HYDROXYAROMATIC COMPOSITION

PRIORITY

[0001] This application claims the benefit under 35 U.S.C. § 1 1 to U.S. Provisional

Patent Application No. 61 580,562, filed on December 27, 20! 1, the contents of which are incorporated by reference herein.

BACKGROUND OF THE INVENTION

1. Technical Field

[00021 The present invention generally relates to a post-treated sulfurized salt of an alkyl-substituted hydroxyaromatic composition. The present invention further relates to a post-treated sulfurized salt of an alkyl-substituied hydroxyaromatic composition having a reduced content of uttsittiurized alkyl-substituted hydroxyaromatic compound and its unsuJfiirized metal salt, methods of making same and their use in lubricating oil compositions. 2- Description of the Related Art

[00 3j The lubricant additive industry generally uses alkyl phenols (e.g., ietrapropenyl phenol, TPP) to prepare detergents comprising sulfurized metal alkyl phenate. Metal salts of sulfurized alkylphenols are useful lubricating oil additives which impart detergency and dispersancy properties to the lubricating oil composition for marine, automotive, railroad and air-cooled engines as well as providing for an alkalinity reserve in the oil. Alkalinity reserve is necessary in order to neutralize acids generated during engine operation. Without this alkalinity reserve, the acids so generated would result in harmful engine corrosion. However, there may be some unreacted alkyi phenols such as tetrapropenyi phenol present in die suifurized metal alkyi phenate as well as in lubricating oils containing one or more of the siilfurized metal alkyi phenates.

|0(I041 A recent reproductive toxicity study in rats sponsored by the Petroleum Additives Panel of the American Chemistry Council shows that free or unreacted TPP may cause adverse effects on male and female reproductive organs. Further, it is believed that TPP may be corrosive or irritating to the skin.

[0005] U.S. Patent Application Publication No. 20080070818 ("the '818 publication") discloses a lubricating oil composition including at least one sulphurized overbased metal phenate detergent prepared from a Cr-Cis alkyi phenol, at least one sulphurizing agent, at least one metal and at least one overbasmg agent; the detergent including less than 6.0% by combined mass of unsulphurized C9-C15 alkyi phenol and unsuiphurized metal salts thereof. Examples A and B disclosed in the '818 publication obtained an overbased detergent having 5.58 and 3.84 mass %, respectively, of unsuphraized alkyi phenol and its unsuiphurized calcium salt,

[0006] U.S. Patent Application Publication No. 20090143264 ("the '264 publication") discloses suifurized metal alkyi phenate compositions having a low alkyi phenol content. The suifurized metal alky! phenate compositions of the '264 publication can be prepared by reacting a phenol compound such as tetrapropenyi phenol with an aldehyde to form a phenoiic resin and then reacting the phenolic resin simultaneously with a metal base and a first suifurizing agent. (0097] U.S. Patent No. 3,649,229 ("the '229 patent") discloses a condensation product of (1) a high molecular weight alkyl-substituted hydroxyaromatic compound, wherein the aikyl group has a molecular weight from about 600 to about 3,000; (2) an amine which contains a HN< group, i.e., an active hydrogen, and (3) an aldehyde, wherein the respective molar ratio of the reactatits is 1:0.1-10:0.140, Example 7 of the '229 paient discloses that Mannich reaction of polypropylphenoi sulfide with dieihylenetTiamine and paraformaldehyde, [0008] U.S. Patent No. 4,088,586 ("the '586 patent") discloses a Mannich base prepared by condensing ietrapropenylphenol, formaldehyde and dieihylenetriamine. The '586 patent further discloses that the calcium salt of the Mannich base is prepared using conventional methods, for example, by treating the Mannich base with calcium hydroxide in the presence of a promoter.

[0009 _. 1 U.S. Patent No, 4,157,308 discloses Mannich bases and the alkaline earth metal salts thereof, which are prepared by condensing formaldehyde and a polyamine with a phenolic mixture consisting of (1) front 95 to 30% phenol alkylated with a propylene ietramer and (2) from 5 to 70% phenol alkylated with a straight-chain aipha-olefin of from 16 to about 28 carbon atoms or aipha-olefin mixtures wherein the alpha-o!efins are of from 16 to about 28 carbon atoms.

