Title: GEAR LUBRICANT COMPOSITIONS

BACKGROUND OF THE INVENTION Field of the Invention This invention concerns lubricating oil composition which are especially adapted for use in mechanical system where gears are subjected to great stress and extremel high pressures such as those found in automotive rea axles or off highway transmissions and gear boxes. Mor particularly, the present invention relates to lubricant and functional fluids which are useful particularly i environments characterized by high pressure and rubbin surfaces. Description of the Related Art U.S. Patent 3,082,187 (Fuchsman, et al, March 19, 1963) broadly stated comprises a polyal ene having inti¬ mately dispersed therein (a) from about 0.005% to about 10% by weight of an organic phosphite ester having the general formula:

wherein R. , R ₂ and R, are each selected from the group consisting of hydrogen and hydrocarbon radicals containing from 1 to 21 carbon atoms, at least two of R. , R« and R_ being a hydrocarbon radical; and (b) from about 0.005% to

- 2

about 10% _^ b weight of a sulfurized phenol having the general formula:

wherein n is from 1 to 10, and R' and R" are each selected from the group consisting of hydrogen and alkyl radicals containing from 1 to 18 carbon atoms, at least one of R' and R" being alkyl. U.S. Patent 3,583,915 (Myers, June 8, 1971) deals with the- combination of a di(organo)hydrogen phosphonate, in which at least one organo group is an aliphatic group containing at least 14 carbon atoms, in admixture with an active sulfur compound evidences synergistic load carrying properties in organic base media.

The di(organo)phosphonates have the structure

RO

^

R'O 'H

wherein R and R ¹ are individually alkyl or alkenyl from 1 to 30 carbon atoms and at least one of which is an aliphatic group of at least 14 carbon atoms, and prefera¬ bly over 16 carbon atoms. These groups may have the same number of carbon atoms or different, and one may be further substituted by the presence of alkoxy ^* , hydroxy and halogen substituents. Dioctadecyl and dioleyl phosphonates are of particular interest. The phosphonates used may be produced by known methods of synthesis.

The second co-additive may be designated as an active sulfur compound. The compounds of this class include organic sulfides and sulfurized hydrocarbons having up to 65% sulfur. Encompassed in this class are those compounds

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wherein the sulfur is "loosely-bound," and th non-corrosive or "firmly-bound" sulfur compounds. Mor specifically, such compounds include sulfurized animal an vegetable oils and fats and ^' mineral oils containing a least 1% and up to 20% sulfur; up to about 10% fo "firmly-bound" and from about 10% to 20% or more fo "loosely-bound. "

U.S. Patent 3,446,739 (Papayannopoulos, May 27, 1969 provides organic compositions which contain additive effective for imparting limited-slip properties thereto but which do not detract from the extreme pressure proper ties of such compositions.

These organic compositions comprise an alky phosphite and an ester of a fatty acid and a fatty alco hoi, wherein alkyl groups of the phosphite and alky groups of the fatty acid and the fatty alcohol eac contain from about 12 to about 30 carbon atoms. I general, in its preferred applications, this paten contemplates organic compositions exhibiting effectiv extreme pressure properties under varying operatin conditions, and which also contain a small amount of th above-described additive limited-slip improver mixture usually from about 0.1% to about 40% by weight, an preferably from about 0.5% to about 10% by weight of th total weight of such composition. Insofar as the additiv mixture itself is concerned, the alkyl phosphite i present in an amount from about 10% to about 90% b weight, and, correspondingly, the ester is present in a amount from about 90% to about 10% by weight of the tota weight of said mixture.

U.S. Patent 3,321,401 (Ford, et al, May 23, 1967) provides for lubricating compositions containing a combi nation of additives that has the effect of improving th load-carrying properties of the compositions. According to the patent, there is provided a lubri cating composition comprising a lubricating base oil

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having dissolved therein small proportions each of (a) an organic phosphite of the formula:

where the R s are alkyl, cycloalkyl, aryl or aralkyl groups and the total number of carbon atoms in the mole¬ cule is 1 to 20 and (b) another oil-soluble organic phosphorus compound of the general formula:

where X is an oxygen or sulfur atom and Y is R 0 or

.E ² —N

where R 1 has the value previously given, R2 and R3 are hydrogen or alkyl, cycloalkyl, aryl or aralkyl groups or together with the nitrogen atom form a ring which, apart from the nitrogen, is made up of hydrocarbon groups or hydrocarbon groups and a second hetero atom, e.g. oxygen, and the total number of carbon atoms in the molecule is 1 to 30.

SUMMARY OF THE INVENTION Gear oil compositions are described which comprise a lubricating base oil having dissolved therein:

(A) at least one sulfur compound characterized by the structural formula

- 5 -

wherein

R ² , R 3 and R4 are each independently H or hydrocarbyl groups;

1 3 1 2

R and/or R may be G or G ;

R 1 and R2 and/or R3 and R4 together may be alkylene

R, C=N, wherein H or a

groups together may be a hydrocarbylene group linking the two nitrogen atoms; when G 1 is CH ₉ 0H and G2 is COOR, a lactone may be

1 2 formed by intramolecular condensation of G and G ; and x is an integer from 1 to about 8; (B) at least one phosphite ester characterized by the formula

R'O 0 II

P- H

R _.

7 8 wherein R and R are hydrocarbyl based groups; and

(C) at least one metal overbased composition,

DETAILED DESCRIPTION OF THE INVENTION (A) Sulfur Compounds

The sulfur compounds which are used in the compositions in accordance with the present invention are compounds characterized by the structural formula

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R ^J R ^" (I)

I

C (S ) C - R ⁴

wherein .1

R ² , and are each independently H or hydrocarbyl groups;

1 3 1 2

R and/or R may be G or G ; R 1 and R2 an-d/ or R3 and R4 together may be alk lene groups containing about 4 to about 7 carbon atoms ;

1 2 G and G are each independently C (X) R, COOR, C=N,

5 6 1

^• R -C=NR , C0N (R) ₂ , or 0 ₂ , and G may be CH ₂ OH, wherein X is 0 or. S , each of R and R are independently H or a g hydrocarbyl group, R is H or a hydrocarbyl group;

^' when both G and G are R C=NR , the two R groups together may be a hydrocarbylene group linking the two nitrogen atoms; when G 1 is CH-,0H and G2 is COOR, a lactone may be formed by intramolecular combination of G 1 and G2; and x is an integer from 1 to about 8.

1 2 3 4 R , R , R and R in Formula I are each independently hydrogen or hydrocarbyl groups. The hydrocarbyl groups may be aliphatic or aromatic groups such as alkyl,

1 2 cycloalkyl, alkaryl, aralkyl or aryl groups. R and R

3 4 and/or R and R together may be alkylene groups containing from about 4 to about 7 carbon atoms. In these

1 2 embodiments, R and R together with the carbon atom

1 2 bonded to R and R in Formula I will form a cycloalkyl

3 4 group. Similarly, R and R together with the carbon atom

3 4 bonded to R and R will form a cycloalkyl group. Also, R 1 and/or R3 may be G1 or G2.

1 2 3 4 The hydrocarbyl groups R , R , R and R usually will contain up to about 30 carbon atoms. Preferably, the hydrocarbyl groups are alkyl groups containing up to about

10 carbon atoms. Specific examples of hydrocarbyl groups include methyl, ethyl, isopropyl, isobutyl, secondary

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butyl, cyclohexyl, cyclopentyl, octyl, dodecyl, octadecyl eicosyl, behenyl, triacontonyl, phenyl, naphthyl phenethyl, octyl-phenyl, tolyl, xylyl, dioctadecyl-phenyl, triethyl-phenyl, chloro-phenyl, methoxy-phenyl dibromo-phenyl, nitrophenyl, 3-chlorohexyl, etc. As use in the specification and claims, the term "hydrocarby group" is intended to include groups which ar substantially hydrocarbon in character. Thus, th hydrocarbyl groups include groups which may contain polar substituent such as chloro, bromo, nitro, ether, etc., provided that the polar substituent is not presen in proportions so as to alter significantly th hydrocarbon character of the group. In most instances, there should be no more than one polar substituent in each group.

The sulfur compounds of the present invention as represented by Formula I may be thia-aldehydes or thia-ketones. That is, G 1 and G2 in Formula I are C(0) groups. Various thia-bisaldehyde compounds are known, and the synthesis of such compounds have been described in the prior art such as in U.S. Patents 3,296,137 and 2,580,695.

Thia-aldehydes and thia-ketones are most conveniently prepared by the sulfurization of a suitable aldehyde or ketone such as one having the structural formula

R ¹ R ² CHC(0)R

wherein R 1 is hydrogen, hydrocarbyl groups or C(0)R, R2 is hydrogen or a hydrocarbyl group, and R is hydrogen or a hydrocarbyl group. In these instances, R 3 and R4 in Formula I will be the same as R 1 and R2, respectively, and both G 1 and G2 are C(0)R groups. When R1 is C(0)R, the sulfurization product contains four C(0)R groups.

The sulfurization can be accomplished by reacting the aldehyde or ketone with a sulfur halide such as sulfur monochloride (i.e., S ₂ C1 ₂ ) , sulfur dichloride, sulfur

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monobromide, sulfur dibromide, and mixtures of sulfur halide with sulfur flowers in varying amounts.

The reaction of an aldehyde or ketone with a sulfur halide may be effected simply by mixing the two reactants at the desired temperature which may range from about -30°C to about 250°C or higher. The preferred reaction temperature generally is within the range of from about 10 to about 80°C. The reaction may 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 the control of the reaction temperature and a thorough mixing of the reactants.

The relative amounts of the aldehyde or ketone and the sulfur halide may vary over wide ranges. In most instances, the reaction involves two moles of the aldehyde or ketone and one mole of the sulfur halide. In other instances, an excess of either one of the reactants may be used. When sulfur compounds are desired which contain more than two sulfur atoms, (e.g., x is an integer from 3-8) these compounds can be obtained by reacting the aldehydes with a mixture of sulfur halide and sulfur. Sulfurization products wherein G 1 and G2 are different and may be obtained by sulfurizing mixtures of aldehydes and ketones or mixtures of ketones containing different C(0)R groups.

Specific examples of thia-aldehydes and thia-ketones include compounds as represented by Formula I wherein G and G are C(0)R groups, x is 1 to 4 and R ¹ , R ² , R ³ , R ⁴ and R are as follows:

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si R! R R! R H ₃ H CH ₃ H H

CH ₃ CH ₃ CH ₃ CH ₃ CH ₃

^C 25 H C ₂ H ₅ H H

CH ₃ C(0)- H CH ₃ C(0)- H CH ₃

CH ₃ C(0)- H CH ₃ C(0)- H H

C ₂ H ₅ C ₂ H ₅ H

^C 4 ^H 11 ^C 4 ^H 11

The thia-aldehydes and thia-ketones which can be prepared as described above can be converted to derivatives containing other functional groups which are normally derivable therefrom. Thus, in some of the embodiments of the invention, a thia-aldehyde or thia-ketone is converted to a derivative through contemporaneous conversion of the aldehyde or ketone groups to other terminal groups by chemical reactants and/or reagents. In such reactions, the thia group (S ) and the R 1-R4 groups are inert and remain unchanged in the compound. For example, the thia-bisaldehydes can be converted to hydroxy-acid derivatives wherein one of the aldehyde groups (G ) is converted to a COOH group, and the

2 other aldehyde groups (G ^Λ ) is converted to a CH.-0H group.

