FI96223C - Composition useful in lubricants and functional fluids - Google Patents

Abstract

A composition is disclosed which comprises: (A) at least one neutral or basic metal salt or boron-containing neutral or basic metal salt of at least one acidic organic compound, the metal in said salt being 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) at least one compound selected from the group consisting of (C-1) phosphorus-containing amide; (C-2) phosphorus-containing ester; (C-3) sulfur-coupled dithiocarbamate; (C-4) sulfur-containing compound represented by the formula (I), wherein R<1>, R<2>, R<3> and R<4> are each independently H or hydrocarbyl groups, R<1> and/or R<3> may be G<1> or G<2>; R<1> and R<2> and/or R<3> and R<4> together may be alkylene groups containing 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 NO2, and G<1> also may be CH2OH, wherein X is O or S, each of R and R<5> are independently H or a hydrocarbyl group, R<6> is H or a hydrocarbyl group; when both G<1> and G<2> are R<5>C=NR<6>, the two R<6> groups together may be a hydrocarbylene group linking the two nitrogen atoms; when G<1> is CH2OH and G<2> is COOR, a lactone may be formed by intramolecular condensation of G<1> and G<2>; and x is an integer from 1 to about 8; and (C-5) mixture of two or more of any of (C-1) to (C-4). These compositions are useful as additives for lubricants and functional fluids, particularly hydraulic fluids, gear oils, greases and the like.

Description

- 96223

Composition useful in lubricants and functional fluids

TECHNICAL FIELD This invention relates to compositions comprising (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 a phosphorus-containing compound. These compositions are useful for producing lubricants and functional fluids that are thermally stable and have improved anti-wear, high pressure, load-bearing and / or anti-corrosion properties.

15 Background of the Invention

Zinc-containing hydraulic fluids are widely accepted for numerous applications. These hydraulic fluids typically have excellent thermal stability and anti-wear properties due to the zinc-containing anti-wear agents used in them. In recent years, however, more attention has been paid to the accumulation of heavy metals such as zinc in the workplace and the environment. This has led to a demand for hydraulic fluids containing ashless anti-wear agents. Ashless anti-wear agents are available, but the hydraulic fluids based on them typically lack sufficient thermal stability to be acceptable for many uses.

Book "Lubricant Additives" by M.W. Ran-30 ney, published by Noyes Data Corporation of Parkridge, N.J. (1973), discloses a number of metal salts of various sulfonic and carboxylic acids and phenols useful as surfactants / dispersants in lubricating oil products. A book, also called 35 "Lubricant Additives," by C.V Smallheer and R.K.

2 - 96223

Smith, published by Lezius-Hiles Co., Cleveland, Ohio (1967), likewise discloses a number of surfactants / dispersants comprising sulfonates, phenates and carboxylates useful as dispersants. U.S. Pat. No. 4,100,082 discloses the use of neutral or basic metal salts of organic sulfuric acids, carboxylic acids and phenols as surfactants / dispersants for use in fuels and lubricants.

U.S. Pat. No. 4,627,928 describes the use of basic magnesium salts of substituted aromatic hydroxycarboxylic acids as dispersants, surfactants, antioxidants, etc., in lubricants and fuels.

The use of triazoles such as benzotriazole as metal deactivators in lubricant compositions is described in U.S. Pat. No. 3,413,227, U.S. Pat. No. 4,162,225, U.S. Pat. No. 4,174,285 and U.S. Pat. No. 4,187,186.

The use of phosphorus-containing amides as anti-wear agents for lubricant-20 compositions is described in U.S. Patent Nos. 4,032,461, 4,208,357, 4,282,171 and 4,670,169.

The use of phosphorus-containing esters as anti-wear agents for lubricant compositions is described in U.S. Pat. No. 3,359,203. The use of such agents as E.P. agents in lubricant compositions is described in GB-1,347,845.

Compositions prepared by embroidering various organic materials such as olefins are known in the art, and lubricants containing these compositions are also known. U.S. Pat. No. 4,191,659 describes the preparation of embroidered olefinic compounds by the catalytic reaction of sulfur and hydrogen sulfide with olefinic compounds having from 3 to 30 atoms. Compounds 35 are reported to be useful in lubricant formulations.

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- 96223 3 in particular for use in industrial gear lubricants. U.S. Pat. No. 4,119,549 describes a similar process for sulfurizing olefins using sulfur and hydrogen sulfide, after which low-boiling materials are removed from said embroidered mixture.

Sulfur-containing compositions characterized by the presence of at least one cycloaliphatic group containing at least two nuclear carbon atoms or two different cycloaliphatic groups linked together by a divalent sulfur bond are described in re-published patent Re-27 331. The sulfur bond comprises at least two sulfur atoms, and examples include embroidered 15 Diels-Alder insertion products described in a republished patent. Sulfur-containing compositions are useful as high pressure and anti-wear additives in various lubricating oils.

Disdehyde - containing dialdehydes of formula 20

R R

I ·

OCH -C-S-S-C-CHO

wherein both R groups are the same alkyl groups having 1 to 18 carbon atoms and both R 1 groups are the same alkyl or aryl groups are described in U.S. Patent No. 2,580,695. The compounds are reported to be useful as crosslinking agents and chemical intermediates.

30 Sulphide-containing lubricant compositions having the formula la

Ri Rx I »

H (O) C - C - Sx - C - C (0) H

R 2 R 2 to 96223 wherein R x is a hydrocarbon group, R 2 is hydrogen or a hydrocarbon group, and x is 1-2 are disclosed in U.S. Patent No. 3,296,137.

CA-1 168 222 discloses a combination for use in lubricants comprising (A) at least one benzotriazole or benzotriazole reaction product with at least one aliphatic amine, and (B) at least one embroidered aliphatic or alicyclic compound having from about 3 to about 30 carbon atoms. This patent-10 discloses that lubricants may also contain ash-producing surfactants, for example, oil-soluble neutral or basic alkali or alkaline earth metal salts of sulfonic acids, carboxylic acids or organic phosphoric acids.

15 Summary of the Invention

The invention relates to a composition comprising (A) at least one acidic organic compound, at least one neutral or basic metal salt or a boron-containing neutral or basic metal salt, wherein the acidic organic compound is selected from one or more carboxylic acids, sulfuric acids, phenols or two or more a mixture thereof, said salt metal being an alkali metal, alkaline earth metal, zinc, copper, aluminum or a mixture of two or more of said metals; (B) at least one metal deactivator which is benzotriazole; alkyl, aryl, alkaryl or arylalkyl substituted benzotriazole; hydroxy-, alkoxy-, halogen-, nitro-, carboxy- or carbalkoxy-substituted benzotriazole; the reaction product of at least one of said benzotriazole and at least one amine; a reaction product of at least one of said benzotriazole and at least one nitrogen-containing ashless dispersant; or a mixture of two or more thereof; and 35 (C) at least one compound from the group consisting of

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5 to 96223 (C-1) phosphorus-containing amide of formula R1 (χ1) \ X3 R3 R5 X5 R7 a \ ll Alitti 8, P-X4-C - C - C-N - R (XIII)

5 2 2 / "I 4 U

R 2 (X 2); R LR jn J n 'wherein X1, X2, X3, X4 and X5 independently of one another denote oxygen or sulfur; R1 and R2 independently represent hydrogencarbyl groups; R3, R4, R5, R6 and R7 independently of one another denote hydrogen, halogen or a hydrocarbyl group; 15 a and b independently represent 0 or 1; n is 0 or 1; n 'is 1, 2 or 3; provided that (1) when n 'is 1, then R 8 is hydrogen, -R, -RÖH, -ROR, 20 -RSR, or

R

-RN-R; (2) when n 'is 2, then R 8 is a linking group selected from 25 -R-, -R * -, -R-O-R-, -R-S-R-,

0 S H R

Il II I I

-R-, -R-, -R-N-R- or -R-N-R-; and (3) when n 'is 3, then R8 is a linking group -R-N-R-

R

wherein each R is independently a hydrocarbyl group having 1 to 12 carbon atoms; and R * is a hydrocarbyl or carboxyhydrocarbyl group having 1 to 60 carbon atoms; «· -96223 6 (C-2) Phosphorus but not metal ester of formula c« V. il 4 1 1 £ 5 ^ P — X4-C-C-C-OR ° -, I a I (XVI)

R2 (X2) b R H

wherein X1, X2, X3 and X4 independently of one another denote oxygen or sulfur; R1 and R2 independently represent hydrogencarbyl groups; R3, R4 and R5 independently of one another are hydrogen or a hydrocarbyl group; R6 is a hydrocarbyl group; and a and b independently represent 0 or 1; (C-3) sulfur-combined dithiocarbamate of formula 20

R 1 R 2 is S% -i-C-C-S (S) CNR 5 R 6) 2, (XVII) R 3 J 4 wherein R 1, R 2 and R 3 independently represent hydrogen or a hydrocarbyl group; R 4 is H, OH or a hydrocarbyl group; R5 and R6 independently of one another are hydrogen, hydrocarbyl or hydroxyhydrocarbyl; or R 3 and R 4 together and / or R 5 and R 6 together and / or R 1 and R 3 together and / or R 2 and R 4 together may form cyclic groups; 35 and x is a number from 1 to 8;

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-.96223 7 (C-4) sulfur-containing compound of formula R1 R3 5 (31-C- (S) xC-G2l, (1) R2 R4 wherein R1, R2, R3 and R4 independently of one another are 10 hydrogen or a hydrocarbyl group, R1 and / or R3 may be G1 or G2, R1 and R2 and / or R3 and R4 may together represent an alkylene group having about 4 to 7 carbon atoms, G1 and G2 independently represent 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, R and R 5 independently represent hydrogen or a hydrocarbyl group, R 6 is H or a hydrocarbyl group; and G1 and G2 are RSC = NR6, the two R6 groups together may denote two hydrocarbylene groups connecting the nitrogen tower, when G1 in CH2OH and G2 is COOR, the intramolecular condensation of G1 and G2 may form a lactone, and 25 x is an integer from 1 to 8, and (C-5) is a mixture of any two or more (Cl) - (C-4).

These compositions are useful in lubricants and functional fluids, especially hydraulics. 30 as additives for fluids, gear oils, greases and the like.

DESCRIPTION OF THE PREFERRED EMBODIMENTS As used in this specification and the appended claims, the term "hydrocarbyl" denotes a group in which a carbon atom is directly attached to another molecule, and has a hydrocarbon or is hydrocarbon in the sense of this invention. Such groups include the following: (1) hydrocarbon groups; i.e. aliphatic, (e.g. alkyl or alkenyl), alicyclic (e.g. cycloalkyl or cycloalkenyl), aromatic, aliphatic and alicyclic substituted aromatic, aromatically substituted aliphatic and alicyclic moieties and the like, as well as cyclic groups in which the ring has a ring i.e., any of the two indicated groups may together form a subcyclic group). Such groups are known to those skilled in the art. Examples of these are methyl, ethyl, octyl, decyl, octadecyl, cyclohexyl, phenyl, etc.

(2) substituted hydrocarbon groups; i.e. groups containing non-hydrocarbon substituents which do not alter the predominant hydrocarbon nature of the group for the purposes of this invention. Suitable substituents are known to those skilled in the art. Examples of these are halogens, hydroxy, nitro, cyano, alkoxy, acyl, etc.

20 (3) hetero groups; i.e. groups which, although predominantly hydrocarbon in nature within the meaning of this invention, otherwise contain atoms other than carbon in the carbon-containing chain or ring. Suitable heteroatoms are known to those skilled in the art and include, for example, nitrogen, oxygen and sulfur.

In general, there are no more than about 3 substituents or heteroatoms per 10 carbon atoms of the carbyl group, and preferably no more than 1.

Terms such as "alkyl-based" and "aryl-based" and the like have the same meaning as above for alkyl groups, aryl groups and the like.

The term "hydrocarbon-based" has the same meaning and is interchangeable with the term "hydrocarbyl" in the case of molecular groups in which a carbon atom is directly attached to another molecule.

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9-96223 The term "lower" as used herein in conjunction with terms such as hydrocarbyl, alkyl, alkenyl, alkoxy and the like is intended to mean groups containing a total of 7 carbon atoms or 5 less.

The term "oil soluble" refers to a substance that is soluble in mineral oil at least about 1 g / liter at 25 ° C.

Component (A):

Component (A) is a neutral or basic metal salt or a neutral or basic metal salt containing at least one acidic organic compound, the metal in said salt being an alkali metal, alkaline earth metal, zinc, copper, aluminum or a mixture of two or more of the above metals.

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

The term "basic" is the common term currently used for well-known classes of metal salts, and these basic metal salts are also referred to as "overbased", "superbased", "hyperbasic", "high metal salts" and the like.

The basic metal salts are characterized by an excess of metal compared to the amount that would be present with the metal and a particularly acidic organic compound to be reacted with the metal, for example a sulfonic acid. 30 pon, based on stoichiometric volume. Thus, if the monosulfonic acid is 0

II

R - S - OH II

35 O

«10 to 96223 neutralized with a basic metal compound, for example calcium hydroxide, would contain the" neutral "or" basic "metal salt produced, one equivalent of calcium for each acid equivalent, i.

5

O O

li II

R-S-O-Ca-O-S-R II II

o o 10 Methods for preparing such neutral and basic metal salts are well known in the art. Neutral salts can be prepared by heating a mineral oil solution of an acidic organic compound with a stoichiometric amount of a metal neutralizing reagent such as a metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature above about 50 ° C and filtering the resulting mass. Alkaline salts are prepared in the same manner except that a stoichiometric excess of metal is used. In the neutralization step, 20 "promoters" can also be used to aid in the addition of excess metal in the preparation of basic salts. Examples of suitable compounds as promoters include phenolic compounds such as phenol, naphthol, alkylphenol, thiophenol, embroidered alkylphenol, and condensation products of formaldehyde with a phenolic compound; alcohols such as methanol, 2-propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol and cyclohexyl alcohol; and amines such as aniline, phenylenediamine, phenothiazine, phenyl-6-naphthylamine and dodecylamine. Particularly effective method. To prepare basic salts, mixing the acidic organic compound with an excess of a basic neutralizing reagent and at least one alcoholic promoter, and carbonating the mixture at an elevated temperature such as 60-200 ° C.

Il 11 - 96223

Component (A) typically contains from about 100 to about 4000%, preferably from about 100 to about 3000%, more preferably from about 100 to about 2800%, more preferably from about 200 to about 1000% metal in the corresponding neutral salt. In a preferred embodiment, component (A) has from about 110 to about 4000%, preferably from about 110 to about 3000%, more preferably from about 110 to about 2800%, even more preferably from about 110 to about 1000% metal in the corresponding neutral salt.

Preferred metals for the salts (A) are lithium, sodium, magnesium, calcium, potassium, barium, aluminum, zinc and copper. Mixtures of two or more of the metals described above may be used. Particularly preferred metals are sodium, magnesium, calcium or mixtures of two or more of these.

carboxylic acids:

The carboxylic acids useful in the preparation of the salts (A) of the invention may be aliphatic or aromatic, mono- or polycarboxylic acids or acid-producing compounds. These carboxylic acids include lower molecular weight carboxylic acids (e.g., carboxylic acids having about 18 carbon atoms such as fatty acids having about 10 to about 18 carbon atoms or tetrapropenyl-substituted succinic anhydride) as well as higher molecular weight carboxylic acids. Throughout this disclosure and the appended claims, all references to carboxylic acids are intended to include their acid-forming derivatives, such as anhydrides, esters, acyl halides, lactones, and the like. 30 mixtures unless expressly stated otherwise.

The carboxylic acids of this invention are preferably oil soluble and the number of carbon atoms in the acid is important for the desired solubility of the salts (A). To give the desired oil solubility, the number of 35 carbon atoms in the carboxylic acid should usually be at least 12 to 96223, about 8 carbon atoms, more preferably at least about 18 carbon atoms, more preferably at least about 30 carbon atoms, more preferably at least about 50 carbon atoms. In general, these carboxylic acids do not contain more than about 400 carbon atoms per molecule.

Carboxylic acids may contain polar substituents provided that the polar substituents are not too large to significantly alter the hydrocarbon nature of the carboxylic acid. Typical suitable polar substituents include halogens such as chlorine and bromine, oxo, oxy, formyl, sulfenyl, sulfinyl, thio, nitro, etc. Such polar substituents, when present, are preferably not present in excess of about 10% by weight of the total weight of the carboxylic acid hydrocarbon moiety. excluding carboxyl groups.

The lower molecular weight monocarboxylic acids used in this invention include saturated and unsaturated acids. Examples of such acids are dodecylic acid, palmitic acid, decanoic acid, oleic acid, lauric acid, stearic acid, myristic acid, linoleic acid, linolenic acid, naphthenic acid, chloro-stearic acid and more. A mixture of two or more such substances may also be used. These acids have been extensively discussed in the book

Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Edition, 1978, John Wiley & Sons, New York, pp. 814-871; the content of these pages is incorporated into this application by this reference.

. Examples of lower molecular weight polycarboxylic acids include dicarboxylic acids and their derivatives such as sebacic acid, cetylmalonic acid, tetrapropylene-substituted succinic anhydride, etc. Lower alkyl esters of these acids can also be used.

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- 96223 13

Lower molecular weight hydrogen carbyl substituted succinic acids and anhydrides can also be used. Typically, these compounds are represented by Formulas 5

R-CHCOOH and R-CH - C

CH 2 CO 2 | ^ 0

CH2-C

In formulas II and III, R is a hydrocarbyl group having from about 8 to about 18 carbon atoms. R is preferably an aliphatic or alicyclic hydrocarbyl group in which less than 10% of the carbon / carbon bonds are unsaturated. Examples of such groups include 4-butylcyclohexyl, di (iso-butyl), decyl, etc. The preparation of such substituted succinic acids and their derivatives by alkylation of maleic acid or a derivative thereof with a halohydrocarbon is well known to those skilled in the art and need not be discussed in detail herein.