[9010f U.S. Patent No, 4,157,309 discloses Mannich bases and the alkaline earth metal salts thereof, which are prepared by condensing formaldehyde and a polyamine with a sulfur-containing phenolic mixture consisting of (I) from 5 to 35 mol percent of a sxilfurized alkylphenol wherein the aikyl group is Cg-Cje aikyl, and (2) from 95 to 65 mol percent of phenol alkylated with a propylene tetramer. fOOiij U.S, Patent No. 4,175,044 discloses Mannich bases and the alkaline earth metal salts thereof, which are prepared by condensing formaldeiiyde and a polyamine with a sulfur-containing phenolic mixture consisting of (1) from 5 to 40% of a sulfurized alkylphenol wherein the alkyl group is C e a k l, and (2) from 95 to 60% of a phenolic mixture consisting of (a) from 95 to 30% phenol alkylated with a propylene tetramer and (b) from 5 to 70% phenol alkylated with a straight-chain alpha-olefin of from 16 to about 28 carbon atoms or alpha-olefin mixtures wherein the alpha-olefms are of from 16 to about 2S carbon atoms. |0012j GB 1604609 discloses in Examples G and 2 the condensation product of a mixture of alkyl phenol and a carbonated and non carbonated sulfurized alkylphenol salt mixture, diethylamine iriamine, and paraformaldehyde.

|Θ013| However, problems associated, with the use of a polyamine in preparing a

Mannich reaction product includes formation of sediment and plugging issues due to the multiple reactions occurring from the highly reactive polyamine, as well as being too viscous a material.

[0014] To reduce any potential health risks to customers and to avoid potential regulatory issues, there is a need to reduce the amount of free unsulfurized alkyi-substituted hydroxyaromatic compound and its metal salt in ihe salts of sulfurized alkyi-substituted hydroxyaromatic compositions. Accordingly, it is desirable to provide an improved process for making post-treated salts of sulfurized alkyi-substituted hydroxyaromatic compositions which have relatively low levels of unsulfurized alkyi-substituted hydroxyaromatic compound and its metal salt. SUMMARY OF THE INVENTION

(001 1 ∑ ⁿ accordance with one embodiment of the present invention, there is provided a post-treated salt of a sulfurized alkyl-substituted hydroxyaromatic composition which is a reaction product of (a) a salt of a sulfurized alk ! -substituted hydroxyaromatic composition, wherein the alkyl-substituted hydroxyaromatic compound is derived from alkylation of a hydroxyaromatic compound with one or more olefins comprising (¼ to Cjg oligomers of monomers selected from propylene, butylene or mixtures thereof, (b) a source of an aldehyde and (c) a primary and'or secondary monoamine compound having at least one active hydrogen,

[0016} In accordance with a second embodiment of the present invention, there is provided a post-treated salt of a sulfurized alkyl-substituted hydroxyaromatic composition having a. reduced content, by combined mass, of an unsulfurized alkyl-substituted hydroxyaromatic compound and its unsulfurized metal salt, the post-treated salt of the sulfurized alkyl-substituted hydroxyaromatic composition being prepared by a process comprising:

[0017] (a) providing a salt of a sulfurized alkyl-substituted hydroxyaromatic composition containing an unsulfurized alkyl-substituted hydroxyaromatic compound and its unsulfurized metal salt; wherein the alkyl-substituted hydroxyaromatic compound is derived from alkylation of a hydroxyaromatic compound with one or more olefins comprising C9 to C$8 oligomers of monomers selected from propylene, butylene or mixtures thereof; and

100181 (b) reacting the salt of a sulfurized alkyl-substituted hydroxyaromatic composition with an effective amount of aldehyde and a primary and or secondary monoamine compound having at least one active hydrogen and under reaction conditions sufficient to provide a post-treated salt of the sulfurized alkyl-substituted hydroxyaromatic composition having at least about 70% reduced content, by combined mass, of the unsulfurized alkyl-substituted hydroxyaromatic compound and its unsulfurized metal salt, compared to the content, by combined mass, of the unsulfurized alkyl-substituted hydroxyaromatic compound and its unsulfurized metal salt present in the non-post-treated salt of a sulfurized aikyl-substituied hydroxyaromatic composition.

[00191 in accordance with a third embodiment of the present invention, there is provided a process for preparing a post-treated salt of a sulfurized alkyl-substituted hydroxyaromatic composition having a reduced content of unsulfurized alkyl-substituted hydroxyaromatic compound and its unsulfurized metal salt, the process comprising the steps of:

{0020] (a) providing a salt of a sulfurized alkyl-substituted hydroxyaromatic composition containing an unsulfurized alkyl-substituted hydroxyaromatic compound and its unsulfurized metal salt; wherein the alkyl-substituted hydroxyaromatic compound is derived from alkylation of a hydroxyaromatic compound with one or more olefins comprising to t½ oligomers of monomers selected from propylene, butylene or mixtures thereof; and

[00211 ) reacting the salt of a sulfurized alkyl-substituted hydroxyaromatic composition with an effective amount of an aldehyde and a primary and/or secondary monoamine compound having at least one active hydrogen and under reaction conditions sufficient to provide a post-treated salt of the sulfurized alky i -substituted hydroxyaromatic composition having at least about 70% reduced content, by combined mass, of the unsulfurized alkyl-substituted hydroxyaiomatic compound and its imsuliurized metal salt, compared to the content, by combined mass, of the unsulfurized alkyl-substituted hydroxyaroraatic compound and its unsulflirized metal salt presentt in the non-post~treated salt of a suifurized alkyl-substituted hydroxyaromatic composition.