The hydroxy-acid derivatives are obtainable most conveniently by treating the corresponding thia-bisaldehyde with an alkaline reagent such as an alkali metal hydroxide or alkaline earth metal hydroxide, preferably a dilute aqueous solution thereof containing from about 5 to about 50% by weight of the hydroxide in water. Such alkaline reagents may be sodium hydroxide, potassium hydroxide, lithium hydroxide, barium hydroxide, calcium hydroxide, strontium hydroxide, etc. The hydroxy-acid is isolated from the reaction mixture by acidification with a mineral acid such as hydrochloric acid. The hydroxy-acid derivatives of thia-bisaldehydes can be represented by Formula la below.

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R ^J R ^w (la)

I I

HOCH, C' x C- •COOH

14

wherein R 1, R2 R3, R4 and x are as previously defined. Specific examples of such hydroxy-acid derivatives include

6-hydroxy-2,2,5,5-tetramethyl-3,4-dithiahexanoic acid

1 2 3 4 (i.e., conforming to Formula la wherein R , R , R and R are methyl and x is 2) ; 6-hydroxy-2,2-diethyl-5-propyl-5- butyl-3,4-dithiahexanoic acid; 6-hydroxy-2,2,5,5-tetra- ethyl-3,4-dithiahexanoic acid; etc.

By virtue of the presence of the hydroxy group and the carbpxylic group in the hydroxy-acids described by Formula la above, various other sulfur-containing compounds useful in the present invention can be obtained by the conversion of such hydroxy group and/or the carboxylic group to other polar groups normally derivable therefrom. Examples of such derivatives include esters formed by esterification of either or both of the hydroxy group and the carboxylic group; amides, imides, and acyl halides formed through the carboxylic group; and lactones formed through intramolecular cyclization of the hydroxy-acid accompanied with the elimination of water. The procedures for preparing such derivatives are well known to those skilled in the art, and it is not believed necessary to unduly lengthen the specification by including a detailed description of such procedures. More specifically, the carboxylic group (COOH) in Formula la can be converted to ester groups (COOR) and amide groups (CON(R) ₂ ) wherein the R groups may be hydrogen or hydrocarbyl groups containing from 1 to 30 carbon atoms and more generally from 1 to about 10 carbon atoms. Specific examples of such R groups include ethyl, propyl, butyl, phenyl, etc.

The procedures for preparing lactones through intramolecular cyclization of hydroxy-acids of Formula la

11 -

accompanied by the elimination of water are well known in the art. Generally, the cyclization is promoted by the presence of materials such as acetic anhydride, and the reaction is effected by heating the mixtures to elevated temperatures such as the reflux temperature while removing volatile materials including water.

The sulfur compounds characterized by structural

Formula I wherein G and/or G are R C=NR can be prepared from the corresponding thia-aldehydes and thia-ketones. These mono- and di-imine compounds are prepared by reacting one mole of the dialdehyde (C(O)H) or diketone

₅ (C(O)R ) with one and two moles of an amine, respectively.

The amines may be monoamines or polyamines. When polyamines are reacted with the thia-aldehydes or

5 thia-ketones [-C(0)R ], cyclic di-imines can be formed.

1 2 5 6

For example, when both G and G in Formula I are R C=NR , c the two R groups together may be a hydrocarbylene group linking the two nitrogen atoms. The amines which are reacted with the thia-aldehydes and thia-ketones to form the imines may be characterized by the formula

R ^β NH ₂

wherein R is hydrogen, or hydrocarbyl, or an amino hydrocarbyl group. Generally, the hydrocarbyl groups will contain up to about 30 carbon atoms and will more often be aliphatic hydrocarbyl groups containing from 1 to about 30 carbon atoms.

In one preferred embodiment, the hydrocarbyl amines which are useful in preparing the i ine derivatives of the present invention are primary hydrocarbyl amines 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 are the lower alkyl amines such as methyl amine, ethyl amine,

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n-propyl amine, n-butyl amine, n-amyl amine, n-hexyl amine-; those known as aliphatic primary fatty amines and commercially known as "Armeen" primary amines (products available from Armak Chemicals, Chicago, Illinois) . Typical fatty amines include alkyl amines such as n-hexylamine, n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-octadecylamine (stearyl amine) , etc. These Armeen primary amines are available in both distilled and technical grades. While the distilled grade will provide a purer reaction product, the desirable amides, imines and imides will form in reactions with the amines of technical grade. Also suitable are mixed fatty amines such as Armak*s Armeen-C, Armeen-0, Armeen-OL, Armeen- , Armeen-HT, Armeen S and Armeen SD.

In another preferred embodiment, the amine derived products of this invention are those derived from tertiary-aliphatic primary amines having at least about 4 carbon atoms in the alkyl group. For the most part, they are derived from alkyl amines having a total of less than about 30 carbon atoms in the alkyl group.

Usually the tertiary aliphatic primary amines are monoamines represented by the formula

CH,

C — NH, I

CH„

wherein R is a hydrocarbyl group containing from one to about 30 carbon atoms. Such amines are illustrated by tertiary-butyl amine, tertiary-hexyl primary amine, 1-methyl-1-amino-cyclohexane, tertiary-octyl primary amine, tertiary-decyl primary amine, tertiary-dodecyl primary amine, tertiary-tetradecyl primary amine, tertiary-hexadecyl primary amine, tertiary-octadecyl primary amine, tertiary-tetracosanyl primary amine, tertiary-octacosanyl primary amine.

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Mixtures of amines are also useful for the purposes of this invention. Illustrative of amine mixtures of this type are "Primene 81R" which is a mixture of C,, ,, tertiary alkyl primary amines and "Primene JM-T" which is a similar mixture of C,g_ ₂₂ tertiary alkyl primary amines (both are available from Rohm and Haas Company) . The tertiary alkyl primary amines and methods for their preparation are well known to those of ordinary skill in the art and, therefore, further discussion is unnecessary. The tertiary alkyl primary amine useful for the purposes of this invention and methods for their preparation are described in U.S. Patent 2,945,749 which is hereby incorporated by reference for its teaching in this regard.

Primary amines in ^' which the hydrocarbon chain comprises olefinic unsaturation also are useful. Thus, the R group may contain one or more olefinic unsaturation depending on the length of the chain, usually no more than one double bond per 10 carbon atoms. Representative amines are ^' dodecenylamine, myristoleylamine,. palmitoleylamine, oleylamine and linoleylamine. Such unsaturated amines also are available under the Armeen tradename.

The thia-aldehydes and thia-ketones also can be reacted with polyamines. Examples of useful polyamines include diamines such as mono- or dialkyl, symmetrical or asymmetrical ethylene diamines, propane diamines (1,2, or 1,3), and polyamine analogs of the above. Suitable commercial fatty polyamines are "Duomeen C" (N-coco-3,3- diaminopropane) , "Duomeen S" (N-soya-1,3-diaminopropane) , "Duomeen T" (N-tallow-1,3-diamonopropane) , or "Duomeen 0" (N-oleyl-1,3-diaminopropane) . "Duomeens" are commercially available diamines described in Product Data Bulletin No. 7-10R1 of Armak Chemical Co., Chicago, Illinois.

The reaction of thia-aldehydes (and ketones) with primary amines or polyamines can be carried out by techniques well known to those skilled in the art. Generally, the thia-bisaldehyde or ketone is reacted with

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the amine or polyamine by reaction in a hydrocarbon solvent at an elevated temperature, generally in an atmosphere of nitrogen. As the reaction proceeds, the water which is formed is removed such as by distillation. Sulfur compounds characterized by structural Formula I wherein G 1 and G2 may be COOR, CsN and N0 ₂ can be prepared by the reaction of compounds characterized by the structural formula

R ¹ (ID H C G

I. ²

wherein R 1 and R2 are as defined above, and G is COOR, C=N or O-, or mixtures of different compounds represented by

Formula II with a sulfur halide or a mixture of sulfur halides and sulfur. Generally, about one mole of sulfur halide is reacted with about two moles of the compounds represented by Formula II. In one embodiment, R also may G. In such instances, the sulfur compounds which are formed as a result of the reaction with the sulfur halide will contain four G groups which may be the same or different depending upon the starting material. For example, when a di-ketone such as 2,4-pentanedione is reacted with sulfur monochloride, the resulting product contains four ketone groups; when the starting material contains a ketone group and an ester group (e.g. , ethylacetoacetate) , the resulting product contains two ketone groups and two ester groups; and when the starting material contains two ester groups (e.g., diethylmalonate) , the product contains four ester groups. Other combinations of functional groups can be introduced into the sulfur products utilized in the present invention and represented by Formula I by selecting various starting materials containing the desired functional groups.

Sulfur compounds represented by Formula I where G 2 and/or G are C=N groups can be prepared by the reaction

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of compounds represented by Formula II wherein G is C=N and R 1 and R2 are hydrogen or hydrocarbyl groups.

Preferably, R 1 is hydrogen and R2 is a hydrocarbyl group.

Examples of useful starting materials include, for example, propionitrile, butyronitrile, etc. Compounds of Formula I where G 1 and G2 are N0 ₂ groups can be prepared by (1) reacting a nitro hydrocarbon R 1R2C(H)N0 _? with an alkali metal or alkaline earth metal alkoxide to form the salt of the nitro hydrocarbon, and (2) reacting said salt with sulfur monochloride in an inert, anhydrous nonhydroxylic medium to form a bis

(1-nitrohydrocarbyl) disulfide. Preferably the nitro hydrocarbon is a primary nitro hydrocarbon (R is hydrogen

2 and R is hydrocarbyl) . The starting primary nitro compounds used in carrying out this synthesis are well known. Illustrative compounds are nitroethane, 1-nitropropane, 1-nitrobutane, l-nitro-4-methylhexane, (2-nitroethyl) benzene, etc.

The nature of the alkanol used in obtaining the alkali or alkaline earth metal salt of the starting primary nitro compound is not critical. It is only necessary that it be appropriate for reaction with the metal to form the alkoxide. Because they are easily obtainable and inexpensive, the lower alkanols (i.e., alkanols of 1 to 4 carbon atoms) such as methanol, ethanol and butanol will usually be employed in the synthesis.

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

Ordinarily, it is preferable to maintain a temperature of about 0-10°C during the preparation of the metal salt. However, temperatures from about 0 to 25?C may be used in this step of the process. In the preparation of the bisdisulfide temperatures in the range

- 16 -

of -5 to +15°C may be used. Preferably, temperatures between about 0 to 5°C are used in this step of the process.

The -preparation of various thia-bisnitro compounds useful in the present invention is described in some detail in U.S. Patent 3,479,413, and the disclosure of this patent is hereby incorporated by reference. Representative examples of nitro sulfides useful in the present invention are: bis(l-nitro-2-phenylethyl) disulfide, bis(1-nitrodecyl) disulfide, bis(l-nitro- dodecyl) disulfide, bis (l-nitro-2-phenyldecyl) disulfide, bi(l-nitroτ2-cyclohexylethyl) disulfide, bis (1-nitropenta- decyl) disulfide, bis(l-nitro-3-cyclobutylpropyl) disulfide bis(l-nitro-2-nap thylethyl) disulfide, bis(l-nitro-3-p-tolylpropyl) disulfide, bis(l-nitro-2- σyclooctylethyl) .disulfide, and the like.

The carboxylic ester-containing sulfur compounds

(i.e., G is COOR) described above can be utilized to prepare other sulfur compounds useful in the present invention. For example-, the _. ester (COOR) can be hydrolyzed to the 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 those represented by the formula

(R) ₂ NH

wherein each R is hydrogen or a hydrocarbyl group. These hydrocarbyl groups may contain from 1 to about 30 carbon atoms and more generally will contain from about 1 to 10 carbon atoms.

1 2 3 .

