal compounds include calcium hydroxide, magnesium hydroxide, water Barium oxide, strontium hydroxide, calcium oxide, magnesium oxide, acid Barium oxide, strontium oxide, calcium hydride, magnesium hydride, water Barium chloride, strontium hydride, calcium ethoxide, calcium but Included are oxides and calcium amides. Calcium oxide and calcium hydroxide lucium, and calcium lower alkoxides (i.e. up to 7 carbon atoms) Particularly preferred are alkoxides having

For the purpose of the present invention, the equivalent weight of component A-2-b is determined because this alkaline earth metal is divalent. , equal to twice its molecular weight.

Component A-2-c is at least one lower aliphatic alcohol.

Exemplary alcohols, preferably monohydric or dihydric alcohols, include methanol. alcohol, ethanol, 1-propanol, 1-hexanol, isopropanol, sobutanol, 2-pentanol, 2,2-dimethyl-1-propatol, ethyl lene glycol, 1-3-propanediol, and 1,5-bentanediol There is. Among these, the preferred alcohol is methanol.

ethanol and propatool, with methanol being particularly preferred. Component B-2 The equivalent weight of -c is the value obtained by dividing its molecular weight by the number of hydroxyl groups per molecule.

Component A-2-d is at least one oil-soluble carboxylic acid as described above; is a functional derivative of Particularly suitable carboxylic acids are those of formula 5 R'(COOH), It is bonic acid. Here, n is an integer of 1 to 6, preferably 1 or 2, And R5.

Contains at least 8 aliphatic carbon atoms. saturated or substantially saturated aliphatic group (preferably a hydrocarbon group). Depending on the value of n, B% is monovalent to hexavalent It is the basis.

R5 may contain non-hydrocarbon substituents. However, this substituent does not substantially change its properties. Such substituents preferably exceed about 10% by weight. It exists in an impossible amount.

Exemplary substituents include the non-hydrocarbon substituents listed above in connection with component A-2-a. R5, which includes substituents, is also based on the total number of carbon-carbon covalent bonds present. up to a maximum of 5%.

Preferably it may have an olefinic unsaturation of not more than 2% of olefinic bonds. R The number of carbon atoms in s depends on the origin of R5.

Usually about 8 to 700 pieces. Carboxylic acids and their derivations, as discussed below A preferred series of polymers are olefin polymers or hydrogenated olefin polymers and α , β-unsaturated acids or their anhydrides (e.g. acrylic acid, methacrylic acid, maleic acid) or fumaric acid, or maleic anhydride) to produce the corresponding substitution. prepared by forming an acid or its derivative. R in these products 5 is about 150 to 9, for example, as determined by gel permeation chromatography. It has a number average molecular weight of about 10,000° and usually about -700 to about 5000.

Monocarboxylic acids useful as component A-2-d have the formula R5COO[(; Examples of acids such as caprylic acid, capric acid, valmitic acid, stearic acid, These include isostearic acid, linoleic acid and behenic acid. Particular preference for monocarboxylic acids A beautiful group.

Hydrogenated olefin polymers (e.g. chlorinated polybutene) and acrylic acid Or prepared by reaction with methacrylic acid.

Suitable dicarboxylic acids include substituted succinic acids having the linear formula: RbC)IcOOH Here Rh is the same as R5 defined above. R6 is the following things is a group derived from an olefinic polymer, such as formed by the polymerization of mer ; this monomer is 9 e.g. ethylene, propylene, 1-butene, isobutyne, 1 -pentene, 2-pentene, 1-hexene and 3-hexene. R6 is.

It may also be derived from high molecular weight, substantially saturated petroleum fractions. This hydrocarbon substituted Citric acid and derivatives thereof are component A-2-d.

The above-mentioned classes of carboxylic acids derived from olefin polymers and their derivatives Conductors are known in the art.

These t! ! The am method is one representative of the types useful in the present invention, as well as a number of It is described in detail in US Pat. No. 1, eg, US Pat. No. 4,119,549.

Functional derivatives of the acids discussed above are useful as component A-2-d.

Included are anhydrides, esters, amides, imides, amidines, and metal salts. O Succinic acid substituted with a refin polymer.

and mono- or polyamines (particularly polyamines having up to about 10 nitrogen atoms) Realkylene polyamines) are particularly suitable. Such reaction products are generally contains a mixture of one or more amides, imides and amidines.