The monohydric acid halides of the lower molecular weight polycarboxylic acids described above can be used as the lower molecular weight carboxylic acids of this invention. These can be prepared by reacting such acids or their anhydrides with halogenating reagents such as phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride or thionyl chloride. Esters of such acids can be prepared in the same way as acids, acid. By the reaction of halides or anhydrides with an alcohol or a phenolic compound. Lower alkyl and alkenyl alcohols such as methanol, ethanol, allyl alcohol, propanol, cyclohexanol, etc. are particularly useful.

Monocarboxylic acids include isoaliphatic acids, i.e. acids having one or more lower cyclic alkyl side groups. Such acids often contain a backbone of from about 14 to about 20 saturated aliphatic carbon atoms and at least 1 but usually not more than about 4 acyclic alkyl side groups. For example, the acid backbone is a group derived from tetrade-10, pentadecane, hexadecane, heptadecane, octadecane and eicosadecane. The side group is preferably a lower alkyl group such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-hexyl or another group having 7 carbon atoms or less. The side group may also be a polarly substituted alkyl group such as chloromethyl, bromobutyl, methoxyethyl or the like, but preferably does not have more than one polar substituent per group. Specific examples of such isoaliphatic acids are 10-methyltetradecanoic acid-20 po, 11-methylpentadecanoic acid, 3-ethylhexadecanoic acid, 15-methylheptadecanoic acid, 16-methylheptadecanoic acid, 8-methylheptadecanoic acid, 6-methyloctadecanoic acid, 8-methyloctadecanoic acid, 8-methyloctadecanoic acid, -po, 16-methyloctadecanoic acid, 15-ethylheptadecanoic acid: 25 po, 3-chloromethylnonadecanoic acid, 7,8,9,10-tetramethyloctadecanoic acid and 2,9,10-trimethyloctadecanoic acid.

Isoaliphatic acids comprise mixtures of branched acids prepared by isomerization of commercial fatty acids, for example containing from about 16 to about 20 carbon atoms. In one useful process, the fatty acid is heated at a temperature above about 250 ° C and a pressure of about (13.8 to 48.3) · 10'2 bar, the crude isomerized acid is distilled and the distilled substance is hydrogenated to a substantially saturated isomerized acid. Isomerization can be promoted with a catalyst such as mineral clay, diatomaceous earth.

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15 5C 223 Ia, with aluminum chloride, zinc chloride, ferric chloride or some other Friedel-Craft catalyst. The concentration of the catalyst may be as low as about 0.01% by weight, but is most often about 0.1-5 to about 3% by weight of the isomerization mixture. Water also promotes isomerization, and therefore a small amount of water, from about 0.1% to about 5% by weight, is preferably added to the isomerization mixture. Unsaturated fatty acids from which isoaliphatic acids can be derived include oleic acid, linoleic acid, Lino-10 lenic acid, and commercial fatty acid mixtures such as tall oil.

Higher molecular weight mono- and polycarboxylic acids suitable for the preparation of salts (A) are well known in the art and are described in detail in, for example, the following U.S., British, and Canadian patents: U.S. Patent Nos. 3,024,237; 3,087,936; 3,163,603; 3,172,892; 3,215,707; 3,219,666; 3,231,587; 3,245,910, 3,254,025; 3,271,310; 3,272,743; 3,272,746; 3,278,550; 3,288,20714; 3,306,907; 3,307,928; 3,312,619; 3,341,542; 3,346,354; 3,367,943; 3,373,111; 3,374,174; 3,381,022; 3,394,179; 3,454,607; 3,346,354; 3,470,098; 3,630,902; 3,652,616; 3,755,169; 3,868,330; 3,912,764; 4,234,435; and 4,368,133; GB Patent Publications 944,136; 1,085,903; 1,162,436; - 25 and 1,440,219; and CA Patent Publication 956,397. the substance of the publications is incorporated herein by reference.

As disclosed in the aforementioned patents, there are several methods for preparing these higher molecular weight carboxylic acids. In general, these reactions comprise (1) reacting an ethylenically unsaturated carboxylic acid, acid halide, anhydride or ester reactant with (2) an ethylenically unsaturated hydrocarbon containing at least 18 aliphatic carbon atoms; at a temperature in the range of about 100 to 300 eC. The chlorinated hydrocarbon - or ethylenically unsaturated hydrocarbon reactant preferably contains at least about 20 carbon atoms, more preferably at least about 30 carbon atoms, more preferably at least about 40 carbon atoms, more preferably at least about 50 carbon atoms, and may contain polar substituents, oil-soluble dependent groups, and may be unsaturated within the general limitations described above. These 10 hydrocarbon-containing reactants produce most of the aliphatic carbon atoms present in the acyl portion of the final product.

In the preparation of higher molecular weight carboxylic acids, the carboxylic acid reactant is generally of the formula Ro (C00H), wherein R0 is characterized by the presence of at least one ethylenically unsaturated carbon / carbon double bond and n is an integer from 1 to about 6 and preferably 1 or 2 The acid reactive agent may also be the corresponding carboxylic acid halide, anhydride or ester. Generally, the total number of carbon atoms in the acidic reactive substance is not more than about 20, preferably not more than about 10, and generally not more than about 6. Preferably, the acidic reactant has at least one ethylene bond at the ό, β position relative to at least one carboxyl group. Exemplary acidic reactants include acrylic acid, methacrylic acid, malic acid, fumaric acid, itaconic acid, ita-conic acid anhydride, citraconic acid, citraconic acid anhydride, methaconic acid, glacaconic acid, glutaconic acid, chloroacetic acid, chloroacetic acid, , 10-decenoic acid and the like. Preferred acid reactive agents include acrylic acid, methacrylic acid, malic acid and malic anhydride.

The ethylenically unsaturated carboxylic acids used in the preparation of these high molecular weight carboxylic acids

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96223 17 non-hydrocarbon reactants and chlorinated hydrocarbon reactants are preferably high molecular weight, substantially substituted petroleum fractions and substantially saturated olefin polymers and corresponding chlorinated products. Polymers containing 2 to about 30 carbon atoms and chlorinated polymers derived from monoolefins are preferred. Particularly useful polymers include 1-monoolefins such as ethylene, propylene, 1-butene, isobutene, 1-hexene, 1-octene, 2-methyl-1-heptene-10, 3-cyclohexyl-1-butene and 2-methyl Polymers of -5-propyl-1-hexene. Also useful are polymers of medial olefins, i. olefins in which the olefinic bond is not in the terminal position. Examples are 2-butene, 3-pentene and 4-octene.

Copolymers of 1-monoolefins of the type described above with each other and with other copolymerizable olefins such as aromatic olefins, cyclic olefins, and polyolefins are also important sources of ethylenically unsaturated reactants. Such copolymers include, for example, by polymerizing isobutylene with styrene, isobutene with butadiene, propylene with isoprene, propylene with isobutene, ethylene with piperylene, isobutene with chloroprene, isobutene with p-methylstyrene, 1-hexene-1,3-hexadiene, 1-hexadiene, 1-hexadiene, Copolymers of 1-heptene with 1-pentene, 3-methyl-1-butene 1-octene, 3,3-dimethyl-1-pentene 1-hexene, isobutene styrene and piperylene, etc.

Because of their solubility, the copolymers useful in preparing the carboxylic acids of this invention are preferably substantially aliphatic and substantially saturated, i. they should contain at least about 80% and preferably about 95% by weight of units derived from aliphatic monoolefins. Preferably, they do not contain more than about 5% of the total number of carbon / carbon bonds present in the olefinic bonds present from 18 to 96223.

In one embodiment of the invention, the polymers and chlorinated polymers are obtained by polymerizing a C4 refinery stream having a butene content of about 35 to 75% by weight and an isobutene content of about 30 to about 60% by weight in the presence of a Lewishap post-catalyst such as aluminum chloride or boron trifluoride. These polyisobutenes preferably contain predominantly (i.e., greater than about 80% of the total repeat units) isobutene repeat units in their structure.

Chlorinated hydrocarbons and ethylenically unsaturated hydrocarbons used for the preparation of higher molecular weight carboxylic acids may have a numerical average molecular weight of up to 100,000 and even higher, although preferably up to about 10,000 molecules of higher molecular weight carboxylic acids. more preferably up to about 5000. Preferred higher molecular weight carboxylic acids contain at least about 18 carbon atoms, preferably at least about 30 carbon atoms, more preferably at least about 40 carbon atoms, more preferably at least about 50 carbon atoms.

Higher molecular weight carboxylic acids can also be prepared by halogenating a high molecular weight hydrocarbon such as the olefinic polymers described above to produce a polyhalogenated product by converting the polyhalogenated. product to dust nitrile and then hydrolyzing the polynitrile. They can be prepared by oxidation of a high molecular weight polyhydric alcohol with potassium permanganate, nitric acid or a similar oxidizing agent.

35 The second method comprises olefin or polar substituents

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96223 19 reaction of an imported hydrocarbon such as chloropolyisobutene with an unsaturated carboxylic acid such as 2-pentene-1,3,5-tricarboxylic acid prepared by dehydration of citric acid.

Monocarboxylic acids can be obtained by oxidizing a monoalcohol with potassium permanganate or by reacting a halogenated high molecular weight olefin polymer with ketene. Another suitable method for preparing monocarboxylic acids involves the reaction of sodium metal 10 with an alkanol acetoacetic ester or malonic ester to form a sodium derivative of the ester followed by reaction of the sodium derivative with a halogenated high molecular weight hydrocarbon such as brominated wax or brominated polyisobutylene.

Monocarboxylic and polycarboxylic acids can also be obtained by reacting chlorinated mono- and polycarboxylic acids, anhydrides, acyl halides and the like with ethylenically unsaturated hydrocarbons or polyethylated polyols as described above. U.S. Pat. No. 3,340,281, the contents of this patent are incorporated herein by reference.

Monocarboxylic and polycarboxylic acids can also be obtained from the corresponding acids by dehydration. The dehydration is readily performed by heating the acid to a temperature above about 70 ° C, preferably in the presence of a dehydrating reagent, for example acetic anhydride. Cyclic anhydrides are usually obtained from polycarboxylic acids in which the acid groups are no longer separated from each other. than 3 carbon atoms such as substituted succinic or glutaric acid, while linear anhydrides are usually obtained from polycarboxylic acids having acid groups separated by 4 or more carbon atoms.

20 - 96223

Acid halides of monocarboxylic and polycarboxylic acids can be prepared by the reaction of acids or their anhydrides with a halogenating reagent such as phosphorus tribromide, phosphorus pentachloride or thionyl chloride.

Hydrocarbyl-substituted succinic acids and anhydrides, acid halides and their ester derivatives can be prepared by reacting malic anhydride with a high molecular weight olefin or a chlorinated hydrocarbon such as a chlorinated polyolefin. The reaction essentially comprises heating the two reactants in a temperature range of about 100 to about 300 ° C, preferably about 100 to about 200 ° C. The product of this reaction is a hydrocarbyl-substituted amber aldehyde in which the substituent is an olefin or chlorinated hydrocarbon derivative. If desired, the product may be hydrogenated to remove all or part of any ethylenically unsaturated covalent bonds by standard hydrogenation techniques. Hydrocarbyl-substituted succinic anhydrides may be hydrolyzed to the corresponding acids, and either the anhydride or acid may be converted to the corresponding acid halide or ester by reaction with a phosphorus halide, phenol, or alcohol. Useful higher molecular weight hydrocarbyl substituted succinic acids and anhydrides are of the formulas (IIA) and (IIIA) .0 R-CH-COOH R-CHCl3 or I "

CH2-C00H I JS

CH 2 Cl 2 (IIA) (IIIA) wherein R contains at least about 18 carbon atoms, more preferably at least about 30 carbon atoms, even more preferably up to about 35 carbon atoms, even more preferably at least about 96223 21 50 carbon atoms. The numerical average molecular weight of R is generally not more than about 100,000, preferably not more than about 10,000, more preferably not more than about 7,500, even more preferably not more than about 5,000.

A group of carboxylic acid derivatives which are particularly suitable for the preparation of the salts (A) of the invention are the lactones of the formula IV 10 - Xc independently hydrogen or a hydrocarbyl group having 1 to about 30 carbon atoms, R2 and R3 may be joined to form an aliphatic or aromatic ring, and a is a number from 0 to about 4. Within this group, lactones of formula V are particularly useful. 20 (R8) 5tJI-1 (OH) a: wherein R7 and R8 are aliphatic hydrocarbyl groups having 1 to about 30 carbon atoms, and a and b are numbers in the range 0-5 provided that a and The sum of b is not more than 5, 30 and c is a number between 0-4. Methods for preparing this type of lactone by intramolecular ring formation of a hydroxy-containing carboxylic acid followed by cleavage of water are well known in the art. Generally, ring formation is promoted in the presence of substances such as acetic anhydride, and the reaction is accomplished by heating the mixtures to elevated temperatures such as reflux while removing volatile material including water.

Preferred carboxylic acids useful in the preparation of the salts (A) of the invention are aromatic carboxylic acids. These acids can be represented by formula VI

"xi (R) a- (Ar) - [- C-X2H b (VI) 10 wherein R is an aliphatic hydrocarbyl group preferably having from about 4 to about 400 carbon atoms, a is a number from 0 to about 4, Ar is an aromatic group , X 1 and X 2 independently represent sulfur or oxygen, and b is a number from about 1 to about 4, provided that the sum of a and b does not exceed the number of unsaturated valencies of Ar. that R in each group has at least about 8 aliphatic carbon atoms in all compounds of formula VI.

The aromatic group Ar in formula VI may have the same structure as any of the aromatic groups Ar discussed below under the heading "Phenols". Examples of aromatic groups useful herein include polyvalent aromatic benzene, naphthalene, anthracene, phenanthrene, indene, fluorene, biphenyl and the like. In general, the groups Ar used herein are polyvalent benzene or naphthalene-derived nuclei such as phenylenes and naphthylenes, for example, methylphenylenes, ethoxyphenylenes, nitrophenylenes, isopropylphenylenephenylenephenylenes, mercaptophenylenes, N-N-diol and similar tri-, tetra-, pentavalent nuclei, etc. These groups Ar may contain non-hydrocarbon substituents, for example 35 separate substituents such as lower alkoxy ·

II

96223 23 si, lower alkyl mercapto, nitro, halogen, alkyl or alkenyl groups having less than about 4 carbon atoms, hydroxy, mercapto and the like.

Examples of R groups in the compound of formula VI include butyl, isobutyl, pentyl, octyl, nonyl, dodecyl, docosyl, tetracontyl, 5-chlorohexyl, 4-ethoxypentyl, 4-hexenyl, 3-cyclohexyloctyl, 4 - (p-chlorophenyl) octyl, 2,3,5-trimethylheptyl, 4-ethyl-5-methyloctyl and substituents derived from polymerized olefins such as polychloroprenes, polyethylenes, polypropylenes, polyisobutylenes, ethylene / propylene copolymers, chlorinated olefin polymers, oxidized ethylene / propylene copolymers and the like.

One group of useful carboxylic acids is of formula VII

xl

Il (C-X2H) b

Ra-A / <VII) N (X3H) c wherein R, Ar, X1, X2, a and b are as defined above in formula VI, X3 is oxygen or sulfur and c is a number in the range of 1 to about 25, generally 1 to about 2 provided that the sum of a, b and c does not exceed the number of unsaturated valencies of Ar.

A useful group of carboxylic acids within this group is the (COOH) b) of formula VIII (VIII)

Ra-1 · 35 (OH) c - 96223 24 wherein R is an aliphatic hydrocarbyl group preferably containing from about 4 to about 400 carbon atoms, a is a number in the range of 0 to about 4, preferably 1 to about 3; b is a number in the range of 1 to about 4, preferably 1 to about 2, 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 not not more than 6. Preferably, R and a are such that the acid molecules contain an average of at least about 12 aliphatic carbon atoms in the aliphatic hydrocarbon substituents per acid molecule.

Also useful are hydrocarbon-substituted alicyclic acids in which each aliphatic hydrocarbon substituent contains on average at least about 8 carbon atoms per substituent and 1 to 3 substituents per Mole-15. Salts prepared from such alicyclic acids in which the aliphatic hydrocarbon substituents are derived from polymerized olefins, especially polymerized lower 1-monoolefins such as polyethylene, polypropylene, polyisobutylene, ethylene / pro-20 polyene copolymers, and the like, about 400 carbon atoms are particularly useful.

The carboxylic acids of formulas VII and VIII are well known in the art and can be prepared in ways known in the art. Carboxylic acids of these formulas and methods for preparing their neutral and basic metal salts are well known and are disclosed, for example, in U.S. Patent Nos. 2,197,832; 2,197,835; 2,252,662; 2,252,664; 2,30,714,092; 3,410,798; and 3,595,791.

Sulfur-containing acids:

Sulfur-containing acids useful in the preparation of salts (A) include sulfonic, sulfamic, thiosulfonic, sulfinic, sulfenic, partial ester acids, sulfuric acid and thiosulfuric acids. In general, they are salts of carbocyclic or aliphatic sulfonic acids.

