JP2000044975A - Composition, lubricant, and functional fluid containing them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compsn. which imparts thermal stability, abrasion resistance, extreme pressure properties, corrosion-preventing properties, etc., to lubricants and functional fluids by incorporating a specific neutral or basic metal salt of an acidic org. compd., a metal deactivator, and a specific S- and/or P-contg. compd. into the same. SOLUTION: This compsn. contains a neutral or basic metal salt or B-contg. neutral or basic metal salt of an acidic org. compd. provided the metal is at least one selected from among alkali or alkaline earth metals, Zn, Cu, and Al; a metal deactivator; and at least one compd. selected from among P-contg. amides, P-contg. esters, S-bonded dithiocarbamates, and a compd. of the formula. In the formula, R1 to R4 are each H or hydrocarbyl provided each of R1 and R3 may be G1 or G2; R1 may combine with R2 to form a 4-7C alkylene, and so may R3 with R4; G2 is C(X)R, COOR, CN, R5C=NR6, CON(R)2, or NO2; G1 is G2 or CH2OH; X is O or S; R, R5, and R6 are each R1; when G1 and G2 are both R5C=NR6, then two R6 groups may combine with each other to form a hydrocarbylene group bonded to two N atoms; and x is 1 to about 8.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the following (A):
For compositions containing (B) and (C): (A) at least one neutral or basic metal salt or boron-containing neutral or basic metal salt of at least one acidic organic compound; (B) at least one metal deactivator; and (C) at least one sulfur and / or phosphorus containing compound. These compositions are useful in providing thermal stability and improved wear resistance, extreme pressure properties, load transfer properties and / or corrosion protection to lubricants and functional fluids.

[0002]

BACKGROUND OF THE INVENTION Hydraulic fluids containing zinc are widely accepted for numerous applications. These hydraulic fluids typically have excellent thermal stability and wear resistance due to the use of a zinc-containing antiwear agent therein.
Recently, however, problems with the accumulation of heavy metals such as zinc have increased in and around workplaces. This problem has led to a demand for hydraulic fluids containing ashless antiwear agents. Although ashless antiwear agents are available, hydraulic fluids based thereon typically lack sufficient thermal stability to be acceptable for many applications.

[0003] The document "Lubricant Additives" (published by MW Ranney from Neus-Data, Inc., Park Ridge, NJ (19)
73)) discloses many of the various metal salts of sulfonic and carboxylic acids and phenols. They are,
Useful as a detergent / dispersant in lubricating oil products.
Also, a document entitled "Lubricant Additives" (which is described in CV.
Smallheer and R.S. K.
Smith, Regius-Heels (L
(1967), published by the company ezius-Hiles (Cleveland, Ohio), also includes a number of detergents / dispersants, including sulfonates, phenates and carboxylates useful as dispersants. ) Was disclosed. U.S. Pat. 4,10
No. 0,082 discloses the use of neutral or basic metal salts of organic sulfur-containing acids, carboxylic acids or phenols as detergents / dispersants for fuels and lubricants.

[0004] US Pat. No. 4,627,928,
It discloses the use of a basic magnesium salt of a substituted aromatic hydroxycarboxylic acid as a dispersant, detergent, antiwear agent and the like for lubricants and fuels.

In a lubricating composition, as a metal deactivator,
The use of triazoles (eg, benzotriazoles) is described in US Pat. 3,413,227;
Nos. 4,162,225; 4,174,285; and 4,187,186.

The use of phosphorus-containing amides as antiwear agents for lubricating compositions is disclosed in US Pat. 4,032,461
Nos. 4,208,357; 4,282,171; and 4,670,169.

The use of phosphorus-containing esters as antiwear agents for lubricating compositions is disclosed in US Pat. 3,359,203
Issue. E. In lubricating compositions P. The use of such esters as agents is described in GB Pat. 1,
No. 347,845.

[0008] Compositions prepared by the sulfurization of various organic materials containing olefins are known in the art. Lubricants containing these compositions are also known. U.S. Pat. No. 4,191,659 describes the preparation of sulfurized olefinic compounds by the catalytic reaction of sulfur and hydrogen sulfide with olefinic compounds having 3 to 30 carbon atoms. This compound is reported to be useful in lubricating compositions, particularly in lubricating compositions prepared for use as industrial gear lubricants. U.S. Pat. No. 4,119,549 describes a similar process for sulfurizing olefins with sulfur and hydrogen sulfide, followed by the removal of low boilers from the sulfurized mixture.

A sulfur-containing composition characterized by the presence of at least one cycloaliphatic group is described in reissue patent Re 27,331, wherein the cycloaliphatic group comprises one cycloaliphatic group. It has at least two nuclear carbon atoms of an aliphatic group, or two nuclear carbon atoms of different cycloaliphatic groups, which are linked via a divalent sulfur bond. The sulfur bond has at least two sulfur atoms. Sulfurized Diels-
Alder adducts are exemplary of the compositions disclosed in this reissued patent. This sulfur-containing composition is useful as an extreme pressure additive and an antiwear additive in various lubricating oils.

A dialdehyde having a disulfide group and represented by the following formula is disclosed in US Pat. No. 2,580,695:

[0011]

Embedded image

Here, the two R groups are the same alkyl groups having 1 to 18 carbon atoms. The two R ¹ groups are the same alkyl or aryl group. This compound has been reported to be useful as a crosslinker and as a chemical intermediate.

A lubricating composition containing sulfide and represented by the following formula is disclosed in US Pat. No. 3,296,137:

[0014]

Embedded image

Here, R ₁ is a hydrocarbon group, R ₂ is a hydrogen or hydrocarbon group, and x is 1-2.

[0016] Canadian patent no. No. 1,168,222 discloses (A) at least one benzotriazole or the reaction product of benzotriazole and at least one aliphatic amine as an additive for a lubricant;
(B) at least one having about 3 to 30 carbon atoms;
Disclosed is the use of a combination with certain sulfurized aliphatic or cycloaliphatic compounds. This patent includes an ash-forming detergent in which the lubricant is also exemplified by oil-soluble, neutral and basic alkali and alkaline earth metal salts of sulfonic, carboxylic or organic phosphorus containing acids. It is possible to do.

[0017]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems, and it is an object of the present invention to provide a lubricant and a functional fluid with improved thermal stability and improved wear resistance. To provide compositions and lubricants and functional fluids containing them that are useful in providing extreme pressure, load transfer and / or corrosion protection.

[0018]

SUMMARY OF THE INVENTION The present invention provides a composition comprising: (A) at least one neutral or basic metal salt of at least one acidic organic compound;
Or a boron-containing neutral or basic metal salt; wherein the metal in the salt is an alkali metal, an alkaline earth metal, zinc, copper,
Selected from the group consisting of aluminum or a mixture of two or more of said metals; (B) at least one metal deactivator; and (C) the following (C-1), (C
At least one compound selected from the group consisting of (C-2), (C-3), (C-4) and (C-5);
1) phosphorus-containing amide; (C-2) phosphorus-containing ester;
(C-3) sulfur-coupled dithiocarbamate; (C-4) a sulfur-containing compound represented by the following formula;

[0019]

Embedded image

Here, in the formula I, R¹, R^Two, R^Threeand
R^FourIs independently H or hydrocarbyl
Group; R¹And / or R^ThreeIs G¹Or G^TwoEven
Good; R ¹And R^TwoAnd / or R^ThreeAnd R^FourIs one
Alkyl having about 4 to about 7 carbon atoms
G may be a ren group;¹And G^TwoAre independent
And C (X) R, COOR, C=N, R^Five-C = NR⁶,
CON (R)_TwoOr NO_TwoAnd G¹Is also CH_TwoO
It may be an H group. Here, X is O or S, and each R and
And R^FiveIs independently H or a hydrocarbyl group, R⁶
Is H or a hydrocarbyl group; G¹And G^TwoAre both R
^FiveC = NR⁶When two R⁶The radicals, together,
Can be a hydrocarbylene group bonded to two nitrogen atoms
G¹Is CH_TwoOH and G^TwoWhen is COOR, G¹You
And G^TwoLactones can be formed by intramolecular condensation of
And x is an integer from 1 to about 8. And (C
-5) Any one of the above (C-1) to (C-4)
A mixture of seeds or more. These compositions contain a lubricant
And functional fluids (especially hydraulic fluids, gear oils, greases)
Useful as additives for the To this
The above object is achieved.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

As used in this specification and the appended claims, the term "hydrocarbyl" refers in the context of the present invention to groups having a carbon atom directly attached to the remainder of the molecule, and to hydrocarbon-like or It represents a group having mainly hydrocarbon-like properties. Such groups include: (1) hydrocarbon groups; ie, aliphatic groups (eg, alkyl or alkenyl), alicyclic groups (eg, cycloalkyl or cycloalkenyl), aromatic groups. Cyclic groups as well as aliphatic and alicyclic-substituted aromatic groups, aromatic-substituted aliphatic and alicyclic groups, and the like; (Ie, any two indicated substituents may together form an alicyclic group). Such groups are known to those skilled in the art; examples include methyl,
Ethyl, octyl, decyl, octadecyl, cyclohexyl, phenyl and the like are included.

(2) a substituted hydrocarbon group;
Groups containing non-hydrocarbon substituents. The non-hydrocarbon substituent does not, in the context of the present invention, primarily alter the hydrocarbon nature of the group. One skilled in the art is aware of suitable substituents;
Examples include halo, hydroxy, nitro, cyano, alkoxy, acyl, and the like.

(3) Hetero group; that is, in the context of the present invention, a group which exhibits a predominantly hydrocarbon character, but contains atoms other than carbon in its chain or ring. Other parts of this group
Consists of carbon atoms. Suitable heteroatoms will be apparent to those of skill in the art and include, for example, nitrogen, oxygen and sulfur.

In general, no more than about 3 (preferably no more than 1) substituents or heteroatoms are present for each 10 carbon atoms in the hydrocarbyl group.

Terms such as "alkyl-based,""aryl-based," and the like, have similar meanings to the above definitions for alkyl, aryl, and the like.

The term "hydrocarbyl-based" has the same meaning as the term hydrocarbyl and can be used interchangeably when referring to a molecular group having a carbon atom directly attached to the remainder of the molecule.

The term "lower", as used herein in connection with terms such as hydrocarbyl, alkyl, alkenyl, alkoxy and the like, describes such groups having a total of up to 7 carbon atoms. It is intended.

The term "oil-soluble" refers to a substance that is soluble in mineral oil up to at least about 1 gram per liter at 25 ° C.

(Component (A)) The component (A) is a neutral or basic metal salt of at least one acidic organic compound, or a boron-containing neutral or basic metal salt. The metal in the salt is an alkali metal, an alkaline earth metal, zinc,
It is selected from the group consisting of copper, aluminum or a mixture of two or more of said metals.

The acidic organic compounds from which these salts are derived include one or more carboxylic acids, sulfur-containing acids,
It may be a phosphorus acid, a phenol, or a mixture of two or more thereof. These acidic organic compounds are discussed in more detail below.

The term "basic" is a technical term generic to the known class of metal salts. These basic metal salts can also be used as “overbased”, “superbased”, “hyperbased”, “high metal content salts” and the like. ,It is shown. Basic metal salts are formed according to the stoichiometry of the metal and the particular acidic organic compound (eg, sulfonic acid) that is subjected to the reaction with the metal, with a metal content in excess of the metal content present.
Characterized. Therefore, monosulfonic acid,

[0033]

Embedded image

If neutralized with a basic metal compound (eg, calcium hydroxide), the "neutral"
That is, a "positive" metal salt contains one equivalent of calcium per equivalent of acid:

[0035]

Embedded image

Methods for preparing such neutral and basic metal salts are known in the art. Neutral salts are prepared by mixing a mineral oil solution of an acidic organic compound with a stoichiometric equivalent of a metal neutralizing agent (eg, a metal oxide, hydroxide, carbonate, bicarbonate or sulfide) at about 50 ° C. By heating at a temperature above and filtering the resulting mass. Basic salts are prepared similarly except that a stoichiometric excess of metal is used. Also, "promoters" may be used in making this basic salt to assist in mixing excess metal in the neutralization step. Examples of compounds useful as the accelerator include phenolic substances (eg, phenol, naphthol, alkylphenols, triphenols, sulfurized alkylphenols, and condensation products of formaldehyde and phenolic substances); alcohols (eg, methanol, -Propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol); and amines (eg, aniline, phenylenediamine, phenothiazine, phenyl-β-naphthylamine, and dodecylamine). For a particularly effective method of preparing the basic salt, the acidic organic compound is mixed with an excess of a basic metal neutralizer and at least one alcohol promoter and heated at an elevated temperature (e.g., 60-200C). ) Involves carbonating this mixture.

Component (A) typically comprises about 100% to about 4000%, preferably about 100% to about 3000%, more preferably about 100% of the metal present in the corresponding neutral salt. From 100% to about 2800%, even more preferably from about 200% to about 1000%. In an advantageous embodiment, component (A) comprises from about 110% to about 4000%, preferably about 110%, of the metal present in the corresponding neutral salt.
% To about 3000%, more preferably from about 110% to about 2%.
800%, even more preferably from about 110% to about 10%
00%.

More preferred metals for this salt (A) include lithium, sodium, magnesium, calcium, potassium, barium, aluminum, zinc and copper. Mixtures of two or more of the foregoing metals can be used. Particularly preferred metals are sodium, magnesium, calcium or mixtures of two or more thereof.

(Carboxylic acid) The carboxylic acid useful in producing the salt (A) of the present invention may be an aliphatic or aromatic mono- or polycarboxylic acid or an acid-generating compound. These carboxylic acids include lower molecular weight carboxylic acids (e.g., carboxylic acids having up to about 18 carbon atoms (e.g., fatty acids having about 10 to about 18 carbon atoms or tetrapropenyl substituted succinic anhydrides). ))
As well as higher molecular weight carboxylic acids.
Throughout this specification and the appended claims, references to carboxylic acids, unless otherwise stated, include their acid-forming derivatives (eg, anhydrides, esters, acyl halides, lactones, and Mixtures thereof).

The carboxylic acids of the present invention are preferably oil-soluble, and many of the carbon atoms present in the acid are important in contributing to the desired solubility of salt (A). Usually, the number of carbon atoms in the carboxylic acid will be at least about 8 carbon atoms, more preferably at least about 18 carbon atoms, and more preferably at least about 30 carbon atoms, in order to obtain the desired oil solubility. Should be even more preferably at least about 50 carbon atoms. Generally, these carbon atoms do not have more than about 400 carbon atoms per molecule.

The carboxylic acid may contain a polar group under the following conditions: the polar group is not present to a large enough extent to significantly alter the hydrocarbon nature of the carboxylic acid. Typically suitable polar groups include halo (eg,
Chloro and bromo), oxo, oxy, formyl, sulfenyl, sulfinyl, thio, nitro and the like. Such polar substituents, if present, preferably do not exceed about 10% by weight of the total hydrocarbon moiety other than the carbonyl groups of the carboxylic acid.

The lower molecular weight monocarboxylic acids contemplated for use in the present invention include saturated and unsaturated acids. Examples of such useful acids include dodecanoic, palmitic, decanoic, oleic, lauric, stearic, myristic, linoleic, linolenic, naphthenic, chlorostearic, tall oil, and the like. Included. The anhydrides and lower alkyl esters of these acids can also be used. 2 of such reagents
Mixtures of species or more can also be used. An extensive discussion of these acids can be found in Kirk-Ozmer.
-Othmer), encyclopedia of chemical technology, 3rd edition, 1978.
Years, John Willey and Sands (John Wil
Eyes & Sons), New York, pp. 814-
871; their contents are shown on these pages.

Examples of lower molecular weight polycarboxylic acids include:
Dicarboxylic acids and their derivatives (eg, sebacic acid, cetyl malonic acid, tetrapropylene substituted succinic anhydride, etc.). Lower alkyl esters of these acids can also be used.

[0044] Low molecular weight hydrocarbyl-substituted succinic acids and anhydrides may also be used. Typically, these compounds are represented exactly by the formula:

[0045]

Embedded image

Where, in Formulas II and III, R is
Hydrocarbyl groups having about 8 to about 18 carbon atoms. Preferably, R is an aliphatic or cycloaliphatic hydrocarbyl group. Less than 10% of the carbon-carbon bonds are unsaturated. Examples of these groups include 4-butylcyclohexyl, di (isobutyl), decyl and the like. The formation of such substituted succinic acids and their derivatives by alkylation of maleic acid or its derivatives with halohydrocarbons is known to those skilled in the art and need not be discussed here in further detail.