Polyethylene amines containing up to about 10 nitrogen atoms and polybutene-substituted Citric anhydride (where this polybutene group is

The reaction products with 0-functional inducers (predominantly containing isobutyne units) are particularly useful. This group of conductors includes amic acids in the following compounds: Carbon sulfide, boron compounds, nitrile, urea, thiourea, guanidine, alkylene There are oxides, etc. Such substituted succinic anhydride semiamides, semimetallic salts, and Also useful are semiesters and semimetallic salt derivatives.

This substituted acid or its anhydride and a heptano or polyhydroxy compound (e.g. Esters prepared by reaction with fatty alcohols or phenols) are also useful It is. Succinic acid or its anhydride substituted with an olefin polymer and a polyvalent fat group alcohols (which contain 2 to 10 hydroxyl groups and up to about 40 aliphatic carbons) esters containing atoms) are preferred.

This class of alcohol includes ethylene glycol, glycerol, and sorbitol. pentaerythritol, polyethylene glycol, jetanolamine, Reethanolamine.

N,N-di(hydroxyethyl)ethylenediamine, and the like are included. This a When the alcohol has a reactive amino group.

The reaction products include the reaction of acid groups with both hydroxyl and amino functional groups. The resulting products are included. therefore.

This reaction mixture contains half-esters, half-amides, esters, amides, and imides. may be included.

In summary, this non-metal moiety or anion is acetate.

Formate, carbonate, bicarbonate, sulfide, hydrogen sulfide, sulfite, bisulfite , chloride, or mixtures thereof.

The equivalent ratios of the constituents of reagent ^-2 can be varied over a wide range. Generally, component A-2- The ratio of components A-2-b to a is at least about 4:11 and usually greater than about 40=1. preferably between 61 and 30=1, most preferably between 8:1 and 25:1. It is between. This ratio may exceed 40:1 at one time, but such an excess Usually unfit for any useful purpose.

The equivalent ratio of component A-2-c to component A-2-a is between about 1:1 and 80:1. , preferably between about 2:1 and 50:1 and to component A-2-a. The equivalent ratio of component A-2-d is about 1:1 to about 1:20°, preferably about 1:2 to about 1 :10.

Reagent A-1 and Reagent A-2 are generally combined in such a way that no further reaction occurs between them. or until the reaction is substantially complete.

be contacted. Typically, this reaction results in no further formation of overbased products. Useful dispersions include the following: prepared when: i.e., the reaction has reached its completion point or “end point” Approximately 70% of reagent A-1 is sufficient for the reaction in terms of the amount needed if it is possible to proceed. If the contact between reagent 64 and reagent A-2 is maintained for a period of be.

The point at which the reaction is complete or substantially terminated can be determined by any of a number of conventional methods. It can be determined by One such method is to control gas (sample) entering and exiting the mixture. Measuring the amount of drug A-1): This reaction shows that the amount of gas leaving is equal to the amount of gas entering. It can be considered substantially complete when about 90-100% of the amount is reached. these Volume is easily determined by using metered inlet and outlet valves be done.

(Margin below) Reaction temperature is not critical. Generally, this temperature is the solidification temperature of the reaction mixture; (i.e., the lowest decomposition temperature of all these components). General Normally, this temperature is.

About 25°C to about 200°C, preferably about 150°C. Reagent A-1 and reagents A-2 can be conveniently contacted at the reflux temperature of this mixture. This temperature It clearly depends on the boiling points of the various components: therefore, as component A-2-c, If methanol is used, this contact temperature is approximately the reflux temperature of methanol. .

This reaction is usually carried out at atmospheric pressure. However, pressures above atmospheric pressure accelerate the reaction. and promote optimal utilization of Reagent A-1. This process is carried out under reduced pressure. is also possible.

For obvious practical reasons, this is rarely done.

This reaction is usually carried out using a substantially inert, usually liquid organic diluent (this may be a dispersion medium or and reaction medium). This diluent has 9 reactions Contains at least about 10% of the total weight of the part. Usually it is about 80% by weight and preferably from about 30 to about 70% by weight.