[4HJ22] in accordance with a fourth embodiment of the present invention, there is provided a lubricating oil composition comprising:

{0023] (a) a major amount of an oil of lubricating viscosity; and

{08241 (b) at least one post-treated salt of a suifurized alkyl-substituted hydroxyaromatic composition which is a reaction product of (i) a sal of a suifurized alkyl- substituted hydroxyaromatic composition, wherein t e alkyl-substituted hydroxyaromatic compound is derived from alkylation of a hydroxyaromatic compound with one or more olefins comprising ¼ to Cig oligomers of monomers selected from propylene, butylene or mixtures thereof, (ii) a source of an aldehyde and (iii) a primary and/or secondary monoamine compound having at least one active hydrogen,

{0025j In accordance with a fifth embodiment of the present invention, there is provided a lubricating oil composition comprising:

{0026] (a) a major amount of an oil of lubricating viscosity; and

{0027] (b) at least one post-treated salt of a suifurized alkyl-substituted hydroxyaromatic composition having a reduced content, by combined mass, of an unsulfurized alkyl-substituted hydroxyaromatic compound and its unsulfurized metal salt, the salt of a suifurized alkylhydroxyarornatie composition being produced b a process comprising: [0028] (i) providing a salt of a sulfurized alkyl -substituted hydroxyaromatic composition containing an unsuiiurized alkyl-substituted hydroxyaromatic compound and its unsulfurized metal salt; wherein the alkyl-substituted hydroxyaromatic compound is derived from alkyiaiion of a hydroxyaromatic compound with one or more olefins comprising <¾ to C _f s oligomers of monomers selected from propylene, butylene or mixtures thereof; and

|0029| (ii) reacting the salt of a sulfurized alkyl-substituted hydroxyaromatic composition with an effective amount of an aldehyde and a primary and/or secondary monoamine compound having at least one active hydrogen and under reaction conditions sufficient to provide a post-treated salt of the sulfurized alkyl-substituted hydroxyaromatic composition having at least about 70% reduced content, by combined mass, of the unsujfurized alkyl-substituted hydroxyaromatic compound and its unsuiiurized metal salt, compared to the content, by combined mass, of the unsulfurized alkyl-substituted hydroxyaromatic compomid and its unsulfurized metal salt present in the non-post-treated salt of a sulfurized alkyl-substituted hydroxyaromatic composition.

[0030] In accordance with a sixth embodiment of the present invention, there is provided a method of operating an internal combustion engine comprising operating the internal combustion engine with a lubricating oil composition comprising:

|O031 J (a) a major amount of an oil of lubricating viscosity ; and

f0032f fb) at least one post-treated salt of a sulfurized alkyl-substituted hydroxyaromatic composition which is a reactio product of (i) a salt of a sulfurized alkyl- substituted hydroxyaromatic composition, wherein the alkyl-substituted hydroxyaromatic compound is derived from alkyiaiion of a hydroxyaromatic compound with one or more olefins comprising C to Cjg oligomers of monomers selected from propylene, butylene or mixtures thereof, (ii) a source of an aldehyde and (iii) a primary' and/or secondary monoamine compound having at least one active hydrogen,

0033| In accordance with a seventh embodiment of the present invention, there is provided a method of operating an interna! combustion engine comprising operating the internal combustion engine with a lubricating oil composition comprising;

[0034] (a) a major amount of an oil of lubricating viscosity; and

10035] ( ) a least one post-treated salt of a sulfurized alky I -substituted hydroxyaromatic composition having a reduced content, by combined mass, of an unsulfurized aikyi-substituted hydroxyaromatic compound and its unsulfurized metal salt, the post-treated salt of a sulfurized alkylhydroxyaromatk composition being produced by a process comprising:

[0O36J (i) providing a salt of a sulfurized aikyi-substituted hydroxyaromatic composition containing an unsulfurized aikyi-substituted hydroxyaromatic compound and its unsulfurized metal salt; wherein the alkyl-substituted hydroxyaromatic compound is derived from alkylation of a hydroxyaromatic compound with one or more olefins comprising€9 to Cig oligomers of monomers selected from propylene, butylene or mixtures thereof; and