The lower molecular weight mono- and polycarboxylic acid acid halides described above may be used in the present invention as lower molecular weight carboxylic acids. They can be prepared by reaction of such acids or their anhydrides with a halogenating agent, for example, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride or thionyl chloride. Esters of such acids can be prepared simply by reacting the acid, acid halide or anhydride with an alcohol or phenol compound. Lower alkyl or alkenyl alcohols (eg, methanol, ethanol, allyl alcohol, propanol, cyclohexanol, etc.) are particularly useful. The esterification reaction is usually performed with an alkali catalyst (eg, sodium hydroxide or sodium alkoxide) or an acidic catalyst (eg, sulfuric acid or toluenesulfonic acid).
Is facilitated by the use of

The monocarboxylic acids include isoaliphatic acids
(Ie, acids having one or more lower acyclic pendant alkyl groups). Such acids often have the following major chains: the chains have about 14 to about 20 saturated aliphatic carbon atoms, and usually at least one, but usually about four. Not more than pendant acyclic alkyl groups. The main chain of this acid is exemplified by groups derived from: tetradecene, pentadecene, hexadecene, heptacene, octadecene and eicosene. The pendant group preferably has a lower alkyl group (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-hexyl), or up to about 7 carbon atoms Other groups. The pendant group may also be a polar substituted alkyl group (eg, chloromethyl, bromobutyl, methoxyethyl or the like). However, it preferably does not have more than one polar substituent per group. Specific examples of such isoaliphatic acids include 10-
Methyl-tetradecanoic acid, 11-methyl-pentadecanoic acid, 3-ethyl-hexadecanoic acid, 15-methyl-heptadecanoic acid, 16-methyl-heptadecanoic acid, 6-methyl-octadecanoic acid, 8-methyl-octadecanoic acid, 1
0-methyl-octadecanoic acid, 14-methyl-octadecanoic acid, 16-methyl-octadecanoic acid, 15-ethyl-heptadecanoic acid, 3-chloromethyl-nonadecanoic acid,
7,8,9,10-tetramethyl-octadecanoic acid and 2,9,10-trimethyl-octadecanoic acid are included.

The isoaliphatic acids include, for example, mixtures of branched acids prepared by isomerization of a commercially available fatty acid having from about 16 to about 20 carbon atoms. Useful methods include temperatures above about 250 ° C and about 200 ° C.
heating the fatty acid at a pressure between psi and 700 psi, distilling the crude isomerized acid, and hydrogenating the distillate to obtain a substantially saturated isomerized Generating the acid is included. This isomerization can be promoted by a catalyst such as mineral clay, diatomaceous earth, aluminum chloride, zinc chloride, ferric chloride, or some other Friedel-Crafts catalyst. The concentration of the catalyst is about 0.01% by weight of the isomerization mixture.
Often about 0.1% to about 3% by weight
% By weight. Water also promotes this isomerization. Therefore, small amounts of water, such as from about 0.1% to about 5% by weight, may be conveniently added to the isomerization mixture. The unsaturated fatty acids from which the isoaliphatic acids can be derived include oleic acid, linoleic acid, linolenic acid, and commercially available fatty acid mixtures (eg, tall oil).

Higher molecular weight mono- and polycarboxylic acids suitable for use in preparing salt (A) include:
Known in the art, for example, the following U.S. Patents:
It is described in detail in UK and Canadian patents:
U.S. Pat. 3,024,237; 3,087,9
No. 36; 3,163,603; 3,172,892
No. 3,215,707; 3,219,666;
3,231,587; 3,245,910; 3,2
54,025; 3,271,310; 3,272
No. 743; 3,272,746; 3,278,550
No. 3,288,714; 3,306,907;
3,307,928; 3,312,619; 3,3
41,542; 3,346,354; 3,367,
943; 3,373,111; 3,374,174
No. 3,381,022; 3,394,179;
3,454,607; 3,346,354; 3,4
No. 70,098; 3,630,902; 3,652
No. 616; 3,755,169; 3,868,330
Nos. 3,912,764; 4,234,435 and 4,368,133: British Patent No. 944,13
No. 6; 1,085,903; 1,162,436;
And 1,440,219: Canadian Patent No. 95
6,397. The contents of these patents are set forth here.

As previously disclosed in the patents, there are several ways to prepare these higher molecular weight carboxylic acids. In general, these methods include (1) an ethylenically unsaturated carboxylic acid, acid halide, anhydride or ester reactant, and (2) an ethylenically unsaturated hydrocarbon having at least about 18 aliphatic carbon atoms. Or a chlorinated hydrocarbon having at least about 18 aliphatic carbon atoms at a temperature in the range of about 100-300 ° C. The chlorinated hydrocarbon reactant or ethylenically unsaturated hydrocarbon reactant preferably has at least about 20 carbon atoms, more preferably at least about 30 carbon atoms.
Contains more preferably at least about 40 carbon atoms, more preferably at least about 50 carbon atoms. The reactants may contain polar substituents, oil-soluble pendant groups, and are unsaturated within the general ranges set forth above. It is these hydrocarbon reactants that provide most of the aliphatic carbon atoms present in the acyl portion of the final product.

In preparing higher molecular weight carboxylic acids, the carboxylic reactant usually has the formula R _0- (C
00H) _n . Here, R ₀ is characterized by the presence of at least one ethylenically unsaturated carbon-carbon covalent bond. n is an integer from 1 to about 6, preferably 1 or 2. The acidic reactant can also be the corresponding carboxylic acid halide, anhydride or ester. Usually, the total number of carbon atoms in the acidic reactant will not exceed about 20, preferably the number will not exceed about 10,
And in general, it does not exceed about 6. Preferably, the acidic reactant has at least one ethylenic bond in the α, β-position with respect to at least one carboxyl functionality. Exemplary acidic reactants include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, glutaconic acid, chloromaleic acid, aconitic acid, Crotonic acid, methyl crotonic acid, sorbic acid, 3-hexenoic acid, 10-decenoic acid and the like. More preferred acid reactants include acrylic acid, methacrylic acid, maleic acid and maleic anhydride.

The ethylenically unsaturated hydrocarbon reactants and chlorinated hydrocarbon reactants used in preparing these high molecular weight carboxylic acids are preferably high molecular weight, substantially saturated petroleum fractions, and Substantially saturated olefinic polymers, and the corresponding chlorinated products. More preferred are polymers and chlorinated polymers derived from monoolefins having from about 2 to about 30 carbon atoms. Particularly useful polymers are 1-monoolefins such as ethylene, propene, 1-butene, isobutene, 1-hexene, 1-octene, 2-methyl-1-heptene, 3-cyclohexyl-1-butene, and 2 -Methyl-5-propyl-1-hexene). Polymers of intermediate olefins (ie, olefins in which the olefinic bond is not at a terminal position) are also useful. These are exemplified by 2-butene, 3-pentene and 4-octene.

Mixed polymers of 1-monoolefins, as exemplified above, with each other and with other mixed polymerizable olefinic materials (eg, aromatic olefins, cyclic olefins, and polyolefins) are also Is a useful raw material for ethylenically unsaturated reactants. Such mixed polymers include, for example, isobutene and styrene, isobutene and butadiene, propene and isoprene, propylene and isobutene, ethylene and piperylene, isobutene and chloroprene, isobutene and p-methylstyrene, 1-
Hexene and 1,3-hexadiene, 1-octene and 1-
Hexene, 1-heptene and 1-pentene, 3-methyl-
Mixed polymers prepared by polymerization of 1-butene and 1-octene, 3,3-dimethyl-1-pentene and 1-hexene, isobutene and styrene and piperylene and the like are included.

Because of their oil solubility, the mixed polymers contemplated for use in preparing the carboxylic acids of this invention are preferably substantially aliphatic and substantially saturated. That is, they contain at least about 80%, preferably by weight, units derived from aliphatic monoolefins, preferably
Should have about 95%. Preferably, they are
Has no more than about 5% olefinic bonds, based on the total number of carbon-carbon covalent bonds present.

[0056] In certain embodiments of the invention, the polymers and chlorinated polymers, by polymerization of the following C ₄ refinery stream obtained. The C ₄ refinery stream, a Lewis acid catalyst (e.g., aluminum chloride or boron trifluoride) in the presence of a butene content of about 35 wt% to about 75 wt%, and about 30 wt% to about 60 weight % Isobutene content. These polyisobutenes preferably have predominantly (ie, greater than about 80% of the total repeat units) isobutene repeat units of the following configuration:

[0057]

Embedded image

The chlorinated hydrocarbons and ethylenically unsaturated hydrocarbons used in preparing higher molecular weight carboxylic acids can have a number average molecular weight of up to about 100,000 or more. However, more preferred high molecular weight carboxylic acids have a molecular weight up to about 10,000, more preferably up to about 7,500, more preferably up to about 5,000. More preferred high molecular weight carboxylic acids have at least about 18 carbon atoms, preferably at least about 30 carbon atoms, more preferably at least about 40 carbon atoms, and more preferably at least about 50 carbon atoms. Having a hydrocarbyl group having the formula:

This higher molecular weight carboxylic acid also hydrogenates high molecular weight hydrocarbons (eg, the olefin polymers described above) to produce a polyhydrogenated product, which is converted to polynitrile. Can then be prepared by hydrolyzing the polynitrile. These carboxylic acids can be prepared by oxidizing high molecular weight polyhydric alcohols with potassium permanganate, nitric acid or similar oxidizing agents. Other methods include olefins or polar substituted hydrocarbons (eg, chloropolyisobutene) and unsaturated polycarboxylic acids (eg, 2-pentene-1,3,5-prepared by dehydration of citric acid).
Tricarboxylic acid).

Monocarboxylic acids are obtained by oxidizing monoalcohols with potassium permanganate or by reacting a hydrogenated high molecular weight olefin polymer with ketene. Another convenient method for preparing monocarboxylic acids is to react sodium metal with an acetoacetate or malonate of an alkanol to form a sodium derivative of the ester; and Subsequent reaction with a hydrogenated high molecular weight hydrocarbon (eg, a brominated wax or a brominated polyisobutene) is included.

Monocarboxylic acids and polycarboxylic acids also include chlorinated monocarboxylic acids and polycarboxylic acids, anhydrides, acyl halides and the like, as well as ethylenically unsaturated hydrocarbons or ethylenically unsaturated substituted hydrocarbons. (E.g., polyolefins and substituted polyolefins; these were previously described in the manner described in U.S. Patent No. 3,340,281, the contents of which are hereby incorporated by reference). Obtained by reaction.

The monocarboxylic and polycarboxylic anhydrides are obtained by dehydration of the corresponding acids. Dehydration is
Preferably, this is easily achieved by heating the acid to a temperature above about 70 ° C. in the presence of a dehydrating agent (eg, acetic anhydride). Cyclic anhydrides are usually
Obtained from polycarboxylic acids having acid groups separated by no more than three carbon atoms (eg, substituted succinic or glutaric acids). In contrast, linear anhydrides are usually obtained from polycarboxylic acids having acid groups separated by four or more carbon atoms.

The acid halides of the monocarboxylic acids and polycarboxylic acids can be combined with the acids or their anhydrides,
It can be prepared by reacting with a halogenating agent such as phosphorus tribromide, phosphorus pentachloride or thionyl chloride.

The hydrocarbyl-substituted succinic acids and anhydrides, their acid halide and ester derivatives are prepared by reacting maleic anhydride with a high molecular weight olefin or a chlorinated hydrocarbon (eg, a chlorinated polyolefin). obtain. This reaction takes about 100
C. to a temperature in the range of about 300.degree. C., preferably about 100.degree.
It involves simply heating the two reactants at a temperature in the range of ~ 200 ° C. The product of this reaction is a hydrocarbyl-substituted succinic anhydride. Here, the substituent is derived from an olefin or a chlorinated hydrocarbon. The product can be hydrogenated, if necessary, to remove all or some of the ethylenically unsaturated covalent bonds by conventional hydrogenation methods. The hydrocarbyl-substituted succinic anhydride can be hydrolyzed to the corresponding acid by treatment with water or steam. Either the anhydride or the acid can be converted to the corresponding acid, halide or ester by reaction with a phosphorus halide, phenol or alcohol. Useful high molecular weight hydrocarbyl-substituted succinic acids and anhydrides are represented by the formula:

[0065]

Embedded image

Here, in formulas IIA and IIIA, R
Is at least about 18 carbon atoms, more preferably
It has at least about 30 carbon atoms, more preferably at least about 40 carbon atoms, and more preferably at least about 50 carbon atoms. The number average molecular weight relative to R generally does not exceed about 100,000, preferably does not exceed about 10,000, more preferably about 7,7.
Not more than 500, more preferably not more than about 5,000.

A group of carboxylic acid derivatives which are particularly useful in preparing the salts (A) of this invention are the lactones represented by the following formula:

[0068]

Embedded image

Here, in the formula IV, R¹, R^Two,
R^Three, R^Four, R^FiveAnd R⁶Is independently H or 1
A hydrocarbyl group having from about 30 to about 30 carbon atoms.
R ^TwoAnd R^ThreeAre linked together to form an aliphatic ring or
Can form an aromatic ring; and a ranges from 0 to about 4
Is the number of Among these groups, lacto represented by the following formula
Is particularly useful:

[0070]

Embedded image

Where, in Formula V, R ⁷ and R ⁸ are aliphatic hydrocarbyl groups having 1 to about 30 carbon atoms, and a and b are numbers ranging from 0 to about 5 . However, the sum of a and b does not exceed 5. And c
Is a number in the range of 0-4.

Methods for preparing this type of lactone by intramolecular cyclization of a hydroxy-containing carboxylic acid with elimination of water are known in the art. Generally, this cyclization is facilitated by the presence of a substance such as acetic anhydride. The reaction is performed by heating the mixture to an elevated temperature, such as the reflux temperature, while removing volatiles, including water.

A more preferred group of carboxylic acids useful in preparing salts (A) of the present invention are aromatic carboxylic acids. These acids can be represented by the formula:

[0074]

Embedded image

Wherein, in Formula VI, R is preferably an aliphatic hydrocarbyl group having from about 4 to about 400 carbon atoms, a is a number ranging from 0 to about 4, and Ar is aromatic. The group groups, X ¹ and X ^2, are independently sulfur or oxygen, and b is a number ranging from 1 to about 4. However, the sum of a and b does not exceed the number of valences that cannot be satisfied by Ar. Preferably, R and a are such that in each compound represented by Formula VI, there are on average at least about 8 aliphatic carbon atoms provided by the R groups.

The aromatic group Ar of the formula VI is a “phenol”
May have the same structure as any of the aromatic groups Ar discussed below under the heading. Examples of aromatic groups useful herein include polyvalent aromatic groups derived from: benzene,
Naphthalene, anthracene, phenanthrene, indene, fluorene, biphenyl and the like. Generally, an Ar group as used herein is a polyvalent nucleus derived from benzene or naphthalene (eg, phenylene and naphthylene;
For example, methylphenylene, ethoxyphenylene, nitrophenylene, isopropylphenylene, hydroxyphenylene, mercaptophenylene, N, N-diethylaminophenylene, chlorophenylene, dipropoxynaphthylene, triethylnaphthylene and similar trivalent, tetravalent, Pentavalent nucleus). These Ar groups may have non-hydrocarbon substituents (eg, heterogeneous groups such as: lower alkoxy, lower alkyl mercapto, nitro, halo, alkyl groups having less than about 4 carbon atoms). Or an alkenyl group, hydroxy, mercapto and the like.

Examples of R groups in formula VI include butyl, isobutyl, pentyl, octyl, nonyl, dodecyl, docosyl, tetracontyl, 5-chlorohexyl, 4-ethoxypentyl, 4-hexenyl, 3-cyclohexyloctyl, (P-chlorophenyl) -octyl,
Includes substituents derived from 2,3,5-trimethylheptyl, 4-ethyl-5-methyloctyl, and polymerized olefins such as: polychloroprene, polyethylene, polypropylene, polyisobutylene, ethylene- Propylene copolymer, chlorinated olefin polymer, oxidized ethylene-propylene copolymer and the like.

A group of useful carboxylic acids has the formula:

[0079]

Embedded image

Here, in the formula VII, R, Ar, X ¹ ,
X ² , a and b are the same as defined in Formula VI. X ³ is oxygen or sulfur, and c is 1 to about 4
And is typically from 1 to about 2. However, a, b and c do not exceed the unstable valence of Ar.

Of this group, a useful class of carboxylic acids is of the formula:

[0082]

Embedded image

Wherein, in Formula VIII, R is preferably an aliphatic hydrocarbyl group having from about 4 to about 400 carbon atoms, and a is a number ranging from 0 to about 4, preferably B is a number ranging from 1 to about 4;
Preferably, it is 1 to about 2, and c is a number in the range of 1 to about 4, preferably 1 to about 2, and more preferably 1, provided that the sum of a, b and c is 6 Not exceed. Preferably, R and a are such that the acid molecule has an average of about 12 aliphatic carbon atoms at the aliphatic hydrocarbon substituents per acid molecule.