Although a wide variety of diluents are useful, it is preferred to use diluents that are soluble in the lubricating oil. This diluent usually contains a lubricating oil which itself has a low viscosity.

Other organic diluents may be used alone or in combination with the lubricating oil. this eye Preferred diluents for this purpose include aromatic hydrocarbons (e.g., benzene, toluene, and xylene); their halogenated derivatives (e.g. chlorobenzene); low boiling point petroleum distillates (e.g. petroleum ether and various naphthas); usually liquid fats group hydrocarbons and cycloaliphatic hydrocarbons (e.g. hexane, heptane, hexane) cyclohexene, cyclopenkune, cyclohexane and ethylcyclohexane Sun).

and halogenated derivatives thereof. Dialkyl ketones (e.g. di- propyl ketone and ethyl butyl ketone), and alkylaryl ketone ( For example, acetophenone), ethers (e.g., n-propyl ether, n- butyl ether, n-butyl methyl ether and isoamyl ether) are equally useful.

When a combination of oil and other diluents is used, the weight ratio of oil to other diluents is: Generally, about 1:20 to about 20=1.

Mineral lubricating oils are usually used, especially if the product can be used as a lubricating additive. preferably contains at least about 50% by weight diluent, the diluent being inert. As such, the total amount of diluent present is not particularly important. However, this The diluent 9 usually contains about 10 to 80% by weight of the reaction mixture, preferably about 30 to 70% by weight. Contains compounds.

This reaction is preferably carried out under anhydrous conditions. but.

Small amounts of water may be present (e.g. because industrial grade reagents are used) . Water may be present in amounts up to about 10% by weight of the reaction mixture without deleterious effects. You may do so.

Once the reaction is complete, any solids in the mixture are preferably removed by filtration or other removed by conventional means. Easily removable diluent, alcohol alcoholic promoter, and water (which are formed during one reaction) in a conventional process such as distillation. Typically, substantially all of the water that can be removed by conventional methods is added to the reaction mixture. It is desirable to remove it from The presence of water makes filtration difficult and fuel This is because an undesirable emulsion is formed in the lubricant. these that exist All water can be easily purified by heating at atmospheric or reduced pressure, or by azeotropic distillation. removed.

The chemical structure of component A is not known with certainty. This basic salt or complex is It can be a solution or, more commonly, a stable dispersion. On the other hand, these are acidic substances formed by the reaction of oil-soluble acids, overbased oil-soluble acids, and metal compounds. It will be done. May be considered "polymerizable salts". Considering the above, these compositions , with reference to the way they are formed.

most conveniently defined. Representative examples of such useful compositions are provided in the Examples below. More exemplified.

l plying A 60% oil solution of 750 parts of sodium mahogany sulfonate was added to calcium chloride. Mahogany sulfonic acid Prepare calcium. When this reaction mass is heated at 90-100°C for 4 hours, , this sodium mahogany sulfonate is converted to calcium mahogany sulfonate. become 54 parts of 91% calcium hydroxide solution are then added and this material is Heat to 150°C for hours.

Once the material had cooled to 40°C, 98 parts of methanol was added.

Then, 152 parts of carbon dioxide is introduced at 42-43°C for 2 hours. Next, water and alcohol are removed by heating this mass to 150°C. Remove. Residue from reaction vessel.

Dilute with 100 parts of mineral oil. This filtered oil solution and the desired carbonation Calcium sulfonate overbased material obtained has the following analysis: Acid ash content, 16.4%; neutralization value (this is the ), 0.6 (acidic); and metal ratio, 2.5° 2890 parts of the overbased material of Example 1 (based on sulfonate anion) , 2.7 g equivalent), calcium phenate 2 prepared as shown below. 17 parts (0.25 equivalents), 939 parts of mineral oil, 494 parts of methanol, isobutyral 201 parts of coal, 128 parts of mixed isomerized 17th mill alcohol, which is Approximately 65% normal amyl alcohol, 3% isoamyl alcohol and 32 % 2-methyl-1-butyl alcohol).

4.7 parts of calcium chloride dissolved in 5.8 parts of water and 91% calcium hydroxide A mixture containing 428 parts (10,6 equivalents) of um.