Il 96223 25

Cyclic sulfonic acids include mono- or poly-core aromatic or cycloaliphatic compounds. The oil - soluble sulphonates generally correspond to the following formulas IX and X:

Rxa-T- (SO 3) b (IX) R 2 - (SO 3) a (X) 10 In the above formulas IX and X, T denote a cyclic ring such as, for example, benzene, naphthalene, anthracene, phenanthrene, diphenyloxide, thiantrene, pheno- thioxine, diphenylene sulfide, phenothiazine, diphenyloxide, diphenyl sulfide, diphenylamine, cyclohexane, petroleum naphthenia, decahydronaphthalene, cyclopentane, etc .; R 1 is an aliphatic group such as alkyl, alkenyl, alkoxy, alkoxyalkyl, carboalkoxyalkyl, etc .; a is at least 1 and R 1 + T contains 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 include alkyl, alkenyl, alkoxyalkyl, carboalkoxyalkyl, etc. Specific examples of R 2 include groups derived from petrolatum, saturated and unsaturated paraffin waxes, and polyolefins, including polymerized C 2, C 3, C 4, C 5, C 6, -, groups derived from olefins containing about 15 to 7000 carbon atoms or more. The groups T, R1 and R2 in the above groups IX and X may also contain other inorganic or organic substituents in addition to those listed above, for example hydroxy-30, mercapto, halogen, nitro, amino, nitroso, sulphonyl fide, disulfide substituents, etc. In formula IX a and b are at least 1 and likewise in formula X a is at least 1.

The following are specific examples of oil-soluble sulfonic acids within the scope of formula IX and X above, and it is to be understood that such examples also describe salts of such sulfonic acids useful in this invention. In other words, for each sulfonic acid listed, its corresponding neutral or basic metal salt is also meant to be considered. Such sulfonic acids are mahogany sulfonic acids; bleached cylinder oil sulfonic acids; sulfonic acids from lubricating oil fractions having a Saybolt viscosity of about 100 s at 38 ° C to about 200 s at 99 ° C; petrolatum sulfonic acids; for example, mono- and polysulfonic acids substituted with benzene, naphthalene, phenol-10, diphenyl ether, naphthalene disulfide, diphenylamine, thiophene, O-chloronaphthalene, etc .; other substituted sulfonic acids such as alkylbenzenesulfonic acids (having at least 8 carbon atoms in the alkyl group), cetylphenol monosulfide sulfonic acids, disethylthianthienidisulfonic acids, dilauryl-β-naphthylsulfonic acid and diphenylsulfonic acids, dicapryl sulfonic acids, dicaprylonitrile

The latter acids are benzene derivatives alkylated with propylene tetramers or isobutylene nitrimers to add 1, 2, 3 or more branched C12 substituents to the benzene ring. Dodecylbenzene heavy fractions, mainly mixtures of mono- and didodecylbenzenes, are available as by-products from the manufacture of household surfactants. Similar products obtained from alkylation heavy fractions in the preparation of straight chain alkyl sulfonates (LAS) are also useful in the preparation of the sulphates of this invention. 30 phonates.

The preparation of sulfonates from the by-products of the production of surfactants by reaction with, for example, SO 3 is well known to those skilled in the art. See, e.g., the article "Sulfonates" in Kirk-Othmer, "Ency-35 Clopedia of Chemical Technology," 2nd Edition, Vol. 19, p.

291-, published by John Wiley & Sons, N.Y. (1969).

«I! - 96223 27

Other descriptions of neutral and basic sulfonate salts and techniques for their preparation are set forth in the following U.S. Patents: 2,171,410; 2,174,506; 2,174,508; 2,193,824; 2,197,800; 2,202,781; 2 5 212 786; 2,213,360; 2,228,598; 2,233,676; 2,239,974; 2,263,312; 2,276,090; 2,276,097; 2,315,514; 2,319,121; 2,321,022; 2,333,568; 2,333,788; 2,335,359; 2,337,552; 2,346,568; 2,366,027; 2,374,193; 2,383,319; 3,312,618; 3,471,403; 3,488,284; 3,595,790; 3,798,012. The subject matter of these patents is incorporated herein by reference.

Sulfonohappoihin also include aliphatic sul-acids such as paraffin wax, unsaturated paraffin wax-groups, hydroxy-substituted para-15 fiinivahasulfonihapot, heksapropyleenisulfonihapot, tetra amyleenisulfonihapot, polyisobuteenisulfonihapot, wherein the polyisobutene contains from 20 - 7000 or more carbon atoms, chloro-substituted paraffin wax, etc. nitropara-fiinivahasulfonihapot; cycloaliphatic sulfonic acids such as petroleum naphthenic sulfonic acids, cetylcyclopentylsulfonic acids, laurylcyclohexylsulfonic acids, bis- (diisobutyl) cyclohexylsulfonic acids, mono- or polyvinyl substituted cyclohexylsulfonyl

In the context of the sulfonic acids or their salts described herein and in the appended claims 25, the terms "petroleum sulfonic acids" or "petroleum sulfonates" are intended to include all sulfonic acids or salts thereof derived from petroleum products. A useful group of petroleum sulfonic acids are mahogany sulfonic acids (named after their reddish-brown color) obtained in the manufacture of bleached petroleum using the sulfuric acid method.

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

28 - 96223

Other patents that specifically describe methods for preparing the sulfonic acids, carboxylic acids described above, and basic salts of two or more mixtures thereof include U.S. Patent Nos. 2,550,731; 2,616,904; 2,616,905; 2,616,906; 2,616,911; 2,616,924; 2,616,925; 2,617,049; 2,777,874; 3,027,325; 3,256,186; 3,282,835; 3,384,585; 3,373,108; 3,365,396; 3,342,733; 3,320,162; 3,312,618; 3,318,809; 3,471,403; 3,488,284; 3,595,790; and 3,629,109. The disclosures of these patents 10 and the descriptions of suitable basic metal salts set forth therein are incorporated herein by reference.

Phosphoric acids:

Phosphorus-containing acids useful in the preparation of the salts (A) of the invention may be represented by Formula XI

X3

R1 (X1) av ^ (XI)

P-X4H

R 2 (x 2) t f 20 wherein X 1, X 1, X 2 and X * independently represent oxygen or sulfur; a and b independently represent 0 or 1, and R1 and R1 independently of one another denote hydrocarbyl groups. Illustrative examples of some preferred phosphorus-containing acids are: 1. Divethycarbylphosphinodithionic acids of formula

S

30 Rl \

J ^ P-SH

R2 ^

II

S-hydrocarbylhydrocarbylphosphonotrithionic acids, 2 35 which correspond to the formula

S

29 - 96223

rl

^ P-SH

R2- 3. O-hydrocarbylhydrocarbylphosphonodithionic acids corresponding to the formula

S

Ri

P-SH

r2-10 4. S, S-dihydrocarbylphosphorotetrathionic acids corresponding to the formula

S

RI-

15 ^ P-SH

r2-5.0, S-dihydrocarbylphosphorotrithionic acids corresponding to the formula

20 S

Rl— O'v.

R2— 6. 6. Ο, Ο-Ceticarbylphosphorodithionic acids corresponding to the formula

S

R1 —0 ^^

P-SH

30 r2—

Preferred acids of formula

S

R-0 ^^

P-SH

r2 -0 35 to 96223 30 is easily obtained by the reaction of phosphorus pentasulfide (P2S5) with an alcohol or phenol. The reaction comprises stirring at a temperature of about 20 to about 200 ° C, 4 moles of alcohol or phenol with 1 mole of phosphorus pentasulfide. This reaction releases hydrogen sulfide. Oxygen-containing analogs of these acids are conveniently prepared by treating dithionic acid with water or steam which, in operation, replaces either one or both of the sulfur atoms.

Preferred phosphorus-containing acids are phosphorus-10 and sulfur-containing acids. These preferred acids preferably comprise acids in which at least one of X3 or X4 is sulfur, and more preferably both X3 and X4 are sulfur, at least one of X3 or X2 is oxygen or sulfur, more preferably both X1 and X2 are oxygen , and a and b are both 15 1. Mixtures of these acids can be used in accordance with this invention.

R 1 and R 2 independently represent hydrogen carbyl groups which preferably have neither acetylene unsaturation nor usually ethylene unsaturation, and preferably have from about 1 to about 50 carbon atoms, more preferably from about 1 to about 30 carbon atoms, and even more preferably from about 3 to about 18 carbon atoms. , even more preferably about 4 to about 8 carbon atoms. R 1 and R 2 may be the same, although they may be different, and the other or both may be mixtures. Examples of preferred R1 and R2 groups are t-butyl, isobutyl, amyl, isooctyl, decyl, dodecyl, eicosyl, 2-pentenyl, dodecenyl, phenyl, naphthyl, alkylphenyl, alkylnaphthyl, phenylalkyl, naphthylalkyl, alkylphenyl. alkyl, alkylnaphthylalkyl and the like.

phenols:

Phenols useful in the preparation of the salts (A) of the invention include the 35 Ra-Ar- (OH) b (XII)

II

si '-6223 wherein R is a hydrocarbyl group having from about 4 to about 400 carbon atoms; Ar is an aromatic group? a and b denote independently of one another the numbers at least 1, the sum of a and b being from 2 up to the number of substitutable hydrogens of the aromatic ring Ar. Preferably a and b independently represent 1 to about 4, more preferably 1 to about 2. R and a are preferably such that each phenolic compound of formula XII has an average of at least about 8 carbon atoms in the R groups.

10 As used herein, the term "phenol" is to be understood as not intended to limit the aromatic group of the phenol to benzene. Accordingly, it is to be understood that the aromatic group represented by Formula XII as "Ar", as elsewhere in the other formulas of this specification and the appended claims, may be mononuclear such as phenyl, pyridyl, thienyl, or polynuclear. Poly-core groups can be of the fused type, in which the aromatic core is fused at two points to another core in the manner present in naphthyl, ant-20 ranyl, azanaphthyl, and the like. The dust core group may be of the fused type, in which at least two cores (either single-core or poly-cores) are joined together by bridging bonds. These bridging bonds may be selected from the group consisting of carbon / carbon-single bond, ether bonds, keto bonds, sulfide bonds, polysulfide bonds having from 2 to about 6 sulfur atoms, sulfinyl bonds, sulfonyl bonds, alkylene bonds, alkylidine bonds, lower alkylene ether linkages, lower alkylene ether linkages, , 30 lower alkylene polysulfide bonds having from 2 to about 6 carbon atoms, amino bonds, polyamine bonds, and mixtures of such divalent bridging bonds. In certain cases, Arra may have more than 1 bridging bond between two aromatic rings; for example, 35 fluorene nuclei having two benzene nuclei 32 to 96223 joined by both a methylene bond and a covalent bond. Such a nucleus can be considered to have 3 nuclei, however, only 2 of them are aromatic. Usually, however, Ar contains only carbon atoms in the aromatic nuclei per se (and any alkyl or alkoxy substituent present).

The number of aromatic nuclei in the arts, fused and / or joined, may be relevant in determining the ar-10 values of the integers a and b of formula XII. For example, when Ar contains a single aromatic ring, the sum of a and b is 2-6. When Ar contains 2 aromatic nuclei, the sum of a and b is 2-10. For a 3-membered Ar moiety, the sum of a and b is 2 to 15. The sum of a and b is limited by the fact that it cannot exceed the total number of substitutable hydrogens in the aromatic moiety or moieties.

A single ring aromatic ring, which may be a group Ar, may be represented by the general formula 20 ar (Q) m wherein ar represents a single ring aromatic compound (e.g. benzene) having 4 to 10 carbons, each Q independently represents a lower alkyl group, a lower alkoxy group, a nitro group, or a halogen atom, and m is 0 to 4.

Halogen atoms include fluorine, chlorine, bromine and iodine atoms; usually halogen atoms are fluorine or chlorine atoms.

Specific examples of cases where Ar is 30 single ring aromatic groups are as follows:

II

33 - 96223 5 Η 10 j ^ x: χ ^ χα j ^ e:] ΥΛ '

Η-ΙH, -J

H, 15 I f * '- 9 *> hVh ^ 20, etc., where Me is methyl. You are not ethyl. Pr is propyl and Nit is nitro.

When Ar is a poly-core fused ring aromatic group, it can be represented by the following general formula 25 ar ar m ', (Q) mm' wherein ar, Q and m are as defined above, m 'is 1 to 4 and represents a pair of fused bonds , which fuses two rings to make two carbon atoms into each of two adjacent rings. Specific examples of cases where Ar is a fused ring aromatic group are:% 34-96223 "<iXr

10 H H

McO — H H

15

When the ring aromatic group Ar is a crosslinked poly-core aromatic group, it can be represented by the general formula 20 ar - (- Lng-ar -) - w (Q) mw where w is an integer from 1 to about 20, ar is as defined above, provided that it has a total of at least 2 unsaturated (i.e. free) valencies in the groups ar as a whole, Q and m are as defined above and each 25 Lng independently represents a bridged group carbon / carbon-simple bonds, ether bonds (e.g. -O-) keto bonds (e.g.

O

n 30 “C”) sulfide bonds (e.g. -S-), polysulfide bonds having 2 to 6 sulfur atoms (e.g. -S-2-6), sulfinyl bonds (e.g. -S (O) 2-), lower alkylene bonds- (for example

II

# · 35 96223 -CH2-, -CH2-CH2-, -CH-CH-, R0, etc.), di (lower alkyl) methylene bonds (e.g. 5 CR ° 2-), lower alkylene ether bonds (e.g. -CH2O-, -CH2O-) CH2- / -CH2-CH2-O-, -CH2CH2OCH2CH2- / -CH2CHOCH2CH-

i I

10 ° C ° -CH 2 CHOCHCH 2 -, I and R ° R °, etc.), lower alkylene sulfide bonds (e.g. those in which 1 or more of the lower alkylene ether bond bonds -O- have been replaced by -S-), lower alkylene polysulfide bonds (e.g. in which 1 or more bonds -O- have been replaced by -S-2-6), amino bonds (e.g. 20

-N-, -N-, -CH2N-, -CH2NCH2- / -alk-N-, account I

H r ° I I I

wherein alk is lower alkylene, etc.), polyamino bonds (e.g., 25 -N (alk N -) ^ 10 wherein the unsaturated free valences of N are filled with hydrogen atoms or R 0 groups), and combinations of such bridging bonds (each R 0 being a lower alkyl group). It is also possible to replace one or more of the above-mentioned crosslinked aromatic groups with fused nuclei such as ar (ar) m '. Specific examples of cases where Ar is a crosslinked poly-core aromatic group are: • · 36 - 96223 "Ο — φ-" -A— -.XlXflXfX] ^ _Χ_0_ ^ γ 10 X ^ vCX? "I", "Λ- / π" I (I ^ η- \ Α / ^ Η Αη> I \ I / 1-1 »15

Usually, these groups Ar are unsubstituted except for the groups R and -O- (and any crosslinking group).

20 For reasons such as cost, availability, operation, etc., the group Ar is usually a benzene nucleus, a lower alkylene crosslinked benzene nucleus, or a naphthalene nucleus.

The group R of formula XII is a hydrocarbyl group directly attached to the aromatic group Ar. R preferably contains from about 6 to about 80 carbon atoms, preferably from about 6 to about 30 carbon atoms, more preferably from about 8 to about 25 carbon atoms, and preferably from about 8 to about 15 carbon atoms. Examples of the group R are butyl, isobutyl, pentyl, octyl, nonyl, dodecyl, tetracontyl, 5-chlorohexyl, 4-ethoxypentyl, 4-hexenyl, 3-cyclohexyloxyl, 4- (p-chlorophenyl) octyl, 2, 3,5-trimethylphenyl, 4-ethyl-5-methyloctyl, and substituents derived from polymerized olefins such as polychloroprene, polyethylenes, polypropylenes, polyisobutylenes,

II

96223 37 ethylene / propylene copolymers, chlorinated olefin polymers, oxidized ethylene / propylene copolymers, propylene tetramer and tri (isobutene).

Attachment of the hydrocarbyl group R to the aromatic group Ar can be accomplished by a number of techniques well known to those skilled in the art. One particularly suitable technique is the Friedel-Crafts reaction in which an olefin (e.g., a polymer containing an olefinic bond), or a halogenated or hydrogen halogenated analog thereof, is reacted with a phenol. The reaction takes place in the presence of a Lewis acid catalyst (e.g., boron trifluoride and its ether complexes, phenols, hydrogen fluoride, aluminum chloride, aluminum bromide, zinc chloride, etc.). Methods and conditions for carrying out such reactions are well known to those skilled in the art. See, for example, the description in an article entitled "Alkylation of Phenols" in "Kirk-Othmer Encyclopedia of Chemical Technology", 2nd Edition, Volume 1, pp. 894-895, Interscience Publishers, John Wiley and Company. New York, 1963. Other equally suitable and expedient techniques for attaching a hydrocarbyl group R to an aromatic group Ar are also known to those skilled in the art.

As will be seen when considering Formula XII, the phenol group of salt (A) of the present invention contains at least one R 1 as defined above and OH. Each of the foregoing must be attached to a carbon atom that is part of the aromatic nucleus of the group Ar. However, they do not have to be attached to the same aromatic nucleus in the group Ar.

30 Salts containing boron (A):

The boron-containing neutral or alkaline metal salts of the invention are prepared by a process for reacting (1) at least one acidic organic compound or a precursor thereof; (2) at least one metal-containing compound of the group consisting of alkali metals, alkaline earth metals, zinc, 38 96223 copper, aluminum, or an alloy of two or more thereof; (3) at least one boron compound; and (4) at least one promoter.