[0084] Aliphatic hydrocarbon substituted salicylic acids are also useful. Here, each aliphatic hydrocarbon substituent has an average of at least about 8 carbon atoms per substituent and 1 to 3 substituents per molecule. Salts prepared from such salicylic acids are particularly useful. Here, the aliphatic hydrocarbon substituent is derived from a polymerized olefin, particularly a polymerized lower 1-monoolefin (e.g., polyethylene, polypropylene, polyisobutylene, ethylene / propylene copolymer, etc.) and has a molecular weight of about 30. It has an average carbon content of from about 400 to about 400 carbon atoms.

The aromatic carboxylic acids corresponding to formulas VII and VIII are known or can be prepared according to methods known in the art. Carboxylic acids of the type exemplified by these formulas and methods for preparing their neutral and basic metal salts are known and are described, for example, in US Pat. 2,197,832; 2,19
7,835; 2,252,662; 2,252,6
No. 64; 2,714,092; 3,410,798
No. 3,595,791.

(Sulfur-containing acid) Sulfur-containing acids useful in producing the salt (A) of the present invention include sulfonic acid, sulfamic acid, thiosulfonic acid, sulfinic acid, sulfenic acid, partially esterified sulfuric acid, sulfurous acid and Thiosulfuric acid is included. Generally, these are salts of carboxylic acids or aliphatic sulfonic acids.

The carbocyclic sulfonic acids include mono- or polynuclear aromatic or cycloaliphatic compounds. The oil-soluble sulphonate can in most cases be represented by the following formula:

[0088]

Embedded image

In the above formulas IX and X, T is a cyclic nucleus.
(E.g., benzene, naphthalene, anthracene, phenanthrene, diphenylene oxide, thianthrene, phenothioxine, diphenylene sulfide, phenothiazine, diphenyl oxide, diphenyl sulfide, diphenylamine, cyclohexane, petroleum naphthalene, decahydro-naphthalene, cyclopentane, etc.). :
R ¹ is an aliphatic group (eg, alkyl, alkenyl, alkoxy, alkoxyalkyl, carboalkoxyalkyl, etc.); a is at least 1, and R ¹ a
+ T has a total of at least about 15 carbon atoms. R ² is an aliphatic hydrocarbyl group having at least about 15 carbon atoms. Examples of R ² are alkyl, alkenyl, alkoxyalkyl, cycloalkyl alkoxyalkyl like. Specific examples of R ² include petrolatum, saturated and unsaturated paraffin wax, and polyolefins _{(this, C 2, C 3, C} 4 of polymerized,
C _5, such as C _6, i.e., olefins are encompassed with about 15 ～7000 or more carbon atoms)
There are groups derived from In formulas IX and X above, the groups T, R ¹ and R ² may also have, in addition to the substituents listed above, other inorganic or organic substituents, for example: Hydroxy, mercapto, halogen,
Nitro, amino, nitroso, sulfide, disulfide and the like. In Formula IX, a and b are at least 1;
Similarly, in Formula X, a is at least 1.

The following are specific examples of oil-soluble sulfonic acids within formulas IX and X above. It should be understood that such examples are also provided to illustrate such sulfonic acid salts useful in the present invention. In other words, for each sulfonic acid listed, their corresponding neutral and basic metal salts are also intended to be understood as examples. Such sulfonic acids include mahogany-sulfonic acid; bright stock sulfonic acid;
Sulfonic acid derived from lubricating oil fractions having Saybolt clay from about 100 seconds at 00 ° F to about 200 seconds at 210 ° F; petrolatum sulfonic acid; mono- and polywax substituted sulfonic acids and polysulfonic acids ( For example,
Benzene, naphthalene, phenol, diphenyl ether, naphthalene disulfide, diphenylamine, thiophene, α-chloronaphthalene, etc .; other substituted sulfonic acids (eg, alkyl benzene sulfonic acids, wherein the alkyl group has at least 8 carbon atoms ), Cetylphenol monosulfide sulfonic acid,
Dicetyl thianthylene sulfonic acid, dilauryl-β-
Naphthylsulfonic acid, dicaprylnitronaphthalenesulfonic acid, and alkarylsulfonic acids (eg, dodecylbenzene "bottoms" sulfonic acid).

The latter are acids derived from benzene, which are alkylated with propylene tetramers or isobutene trimers, on which 1, 2, 3, or more branched C ₁₂ substituents are present. be introduced. Dodecylbenzene bottoms (primarily a mixture of mono- and di-dodecylbenzene) are available as by-products in the manufacture of household cleaners. Similar products, such as those obtained from alkylated bottoms formed during the production of linear alkyl sulfonates (LAS), are also useful in preparing the sulfonates used in this invention.

The formation of sulphonates from by-products of the production of detergents, for example by reaction with SO ₃ , is known to the person skilled in the art. For example, Kirk-Osmer
-Othmer) "Encyclopedia of Chemical Technology" (2nd edition, volume 19,
pp. 291 et seq., Which is published by John Wiley & Sons, N.W. Y. (1969)) "Sulfonate"
See section.

Other descriptions of neutral and basic sulfonates, and methods of making them, can be found in the following US patents: US Pat. 2,174,110
No. 2,174,506; 2,174,508;
2,193,824; 2,197,800; 2,2
02,781; 2,212,786; 2,213
No. 360; 2,228,598; 2,233,676
No. 2,239,974; 2,263,312;
2,276,090; 2,276,097; 2,3
No. 15,514; 2,319,121; 2,321,
No. 022; 2,333,568; 2,333,788
No. 2,335,359; 2,337,552;
2,346,568; 2,366,027; 2,3
74,193; 2,383,319; 3,312
No. 618; 3,471, 403; 3,488,284
No. 3,595,790; and 3,798,012
issue. These patents are hereby shown for their disclosure in this regard.

Aliphatic sulfonic acids (for example, paraffin wax sulfonic acid, unsaturated paraffin wax sulfonic acid, hydroxy-substituted paraffin wax sulfonic acid,
Hexapropylene sulfonic acid, tetraamylene sulfonic acid, polyisobutene sulfonic acid (where the polyisobutene has 20 to 7000 or more carbon atoms), chloro-substituted paraffin wax sulfonic acid, nitro paraffin wax sulfonic acid, etc. ); Cycloaliphatic sulfonic acids (such as petroleum naphthenic sulfonic acid, cetyl cyclopentyl sulfonic acid, lauryl cyclohexyl sulfonic acid, bis- (di-isobutyl) cyclohexyl sulfonic acid, mono- or polywax-substituted cyclohexyl sulfonic acids, etc.). Is done.

The term "petroleum sulphonic acid" or "petroleum sulphonate" with respect to the sulphonic acids or their salts described herein and in the appended claims refers to all petroleum products derived from petroleum products. It is intended here to be used including sulfonic acids or their salts. A useful group of petroleum sulfonic acids is mahogany-sulfonic acid, which is obtained by the sulfuric acid process as a by-product of the production of petroleum white oil, so called because of its reddish brown color.

In general, the neutral and basic petroleum sulfonic acids of the above synthesis are useful in the practice of this invention.

The sulfonic acids, carboxylic acids described above,
And other patents specifically describing techniques for producing mixtures of two or more thereof include the following US patents: US Pat. 2,501,731
No. 2,616,904; 2,616,905;
2,616,906; 2,616,911; 2,6
16,924; 2,616,925; 2,617,
No. 049; 2,777,874; 3,027,325
No. 3,256,186; 3,282,835;
No. 3,384,585; No. 3,373,108; 3,3
No. 65,396; 3,342,733; 3,320,
No. 162; 3, 312, 618; 3, 318, 809
No. 3,471,403; 3,488,284;
3,595,790; and 3,629,109.
The disclosures of these patents are set forth herein with respect to this disclosure, as well as particularly with respect to the disclosure of suitable basic metal salts.

(Phosphorus-Containing Acid) Phosphorus-containing acids useful in preparing the salt (A) of the present invention can be represented by the following formula:

[0099]

Embedded image

Here, in the formula XI, X ¹ , X ² , X ³ and X ⁴ are independently oxygen or sulfur; a and b
Is independently 0 or 1, and R ¹ and R ²
Is independently a hydrocarbyl group.

Illustrative examples of certain more preferred phosphorus-containing acids include the following: Dihydrocarbylphosphinodithioic acid corresponding to the formula:

[0102]

Embedded image

2. S-hydrocarbyl hydrocarbyl phosphonotrithioic acid corresponding to the formula:

[0104]

Embedded image

3. O-hydrocarbyl hydrocarbyl phosphonodithioic acids corresponding to the formula:

[0106]

Embedded image

4. S, S-dihydrocarbyl phosphorotetrathioic acid corresponding to the formula:

[0108]

Embedded image

5. O, S-dihydrocarbyl phosphorotrithioic acid corresponding to the formula:

[0110]

Embedded image

6. O, O-dihydrocarbyl phosphorotrithioic acid corresponding to the formula:

[0112]

Embedded image

A more preferred acid of the following formula is phosphorus pentasulfide (P
₂ S ₅ ) by reaction with alcohol or phenol,
Easily obtained:

[0114]

Embedded image

The reaction involves mixing 4 moles of alcohol or phenol with 1 mole of phosphorus pentasulfide at a temperature of about 20 ° C to about 200 ° C. In this reaction, hydrogen sulfide is released. Oxygen-containing analogs of these acids are conveniently prepared by treating a dithioic acid with water or steam. This water or steam actually replaces one or both of the sulfur atoms.

Preferred phosphorus-containing acids are phosphorus and sulfur-containing acids. These preferred acids preferably contain the following acids: in which at least one X ³ or X ⁴ is sulfur, more preferably X ³
And X ⁴ are both sulfur. At least one X ¹
Or X ² is oxygen or sulfur, more preferably both X ¹ and X ² are oxygen. A and b are 1 each. Mixtures of these acids can be used according to the invention.

R ¹ and R ² are independently preferably a hydrocarbyl group free of acetylenic unsaturation, and usually also a hydrocarbyl group free of ethylenic unsaturation. The R ¹ and R ² are preferably from about 1 to about 50 carbon atoms, more preferably from about 1 to about
About 30 carbon atoms, more preferably about 3 to about 18
And more preferably from about 4 to about 8 carbon atoms. Each R ¹ and R ² can be identical to the others. However, they may be different, and either or both may be a mixture. Examples of more preferred R ¹ and R ² groups include t-butyl, isobutyl, amyl, isooctyl, decyl, dodecyl, eicosyl, 2-pentenyl, dodecenyl, phenyl, naphthyl, alkylphenyl, alkylnaphthyl, phenylalkyl, naphthyl Alkyl, alkylphenylalkyl, alkylnaphthylalkyl and the like are included.

(Phenol) A phenol useful in preparing the salt (A) of the present invention may be represented by the formula: R _a -Ar- (OH) _b (XII) Is a hydrocarbyl group having about 4 to about 400 carbon atoms; Ar is an aromatic group; a and b are independently at least one number, and the sum of a and b is , 2 to the number of hydrogen atoms that can be substituted on one or more nuclei of Ar. Preferably, a and b are independently in the range of 1 to about 4, more preferably 1 to about 2. R and a are
Preferably, the value is such that, on average, at least about 8 aliphatic carbon atoms are provided, which is provided by the R group for each phenolic compound represented by Formula XII.

Although the term "phenol" is used herein, it should be understood that the term is not intended to limit the aromatic group of phenol to benzene.
Accordingly, in this specification and the appended claims,
Aromatic groups as represented by “Ar” elsewhere in Formula XII as well as in other formulas are mononuclear (eg, phenyl,
Pyridyl, thienyl) or polynuclear. The polynuclear group can be of the condensation type. Here, the aromatic nucleus is fused at two points to other nuclei, as found in naphthyl, anthranyl, azanaphthyl and the like. The polynuclear group can also be of the linked type. Here, at least two nuclei (either mononuclear or polynuclear) are linked to one another via cross-links. These crosslinks are
It can be selected from the group consisting of: carbon-carbon single bond, ether bond, keto bond, sulfide bond, 2 to
Polysulfide bond having about 6 sulfur atoms, sulfinyl bond, sulfonyl bond, alkylene bond, alkylidene bond, lower alkylene ether bond, alkylene keto bond, lower alkylene sulfur bond, lower alkylene having 2 to about 6 carbon atoms Polysulfide bonds, amino bonds, polyamino bonds, and mixtures of such divalent crosslinks. In some cases, between two aromatic nuclei, one or more cross-links are present in Ar;
There is a fluorene nucleus having two benzene nuclei linked by both methylene and covalent bonds. Such a nucleus can be considered to have three nuclei. However, only two of them are aromatic. However, usually, Ar
Has carbon atoms only in the aromatic nucleus itself (and any alkyl or alkoxy substituents present).

The number of condensed, linked or both aromatic nuclei may play a role in determining the integer values of a and b in Formula XII for Ar. For example, when Ar has a single aromatic nucleus, the sum of a and b is 2-6. When Ar has two aromatic nuclei, the sum of a and b is 2-10. In the Ar moiety of the three nuclei, the sum of a and b is 2-15. The value of the sum of a and b is limited by the fact that it cannot exceed the total number of hydrogens that can be substituted on one or more aromatic nuclei of Ar.

A single ring aromatic nucleus which may be an Ar group may be represented by the formula: ar (Q) _m where ar is a single ring aromatic nucleus having 4 to 10 carbon atoms (eg, , Benzene). Each Q independently represents a lower alkyl group, a lower alkoxy group, a nitro group, or a halogen atom. And m is 0-4.

The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; usually, the halogen atom is a fluorine atom and a chlorine atom.

When Ar is a single ring, specific examples of aromatic groups include:

[0124]

Embedded image

Here, Me is methyl, Et is ethyl, P
r is propyl and Nit is nitro. When Ar is a polynuclear fused ring aromatic group, it can be represented by the following general formula:

[0126]

Embedded image

Here, ar, Q and m are the same as defined above. m 'is 1-4, and

[0128]

Embedded image

Represents a pair of fused bonds that fuse two rings to make two carbon atoms part of the rings of each two adjacent rings. When Ar is a fused ring, specific examples of aromatic groups include:

[0130]

Embedded image

When the aromatic group Ar is a linked polynuclear aromatic group, it can be represented by the following general formula:

[0132]

Embedded image

Here, w is an integer of 1 to about 20;
r is the same as described above. However, there are at least two unsatisfied (ie, free) valences throughout the ar group. Q and m are the same as defined above. Each Lng is a cross-linking individually selected from the group consisting of: a carbon-carbon single bond, an ether bond (e.g., -O-), a keto bond (e.g.,

[0134]

Embedded image

A sulfide bond (for example, -S-), a polysulfide bond having 2 to 6 sulfur atoms (for example, -S- _2-6 ), a sulfinyl bond (for example, -S-)
(O)-), a sulfonyl bond (for example, -S (O)
_2- ), lower alkylene bond (for example,

[0136]

Embedded image

[0137] etc.), di (lower alkyl) methylene linkages (e.g., CR ⁰ ₂ -) lower alkylene ether linkages (e.g.,

[0138]

Embedded image

Etc.), lower alkylene sulfide bonds (eg, wherein one or more —O— in the lower alkylene ether bond is replaced by an —S— atom), lower alkylene polysulfide bond (eg, Here, one or more -O- is -S-
_2-6 ), amino bond (eg,

[0140]

Embedded image

Here, alk is a lower alkylene group or the like, a polyamino bond (for example,

[0142]

Embedded image

Here, the unsatisfied free N valence is
Occupied by H atoms or R ⁰ groups), and mixtures of such bridging groups (each R ⁰ is a lower alkyl group). One or more ar at the aromatic group linked above
The group is a fused nucleus (eg,

[0144]

Embedded image

Can be replaced by When Ar is a linked polynuclear aromatic group, specific examples include:

[0146]

Embedded image

Normally, all these Ar groups are unsubstituted, except for the R group and the -O- group (and certain bridging groups).

For reasons such as price, utility, performance, etc., the Ar group is usually a benzene nucleus, a lower alkylene bridged benzene nucleus, or a naphthalene nucleus.

The R group in Formula XII is a hydrocarbyl group bonded directly to the aromatic group Ar. R is preferably
It has about 6 to about 80 carbon atoms, and preferably has about 6
Having from about 30 to about 30 carbon atoms, more preferably about 8
Has from about 25 to about 25 carbon atoms, and advantageously has from about 8 to about 15 carbon atoms. Examples of R groups include butyl, isobutyl, pentyl, octyl, nonyl, dodecyl, dodecosyl, tetracontyl, 5-chlorohexyl,
Ethoxypentyl, 4-hexenyl, 3-cyclohexyloctyl, 4- (p-chlorophenyl) octyl,
Includes substituents derived from 2,3,5-trimethylheptyl, 4-ethyl-5-methyloctyl, and polymerized olefins such as: polychloroprene, polyethylene, polypropylene, polyisobutylene, ethylene- Propylene copolymer, chlorinated olefin polymer, oxidized ethylene-propylene copolymer, propylene tetramer and tri (isobutene).