As mentioned above, R and R and/or R and R ^" together may be alkylene groups containing from about 4 to about 7 carbon atoms. In this embodiment, R 1 and R2 (and

3 4 R and R ) form a cyclic compound with the common carbon atom (i.e., the carbon atoms which is common to R 1 and R2

- 17 -

in Formula I. Such derivatives of structural Formula can be prepared by reacting the appropriately substitute saturated cyclic material with sulfur halides as describe above. Examples of such cyclic starting materials includ cyclohexane carboxaldehyde (CgH^CHO) , cyclohexan carbonitrile (C _fi H_._.CN), cyclohexane carboxamid (C _fi H ₁ .CONH-) , cyclohexane carboxylic acid (C _g H- ..COOH) cyclobutane carboxylic acid (C.H-COOH) , cycloheptan carboxylic acid ( ^C ₇ ^H _ι COOH) / cycloheptyl cyanid (C ₇ H ₁₃ C ) , etc.

The following Examples A-l to A-20 illustrate th preparation of the sulfur compositions represented b Formula I. Unless otherwise indicated in the examples an elsewhere in this specification and claims, all parts an percentages are by weight, and all temperatures are i degrees centigrade.

Example A-l Sulfur monochloride (1620 parts, 12 moles) is charge to a 5-liter flask and. warmed under nitrogen to temperature of about 53°C whereupon 1766 parts (24. moles) of isobutyraldehyde are added dropwise unde nitrogen at a temperature of about 53-60°C over a perio of about 6.5 hours. After the addition of th isobutyraldehyde is completed, the mixture is heate slowly over a period of 6 hours to a temperature of abou 100°C while blowing with nitrogen. The mixture is maintained at 100°C with nitrogen blowing for a period o about 6 hours and volatile materials are removed from the reaction vessel. The reaction product then is filtered through a filter aid, and the filtrate is the desired product containing 31.4% sulfur (theory, 31.08%). The desired reaction product, predominantly 2,2'-dithiodi- isobutyraldehyde, is recovered in about 95% yield.

Example A-2 Sulfur monochloride (405 parts, 3 moles) is charged to a 2-liter flask and warmed to about 50°C under nitrogen whereupon 769.2 parts (6 moles) of 2-ethylhexanal are

added dropwise. After about 45 minutes of addition, the reaction mixture exotherms to about 65°C. The addition of the remaining aldehyde is continued at about 55°C over a period of about 5 hours. After allowing the mixture to stand overnight, the mixture is heated slowly to 100°C and maintained at this temperature. Additional 2-ethylhexanal (20 parts) is added, and the mixture is maintained at 100°C while blowing with nitrogen. The reaction mixture is stripped to 135°C/10 mm. Hg. and filtered through a filter aid. The filtrate is the desired product containing 19.9% sulfur (theory, 20.09).

Example A-3 Sulfur monochloride (270 parts, 2 moles) and 64 parts (2 moles) of sulfur are charged to a 1-liter flask and heated to 100°C for 3 hours. The mixture is cooled to about 50°C whereupon 288.4 parts (4 moles) of isobutyraldehyde are added dropwise under nitrogen at about 50-57°C. After all of the aldehyde is added, the mixture is heated to 100°C and maintained at this temperature for about one day under nitrogen. . The reaction mixture is cooled to room temperature and filtered through a filter aid. The filtrate is the desired product containing 38% sulfur (theory, 31.5-40.3% for a di- and tri-sulfide product) . Example A-4

Sulfur monochloride (270 parts, 2 moles) and sulfur

(96 parts, 3 moles) are charged to a 1-liter flask and heated to 125°C. After maintaining the mixture at this temperature for several hours, the mixture is cooled to 50°C, and 288.4 parts (4 moles) of isobutyraldehyde are added while blowing with nitrogen. The reaction temperature is maintained at about 55°C, and the addition of the isobutyraldehyde is completed in about 4 hours. The mixture is heated to 100°C while blowing with nitrogen and maintained at this temperature for several hours. The mixture is filtered, and the filtrate is the desired product containing 40.7% sulfur indicating the product to

- 19 - -

be a mixture of di-, tri- and possibly tetra-sulfid product.

Example A-5 Sulfur dichloride (257.5 parts, 2.5 moles) is charge to a 1-liter flask and warmed to 40°C under nitroge whereupon 360.5 parts (5 moles) of isobutyraldehyde are added dropwise while maintaining the reaction temperature at about 40-45°C. The addition of the isobutyraldehyde requires about 6 hours, and the reaction initially is exothermic. The reaction mixture is maintained at room temperature overnight. After maintaining the reaction mixture at 50°C for one hour while blowing with nitrogen, the mixture is heated to 100°C while collecting volatile materials. An additional 72 parts of isobutyraldehyde is added, and the mixture is maintained at 100°C for 4 hours, stripped, and filtered through filter aid. The filtrate is the desired product containing 24% sulfur indicating that the product is a mixture of the mono- and di-sulfide products. Example A-6

Methanol (500 parts) is charged to a 1-liter flask, and 23 parts (1 mole) of sodium are added slowly in a nitrogen atmosphere. The mixture is cooled in an ice bath to about 5-10°C whereupon 89 parts (1 mole) of 1-nitropropane are added dropwise. The reaction mixture is filtered, and the solids are washed with ether. A slurry is prepared of the solids in ether, and the slurry is cooled to 0-5°C whereupon 65.5 parts (0.5 mole) of sulfur monochloride are added dropwise under nitrogen over a period of about 2.5 hours. An additional 200 parts of ether are added, and the mixture is filtered. The ether layer is washed with ice water and dried over magnesium sulfate. Evaporation of the ether yields the desired product containing 9.24% nitrogen and 38% sulfur. Example A-7

Sodium hydroxide (240 parts, 6 moles) is dissolved in water, and the solution is cooled to room temperature

- 20 -

whereupon 824 parts (4 moles) of 2,2*-dithiodiisobutyral- dehyde prepared as in Example A-l are added over a period of about 0.75 hour. The reaction mixture exotherms to about 53°C and after stirring for about 3 hours, the 5 reaction mixture is extracted three times with 500 parts of toluene. The aqueous layer is cooled in an ice bath to about 7°C, and 540 parts of concentrated hydrochloric acid are added slowly at a temperature below about 10°C. A white solid forms in the reaction vessel, and the mixture 0 is filtered. The solid is washed with ice water and dried. The solid material is the desired product containing 27.1% sulfur (theory, 28.6%).

Example A-8 Methyl isobutyl ketone (300.6 parts, 3 moles) is 5 charged to a 1-liter flask and heated to 60°C whereupon 135 parts (1 mole) of sulfur monochloride are added dropwise under nitrogen over a period of about 4 hours. The- reaction mixture is maintained at about 60-70°C during the addition, and when all of the sulfur monochloride has 0 been added, the material is blown with nitrogen while

- heating to 105°C. The mixture is maintained at 105-110°C for several hours while collecting volatile materials.

After stripping to 95°C at reduced pressure, the reaction mixture is filtered at room temperature through a filter 5 aid and the filtrate is the desired product containing 30.1% sulfur (theory, 24.4%).

Example A-9 A mixture of 400 parts (4 moles) of 2,4-pentanedione and 800 parts of ethyl acetate is prepared, cooled to 0 10°C, and 270 parts (2 moles) of sulfur monochloride are added dropwise over a period of 4 hours at about 10-18°C. The mixture is allowed to stand at room temperature overnight, and after cooling to -about 5°C is filtered. The solid is washed with mineral spirits and air dried.

35 The solid material is the desired product containing 26.3% sulfur (theory, 24.4%).

- 21 -

Example A-10 A mixture of 390 parts (3 moles) of ethylacetoacetat and 900 parts of ethyl acetate is prepared and cooled t 10°C whereupon 202.5 parts (1.5 moles) of sulfu monochloride are added dropwise under nitrogen over period of 3 hours. The temperature of the reactio reaches about 20°C during the addition. After standin overnight at room temperature, the mixture is cooled t about 7°C and filtered. The solids are washed wit textile spirits and air dried. The solid material is th desired product containing 9.99% sulfur and having melting point of 104-108°C.

Example A-11 A mixture of 650 parts (5 moles) of ethylacetoacetat and 730 parts (5 moles) of Alfol 810, a commercial mixtur of alcohols containing from 8 to 10 carbon atoms, i prepared and heated to a temperature of 130°C whil collecting distillate. The temperature is slowl increased to 200°C as ethanol is distilled. The residu is stripped to 10 mm. Hg./120°C, and the residue is th desired product.

A mixture of 1035 parts (4.5 moles) of th ethylacetoacetate/Alfol 810 product and 800 parts of ethy acetate is prepared and cooled to 10°C whereupon 304 part (2.25 moles) of sulfur monochloride are added dropwis under nitrogen for a period of about 3 hours whil maintaining the reaction temperature between 10-15°C. After allowing the mixture to stand overnight at roo temperature, the mixture is blown with nitrogen and heate to 110°C while collecting solvent. After stripping -to 133°C/70 mm. Hg. , the mixture is filtered through a filte aid, and the filtrate is the desired product containing 11.75% sulfur (theory, 12.26%).

Example A-12 A mixture of 480 parts (3 moles) of diethylmalonate and 800 parts of ethyl acetate is prepared and cooled to 10°C whereupon 202.5 parts (1.5 moles) of sulfur

- 22 -

monochloride are added dropwise under nitrogen at 10-15°C over a period of one hour. After allowing the mixture to stand overnight at room temperature, the mixture is heated to reflux to remove most of the solvent. The mixture then is heated to 120°C while blowing with nitrogen, stripped to a temperature of 130°C/90 mm. Hg. , and filtered through a filter aid at room temperature. The filtrate is the desired product containing 15.0% sulfur.

Example A-13 A mixture of 280 parts (3 moles) of diethylmalonate, 876 parts (6 moles) of Alfol 810 and 3 parts of para-toluenesulfonic acid is prepared and heated to 140°C as ethanol is distilled. The temperature is slowly increased to 180°C while removing additional ethanol. A total of 237 parts of ethanol is collected, and 6 parts of sodium bicarbonate is added to the reaction mixture which is then stripped to 130°C at 10 mm. Hg. The residue is filtered through a filter aid, and the filtrate is the desired ester. A mixture . of 720 parts (2 moles) of the above-prepared diethylmalonate/Alfol 810 product and 500 parts of ethyl acetate is prepared and cooled to about 7°C whereupon 135 parts (1 mole) of sulfur monochloride are added dropwise under nitrogen over a period of about 2 hours while maintaining the reaction mixture at 7-12°C. The solution is allowed to stand at room temperature overnight, warmed to reflux for 3 hours, and blown with nitrogen while heating to a temperature of about 140°C to remove solvent. The mixture then is stripped to 140°C at reduced pressure and filtered at room temperature. The filtrate is the desired product containing 7.51% sulfur.

Example A-14 A mixture of 310 parts (4.2 moles) of 1,2-diaminopropane and 1200 parts of water is prepared and cooled to room temperature whereupon 412 parts (2 moles) of a product prepared as in Example A-l are added. The temperature of the mixture reaches 40°C whereupon solids

- 23 -

begin to form. The __ slurry is maintained at roo temperature for about 4 hours and filtered. The solid i washed with water, dried and recovered. The solid is th desired product containing 10.1% nitrogen and 25.7 sulfur. The crude product melts at about 106-112°C an the product recrystallized from a methanol/ethanol mixtur has a melting point of 114-116°C.