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

The metal-containing compound (2) is preferably metal oxide, metal hydroxide, metal halide, metal carbonate or metal borate. It may also be a mixture of two or more of the above. Preferred metals in the metal-containing compounds (2) are lithium, sodium, magnesium, calcium, potassium, barium, aluminum-15, zinc and copper. Mixtures of two or more of the aforementioned metals may also be used. Particularly preferred metals are sodium, magnesium, calcium or a mixture of two or more of these.

Boron compounds (3) include boron oxide, boron oxide hydrate, boron trioxide, boron trifluoride, boron tribromide, boron trichloride, boric acids such as boronic acid (i.e. alkyl-B (OH) 2 or aryl-B (OH) 2), boric acid (i.e. H3BO3), tetraboric acid (i.e. H2B407), metaboric acid (i.e. HBO2), boric anhydrides, boramide amides and various esters of such boric acids.

The use of complexes of boron trihalides and ethers, organic acids, inorganic acids or hydrocarbons is a suitable way of adding a boron-containing reactant to the reaction mixture. Such complexes are known and include, for example, boron trifluoride / triethyl ester, boron trifluoride / phosphoric acid, boron trichloride / chloroacetic acid, boron tribromide / dioxane, and boron trifluoride / methyl ethyl ether.

Specific examples of boronic acids include methyl-boronic acid, phenylboronic acid, cyclohexylboronic acid, p-heptylphenylboronic acid and dodecylboronic acid.

I! . · 39 - 96225

In particular, boronic acid esters include mono-, di-, and triorganic esters of boric acid with alcohols or phenols such as methanol, ethanol, isopropanol, cyclohexanol, cyclopentanol, 1-octanol, 2-5 octanol, dodecanol, behenyl alcohol, oleyl alcohol, stearyl alcohol, stearyl alcohol, -butylcyclohexanol, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 2,4-hexanediol, 1,2-cyclohexanediol, 1,3-octanediol, glycerol, pentaerythritol, diethylene glycol, carbitol, cellosin, substituted phenolenylene of triethylene glycol, tripropylene glycol, phenol, naphthol, p-butylphenol, o, p-diheptylphenol, n-cyclohexylphenol, 2,2-bis (p-hydroxyphenyl) propane, polyisobutylene (molecular weight 1500), phenylene , m-nitrophenol, 6-bromooctanol and 7-ketodecanol. Lower alcohols, 1,2-glycols and 1-3-glycols, i. those having less than about 8 carbon atoms are particularly suitable for the preparation of boric acid esters for the purposes of this invention.

Methods for preparing boronic acid esters are known and described in the art (such as "Chemical Reviews", pp. 959-1064, part 56). Thus, one method involves the reaction of boron trichloride with three moles of alcohol or phenol to give the triorgano borate. Another method involves the reaction of boron oxide with an alcohol or phenol. A further process comprises the direct esterification of tetraboric acid with 3 moles of alcohol or phenol. In a further method, boric acid is blocked directly with glycol to form, for example, cyclic alkylene borate.

The promoter (4) is a chemical used to facilitate the addition of metal to basic metal compositions. Such useful promoters include water, ammonium hydroxide, organic acids having up to about 8 carbon atoms, from 40 to 96223 atoms, nitric acid, sulfuric acid, hydrochloric acid, metal complexing agents such as alkyl salicylaldoxime and alkali metal hydroxide and sodium hydroxide, such as lithium hydroxide, and polyhydric alcohols having up to about 30 carbon atoms. Examples of alcohols are methanol, ethanol, isopropanol, cyclohexanol, dodecanol, decanol, behenyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, benzene glycol, ethylene glycol monomethyl ether, trimethylene glycol, trimethylene glycol, -panol, chloroethanol, aminoethanol, cinnamyl alcohol, allyl alcohol and the like. Particularly useful are monohydric alcohols having up to about 10 carbon-15 liatoms and mixtures of methanol with higher monohydric alcohols.

The boron-containing salts (A) are preferably formed by reacting an organic acid (1) with a portion of a metal-containing compound (2) to form a neutral metal salt of an organic acid. An additional metal-containing compound (2) is then added together with the boron compound (3) and the promoter (4). The reaction mixture is heated to reflux and reflux is continued for several hours.

Preferred ratios of components (1), (2), (3) and (4) for the above reaction can be determined from the equation (where eq means equivalent): moles of boron ratio = -———- 30 eq (2) eq ( 1) -eq acid in (4) + eq base in (4) This ratio is preferably in the range of 0.2 to about 3, more preferably about 0.5 to about 2.

For the purposes of the above formula, 1 mol of boron is equivalent to the molar amount of the boron compound (3) times 35 the number of borons in this boron compound. Thus, »• ·

II

96223 41 if 3.2 moles of boric acid H3BO3 are used, the molar amount of boron is 3.2 times 1, i.e. 3.2. If 2 moles of tetraboric acid H2B407 are used, the molar amount of boron is 2x4, i.e. 8.

For the purposes of the above formula, 1 equivalent of 5 metals is equal to the molecular weight of this metal divided by the valence of the metal ion. Thus, the equivalent weight of sodium is 23 (i.e., 23 divided by 1 = 23) while the equivalent weight of calcium is 20 (i.e., 40 divided by 2: 11a = 20).

The above reactions can be performed in the presence of a substantially inert solvent / diluent. This solvent / diluent desirably helps maintain contact between the components and facilitates control of the reaction temperature. Examples of suitable solvent / diluents include aliphatic and aromatic hydrocarbons such as benzene, toluene, naphtha, mineral oil, hexane, chlorinated hydrocarbons such as dichlorobenzene and heptyl chloride and ethers such as methyl n-amyl ether and n-butyl.

Component (B): The metal deactivator (B) preferably comprises at least one benzotriazole, which may be substituted or unsubstituted. Examples of suitable compounds include benzotriazole, alkyl-substituted benzotriazole (for example, tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.), substituents (aryl-substituted benzotriazole), aryl-substituted benzotriazole and / or substituents (e.g. phenyl-benzotriazole) for example hydroxy, alkoxy, halogen (especially chlorine), nitro, carboxy or carbalkoxy. Preferred are benzotriazoles and alkylbenzotriazoles in which the alkyl group contains 1 to about 20 carbon atoms and especially 1 to about 8 carbon atoms, most preferably benzotriazole and tolyltriazole.

m · 42 - 96223

The metal deactivator (B) may also be the reaction product of at least one of the above-mentioned benzotriazoles and at least one amine into a nitrogen-containing composition. The amine may be one or more monoamines or poly-5 amines. These monoamines and polyamines can be primary, secondary or tertiary amines. The amines may be aliphatic, cycloaliphatic, aromatic or heterocyclic, including aliphatic-substituted cycloaliphatic, aliphatic-substituted 10 aromatic, aliphatic-substituted heterocyclic, cycloaliphatic-substituted aliphatic, cycloaliphatic-substituted aromatic, cycloaliphatic-substituted heterocyclic, aromatic-substituted aliphatic, aromatic-substituted cyclo-15 aliphatic, aromatically substituted heterocyclic-substituted alicyclic, and heterocyclic-substituted aromatic amines, and may be saturated or unsaturated. Amines may also contain non-hydrocarbon substituents or groups as long as these do not significantly affect the reaction of the amines with the acylation reagents of this invention. Such non-hydrocarbon substituents or groups include lower alkoxy, lower alkyl mercapto, nitron, interrupting groups such as -O- and -S- (for example in groups such as -25 CH 2 CH 2 -X-CH 2 CH 2 - wherein X is -O- or -S -). In general, the amine can be characterized by the formula, Rä

Rx-N-R2 wherein Rx, R2 and R3 each independently represent hydrogen or hydrocarbyl, amino-substituted hydrocarbyl, hydroxy-substituted hydrocarbyl, alkoxy-substituted hydrocarbyl, amino, carbamyl, thiocarbamyl, guanyl or acyl-imidoyl.

li - 96223 43

With the exception of branched polyalkylene polyamine, polyoxyalkylene polyamines, and high molecular weight hydrocarbyl-substituted amines, which will be described more fully later, amines usually contain less than about 40 carbon atoms in total, usually no more than about 20 carbon atoms in total.

Aliphatic monoamines include mono-, di-, and trialiphatically substituted amines in which the aliphatic groups may be saturated or unsaturated and straight-chain or branched. Such amines include, for example, mono-, di- and trialkyl-substituted amines; mono-, di- and trialkenyl-substituted amines; and amines having one or more N-alkenyl substituents and one N-alkyl substituent and the like. The total number of carbon atoms in these aliphatic monoamines, as mentioned 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-bu-20ylamine, di-n-butylamine, tri-n-butylamine, allylamine, isobutylamine, coconut amine, stearylamine, laurylamine, methyl laurylamine, oleyl -methyloctylamine, dodecylamine, octadecylamine and the like. Examples of cycloaliphatically substituted aliphatic amines, aromatically substituted aliphatic amines and heterocyclic-substituted aliphatic amines are 2- (cyclohexyl) ethylamine, benzylamine, phenethylamine and 3- (phenethylamine).

Cycloaliphatic monoamines are monoamines in which one cycloaliphatic substituent is attached directly to the amino nitrogen by a carbon atom of the cyclic ring structure. Examples of cycloaliphatic monoamines include cyclohexylamines, cyclopentylamines, cyclohexenylamines, cyclopentenylamines, N-ethylcyclohexylamines, dicyclohexylamines and the like. Examples of aliphatically substituted, aromatically substituted and heterocyclic-substituted cycloaliphatic monoamines include propyl-substituted cyclohexylamines, phenyl-substituted cyclopentylamines and pyranyl-substituted cyclohexylamycloamine.

Aromatic amines include monoamines in which the carbon atom of the aromatic ring structure is attached directly to the amino nitrogen. The aromatic ring is usually a mononuclear aromatic ring (i.e., a benzene derivative), but may contain fused aromatic rings, especially naphthalene derivatives. Examples of aromatic monoamines include aniline, di (para-methylphenyl] amine, naphthylamine, N- (n-butyl) aniline, etc. Examples are aliphatically substituted, cycloaliphatically substituted and cycloaliphatic-dodecyl-arylamino -hexyl-substituted naphthylamine and thienyl-substituted aniline.

Polyamines mainly comprise alkylene amines of the formula

R-N — f — my region-N Tn ~ R i I

25 R R

wherein n is preferably less than about 10, each R is independently hydrogen or a hydrocarbyl group, preferably up to about 30 carbon atoms, and the alkylene group is preferably lower alkylene having less than about 8 carbon atoms. Alkyleneamines are mainly methyleneamines, ethyleneamines, butyleneamines, propyleneamines, pentyleneamines, hexyleneamines, heptyleneamines, octyleneamines and other polymethyleneamines. Examples are ethylenediamine, triethylenetetramine, propylenediamine, decamethylenediamine, octamethylenediamine

II

• 96223 45, di (heptamethylene) triamine, tripropylene tetramine, tetraethylenepentamine, trimethylenediamine, pentaethylenehexamine, di (trimethylene) triamine. Larger homologues such as those obtained by condensing two or more of the alkyleneamines described above are equally useful.

Ethyleneamines are particularly useful. They are described in some detail in the article "Ethylene Amines" in "Encyclopedia of 10 Chemical Technology", Kirk and Othmer, Vol. 5, pp. 898-905, Xnterscience Publishers, New York (1950). Such compounds are preferably prepared by the reaction of alkylene chloride with ammonia. The reaction produces a somewhat complex mixture of alkyleneamines, including cyclic condensation products such as piperazines. These mixtures have utility in the method of this invention. On the other hand, quite satisfactory products can also be obtained using pure alkyleneamines. A particularly useful alkylene amine from an economic point of view, as well as from the efficiency of the products derived therefrom, is a mixture of ethyleneamines prepared by the reaction of ethylene chloride and ammonia and having a composition corresponding to tetraethylenepentamine.

Hydroxyalkyl substituted alkyleneamines, i.

• Alkyleneamines having one or more hydroxyalkyl substituents in nitric acid are also contemplated herein. Larger homologues such as those obtained by condensation of the alkyleneamines or hydroxyalkyl-substituted alkyleneamines described above via amino radicals or hydroxy radicals are likewise useful. Understandably, condensation with amino radicals produces larger amines while removing ammonia and condensation via hydroxy radicals produces products containing ether bonds while removing water at the same time.

4 I

Λ6 96223 46

The metal deactivator (Β) may also be the reaction product of at least one of the above-mentioned benzotriazole with at least one nitrogen-containing ashless dispersant of the type described below under the heading "Lubricants and functional fluids". Particularly preferred are nitrogen-containing carboxylic dispersants, amine dispersants and Mannich dispersants, which are described below.

The benzotriazolamine and benzotriazole ash dispersant reaction products can be prepared mainly by mixing the reagents and allowing the reaction to proceed. The reaction may be carried out in a substantially inert, usually liquid organic diluent (which may be an oil or diluent component of a lubricant or a concentrate containing a composition of this invention) such as mineral oil, benzene, toluene, xylene, naphtha, aliphatic ether or the like. as low as about 15 ° C. It is usually preferable to carry out the reaction at a temperature of up to about 160 ° C, with a temperature range of about 60 to about 140 ° C being useful.

The ratios of benzotriazole to amine or ashless dispersant used to prepare the reaction products useful as components (B) may vary widely. In general, it is preferred to add as much benzotriazole as possible in an oil-dispersible medium, and this can be done 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 its basic nitrogen atoms, and the equivalent weight of benzotriazole is its molecular weight divided by the number of its triazole rings.). However, in some cases it may be advantageous to use more than 35 or less equivalents of amine or ashless dispersant per benzotriazole equivalent.

The exact molecular structures of the benzotriazole / amine and benzotriazole / ashless dispersant reaction products are not well known and are not critical. However, it is believed that benzotriazoles are generally more acidic than amines or ashless dispersants and thus the compositions may comprise amine salts of benzotriazoles.

10 Phosphorus-containing amides (C-1):

Phosphorus-containing amides (Cl) preferably comprise at least one compound represented by the formula r1 <x1> »\ * 3 1.3 r5 X5 r7 _κ2 (χ \ * 4U> 6Jn J" · wherein X1, X2, X3, X4 and X5 independently represent oxygen or sulfur, R1 and R2 independently represent hydrocarbyl groups, R3, R4, R5, R6 and R7 independently represent hydrogen, halogen or hydrocarbyl groups, a and b independently represent 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, -RÖH, -ROR, -RSR

.· or

R

-RN-R; 96223 48 (2) when n 'is 2, R8 is a linking group from the group -R-, -R * -, -R-O-R-, -R-S-R-,

O S H R

-R-, -R-, -R-N-R- or -R-N-R-; 5 or; and (3) when n 'is 3, the R® linking group is -R-N-R-

10 I

R

wherein each R is independently a hydrogen carbyl group having 1 to about 12 lattice atoms; and R * is a hydrocarbyl or carboxyhydrocarbyl group having 1 to about 60 carbon atoms.

X1, X2 and X5 preferably denote oxygen. X3 and X4 preferably denote sulfur.

R 1 and R 2 independently represent hydrogen carbon groups having about 50 carbon atoms, more preferably 1 to about 30 carbon atoms, even more preferably about 3 to about 18 carbon atoms, even more preferably about 4 to about 8 carbon atoms. Examples of R1 and R2 are - independently t-butyl, isobutyl, amyl, isooctyl, decyl, dodecyl, eicosyl, 2-pentenyl, dodecenyl, phenyl, naphthyl, alkylphenyl, alkylnaphthyl, phenylalkyl , naphthylalkyl, alkylphenylalkyl, alkylnaphthylalkyl and the like.

R 3, R 4, R 5, R 6 and R 7 independently represent hydrogen or a hydrocarbyl group having 1 to about 50 carbon atoms, more preferably 1 to about 30 carbon atoms, even more preferably 1 to about 18 carbon atoms, even more preferably 1 to about 8 carbon atoms. Preferably R3, R4, R5, R6 and R7 independently of one another are hydrogen; alkyl groups having 1 to about 22 carbon atoms; cycloalkyl groups, 11 49 PC223 having from about 4 to about 22 carbon atoms; or aromatic, alkyl-substituted aromatic or aromatically substituted alkyl groups having from about 4 to about 34 carbon atoms.

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.

Phosphorus-containing amides of formula XIII can be prepared by a variety of alternative routes. In one embodiment, the preparation of these amides comprises reacting a phosphorus-containing acidic reactant, wherein the reactant is an acrylamide-type reactant of the formula A with a acrylamide-type reactant of the formula B. χ5 r7 I 1 H l, D.

C = C-C-NH (B) R 4 wherein the various groups R and X are as described for formula XIII. The reactant (A) is described above under the title "Phosphorus-Containing Acids". Examples of the reactants 30 (B) are acrylamide, methacrylamide in which R5 is methyl, and crotonamide.

The reaction between the reactants (A) and (B) is exothermic and thus requires only a slight addition of heat. The reaction may conveniently be carried out in an inert atmosphere such as nitrogen at about 25 to about 100 ° C, preferably <50 to 96223 at 70 to 90 ° C. The reaction can be carried out in a solvent or without a solvent. The reaction is preferably carried out in a solvent medium which is typically a hydrocarbon such as toluene, xylene, hexane, heptane, fuel oil, fuel oil, lubricating oil or the like or a chlorohydrocarbon such as chloroform, carbon tetrachloride or the like, or an alcohol such as methanol, ethanol, propanol butanol, 2-ethylhexanol or the like. In addition to acting as a solvent, the solvent preferably gives the reaction the desired processing properties, it enables, for example, the control of an exothermic reaction and the prevention of undesired side reactions. The temperature-dependent reaction time is usually as short as 1 to 2 hours or less.