Stir vigorously at 40 °C and oxidize for 1.2 h at 40-55 °C. 146 parts of carbon are introduced. After that, add calcium hydroxide in 5 doses, each time. and each such addition, as previously indicated, was added in an amount of 173 parts. , introducing carbon dioxide. 6th addition of calcium hydroxide and carbonation After the process was completed, the reaction mass was carbonated for an additional hour at 40-55°C. The neutralization value of this mass is reduced to 55 (basic). This carbonated The reaction mixture was then heated to 150°C under a nitrogen atmosphere, and the alcohol and Remove by-product water. Add 908 parts of oil and then add the contents of this reaction vessel. filter things. This filtrate, i.e. the desired carbonated starch with a high metal ratio, An oil solution of calcium sulfonate overbased material has the following analytical values: S: Sulfate ash content 52.7; Neutralization number 50.9 (basic); Total base number 42 0 (basic): and metal ratio 20.25° 2550 parts of mineral oil, 960 parts (5 moles) of heptylphenol, and 50 parts of water were reacted. Calcium used above was added to the reaction vessel and stirred at 25°C. A phenate is prepared. This mixture was heated to 40°C and the calcium hydroxide Um 7 parts.

and 231 parts (7 moles) of 91% commercially available rose formaldehyde over 1 hour. Add it up. Heat the contents to 80°C.

and an additional 200 parts of calcium hydroxide (this totals 207 parts or 5 molar) is added over a period of 1 hour at 80-90°C. Helps remove water To do this, heat the contents to 150°C while blowing nitrogen through the mixture; This temperature is then maintained for 12 hours. If foaming occurs, use 9-polymerized dimethylene. A few drops of silicone antifoam may be added to control foaming.

The reaction mass is then filtered. This filtrate, i.e. heptylphenol- 33.6% oil of the desired calcium phenate of formaldehyde condensation product The solution is found to contain 7.56% sulfate ash. this type The boronated complexes of the basic alkaline earth metal salts can be prepared by It can be prepared by heating with uric acid. The number of equivalents of boric acid is Equal to about half the equivalent number of potash earth metals. Of U.S. Patent No. 3,929,650 is incorporated herein by reference for its disclosure of boronated complexes.

1 ship group leader (a) 1.145 grams of a 40% solution of barium mahogany sulfonate in mineral oil (1,0 equivalents) and grams of methyl alcohol at 55°C. While blowing carbon dioxide through the mixture at a rate of 2 to 3 cubic feet per hour, Add 220 grams of barium oxide. to this mixture. Spraying carbon dioxide , add an additional 78 grams of methyl alcohol, then add 460 grams of barium oxide. Add mu. The carbonated product was heated to 150°C for 1 hour and filtered. pass. This filtrate.

The barium sulfate ash content was found to be 53.8% and the metal ratio to be 8.9. be done.

(b) A total of 16 equivalents of barium oxide per equivalent of barium mahogany sulfonate. Carbonated basic metal salts according to procedure (a), except using Prepare. This product has a metal ratio of 13.4.

Back soil Mineral oil 520 parts (weight basis), sodium petroleum sulfonate (molecular weight 480) 48 A mixture of 0 parts and 84 parts of water is heated at 100°C for 4 hours. Then this The mixture was mixed with 86 parts of a 76% aqueous solution of calcium chloride, and 72 parts of lime (90% purity). 2 hours at 100°C until the water content is less than 0.5%. Heat to dehydrate, cool to 50°C, mix with 130 parts of methyl alcohol, Then blow carbon dioxide at 50°C until substantially neutral. This mixture was heated to 150°C to remove methyl alcohol and water, and the obtained Filter the basic calcium sulfonate oil solution. This filtrate is May have a lucium ash content of 16%, and a metal ratio of 2.5.

be discovered.

1, 305 grams of carbonated calcium sulfonate as described above.

930 grams of mineral oil, 220 grams of methyl alcohol, 72 grams of isobutyl alcohol Prepare a mixture of 38 grams of alcohol, and 38 grams of 17th mill alcohol and heat to 35°C. and perform the following operating cycle four times; 90% calcium hydroxide. and this mixture until it has a base number of 32-39. .

The resulting product was then treated with carbon dioxide at 155 °C for 9 hours. The alcohol is removed by heating to 70°C and filtered through a ridge filter aid at this temperature. child The filtrate has a calcium sulfate ash content of 39.5% and a metal ratio of 12.2. have.