[0037] (ii) reacting the salt of a sulfurized aikyi-substituted hydroxyaromatic composition with an effective amount of an aldehyde and a primary and/or secondary monoamine compound having at least one active hydrogen and under reaction conditions sufficient to provide a post-treated salt of the sulfurized aikyi-substituted hydroxyaromatic composition having at least about 70% reduced content, by combined, mass, of the unsulfurized alkyl-substituted hydroxyaromatic compound and its unsulfurized metal salt, compared to the content, by combined mass, of the unsulfurized alkyl-substituted hydroxyaromatic compound and its unsulfurized metal salt present in the non-posf-treated salt of a sulrurized alkyl-substituted hydroxyaromatic composition.

(0038] In accordance with a eighth embodiment of the present invention, there is provided a method for reducing the endocrine disrupting properties of a lubricating oil composition on exposure to mammals, the method comprising adding at least one post-treated salt of a sulfurized alkyl-substituted hydroxyaromatic composition which is a reaction product of (i) a salt of a sulfurized alkyl-substituted hydroxyaromatic composition, wherein the alkyl- substituted hydroxyaromatic compound is derived from alkyiation of a hydroxyaromatic compound with one or more olefins comprising C9 to€;g oligomers of monomers selected from propylene, butylene or mixtures thereof, (ii) a source of an aldehyde and (iii) a primary and/or secondary monoamine compound having at least one active hydrogen, to a lubricating oil composition comprising a major amount of an oil of lubricating viscosity.

[0039} In accordance with a ninth embodiment of the present invention, there is provided a method for reducing the endocrine disrupting properties of a lubricating oil composition on exposure to mammals, the metliod comprising adding at least one post-treated salt of a suifitrized alkylhydroxyaromatic composition which is produced by a process comprising:

{0040} (i) providing a salt of a su!furized alkyl-substituted hydroxyaromatic composition containing an unsulfurized alkyl-substituted hydroxyaromatic compound and its unsulfurized metal salt; wherein the alkyl-substituted hydroxyaromatic compound is derived from alkylation of a hydroxyaromatic compound with one or more olefins comprising ¾ to Cis oligomers of monomers selected from propylene, butylene or mixtures thereof; and

[0041] (ii) reacting the salt of a sulfurized alkyi-substituted hydroxyaromatic composition with an effective amount of an aldehyde and a primary and or secondary monoamine compound having at least one active hydrogen and under reaction conditions sufficient to provide a post-treated salt of the suifurized alkyl-substiiuied hydroxyaromatic composition having at least about 70% reduced content, by combined mass, of the unsulfurized aikyl-substitiited hydroxyaromatic compound and its unsulfurized metal salt, compared to the content, by combined mass, of the unsulfurized alkyl-substiraied hydroxyaromatic compound and its unsuifimzed metai salt present in the non-post-treated salt of a sulfurized alkyi-substituteti hydroxyaromatic composition, to a lubricating oil composition comprising a major amount of an oil of lubricating viscosity.

[01142] The process of the present invention advantageously provides a post-treated salt of a sulfurized aikyl -substituted hydroxyaromatic composition containing relatively low levels of unsulfurized alkyi-substituted hydroxyaromatic compound and its unsulfurized metal salt that can be prepared in a simple, cost efficient manner. This is an unexpected improvement in that the presence of the unsulfurized alkyi-substituted hydroxyaromatic compound and its unsiti&red metal salt in a sail of a sulfurized alkyi-substituted hydroxyaromatic composition is undesirable because of their deleterious estrogenic behavior and there is a growing concern of their potential release in the environment. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 is a bar graph showing the difference in mean blotted and wet uterine weights for the four treatment groups (75, 250, 500, and 1000 mg/kg/day) compared to the vehicle control group.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

f0044) Prior to discussing the invention in further detail, the following terms will he defined:

(0045J DEFINITIONS

[0046| As used herein, the following terms have the following meanings, unless expressly stated to the contrary;

[0047) The term "lime" as used herein refers to calcium hydroxide, also known as slaked lime or hydrated lime,

[0048 J The term "Total Base Number" or "TBN" as used herein refers to the amount of base equivalent to milligrams of KOH in 3 gram of sample. Thus, higher TBN numbers reflect more alkaline products, and therefore a greater alkalinity reserve. The TBN of a sample can be determined by ASTM Test No, D2896-1 1 issued Ma 15, 201 1 or any other equivalent procedure.