The reaction between the reactants (A) and (B) gives a compound of formula (XIV)

R1 (xl) s \ ji3 4 ff if5.7 P-X4-cCc-NH (XIV) 20 R2 ^ 2) ^ r4h At this point, the group of formula XIII R8 is hydrogen and n is 1. The reaction product of formula XIV is an intermediate . However, it may also serve as a final product additive (C-1) for the invention. This product is suitable for use in the manufacture of lubricants and functional fluids with improved loadability, high pressure, anti-wear and / or corrosion protection properties.

The intermediate of formula XIV may be attached as described below and / or further reacted in various ways known to those skilled in the art to attach other functional groups R8 to the nitrogen atom, comprising -RÖH, -ROR, -RSR, 35 -RN2.

II

51-96223 wherein R is as defined in formula XIII above.

In another embodiment of the invention, the preparation of phosphorus-containing amides of formula XIII involves reacting a reactant (A) with a compound of formula (D) 5 r3 r5 χ5 r7 C = CCN - R8 (D) I 4, 10 RJ n wherein the various groups R and X and n 'are defined in formula XIII.

Reactive compound (D) is similar to reactive compound (B) except that it is attached with a linking group R8 (i.e., one of the groups indicated above for R8 when n '= 2 or 3). Accordingly, R 3, R 4, R 5 and R 7 have the same meaning as shown in formula B above. R 8 is as defined above in formula XIII when n '= 2 or 3, wherein n' is preferably 2 and R 8 is preferably -CH 2 -O-CH 2 -.

The reaction between the reactants (A) and (B) is exothermic and thus requires only a small amount of heat. The reaction is preferably carried out in an inert atmosphere at a temperature of about 25 to about 100 ° C, preferably about 70 to about 90 ° C. The reaction time is generally short, for example in the order of less than 1 to 2 hours. Hydrocarbon solvents such as toluene, xylene, hexane, heptane, fuel oil, fuel oil, lubricating oil or the like or chlorohydrocarbons such as chloroform, carbon tetrachloride or the like, or alcohols or the like can be used. ethanol, propanol, butanol, 2-ethylhexanol or the like. Once the product is formed, the solvents can be removed by stripping in vacuo or the like.

Another alternative process for the preparation of phosphorus-containing amides of formula XIII, and in particular for the preparation of the above R6-containing coupled compounds, is a displacement reaction. The metal salt of the compound of formula (A) is used in this reaction. I.e. a metal salt of the following formula (A ') R1 (X1) a ^ x3 (A1) R2 (X2) b ^ is reacted with a compound of formula (F) 10 r3 r5 χ5 r7 χ6-C - C - C-NH (F) R 4 r 6 is wherein 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 as defined above in formula XIII. M is an alkali metal (for example sodium, potassium or the like) or an alkaline earth metal (for example manganese, calcium or the like) or hydrogen, preferably sodium or potassium. X6 is a displaceable halogen or carbon-containing group such as Cl, Br, I, tosyl, mesyl or the like. The reaction between the reactants A 'and F' proceeds in the same manner as the reaction between the reactants (A) and * 25 (B) described above. Briefly, the reaction is carried out at a temperature of about 10 to about 200 ° C, preferably about 50 to about 150 ° C. The reaction is carried out in an inert atmosphere such as nitrogen. The reaction can be performed in menstruation although it is not necessary. The reaction also produces by-product salts insoluble in the reaction medium (e.g., KCl, NaCl, NaBr, KBr, etc.) which can be removed by filtration. The amounts of reactants A 'and F are generally equivalent. The reaction produces a compound of formula XV 53-96223 RKX1) a - ^ _ if3 f3 f5 jf5 f7 P-x4-C-C-C-NH (XV) R2 (X2) b R4 R6 5 [Jn

The product formed from the reaction between the reactants (A) and (B) can be coupled by reacting it with a coupling reagent which is an aldehyde or ketone of formula (C) 10 (or the reaction syntonon equivalent of the aldehyde or ketone).

r9 - C -R10 (O

Wherein R 9 and R 10 independently represent hydrogen, an alkyl group having from 1 to about 12 carbon atoms, phenyl, or an alkyl-substituted phenyl having from about 7 to about 12 carbon atoms. The coupling reagent of formula C is preferably an aldehyde (i.e. R 10 is H) having a total of 1 to about 3, preferably 1 carbon atom. Formaldehyde and paraformaldehyde are preferred; these may produce methylene and dimethylene ether linking groups.

The coupling reaction is preferably carried out with a strong mineral; In the presence of a fatty acid or an organic acid catalyst such as HCl, H 2 SO 4, H 4 PO 4, CH 3 SO 3 H, p-toluenesulfonic acid or the like. The amount of acid catalyst is generally from about 0.3% to about 1.5% by weight, preferably from about 0.8% to about 1.2%, and more preferably from about 0.9% to about 1.1% by weight of the total weight of the product formed. Although smaller amounts of catalyst may be used, the reaction is generally slower and a smaller proportion of the desired product is formed. The reaction with the coupling reagent (C) preferably takes place at an initial temperature of about 80 to about 120 ° C, more preferably about 80 to about 35 ° C in an inert atmosphere. The final reaction temperature <96223 54 is generally higher than about 100 to about 150 ° C, and preferably about 125 to about 135 ° C.

If it is desired to stop the reaction in the carbinol step (formula XV where X5 is oxygen), the reaction between (A) and (B) is preferably carried out using a basic catalyst (i.e. NaHCO 3, KHCO 3, Na 2 CO 3, K 2 CO 3 / NaOH, KOH, etc.). the reaction mixture can be neutralized with acid and heated to remove water; may react with H 2 S, NaHS or Na 2 S or another suitable source of S =; or with NH 3 or 10 R "NH 2, wherein R" is optionally H, alkyl of 1 to about 60 carbon atoms, aryl, alkyl-substituted aryl, or aryl-substituted alkyl of about 6 to about 30 carbon atoms, or acyl of 1 to about 60 carbon atoms. - about 22 carbon atoms.

The ratio of reactants (A) to (B) used is preferably an equivalent weight ratio of 1: 1, although higher or lower amounts may be used. An equivalent weight ratio of two reactants of 1: 1 is preferred because otherwise a higher than desired amount of acid will be achieved or one of the reactants will be washed away. The amount of the reaction product formed which is reacted with the coupling reagent (C) is from about 0.3 to about 3 weight equivalents per weight equivalent of said coupling reagent (C), with an equivalent ratio of 1: 1 being preferred. The coupling reagent (C) may be a mixture of different coupling agents and preferably contains paraformaldehyde.

The combination of formaldehyde and phosphorus-containing amide compound described above may join two amides or may result in the formation of -CH 2 OH on the amide nitrogen atom. Two such amides having a -CH 2 OH group may then react to form a linked amide, the linking group being / ° \ -CH 2 CH 2 -.

II

«96223 55 Such a coupling reaction may take place using such unbound compounds, the reaction being endothermic. An endothermic reaction may be advantageous for the load-bearing lubricating properties of the total oil composition.

Other linking groups (R8 in formula XIII when n 'is 2 or 3) and functional groups (R8 in formula XIII when n' is 1) can be attached to the nitrogen atoms of the phosphorus-containing amides described above by methods known to those skilled in the art.

10 Phosphorus-containing esters (C-2):

The phosphorus-containing esters (C-2) of the invention are of the structural formula XVI 15 x 3 f f5 9 13 eVsj a I I II g p-X4-c-C-C-OR (XVI)

o 2 I 4 I

R 1 (X 2) b R H

Wherein X1, X2, X3 and X4 independently of one another denote oxygen or sulfur; R1 and R2 independently of one another denote hydrocarbyl groups; R3, R4 and R5 independently of one another are hydrogen or a hydrocarbyl group; R6 is a hydrogen carbyl group; and a and b independently denote 0 or 1.

X1 and X2 in formula XVI are preferably oxygen, and X3 and X4 are preferably sulfur.

R1 and R2 independently represent from about 1 to about 50 carbon atoms, more preferably from 1 to about 30 carbon atoms, even more preferably from 3 to about 18 carbon atoms, even more preferably from 4 to about 8 carbon atoms. Examples of R 1 and R 2 are independently t-butyl, isobutyl, amyl, isooctyl, decyl, dodecyl, eicosyl, 2-pentenyl, dodecyl, phenyl, naphthyl, alkylphenyl, alkylnaphthyl, phenylalkyl. , naphthylalkyl, alkylphenylalkyl, alkylnaphthylalkyl and the like.

R 3, R 4 and R 5 preferably independently represent hydrogen or hydrocarbyl groups having 1 to about 30 carbon atoms. More preferably, R 3, R 4, and R 5 independently represent hydrogen, an alkyl group of 1 to about 22 carbon atoms, a cycloalkyl group of about 4 to about 22 carbon atoms, or an aromatic, alkyl-substituted aromatic group, or an aromatically substituted alkyl group of about 4 to about 10 carbon atoms. 34 carbon atoms.

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

In a particularly preferred embodiment, R 1 and R 2 independently represent an alkyl group having from about 3 to about 18 carbon atoms; X1 and X represent oxygen; X3 and X4 represent sulfur; R 3, R 4 and R 5 independently represent hydrogen or methyl; and n "is 1.

Phosphorus-containing esters of formula XVI can be prepared by reacting a phosphorus-containing acid of formula (A) R1 (X1) 3χ ^ 3 5> -X4h (A) R2 (X2)] ^ with a compound of formula (B).

·. I I H

C == c-C-R 6 (B) R 4 wherein the various groups R and X are as defined for ede-35 in formula XVI.

<

II

96223 57

The reactive compound (A) is described above under the title "phosphorus-containing acids". Reactive compound (B) can be prepared by reacting an alcohol of formula R60H with a ό, β-unsaturated carboxylic acid of formula r3 r5

I I

C == C-COOH

R 10 is wherein R 3, R 4 and R 5 are as defined above in formula XVI. The reaction between the reactants (A) and (B) can be carried out by adding either the reactant (A) or (B) to the other over a period of time while stirring, preferably in the presence of an inert organic solvent such as benzene, toluene or methylene chloride. The addition is preferably carried out at an elevated temperature, for example at reflux. The reaction mixture is then further refluxed for a period of time, for example 1-4 hours. The product of Sit-20 is cooled and neutralized, for example by washing with aqueous sodium carbonate solution and then, if desired, brine. The solvent is then removed by evaporation and then, if desired, the product is steam distilled. The product may be subsequently purified by conventional techniques, for example by filtration.

Sulfur-linked dithiocarbamates (C-3): The sulfur-linked dithiocarbamates (C-3) of this invention are of formula XVII.

Sx -i-C-C-S (S) CNR5r6) 2 (XVII) R3 r4 wherein R1, R2 and R3 independently of one another are hydrogen or hydrocarbyl; R 4 is H, OH or a hydrocarbyl group; R5 and R6 independently represent hydrogen, 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 / or R 2 and R 4 together may form a ring-5 group, and x is a number from 1 to about 8.

Hydrocarbyl groups R1 to R4 may be straight-chain or branched hydrocarbyl groups. Each R1 to R6 may independently contain 1 to about 100 carbon atoms, preferably 1 to about 30 carbon atoms.

The groups R1 to R4 may be aliphatic or aromatic groups such as alkyl, cycloalkyl, alkaryl, aralkyl or aryl. R3 and R4 together and / or R5 and R6 together may be alkylene groups containing from about 4 to about 7 carbon atoms. In these embodiments, R 3 and R 4 together with the carbon attached to R 3 and R 4 of formula XVII form a cycloalkyl group, and R 5 and R 6 together with the nitrogen atom of formula XVII attached to R 5 and R 6 form a heterocyclic group.

Specific examples of hydrocarbyl groups R1 to R6 include methyl, ethyl, isopropyl, isobutyl, secondary butyl, cyclohexyl, cyclopentyl, octyl, dodecyl, octadecyl, eicosyl, behenyl, triacontyl, phenyl, naphthyl, phenethyl, octylphenyl, octylphenyl , dioctadecylphenyl, triethylphenyl, chlorophenyl, methoxyphenyl, dibromophenyl, nitrophenyl, 3-chlorohexyl, etc.

In one embodiment of this invention, the sulfur-containing dithiocarbamate is of formula XVII-A

Sx - {- CH (R3) -CH (R4) S (S) CNR5R6) 2 (XVII-A) wherein x is 1-2, R3 and R4 represent hydrogen or a hydrocarbyl group, and R5 and / or R6 both -35 independently of a hydrocarbyl group.

Il - 96223 59

The hydrocarbyl groups of formula XVII-A may be any of those defined above in formula XVII. In general, R 5 and R 6 contain from 1 to about 50 carbon atoms, and R 3 and R 4 are hydrocarbyl groups having from 1 to about 100 carbon atoms.

In another embodiment of this invention, the dithiocarbamates are of formula XVII-B

R1 R2

Sx-fr-C C — S (S) CNR5R6) 2 (XVII-B) I. '

10 R3 OH

wherein R 1, R 2, R 3, R 5, R 6 and x are as defined above in formula XVII.

In one embodiment, sulfur-containing dithio-15-carbamates are prepared by a process comprising the steps of: (A) reacting a sulfur halide with an approximately stoichiometric amount of (i) at least one olefinic hydrocarbon, or (ii) an aldehyde or ketone at such a temperature, and so on. long enough to produce a di (halohydrocarbyl) sulfur intermediate or a dialdehyde or dichlorosulfur intermediate, and (B) reacting the intermediate with an amount of dithiocarbamate salt sufficient to replace both halogen groups with dithiocarbamate groups or to react the dialdehyde with dithiocarbamate groups.

When the starting material is (i) at least one olefinic hydrocarbon, the product obtained is either of formula XVII or formula XVII-A or a mixture consisting essentially of substances of formulas XVII and. * XVII-A. When the starting material is (ii) an aldehyde or ketone, the product is essentially of formula XVII-B.

The sulfur halide used in the first step (A) may be sulfur monochloride (i.e., S2C12), sulfur dichloride, sulfur monobromide, sulfur dibromide, or a mixture of any of the aforementioned sulfur halides with varying amounts of elemental sulfur.

Various olefins and olefin mixtures can be used as starting material for step (A). Mixtures of olefins from the oligomerization of ethylene and / or propylene are preferably available. Olefinic hydrocarbons contain at least one olefinic double bond, which is defined as a non-aromatic double bond. That is, a double bond connects two aliphatic carbon atoms. In the most general sense, an olefin can be defined by the formula R 1 R 3 C = CR 2 R 4 wherein each of R 1, R 2, R 3 and R 4 represents hydrogen or a hydrocarbyl group as defined in formulas XVII, XVII-A or XVII-B above. Although diolefinic hydrocarbons may be used, the olefin is preferably a monoolefin and the olefin may be a terminal monoolefinic hydrocarbon; i.e. those olefins in which R 1 and R 3 represent hydrogen and R 20 and / or R 4 represent alkyl or aryl. Internal olefinic compounds, for example those in which R1 and R2 are alkyl-aryl groups, are also useful. Olefinic compounds having from 3 to about 100 carbon atoms, and more preferably from 3 to 30 carbon atoms, are particularly preferred.

Isobutylene, propylene and their dimers, trimers, tetramers, etc. and mixtures thereof are also useful olefinic compounds. Of these compounds, iso-butylene, diisobutylene, triisobutylene and tetraisobutylene are particularly preferred due to their availability.

* The product obtained from the reaction of a sulfur halide with one or more of the abovementioned olefinic hydrocarbons is a di (halohydrocarbyl) sulphide intermediate formed by the addition of parts of a sulfur halide to the unsaturated carbon atoms of the olefin. The reaction proceeds with stirring.

II

- 96223 61 olefin and sulfur halide, although the reaction rate increases as the temperature of the mixture increases. Thus, the mixture is generally maintained at a temperature between -20 and 120 ° C until the reaction is complete. The thermal stability of the starting olefin and the reaction product determines the reaction temperature.

Alternatively, the olefin may be heated to the desired temperature whereby the sulfur halide may be added dropwise, generally at an inert temperature at a sufficient rate of no-10 to maintain the desired temperature. After the addition of the sulfur halide is complete, the reaction mixture may be heated for an extended period of time to complete the reaction.

The amount of sulfur halide reacted with the olefinic hydrocarbon is generally the stoichiometric equivalent. For example, when a sulfur monohalide is used as the sulfur halide source, 1 mole of sulfur halide is reacted with 2 moles of olefin or olefin mixture.

Catalysts or reaction promoters may be used, although they are generally unnecessary. Examples of such catalysts or promoters are lower aliphatic amines and aromatic amines, especially tertiary amines.

The aldehydes or ketones used as starting materials with the sulfur halide have the following formula

RxR3CHC (O) R2 wherein R1, R2 and R3 each independently represent hydrogen or a hydrogen carbyl group as defined in formulas XVII, XVII-A or XVII-B above. When the starting material is an aldehyde, the intermediate has 2 aldehyde groups, and when the starting material is a ketone, the intermediate contains 2 keto groups.

Aldehydes and ketones can be reacted with sulfur halides such as sulfur monochloride, sulfur dichloride 62-96223, sulfur monobromide, sulfur dibromide, and mixtures of sulfur halide with elemental sulfur.

The reaction of the aldehyde or ketone with the sulfur halide can be accomplished simply by stirring the reactant at a desired temperature of about -30 to about 250 ° C or above. The preferred reaction temperature is generally in the range of about 10 to about 80 ° C. The reaction can be carried out in the presence of a diluent or solvent such as benzene, naphtha, hexane, carbon tetrachloride, chloroform, mineral oil, etc. The diluent / solvent facilitates control of the reaction temperature and thorough mixing of the reactants.