Example A-15 A mixture of 291 parts (1.3 moles) of the hydrox monoacid prepared as in Example A-7, 156 parts (2.6 moles) of normal propanol, 100 parts of toluene and 2 parts o para-toluenesulfonic acid is prepared and heated to th reflux temperature while removing water. After wate elimination begins to slow down, an additional one part o the para-toluenesulfonic acid is added, and the refluxin is continued while collecting additional water. Sodiu bicarbonate (5 parts) is added and the mixture is strippe at atmospheric pressure to a temperature of 110°C, an thereafter under reduced pressure to 120°C. The residu is filtered at room temperature through a filter aid, an the filtrate is the desired product containing 24.4% sulfur (theory, 24%) .

Example A-16 A mixture of 448 parts (2 moles) of the hydroxy monoacid prepared as in Example A-7, and 306 parts (3 moles) of acetic anhydride is prepared, heated to about 135°C and maintained at this temperature for about 6 hours. The mixture is cooled to . room temperature, filtered, and the filtrate is stripped to 150°C at reduced pressure. The residue is filtered while hot, and the filtrate is the desired lactone containing 29.2% sulfur (theory, 31%) .

Example A-17. A mixture of 412 parts (2 moles) of a dithiabisalde- hyde prepared as in Example A-l and 150 parts of toluene is prepared and heated to 80°C whereupon 382 parts (2 moles) of Primere 81R are added dropwise while blowing

- 24 -

with nitrogen at a temperature of 80-90°C. A water azeotrope is removed during the addition of the Primene 81R, and after the addition is completed, the temperature is raised to 110°C while removing additional azeotrope. 5 The residue is stripped to 105°C at reduced pressure and filtered at room temperature through a filter aid. The filtrate is the desired product containing 16.9% sulfur (theory, 16.88%) and 3.64% nitrogen (theory, 3.69%).

Example A-18 0 The general procedure of Example A-17 is repeated except that only 206 parts of the thia-bisaldehyde of Example A-l is utilized in the reaction.

Example A-19 The general procedure of Example A-17 is repeated 5 except that the bisaldehyde of Example A-l is replaced by an equivalent amount of the bisaldehyde of Example A-2.

Example A-20 The general procedure of Example A-17 is repeated except that the bisaldehyde of Example A-l is replaced by 0 . an equivalent amount of the bisaldehyde of Example A-4.

(B) The Phosphite Ester

The phosphite esters which are included in the compositions of the present invention are characterized by the formula:

25

7 8 wherein R and R are ^' hydrocarbyl based groups. The

1 2 hydrocarbyl groups R and R each contain from 1 to about

30- 30 carbon atoms; preferably from 4 to 12 carbon atoms and most preferably from 8 to 10 carbon atoms.

As used in this specification and appended claims, the terms "hydrocarbyl" or hydrocarbon-based" denote a

. group having a carbon atom directly attached to the

- 25 -

remainder of the molecule and having predominantly hydro carbon character within the context of this invention Such groups include the following:

(1) Hydrocarbon groups; that is, aliphatic, (e.g. alkyl or alkenyl) , alicyclic (e.g., cycloalkyl o cycloalkenyl) , aromatic, aliphatic- and aliσyclic substituted aromatic, aromatic-substituted aliphatic an alicyclic groups, and the like, as well as cyclic group wherein the ring is completed through another portion o the molecule (that is, any two indicated substituents ma together form an alicyclic group) . Such groups are know to those skilled in the art. Examples include methyl, ethyl, octyl, decyl, octadecyl, cyclohexyl, phenyl, etc.

(2) Substituted hydrocarbon groups; that is, group containing non-hydrocarbon substituents which, in th context of this invention, do not alter the predominantl hydrocarbon character of the group. Those skilled in th art will be aware of suitable substituents: Example include halo, hydroxy, nitro, cyano, alkoxy, acyl, etc. (3) Hetero groups; that is, groups which, whil predominantly hydrocarbon in character within the contex of this invention, contain atoms other than carbon in chain or ring otherwise composed of carbon atoms. Suit able hetero atoms will be apparent to those skilled in the art and include, for example, nitrogen, oxygen and sulfur.

In general, no more than about three substituents or hetero atoms, and preferably no more than one, will be present for each 10 carbon atoms in the hydrocarbyl group.

Terms such as "alkyl-based group", "aryl-based group" and the like have meaning analogous to the above with respect to alkyl and aryl groups and the like.

The R group may comprise a mixture of hydrocarbyl groups derived from commercial alcohols. Examples of some preferred monohydric alcohols and alcohol mixtures include the commercially available "Alfol" alcohols marketed by Continental Oil Corporation. Alfol 810 is a mixture containing alcohols consisting essentially of

- 26 -

straight-chain, primary alcohols having from 8 to 10 carbon atoms. Alfol 12 is a mixture comprising mostly C, ₂ fatty alcohols. Alfol 1218 is a mixture of synthetic, primary, straight-chain alcohols having 12 to 18 carbon 5 atoms. The Alfol 20+ alcohols are mostly, on an alcohol basis, C _2n alcohols as determined by GLC (gas-liquid-chromatography) . The Alfol 22+ alcohols are C _ια __ primary alcohols having mostly, on an alcohol basis, C_ ₉ alcohols. These Alfol alcohols can contain a

10 fairly large percentage (up to 40% by weight) of paraffinic compounds which can be removed before the reaction if desired.

Another example of a commercially available alcohol mixture .is Adol 60 which comprises about 75% by weight of

15 a straight-chain C ₂₂ primary alcohol, about 15% of a C _2Q primary alcohol and about 8% of C _lg and C ₂₄ alcohols. Adol 320 comprises predominantly oleyl alcohol. The Adol alcohols are marketed by Ashland Chemical.

A variety of mixtures of monohydric fatty alcohols

20 derived from naturally occurring triglycerides and ranging in chain length of from C _g to C, _g are available from Procter & Gamble Company. These mixtures contain various amounts of fatty alcohols containing mainly 12, 14, 16, or 18 carbon atoms. For example, CO-1214 is a fatty alcohol

25 mixture containing 0.5% of C. - alcohol, 66.0% of C._ alcohol, 26.0% of C.4. alcohol and 6.5% of Cl.b _. alcohol.

Another group of commercially available mixtures include the "Neodol" products available from Shell Chemi¬ cal Co. For example, Neodol 23 is a mixture of C. _ and 30 C _j - alcohols; Neodol 25 is a mixture of C ₁₂ and C ₁₃ alcohols, Neodol 25 is a mixture of C ₁₂ and C. alcohols; and Neodol 45 is a mixture of C. . to C ₁₅ linear alcohols. Neodol 91 is a mixture of C _g , C. and C. . alcohols.

The dihydrocarbyl phosphites (A) useful in the ^' 35 present invention may be prepared by techniques well known in the art, and many dihydrocarbyl phosphites are avail¬ able commercially. In one method of preparation, a lower

- 27 -

molecular weight dialkylphosphite (e.g., dimethyl) i reacted with alcohols comprising a straight-chain alcohol a branched-chain alcohol or mixtures thereof. As note above, each of the two types of alcohols may themselve comprise mixtures. Thus, the straight-chain alcohol ma comprise a mixture of straight-chain alcohols and th branched-chain alcohols may comprise a mixture o branched-chain alcohols. The higher molecular weigh alcohols replace the methyl groups (analogous to classi transesterification) with the formation of methanol whic is stripped from the reaction mixture.

In another embodiment, the branched chain hydrocarby group can be introduced into a dialkylphosphite by react ing the low molecular weight dialkylphosphite such a dimethylphosphite with a more sterically hindere branched-chain alcohol such as neopentyl alcoho

(2,2-dimethyl-l-propanol) . In this reaction, one of th methyl groups is replaced by a neopentyl group, and apparently because of the size of the neopentyl group, th second methyl group is not displaced by the neopenty alcohol. Another neo alcohol having utility in thi invention is 2,2,4-trimethyl-l-pentanol.

The following examples illustrate the preparation o the phosphite esters (B) which are useful in the composi tions of the present invention. Unless otherwise indicat ed in the following examples and elsewhere in th specification and claims, all parts and percentages are b weight, and all temperatures are in degrees centigrade.

Example B-l A mixture of 911.4 parts (7 moles) of 2-ethylhexanol, 1022 parts (7 moles) of Alfol 8-10, and 777.7 parts (7 moles) of dimethylphosphite is prepared and heated t 125°C while sparging with nitrogen and removing methanol as a distillate. After about 6 hours, the mixture was heated to 145°C and maintained at this temperature for a additional 6 hours whereupon about 406 parts of distillate are recovered. The reaction mixture is stripped to 150°C

- 28 -

at 50 mm. Hg. , and an additional 40 parts of distillate are recovered. The residue is filtered through a filter aid and the filtrate is the desired mixed dialkyl hydrogen phosphite containing 9.6% phosphorus (theory, 9.7%). 5 Example B-2

A mixture of 468.7 parts (3.6 moles) of 2-ethylhexanol, 1050.8 parts (7.20 moles) of Alfol 8-10, and 600 parts (5.4 moles) of dimethylphosphite is prepared and heated to 135°C while purging with nitrogen. The 0 mixture is heated slowly to 145°C and maintained at this temperature for about 6 hours whereupon a total of 183.4 parts of distillate are recovered. The residue is vacuum stripped to 145°C (10 mm. Hg.) and 146.3 parts of addi¬ tional distillate are recovered. The residue is filtered 5 through a filter aid, and the filtrate is the desired product containing 9.3% phosphorus (theory, 9.45%).

Example B-3 A mixture of 518 parts (7 moles) of n-butanol, 911.4 parts (7 moles) of 2-ethylhexanol, and 777.7 parts (7 0 moles) of dimethylphosphite is prepared and heated to 120°C while blowing with nitrogen. After about 7 hours, 322.4 parts of distillate are collected, and the material then is vacuum stripped (50 mm. Hg. at 140°C) whereupon an additional 198.1 parts of distillate are recovered. The 5 residue is filtered through a filter aid, and the filtrate is the desired product containing 12.9% phosphorus (theo¬ ry, 12.3%) .

Example B-4 A mixture of 193 parts (2.2 moles) of 0 2,2-dimethyl-l-propanol and 242 parts (2.2 moles) of dimethylphosphite is prepared and heated to about 120°C while blowing with nitrogen. A distillate is removed and collected, and the residue is vacuum stripped. The residue is filtered and the filtrate is the desired 5 product containing 14.2% phosphorus.

- 29 -

(C) The Metal Overbased Composition

Overbased salts of organic acids are widely known t those of skill in the art and generally include meta salts wherein the amount of metal present in them exceeds the stoichiometric amount. Such salts are said to hav conversion levels in excess of 100% (i.e., they comprise more than 100% of the theoretical amount of metal neede to convert the acid to its "normal" "neutral" salt) . Such salts are often said to have metal ratios in excess of one (i.e., the ratio of equivalents of metal to equivalents of organic acid present in the salt is greater than that required to provide the normal or neutral salt which required only a stoichiometric ratio of 1:1) . They are commonly referred to as overbased, hyperbased or superbased salts and are usually salts of organic sulfur acids, organic phosphorus acids, carboxylic acids, phenols or mixtures of two or more of any of these. As a skilled worker would realize, mixtures of such overbased salts can also be used.™ The terminology "metal ratio" is used in the prior art and herein to designate the ratio of the total chemi¬ cal equivalents of the metal in the overbased salt to the chemical equivalents of the metal in the salt which would be expected to result in the reaction between the organic acid to be overbased and the basically reacting metal compound according to the known chemical reactivity and stoichiometry of the two reactants. Thus, in a normal or neutral salt the metal ratio is one and in an overbased salt the metal ratio is greater than one. The overbased salts used as (C) in this invention usually have metal ratios of at least about 3:1. Typical¬ ly, they have ratios of at least about 12:1. Usually they have metal ratios not exceeding about 40:1. Typically salts having ratios of about 12:1 to about 20:1 are used. The basically reacting metal compounds used to make these overbased salts are usually an alkali or alkaline earth metal compound (i.e., the Group IA, IIA, and IIB

30 -

metals excluding francium and radium and typically excluding rubidium, cesium and beryllium) although other basically reacting metal compounds can be used. Compounds of Ca, Ba, Mg, Na and Li, such as their hydroxides and alkoxides of lower alkanols are usually used as basic metal compounds in preparing these overbased salts but others can be used as shown by the prior art incorporated by reference herein. Overbased salts containing a mixture of ions of two or more of these metals can be used in the present invention.