[0049] The term "phenate" means a metal salt of a phenol

[0050] The term "alkylphenate" means a metai salt of an alkylphenol. [0051 J The term "aikylphenoi" means a phenol having one or more alkyl substituents, wherein at least one of the alkyl substituents has a sufficient number of carbon atoms to impart oil solubility to the phenol

[0052| The term "lime" refers to calcium hydroxide, also known as slaked lime or hydrated lime.

[00531 The term "metal" means alkali metals, alkaline earth metals, or mixtures thereof,

[00541 The rm "alkaline earth metal" refers to calcium, barium, magnesium, and strontium,

[0O55j The term "alkali metal" refers to lithium, sodium, potassium, rubidium, and cesium.

[00561 The ter "metal base" refers to a metal hydroxide, metal oxide, metal aikoxides and the like and mixtures thereof, wherein the meial is an alkaline earth metal or alkali metal.

[0O57| The term "overbased" refers to a class of metal salts or complexes. These materials have also been referred to as "basic", "superbased", "hyperbased", "complexes", "metal complexes", "high-metal containing salts", and the like. Overbased products are metal salts or complexes characterized by a metal content in excess of that which would be present according to the stoichiometry of the metal and the particular acidic organic compound reacted with the metal, e.g., a carboxyiic acid. Suitable overbasing metals include alkaline earth metals such as magnesium, calcium, barium, and strontium. Suitabie overbasing metals can be provided from the corresponding metal hydroxides, for example, calcium hydroxide and magnesium hydroxide provide the source for the alkaline earth metals calcium and magnesium, respectively. Additional overbasing can be achieved by the addition of acidic overbading compounds for example, carbon dioxide and boric acid.

[0058] The terra "sulfated ash content' ¹ refers to the amount of metal-containing additives {e.g., calcium, magnesium, molybdenum, zinc, elc.) in a lubricating oil composition and is typically measured according to ASTM D874, which is incorporated herein by reference.

[0059] The present invention is directed to a post-treated salt of a sulfurized alkyi- substituted hydroxyaromatic composition which is a reaction product of (a) a salt of a sulfurized alkyl-substituted hydroxyaromatic composition, wherein the alkyl-substituted hydroxyaromatic compound is derived from a!kylation of a hydroxyaromatic compound with one or more olefins comprising £¾ to g oligomers of monomers selected from propylene, butylene or mixtures thereof, (b) a source of an aldehyde and (c) a primary and/or secondary monoamine compound having at least one active hydrogen.

{ΌΘ6Θ] In another embodiment, the present invention is further directed to a post- treated salt of a sulfurized alkyl-substituted hydroxyaromatic composition having a reduced content of at least about 70%, by combined mass, of an unsuifurized alkyl-substituted hydroxyaromatic compound and its unsuifurized metal salt _> compared to the content, by combined mass, of the unsuifurized alky! -substituted hydroxyaromatic compound and its unsuifurized metal sal present in the non-post-treated salt of a suiftrized alkyl-substituted hydroxyaromatic composition. [0061 J In general, the post-treated salt of a sulfurized alkyl-substituled hydroxyarornatic composition is obtained by (a) providing a salt of a suifurized aikyl- substituted hydroxyaromatic composition containing an unsuifurized alkyl-subsiituted hydroxyaromatic compound and its unsulfurized metal salt; wherein the aikyl-substituted hydroxyaromatic compound is derived from alkylation of a hydroxyaromatic compound with one or more olefins comprising to m oligomers of monomers selected from propylene, butylene or mixtures thereof; and (b) reacting the salt of a sulfurized aikyl-substituted hydroxyaromatic composition an effective amount of an aldehyde and a primary and/or secondary monoamine compound having at least one active hydrogen and under reaction conditions sufficient to provide a post-treated salt of the sulfurized alkyi-substituted hydroxyaromatic composition having at least about 70% reduced content, by combined mass, of the unsulfurized aikyl-substituted hydroxyaromatic compound and its unsulfurized metal salt, compared to the content, by combined mass, of the unsulfurized alky! -substituted hydroxyaromatic compound and its unsulfurized metal salt present in the non-post-treated salt of a sulfurized alkyl -substituted hydroxyaromatic composition.

[0062} In step (a), a salt of a sulfurized aikyl-substituted hydroxyaromatic composition containing an unsuifurized aikyl-substituted hydroxyaromatic compound and its unsulfurized metal salt is provided, In general, the composition is obtained by (i) alkylating a hydroxyaromatic compound with one or more olefins comprising C<> to Cj8 oligomers of monomers selected from propylene, butylene or mixtures thereof, to provide an aikyl- substituted hydroxyaromatic compound; (it) sulfuriziag and neutralizing the aikyl-substituted hydroxyaromatic compound in any order to provide a salt of a sulfurized aikyl-substituted hydroxyaromatic composition; and (tii) optionally overbasing the salt of a sulfimzed alkyl- subsiituted hydroxyaromatic composition. In one embodiment, the unsulfurized alkyl- substituted hydroxyaromatic compound is tetrapropenyl phenol. In certain embodiments, the tetrapropenyl phenol comprises a mixture of the isomers of tetrapropenyl phenol, such as a mixture of p-dodecy!phenol, m-dodecylphenol and o-dodecylphenol.