Attaching the hydrocarbyl group R to the aromatic group Ar can be accomplished by a number of methods known to those skilled in the art.
Can be achieved. One particularly suitable method is Friedel-
It is a craft reaction. Here, an olefin (eg, a polymer containing an olefinic bond), or a halogenated or hydrohalogenated analog thereof, is subjected to a reaction with a phenol. The reaction takes place in the presence of a Lewis acid catalyst (eg, boron trifluoride and its complexes with ether, phenol, hydrogen fluoride, aluminum chloride, aluminum bromide, zinc dichloride, etc.). Methods and conditions for performing such reactions are known to those skilled in the art. For example, in the Kirk-Othmer Chemical Technical Dictionary,
Reference titled “Alkylation of phenol” (2
Edition, Volume 1, p. 894-895, Interscience Publishing, Division of John Wiley, New York, 1963). Other equally suitable and convenient methods for attaching the hydrocarbyl group R to the aromatic group Ar will be apparent to those skilled in the art.

As can be seen from inspection of formula XII, the phenolic groups of the salts (A) according to the invention contain at least one R group and OH, as defined above. Each of the foregoing must be attached to a carbon atom that is part of an aromatic nucleus in the Ar group. However, if there is more than one aromatic nucleus in the Ar group, each need not be attached to the same aromatic ring.

(Boron-Containing Salt (A)) The boron-containing neutral or basic metal salt (A) of the present invention is obtained by reacting the following (1), (2), (3) and (4). Prepared by a method comprising: (1) at least one acidic organic compound or a precursor thereof; (2) at least one metal-containing compound containing a compound selected from the group consisting of: alkali Metals, alkaline earth metals, zinc, copper, aluminum or mixtures of two or more thereof; (3) at least one boron-containing compound; and (4) at least one precursor.

The acidic organic compound can be any of the carboxylic or acid generating compounds discussed above, sulfur-containing acids, phosphorus-containing acids or phenols. The acid (1) can also be a mixture of two or more thereof.

The metal-containing compound (2) is preferably a metal oxide, a metal hydroxide, a metal halide, a metal carbonate or a metal borate. It is also the top 2
It can be a mixture of seeds or more. More preferred metals of this metal-containing compound (2) include lithium, sodium, magnesium, calcium, potassium, barium, aluminum, zinc and copper. Mixtures of two or more of the above metals can be used. Particularly preferred metals are sodium, magnesium, calcium or mixtures of two or more thereof.

The boron compound (3) includes boron oxide, boron oxide hydrate, boron trioxide, boron trifluoride, boron tribromide, boron trichloride, boric acid (for example, boronic acid (boronic acid) That is, alkyl-B (OH) ₂ or aryl-B (OH) ₂ ), boric acid (ie, H ₃ BO ₃ ), tetraboric acid (ie, H
₂ B ₄ O _7), metaboric acid (i.e., HBO _2)), boron anhydrides, boron acid amides and various esters of such boron acids, and the like. Using complexes of boron trihalides with ethers, organic acids, inorganic acids or hydrocarbons is a convenient way to introduce boron reactants into the reaction mixture. Such complexes are known and include boron trifluoride-triethyl ester, boron trifluoride-phosphoric acid, boron trichloride-chloroacetic acid, boron tribromide-dioxane, and boron trifluoride-methyl ethyl ether. Is exemplified.

Particular examples of boronic acids include methylboronic acid, phenylboronic acid, cyclohexylboronic acid, p-
Heptylphenylboronic acid and dodecylboronic acid are included.

The borate esters include, in particular, mono-, di- and tri-organic esters of boric acid with alcohols or phenols. Examples of alcohols or phenols include methanol, ethanol, isopropanol, cyclohexanol, cyclopentanol, 1-octanol, 2-octanol, dodecanol, behenyl alcohol, oleyl alcohol, stearyl alcohol, benzyl alcohol, 2-butylcyclohexanol, Ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 2,4-hexanediol, 1,2-cyclohexanediol, 1,3-octanediol, glycerol, pentaerythritol diethylene glycol, carbitol, cellosolve, trisolvent Ethylene glycol, tripropylene glycol, phenol, naphthol, p
-Butylphenol, o, p-diheptylphenol,
n-cyclohexylphenol, 2,2-bis- (p-
Hydroxyphenyl) propane, polyisobutene (molecular weight 1,500) -substituted phenol, ethylene chlorohydrin, o-chlorophenol, m-nitrophenol, 6
-Bromooctanol, and 7-ketodecanol. Lower alcohols such as 1,2-glycol and 1,3-glycol (ie, alcohols having less than about 8 carbon atoms) are particularly useful in preparing borate esters for this invention.

Methods for preparing esters of boric acid are known in the art (see, eg, “Chemical Review” p.
p. 959-1064, vol. 56).
Therefore, one method involves the reaction of boron trichloride with 3 moles of an alcohol or phenol to give a tri-organoborate. Other methods include the reaction of boron oxide with an alcohol or phenol. Other methods include direct esterification of tetraboric acid with 3 moles of an alcohol or phenol. Still other methods include direct esterification of boric acid with a glycol to form, for example, a cyclic alkylene borate.

The promoter (4) is a chemical substance used to promote mixing of the metal into the basic metal composition. Of this chemical, the following are useful as accelerators: water, ammonium hydroxide, organic acids having up to about 8 carbon atoms, nitric acid, sulfuric acid, hydrochloric acid, metal complexing agents (eg, alkyl salicylaldoxime) ), And alkali metal hydroxides (eg, lithium hydroxide, sodium hydroxide, and potassium hydroxide), and monohydric and polyhydric alcohols having up to about 30 carbon atoms. Examples of this alcohol include methanol, ethanol, isopropanol, cyclohexanol, dodecanol, decanol, behenyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, monomethyl ether of ethylene glycol, trimethylene glycol, hexamethylene glycol, glycerol, pentaerythritol, benzyl alcohol,
Examples include phenylethyl alcohol, sorbitol, nitropropanol, chloroethanol, aminoethanol, cinnamyl alcohol, allyl alcohol and the like. A monohydric alcohol having up to about 10 carbon atoms,
And mixtures of methanol with higher polyhydric alcohols are particularly useful.

The boron-containing salt (A) is preferably formed by reacting the organic acid (1) with a part of the metal-containing compound (2) to form a neutral metal salt of the organic acid. Is done. Then, an additional metal-containing compound (2) is added along with the boron-containing compound (3) and the accelerator (4). The contents are heated to reflux and maintained at reflux for several hours.

The components (1), (2),
A more preferred ratio of (3) and (4) can be determined by the following equation (where Eqs. Means equivalent):

[0162]

(Equation 1)

This ratio preferably ranges from about 0.2 to about 3, more preferably from about 0.5 to about 2.

For the above equation, one mole of boron is equal to the number of moles of boron compound (3) multiplied by the number of borons present in the boron compound. Therefore, if 3.2 moles of boric acid H ₃ BO ₃ are used, then the number of moles of boron is 3.2 times 1, ie, 3.
It becomes 2. If 2 moles of tetraborate H ₂ B ₄ O ₇ are used, the number of moles of boron is 2 × 4, or 8.

For the above equation, one equivalent of a metal is equal to the molecular weight of the metal divided by the valency of the metal ion. Therefore, the sodium weight is 23 (ie,
23 divided by 1 = 23). In contrast, the equivalent of calcium is 20 (ie, 40 divided by 2 = 20).

The above reaction can be carried out in the presence of a substantially inert, liquid solvent / diluent medium. The solvent / diluent medium is desirably provided to maintain contact of the components and to facilitate control of the reaction temperature. Examples of suitable solvents / diluents include aliphatic and aromatic hydrocarbons (eg, benzene, toluene, naphtha, mineral oil, hexane, chlorinated hydrocarbons (eg, benzene dichloride and heptyl chloride), and ethers. (Eg, methyl n-amyl ether and n-butyl ether))
Is included.

(Component (B)) The metal deactivator (B) is
Preferably, at least one of which may be substituted or unsubstituted
Contains some benzotriazoles. Examples of suitable compounds include benzotriazole, alkyl-substituted benzotriazole (eg, toluyltriazole, ethylenebenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.), aryl-substituted benzotriazole (eg, phenylbenzotriazole, etc.), alkaryl Or arylalkyl-substituted benzotriazole, and substituted benzotriazole, where the substituent is, for example, hydroxy, alkoxy, halo (especially chloro), nitro, carboxy or carboalkoxy. More preferred are benzotriazoles and alkylbenzotriazoles, where the alkyl group has 1 to about 20 carbon atoms, especially 1 to about 8 carbon atoms, and benzotriazole and toluyltriazole are most preferred. .

The metal deactivator (B) also contains nitrogen.
At least one upper ben to form the composition;
Reaction product of zotriazole with at least one amine
It can be an adult. The amine may comprise one or more
It can be a monoamine or a polyamine. These things
Amines and polyamines are primary amines, secondary amines.
Or a tertiary amine. This amine is fat
May be an aromatic, cycloaliphatic, aromatic, or heterocyclic ring
No. The amine includes an aliphatic-substituted cycloaliphatic
Amine, aliphatic substituted aromatic amine, aliphatic
Heterocyclic amines substituted, cycloaliphatic substituted fats
Aromatic amines, aromatic amines substituted with cycloaliphatic,
Cycloaliphatic substituted heterocyclic amines, aromatic substituted
Aliphatic amines, aromatic-substituted cycloaliphatic amines
Min, alicyclic amine substituted with aromatic and heterocyclic
And aromatic amines substituted with heterocycles
You. These amines may be saturated or unsaturated.
No. The amine may also have a non-hydrocarbon substituent or group.
You may have. However, if these groups are amines
As long as it does not significantly hinder the reaction with the acylating reagent of the present invention.
Please. As such non-hydrocarbon substituents or groups
Represents a lower alkoxy group, a lower alkyl mercapto group,
Toro groups and interrupting groups such as -O- and -S-
(For example, -CH _TwoCH_Two-X- CH_TwoCH_Two-(Here
Wherein X is -O- or -S-)).
In general, the amine may be characterized by the formula:

[0169]

Embedded image

Here, R ₁ , R ₂ and R ₃ each independently represent hydrogen or a hydrocarbyl group, an amino-substituted hydrocarbyl group, a hydroxy-substituted hydrocarbyl group, an alkoxy-substituted hydrocarbyl group, an amino group, a carbamyl group, a thiocarbamyl group, A guanyl group and an acylimidoyl group.

Except for the branched polyalkylene polyamines, polyoxyalkylene polyamines, and amines substituted with high molecular weight hydrocarbyl groups, more fully described hereinafter, the amines are generally about 40 Fewer carbon atoms, usually no more than about 20 carbon atoms in total.

The aliphatic monoamine includes a monoaliphatic substituted amine, a dialiphatic substituted amine and a trialiphatic substituted amine. Here, the aliphatic group can be saturated or unsaturated, and straight or branched. Such amines include, for example, mono-, di- and trialkyl-substituted amines; mono-, di- and trialkenyl-substituted amines; and one or more N-alkenyl substituents and one N-alkyl. And substituted amines, and the like. The total number of carbon atoms in these aliphatic monoamines, as noted above, usually does not exceed about 40, and usually does not exceed about 20 carbon atoms. Specific examples of such monoamines include ethylamine, diethylamine, triethylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, allylamine, isobutylamine, cocoamine, stearylamine, laurylamine, methyllaurylamine, oleylamine , N-methyloctylamine, dodecylamine, octadecylamine, and the like. An aliphatic amine substituted with a cycloaliphatic,
Examples of the aliphatic amine substituted with an aromatic group and the aliphatic amine substituted with a heterocyclic group include 2- (cyclohexyl)
Includes ethylamine, benzylamine, phenylethylamine, and 3- (furylpropyl) amine.

Cycloaliphatic monoamines are monoamines having one cycloaliphatic substituent directly attached to the amino nitrogen by a carbon atom in a cyclic ring structure. Examples of cycloaliphatic monoamines include cyclohexylamine,
Includes cyclopentylamine, cyclohexenylamine, cyclopentenylamine, N-ethylcyclohexylamine, dicyclohexylamine, and the like. An aliphatic-substituted cycloaliphatic monoamine,
Examples of aromatic-substituted cycloaliphatic monoamines and heterocyclic-substituted cycloaliphatic monoamines include propyl-substituted cyclohexylamine, phenyl-substituted cyclopentylamine, and pyranyl-substituted cyclohexylamine.

The aromatic amine includes a monoamine in which a carbon atom of the aromatic ring structure is directly bonded to an amino nitrogen. The aromatic ring is usually mononuclear
(Leather) aromatic ring (that is, a ring derived from benzene). However, the ring may include fused aromatic rings, especially rings derived from naphthalene. Examples of aromatic monoamines include aniline, di (p-methylphenyl) amine, naphthylamine, N- (n-butyl)
Includes aniline, and the like. Examples of aliphatic-substituted aromatic monoamines, cycloaliphatic-substituted aromatic monoamines, and heterocyclic-substituted aromatic monoamines include p-ethoxyaniline, p-dodecylaniline, cyclohexyl-substituted naphthylamine and Thienyl-substituted anilines are included.

The polyamines mainly include the alkylene amines which, for the most part, correspond to the following formula:

[0176]

Embedded image

Wherein n is preferably a number less than about 10, each R is independently a hydrogen group, or a hydrocarbyl group, preferably having up to about 30 carbon atoms, and an alkylene group is preferably , A lower alkylene group having less than about 8 carbon atoms.

The alkylene amines mainly include methyleneamine, ethyleneamine, butyleneamine, propyleneamine, pentyleneamine, hexyleneamine,
Heptyleneamine, octyleneamine, other polymethyleneamines are included. These are particularly exemplified by: ethylenediamine, triethylenetetramine,
Propylenediamine, decamethylenediamine, octamethylenediamine, di (heptamethylene) triamine, tripropylenetetramine, tetraethylenepentamine,
Trimethylenediamine, pentaethylenehexamine, di (trimethylene) triamine. Higher molecular weight analogs, such as those obtained by the condensation of two or more of the above alkyleneamines, are also useful.

Ethyleneamine is particularly useful. These are entitled "Ethyleneamine" and are entitled Chemical Encyclopedia,
Kirk and Othme
r), 5 vol. 898-905, Interscience Publishing, New York (1950). Such compounds are most conveniently prepared by the reaction of an alkylene chloride with ammonia. This reaction produces a complex mixture of alkyleneamines to some extent. The amine includes a cyclic condensation product such as piperazine. These mixtures find use in the process of the present invention. On the other hand, the use of pure alkyleneamines also gives the completely desired product. Particularly useful alkylene amines include ethylene amine mixtures prepared by the reaction of ethylene chloride with ammonia, not only because of economics but also the efficiency of the resulting product. This mixture has a composition corresponding to the mixture of tetraethylenepentamine.

A hydroxyalkyl-substituted alkyleneamine (ie, an alkyleneamine having one or more hydroxyalkyl substituents on a nitrogen atom) is
It is also considered for use here. Higher molecular weight analogs, such as those obtained by condensation of the above exemplified alkyleneamines or hydroxyalkyl-substituted alkyleneamines via amino or hydroxy groups, are also useful. Condensation via amino groups gives higher molecular weight amines with the removal of ammonia, and condensation via hydroxy groups gives products containing ether linkages with removal of water. Will be understood.

The metal deactivator (B) may also comprise at least one of the above benzotriazoles and at least one nitrogen-containing compound of the type described below under the heading "Lubricants and functional fluids" It can be a reaction product with an ashless dispersant. The nitrogen-containing carboxylic dispersants and the Mannich dispersants described below are particularly preferred.

The reaction product of the benzotriazoleamine and the benzotriazole ashless dispersant can be prepared by simply mixing the reagents and allowing the reaction to proceed. The reaction is carried out with a substantially inert, normally liquid organic diluent, which can be the oil or diluent component of a lubricant or concentrate containing the composition of the invention; for example, mineral oil, benzene, toluene , Xylene, petroleum naphtha, aliphatic ethers or the like). In contrast, this reaction can be performed at a low temperature, such as about 15 ° C. Generally, it is preferred to carry out the reaction at a temperature up to about 160C, with temperatures in the range of about 60C to about 140C being useful.