These overbased salts can be of oil-soluble organic sulfur acids such as sulfonic, sulfamic, thiosulfonic, sulfinic, sulfenic, partial ester sulfuric, sulfurous and thiosul uric acid. Generally they are salts of carbocylic or aliphatic sulfonic acids.

The carbocylic sulfonic acids include the mono- or poly-nuclear aromatic or cycloaliphatic compounds. The oil-soluble sulfonates can be represented for the most part by the following formulae:

[Rx—T—(SO3,)y]zMb. (IV)

[R ⁹ (S0 ₃ ) _a ] _d M _b (V)

In the above formulae, M is either a metal cation as described hereinabove or hydrogen; T is a cyclic nucleus such as, for example, benzene, naphthalene, anthracene, phenanthrene, diphenylene oxide, thianthrene, phenoxazine, diphenylene sulfide, phenothiazine, diphenyl oxide, diphenyl sulfide, diphenylamine, cyclohexane, petroleum naphthenes, decahydro-naphthalene, cyσlopentane, etc.: R in Formula IV is an aliphatic group such as alkyl, alkenyl, alkoxy, alkoxyalkyl, carboalkoxyalkyl, etc; x is at least 1, and R + T contains a total of at. least about 15 carbon atoms, ^x R9 in Formula V is an aliphatic radical containing at least about 15 carbon atoms and M is either

Q a metal cation or hydrogen. Examples of type of the R

- 31 -

radical are alkyl, alkenyl, alkoxyalkyl, carboalkoxyalkyl,

9 etc. Specific examples of R are groups derived fro petrolatum, saturated and unsaturated paraffin wax, ^' an polyolefins, including polymerized C_, C_, G., C_, C,, etc., olefins containing from about 15 to 7000 or ^' mor

9 carbon atoms. The groups T, R, and R in the abov formulae can also contain other inorganic or organic substituents in addition to those enumerated above suc as, for example, hydroxy, mercapto, halogen, nitro, amino, nitroso, sulfide, disulfide, etc. In Formula IV, x, y, z and b are at least 1, and likewise in Formula V, a, b and d are at least 1. .

Specific examples of sulfonic acids useful in this invention are mahogany sulfonic acids; bright stock sulfonic acids; sulfonic acids derived from lubricating oil fractions having a Saybolt viscosity from about 100 seconds at 100°F to about 200 seconds are 210°F;, petrolatum sulfonic acids; mono- and poly-wax substituted sulfonic and polysulfonic acids of, e.g., benzene, naphthalene, phenol, diphenyl ether, napthalene disulfide, diphenylamine, thiophene, alpha-chloronaphthalene, etc.; other substituted sulfonic acids such as alkyl benezne sulfonic acids (where the alkyl group has at least 8 carbons), cetylphenol mono-sulfide sulfonic acids, dicetyl thianthrene disulfonic acids, dilauryl beta naphthyl sulfonic acid, dicapryl nitronaphthalene sulfonic acids, and alkaryl sulfonic acids such as dodecyl benzene "bot¬ toms" sulfonic acids.

The latter acids derived from benzene which has been alkylated with propylene tetramers or isobutene trimers to introduce 1,2,3, or more branched-chain C, ₂ substituents on the benzene ring. Dodecyl benzene bottoms, principally mixtures of mono-and di-dodecyl benzenes, are available as by-products from the manufacture of household detergents. Similar products obtained from alkylation bottoms formed during manufacture of linear alkyl sulfonates (LAS) are

- 32 -

also useful in making the sulfonates used in this invention.

The production of sulfonates from detergent manufacture-by-products by reaction with, e.g., S0 ₃ , is well known to those skilled in the art. See, for example, the article "Sulfonates" in Kirk-Othmer "Encyclopedia of Chemical Technology", Second Edition, Vol. 19, pp. 291 at seq. published by John Wiley & Sons, N.Y. (1969) .

Other descriptions of overbased sulfonate salts and techniques for making them can be found in the following U.S. Pat. Nos. 2,174,110; 2,174,506; 2,174,508; 2,193,824

2,197,800 2,202,781; 2,212,786; 2,213,360; 2,228,598 2,223,676 2,239,974; 2,263,312; 2,276,090; 2,276,297 2,315,514 2,319,121; 2,321,022; 2,333,568; 2,333,788 2,335,259 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; and 3,798,012. These are hereby incorporated by reference for their disclosures in this regard.

Also included are aliphatic sulfonic acids such as paraffin wax sulfonic acids, unsaturated paraffin wax sulfonic acids, hydroxy-substituted paraffin wax sulfonic acids, hexapropylene sulfonic acids, tetra-amylene sulfonic acids, polyisobutene sulfonic acids wherein the polyisobutene contains from 20 to 7000 or more carbon atoms, chloro-substituted paraffin wax sulfonic acids, nitroparaffin wax sulfonic acids, etc.; cycloaliphatic sulfonic acids such as petroleum naphthene sulfonic acids, σetyl cyclopentyl sulfonic acids, lauryl cyclohexyl sulfonic acids, bis-(di-isobutyl) cyclohexyl sulfonic acids, etc.

With respect to the sulfonic acids or salts thereof described herein and in the appended claims, it is intend¬ ed that the term "petroleum sulfonic acids" or "petroleum sulfonates" includes all -sulfonic acids or the salts thereof derived from petroleum products. A particularly valuable group of petroleum sulfonic acids are the mahoga¬ ny sulfonic acids (so called because of their

- 33 -

reddish-brown color) obtained as a by-product from the manufacture of petroleum white oils by a sulfuric acid process.

Generally Group IA, IIA and IIB overbased salts of the above-described synthetic and petroleum sulfonic acids are typically useful in making (C) of this invention.

The carboxylic acids from which suitable overbased salts for use in this invention can be made include aliphatic, cycloaliphatic, and aromatic mono- and polybasic carboxylic acids such as the napthenic acids, alkyl- or alkenyl-substituted cyclopentanoic acids, alkyl- or alkenyl-substituted cyclohexanoic acids, alkyl- or alkenyl-substituted aromatic carboxylic acids. The aliphatic acids generally contain at least 8 carbon atoms and preferably at least 12 carbon atoms. Usually they have no more than about 400 carbon atoms. Generally, if the aliphatic carbon chain is branched, the acids are more oil-soluble for any given carbon atoms content. The cycloaliphatic and aliphatic carboxylic acids can be saturated or unsaturated. Specific examples include 2-ethylhexanpic acid, a-linolenic acid, propylene- tetramer-substituted maleic acid, behenic acid, isostearic acid, pelargonic acid, capric acid, palmitoleic acid, linoleic acid, lauric acid, oleic acid, ricinoleic acid, undecylic acid, dioctylcyclopentane carboxylic acid, myristic acid, dilauryldecahydronaphthalene carboxylic acid, stearyl-octahydroindene carboxylic acid, palmitic acid, commercially available mixtures of two or more carboxylic acids such as tall oil acids, rosin acids, and the like.

A typical group of oil-soluble carboxylic acids useful in preparing the salts used in the present inven¬ tion are the oil-soluble aromatic carboxylic acids. These acids are represented by the general formula:

- 34 -

wherein R* is an aliphatic hydrocarbon-based group of at least 4 carbon atoms, and no more than about 400 aliphatic carbon atoms, a is an integer from one to four, Ar* is a polyvalent aromatic hydrocarbon nucleus of up to about 14 carbon atoms, each X is independently a sulfur or oxygen atom, and m is an integer of from one to four with the proviso that R* and a are such that there is an average of at least 8 aliphatic carbon atoms provided by the R* groups for each acid molecule represented by Formula VI. Examples, of aromatic nuclei represented by the variable Ar* are the polyvalent aromatic radicals derived from benzene, napthalene anthracene, phenanthrene, indene, fluorene, biphenyl, and the like. Generally, the radical represented by Ar* will be a polyvalent nucleus derived from benzene or naphthalene such as phenylenes and naphthylene, e.g., methyphenylenes, ethoxyphenylenes, nitrophenylenes, isopropylenes, hydroxyphenylenes, mercaptophenylenes, N,N-diethylaminophenylenes _r chloro- phenylenes, N,N-diethylaminophenylenes, chlorophenylenes, dipropoxynaphthylenes, triethylnaphthylenes, and similar tri-, tetra-, pentavalent nuclei thereof, etc.

The R* groups are usually hydrocarbyl groups, prefer- ably groups such as alkyl or alkenyl radicals. However, the R* groups can contain small number substituents such as phenyl, cycloalkyl (e.g., cyclohexyl, cyclopentyl, etc.) and nonhydrocarbon groups such as nitro, amino, halo (e.g., chloro, bromo, etc.), lower alkoxy, lower alkyl mercapto, oxo substituents (i.e., =0), thio groups (i.e., =S) , interrupting groups such as —NH—, —O—, —S—, and the like .provided the essentially hydrocarbon character of the R* group is retained. The hydrocarbon character is retained for purposes of this invention so long as any non-carbon atoms present in the R* groups do not account

- 35 -

for more than about 10% of the total weight of the R* groups.

Examples of R* groups include butyl, isobutyl, pentyl, octyl, nony.l, dodecyl, docosyl, tetracontyl, 5-chlorohexyl, 4-ethoxypentyl, 4-hexenyl, 3-cyclohexyl- octyl, 4-(p-chlorophenyl)-octyl, 2,3,5-trimethylheptyl, 4-ethyl-5-methyloctyl, and substituents derived from polymerized olefins such as polychloroprenes, polyethyl- enes, polypropylenes, polyisobutylenes, ethylene-propylene copolymers, chlorinated olefin polymers, oxidized ethylene-propylene copolymers, and the like. Likewise, the group Ar* may contain non-hydrocarbon substituents, for example, such diverse substituents as lower alkoxy, lower alkyl mercapto, nitro, halo, alkyl or alkenyl groups of less than 4 carbon atoms, hydroxy, mercapto, and the like.

Another group of useful carboxylic acid ^' s are those of the formula:

wherein R*, X, Ar*, m and a are as defined in Formula IV and p is an integer of 1 to 4, usually 1 or 2. Within this group, an especially preferred class of oil-soluble carboxylic acids are those of the formula:

(VIII)

0 II

C—OH

(R ** ^■ Hof (OH)

- 36 -

wherein R** in Formula VIII is an aliphatic hydrocarbon group containing at least 4 to about 400 carbon atoms, a is an integer of from 1 to 3, b is 1 or 2, c is zero, 1, or 2 and preferably 1 with the proviso that R** and a -are such that the acid molecules contain at least an average of about 12 aliphatic carbon atoms in the aliphatic hydrocarbon substituents per acid molecule. And within this latter group of oil-soluble carboxylic acids, the aliphatic-hydrocarbon substituted salicyclic acids wherein each aliphatic hydrocarbon substituent contains an average of at least about 16 carbon atoms per substituent and 1 to 3 substituents per molecule are particularly useful. Salts prepared from such salicyclic acids wherein the aliphatic hydrocarbon substituents are derived from polymerized olefins, particularly polymerized lower 1-mono-olefins such as polyethylene, polypropylene, polyisobutylene, ethylene/-propylene copolymers and the like and having average carbon contents of about 30 to about 400 carbon atoms. The carboxylic acids corresponding to Formulae VI-VII above are well known or can be prepared according to procedures known in the art. Carboxylic acids of the type illustrated by the above formulae and processes for preparing their overbased metal salts are well known and disclosed, for example, in such U.S. Pat. Nos. as 2,197,832; 2,197,835; 2,252,662; 2,252,664; 2,714,092; 3,410,798 and 3,595,791 which are incorporated by refer¬ ence herein for their disclosures of acids and methods of preparing overbased salts. Component C may also be a borated complex of either an alkali overbased sulfonic acid or an alkaline overbased carboxylic acid such as described hereinabove. Borated complexes of this type may be prepared by heating the overbased sulfonic acid or overbased carboxylic acid with boric acid at about 50°-100°C, the number of equivalents ^' of boric acid being roughly equal to the number of equivalents of alkali metal in the salt. U.S. Patent No.