[0063] The alkyl-substituted hydroxyaromatic compound employed in the present invention is prepared by methods that are well known in the art, Useful hydroxyaromatic compounds mat may be alkylated include mononuclear monohydroxy and poiyhydroxy aromatic hydrocarbons having 1 to 4, and preferably 1 to 3, hydroxyl groups. Suitable hydroxyaromatic compounds include phenol _* catechol, resorcinol, hydroquinone, pyrogallol, cresol, and the like and mixtures thereof. In one embodiment, the hydroxyaromatic compound is a phenol,

{ ^' 0064] The alkylating agent employed to alkylate the hydroxyaromatic compound includes one or more olefins comprising Co to Cn oligomers of monomers selected from propylene, butylene or mixtures thereof Generally, the one or more olefins will contain a major mount of the ¾ to C½ oligomers of monomers selected from propylene, butylene or mixtures thereof- Examples of such olefins include propylene tetramer, butylene irimer and the like. As one skilled in the art will readily appreciate, other olefins may be present. For example, the other olefins that can be used in addition io the to Cjg oligomers include linear olefins, cyclic olefins, branched olefins other than propylene oligomers such as butylene or isobutylene oligomers, arytaikylenes and the like and mixtures thereof Suitable linear olefins include 1-hexene, 1-nonene, 1 -decene, 1-dodecene and the like and mixtures thereof. Especially suitable linear olefins are high molecular weight normal aipha-oiefms such as to C30 normal alpha-oiefms, which can be obtained from processes such as ethylene oligomerization or wax cracking, Suitable cyclic olefins include cyclohexene, cyeiopentene, cycboctene and the like and mixtures thereof. Suitable branched olefins include butylene dimer or trimer or higher molecular weight isobutylene oligomers, and the like and mixtures thereof. Suitable arylalkylenes include styrene, methyl styrene, 3- phenylpropene. 2-phenyi-2-hutene and the like and mixtures thereof,

[0065] Alkylation of the hydroxyaromatic compound with the one or more olefins comprising Cg to Cn oligomers of monomers selected from propylene, butylene or mixtures thereof is generally carried out in the presence of an alkylation catalyst. Useful alkylation catalysts include Lewis acid catalysts, solid acid catalysts, trifluoromethanesulfonic acid, and acidic molecular sieve catalysts. Suitable Lewis acid catalysts include aluminum trichloride, aluminum tribromide, aluminum triiodide, boron inf!uoride, boron tri bromide,, boron triiodide and the like,

[0066] Suitable solid acidic catalysts include zeolites, acid clays, and/or silica- alumina. The catalyst may be a molecular sieve. Eligible molecular sieves are silica- aluminophosphate molecular sieves or metal silica-aluminophosphate molecular sieves, in which the metal may be, fo example, iron, cobalt or nickel In one embodiment, a solid catalyst is a cation exchange resin in its acid form, for example, cross!inked sulfonic acid catalyst. Suitable sulfonated acidic ion exchange resin type catalysts include Amberlyst 36 ^s5 , available from Rohm and Hass (Philadelphia, Pa.). The acid catalyst, may be recycled or regenerated when used in a batch process or a continuous process. [01)67] The reaction conditions for the aikyiation depend upon the type of catalyst used, and any suitable set of reaction conditions thai result in high conversion to the aikylhydroxyaromatic product can be employed. Typically, the reaction temperature for the aikyiation reaction will be in tlie range of about 25°C to about 200°C and preferably from about 85°C to about 135°C. The reaction pressure will generally be atmospheric, although higher or lower pressures may be employed. The aikyiation process can be practiced in a batchwise, continuous or semi-continuous manner. The molar ratio of the hydroxyaromaiic compound to one or more olefins is normally in the range of about 10: 1 to about 0.5:1, and preferably will be in the range of about 5; I to about 3:1.

[Θ068] The aikyiation reaction may be carried out neat or in the presence of a solvent which is inert to the reaction of the hydroxyaromatic compound and the olefin mixture. When employed, a typical solvent is hexane.

[0069] Upon completion of the reaction, the desired alkymydroxyaromatk compound can be isolated using conventional techniques. Typically, excess hydroxyaromatic compound is distilled from the reaction product.