The proportions of benzotriazole and amine or ashless dispersant used in preparing the reaction products useful as component (B) can vary widely.
Generally, it is more preferable to mix as much benzotriazole as possible in an oil-dispersible medium. This can be done by using about 1 equivalent of amine or ashless dispersant per equivalent of benzotriazole. (The equivalent weight of an amine or ashless dispersant is its molecular weight divided by the number of basic nitrogen atoms therein.
The equivalent weight of a benzotriazole is its molecular weight divided by the number of triazole rings therein.) However, in some cases, it is desirable to use one or more equivalents of the amine or ashless dispersant per equivalent of benzotriazole.

The exact molecular structure of the reaction product of the benzotriazole-amine and benzotriazole-ashless dispersant is certainly unknown and not critical. However, the benzotriazole is generally considered more acidic than the amine or ashless dispersant. Thus, the composition may contain an amine salt of benzotriazole.

(Phosphorus-Containing Amide (C-1)) The phosphorus-containing amide (C-1) preferably contains at least one compound represented by the following formula:

[0186]

Embedded image

Here, in the formula XIII, X ¹ , X ² ,
X ³ , X ⁴ and X ⁵ are independently oxygen or sulfur; R ¹ and R ² are independently hydrocarbyl groups; R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ Is, independently,
A and b are independently 0 or 1; n is 0 or 1
N ′ is 1, 2 or 3; provided that: (1) When n ′ is 1, R ⁸ is hydrogen, —R, —ROH,
-ROR, -RSR or

[0188]

Embedded image

(2) When n 'is 2, R ⁸ is a bonding group selected from the following: -R-, -R ^* -, -RO
-R, -RSR-,

[0190]

Embedded image

(3) When n ′ is 3, R ⁸ is a bonding group

[0192]

Embedded image

Is as follows.

Here, each R is independently 1 to about 12
And R ^* is a hydrocarbyl group having 1 to about 60 carbon atoms or a carboxyhydrocarbyl group.

X ¹ , X ² and X ⁵ are preferably oxygen. X ³ and X ⁴ are preferably sulfur.

R¹And R^TwoAre independently one to about 50
Hydrocarbyl group having 2 carbon atoms, more preferred
Is a hydrocarbyl having from about 1 to about 30 carbon atoms.
Group, more preferably about 3 to about 18 carbon atoms.
Hydrocarbyl groups, more preferably from about 4 to about
Hydrocarbyl groups having 8 carbon atoms. R ¹
And R^TwoExamples of independently a t-butyl group, isobutyl
Tyl, amyl, isooctyl, decyl, dodecyl
Group, eicosyl group, 2-pentenyl group, dotenyl
Group, phenyl group, naphthyl group, alkylphenyl group,
Lucirnaphthyl group, phenylalkyl group, naphthyl al
Kill group, alkylphenylalkyl group, alkylnaphthy
And an alkyl group.

R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently hydrogen or a hydrocarbyl group having 1 to about 50 carbon atoms, more preferably 1 to about 30 Hydrocarbyl groups having carbon atoms, more preferably hydrocarbyl groups having 1 to about 18 carbon atoms, more preferably hydrocarbyl groups having 1 to about 8 carbon atoms. ^{Advantageously, R 3, R 4, R} 5, R 6 and R ⁷ are independently hydrogen, alkyl groups having 1 to about 22 carbon atoms; about 4 to about 22 carbon atoms Or an aromatic group having about 4 to about 34 carbon atoms, an alkyl-substituted aromatic group or an aromatic-substituted alkyl group.

When R is a linking group, it is preferably methylene. R ^* is preferably an alkylene or alkylidene group having 1 to about 28 carbon atoms.

The phosphorus-containing amide of the formula XIII is
It can be manufactured by various selectable routes. In one embodiment, the preparation of these amides involves the reaction of a phosphorus acid reactant of formula (A) with an acrylamide type reactant of formula (B):

[0200]

Embedded image

Here, various R groups and X groups are represented by the formula XI
Same as shown above in II. Reactant (A) is described above under the heading "Phosphorus-containing acid". Examples of reactant (B), acrylamide, methacrylamide (wherein, R ⁵ is methyl), and crotonamide are included.

The reaction between reactants (A) and (B) is exothermic. Therefore, only slight heating is required for the reaction. The reaction is conveniently carried out at about 25 ° C to about 1 ° C.
It may be carried out at a temperature of 00C (preferably at a temperature of about 70C to about 90C) under an inert atmosphere (e.g., under nitrogen). This reaction can be performed in the presence or absence of a solvent. Preferably, the reaction takes place in a solvent medium. The solvent medium typically includes a hydrocarbon (eg, toluene, xylene, hexane, heptane,
Kerosene, fuel oil, oil with lubricating viscosity, etc., or chlorinated hydrocarbons (eg, chloroform, carbon tetrachloride, etc.), or alcohols (eg, methanol, ethanol, propanol, butanol, 2-ethylhexanol, etc.). . This solvent, in addition to its own action, preferably provides suitable processing properties, such as controlling exothermic reactions and preventing unwanted side reactions. The reaction time is usually as short as 1 hour or 2 hours or less, depending on the temperature.

The reaction between reactants (A) and (B) yields a compound having the formula:

[0204]

Embedded image

At this point, the R ⁸ group of formula XIII is hydrogen and n is 1. This reaction product XIV is an intermediate. However, it can also serve as the final product for use as additive (C-1) of the present invention. The reaction products are useful in providing high load carrying, extreme pressure, antiwear and / or corrosion inhibiting properties to lubricants and functional fluids.

The intermediate reaction product XIV may be coupled in a manner as described below to contain another functional group R ⁸ on the nitrogen atom, and / or by various methods known to those skilled in the art. For further reaction. This group includes:
-ROH, -ROR, -RSR,

[0207]

Embedded image

Is included.

Wherein R is the same as defined above in connection with formula XIII.

In another embodiment of the present invention, the preparation of phosphorus-containing amide XIII involves reacting reactant (A) with compound (D) having the formula

[0211]

Embedded image

Here, various R groups and X groups and n ′
Is the same as previously shown in Formula XIII.

Reactant (D) has an R ⁸ linking group attached thereto (ie, one of the groups shown above for R ⁸ when n ′ is 2 or 3). Other than that, it is similar to the reactant (B). Thus, the definitions of R ³ , R ⁴ , R ⁵ and R ⁷ are the same as given above for reactant (B). R ⁸ is the same as discussed above for Formula XIII when n ′ is 2 or 3. n ′ is preferably 2, and R ⁸ is preferably —CH ₂ —O—CH ₂ —.

The reaction between reactants (A) and (D) is exothermic and therefore requires only slight heavy heating. The reaction is preferably conducted at a temperature of about 25 ° C to about 100 ° C (preferably at a temperature of about 70 ° C to about 90 ° C).
Performed under an inert atmosphere. The reaction time is generally short, for example of the order of 1 hour or less, or 2 hours or less. Hydrocarbon solvents (eg, toluene, xylene, hexane, heptane, kerosene, fuel oil, oils with lubricating viscosity, etc.), or chlorinated hydrocarbons (eg, chloroform, carbon tetrachloride, etc.), or alcohols (eg, methanol, Ethanol, propanol, butanol, 2-ethylhexanol, etc.) can be used. Once this product is formed, various solvents can be removed, such as by removal of volatile components under vacuum.

Phosphorus-containing amides of formula XIII (especially R
A linked compound as shown above containing ^six groups)
Another alternative method for preparing is by a displacement reaction.
In this reaction, a metal salt of the reactant (A) is used. It is the reaction of a metal salt according to the following formula (A ') with a compound of the following formula (F):

[0216]

Embedded image

Here, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , R ¹ ,
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and n are of the formula XIII
Is the same as indicated above for M is an alkali metal (eg, sodium, potassium, etc.) or an alkaline earth metal (eg, manganese, calcium, etc.) or hydrogen. Sodium and potassium are preferred. X ⁶ is a substitutable halogen or carbon group (eg, Cl, Br, I, tosyl, mesyl, etc.).

The reaction between A 'and F proceeds in a manner very similar to that shown above for the reaction product between reactants (A) and (B). In summary, the reaction is carried out at a temperature of about 10 ° C to about 200 ° C (preferably about 5 ° C).
0 ° C. to about 150 ° C.). An inert atmosphere (eg, nitrogen) is used. Although not required, this reaction can take place in a solvent. The solvent also renders by-product salts (eg, KCl, NaCl, NaBr, KBr, etc.) insoluble in the reaction medium. This salt can be removed by filtration. The amount of reactants A 'and F is generally
Is equivalent. The resulting product has the formula:

[0219]

Embedded image

The reaction product formed by the reaction between reactants (A) and (B) is combined with a coupling agent (C) (which is an aldehyde or ketone of the formula Synthetic equivalent)
Can be combined by reacting with:

[0221]

Embedded image

Wherein R ⁹ and R ¹⁰ are independently hydrogen, an alkyl group having 1 to about 12 carbon atoms, phenyl, or an alkyl substituted having about 7 to about 12 carbon atoms. Phenyl.

Preferably, the coupling agent (C) is an aldehyde having a total of from 1 to about 3 carbon atoms (preferably one carbon atom) (ie, R ¹⁰ is H). . Formaldehyde and paraformaldehyde are more preferred; they can give rise to methylene and dimethylene ether linking groups.

The coupling reaction is preferably carried out using a strongly acidic mineral or organic acid catalyst (eg, HCl, H ₂ S
_{O 4, H 4 PO 4,} CH 3 SO 3 H, in the presence of p- toluenesulfonic acid), occurs. The amount of the acid catalyst is generally from about 0.3% to about 1.5%, preferably from about 0.8% to about 1.2% by weight, based on the weight of the total product formed. And more preferably from about 0.9% to about 1.1% by weight. Although smaller amounts of catalyst may be utilized, the reaction is generally slowed and a small fraction of the desired product is formed. Coupling agent (C)
Reaction is preferably carried out under an inert atmosphere at about 80
° C to about 120 ° C (more preferably, about 80 ° C to about 100 ° C).
C) at an initial temperature. The final reaction temperature will generally be higher, on the order of about 100 ° C to about 150 ° C, preferably
From about 125 ° C to about 135 ° C.

If the reaction is stopped at the carbinol stage
Is desirable (in equation XV, X ^FiveIs oxygen), (A)
The reaction between (B) and (B) is preferably carried out with a basic catalyst (e.g.
That is, NaHCO_Three, KHCO_Three, Na_TwoCO_Three, KCO
_Three, NaOH, KOH, etc.). This anti
The reaction mixture is neutralized with acid and heated to remove water.
The mixture is H_TwoS, NaHS or Na_TwoS
Or other S = raw material, or NH_ThreeOr R "NH_TwoAnd anti
Can be provided in response. Here, R ″ is selectively H, 1
Alkyl having from about 60 to about 60 carbon atoms, from about 6 to about 3
Aryl, alkyl-substituted aryl having 0 carbon atoms
Or aryl-substituted alkyl, or 1 to about 22
Acyl having a carbon atom of

The ratio of reactant (A) to reactant (B) used is preferably a 1: 1 equivalent ratio. However, higher and lower amounts can be used. 2
A 1: 1 equivalent ratio of the two reactants is preferred. If not, an acid number higher than desired is obtained, or one of the reactants is wasted. Formed coupling agent (C)
The amount of the reaction product to be subjected to the reaction is about 0.3 to about 3 equivalents of the reaction product per equivalent of the coupling agent (C), and a 1: 1 equivalent ratio is more preferable. . The coupling agent (C) can be a mixture of various couplers, and preferably contains paraformaldehyde.

The combination of formaldehyde with the phosphorus-containing amide compounds described above results in the coupling of two amides or -CH ₂ on the nitrogen atom of the amide.
OH can be formed. _Two such amides having a -CH2OH group are then subjected to a reaction to form a linked amide having the following linking group. This linking group is

[0228]

Embedded image

Is as follows. Such a coupling reaction is
This can occur during the use of unbound compounds such that the reaction becomes endothermic. This endothermic reaction can be beneficial to the load bearing lubricating properties of the overall oil composition.

The other couplers (R ⁸ of formula XIII when n ′ is 2 or 3) and the functional groups (R ⁸ of formula XIII when n ′ is 1) can be prepared by methods known to those skilled in the art.
It can be attached to the nitrogen atom of the phosphorus-containing amide described above.

(Phosphorus-Containing Ester (C-2)) The phosphorus-containing ester (C-2) of the present invention can be characterized by the following structural formula:

[0232]

Embedded image

Wherein, in formula XVI, X ¹ , X ² , X ³ and X ⁴ are independently oxygen or sulfur; R ¹ and R ² are independently hydrocarbyl groups; R ³ ,
R ⁴ and R ⁵ are independently hydrogen or a hydrocarbyl group; R ⁶ is a hydrocarbyl group; and a and b are independently 0 or 1.

In the formula XVI, X ¹ and X ² are preferably oxygen and X ³ and X ⁴ are preferably sulfur.

R ¹ and R ² are independently 1 to about 50
Hydrocarbyl groups having from 1 to about 30 carbon atoms, more preferably from 3 to about 18 carbon atoms, and more preferably from 4 to about 8 carbon atoms. It is. Examples of R ¹ and R ² include independently t-butyl, isobutyl, amyl, isooctyl, decyl, dodecyl, eicosyl, 2-pentenyl, dodecenyl, phenyl, naphthyl ,
Examples include an alkylphenyl group, an alkylnaphthyl group, a phenylalkyl group, a naphthylalkyl group, an alkylphenylalkyl group, an alkylnaphthylalkyl group and the like.

Preferably, R ³ , R ⁴ and R ⁵ are independently hydrogen or a hydrocarbyl group having 1 to about 50 carbon atoms. More preferably, R ³ and R ⁴
And R ⁵ are independently hydrogen; an alkyl group having 1 to about 22 carbon atoms; a cycloalkyl group having about 4 to about 22 carbon atoms; or about 4 to about 34 carbon atoms. An aromatic group having a carbon atom, an alkyl-substituted aromatic group or an aromatic-substituted alkyl group.

R ⁶ is preferably an alkyl group having 1 to about 22 carbon atoms; a cycloalkyl group having about 4 to about 22 carbon atoms; or about 4 to about 34 carbon atoms. An aromatic group having an atom, an alkyl-substituted aromatic group, or an aromatic-substituted alkyl group.

In a particularly more preferred embodiment, R ¹ and R ² are independently an alkyl group having from about 3 to about 18 carbon atoms; X ¹ and X ² are oxygen; X ³ and X ⁴ are Sulfur; R ³ , R ⁴ and R ⁵ are independently hydrogen or methyl; and n ″ is 1.

The phosphorus-containing esters represented by the formula XVI can be prepared by reacting a phosphorus-containing acid (A) with a compound represented by the following formula (B):

[0240]

Embedded image

Here, various R groups and X groups are represented by the formula XV
Same as defined for I.

Reactant (A) is defined above under the heading "Phosphorus Acid". Reactant (B) has the formula R ⁶ O
It can be prepared by reacting an alcohol represented by H with an α, β-unsaturated carboxylic acid represented by the formula:

[0243]

Embedded image

Here, R ³ , R ⁴ and R ⁵ are represented by the formula XVI
Is the same as defined above for

The reaction between reactants (A) and (B) is carried out in the presence of an inert organic solvent (eg benzene, toluene or methylene chloride), preferably with stirring, over a period of time. This can be done by adding either the product (A) or (B) to the other. This addition is preferably performed at an elevated temperature (eg, at reflux). The reaction mixture is then further, for example, 1-4
Reflux over a period of time. The product is then cooled and neutralized, for example, by washing with aqueous sodium carbonate and, if necessary, by washing with brine. The solvent is then removed by distillation and, if necessary, the product is steam distilled.
The product can then be purified, for example, by conventional methods such as filtration.

(Sulfur-bonded dithiocarbamate (C-
3)) The sulfur-bonded dithiocarbamate of the present invention (C-
3) can be characterized by the following structural formula:

[0247]

Embedded image

Wherein, in formula XVII, R ¹ , R ² and R ³ are independently H or a hydrocarbyl group; R ⁴ is an H, OH or hydrocarbyl group; R ⁵ and R ⁶ are independently H, a hydrocarbyl group or a hydroxyhydrocarbyl group; or R ³ and R ⁴ together, and / or R ⁵ and R ⁶ together, and / or R ¹ and R ³ together, and And / or R ² and R ⁴ may together form a cyclic group. And x is a number from 1 to about 8.

The hydrocarbyl groups R ¹ to R ⁴ can be straight-chain or branched-chain hydrocarbyl groups. Each of R ¹ to R ⁶ may independently have 1 to about 100 carbon atoms, preferably 1 to about 30 carbon atoms.