1st ■1 Tridecylbenzene bottoms (canned liquid, these bottoms.

sulfonic acids (consisting of a mixture of mono-, di- and tridecylbenzenes) 880 grams (0,968 moles) of a 57.5% solution of calcium in oil, methane 1,549 grams of calcium hydroxide, and 59 grams (1,58 equivalents) of calcium hydroxide. The mixture is introduced into one reaction vessel and stirred vigorously. This whole thing is heated to 40-45℃ Heat it up.

Zero-order carbon dioxide is introduced for 0.5 hours at a rate of 2 cubic feet per hour. The carbonated reaction mixture was then heated to 150°C to remove the alcohol and the remaining Remove all water present.

The residue is then filtered for purification purposes. This product i.e. the desired over A 61% oil solution of based and carbonated calcium sulfonate is: Analytical values are shown: Ash content, 16.8%: Neutralization value, 7.0 (acidic); and gold Metal ratio, 2.42゜Alkali metal or alkaline earth metal oxide, hydroxide or By further carbonation in the presence of alkoxides or alkoxides, this metal ratio can be reduced. , can easily be increased to 3.5 or more.

Particular species of component (B) as well as component (A) of this additive mixture.

That is, the sulfurized organic compound is not particularly important to the present invention. death However, sulfur is present as a sulfide moiety (i.e. in the divalent oxidation state). , incorporated into the organic compound, and the component is preferably oil-soluble. Growth Component (B) is aliphatic hydrocarbon, arylaliphatic hydrocarbon or alicyclic hydrocarbon. It can be a product. Olefinic hydrocarbons having about 3 to about 30 carbon atoms are 2 Preferred for the purposes of the present invention.

The olefinic hydrocarbons that can be sulfurized to form component B are diverse in nature. Ru. These are non-aromatic double bonds (i.e. connecting two aliphatic carbon atoms). has at least one olefinic double bond defined as Ru. In its broadest sense, this olefinic hydrocarbon has the formula R'R"C=C R'R' can be defined as: , : , R', R'', R' and RI each of G is hydrogen or a hydrocarbon group (especially alkyl or alkenyl) . Any two of R7, a8.2% and RIG together form an alkylene or a substituted alkylene group; i.e., this olefin The compound may be cycloaliphatic.

Monoolefin compounds and diolefin compounds, especially the former, are used to prepare component B. preferred, especially for terminal monoolefinic hydrocarbons; i.e. R9 and RI G is hydrogen and R’! and R8 is alkyl (i.e., this olefin is aliphatic), preferably having about 3 to 30, especially about 3 to 20 carbon atoms. Particularly desirable are olefinic compounds having children.

Propylene, isobutyne and their dimers, trimers and tetramers, and mixtures thereof are particularly preferred olefin compounds. These compounds Of these, isobutyne and diisobutene are important because of their usefulness and It is particularly desirable because high sulfur content compositions can be prepared from the sulfur content.

The sulfiding reagent used to prepare component B may be one such as sulfur, halogenated ion, etc. (e.g. - sulfur chloride or sulfur dichloride), hydrogen sulfide and sulfur or diacids It may be a mixture with sulfur chloride, etc. Sulfur-hydrogen sulfide mixtures are often preferred. and will be referred to frequently hereinafter; however, where appropriate.

It is understood that other sulfiding agents may be substituted therein.

The amount of sulfur and hydrogen sulfide per mole of olefin compound is usually 1, respectively. about 0.3 to 3.0 gram atoms and about 0.1 to 1.5 moles. preferable The range is about 0.5 to 2.0 gram atoms and about 0.4 to 1.25 moles, respectively. and the most desirable ranges are about 1.2 to 1.8 gram atoms and about It is 0.4 to 0.8 mol.

The temperature range in which this sulfurization reaction is carried out is generally about 50-350°C. Like The preferred range is about 100-200"C, with about 125-180"C being particularly suitable. be. This reaction is often preferably carried out at or above atmospheric pressure; Natural pressure (i.e.

The pressure naturally occurring during the reaction process can be (and usually is) the pressure that occurs naturally during the reaction process. But this Alternatively, pressure applied from the outside may be used. The exact pressure developed during the reaction depends on the system settings and operation.