[0070] The alkyl group of the aikylhydroxyaromatic compound is typically attached to the hydroxyaromatic compound primarily in the ortho and para positions, relative to the hydroxy! group,

[0071] The alkyl-substituted hydroxyaromatic compound is subsequently sulfurized and neutralized in any order to provide a salt of a sulfurized alk i -substituted hydroxyaromatic composition. The sulfurization and neutralization steps can he performed in any order so as to provide the salt of the sulfurized alkyl-substituted hydroxyaromatic composition. Alternatively, the neutralization and sulfurization steps can be carried out simultaneously.

(9072] In general, sulfurization is carried out by contacting the alkyl-substituted hydroxyaromatic compound with a sulfur source which introduces S bridging groups between alkyl-substituted hydroxyaromatic compounds, wherein x is 1 to 7, in the presence of a base. Any suitable sulfur source can be used such as, for example, elemental sulfur or a halide thereof such as sulphur monochJoride or sulphur dichloride, hydrogen sulfide, suifur dioxide and sodium sulfide hydrates. The sulfur can be employed either as molten sulfur or as a solid (e.g., powder or particulate) or as a solid suspension in a compatible hydrocarbon liquid.

[0073] The base catalyzes the reaction to incorporate sulfur onto the alkylhydroxyaromatic compound, A suitable base includes, but is not limited to, NaOH. K.OH. Ca(OH)a and the like and mixtures thereof.

100741 The base is generally employed at from about 0.01 to about 1 mole percent to the alkyl-substituted hydroxyaromatic compound in the reaction system. In one embodiment, the base is employed at from about 0.01 to about 0.1 mole percent to the alkyl-substituted hydroxyaromatic compound in the reaction system. The base can be added to the reaction mixture as a solid or a liquid. In one preferred embodiment., the base is added as an aqueous solution.

(0075] Sulfur is generally employed at from about 0.5 to about 4 moles per mole of the alkyl-substituted hydroxyaromatic compound in the reactio system, in one embodiment, sulfur is employed at from about 0.8 to 2 moles per mole of the alkyl-substituted hydroxyaromatic compound, in one embodiment, sulfur is employed at from about 1 to 1.5 moles per mole of alkyl-substituted hydroxyaromatic compound.

(0076) The temperature range in which the sulfurization reaction is carried out is generally about 150°C to about 200°C. In one embodiment, the temperature range is from about 160°C to about 180°C. The reaction can be conducted under atmospheric pressure (or slightly lower) or at elevated pressures. During sulfurization a significant amount of byproduct hydrogen sulfide gas is evolved. In one embodiment the reaction is carried out under vacuum to facilitate the 1¾S elimination. The exact pressure developed during the reaction is dependent upon such factors as the design and operation of the system, the reaction temperature, and the vapor pressure of the reactants and products and it may vary during the course of the reaction. In one embodiment, the process pressures are at atmospheric to about 20 mm Hg,

fO0?7j Neutralization of the sulturized or unsulfurized alkyl-substituted hydroxyaromatic compound may be carried out in a continuous or batch process by any method known to a person skilled in the art. Numerous methods are known in the art to neutralize the sulfurized or unsulfurized alkyl-substituted hydroxyaromatic compounds and to produce basic phenates by incorporation of a source of base, in general, neutralization can be carried out by contacting the sulfurized or unsulfurized alkyl-substhuted hydroxyaromatic compound with a metal base under reactive conditions, preferably in an inert-compatible liquid hydrocarbon diluent, if desired, the reaction can be conducted under an inert gas, typically nitrogen. The metal base may be added either in a single addiiion or in a plurality of additions at intermediate points during the reaction. £0Θ78| Suitable metal basic compounds include hydroxides, oxides or alkoxides of the metal such as (1) an alkali metal salt derived from a metai base selected from an alkali hydroxide, alkali oxide or an alkali aikoxide, or (2) an alkaline earth metal sail derived from a metal base selected from an alkaline earth hydroxide, alkaline earth oxide or alkaline earth aikoxide. Representative examples of metal basic compounds with hydroxide functionalky include lithium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, aluminum hydroxide and the like. Representative examples of meial basic compounds with oxide functionality include lithium oxide, magnesium oxide, calcium oxide, barium oxide and the like, in one embodiment, the alkaline earth metal base is slaked lime (calcium hydroxide), because of its handling convenience and cost versus, for example, calcium oxide.