The relative amounts of aldehyde or ketone and sulfur halide may vary over a wide range. Most-15 how the reaction uses 2 moles of aldehyde or ketone and 1 mole of sulfur halide. In other cases, an excess of one of the two reactants is used. When sulfur compounds containing more than 2 sulfur atoms (e.g., x is an integer from 3 to 8) are desired, these compounds can be obtained by reacting aldehydes and ketones with a mixture of sulfur halide and sulfur. This is usually accomplished by reacting the sulfur halide and sulfur before reacting them with an aldehyde or ketone.

Specific examples of aldehydes that can be reacted with sulfur halides include, for example, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, 2-ethyl-1-hexaldehyde, cyclohexanecarboxaldehyde, (C2HnCHO). Examples of ketones include dimethyl 30 ketone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, and the like.

The sulfur-linked dithiocarbamates of this invention are prepared by introducing the sulfur intermediates described above, together with a sufficient amount of dithiocarbamate salt, into the halogen groups with dithiocarbamate groups or

(I

96223 63 to react a dialdehyde or diketone intermediate with both carbonyl groups. Dithiocarbamate salts are of the following formula

5 R5R6NC (S) SX

wherein R 5 and R 6 each independently represent hydrogen, a hydrogencarbyl or hydroxyhydrocarbyl group and X is an alkali metal, tertiary amine or other basic material. Salts of dithiocarbamic acid can be prepared by reacting the amine R5R6NH with carbon disulfide in the presence of a base, usually an alkali metal, in a molar ratio of 1: 1: 1. The base is preferably an alkali metal hydroxide such as sodium or potassium hydroxide, and more generally sodium hydroxide. However, the base may be a tertiary amine or an excess of the amine used in the reaction.

Hydrocarbyl or hydroxyhydrocarbyl groups R5 and R6 may contain from 1 to about 50 carbon atoms. R5 and R6 preferably represent a lower hydrocarbyl group. In one embodiment, R 5 and R 6 represent alkylene groups having from about 4 to about 7 carbon atoms, and in this embodiment, R 5 and R 6 together with the nitrogen atom attached to R 5 and R 6 form a heterocyclic group. The heterocyclic group (and the alkylene group) may contain others: atoms such as oxygen and sulfur.

Specific examples of amines used to form dithiocarbamates (R5R6NH) include, for example, methylamine, propylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, methylethylamine, methylocyclohexylamine, piperidine, morpholamine, n-diol, di di-hydroxyethylamine, piperazine, etc.

Metal salts of dithiocarbamates are known and can be readily prepared by one skilled in the art. One method of preparing early metal salts of dithiocarbamic acids comprises the reaction of an amine, a carbon disulfide and an alkali metal hydroxide. Generally, these reactants are stirred at low temperatures between about 0 and 15 ° C. In one embodiment, the aqueous amine solution is cooled to 0-15 ° C and the carbon disulfide is added dropwise, usually in an inert atmosphere, before or after the addition of the alkali metal hydroxide. In another embodiment, the aqueous amine solution is cooled, followed by the addition of an alkali metal salt, followed by the addition of carbon disulfide. After all these reactants have been stirred at a low temperature of 0 to 15 ° C, the mixture is allowed to warm to ambient temperature with stirring.

The salts of dithio-15 carbamic acids prepared by the process described above are generally reacted immediately with the sulfur intermediates described above. Solvents can be added to facilitate the reaction, and alcohols have proven to be satisfactory solvents. The reaction between the sulfur intermediate and the dithiocarbamate salts is generally carried out at ambient temperature - the reflux temperature of the mixture. The reaction is continued until it is complete, which usually requires about 5 to about 24 hours. At the end of the reaction, the aqueous phase is separated and the product is recovered from the organic layer.

The product obtained from the reaction between a sulfur monohalide and an olefinic hydrocarbon, followed by reaction with a dithiocarbamate, is usually a mixture of products of structural formula XVII or XVII-A. When the reaction is carried out with an aldehyde or ketone instead of an olefinic hydrocarbon, the reaction product is also a mixture in which the main product is believed to be of formula XVII-B.

It is not necessary to isolate different products because the product mixtures are useful in lubricants and functional fluids.

<1 «

II

- 96223 65

Sulfur-linked dithiocarbamates (C-3) can also be prepared by a process comprising the following steps: (A) reacting an olefinic hydrocarbon with halogen to give a halogen-containing intermediate, and (B) reacting said intermediate with an alkali metal sulfide and sufficient with an amount of dithiocarbamate salt, the halogen groups present being replaced in part by dithiocarbamate groups and / or in part by sulphide groups.

Any of the olefinic hydrocarbons and dithiocarbamate salts described above can be used in this process. The reaction of halogen with an olefinic hydrocarbon 15 is well known in the art, and any method can be used to react halogen with an olefinic hydrocarbon to produce a halogen-containing intermediate.

The alkali metal sulphide generally used in the second step has the structural formula M2Sx wherein M is an alkali metal and x is 1, 2 or 3. Sodium sulfide is preferred as the alkali metal sulfide for economic and efficiency reasons.

In one embodiment, the halogen-containing intermediate is first reacted with an alkali metal sulfide and then a dithiocarbamate salt. Although the reactants described above may be reacted in various ratios, it is generally preferred to react 4 equivalents of a halogen-containing intermediate with 1 mole of alkali metal and 2 moles of dithiocarbamate salt. The reaction can be carried out at any suitable temperature up to about 100 ° C and in some cases even higher. The product obtained by this reaction is generally a mixture comprising predominantly sulfur-linked dithiocarbamates useful in lubricants and functional fluids.

Sulfur-Containing Compounds (C-4): The sulfur-5 compounds (C-4) useful in the compositions of this invention are of structural formula (I)

R1 R3

G1-C - (S) x - C -G2 (I) R2 R4 wherein R1, R2, R3 and R4 independently of one another denote hydrogen or a hydrocarbyl group; R1 and / or R3 may be G1 or G2; R 1 and R 2 and / or R 3 and R 4 together may form an alkylene group having from about 4 to about 7 carbon atoms; G1 and G2 independently represent C (X) R, COOR, C-N, R5-C = NR6, CON (R) 2 or NO2, and G1 may be CH2OH, where X is O or S, both groups R and R5 independently represent hydrogen or a hydrocarbyl group, R6 is H or a hydrocarbyl group; when both G1 and G2 are R5C = NR6f, two R6 groups may together denote a hydrogen carbylene group attaching 2 nitrogen atoms; when G1 is CH2OH and G2 is COOR, an intramolecular coupling of G1 and G2 may form a lactone; and x is a number from 1 to about 8.

In formula I, R1, R2, R3 and R4 independently of one another denote hydrogen or a hydrocarbyl group. Hydrocarbyl groups may be aliphatic or aromatic such as alkyl, cycloalkyl, alkaryl, aralkyl or *. aryl groups. R 1 and R 2 and / or R 3 and R 4 together may be alkylene groups having from about 4 to about 7 carbon atoms. In these embodiments, R 1 and R 2 together with the carbon atom attached to R 1 and R 2 of formula I form a 35 cycloalkyl group. Likewise, R3 and R4 together with the carbon atom attached to R3 and R4 I) to 96223 form a cycloalkyl group. R1 and / or R3 may also be G1 or G2.

Hydrocarbyl groups R1, R2, R3 and R4 usually contain up to about 30 carbon atoms. Hydrocarbyl groups are preferably alkyl groups containing up to about 10 carbon atoms. Specific examples of hydrocarbyl groups include methyl, ethyl, isopropyl, isobutyl, secondary butyl, cyclohexyl, cyclopentyl, octyl, dodecyl, octadecyl, eicosyl, behenyl, triacontonyl, phenyl, naphthyl, phenethyl, octylphenyl, tolyl, xyl, chlorophenyl, methoxyphenyl, dibromophenyl, nitrophenyl, 3-chlorohexyl, etc.

The sulfur compounds of formula I (C-4) may be thia-aldehydes or thiacetones. this means that G1 and G2 are groups C (O) R in formula I. Various thiabisaldehyde compounds are known, and the synthesis of such compounds is described in the prior art, such as in U.S. Patent Nos. 3,296,137 and 2,580,695. Thia-aldehydes and thiacetones are preferably prepared by ticking a suitable al-dehyde or ketone such as one of the formula

R R2CHC (0) R

: Wherein R 1 is hydrogen, a hydrocarbyl group or C (O) R, R 2 is hydrogen or a hydrocarbyl group and R is hydrogen or a hydrocarbyl group. In these cases, R 3 in formula I is the same as R 1 and R 4 is the same as R 2, and both G 1 and G 2 are C (O) R.

Sulfurization can be performed by placing an aldehyde or ·. a ketone to react with a sulfur halide such as sulfur monochloride (i.e., S2Cl2), sulfur dichloride, sulfur monobromide, sulfur dibromide, and mixtures of sulfur halides with varying amounts of sulfur flowers.

68 - 96223

The reaction of the aldehyde or ketone with the sulfur halide can be accomplished simply by mixing the two reactants at the desired temperature, which may range from about -30 to about 250 ° C. The preferred reaction temperature is generally in the range of about 10 to about 80 ° C. The reaction can be carried out in the presence of a diluent or solvent, such as benzene, naphtha, hexane, carbon tetrachloride, chloroform, mineral oil, and the like. The diluent / solvent facilitates the control of the reaction temperature and the thorough mixing of the reactants.

The relative amounts of aldehyde or ketone and sulfur halide may vary over a wide range. Most often, 2 moles of aldehyde or ketone 15 and 1 mole of sulfur halide are used in the reaction. In other cases, an excess of one of the two reactants is used. When sulfur compounds containing more than 2 sulfur atoms (e.g., x is an integer from 3 to 8) are desired, these compounds can be obtained by reacting aldehydes and ketones with a mixture of sulfur halide and sulfur. Sulfurization products in which G1 and G2 are different can be obtained by ticking mixtures of aldehydes and ketones containing different groups C (O) R.

Specific examples of thia-aldehydes and thiaceto * compounds are compounds of formula I in which G1 and G2 are C (O) R, x is 1 to 4 and R1, R2, R3, R4 and R are as follows:

R1 R2 R3 R4 R

30 CH3 H CH3 H H

·. CH3 ch3 ch3 ch3 ch3

C2H5 H C2H5 H H

CH3C (0) - H CH3C (0) - h ch3 CH3C (0) - H CH3C (0) - h h

35 C2H5 C4Hn C2H5 C4Hu H

II

- 96223 69

Thia-aldehydes and thiacetones, which can be prepared as described above, can be converted to derivatives containing other functional groups, usually derived therefrom. Thus, in some embodiments of the invention, the thia-aldehyde or thiacetone is derivatized by the simultaneous conversion of aldehyde or ketone groups with chemically reactive agents and / or reagents to other end groups. The thio group (Sx) and the groups R1 to R4 are inert in such reactions and remain unchanged in the compound. For example, thiabisaldehydes can be converted to hydroxy acid derivatives in which 1 of the aldehyde groups (G1) is converted to COOH and the other aldehyde group (G2) is converted to CH2OH. The hydroxy acid derivatives are preferably obtained by treating the corresponding thiabisaldehyde with a basic reagent such as an alkali metal hydroxide or an alkaline earth metal hydroxide, preferably a dilute aqueous solution thereof, containing from about 5 to about 50% by weight of hydroxide in water. Such basic reagents may include sodium hydroxide, potassium hydroxide, lithium hydroxide, barium hydroxide, calcium hydroxide, strontium hydroxide, etc. Hydroxy acid is isolated from the reaction mixture by acidification with a mineral acid such as hydrochloric acid. The hydroxy acid derivatives are of formula I-A below.

: 25

R 1 R 3 HOHCH 2 -C -Sx -C-COOH (I "A) R 2 R4 wherein R 1, R 2, R 3, R 4 and x are as defined above -30. Specific examples of such hydroxy acid ·. the sub-derivatives are 6-hydroxy-2,2,5,5-tetramethyl-3,4-dithiahexanoic acid (i.e. of formula I-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-ditiaheksaanihappo; 6-35 hydroxy-2,2,5,5-tetraethyl-3,4-dithiahexanoic acid; and so on.

96223 70

Due to the hydroxy groups and carboxyl groups in the hydroxy acids of the formula I-A, numerous other sulfur-containing compounds useful in this invention can be obtained by converting such hydroxy groups and / or carboxyl groups into other polar groups normally obtained therefrom. Examples of such derivatives are esters formed by esterification of either or both of a hydroxy group and a carboxyl group; amides, imides, and acyl halides formed with a carboxyl group; and lactones formed by intramolecular cyclization of hydroxy acid followed by elimination of water. Methods for preparing such derivatives are well known to those skilled in the art, and it is not considered necessary herein to unduly prolong the description by including a detailed description of such methods. More specifically, the carboxyl group (COOH) in formula I-A can be converted to an ester group (COOR) and an amide group (CON (R) 2), where the groups R may represent hydrogen or a hydrocarbyl group containing 20 to 30 carbon atoms and more generally 1 to about 10 carbon atoms.

Specific examples of such groups R include ethyl, propyl, butyl, phenyl, etc.

Methods for preparing lactones by intramolecular cyclization of hydroxy acids of formula I-A followed by elimination of water are well known in the art. In general, cyclization is promoted in the presence of materials such as acetic anhydride and the reaction is accomplished by heating the mixtures to an elevated temperature such as reflux while removing volatile material including water.

· Sulfur compounds of formula I-A in which G1 and / or G2 are R5C = NR6 can be prepared from the corresponding thia-aldehydes and thiacetones. These monoimine compounds are prepared by reacting 1 mole of dialdehyde (C (O) H) or diketo-35 (C (O) R5) with 1 mole of amine and di- • il 96223 71 imine compounds are prepared by reacting 1 mole of dialdehyde (C (O) H O) H) or diketone (C (O) R5) to react with 2 moles of amine. The amines may be monoamines or polyamines. When polyamines are reacted with thia-5 aldehydes or thiacetones [-C (O) R5], cyclic diimines may be formed. For example, when both G1 and G2 in formula I are R5C = NR6, the 2 R6 groups may together form a hydrogen carbylene group linking 2 nitrogen atoms. The amines which are reacted with thia-aldehydes and thiacetones to form imines are of the following formula R 6 NH 2 wherein R 6 is hydrogen, hydrocarbyl, or aminohydrocarbyl. Hydrocarbyl groups usually contain up to about 30 carbon atoms and are more often aliphatic hydrocarbyl groups containing from 1 to about 30 carbon atoms.

In one embodiment, the hydrocarbylamines useful in preparing the imine derivatives of this invention are primary hydrocarbylamines containing from about 2 to about 30 carbon atoms in the hydrocarbyl group, and more preferably from about 4 to about 20 carbon atoms in the hydrocarbyl group. The hydrocarbyl group may be saturated or unsaturated. Representative examples of primary saturated amines include lower alkyl amines such as methylamine, ethylamine, n-propylamine, n-butylamine, n-amylamine, n-hexylamine; known as aliphatic primary fatty amines and commercially known as "Armeen" primary amines (products supplied by Armak Chemicals, Chicago, Illinois). Typical fatty amines include alkylamines such as n-hexylamine, ·. n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-octadecylamine (stearylamine), etc. These primary amines of Armenia are available in both distilled and technical grades. When the distilled grade gives a purer »s 96223 72 product, the desired amides, imines and imides can be formed in the reactions with technical grade amines. Mixtures of fatty amines such as Armak's Armeen-C, Armeen-O, Ar-meen-OL, Armeen-T, Armeen-HT, Armeen S and Armeen SD are also suitable.

In another embodiment, the amine derivative products of this invention are derivatives of primary amines containing a tertiary aliphatic group having at least about 4 carbon atoms in the alkyl group. Mostly, they are derived from alkylamines having a total of less than about 30 carbon atoms in the alkyl group.

Typically, primary amines containing a tertiary aliphatic group are monoamines of the following formula CH 3 R - C - NH 2 and CH 3 wherein R is a hydrocarbyl group having 1 to about 30 carbon atoms. Examples of such amines are tertiary butylamine, tertiary hexyl primary amine, 1-methyl-1-aminocyclohexane, tertiary octyl primary amine, tertiary decyl primary amine, tertiary dodecyl primary tertiary tertiary amine, tertiary dodecyl primary tertiary amine. amine, tertiary octadecyl primary amine, tertiary tetracosanyl primary amine, tertiary octacosanyl primary amine.

*. Mixtures of amines are also useful for the purposes of this invention. Examples of amine mixtures of this type are "Primene 81R", a mixture of primary amines of Cn-C14 tertiary alkyls, and "Primene JM-35 T", a similar mixture of primary amines of C18-C22 tertiary alkyls (both supplied by Rohm Ja Haas Company). ). The primary amines of tertiary alkyls and methods for their preparation are well known to those skilled in the art and therefore a more detailed description is unnecessary. Primary amines of tertiary alkyls useful in the present invention and methods for their preparation are described in U.S. Patent No. 2,945,749, the subject matter of which is incorporated herein by reference.

Primary amines with olefinic unsaturation in the hydrocarbyl chain are also useful. Thus, the group R6 may contain 1 or more olefinic double bonds depending on the length of the chain, usually no more than 1 double bond per 10 carbon atoms. Representative amines include dodecenylamine, myristolylamine, palmitoleylamine, oleylamine and linolylamine. Such unsaturated amines are also available under the tradename Armeen.