This depends on factors such as the reaction temperature and the vapor pressures of the reactants and products; This may change during the two reaction steps.

Incorporation of materials useful as sulfidation catalysts into this reaction mixture is often not acceptable. It becomes peace. These substances can be acidic, basic or neutral. But this thing The quality is preferably a basic substance, especially a nitrogen salt containing ammonia and amines. group, most often an alkylamine. The amount of catalyst used is generally It is about 0.05-2.0% by weight of the olefin compound. preferred ammonia In the case of acatalysts and amine catalysts, from about 0.0005 to 1 mole of olefin. 0.5 mole is preferred, and about 0.001 to 0.1 mole is particularly desirable.

Following preparation of this sulfurized mixture, substantially all of the low boiling materials are typically removed. can be carried out by providing an escape port in the reaction vessel, or by distillation at atmospheric pressure, vacuum by distillation or stripping or at a suitable temperature and pressure for this mixture. by passing an inert gas (e.g. nitrogen gas) through.

Preferably, it is removed.

A further optional step in preparing component B is the sulfidation obtained as described above. The product is treated to reduce active sulfur. An exemplary method is This is a treatment using remetal sulfide. Other selective treatments remove insoluble by-products. removes and properties of the sulfided composition (e.g. aroma properties9 color properties and dyeing properties) can be used to improve

U.S. Pat. No. 4,119,549 discloses suitable sulfurized compounds useful as component B. It is incorporated herein by reference for product disclosure. some specific sulfides The composition is described with respect to examples of its manufacture. The example below shows such The preparation of two compositions is illustrated.

disaster 1 plate person Jacketed high-pressure reactor (which includes a stirrer and internal cooling coils) (equipped with a) was charged with sulfur (629 parts, 19.6 moles). gas Chilled brine (br) is added to cool the reactor prior to the introduction of the reactants. ine).

Circulate through this coil. The reactor was sealed and depressurized to approximately 6 torr, After cooling, 1100 parts (19.6 moles) of isobutyne and sulfur were added to the reactor. Charge 334 parts (9.8 moles) of hydrogen hydride and 7 parts of n-butylamine. This anti The reactor was heated for about 1.5 hours using steam in an external jacket. Heat to a temperature of 71°C. During this heating, 720 psig at approximately 138°C reaches maximum pressure. Before reaching the maximum reaction temperature, the pressure begins to drop and As this gaseous reactant is consumed.

continues to decrease uniformly. After about 4.75 hours at about 171°C, unreacted hydrogen sulfide and and isobutine to a single recovery system. After the pressure inside the reactor begins to decrease to atmospheric pressure , this sulfurized product is recovered as a liquid.

Ura Rikudan Substantially in accordance with the procedure of Example 3, at a temperature of about 150-155°C, autogenous pressure was applied. in the presence of 2.6 parts of n-butylamine.

773 parts of diisobutene, 428.6 parts of sulfur, 143.6 parts of hydrogen sulfide and 1 Provide for reaction. The volatiles are removed and the sulfurized product is recovered as a liquid.

Component (A) combined with component (B) to formulate the additive mixture of the invention The amount of can be varied within a wide range. for example.

The weight ratio of (A):(B) can range from about 50:1 to about 1:1.

However, the preferred range is the weight ratio of (A):(B).

The ratio is about 20:1 to about 10:1.

Components (A) and (B) of this additive mixture are used to obtain the grease composition of the present invention. Divided into nine base materials for base grease or gear lubricants. Can it be added?

or can be added as a mixture.

Grease compositions, or base grease ingredients, are derived from both mineral and synthetic oils. be guided. This synthetic oil includes polyolefin oils (e.g., polybutene oil, oligomers, etc.).

Synthetic esters (e.g. dinonyl sebacate, trimethylolpropane trio) ctanoic acid esters, etc.), polyglycol oils, and the like. this grease The composition is first order.

Thickeners (e.g. sodium salts, calcium salts of fatty acids such as stearic acid, produced from these oils by adding lithium salts or aluminum salts). Ru. Only one component of the additive mixture of the present invention is added to this base grease raw material. Instead, other known or conventional additives may be mixed. Grease composition of the present invention 1 of the additives of the present invention, from about 1% to about 50% by weight of component A, and 0. Contains from 1% to about 5% by weight of component B. In a preferred embodiment, this group The effective amount of Component A in the wreath composition ranges from about 5% to about 25% by weight; And the effective amount of component B is about 0.5% to about 2% by weight.

may optionally be present in the grease composition and gear lubricant used in the present invention. Other additives include: Antioxidants, typically sterically hindered phenols.