The groups R ¹ to R ⁴ may be an aliphatic group or an aromatic group (for example, an alkyl group, a cycloalkyl group, an alkaryl group, an aralkyl group or an aryl group). R ³ and R ⁴ together and / or R ⁵
And R ⁶ together can be an alkylene group containing from about 4 to about 7 carbon atoms. In these embodiments, in Formula XVII, R ³ and R ⁴ are R ³ and R ⁴
Together with the carbon atom bonded to form a cycloalkyl group. R ⁵ and R ⁶ together with the nitrogen atom bonded to R ⁵ and R ⁶ in Formula XVII form a heterocyclic group.

Specific examples of hydrocarbyl groups R ¹ to R ⁶ include methyl, ethyl, isopropyl, isobutyl, secondary butyl, cyclohexyl, cyclopentyl, octyl, dodecyl, octadecyl, eicosyl, behenyl,
Triacontnil, phenyl, naphthyl, phenethyl,
Octylphenyl, toluyl, xylyl, dioctadecylphenyl, triethylphenyl, chlorophenyl, methoxyphenyl, dibromophenyl, nitrophenyl,
3-chlorohexyl and the like are included.

In one embodiment of the present invention, the sulfur-linked dithiocarbamate is characterized by the following structural formula:

[0253]

Embedded image

Here, in the formula XVII-A, x is 1 to
A number of 2, R ³ and R ⁴ are hydrogen or hydrocarbyl groups, and R ⁵ and / or R ⁶ are each independently a hydrocarbyl group.

The hydrocarbyl group in Formula XVII-A is
It can be any of the hydrocarbyl groups described above for formula XVIl. In general, R ⁵ and R ⁶ has from 1 to about 50 carbon atoms. And R ³ and R ⁴ are
Hydrocarbyl groups having 1 to about 100 carbon atoms.

In another embodiment of the present invention, the dithiocarbamate is characterized by the following structural formula:

[0257]

Embedded image

Here, in the formula XVII-B, R ¹ , R ² ,
R ³ , R ⁵ , R ⁶ and x are the same as defined above with respect to formula XVII.

In one embodiment, the sulfur-linked dithiocarbamate is prepared by a method comprising the following steps (A) and (B): (A) a sulfur halide; and (i) at least one Reacting a near stoichiometric equivalent with the olefinic hydrocarbon or (ii) aldehyde or ketone for a temperature and for a time sufficient to produce a di (halohydrocarbyl) sulfur intermediate or dialdehyde or diketosulfur intermediate. And (B) this intermediate is generally in an amount sufficient to replace the two halo groups with a dithiocarbamate group, or the dialdehyde or diketone 2
Generally sufficient to react with two carbonyl groups,
React with dithiocarbamate salts.

When the starting material is (1) at least one olefinic hydrocarbon, the product obtained is of the formula XVI
Or the product is characterized by the formula XVII and XVII
A mixture mainly containing a substance characterized by -A. When the starting material is (ii) an aldehyde or ketone, the product is primarily characterized by Formula XVII-B.

The sulfur halide used in the first step (A) may be sulfur monochloride (ie, S ₂ Cl ₂ ), sulfur dichloride, sulfur monobromide, sulfur dibromide, or the above sulfur halide. And elemental sulfur in varying amounts.

Various olefins and olefin mixtures can be used as starting materials in step (A). Olefin mixtures obtained by oligomerization of ethylene and / or propylene are available at low cost.
The olefinic hydrocarbon has at least one olefinic double bond defined as a non-aromatic double bond. That is, this double bond connects two aliphatic carbon atoms. In its broadest sense, the olefin may be defined by the formula: R ¹ R ³ C = CR ² R ⁴ wherein each R ¹ , R ² , R ³ and R ⁴ is hydrogen or a compound of formula XVII, A hydrocarbyl group as defined above for XVII-A or XVII-B.

Although a diolefinic hydrocarbon may be used, it is more preferred that the olefin is a monoolefin and that the olefin is a terminal monoolefinic hydrocarbon (ie, R ¹ and R ³ are hydrogen;
And R ² and / or R ⁴ is an olefin which is alkyl or aryl). Internal olefinic compounds (eg, compounds where R ¹ and R ² are alkyl or aryl groups) are also useful. 3 to about 100
Olefinic compounds having 3 carbon atoms, more usually 3 to about 30 carbon atoms, are particularly desirable.

Isobutene, propylene and their dimers, trimers, tetramers, and the like, and mixtures thereof are also useful olefinic compounds. Of these compounds, isobutylene, diisobutylene, triisobutylene and tetraisobutylene are particularly desirable due to their usefulness.

The product resulting from the reaction of the sulfur halide with one or more of the olefinic hydrocarbons identified above is obtained by adding the components of the sulfur halide to the unsaturated carbon atoms of the olefin. And a di (halohydrocarbyl) sulfide intermediate. The reaction proceeds as soon as the olefin is mixed with the sulfur halide. However, the reaction rate is
Increased by increasing the temperature of the mixture. Therefore, the mixture is generally kept at -2 until the reaction is complete.
At a temperature between 0 ° C and 120 ° C. The reaction temperature is dictated by the reactivity of the starting olefin and the thermal stability of the reaction product.

Alternatively, the olefin is warmed to the desired temperature, whereas the sulfur halide is generally added dropwise under an inert atmosphere at a rate sufficient to maintain the desired temperature. You may add each. Following completion of the sulfur halide addition, the reaction mixture is heated for an extended period of time to complete the reaction.

The amount of sulfur halide to be reacted with the olefinic hydrocarbon is generally a stoichiometric equivalent. For example, when a sulfur monohalide is utilized as the sulfur halide feed, one mole of the sulfur monohalide is subjected to a reaction with two moles of an olefin or olefin mixture.

Although a catalyst or reaction accelerator may be utilized,
They are generally known to be unnecessary. Examples of such catalysts or promoters include lower aliphatic amines and aromatic amines, especially tertiary amines.

Aldehydes or ketones which can be utilized as starting materials for the reaction with sulfur halides can be characterized by the following formula: R ¹ R ³ CHC (O) R ² where R ¹ , R ² and R ³ is each independently hydrogen or a formula XVII, XVII-A or XVII-
A hydrocarbyl group as defined above for B.

When the starting material is an aldehyde, this intermediate contains two aldehyde carbonyl groups. When the starting material is a ketone, the sulfur intermediate contains two keto groups.

The aldehydes and ketones can be subjected to a reaction with a sulfur halide, such as sulfur monochloride, sulfur dichloride, sulfur monobromide, sulfur dibromide, and a mixture of sulfur halide and elemental sulfur. .

The reaction of the aldehyde or ketone with the sulfur halide is carried out at the desired temperature (from about -30 ° C to about 2 ° C).
(Which can be in the range of 50 ° C. or more) by simply mixing the two reactants. More preferred reaction temperatures are generally in the range of about 10C to about 80C. The reaction can be performed in the presence of a diluent or a solvent such as benzene, naphtha, hexane, carbon tetrachloride, chloroform, mineral oil, and the like. This diluent / solvent facilitates control of the reaction temperature and thorough mixing of the reactants.

The relative amounts of the aldehyde or ketone and sulfur halide can vary over a wide range.
In most cases, this reaction involves 2 moles of aldehyde or ketone and 1 mole of sulfur halide. In other cases, an excess of any one of the reactants may be used. When sulfur compounds containing two or more sulfur atoms (e.g., x is an integer from 3-8) are desired, they react their aldehydes and ketones with a mixture of sulfur halide and sulfur. Thus, it is obtained. This reaction is usually
This is achieved by reacting the sulfur halide with the sulfur before the reaction of the aldehyde or ketone.

Specific examples of aldehydes that can be subjected to the reaction with the sulfur halide include, for example, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, 2-ethyl-1-hexaldehyde, cyclohexanecarboxaldehyde (C ₆ H ₁₁ CHO) ) Is included. Examples of ketones include dimethyl ketone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, and the like.

The sulfur-bonded dithiocarbamate of the present invention can be obtained by reacting the above-mentioned sulfur intermediate with a sufficient amount of a salt of dithiocarbamate, replacing the halo group with a dithiocarbamate group, or using both the dialdehyde or diketone intermediate. And is prepared by reacting with a carbonyl group of The dithiocarbamate salt may be represented by the formula: R ⁵ R ⁶ NC (S) SX where R ⁵ and R ⁶ are each independently a hydrogen, hydrocarbyl or hydroxyhydrocarbyl group, and X is , Alkali metals, tertiary amines, or other basic substances. The dithiocarbamic acid salt is prepared by reacting the amine R ⁵ R ⁶ NH with carbon disulfide in a 1: 1: 1 molar ratio in the presence of a base (usually an alkali metal hydroxide). Can be done. Preferably, the base is an alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide, and more usually, sodium hydroxide. However, for this reaction, using an excess of the amine,
Secondary amine.

This hydrocarbyl group or hydroxy
Drocarbyl group R^FiveAnd R⁶Is from 1 to about 50 carbons
May contain atoms. Preferably, R^FiveAnd R⁶Is low
It is a hydrocarbyl group. In some embodiments, R^FiveAnd
And R⁶Is an alkyl containing from about 4 to about 7 carbon atoms
It is a len group. In this embodiment, R^FiveAnd R⁶Is R
^FiveAnd R⁶Together with the nitrogen atom bonded to
Form a group. This heterocyclic group (and alkylene group)
May contain other atoms such as oxygen and sulfur
You.

Specific examples of the amine (R ⁵ R ⁶ NH) used to form the dithiocarbamate include, for example, methylamine, propylamine, dimethylamine,
Diethylamine, dipropylamine, dibutylamine,
Methylethylamine, methylcyclohexylamine, piperidine, morpholine, dihexylamine, dioctylamine, dicocoamine, methylhydroxyethylamine, di-hydroxyethylamine, piperazine and the like are included.

The metal salts of dithiocarbamates are known in the art and can be readily prepared by those skilled in the art.
One method of preparing alkali metal salts of dithiocarbamic acid involves the reaction of an amine, carbon disulfide and an alkali metal hydroxide. Generally, these reactants are mixed and subjected to the reaction at a low temperature (eg, a temperature between about 0 ° C. and 15 ° C.). In some embodiments, the aqueous amine solution is cooled to 0 ° C. to 15 ° C., and the carbon disulfide is
Before or during the addition of this alkali metal hydroxide,
Generally, they are added dropwise under an inert atmosphere. In another embodiment, the aqueous amine solution is cooled, to which the alkali metal hydroxide is added, followed by the carbon disulfide. All reactions are at 0 ° C
When mixed at a low temperature, such as 15 ° C., the mixture is allowed to warm to room temperature with stirring.

The salts of dithiocarbamic acid prepared by the above method are generally subjected directly to a reaction with the sulfur intermediate described above. A solvent may be included to facilitate this reaction. And alcohol is known to be a suitable solvent. The reaction between the sulfur intermediate and the dithiocarbamate salt is generally performed from room temperature to the reflux temperature of the mixture. The reaction is carried out until the reaction is complete, which is generally between about 5 hours and about 24 hours. At the end of the reaction, the aqueous phase is separated and the product is recovered from the organic phase.

The product of reacting a monohalogenated sulfur with an olefinic hydrocarbon, followed by reaction with a dithiocarbamate, is generally a mixture of products that can be represented by structural formulas XVII or XVII-A. is there. When the reaction is performed with an aldehyde or ketone instead of an olefinic hydrocarbon, the reaction product is also a mixture such that the major product is believed to be represented by structural formula XVII-B. This mixture of products is useful in lubricants and functional fluids, so there is no need to isolate the various products.

Sulfur-bonded dithiocarbamate (C-3)
Can also be prepared by a method comprising the following steps (A) and (B): (A) reacting an olefinic hydrocarbon with a halogen;
Producing a halogen-containing intermediate; and (B) converting the present halogenated alkali metal sulfide and dithiocarbamate in an amount sufficient to partially replace the halogen groups present with dithiocarbamate and / or sulfide groups. React with salt.

Any of the olefinic hydrocarbon and dithiocarbamate salts described above can be utilized by this method. Reactions of halogens with olefinic hydrocarbons are known in the art. A method of reacting a halogen with an olefinic hydrocarbon to produce a halogen-containing intermediate may be used.

The alkali metal sulfide utilized in the second step can generally be represented by the following structural formula: M ₂ S _X where M is an alkali metal and x is 1, 2 or 3 is there.

For reasons of economy and efficiency, sodium sulfide is more preferred as the alkali metal sulfide.

In one embodiment, the halogen containing intermediate is first subjected to a reaction with an alkali metal sulfide,
Then, it is subjected to a reaction with a salt of dithiocarbamate. Although the above reactants can be subjected to the reaction in various proportions, it is generally desirable to react 4 equivalents of this halogen-containing intermediate with 1 mole of alkali metal sulfide and 2 moles of a dithiocarbamate salt. The reaction may in some cases be carried out at a convenient temperature, such as from room temperature to about 100 ° C. or higher. The product resulting from this reaction is generally a mixture containing primarily sulfur-bonded dithiocarbamates, which are useful in lubricants and functional fluids.

(Sulfur-Containing Compound (C-4)) The sulfur composition (C-4) useful in the composition of the present invention may be a compound characterized by the following structural formula:

[0287]

Embedded image

Here, in formula I, R ¹ , R ² , R ³ and R ⁴ are each independently H or a hydrocarbyl group; R ¹ and / or R ³ are G ¹ or G ² R ¹ and R ² and / or R ³ and R ⁴ together may be an alkylene group containing from about 4 to about 7 carbon atoms; G ¹ and G ² are each Independently, C
(X) R, COOR, C = N, R 5 -C = NR 6, CON
(R) ₂ or NO ₂ , and G ¹ may also be CH ₂ OH. Where X is O or S, each R and R ⁵
Is independently H or a hydrocarbyl group; R ⁶ is H
Or G ¹ and G ² are both R ⁵ C ＣNR ⁶ , the two R ⁶ groups together are
When G ¹ is CH ₂ OH and G ₂ is COOR, a lactone can be formed by the intramolecular linkage of G ¹ and G ² when G ¹ is CH ₂ OH and G ₂ is COOR; , 1 to about 8.

In formula I, R ¹ , R ² , R ³ and R
⁴ is each independently hydrogen or a hydrocarbyl group. The hydrocarbyl group is an aliphatic group or an aromatic group (for example, an alkyl group, a cycloalkyl group, an alkaryl group, an aralkyl group, or an aryl group). R
¹ and R ² and / or R ³ and R ⁴ together form about 4
It can be an alkylene group containing from 1 to about 7 carbon atoms. In these embodiments, in Formula I, R ¹ and R
² together with the carbon atoms bonded to R ¹ and R ² form a cycloalkyl group. Similarly, R ³ and R ⁴ together with the carbon atom bonded to R ³ and R ⁴ form a cycloalkyl group. Also, R ¹ and / or
Or, R ³ may be G ¹ or G ² .

The hydrocarbyl groups R ¹ , R ² , R ³ and R ⁴ usually contain up to about 30 carbon atoms. Preferably, the hydrocarbyl group is an alkyl group containing up to about 10 carbon atoms. Particular examples of hydrocarbyl groups include methyl, ethyl, isopropyl,
Isobutyl, sec-butyl, cyclohexyl, cyclopentyl, octyl, dodecyl, octadecyl, eicosyl, behenyl, triacontenyl, phenyl, naphthyl, phenethyl, octyl-phenyl, tolyl, xylyl, dioctadecyl-phenyl, triethyl-phenyl, chloro-phenyl , Methoxy-phenyl, dibromo-phenyl, nitro-phenyl, 3-chlorohexyl and the like.

The sulfur compound represented by the formula I (C-4)
Can be a thia-aldehyde or thia-ketone.
That is, G ¹ and G ² in Formula I are C (O) R groups. Various thia-bisaldehyde compounds are known.
The synthesis of such compounds is described in the prior art (eg, US Pat. Nos. 3,296,137 and 2,580,69).
No. 5). The thia-aldehyde or thia-ketone is a suitable aldehyde or ketone (e.g.,
It is most conveniently prepared by the sulfurization of an aldehyde or ketone having the following structural formula: R ¹ R ² CHC (O) R where R ¹ is hydrogen, hydrocarbyl group or C
(O) R and R ² are hydrogen or hydrocarbyl groups, and R is hydrogen or hydrocarbyl groups. In these examples, R ³ and R ⁴ of Formula I are the same as R ¹ and R ² respectively, and G ¹ and G ² are both C
(O) R group. When R ¹ is C (O) R, the sulfurized product contains four C (O) R groups.

The sulphide reacts with the aldehyde or ketone,
It can occur by reacting sulfur halides or mixtures of sulfur halides with sulfur sulfur in varying amounts. The sulfur halide includes, for example, sulfur monochloride (ie, S ₂ Cl ₂ ), sulfur dichloride, sulfur monobromide, and sulfur dibromide.