Thia-aldehydes and thiacetones can also be reacted with polyamines. Examples of useful polyamines include diamines such as mono- or dialkyl, symmetrical or asymmetric ethylenediamines, propanediamines (1,2 or 1,3), and polyamine analogs of the above. Suitable commercial fatty polyamines include "Duomeen C" (N-coconut-1,3-diaminopropane), "Duomeen S" (N-soya-1,3-diaminopropane), "Duomeen T" (N-tallow-1,3- diaminopropane), or "Duomeen 0" (N-oleyl-1,3-diaminopropane) .Duomeen are commercially available diamines described in Armak Chemical Co., Chicago, Illinois, Product Data Sheet No. 7-10R1.

The reaction of thia-aldehydes (and ketones) with primary amines or polyamines can be performed by methods well known to those skilled in the art. Generally, a thia-bisaldehyde or ketone is reacted with an amine or polyamine in a hydrocarbon solvent at elevated temperature, usually under a nitrogen atmosphere. The water formed is removed as the reaction proceeds in a manner such as distillation.

Sulfur compounds of formula I wherein G 1 and G 2 may be COOR, C-N or NO 2 may be prepared from compounds of formula (IB) R 1 HCG (IB) k 2 wherein R 1 and R 2 are as defined above and G is COOR, C-N or NO 2, or by reaction of various compounds of formula IB with a sulfur halide or a mixture of sulfur halides and sulfur. In general, about 1 mole of sulfur halide is reacted with about 2 moles of a compound of formula I-B. In one embodiment, R 1 may also be G. In such cases, the sulfur compounds formed from the reaction with the sulfur halide contain 4 groups G, which may be the same or different depending on the starting materials. For example, when a diketone such as 2,4-pentanedione is reacted with sulfur monochloride, the resulting product contains 4 ketone groups; when the starting material contains a ketone group and an ester group (for example, ethyl acetoacetate), the resulting product contains 2 keto-25 groups and 2 ester groups; when the starting material contains two ester groups (e.g. diethyl malonate), the product contains 4 ester groups. Other combinations of functional groups may be added to the sulfur compound products of formula I used in this invention by selecting starting materials containing the desired functional groups.

Sulfur compounds of formula I in which G1 and / or G2 are groups C to N can be prepared by reactions of compounds of formula I-B in which G is C N and R1 and R2 represent hydrogen or a hydrocarbyl group. R1 is preferably hydrogen and R2 is a hydrocarbyl group. Examples of useful starting materials include, for example, propionitrile, butyronitrile, etc.

Compounds of formula I wherein G 1 and G 2 are NO 2 may be prepared by (1) reacting nitro carbon-5 hydrogen RxR 2 C (H) NO 2 with an alkali metal or alkaline earth metal alkoxide to form a nitro hydrocarbon salt, and (2) reacting said salt with sulfur monochloride in an inert hydroxyl-free medium to give bis (1-nitrovecycarbyl) -10 disulfide. The nitro hydrocarbon is preferably a primary nitro hydrocarbon (R 1 is hydrogen and R 2 is hydrocarbyl).

The primary nitro compounds used to perform this synthesis are well known. Exemplary compounds include nitroethane, 1-nitropropane, 1-nitrobutan-15, 1-nitro-4-methylhexane, (2-nitroethyl) benzene, and the like.

The nature of the alkanols used to form the starting materials, alkali or alkaline earth metal salts of primary nitro compounds, is not critical. It is only necessary that it be suitable for reaction with a metal to form an alkoxide. Lower alkanols (i.e., alkanols having 1 to 4 carbon atoms) such as methanol, ethanol, and butanol are commonly used in the synthesis because they are readily available and inexpensive.

The medium in which the salt is reacted with S2Cl2 must be inert to both reactants. It is also essential that the medium be anhydrous and hydroxyl-free for the successful formation of new bis (1-nitrohydrocarbyl) disulfides. Examples of suitable intermediates are ether, hexane, benzene, dioxane, higher alkyl ethers, etc.

It is usually preferable to maintain a temperature of about 0 to 10 ° C during the preparation of the metal salt. However, at this stage of the process 35, temperatures of about * · 96223 76 O to 25 ° C can be used. Temperatures in the range of -5 to + 15 ° C can be used in the preparation of bisdisulfides. Temperatures between about 0 and 5 eC are preferably used in this process step.

Various thiabisnitro-5 compounds preferred in this invention are described in some detail in U.S. Patent No. 3,479,414, and the disclosure of this patent is incorporated herein by reference. Exemplary nitrosulfides useful in this invention include: bis (1-nitro-2-phenylethyl) disulfide, bis (1-10 nitrodecyl) 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 (l -nitro-3-p-tolyl-propyl) disulfide, bis (1-nitro-2-cyclooctylethyl) disulfide and the like.

The carboxylic ester-containing sulfur compounds described above (i.e., G1 is COOR) can be used to prepare other sulfur compounds useful in this invention. For example, an ester (COOR) can be hydrolyzed to a carboxylic acid (COOH), which can be converted to other esters by reaction with various alcohols or to amides by reaction with various amines, including ammonia in primary or secondary amines such as the following formula.

(R) 2 NH

wherein each R is hydrogen or a hydrocarbyl group. These hydrogen carbyl groups may contain from 1 to about 30 carbon atoms and more generally contain from about 1 to about 10 carbon atoms. As mentioned above, R 1 and R 2 and / or R 3 and R 4 together may represent alkylene groups containing from about 4 to about 7 carbon atoms. In this embodiment, R 1 and R 2 (and R 3 and R 4) form a cyclic compound having a common carbon atom (i.e., a carbon atom common to R x and R 2 in Formula I). Such structural formulas I • ·

II

Derivatives can be prepared by reacting an appropriately substituted saturated cyclic substance with the sulfur halides described above. Examples Stal-type of the cyclic starting materials include sykloheksaanikar-5 boksaldehydi (C6HuCHO) cyclohexanecarbonitrile (C6HuCN) cyclohexanecarboxamide (CEH ^ CONHj), cyclohexane-saanikarboksyylihappo (CJH ^ COOH), syklobutaanikarboksyyli acid (C4H7COOH), cycloheptane carboxylic acid (C7H13COOH), sykloheptyylisyanidi ( C7H17CN), etc.

The following Example 1 illustrates the preparation of a sulfur compound of formula 1. Unless otherwise indicated, all proportions and percentages by weight in this example, as well as elsewhere in the specification and appended claims, are as follows, and all temperatures are in 15 ° C.

Example 1

Sulfur monochloride (1620 parts, 12 moles) was added to a 5 liter flask and heated under nitrogen to about 53 ° C, adding 1766 parts (24.5 to 20 moles) of isobutyraldehyde under nitrogen at about 53-60 ° C dropwise over about 6.5 h. . After the addition of isobutyraldehyde was complete, the mixture was slowly heated to about 100 ° C over 6 hours while purging with nitrogen. The mixture was kept at 100 ° C while blowing nitrogen and the volatiles were removed from the reaction vessel. The reaction product was then filtered through a filter aid, the filtrate being the desired product containing 31.4% sulfur (theoretical 31.08%). The desired reaction product, mainly 2,2'-dithioisobutyraldehyde, was obtained in about 95% yield.

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

96223 78

Lubricants and Functional Fluids: The compositions of this invention are useful as additives for lubricants and functional fluids. These compositions can be used in a wide variety of lubricants and functional fluids based on a wide variety of oils having a lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof. These lubricants and functional fluids include oils for lubrication of crankcases of spark ignition and compression ignition 10 combustion engines / including car and truck engines, two-stroke engines, aircraft piston engines, and marine and locomotive diesel engines, and the like. They can also be used in gas engines, fixed engines 15 and turbines and the like. The compositions of this invention may also be advantageously added to transmission fluids (including both automatic transmission fluids and manual transmission fluids), rear axle lubricants, transmission lubricants, metalworking lubricants, hydraulic fluids, and other lubricating oils and grease compositions.

Natural oils include animal oils and vegetable oils (e.g. castor oil and lard oil) as well as paraffinic, naphthenic or paraffinic / naphthenic type-25 solvent-refined or acid-refined mineral lubricating oils. Carbon or slate-derived oils with a suitable viscosity for lubrication are also useful as base oils. Synthetic lubricants include hydrocarbon oils and halogen-substituted hydrocarbon oils such as polymerized and copolymerized olefins (e.g., polybutylenes, polypropylenes, propylene / isobutylene copolymers, chlorinated polybutylenes, etc.); alkylbenzenes (for example dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di (2-ethylhexyl-35) benzenes, etc.); polyphenyls (e.g. biphenyls, terphenyls, alkylated polyphenyls, etc.) and the like.

Il 96223 79

Alkylene oxide polymers and copolymers and their derivatives in which the terminal hydroxy groups have been modified by esterification, etherification, etc., form another class of known lubricating oils which can be used.

Examples of these are oils prepared by polymerizing ethylene oxide or propylene oxide, alkyl and aryl ethers of these polyoxyalkylene polymers (for example, methyl polyisopropylene glycol ether having an average molecular weight of about 1000, polyethylene-10 glycol ether having about 50, diethyl ether of polypropylene glycol having an average molecular weight of about 1000 to 1500, etc.) or mono- and polycarboxylic esters thereof, for example acetic acid esters, mixed C3-Ce fatty acid esters, or C13-oxo acid diester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils that can be used are esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkylsuccinic acid, malic acid, azelaic acid, capric acid, malic acid, malic acid, fatty acid, linoleic acid, fumaric acid, linoleic acid, linoleic acid, adipic acid, adipic acid, adipic acid, with (for example, butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol mono-ether, propylene glycol, pentaerythritol, etc.). Specific examples of these esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, dioctyl phthalate, didecyl phthalate, didecyl phthalate ethylhexyl diester, a complex ester formed by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid and the like.

96223 80

Esters useful as synthetic oils also include esters made from C5-C12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipen-5 taerythritol, tripentaerythritol, and the like.

Silicone-based oils such as polyalkyl, polyaryl, polyalkoxy or polyaryloxysiloxane oils and silicate oils comprise another class of useful oils. These include tetraethyl silicate, tetraisoprop-10-silicate, tetra- (2-ethylhexyl) silicate, tetra- (4-methylhexyl) silicate, tetra (p-tert-butylphenyl) silicate, hexyl (4-methyl-2-pentoxy) disiloc -sane, poly (methyl) siloxanes, poly (methylphenyl) siloxanes, etc. Other useful synthetic oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, polymers of decane phosphonic acid, etc.), diethyl ester of decane phosphonic acid, etc.

Crude, refined, or refined oils (and mixtures of each with others) of the type described above may be used in the lubricant and functional fluid-20 compositions of this invention. Unrefined oils are obtained directly from a natural or synthetic source without further purification. For example, shale oil 25 directly from the retort step, fuel oil obtained directly from distillation, or ester oil obtained directly from the esterification step and used without further processing is a crude oil. Refined oils are similar to unrefined oils except that they are further treated in one or more refining steps to improve one or more properties. Many such purification methods are known to those skilled in the art, such as solvent extraction, distillation, acid or base extraction, filtration, percolation, etc. The refined oils are obtained by methods similar to those used for the preparation of the used refined oils. Such refined oils are also known as regenerated or reprocessed oils, and are often further treated by processes designed to remove used additives and oil degradation products.

In general, the lubricants and functional fluids of the present invention contain an effective amount of the composition of the present invention sufficient to improve the anti-wear, load-bearing, high-pressure (E.P.) and / or anti-corrosion properties of said lubricants and functional fluids. Generally, the composition of this invention is used in such lubricants and functional fluids at a level of from about 0.02% to about 20% by weight, preferably from about 0.05% to about 5% by weight of the total weight of the lubricant or functional fluid. Component (A) is preferably used in a concentration of about 0.01 to about 5%, more preferably about 0.01 to about 2%, more preferably about 0.01 to about 1% by weight of the total weight of the lubricant or functional fluid. Component (B) is preferably used in a concentration of about 0.001 to about 0.1% by weight based on the total weight of the lubricant or functional fluid. Component (C) is preferably used in a concentration of about 0.01 to about 5% by weight of the total weight of the lubricant or functional fluid.

In addition to the compositions of this invention, the invention also contemplates lubricants and functional fluids containing other additives. Such additives include, for example, ashless surfactants and dispersants, antioxidants, viscosity enhancers, E.P. reagents, pour point depressants, color stabilizers, antifoams, and the like.

Ashless surfactants and dispersants are called ashless, despite the fact that, depending on their composition, dispersants may produce non-volatile substances such as boron oxide or phosphorus pentoxide upon combustion; however, they do not normally contain metals and therefore do not produce ash containing metal when incinerated.

Many types are known in the art, all of which are suitable for use in the lubricants of this invention. The following are exemplary: (1) reaction products of carboxylic acids (or derivatives thereof) containing at least about 34 and preferably at least about 54 carbon atoms with nitrogen-containing compounds such as amines, organic hydroxy compounds such as phenols and alcohols, and / or inorganic bases. Examples of these "carboxylic dispersants" are described in 15 GB-1,306,529 and in several U.S. patents, including the following: 3,163,603; 3,351,552; 3,541,012; 3,184,474; 3,381,022; 3,543,678; 3,215,707; 3,399,141; 3,542,680; 3,219,666; 3,415,750; 3,567,637; 3,271,310; 3,433,744; 3,574,101; 3,272,746; 3,444,170; 3,576,743; 3,281,357; 3,448,20,048; 3,630,904; 3,306,908; 3,448,049; 3,632,510; 3,311,558; 3,451,933; 3,632,511; 3,316,177; 3,454,607; 3,697,428; 3,340,281; 3,467,668; 3,725,441; 3,341,542; 3,501,405; 4,234,435; 3,346,493; 3,522,179; Re 26,433.

(2) reaction products of relatively high molecular weight aliphatic or alicyclic halides with amines, preferably oxyalkylene polyamines. These can be characterized as "amine dispersants" and examples are described, for example, in the following U.S. Patents: 3,275,554; 3,454,555; 3,438,757; and 3,306,565,804.

(3) reaction products of alkylphenols having at least about 30 carbon atoms in the alkyl group with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines). These can be characterized as "Mannich dispersants". Examples are the following c ·

II

96223 83 U.S. Patents: 2,459,112; 3,442,808; 3,591,598; 2,962,442; 3,448,047; 3,600,372; 2,984,550; 3,454,497; 3,634,515; 3,036,003; 3,459,661; 3,649,229; 3,166,516; 3,461,172; 3,697,574; 3,236,770; 3,493,520; 3,725,277; 3,355,270; 3,539,633; 3,725,480; 3,368,972; 3,558,743; 3,726,882; 3,413,347; 3,586,629; and 3,980,569.

(4) products obtained by post-treatment of carboxylic, amine or Mannich dispersants with reagents such as urea, thiourea, carbon disulphide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, nitriles, nitriles, nitriles phosphorus compounds or the like. Examples of this type of material are described in the following U.S. Patents: 3,036,003; 3,282,955; 3,493,520; 3,639,242; 3,087,936; 3,312,619; 3,502,677; 3,649,229; 3,200,107; 3,366,569; 3,513,093; 3,649,659; 3,216,936; 3,367,943; 3,533,945; 3,658,836; 3,254,025; 3,373,111; 3,539,633; 3,697,574; 3,256,185; 3,403,102; 3,573,010; 3,702 20,757; 3,278,550; 3,442,808; 3,579,450; 3,703,536; 3,280,234; 3,455,831; 3,591,598; 3,704,308; 3,281,428; 3,455,832; 3,600,372; 3,708,422.

(5) copolymers of oil-soluble monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substituents, for example aminoalkyl acrylates or acrylamides and poly (oxyethylene) substrates. These can be characterized as "polymeric dispersants" and examples of these 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 descriptions of the above-mentioned patents on ashless dispersants are attached to this application.

84 96223

High pressure (E.P.) Agents, corrosion inhibitors and antioxidants that may be included in the lubricants and functional fluids of this invention include, for example, chlorinated aliphatic hydrocarbons such as chlorinated waxes; organic sulfides and polysulfides such as benzyl disulfide, bis (chlorobenzyl) disulfide, dibutyl tetrasulfide, Embroidered Methyl Ester of Oleic Acid, Embroidered Alkylphenol, Embroidered Dipentene, and Embroidered Terpene; fosforikitetyt hydrocarbons such as phospho-10 sulfides reaction products with turpentine or methyl oleate, phosphorus esters containing mainly dihiili-hydrogen and trihiilivetyfosfiitteja such as dibutyl phosphite, diheptyylifosfiitti, dicyclohexyl, pentyl phenyl phosphite, dipentylphenyl, tridecyl-15 phosphite, distearyl phosphite, dimetyylinaftyylifosfiit acetate, oleyl 4 -pentylphenyl phosphite, polypropylene (molecular weight 500) substituted phenyl phosphite, diisobutyl-substituted phenyl phosphite; metal thiocarbamates such as zinc dioctyl dithiocarbamate and barium hep-20 phenyl phenyldithiocarbamate; phosphorodithionates of group II metals such as zinc dicyclohexyl phosphorodithioate, zinc dioctyl phosphorodithioate, barium di (heptylphenyl) phosphorodithioate (cadmium dinonyl phosphorodithioate)

Several of the above-mentioned high-pressure agents, corrosion inhibitors and antioxidants also act as anti-wear agents. A well-known example is zinc dialkyl phosphorodithioates.

Freezing point depressants are particularly useful additives that are often added to the lubricants and functional fluids described herein. The use of such 35 pour point depressants in oil-based compositions

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96223 85 in improving the properties of oil-based compositions at low temperatures is well known in the art. See, e.g., page 8 in "Lubricant Additives" by C.V. Smalheer and H. Kennedy 5 Smith (Lezius-Hiles Co. publishes, Cleveland, Ohio, 1967), in which the subject matter is incorporated herein by reference.