Surfactant 7 Usually a nonionic surfactant (eg.

oxyalkylated phenols, etc.).

Corrosion inhibitor, wear inhibitor and rust inhibitor.

The friction modifiers listed below are alkyl esters or alkyl esters of diphosphoric acid or phosphorous acid. Kenyl ester (wherein the alkyl or alkenyl group has about 10 to about 40 carbon atoms), and their metal salts (especially zinc salts); C+ - fatty acid amides of ~2°; alkylamines of C0° to 2° (particularly talloamine and such amines and boric acid or ethoxylated derivatives); C acid (wherein this acid is partially esterified as indicated above) +0 to 2° alkyl-substituted imidacillins and analogous nitrogen heterocycles.

For comparison purposes, various grease formulations were tested in a 4-ball extreme pressure test (i.e., A STM D-2783>, and roller bearing rust test (i.e. A STM D-1748). Evaluated in related tests The results for two different grease compositions are shown in Tables 1 and 2.

(Margin below) As is clear from the results shown in the table above, especially Table I, this additive mixture (i.e. 4-Pole E (a combination of a metal-containing composition and a sulfurized organic compound) The P test yields unexpected synergistically high results for weld point and load wear indicators. You can get results. Benefits for grease compositions containing only component A or only component B It should be noted that the welding points used are 250 (Kg) each. but However, a grease composition containing both of these components (i.e., A and B) The welding point obtained for this is 500 (Kg). This sulfurized organic compound The addition of does not affect the rust and oxidation properties of this grease formulation. , further pointed out.

As previously pointed out, the additive mixture of the present invention may also be used in gear lubricating compositions. obtain. This lubricating composition is suitable for differential gears.

For use in rotating shafts, certain manual transmissions, etc.

Prepared and prescribed. These oils too. Mineral oil or Can be prepared from synthetic oils. however.

-Higher viscosity than tar oil. Moreover, these types of lubricants are suitable for extreme pressure conditions. must be exposed to. Therefore, this lubricant has extreme pressure agents in its formulation. Needs to be included. The additive mixture of the invention is in the same concentration range and thus It has been found to be particularly useful in preparing suitable gear lubricants.

The invention has been described and illustrated with respect to certain preferred embodiments thereof. However, those skilled in the art will be able to make various modifications and improvements here without departing from the spirit of the present invention. and recognizing that substitutions may be made, e.g. the A component of this additive mixture. and different proportions or amounts of component B (other than the preferred ranges indicated above) may be specified. Specific grease space feedstock or gear lubricant based feedstock or engine type or may be used as a result of a change, such as for a specific end use. Therefore, one invention is intended to be limited only by the scope of the following claims: international search report -lRumor-ma-1 frame-m, PCT/IJS 1171007m2 included! v’hT X To τ Sanko IN: ER, N input:: ON input L S”;; CM RE? (+ R” CN1m, -1+4@@kaw% PCT/US Ii17100712

Claims (30)