The reaction of the aldehyde or ketone with the sulfur halide can be carried out at the desired temperature (which can be from about -30 ° C.
At about 250 ° C. or higher) and 2
It can happen by simply mixing the two reactants. More preferred reaction temperatures are generally in the range of about 10C to about 80C. This reaction can be performed in the presence of a diluent or a solvent. Such diluents or solvents include, for example, benzene, naphtha, hexane, carbon tetrachloride, chloroform, mineral oil, and the like. This diluent / solvent facilitates control of the reaction temperature and thorough mixing of the reactants.

The relative amounts of the aldehyde or ketone and the sulfur halide can vary over a wide range. In most cases, the reaction involves 2 moles of aldehyde or ketone, and 1 mole of sulfur halide. In other cases, any one of the reactants can be used in excess. When sulfur compounds containing more than two sulfur atoms are desired (for example when x is an integer from 3 to 8), these compounds are obtained by reacting an aldehyde with a mixture of a sulfur halide and sulfur. Sulfurized products with different G ¹ and G ² can be formed by sulfidation of a mixture of aldehydes and ketones or
(O) obtained by sulfurization of a mixture of ketones containing R groups.

Particular examples of thia-aldehydes and thia-ketones include compounds as represented by Formula I. Here, G ¹ and G ² are C (O) R groups, and x is 1 to
4, and R ¹ , R ² , R ³ , R ⁴ and R are as follows:

[0296]

[Table 1]

The thia-aldehydes and thia-ketones which can be prepared as described above have other functional groups,
(Which is usually derivable therefrom). Therefore, in one embodiment of the present invention,
Thia-aldehydes or thia-ketones are converted to certain derivatives by chemical reactants and / or reagents by co-converting aldehyde or ketone groups to other end groups. In such a reaction, the thia group (S
The x) and R ¹ -R ⁴ groups are inert and remain unchanged in this compound. For example, the thia-bisaldehyde can be converted to a hydroxy-acid derivative. Here, one of the aldehyde groups (G ¹ ) is converted to a COOH group. Other aldehyde groups (G ₂ ) can be converted to CH ₂ OH groups. The hydroxy-acid derivative has the corresponding thia-
It is most conveniently obtained by treating bisaldehyde with the following alkaline reagents. The alkali reagent is, for example, an alkali metal hydroxide or an alkaline earth metal hydroxide, preferably, about 5 to about 5 ml of this hydroxide in water.
These are diluted aqueous solutions containing from about 50% to about 50% by weight. Such alkaline reagents can be sodium hydroxide, potassium hydroxide, lithium hydroxide, barium hydroxide, calcium hydroxide, strontium hydroxide, and the like. The hydroxy-acid is isolated from the reaction mixture by acidification with a mineral acid (eg, hydrochloric acid). The hydroxy-acid derivative of thia-bisaldehyde is
It can be represented by the following formula IA:

[0298]

Embedded image

Here, R ¹ , R ² , R ³ , R ⁴ and x are
Same as previously defined.

A specific example of such a hydroxy-acid derivative is 6-hydroxy-2,2,5,5-tetramethyl-3,4-dithiahexanoic acid (ie, the compound of formula I
True -A, wherein R ^1, R ^2, R ³ and R ⁴ are methyl, and x is 2); 6-hydroxy-2,2
-Diethyl-5-propyl-5-butyl-3,4-dithiahexanoic acid; 6-hydroxy-2,2,5,5-tetraethyl-3,4-dithiahexanoic acid and the like.

In the hydroxy-acids described by Formula IA above, various other sulfur-containing compounds useful in the present invention, due to the presence of a hydroxy group and a carboxyl group, include such hydroxy and / or carboxy groups. It is obtained by converting the group into another polar group, usually derived therefrom. Examples of such derivatives include esters formed by esterification of one or both of a hydroxy group and a carboxyl group; amides, imides, and acyl halides formed through the carboxyl group; -Lactones formed with the elimination of water by intramolecular cyclization of the acid. Methods for preparing such derivatives are known to those skilled in the art. By including a detailed description of such a method, it is believed that the specification need not be excessively long. More specifically, the carboxyl group (COOH) of formula IA can be converted to an ester group (COOR) and an amide group (CON (R) ₂ ). Where R
The group can be hydrogen or a hydrocarbyl group containing 1 to 30 carbon atoms, more usually a hydrocarbyl group containing 1 to about 10 carbon atoms. Specific examples of such R groups include ethyl, propyl, butyl,
Phenyl and the like.

Methods for preparing lactones with the elimination of water by intramolecular cyclization of a hydroxy-acid of the formula IA are known in the art. Generally, this cyclization is facilitated by the presence of a substance such as acetic anhydride. The reaction is accomplished by heating the mixture to an elevated temperature (eg, reflux temperature) while removing volatile components, including water.
Done.

Structural Formula I wherein G ¹ and / or G ²
Wherein R ⁵ C = NR ⁶ ) can also be prepared from the corresponding thia-aldehyde and thia-ketone. These mono- and di-imine compounds are reacted by reacting 1 mol of the dialdehyde (C (O) H) or diketone (C (O) R ⁵ ) with 1 mol or 2 mol of amine, respectively. Prepared. The amine can be a monoamine or a polyamine. This thia-aldehyde or thia-ketone [-
[C (O) R ⁵ ] and a polyamine are subjected to a reaction,
Cyclic di-imines can be formed. For example, G ^{1 of} formula I
And when G ² are both R ⁵ C = NR ⁶ , the two R ⁶ groups are
Together they can be a hydrocarbylene group bonded to two nitrogen atoms. The thia-aldehyde and thia-
Amines that are reacted with ketones to form imines can be characterized by the formula: R ⁶ NH _2, where R ⁶ is hydrogen, a hydrocarbyl group, or an aminohydrocarbyl group.

Generally, the hydrocarbyl group will have about 30
Containing up to about 1 carbon atom, often from 1 to about 1
An aliphatic hydrocarbyl group containing zero carbon atoms.

In one embodiment, the hydrocarbylamines useful in preparing the imine derivatives of the present invention contain from about 2 to about 30 carbon atoms in the hydrocarbyl group.
More preferred are primary hydrocarbylamines containing from about 4 to about 20 carbon atoms. The hydrocarbyl group may be saturated or unsaturated. Representative examples of primary saturated amines include lower alkylamines (e.g., methylamine, ethylamine, n-propylamine, n-butylamine, n-amylamine, n-hexylamine); There are amines known as amines, and those commercially known as "Armeen" primary amines (products available from Armak Chemicals, Inc., Chicago, Ill.). Typical fatty amines include the following alkylamines: n-hexylamine, n-octylamine, n-decylamine, n-dodecylamine, n-
Tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-octadecylamine (stearylamine) and the like. These Armeen primary amines are available in both distilled and industrial grades. Distilled grades result in purer reaction products, but reaction with industrial grade amines also forms the desired amides, imines and imides. Almac's Armeen-C, Armeen-
O, Armeen-OL, Armeen-T, Arme
en-HT, Armeen-S and Armeen-S
Mixed fatty amines such as D are also suitable. In another embodiment, the amine salt-derived product of the present invention is an amine derived from a tertiary aliphatic primary amine having at least about 4 carbon atoms in the alkyl group. For the most part, they are derived from alkylamines having no more than about 30 total carbon atoms in the alkyl group.

Typically, the tertiary aliphatic primary amine is a monoamine represented by the formula:

[0307]

Embedded image

Here, R is a hydrocarbyl group containing from 1 to about 30 carbon atoms. Such amines include tertiary butylamine, tertiary hexyl primary amine, 1-methyl-1-aminocyclohexane, tertiary octyl primary amine, tertiary decyl primary amine,
Tertiary dodecyl primary amine, tertiary tetradecyl primary amine, tertiary hexadecyl primary amine, tertiary octadecyl primary amine, tertiary tetracosanyl primary amine, tertiary octacosanil primary Illustrated by amines.

An amine mixture is also useful for the present invention. Examples of this type of amine mixture include "Pr
imene 81R "(which is a mixture of tertiary alkyl primary amine of C ₁₁ -C _14), and" Pri
mene JM-T "(which is a similar mixture of tertiary alkyl primary amine of C ₁₈ -C ₂₂₎ (both available from Rohm & Haas) is. The third
Primary alkyl primary amines, and methods for their preparation,
It is known to those skilled in the art and therefore does not need to be discussed further. Tertiary alkyl primary amines useful for this invention, and methods for their preparation, are described in US Pat. 2,9
No. 45,749, the teachings of which are hereby incorporated by reference.

Primary amines whose hydrocarbon chains contain olefinic unsaturation are also useful. therefore,
The R ⁶ group can contain one or more olefinically unsaturated, usually no more than one double bond per 10 carbon atoms, depending on the length of the chain. Representative amines include dodecenylamine, myristoleylamine, palmitoleylamine, oleylamine and linoleylamine. Such unsaturated amines are also
Available under the Armeen trademark.

The thia-aldehyde and thia-ketone can also be subjected to a reaction with a polyamine. Examples of useful polyamines include diamines (e.g., mono- or dialkyl, symmetric or asymmetric ethylenediamine, propanediamine (1, or 1,3)), and the above polyamine analogs. "Duomeen C" (N-coco-1,3-
Diaminopropane), "Duomeen S" (N-soya-1,3-diaminopropane), "Duomeen
T "(N-taro-1,3-diaminopropane), or" Duomeen O "(N-oleyl-1,3-diaminopropane)." Duomeen "classes are commercially available diamines, Product Data Report No. 7 for Almac Chemical, Chicago, Illinois
-10R1.

The reaction of the thia-aldehyde (and ketone) with a primary amine or polyamine can be performed by methods known to those skilled in the art. Generally, the thia-bisaldehyde or ketone is reacted with an amine or polyamine by reaction at elevated temperature in a hydrocarbon solvent (generally under a nitrogen atmosphere). As the reaction proceeds, the water formed is removed, for example, by distillation.

Sulfur compounds characterized by Structural Formula I (where G ¹ and G ² can be COOR, C = N and NO ₂ ) are compounds characterized by the following structural formula or Formula I- It can be prepared by reacting a mixture of various compounds represented by B with sulfur halide or a mixture of sulfur halide and sulfur:

[0314]

Embedded image

Where R ¹ and R ² are the same as defined above, and G is COOR, C = N or NO ₂ .

Generally, about 1 mole of sulfur halide is
About 2 moles of the compound represented by Formula IB are reacted. In some embodiments, R ¹ can also be G.
In such cases, the sulfur compound formed as a result of the reaction with the sulfur halide contains four G groups. The G groups are the same or different, depending on the starting material. For example, when a di-ketone (eg, 2,4-pentanedione) is reacted with sulfur monochloride, the resulting product contains four ketone groups; the starting material is a ketone group and an ester group. (Eg, ethyl acetoacetate), the resulting product contains two ketone groups and two ester groups;
When the product contains four ester groups (eg, diethyl malonate), the product contains four ester groups. Other combinations of functional groups can be used in the present invention by selecting various starting materials that contain the desired functional group and have the formula I
Can be introduced into the sulfur product represented by

The sulfur compound represented by the formula I (where G ¹ and / or G ² is a C = N group)
-B (where G is C = N and R
¹ and R ² are hydrogen or a hydrocarbyl group). Preferably, R ¹ is hydrogen,
And R ² is a hydrocarbyl group. Examples of useful starting materials include, for example, propionitrile, butyronitrile, and the like.

Compounds of formula I wherein G ¹ and G ² are N
O ₂ group) is obtained by the following (1) and (2)
Can be prepared: (1) Nitrohydrocarbon R ¹ R ² C (H) N
Reacting O ₂ with an alkali metal alkoxide or an alkaline earth metal alkoxide to form a salt of a nitrohydrocarbon; and (2) reacting the salt with the salt in an inert, hydroxyl-free, anhydrous medium. Reacting with sulfur monochloride to form bis (1-nitrohydrocarbyl) disulfide. Preferably, the nitro hydrocarbon is
Primary nitro hydrocarbons (R ¹ is hydrogen and R ² is hydrocarbyl).

The first primary nitro compounds used in carrying out this synthesis are known. Exemplary compounds include:
Examples include nitroethane, 1-nitropropane, 1-nitrobutane, 1-nitro-4-methylhexane, (2-nitroethyl) benzene, and the like.

In obtaining the first alkali metal and alkaline earth metal salts of the primary nitro compounds, the nature of the alkanol used is not critical. The alkanol need only be suitable for reaction with the metal to form the alkoxide. Because they are easily obtained and inexpensive, lower alkanols (ie 1 to 4
Alkanols having two carbon atoms), such as methanol, ethanol and butanol, are commonly used in this synthesis.

The medium in which this salt is subjected to the reaction with S ₂ Cl ₂ must be inert towards both reactants. The medium must also be anhydrous and free of hydroxyl groups in order to successfully form the new bis (1-nitrohydrocarbyl) disulfide. Examples of suitable media include ether, hexane, benzene, dioxane, higher alkyl ethers, and the like.

Usually, during the preparation of this metal salt, about 0 to 1
Preferably, a temperature of 0 ° C. is maintained. However,
At this stage of the method, a temperature of about 0C to 25C may be used. When preparing bisdisulfide, -5 ° C
Temperatures in the range of ＋+ 15 ° C. can be used. Preferably,
Temperatures between about 0 ° C. and 5 ° C. are used at this stage of the method.

The preparation of various thia-bisnitro compounds useful in the present invention is described in US Pat. 3,479,413
The issue is described in some detail. The disclosure of this patent is set forth herein. Representative examples of nitrosulfides useful in the present invention are: bis (1-nitro-2)
-Phenylethyl) disulfide, bis (1-nitrododecyl) disulfide, bis (1-nitrododecyl) disulfide, bis (1-nitro-2-phenyldecyl)
Disulfide, bis (1-nitro-2-cyclohexylethyl) disulfide, bis (1-nitropentadecyl) disulfide, bis (1-nitro-3-cyclobutylpropyl) disulfide, bis (1-nitro-2-naphthylethyl) Disulfide, bis (1-nitro-3-
p-Toluylpropyl) disulfide, bis (1-nitro-2-cyclooctylethyl) disulfide, and the like.

The carboxylate-containing sulfur compounds described above (ie, G ¹ is COOR) can be utilized to prepare other sulfur compounds useful in the present invention. For example, the ester (COOR) can be hydrolyzed to a carboxylic acid (COOH). The carboxylic acid (COOH) can be converted to other esters by reaction with various alcohols, or can be converted to various amines, including ammonia, primary amines such as (Including secondary amines)
It can be converted to an amide: (R) ₂ NH where each R is hydrogen or a hydrocarbyl group.
Such hydrocarbyl groups contain from 1 to about 30 carbon atoms, and more usually contain from about 1 to 10 carbon atoms.

As mentioned above, R ¹ and R ² and / or R ³ and R ⁴ together can be an alkylene group containing from about 4 to about 7 carbon atoms. In this embodiment, R ¹ and R ² (and R ³ and R ⁴ ) together with the common carbon atom form a cyclic compound (ie, this carbon atom is represented by R ¹ and R ^{2 in} Formula I) Common). Such derivatives of structural formula I can be prepared by reacting an appropriately substituted saturated cyclic with a sulfur halide as described above. Examples of such cyclic starting materials include cyclohexanecarboxaldehyde (C ₆ H ₁₁ CHO),
Cyclohexanecarbonitrile (C ₆ H ₁₁ CN), cyclohexane carboxamide _{(C 6 H 11 CONH 2)} , cyclohexanecarboxylic acid (C ₆ H ₁₁ COOH), cyclobutane carboxylic acid (C ₄ H ₇ COOH), cycloheptane carboxylic acid (C ₇ H ₁₃ COOH), cycloheptyl cyanide (C ₇ H ₁₃ CN) and the like.

Example 1 below illustrates the preparation of a sulfur composition represented by Formula I. All parts and percentages are by weight and all temperatures are degrees Celsius, unless otherwise indicated throughout the specification, as well as in the examples, and in the appended claims.

(Example 1) Sulfur monochloride (1620)
Parts, 12 mol) into a 5 liter flask and warm to a temperature of about 53 ° C. under nitrogen. In contrast, 1766 parts (24.5 moles) of isobutyraldehyde under nitrogen at a temperature of about 53-60 ° C. for about 6.5 hours
Is added drop by drop. After the addition of the isobutyraldehyde is complete, the mixture is allowed to stand for about 10 hours over a period of 6 hours.
Heat slowly to a temperature of 0 ° C. During this time, nitrogen is blown. This mixture is added to 100
Maintain at ℃ for about 6 hours. Volatiles are removed from the reaction vessel. Next, the reaction product is filtered with a filter aid. The filtrate contains 31.4% sulfur (theoretical 31.%).
08%). The desired reaction product (mainly 2,2'-dithiodiisobutyraldehyde) is recovered in a yield of about 95%.