- 37 -

3,929,650 is incorporated by reference herein for its disclosure of borated complexes.

Another type of overbased σarboxylate salt used in making (C) of this invention are those derived from alkenyl succinates of the general formula:

(IX)

R*—CHCOOH I CH ₂ COOH

wherein R* is as defined above in Formula VI. Such salts and means for making them are set forth in U.S. Pat. Nos. 3,271,130, 3,567,637 and 3,632,510, which are hereby incorporated by reference in this regard.

Other patents specifically describing techniques for making overbased salts of the hereinabove-described sulfonic acids, carboxylic acids, and mixtures of any two or more of these include U.S. Pat. Nos. 2,501,731

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 3,365,296 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 are hereby incorporated in this present specifi¬ cation for their disclosures in this regard as well as for their disclosure of specific suitable basic metal salts. In the context of this invention, phenols are consid¬ ered organic acids. Thus, overbased salts of phenols (generally known as phenates) are also useful in making (C) of this invention are well known to those skilled in the art. The phenols from which these phenates are formed are of the general formula:

(X)

(R*)n(Ar*)—(XH)m

wherein R*, n, Ar*, X and m have the same meaning and preferences are described hereinabove with reference to

- 38 -

Formula VI. The same examples described with respect to Formula VI also apply.

A commonly available class of phenates are those made from phenols of the general formula: . (XI)

wherein a is an integer of 1-3, b is of 1 or 2, z is 0 or

1, R in Formula XI is a hydrocarbyl-based substituent having an average of from 4 to about 400 aliphatic carbon

5 atoms and R is selected from the group consisting of lower hydrocarbyl, lower alkoxyl, nitro, amino, cyano and halo groups.

One particular class of phenates for use in this invention are the overbased. Group IIA metal sulfurized phenates made by sulfurizing a phenol as described herein- above with a sulfurizing agent such as sulfur, a sulfur halide, or sulfide or hydrosulfide salt. Techniques for making these sulfurized phenates are described in U.S. Pat. Nos. 2,680,096; 3,036,971; and 3,775,321 which are hereby incorporated by reference for their disclosures in this regard.

Other phenates that are useful are those that are made from phenols that have been linked through alkylene (e.g., methylene) bridges. These are made by reacting single or multi-ring phenols with aldehydes or ketones, typically, in the presence of an acid or basic catalyst. Such linked phenates as well as sulfurized phenates are described in detail in U.S. Pat. No. 3,350,038; particu- larly columns 6-8 thereof, which is hereby incorporated by reference for its disclosures in this regard.

Generally Group IIA overbased salts of the above- described carboxylic acids are typically useful in making (C) of this invention.

- 39 -

The method of preparing metal overbased composition in this _, manner is illustrated by the following examples

Example C-l A mixture consisting essentially of 480 parts of sodium petrosulfonate (average molecular weight of abou 480) , 84 parts of water, and 520 parts of mineral oil i heated at 100°C. The mixture is then heated with 86 part of a 76% aqueous solution of calcium chloride and 72 part of lime (90% purity) at 100°C for two hours, dehydrated b heating to a water content of less than about 0.5%, coole to 50°C, mixed with 130 parts of methyl alcohol, and the blown with carbon dioxide at 50°C until substantiall neutral. The mixture is then heated to 150°C to distil off methyl alcohol and water and the resulting oil solu ' tion of the basic calcium sulfonate filtered. The fil trate is found to have a calcium sulfate ash content o 16% and a metal ratio of 2.5. A mixture of 1305 parts o the above carbonated calcium petrosulfonate, 930 parts o mineral oil, 220 parts of methyl alcohol, 72 parts of isobutyl alcohol, and 38 parts of amyl alcohol is pre¬ pared, heated to 35°C, and subjected to the following operating cycle, four times: mixing with 143 parts of 90% commercial calcium hydroxide (90% calcium hydroxide) and treating the mixture with carbon dioxide until it has a base number of 32-39. The resulting product is then heated to 155°C during a period of nine hours to remove the alcohol and filtered at this temperature. The filtrate is characterized by a calcium sulfate ash content of about 40% and a metal ratio of about 12.2. Example C-2

A mineral oil solution of a basic, carbonated calcium complex is prepared by carbonating a mixture of an alkylated benzene sulfonic acid (molecular weight of 470) an alkylated calcium phenate, a mixture of lower alcohols (methanol, butanol, and pentanol) and excess lime (5.6 equivalents per equivalent of the acid) . The solution has a sulfur content of 1.7%, a calcium content of 12.6% and a

base number of 336. To 950 grams of the solution, there is added 50 grams of a polyisobutene (molecular weight of 1000)-substituted succinic anhydride (having a saponification number of 100) at 25°C. The mixture is stirred, heated to 150°C, held at that temperature for 0.5 hour, and filtered. The filtrate has a base number of 315, and contains 35.4% of mineral oil.

Example C-3 To 950 grams of a solution of a basic, carbonated, calcium salt of an alkylated benzene sulfonic acid (aver¬ age molecular weight - 425) in mineral oil (base number - 406, calcium - 15.2% and sulfur - 1.4%) there is added 50 grams of the polyisobutenyl succinic anhydride of Example C-2 at 57°C. The -mixture is stirred for 0.65 hour at 55°-57°C/ then at 152°-153°C for 0.5 hour and filtered at 105°C. The filtrate has a base number of 387 and contains 43.7% of mineral oil.

Example C-4 A mixture comprising 753 parts (by weight) of mineral oil, 1440 parts of xylene, 84 parts of a mixture of a commercial fatty acid mixture (acid number of 200, 590 parts of an alkylated benzene sulfonic acid (average molecular weight - 500) , and 263 parts of magnesium oxide is heated to 60°C. Methanol (360 parts) and water (180 parts) are added. The mixture is carbonated at 65°C-98°C while methanol and water are being removed by azeotropic distillation. Additional water (180 parts) is then added and carbonation is continued at 87°-90°C for three and a half hours. Thereafter, the reaction mixture is heated to 160°C at 20 torr and filtered at 160°C to give a basic, carbonated magnesium sulfonate-carboxylate complex (78.1% yield) containing 7.69% of magnesium and 1.67% of sulfur and having a base number of 336. To 950 parts of the above basic, carbonated magnesium complex, there is added 50 parts of the polyisobutenyl complex, there is added 50 parts of the polyisobutenyl succinic anhydride of Example C-2 and the mixture is heated to 150°C for one-half hour

and then filtered to give a composition having a base number of 315.

Example C-5

A mixture comprising 906 grams (1.5 equivalents) of an oil solution of an alkylbenzene sulfonic acid (average molecular weight -460-480) , 564 grams of mineral oil, 600 grams of toluene, 95.7 grams of magnesium oxide (4.4 equivalents) , and 120 grams of water is carbonated at a temperature of about 78°-85°C for about 7 hours at a rate of about 3 cubic feet of carbon dioxide per hour. The carbonated product is stripped by heating to 165°C at a pressure of 20 torr and filtered. The filtrate is an oil solution of a basic, carbonated magnesium sulfonate complex having a metal ratio of 3.1 and containing 15.27% of magnesium sulfate ash, 2.66% of sulfur and a base number of 98. To 95 grams of this complex there is added

5 grams of the polyisobutenyl succinic anhydride of

Example B-2 and the mixture is stirred at 150°C and filtered. Example C-6

A mixture of 2,576 grams of mineral oil, 240 grams (1.85 equivalents) of octyl alcohol, 740 grams (20.0 equivalents) of calcium hydroxide, 2304 grams (8 equiva¬ lents) of oleic acid, and 392 grams (12.3 equivalents) of methyl alcohol is heated with stirring to a temperature about 50°C in about 0.5 hour. This mixture then is treated with C0 ₂ (3 cubic feet per hour) at 50°-60°C for a period of about 3.5 hours. The resulting mixture is heated to 150°C and filtered. The filtrate is a basic calcium oleate complex having the following analyses: Sulfate ash (%) 24.1 Metal ratio 2.5

Neutralization No. (acidic) 2.0

Example C-7 A reaction mixture comprising 1044 grams (about 1.5 equivalents) of an oil solution of an alkylphenyl sulfonic acid • (average molecular weight -500) , 1200 grams of

mineral 981, 2400 grams of xylene, 138 grams (about 0.5 equivalents) of tall oil acid mixture (oil-soluble fatty acid mixture sold by Hercules under the name PAMAK-4) , 434 grams (20 equivalents) of magnesium oxide, 600 grams of methanol, and 300 grams of water is carbonated at a rate of 6 cubic feet of carbon dioxide per hour at 65°-70°C.

(methanol reflux) . The carbon dioxide introduction rate was decreased as the carbon dioxide uptake diminished.

After 2.5 hours of carbonation, the methanol is removed and by raising the temperature of the mixture to about 95°C with continued carbon dioxide blowing at a rate of about two cubic feet per hour for one hour. Then 300 grams of water is added to the reaction mixture and carbonation was continued at about 90°C. (reflux) for about four hours. The material becomes hazy with the addition of the water but clarifies after 2-3 hours of continued carbonation. The carbonated product is then stripped to 160°C at 20 torr and filtered. The filtrate is a concentrated oil solution (47.5% oil) of the desired basic magnesium salt, the salt being characterized by a metal ratio of about 10.

Example C-8 Following the general procedure of Example C-7 but adjusting the weight ratio of methanol to water in the initial reaction mixture to 4:3 in lieu of the 2:1 ratio of Example C-7 another concentrated oil-solution (57.5% oil) of a basic magnesium salt is produced. This methanol-water ratio gives improved carbonation at the methanol reflux stage of carbonation and prevents thicken- ing of the mixture during the 90°C carbonation stage.

Example C-9 A reaction mixture comprising 135 parts mineral oil, 330 parts xylene, 200 parts (0.235 equivalent) of a mineral oil solution of an alkylphenylsulfonic acid (average molecular weight - 425), 19 parts (0.068 equiva¬ lent) of the above-described mixture of tall oil acids, 60 parts (about 2.75 equivalents) of • magnesium oxide, 83

parts methanol, and 62 parts water are carbonated at a rate of 15 parts of carbon dioxide per hour for about 2 hours at the methanol reflux temperature. The carbon dioxide inlet rate is then reduced to about 7 parts per hour and the methanol is removed by raising the tempera¬ ture to about 98°C over a 3 hour period. Then 47 parts of water are added and carbonation is continued for an additional 3.5 hours at a temperature of about 95°C. The carbonated mixture is then stripped by heating to a temperature of 140°-145°C over a 2.5 hour period. This results in an oil solution of a basic magnesium salt characterized by a metal ratio of about 10.