Examples of useful pour point depressants include polymethacrylates; polyacrylates; polyakryy-amides; condensation products of halogenated paraffin waxes and aromatic compounds; vinyl carboxylate polymers; and terpolymers of dialkyl fumarates, vinyl esters of fatty acids and alkyl vinyl ethers. Dilution point reducers useful for the purposes of this invention, methods of making the same, and their use are described in U.S. Patent Nos. 2,387,501; 2,015,748; 2,655,479; 1,815,022; 2,191,498; 2,666,746; 2,721,877; 2,721,878; and 3,250,715. The subject matter of these patents is incorporated herein by reference.

Antifoams are used to reduce or prevent the formation of permanent foam. Typical antifoams are silicones or organic polymers. Other antifoam compositions are described in "Foam Control Agents" by Henry T. Kerner (Noyes Data Corporation, 1976), pp. 125-162, in which the subject matter is incorporated herein by reference.

Components (A), (B) and (C) of the compositions of this invention may be added directly to a lubricant or functional fluid. However, they are preferably diluted with a substantially inert, usually liquid, organic diluent such as mineral oil, naphtha, benzene, toluene or xylene to form an additive concentrate. These concentrates contain from about 10% to about 90% by weight of the compositions of the invention and may additionally contain one or more other additives known from the prior art described above. The remainder of the concentrate is a substantially inert, usually liquid, diluent.

Examples of hydraulic fluids within the scope of the invention are as follows (all numerical values 5 are by weight):

ABC

a phosphorus-containing amide derived from di (isooctyl) fossil forodithionic acid, acrylamide and paraformaldehyde.

(antifouling agent) 0.172 0.172 Phosphorus ester derived from the reaction of 0,0-di (alkyl) phosphorodithionic acid containing 65% isobutyl groups and 35% amyl groups and methacrylate, post-treated with pro-20 polyene oxide.

(anti-wear agent) 0.517 0.517 0.50 dibutyl hydrogen phosphite (anti-wear agent) 25 thiophosphate ester (anti-wear agent) dithiocarbamate derived from the reaction of butylamine, carbon disulfide and methyl acrylate with diamine amine 40 disulfide compound of carbon disulfide, sodium hydroxide and methylene chloride (anti-wear agent) prepared from sulfur monochloride and isobutyraldehyde as in Example 1 (anti-wear agent) - - 0.17 45 antioxidant 0.43 0.43 0.43 anti-corrosion agent 0.043 0 .0.0 0.04 emulsion dispersant 50 0.006 0.014 0.007 11 96223 87 tolyltriazole (metal deactivator) 0.005 5 benzotriazole (metal deactivator) alkylated triazole (metal deactivator) 0.0093 0.00465 300 modified calcium phenate 10 (surfactant modified) 0.15 calcium sulphonate (surfactant) - 0,10 700 modified magnesium sulphonate 15 sodium (surfactant) - - 0.15 700 modified magnesium salicylate (surfactant) 2600 modified sodium sulphonate (surfactant) - - 0.05 diluent oil 98.67 98 , 73 98.70

25 D E F

a phosphorus-containing amide derived from di (isooctyl) phosphorodithionic acid, acrylamide and paraformaldehyde.

30 (anti-wear agent) to 0.172 0.172 phosphorus ester derived from 0,0-di (alkyl) phosphorodionic acid containing 65% isobutyl groups and 35%. myyl groups, and from the methacrylate reaction, post-treated with propylene oxide.

(anti-wear agent) 0.50 0.48 0.50 40 dibutyl hydrogen phosphite (anti-wear agent) thiophosphate ester (anti-wear agent) 45 dithiocarbamate resulting from the reaction of butylamine, carbon disulphide and methyl acrylate (anti-wear agent) - amine, carbon disulphide, sodium hydroxide and methylene chloride (anti-wear agent) 0.17 96223 88 sulfur-containing compound prepared from sulfur monochloride and isobutyraldehyde as in Example 1 (anti-wear agent) 5 antioxidant 0.38 0.40 0.38 anti-corrosion agent 04 0.043 0.04 emulsion dispersant 0.007 0.006 0.014 10 tolyltriazole (metal deactivator) 0.005 0.0093 0.01 benzotriazole 15 (metal deactivator) alkylated triazole (metal deactivator) 300 modified calcium phenate (surfactant) - - 0.025 20 2000 modified - Naate (surfactant) 0,05 700 Modified magnesium sulphonate (surfactant) mineral) - - 0,05 25 700 modified magnesium salicylate (surfactant) - 0,075 2600 modified sodium sulphonate (surfactant) 0,15 30 diluent oil 98,70 98,81 98,81

G H I

a phosphorus-containing amide derived from di (isooctyl) phosphorodithionic acid, acrylamide and paraformaldehyde.

(anti-wear agent) 0.17 40 phosphorus ester from the reaction of 0,0-di (alkyl) phosphorodithionic acid containing 65% isobutyl groups and 35% amyl groups and methacrylate 45, treated with propylene oxide.

(anti-wear agent) 0.48 dibutyl hydrogen phosphite 50 (anti-wear agent) thiophosphate ester (anti-wear agent) dithiocarbamate

II

- 96223 89 Synthesis of butylamine, carbon disulphide and methyl acrylate (anti-wear agent) with methylene-containing dithiocarbamate derived from diamylamine, carbon disulphide, sodium hydroxide and methylene chloride (anti-wear agent) - 0.50 0.50 sulfur-containing compound prepared from sulfur monochloride and isobutyraldehyde as in Example 1 (anti-wear agent) - - 0.17 antioxidant 0.40 0.40 0.43 anti-corrosion agent 0.05 0.04 0.05 emulsion disintegrant 0.006 0.014 0.007 tolyltriazole 25 (metal deactivator) benzotriazole (metal deactivator) 0.005 0.005 30 alkylated triazole (metal deactivator) - - 0.01 300 modified calcium phenate (surfactant) - 0.025 35 2000 modified calcium sulphonate (surfactant) 0.05 - 0,10 700 modified magnesium sulphonate (surfactant) 700 modified magnesium salicylate (surfactant) - 0,05 0,05 2600 modified sodium sulphonate 45 sodium (surfactant) 0.025 diluent oil 98.81 98.97 98.68

J K L

A 50 phosphorus amide derived from di (isooctyl) phosphorodionic acid, acrylamide and paraformaldehyde.

96223 90 (anti-wear agent) 0.10 0.10 0.50 phosphorus ester derived from the reaction of 0,0-di (alkyl) phosphorod-5-forodionic acid containing 65% isobutyl groups and 35% amyl groups and methacrylate, post-treated pro -pyleenioksidilla.

10 (anti-wear agent) 0.50 0.50 dibutyl hydrogen phosphite (anti-wear agent) thiophosphate ester 15 (anti-wear agent) dithiocarbamate from the reaction of butylamine, carbon disulphide and methyl acrylate (anti-wear agent) from carbonyl amide, 20 from sodium hydroxide and methylene chloride (anti-wear agent) 0.07 to 0.10 sulfur-containing compound prepared from sulfur monochloride and isobutyraldehyde as in Example 1 (anti-wear agent) to 0.07 0.07 antioxidant 0.38 0.40 0.43 anti-corrosion agent 0.04 0.043 0.05 35 emulsion dispersant 0.006 0.014 0.007 tolyltriazole (metal deactivator) 0.01 to 0.025 benzotriazole 40 (metal deactivator) to 0.005 alkylated triazole (metal deactivator) 300 modified calcium phenate (surfactant) .0545 2000 Modified calcium sulphonate (surfactant) - - 0.10 700 Modified magnesium sulphonate tti (surfactant) 0.10 50 700 modified magnesium salicylate (surfactant) - 0.075 2600 modified sodium sulfonate (surfactant) - - 0.05 L! 96223 91 Dilution oil 98.74 98.79 98.67

M N O

a phosphorus-containing amide derived from di (isooctyl) phosphorodionic acid, acrylamide and paraformaldehyde.

(anti-wear agent) 10-phosphorus ester from the reaction of 0,0-di (alkyl) phosphorodionic acid containing 65% isobutyl groups and 35% amyl groups and methacrylate 15, post-treated with propylene oxide.

(anti-wear agent) 0.50 0.50 dibutyl hydrogen phosphite 20 (anti-wear agent) 0.10 thiophosphate ester (anti-wear agent) - 0.10 25 dithiocarbamate resulting from the reaction of butylamine, carbon disulphide and methyl acrylate (anti-wear agent) - - 0, 60 Methylene-linked dithiocarbamate derived from diamylamine, carbon disulfide, sodium hydroxide and methylene chloride (antifouling agent) Sulfur-containing compound prepared from sulfur monochloride. and isobutyraldehyde as in Example 1 (anti-wear agent) antioxidant 0.50 0.50 0.50 40 anti-corrosion agent 0.05 0.05 0.05 emulsion disintegrant 45 tolyltriazole (metal deactivator) 0.01 benzotriazole 50 (metal deactivator) alkylated triazole (metal deactivator) 0.01 0.01 0.04 96223 92 300 Modified calcium phenate (surfactant) - 0.40 2000 Modified calcium sulphonate (surfactant) 5,700 Modified magnesium sulphonate (surfactant) 700 Modified magnesium salicylate (surfactant) 0.05 to 0.25 10 2600 modified sodium sulfonate (surfactant) diluent oil 98.78 98.44 98.56 The lubricant compositions of this invention may be in the form of fats in which: any oil having a lubricating viscosity as described above can be used as the medium. When the lubricant must be in the form of a fat, a sufficient amount of cream oil is usually used to balance the total fat composition, and generally the fat composition contains varying amounts of thickeners and other additive components to provide the desired properties.

A wide variety of thickeners can be used to make the fats of this invention. Thickeners include alkali and alkaline earth metal salt soaps of fatty acids and fatty materials having from about 12 to about 30 carbon atoms. Typical metals are sodium, lithium, calcium and barium. Examples of fatty materials are stearic acid, hydroxystearic acid, stearin, oleic acid, palmitic acid, myristic acid, cottonseed oleic acid and hydrogenated fish oils.

Other thickeners include salts and salt / soap-35 complexes such as calcium stearate / acetate (U.S. Pat. No. 2,197,963), barium stearate / acetate (U.S. Pat. No. 2,564,561), calcium stearate / caprylate / acetate complexes, U.S. Pat. caprylate / acetate (U.S. Pat. No. 2,999,066), and 40 lower, medium and high molecular weight

II

96223 93 Calcium salts and soaps of acids and nut oils.

Particularly useful thickeners used in fat compositions are those of substantially hydrophilic nature which, however, have been converted to a hydrophobic state by the addition of long chain hydrocarbon radicals to the surface of the clay particles prior to use as components of the fat compositions. Typical onium-10 compounds include tetraalkylammonium chlorides such as dimethyldioctadecylammonium chloride, dimethyldibenzylammonium chloride, and mixtures thereof. This conversion method is well known to those skilled in the art and need not be explained further. More particularly, clays useful as starting materials for the formation of thickeners for use in fat compositions may be naturally occurring chemically unmodified clays. These clays are crystalline complex silicates, the exact composition of which is not further elaborated because their compositions vary greatly depending on the natural source from which they are obtained. These clays can be described as complex inorganic silicates such as aluminosilicates, magnesium silicates, barium silicates, and the like, which contain varying amounts of cationic variable groups such as sodium in addition to the silicate lattice. Hydrophobic clays that are particularly useful in converting them to the desired thickeners include montmorillonite clays such as bentonite, attabulite, hectorite, illite, saponite, sepiolite, biotite, vermiculite, and zeolite. The thickener is used in an amount of about 0.5% to about 30% by weight, preferably 3-15% by weight of the total weight of the fat composition.

Although the invention has been described in terms of preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. It is therefore to be understood that the present invention is intended to cover variations which fall within the scope of the appended claims.

Il

Claims (8)

95 967η A composition useful in lubricants and functional fluids, characterized in that it comprises: (A) at least one acidic organic compound, at least one neutral or basic metal salt or a boron-containing neutral or basic metal salt, wherein the acidic organic compound is selected from one or more a carboxylic acid, sulfur-containing acids, phenols, or a mixture of two or more thereof, said salt metal being an alkali metal, alkaline earth metal, zinc, copper, aluminum, or a mixture of two or more of said metals; (B) at least one metal deactivator which is benzotriazole; alkyl, aryl, alkaryl or arylalkyl substituted benzotriazole; hydroxy-, alkoxy-, halogen-, nitro-, carboxy- or carbalkoxy-substituted benzotriazole; the reaction product of at least one of said benzoth-20-riazole and at least one amine; a reaction product of at least one of said benzotriazole and at least one nitrogen-containing ashless dispersant; or a mixture of two or more thereof; and (C) a phosphorus-containing amide of at least one compound of group 25 (Cl) of the formula R1 »1) ^ x3 R3 R5 χ5 R7 a \ ll 4 1 IJ, I _8 P 'X4-c--C-CNJR ° 30 a2U2) b R4 r6 „Jn. (XIII> wherein X1, X2, X3, X4 and X5 independently of one another denote oxygen or sulfur; • R22 and R2 independently of one another denote hydrocarbyl groups; R3, R4, R5, R6 and R7 independently of one another denote hydrogen) , halogen or a hydrocarbyl group, 5. and b independently represent 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, -RÖH, -ROR, -RSR or R -RN-R; (2) when n 'is 2, then R8 is a linking group selected from -R-, -R1-, -R-O-R-, -R-S-R-, 15. S H R 11 II I -R-, -R-, -R-N-R- or -R-N-R-; and (3) when n 'is 3, then R 8 is a linking group -R-N-R-R 11 wherein each R is independently a hydrocarbyl group having 1 to 12 carbon atoms; and R 1 is a hydrocarbyl or carboxyhydrocarbyl group having 1 to 60 carbon atoms; (C-2) phosphorus but not metal ester of formula R1 ^ 1) ^ X3 R3 R5 0 i_X4_ (L_I ._ {j, _ g Composition according to Claim 1, characterized in that the acidic organic compound comprises at least one aliphatic, cycloaliphatic or aromatic carboxylic acid. 2. I 4 I (XVI) 30 R & \ R H wherein X1, X2, X3 and X4 independently of one another denote oxygen or sulfur; R1 and R2 independently represent a hydrogen carbyl rhythm; L 96223 97 R3, R4 and R5 independently of one another are hydrogen or a hydrocarbyl group; R6 is a hydrocarbyl group; and a and b are each independently 0 0 or 1; (C-3) sulfur-combined dithiocarbamate of formula R1 R2 10 Sx-f-C-rC - S (SJCNRSr6) 2 (XVII) R3 J14 where R1, R2 and R3 independently of one another are hydrogen or a hydrocarbyl group; R 4 is H, OH or a hydrocarbyl group; R 5 and R 6 independently represent hydrogen, hydrocarbyl or hydroxyhydrocarbyl; or R 3 and R 4 together and / or R 5 and R 6 together and / or R 1 and R 3 together and / or R 2 and R 4 together may form cyclic groups; and x is a number from 1 to 8; (C-4) a sulfur-containing compound of the formula R1 «3« 1-C- (S) x -c-52 (I)] t2 wherein R1, R2, R3 and R4 independently of one another are hydrogen or a hydrocarbyl group; R1 and / or R3 may be G1 or G2; R 1 and R 2 and / or R 3 and R 4 may together represent an alkylene group having about 4 to 7 carbon atoms; G1 and G2 independently represent C (X) R, COOR, C = N, R5-C = NR6, CON (R) 2 or NO2, and G1 may also be CH2OH, where X is O or S, R and R5 independently represent hydrogen or a hydrocarbyl group; R6 is H or a hydrocarbyl group; when both G1 and G2 are R5C = NR6, the two R6 groups may together denote a hydrogencarbylene group connecting two nitrogen atoms; when G1 in CH2OH and G2 is COOR, intramolecular condensation of G1 and G2 may form a lactone; and x is an integer from 1 to 8; and (C-5) a mixture of any two or more of (C-1) -15 (C-4). 3 O wherein R is a hydrocarbyl group having from about 4 to about 400 carbon atoms; Ar is an aromatic group; a and b are numbers at least 1, the sum of a and b being in the range 2 up to the number of hydrogens of the aromatic nucleus or nuclei of Arin to be replaced. Composition according to Claim 1, characterized in that the acidic organic compound comprises at least one compound of the formula II or III. 25 R-CHCl 3 CH 2 CO 2 or | CH2 '\ (II) <rII> 30 wherein R is a hydrocarbyl group. Composition according to Claim 1, characterized in that the acidic organic compound is a compound of formula (V) II 96223 99 (R 8) c - (XH) a 5 (V) X (R 7) b wherein R 7 and R 8 are aliphatic hydrocarbyl groups, a and 10b are from 0 to 5, provided that the sum of a and b is not more than 5, and c is from 0 to 4. Composition according to Claim 1, characterized in that the acidic organic compound comprises at least 1 compound of the formula (XII) R -Ar- (OH). (XII) Composition according to claim 1, characterized in that the metal in said salt (A) is lithium, sodium, magnesium, calcium, potassium, barium, aluminum, zinc, copper or a mixture of two or more of these. Composition according to Claim 1, characterized in that component (B) is benzotriazole. A composition according to claim 1, characterized in that it comprises: (A) at least one compound selected from magnesium sulfonate, sodium sulfonate, magnesium salicylate or a mixture of two or more thereof; 96223 100 (B) at least one of benzotriazole sol, tolyltriazole or a mixture thereof; (C) a mixture of (C-1) at least one phosphorodithioic acid amide; and 5 (C-2) at least one phosphorodithioic acid ester. Il 96223 101