The components (A), (B) and (C) of the composition of the present invention can be mixed in any order using methods known to those skilled in the art. Preferably, in the composition of the invention, the relative weight ratios of the components (A) :( B) :( C) are:
Generally, about (1-500) :( 0.1-10) :( 1-
500).

(Lubricants and Functional Fluids) The compositions of the present invention are useful as additives for lubricants and functional fluids. These compositions comprise a wide variety of lubricants and functional fluids based on a wide variety of oils of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof. Can be used. These lubricants and functional fluids include crankcase lubricants for spark-ignition and compression-ignition internal combustion engines. The internal combustion engine includes automobile and truck engines, two-stroke engines, aircraft piston engines, marine and railway diesel engines, and the like. They can also be used in gasoline engines, stationary power engines and turbines and the like. Transmission fluids (this includes both automatic and manual transmission fluids);
Rotary shaft lubricants, gear lubricants, metalworking lubricants, hydraulic fluids, and other lubricants and grease compositions also
It may be useful to add the composition of the present invention therein.

Natural oils include animal and vegetable oils (eg, castor oil, lard oil) and solvent-treated mineral lubricating oils or acid-treated minerals of the paraffin, naphthene, and mixed paraffin-naphthene types. Lubricating oils are included. Oils of lubricating viscosity derived from coal or shale are also useful. Synthetic lubricating oils include the following hydrocarbon oils and halo-substituted hydrocarbon oils. The hydrocarbon oils and halo-substituted hydrocarbon oils include, for example, polymerized olefins and mixed-polymerized olefins (eg, polybutylene, polypropylene, propylene-isobutylene copolymer, chlorinated polybutylene, etc.); alkylbenzenes (eg, ,
Dodecylbenzene, tetradecylbenzene, dinonylbenzene, di- (2-ethylhexyl) -benzene, etc.); polyphenyls (eg, biphenyl, terphenyl, alkylated polyphenyl, etc.).

The alkylene oxide polymers and mixed polymers and their derivatives (in which derivatives the terminal hydroxyl groups have been modified by esterification, etherification, etc.) are other known synthetic lubricating oils which can be used. Configure the class. These are oils prepared by the polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (eg, methyl polyisopropylene glycol ether having an average molecular weight of about 1000, about 50
Polyethylene glycol diphenyl ether having an average molecular weight of 0-1000, polypropylene glycol diethyl ether having an average molecular weight of about 1000-1500, etc., or their mono- and polycarboxylic esters (e.g., acetate esters of tetraethylene glycol, mixed C ₃ -C ₈ fatty acid esters, or the C ₁₃ oxo acid diester) is exemplified by.

Another suitable class of synthetic lubricating oils that can be used include dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipine Acid, linoleic acid dimer, malonic acid, alkylmalonic acid, alkenylmalonic acid, and various alcohols (for example, butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, Esters with pentaerythritol). Specific examples of these esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate,
Dioctyl phthalate, didecyl phthalate, diicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, complex ester formed by reaction of 1 mol of sebacic acid with 2 mol of tetraethylene glycol and 2 mol of 2-ethylhexanoic acid, etc. Included.

Esters useful as synthetic oils also include C
₅ -C ₁₂ monocarboxylic acids and polyols and polyol ethers (e.g., neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.) esters formed from the encompassed.

Silicon-based oils (eg, polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxysiloxane oils and silicate oils)
It constitutes another class of useful oils. These include tetraethyl silicate, tetraisopropyl silicate, tetra- (2-ethylhexyl) silicate, tetra-
(4-methylhexyl) silicate, tetra- (pt
tert-butylphenyl) silicate, hexyl- (4
-Methyl-2-pentoxy) disiloxane, poly (methyl) siloxane, poly (methylphenyl) siloxane and the like. Other useful synthetic oils include liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate, diethyl ester of decanephosphonic acid, and the like), polymerized tetrahydrofuran, and the like.

Unrefined, refined and rerefined oils (and mixtures thereof) of the types disclosed above can be used in the lubricants and functional fluid compositions of the present invention. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, shale oil obtained directly from a retort operation, petroleum oil obtained directly from distillation, or ester oil obtained directly from an esterification step and used without further processing is an unrefined oil. Refined oils are similar to the unrefined oils except they have been further processed in one or more purification stages to improve one or more properties. Many such purification methods are known to those skilled in the art. The methods include, for example, solvent extraction, distillation, acid or base extraction, filtration, osmosis, and the like. Rerefined oils are obtained by processes similar to those used to obtain refined oils. This step is
Applies to refined oils already used. Such rerefined oils are also known as reclaimed or reprocessed oils and are often additionally added, depending on the used additive, and the method indicated to remove the cracked oil refinery. It is processed.

In general, the lubricants and functional fluids of the present invention exhibit improved wear resistance, load bearing properties, extreme pressure (EP) properties and / or corrosion protection properties with respect to the lubricants and functional fluids. Contains an effective amount of the composition of this invention sufficient to provide Typically, the compositions of the present invention comprise from about 0.02% to about 20% by weight of such lubricants and functional fluids, based on the total weight of the lubricant and functional fluid.
(Preferably at a level ranging from about 0.05% to about 5% by weight). Preferably, component (A) is
On the basis of the total weight of this lubricant and functional fluid, about 0.01
% To about 5%, more preferably about 0.01% to about 2%, more preferably about 0.01% to
Used at concentrations in the range of about 1% by weight. Component (B)
Is preferably used at a concentration ranging from about 0.001% to about 0.1% by weight, based on the total weight of the lubricant and functional fluid. Component (C) is preferably based on the total weight of the lubricant or functional fluid
Used in concentrations ranging from about 0.01% to about 5% by weight.

The present invention also contemplates the use of lubricants and functional fluids containing other additives in addition to the compositions of the present invention. Such additives include, for example,
Ashless detergents and dispersants, corrosion inhibitors, antioxidants,
Viscosity improvers, E.I. P. Agents, pour point depressants, color stabilizers,
Defoamers and the like are included.

The ashless detergents and dispersants, depending on their composition, can produce non-volatile substances (eg, boron oxide or phosphorus pentoxide) upon combustion.
Despite the fact that it is so called; however, it usually does not contain metals and therefore
No ash containing metals is produced on burning. Many types of materials are known in the art. Any of them are suitable for use in the lubricants of the present invention. Examples include: (1) a carboxylic acid (or derivative thereof) containing at least about 34 carbon atoms (preferably at least about 54 carbon atoms) and a nitrogen-containing compound (eg, an amine), an organic Reaction products with hydroxy compounds (eg, phenols and alcohols) and / or basic inorganic substances. Examples of these "carboxylic dispersants" are described in British Patent No. No. 1,306,529 and a number of U.S. Patents, including:

[0339]

[Table 2]

(2) Reaction products of relatively high molecular weight aliphatic or alicyclic halides with amines (preferably oxyalkylene polyamines). These can be characterized as "amine dispersants", examples of which are described, for example, in the following U.S. Patents: 3,275,554 3,454,555 3,438,757 3,565 804 (3) The reaction product of an alkylphenol (where the alkyl group contains at least about 30 carbon atoms) with an aldehyde (particularly formaldehyde) and an amine (particularly a polyalkylenepolyamine). This can be characterized as a "Mannich dispersant". The materials described in the following U.S. patents are illustrative:

[0341]

[Table 3]

(4) Products obtained by post-treating carboxylic acid, amine or Mannich dispersant with the following reagents: urea, thiourea, carbon disulfide, aldehyde, ketone, carboxylic acid, hydrocarbon Substituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds and the like. Exemplary materials of this type are described in the following U.S. patents:

[0343]

[Table 4]

(5) A mixed polymer of an oil-soluble monomer (for example, decyl methacrylate, vinyl decyl ether, and a high-molecular-weight olefin) and a monomer having a polar substituent (for example, aminoalkyl acrylate or acrylamide); -(Oxyethylene)
Substituted acrylate. These may be characterized as "polymer dispersants", examples of which are disclosed in the following U.S. Patents: 3,329,658 3,666,730 3,449,250 3,687,849 3,519,565 3,702,300 The contents of the patents noted above are set forth herein with reference to the disclosure of ashless dispersants.

Extreme pressure (EP) agents, corrosion inhibitors and antioxidants which may be included in the lubricants and functional fluids of the present invention may be exemplified by: chlorinated aliphatic hydrocarbons (eg, chlorine) Organic sulfides and polysulfides (eg, benzyl disulfide, bis (chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfide methyl ester of oleic acid, alkyl phenol sulfide, dipentene sulfide, and terpene sulfide; phosphorus sulfide hydrocarbon (eg, phosphorus sulfide Reaction products of terpentine or methyl oleate, mainly dihydrocarbon phosphites and trihydrocarbons (eg, dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite, phosphorous acid) Dipentylphenyl, tritide phosphite Le, phosphorous acid distearyl,
Phosphoric esters including dimethylnaphthyl phosphite, oleyl 4-pentylphenyl phosphite, phenyl phosphite substituted with polypropylene (molecular weight 500), diisobutyl-substituted phenyl phosphite); metal thiocarbamates (for example, Zinc dioctyldithiocarbamate, and barium heptylphenyldithiocarbamate);
Group II metal salts of phosphorodithioic acids (e.g., zinc dicyclohexyl phosphorodithioate, zinc dioctyl phosphorodithioate, barium di (heptylphenyl) phosphorodithioate, cadmium dinonyl phosphorodithioate; and phosphorus pentasulfide and isopropyl alcohol and A zinc salt of phosphorodithioic acid formed by reaction with an equimolar mixture of n-hexyl alcohol.

Many of the above extreme pressure agents, corrosion inhibitors and antioxidants also serve as antiwear agents. Zinc dialkyl phosphorodithioate is a known example.

Pour point depressants are a particularly useful type of additive often included in the lubricants and functional fluids described herein. The use of such pour point depressants in oil-based compositions to improve the low temperature properties of the oil-based compositions is known in the art. For example, C.I. V. Small heel (CV Smallheal)
r) and R.I. Kennedy Smith (R. Kennedy
Smith, “Lubricant Additives” (Lezius-Hiles Co. Publisher, Cleveland, Ohio, 1967). Its contents are shown here.

Examples of useful pour point depressants include polymethacrylates; polyacrylates; polyacrylamides; condensation products of haloparaffin waxes and aromatic compounds;
Vinyl carboxylate polymers; and terpolymers of dialkyl fumarate salts, vinyl esters of fatty acids and alkyl vinyl ethers. Pour point depressants useful for the present invention, their method of preparation and their use are described in US Pat. 2,387,501; 2,01
5,748; 2,655,479; 1,815,0
No. 22; 2,191,498; 2,666,746
Nos. 2,721,877; 2,721,878; and 3,250,715, the contents of which are incorporated herein by reference.

Antifoams are used to reduce or prevent the formation of stable foam. Typical defoamers include silicone or organic polymers. Other antifoam compositions are described in "Foam Control Agents" (Henry T. Kerner, Neuss Data, 1976), p. 125-162,
Its contents are shown here.

The components (A), (B) and (C) of the composition of the present invention can be added directly to a lubricant or functional fluid. Preferably, however, they are substantially inert and normally liquid organic diluents (eg mineral oil, naphtha,
(Benzene, toluene or xylene) to form an additive concentrate. These concentrates typically contain from about 10% to about 90% by weight of the compositions of the present invention, and may further comprise one or more other known or described above in the art. May be contained. The balance of this concentrate is a substantially inert, normally liquid diluent.

Examples of hydraulic fluids within the scope of the present invention are as follows (all numbers are parts by weight):

[0352]

[Table 5]

[0353]

[0354]

[0355]

[Table 6]

[0356]

[0357]

[0358]

[0359]

[Table 7]

[0360]

[0361]

[0362]

[Table 8]

[0363]

[0364]

[0365]

[Table 9]

[0366]

[0367]

[0368]

The lubricating composition of the present invention may be in the form of a grease. In this grease, any of the above oils having the lubricating viscosity can be used as a medium. If the lubricant can be used in the form of a grease, the lubricating oil is generally used in an amount sufficient to balance the entire grease composition. Generally, the grease compositions will contain various amounts of thickeners and other additives that provide the desired properties.

In preparing the greases of this invention, a wide variety of thickeners may be used. Included among these thickeners are alkali and alkaline earth metal soaps of fatty acids and fatty substances having from about 12 to about 30 carbon atoms. This metal is represented by sodium, lithium, calcium and barium. Examples of fatty substances include stearic acid, hydroxystearic acid, stearic acid, oleic acid, palmitic acid, myristic acid, cottonseed oil, and hydrogenated fish oil.

Other thickeners include the following salts and salt-soap complexes: calcium stearate (US Pat. No. 2,197,263), barium acetate stearate (US Pat. No. 2,197,263). 2, 564, 561),
Stearic acid-caprylic acid-calcium acetate complex (U.S. Pat. No. 2,999,065), calcium caprylate (U.S. Pat. No. 2,999,066),
Calcium salts and soaps of low and medium molecular weight acids, medium and high molecular weight acids and nut oils.

Particularly useful thickeners used in grease compositions have inherently hydrophilic properties. However, this can be accomplished by introducing long chain hydrocarbon groups on the surface of the clay particles before using it as a component of the grease composition (e.g., with an organic cationic surfactant such as an onium compound). (By pretreatment), it is converted to hydrophobic conditions. Typical onium compounds are tetraalkyl ammonium chlorides (eg, dimethyl dioctadecyl ammonium chloride, dimethyl dibenzyl ammonium chloride and mixtures thereof). This conversion method
It is known to those skilled in the art and will not require further discussion. More particularly, clays useful as starting materials in forming thickeners that can be used in the grease composition can include naturally occurring, chemically unmodified clays. These clays are crystalline composite silicates. Its exact composition is not explicitly described. Because they can be widely varied from one natural source to another. These clays can be described as inorganic silicate complexes, such as aluminum silicates, magnesium silicates, barium silicates, and the like. They are,
In addition to the silicate lattice, it contains various amounts of cation exchangeable groups (eg, sodium). Particularly useful hydrophilic clays for converting to the desired thickener include, for example,
The following montmorillonite clays are included: bentonite clay, attapulgite clay, hectorite (heclite)
torite) clay, illite clay, saponite clay,
Biotite clay, vermiculite clay, zeolite clay, etc. This thickener comprises about 0.5% by weight of the total grease composition
It is used in an amount of up to about 30% by weight (preferably 3% to 15% by weight).

Although the invention has been described in connection with its preferred embodiments, it should be understood that various modifications thereof will become apparent to those skilled in the art upon reading this specification. It is, therefore, to be understood that in the invention disclosed herein, such modifications are intended to be included within the scope of the appended claims.

[0374]

The present invention is useful in providing lubricants and functional fluids with thermal stability and improved wear resistance, extreme pressure properties, load transfer properties and / or corrosion protection. Certain compositions and lubricants and functional fluids containing them are obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C10M 135: 20 135: 18 159: 24 159: 22 129: 54 133: 44) C10N 30:06 30:08 30:14 40:08 (71) Applicant 591131338 29400 Lakeland Boulevard, Wicklife, Ohio 44092, United States of America (72) Inventor James Noel Vinci Ohio 44124 Mayfield, USA

Claims (1)

[Claims] 1. A composition comprising: (A) at least one neutral or basic metal salt of at least one acidic organic compound, or at least one of boron-containing neutral or basic metal salts; The metal in the salt is selected from the group consisting of alkali metals, alkaline earth metals, zinc, copper, aluminum or a mixture of two or more of said metals; (B) at least one metal deactivator And (C) the following (C-1), (C-2), (C-3),
At least one compound selected from the group consisting of (C-4) and (C-5); (C-1) a phosphorus-containing amide; (C-2) a phosphorus-containing ester; and (C-3) a sulfur-bonded dithio. (C-4) a sulfur-containing compound represented by the following formula: At the formula I, R ^1, R ^2, R ³ and R ⁴ are each, independently, H or a hydrocarbyl group; R ¹ and / or R ³ can be a G ¹ or G ^2, R ¹ and R ² and / or R ³ and R ⁴ can together be an alkylene group containing from about 4 to about 7 carbon atoms; G ¹ and G ² are each independently C (X)
R, COOR, C = N, R 5 -C = NR 6, CON (R)
₂ or NO ₂ , and G ¹ can also be CH ₂ OH;
X is O or S, each R and R ⁵ are independently H or a hydrocarbyl group, R ⁶ is H or a hydrocarbyl group; when G ¹ and G ² are both R ⁵ C ＝ NR ⁶ , The two R ⁶ groups together may be a hydrocarbylene group bonded to two nitrogen atoms; when G ¹ is CH ₂ OH and G ₂ is COOR, by intramolecular condensation of G ¹ and G ² , A lactone may be formed; and x is an integer from 1 to about 8: and (C-5) 2 of any of the (C-1) to (C-4)
A mixture of seeds or more.