Then, the carbonated mixture is cooled to about 60°-65°C and 208 parts xylene, 60 parts magnesium oxide, 83 parts methanol and 62 parts water are added thereto. Carbonation is resumed at a rate of 15 parts per hour for 2 hours at the methanol reflux temperature. - The carbon dioxide addition rate is reduced to 7 parts per hour and the methanol is removed by raising the temperature to about 95°C over a 3 hour period. An additional 41.5 parts of water are added and carbonation is continued at 7 parts per hour at a temperature of about 90°-95°C for 3.5 hours. The carbonated mass is then heated to about 150°-160°C over a 3.5-hour period and then further stripped by reducing the pressure to 20 torr at this temperature. The carbonated reaction product is then filtered. The fil¬ trate is a concentrated oil-solution (31.6% oil) of the desired basic magnesium salt characterized by a metal ratio of 20. Example C-10

To a solution of 790 parts (1 equivalent) of an alkylated benzenesulfonic acid and 71 parts of polybutenyl succinic anhydride (equivalent weight about 560) contain¬ ing predominantly isobutene units in 176 parts of mineral oil is added 320 parts (8 equivalents) of sodium hydroxide and 640 parts (20 equivalents) of methanol. The tempera¬ ture of the mixture increases to 89°C (reflux) over 10

- 44 -

minutes due to exotherming. During this period, the mixture is blown with carbon dioxide at 4 cfh. (cubic feet/hr.). Carbonation is continued for about 30 minutes as the temperature gradually decreases to 74°C. The methanol and other volatile materials are stripped from the carbonated mixture by blowing nitrogen through it at 2 cfh. while the temperature is slowly increased to 150°C over 90 minutes. After stripping is completed, the remaining mixture is held at 155-165°C for about 30 minutes and filtered to yield an oil solution of the desired basic sodium sulfonate having a metal ratio of about 7.75. This solution contains 12.4% oil.

Example C-ll Following the procedure of ^' Example C-10, a solution of 780 parts (1 equivalent) of an alkylated benzenesulfonic acid and 119 parts, of the polybutenyl succinic anhydride in 442 parts of mineral oil is mixed with 800 parts (20 equivalents) of sodium hydroxide and 704 parts (22 equivalents) of methanol. The mixture is blown with carbon dioxide at 7 cfh. for 11 minutes as the temperature slowly increases to 95°C. The rate of carbon dioxide flow is reduced to 6 cfh. and the temperature decreases slowly to 88°C over about 40 minutes. The rate of carbon dioxide flow is reduced to 5 cfh. for about 35 minutes and the temperature slowly decreases to 73°C. The volatile materials are stripped by blowing nitrogen through the carbonated mixture at 2 cfh. for 105 minutes as the temperature is slowly increased to 160°C. After stripping is completed, the mixture is held at 160°C for an additional 45 minutes and then filtered to yield an oil solution of the desired basic sodium sulfonate having a metal ratio of about 19.75.. This solution contains 18.7% oil.

Example C-12 ^' Following the procedure of Example C-10, a solution of 780 parts (1 equivalent) of an alkylated benzenesulfonic acid and 86 parts of the polybutenyl

succinic anhydride in 254 parts of mineral oil is mixed with 480 parts (12 equivalents) of sodium hydroxide and 640 parts (20 equivalents) of methanol. The reaction mixture is blown with carbon dioxide at 6 cfh. for about 45 minutes. During this time the temperature increases to 95°C and then gradually decreases to 74°C. The volatile material is stripped by blowing with nitrogen gas at 2 cfh. for about one hour as the temperature is increased to 160°C. After stripping is complete the mixture is held at 160°C for 0.5 hour and then filtered to yield an oil solution of the desired sodium salt, having a metal ratio of 11.8. The oil content of this solution is 14.7%.

Example C-13 Following the procedure of Example C-10, a solution of 2800 parts (3.5 equivalents) of an alkylated benzenesulfonic acid and 302 parts of the polybutenyl succinic anhydride in 818 parts of mineral oil is mixed with 1680 parts (42 equivalents) of sodium hydroxide and 2240 parts (70 equivalents) of methanol. The mixture is blown with carbon dioxide for about 90 minutes at 10 cfh. During this period, the temperature increases to 96°C and then slowly drops to 76°C. The volatile materials are stripped by blowing with nitrogen at 2 cfh. as the temper¬ ature is slowly increased from 76°C to 165°C by external heating. Water is removed by vacuum stripping. Upon filtration, an oil solution of the desired basic sodium salt is obtained. It has a metal ratio of about 10.8 and the oil content is 13.6%.

Example C-14 Following the procedure of Example C-10 a solution of 780 parts (1.0 equivalent) of an alkylated benzenesulfonic acid and 103 parts of the polybutenyl succinic anhydride in 350 parts of mineral oil is mixed with 640 parts (16 equivalents of sodium hydroxide and 640 parts (20 equiva- lents) of methanol. This mixture is blown with carbon dioxide for about one hour at 6 cfh. During this period, the temperature increases to 95°C and then gradually

decreases to 75°C. The volatile material is stripped by blowing with nitrogen. During stripping, the temperature initially drops to 70°C over 30 minutes and then slowly rises to 78°C over 15 minutes. The mixture is then heated to 155°C over 80 minutes. The stripped mixture is heated for an additional 30 minutes 15 155-160°C and filtered. The filtrate is an oil solution of the desired basic sodium sulfonate, having a metal ratio of about 15.2. It has an oil content of 17.1%. Example C-15

Following the procedure of Example C-10, a solution of 780 parts (1 equivalent) of an alkylated bnezenesulfonic acid and 119 parts of the polybutenyl succinic__ anhydride in 442 parts of mineral oil is mixed well with 800 parts (10 equivalents) of sodium hydroxide and 640 parts (20 equivalents) of methanol. This mixture is blown with carbon dioxide for about 55 minutes at 8 cfh. During this period, the temperature of the mixture increases to 95°C and then slowly decreases to 67°C. The methanol and water are stripped by blowing with nitrogen at 2 cfh. for about 40 minutes while the temperature is slowly increased to 160°C. After stripping, the tempera¬ ture of the mixture is maintained at 160-165°C for about 30 minutes. The product is then filtered to give a solution of the corresponding sodium sulfonate having a metal ratio of about 16.8. This solution contains 18.7% oil.

Example C-16 Following the procedure of Example C-10, 836 parts (1 equivalent) of a sodium petroleum sulfonate (sodium "Petronate") in an oil solution containing 48 % oil and 63 parts of the polybutenyl succinic anhydride is heated to 60°C and treated with 280 parts (7.0 equivalents) of sodium hydroxide and 320 parts (10 equivalents) of methanol. The reaction mixture is blown with carbon dioxide at 4 cfh. for about 45 minutes. During this time,

-the temperature increases to 85°C and then slowly

decreases to 74°C. The volatile material is stripped by blowing with nitrogen at 1 cfh. while the temperature is gradually increased to 160°C. After stripping is completed, the mixture is heated an additional 30 minutes at 160°C, and then is filtered to yield the sodium salt in solution. The product has a metal ratio of 8.0 and an oil content of 22.2%.

Example C-17 To a mixture comprising 125 parts of low viscosity mineral oil and 66.5 parts of heptylphenol heated to about 38°C there is added 3.5 parts of water. Thereafter, 16 parts of paraformaldehyde are added to the mixture at a uniform rate over 0.75 hour. Then 0.5 parts of hydrated lime are added and this mixture is heated to 80°C over a 1 hour period. The reaction mixture thickens and the temperature rises to about 116°C. Then, 13.8 parts of hydrated lime are added over 0.75 hour while maintaining a temperature of about 80°-90°C. The material is then heated to about 140°C for 6 to 7 hours at a reduced pressure of about 2-8 torr to remove substantially all water. An additional 40 parts of mineral oil are added to the reaction product and the resulting material is fil¬ tered. The filtrate is a concentrated oil solution (70% oil) of the substantially neutral calcium salt of the heptylphenol-formaldehyde condensation product. It is characterized by calcium content of about 2.2% and a sulfate ash content of 7.5%.

Example C-18 A solution of 3192 parts (12 equivalents) of a polyisobutene-substituted phenol, wherein the polyisobutene substituent has a molecular weight of about 175, in 2400 parts of mineral is heated to 70°C and 502 parts (12 equivalents) of solid sodium hydroxide is added. The material is blown with nitrogen at 162°C under vacuum to remove volatiles and is then cooled to 125°C and 465 parts (12 equivalents of 40% aqueous formaldehyde is added. The mixture is heated to 146°C under nitrogen, and

volatiles are finally removed again under vacuum. Sulfur dichloride, 618 parts (6 equivalents) , is then added over 4 hours. Water, 1000 parts, is added at 70°C and the mixture is heated to reflux for 1 hour. All volatiles are then removed under vacuum at 155°C and the residue is filtered at that temperature, with the addition of a filter aid material. The filtrate is the desired product (59% solution in mineral oil) containing 3.56% phenolic hydroxyl and 3.46% sulfur. Example C-19

A mixture of 319.2 parts (1.2 equivalents) of a tetrapropene-substituted phenol similar to that used in Example C-18, 240 parts of mineral oil and 45 parts (0.6 equivalent) of 40% aqueous formaldehyde solution is heated to 70°C, with stirring, and 100.5 parts (1.26 equivalents) of 50% .aqueous sodium hydroxide is added over about 20 minutes, while the mixture is blown with nitrogen. Volatile materials are removed by stripping at 160°C, with nitrogen blowing and subsequently .under vacuum. Sulfur dichloride, 61.8 parts (1.2 equivalents), is added below the surface of the liquid at 140°-150°C, over 6 hours. The mixture is then heated at 145°C for one hour and volatile materials are removed by stripping under nitrogen at 160°C. The intermediate thus obtained is filtered with the

- addition of a filter aid material, and 3600 parts (7.39 equivalents) thereof is combined with 1553 parts of mineral oil and 230 parts of the polyisobutenyl succinic anhydride of Example C-2. The mixture is heated to 67°C and there are added 142 parts of acetic acid, 1248 parts of methanol and 602 parts (16.27. equivalents) of calcium hydroxide. The mixture is digested for a few minutes and then blown with carbon dioxide at 60°-65°C. The carbon dioxide-blown material is stripped at 160°C to remove volatiles and finally filtered with the addition of a filter aid. The filtrate is the desired product contain¬ ing 1.68% sulfur and 16.83% calcium sulfate ash.

Example C-20 To a mixture of 3192 parts (12 equivalents) of tetrapropenyl-substituted phenol, 2400 parts of mineral oil and 465 parts (6 equivalents) of 40% aqueous formaldehyde at 82°C, is added, over 45 minutes, 960 parts (12 equivalents) of 50% aqueous sodium hydroxide. Vola¬ tile materials are removed by stripping as in Example B-18, and to the residue is added 618 parts (12 equiva¬ lents) of sulfur dichloride over 3 hours. Toluene, 1000 parts, and 1000 parts of water are added and the mixture is heated under reflux for 2 hours. Volatile materials are then removed at 180°C by blowing with nitrogen and the intermediate is filtered.