[Claims] 1. A grease composition containing an extreme pressure effective amount of a mixture containing the following ingredients: (A) at least one metal-containing composition; and (B) at least one sulfided composition; organic compounds. 2. The composition according to claim 1, wherein the component (A) comprises (A):( B) is combined with component (B) in a weight ratio of about 50:1 to about 1:1. 3. The composition according to claim 2, wherein the weight ratio of (A):(B) is , about 20:1 to about 10:1. 4. The composition according to claim 1, wherein the metal ratio of component (A) is small. At least 5.0. 5. The composition according to claim 1, wherein the component (A) is a metal-containing composition. The metals in the composition include alkali metals, alkaline earth metals, transition metals, and group IV-A metals. , a Group V-A metal or a mixture thereof; provided that the transition metal The genus is not zinc. 6. The composition according to claim 5, wherein the component (A) is a metal-containing composition. The metal of the composition is calcium or sodium. 7. The composition according to claim 5, wherein the non-metallic part of the metal-containing composition Minutes include acetate, fermentation salt, carbonate, bicarbonate, sulfide, hydrogen sulfide, sulfite. , bisulfite, chloride or mixtures thereof. 8. The composition according to claim 7, wherein the non-metallic part of the metal-containing composition Minutes are carbonates or bicarbonates. 9. The composition according to claim 1, wherein the sulfurized organic compound is Aromatic, alkyl or alkenyl sulfides or polysulfides, sulfurized olefin, sulfurized carboxylic acid ester, sulfurized ester olefin oil, sulphurized oil or mixtures thereof. 10. The composition according to claim 9, wherein the sulfurized organic compound is , a sulfurized olefin having about 3 to about 30 carbon atoms. 11. A method for improving load holding properties of grease compositions and gear droplet lubricants, the method comprising: , the grease composition or gear lubricant in an extreme pressure effective amount of a mixture containing the following ingredients: Methods include prescribing: (A) at least one metal-containing composition; and (B) at least one sulfided composition; organic compounds. 12. 12. The method according to claim 11, wherein the component (A) comprises (A): (B) is combined with component (B) in a weight ratio of about 50:1 to about 1:1. 13. 13. The method according to claim 12, wherein the weight ratio of the components (A): ( B) is about 20:1 to about 10:1. 14. 12. The method according to claim 11, wherein the metallization of component (A) comprises: At least 5.0. 15. The method according to claim 11, wherein the metal-containing composition of component (A) is The metals of the components are IV-A group metals, V-A group metals, alkali metals, alkaline earth metals. metals, transition metals, or mixtures thereof; with the proviso that the transition metals The genus is not zinc. 16. 16. The method according to claim 15, wherein the metal-containing composition of component (A) is The component metal is calcium or sodium. 17. 16. The method according to claim 15, wherein the non-metallic composition of the metal-containing composition is Parts are acetate, formate, carbonate, bicarbonate, sulfide, hydrogen sulfide, sulfite selected from the group consisting of salts, bisulfites, chlorides or mixtures thereof. 18. 18. The method according to claim 17, wherein the non-metallic composition of the metal-containing composition is The moiety is carbonate or bicarbonate. 19. 12. The method according to claim 11, wherein the sulfurized organic compound is , aromatic, alkyl or alkenyl sulfide or polysulfide, sulfide olefins, sulfurized carboxylic acid esters, sulfurized ester olefins oil, sulfurized oil, or a mixture thereof. 20. The method according to claim 19, wherein the sulfurized organic compound is , 3 to about 30 carbon atoms. 21. A gear lubricating composition containing an extreme pressure effective amount of a mixture containing the following ingredients: (A) at least one metal-containing composition; and (B) at least one sulfided composition; organic compounds. 22. 22. The composition according to claim 21, wherein the component (A) is (A) :(B) is combined with component (B) in a weight ratio of about 50:1 to about 1:1. 23. The composition according to claim 22, wherein the weight ratio of (A) and (B) is is about 20:1 to about 10:1. 24. The composition according to claim 21, wherein the metal ratio of component (A) is , at least 5.0. 25. The composition according to claim 21, wherein the component (A) contains a metal. The metals in the composition include alkali metals, alkaline earth metals, transition metals, N-A group metals, selected from the group consisting of Group V-A metals or mixtures thereof; with the proviso that said transition metals is not zinc. 26. The composition according to claim 21, wherein the component (A) contains a metal. The metal of the composition is calcium or sodium. 27. The composition according to claim 25, wherein the non-metallic composition of the metal-containing composition The genus part is acetate, formate, carbonate, bicarbonate, sulfide, hydrogen sulfide, sulfite. selected from the group consisting of acid salts, bisulfites, chlorides or mixtures thereof. 28. The composition according to claim 27, wherein the non-metallic composition of the metal-containing composition The genus part is carbonate or bicarbonate. 29. The composition according to claim 21, wherein the sulfurized organic compound is an aromatic, alkyl or alkenyl sulfide or polysulfide, sulfur olefin, sulfurized carboxylic acid ester, sulfurized ester olefin fins, sulfurized oil or a mixture thereof. 30. The composition according to claim 29, wherein the sulfurized organic compound is a sulfurized olefin having about 3 to about 30 carbon atoms.