To 1950 parts (4 equivalents) of the intermediate thus obtained is added 135 parts of the polyisobutenyl succinic anhydride of Example C-2. The mixture is heated to 51°C, and 78 parts of acetic acid and 431 parts of methanol are added, followed by 325 parts (8.8 equiva¬ lents) of calcium hydroxide. The mixture is blown with carbon dioxide and is finally stripped with nitrogen blowing at 158°C and filtered while hot, using a filter aid. The filtrate is a 68% solution in mineral oil of the desired product and contains 2.63% sulfur and 22.99% calcium sulfate ash. Example C-21

A reaction mixture comprising about 512 parts by weight of a mineral oil solution containing about 0.5 equivalent of a substantially neutral magnesium salt of an alkylated salicylic acid wherein the alkyl group has an average of about 18 aliphatic carbon atoms and about 30 parts by weight of an oil mixture containing about 0.037 equivalent of an alkylated benzenesulfonic acid together with about 15 parts by weight (about 0.65 equivalent) of a magnesium oxide and about 250 parts by weight of xylene is added to a flask and heated to a temperature of about 60°C to 70°C. The reaction mass is subsequently heated to about 85°C and approximately 60 parts by weight of water

are added. The reaction mass is held at a reflux tempera¬ ture of about 95°C to 100°C for about 1-1/2 hours and subsequently stripped at a temperature of 155°C-160°C, under a vacuum, and filtered. The filtrate comprises the basic carboxylic magnesium salt characterized by a sulfated ash content of 12.35% (ASTM D-874, IP 163), indicating that the salt contains 200% of the stoichiometrically equivalent amount of magnesium.

Example C-22 A reaction mixture comprising about 506 parts by weight of a mineral oil solution containing about 0.5 equivalent of a substantially neutral magnesium salt of an alkylated salicylic acid wherein the alkyl groups have an average of about 16 to 24 aliphatic carbon atoms and about 30 parts by weight of an oil mixture containing about 0.037 equivalent of an alkylate benzenesulfonic acid together with about 22 parts by weight (about 1.0 equiva¬ lent) of a magnesium oxide and about 250 parts by weight of xylene is added to a flask and heated to temperatures of about 60°C to 70°C. The reaction is subsequently heated to about 85°C and approximately 60 parts by weight of water are added to the reaction mass which is then heated to the reflux temperature. The reaction mass is held at the reflux temperature of about 95°-100°C for about 1-1/2 hours and subsequently stripped at about 155°C, under 40 torr and filtered. The filtrate comprises the basic carboxylic magnesium salts and is characterized by a sulfated ash content of 15.59% (sulfated ash) corre¬ sponding to 274% of the .stoichiometrically equivalent amoun .

Example C-23 A substantially neutral magnesium salt of an alkylated salicylic acid wherein the alkyl groups have from 16 to 24 aliphatic carbon atoms is prepared by reacting approximately stoichiometric amounts of magnesium chloride with a substantially neutral potassium salt of said alkylated salicylic acid. A reaction mass comprising

approximately 6580 parts by weight of a mineral oil solution containing about 6.50 equivalents of said sub¬ stantially neutral magnesium salt of the alkylated salicylic acid and about 388 parts by weight of an oil mixture containing about 0.48 equivalent of an alkylated benzenesulfonic acid together with approximately 285 parts by weight (14 equivalents) of a magnesium oxide and approximately 3252 parts by weight of xylene is added to a flask and heated to temperatures of about 55°C to 75°C. The reaction mass is then heated to about 82°C and approx¬ imately 780 parts by weight of water are added to the reaction which is subsequently heated to the reflux temperature. The reaction mass is held at the reflux temperature of about 95°-100°C for about 1 hour and subsequently stripped at a temperature of about 170°C, under 50 torr and filtered. The filtrate comprises the basic carboxylic magnesium salts and has a sulfated ash content of 15.7% (sulfated ash) corresponding to 276% of the stoichiometrically equivalent amount. As previously indicated, the compositions, of this invention are useful as additives for lubricants, in which they function primarily as extreme pressure and antiwear agents having a relatively long period of e fectiveness. They can be employed in a variety of lubricants based on diverse oils of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof. These lubricants include crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, including automobile and truck engines, two-cycle engines, aviation piston engines, marine and railroad diesel engines, and the like. They can also be used in gas engines, stationary power engines and turbines and the like. Automatic transmission fluids, transaxle lubri¬ cants, gear lubricants (in which their use is especially beneficial), metal-working lubricants, hydraulic fluids and other lubricating oil and grease compositions can also

- 52

benefit from the incorporation therein of the compositions of the present invention.

Natural oils include animal oils and vegetable oils (e.g., castor oil, -lard oil) as well as liquid petroleum oils and solvent-treated or acid-treated mineral lubricat¬ ing oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosi¬ ty derived from coal or shale are also useful base oils. Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropyl¬ enes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes) , poly(1-octenes) , polyd- decenes) , etc. and mixtures thereof); alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes, etc.); ^' polyphenyls (e.g., biphenyl, terphenyls, alkylated polyphenyls, etc.), alkylated- diphenyl ethers and alkylated polyphenyls, etc.),. alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof and the like.

Alkylene oxide polymers and interpolymers and deriva¬ tives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. consti- tute another class of known synthetic lubricating oils. These are exemplified by the oils prepared through poly¬ merization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-1500, etc.) or mono-and polycarboxylic esters there¬ of, for example, the acetic acid ester ^' s, mixed C_-C ₀ fatty acid esters, or the C- Oxo acid diester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Specific examples of these esters include dibutyl adipate, di(2-eth lhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diiosoctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate,. dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid, and the like.

Esters useful as synthetic oils also include those made from C-. to C. ₂ monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylol- propaήe, pentaerythritol, dipentaerythritol, tripenta- erythritol, etc.

Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils comprise another useful class of synthetic lubricants

(e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethyl- hexyl) silicate, tetra-(p-tert-butylphenyl) silicate, hexa- (4-methyl-2-pentoxy)-disiloxane, poly(methyl) - siloxanes-, poly(methylphenyl) siloxanes, etc.). Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid, etc.), polymeric tetrahydrofurans and the like. Unrefined, refined and rerefined oils (and mixtures of each with each other) of the type disclosed hereinabove can be used in the lubricant compositions of the present

invention. Unrefined oils are those obtained directly from a natural or synthetic source without further purifi¬ cation treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques are known to those of skill in the art such as solvent extraction, acid or base extraction, filtration, percolation, etc. Rerefined oils are obtained by process¬ es similar to those used to obtain refined oils applied to refined oils which have been already used in -service. Such rerefined oils are also known as reclaimed or repro¬ cessed oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products. The compositions of the present invention comprise mixtures of the above-described sulfur compounds (A) , the phosphite esters (B) and the metal overbased compositions

(C) . In a blend that ^' contains a lubricating base oil,

(A) , (B) and (C) are generally present in the following levels: (A) at a sulfur level from about 0.1% up to about 10%; (B) at a phosphorus level from about 0.01% up to about 1% and (C) at a total base number level from about 0.1 up to about 10. Preferably the % sulfur level of (A), the phosphorus level of (B) and the total base number of (C) are 0.1 to 3.5 , 0.025 to 0.75, and 1 to 7.5 respectively. Most preferably these levels are 0.25 to 2, 0.05 to 0.5, and 2 to 5 respectively.

A 100 part blend that contains a lubricating oil, (A) 2% sulfur of example A-l, (B) 0.05% phosphorus of example B-4 and 5 total base numbers of example C-3 will contain 91.987 parts lubricating oil, 6.369 parts example A-l, .352 parts example B-4 and 1.292 parts example C-4.

The invention also contemplates the use of other additives in combination with the compositions of this invention. Such additives include, for example, deter¬ gents and dispersants of the ash-producing or ashless type, corrosion- and oxidation-inhibiting agents, pour point depressing agents, auxiliary extreme pressure agents, color stabilizers, friction modifiers and anti-foam agents.

The ash-producing detergents are exemplified by oil-soluble neutral and basic salts of alkali or alkaline earth metals with sulfonic acids, carboxylic acids, or organic phosphorus acids characterized by at least one direct carbon-to-phosphorus linkage such as those prepared by the treatment of an olefin polymer (e.g., polyisobutene having a molecular weight of 1000) with a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphorothioic chloride. The most commonly used salts of such acids are those of sodium, potassium, lithium, calcium, magnesium, strontium and barium.

The term "basic salt" is used to designate metal salts wherein the metal is present in stoichiometrically larger amounts than the organic acid radical. The σommon- ly employed methods for preparing the basic salts involve heating a mineral oil solution of an acid with a stoichiometric excess of a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature above 50°C and filtering the resulting mass. The use of a "promoter" in the neutral¬ ization step to aid the incorporation of a large excess ^' of metal likewise is known. Examples of compounds useful as the promoter include phenolic substances such as phenol, naphthol, alkylphenol, thiophenol, sulfurized alkylphenol, and condensation products of formaldehyde with a phenolic substance; 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-B- naphthylamine, and dodecylamine. A particularly effective method for preparing the basic salts comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing agent and at least one alcohol promoter, and carbonating the mixture at an elevated temperature such as 60-200°C.

Ashless detergents and dispersants are so called despite the fact that, depending on its constitution, the dispersant may upon combustion yield a non-volatile material such as boric oxide or phosphorus pentoxide; however, it does not ordinarily contain metal and there¬ fore does not yield a metal-containing ash on combustion. Many types are known in the art, and any of them are suitable for use in the lubricants of this invention. The following are illustrative:

3,163,603 3,351,552 3,522,179

3,184,474 3,381,022 3,541,012 3,215,707 3,399,141 3,542,678

3,219,666 3,415,750 3,542,680

3,271,310 3,433,744 3,567,637

3,281,357 3,444,170 3,574,101

3,306,908 3,448,048 3,576,743 3,311,558 3,448,049 3,630,904

3,316,177 3,451,933 3,632,510

3,340,281 3,454,607 3,632,511

3,341,542 3,467,668 3,697,428

3,346,493 3,501,405 3,725,441 Re 26,433

(2) "Amine dispersants" and "Mannich dispersants" such as those described hereinabove.

(3) Products obtained by post-treating the carboxylic, amine or Mannich dispersants with such re- agents as urea, thiourea, carbon disulfide, aldehydes.

ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds or the like. Exemplary materials of this kind 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 3,702,757

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 3,708,522

(4) Interpolymers of oil-solubilizing monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substituents, e.g., aminoalkyl acrylates or acrylamides and poly- (oxyethylene)-substituted acrylates. These may be characterized as "polymeric dispersants" and examples thereof 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 above-noted patents are incorporated by reference herein for their disclosures of ashless dispersants.

Auxiliary extreme pressure agents and corrosion- and oxidation-inhibiting agents are exemplified by chlorinated aliphatic hydrocarbons such as chlorinated wax; aromatic or arylaliphatic sulfides and polysulfides such as benzyl disulfide, bis (chlorobenzyl)disulfide and sulfurized alkylphenol; phosphosulfurized hydrocarbons such as the reaction product of a phosphorus sulfide with turpentine or methyl oleate; phosphorus esters including principally

dihydrocarbon and trihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite, dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite, dimethyl napht yl phosphite, oleyl 4-pentylphenyl phosphite, polypropylene (molecular weight 500)- substituted phenyl phosphite, diisobutyl substituted phenyl phosphite; metal thiocarbamates, such as zinc dioctyldithiocarbamate, and barium heptylphenyl dithiocarbamate; Group II metal phosphorodithioates such as zinc dicyclohexylphosphorodithioate, zinc dioctyl- phosphorodithioate, barium di(heptylphenyl)phosphoro- dithioate, cadmium dinonylphosphorodithioate, and the zinc salt of .a phosphorodithioic acid produced by the reaction of phosphorus pentasulfide with an equimolar mixture of isopropyl alcohol and.n-hexyl alcohol.

The compositions of this invention can be added directly to the lubricant.- Preferably, however, they are diluted with a substantialy inert, normally liquid organic diluent such as mineral oil, naphtha, _. benzene, toluene or xylene, to form an additive concentrate which usually contains about 20-90% by weight of .said composition and may contain, in addition, one or more other additives known in the art or described hereinabove.