[0079] Neutralization is typically conducted in a suitable soivent or diluents oil, such as toluene, xylene and commonly with a promoter such as an alcohol, e.g., a Cj to C _½ alcohol, such as methanol, decyl alcohol, or 2-ethyl hexano!; a diol, e.g., C? to C alkylene glycols, such as ethylene glycol; and/or carboxylic acids. Suitable diluent oils include naphthense oils and mixed oils, e.g., pataffmic oils such as 100 neutral oil. The quantity of solvent or diluent oil used is such that the amount of soivent or oil in the final predict constitutes from about 25% t about 65% by weight of the final product preferably from about 30% to about 50%, For example, the source of alkaline earth metal is added in excess as a slurry (i.e., as a pre- mixture of source of an alkaline earth meial lime, soivent or diluent oil) and then reacted with the sul&rized or uns lfurized aikyl-substituted hydroxyaromatic compound. |0080J The neutralization reaction between the metal base and the sulfurked or unsu!furized alkyl-substituied hydroxyaromatic compound is typically conducted at temperatures above room temperature (20°C). In general, neutralization can be carried out at a temperature of between about 20T and about iSCC. it Is however preferred to carry the neutralization at low temperature. In one embodiment, neutralization ean be carried out at a temperature of between about 25°C and about 30°C. The neutralization reaction itself should take place for a period of time of from about 5 to about 60 minutes. If desired, the neutralization reaction is carried out in the presence of a promoter such as ethylene glycol, formic acid, acetic acid, and the like and mixtures thereof,

[0081] Upon completion of the sulfurizing and neutralizing of the aikyl-subsii ed hydroxyaromatic compound, a neutral salt of a sulfurked alkyl-substituted hydroxyaromatic composition is obtained. If desired, the neural salt of a sulfurized alkyl-substituted hydroxyaromatic composition can be overbased to provide an overbased salt of a su!furized alkyl-substituted hydroxyaromatic composition. Overbading can be earned out either during or after one of the sulfurization and neutralization steps and by any method known by a person skilled in the art. Alternatively, sulfurization, neutralization and ovcrbasing ean be carried out simultaneously. In general, the overbasing is carried out by reaction with an acidic ovcrbasing compound such as, for example, carbon dioxide or boric acid. In one embodiment, an overbasing process is by way of carbonation, i.e., a reaction with carbon dioxide. Such carbonation can be conveniently effected by addition of solvents : like aromatic solvents, alcohols or a polyols, typically an alkylene dio!, e.g., ethylene glycol. Conveniently, the reaction is conducted by the simple expedient of bubbling gaseous carbon dioxide through the reaction mixture. Excess solvents and any water formed during the overbasing reaction ca be conveniently removed by distillation either during or after the reaction.

[0082] In one embodiment, the overbasing reaction is carried out in a reactor by reacting the salt of the sulfurized alky 1 -substituted hydroxyaromatic composition with a source of ail alkaline earth metal such as lime (i.e., an alkaline earth metal hydroxide) in the presence of carbon dioxide, and in the presence of an aromatic solvent (e.g., xylene), and a hydroearbyl alcohol such as methanol. Conveniently, the reaction is conducted by the simple expedient of bubbling gaseous carbon dioxide through the reaction mixture. The carbon dioxide is introduced over a period of about 1 hour to about 3 hours, at a temperature ranging from about 30°C to about 60°C. The degree of overbasing may be controlled by the quantity of the source of an alkaline earth metal, carbon dioxide and the reactants added to the reaction mixture and the reaction conditions used during the carbonation process.

|0083] In another embodiment of the invention, the overbasing reaction can be carried out between about 140°C and about 180°C in the presence of a polyol, typically an aik lene diol, e.g., ethylene glycol, and/or aifcanols, e.g., C¾ to Cu alkanols, such as decyl alcohols, 2* ethyl hexanol. Excess solvent and any water formed during the overbasing reaction can be conveniently removed by distillation either during or after the reaction,

[01184] The overbased salt of a sulfurized alkyl-substituted hydroxyaromatic composition may have a TEN of from about 50 to about 500.

[0085] In general, the resulting neutral or overbased salt of a sulfurized alkyl- substituted hydroxyaromatic composition will contain an amount, by combined mass, of unsulfurized alkyi-substituted hydroxyaromatic compound and its unsuiftirized metal salt that will need to be further reduced in order minimize any potential health risks to customers and to avoid potential regulatory issues. In one embodiment, the resulting non-posted neutral or overbased salt of a suifiirized alkyi-substituted hydroxyaromatic composition will ordinarily contain from about 2 to about 10 wt. %, by combined mass, of the unsulfurized alkyi- substituted hydroxyaromatic compound and its unsulfurized metal salt.

[0086] As one skilled in the art wouid understand, the salt of a suifiirized alkyi- substituted hydroxyaromatic composition can contain other components in addition to the unsulfurized alkyi-substituted hydroxyaromatic compound and its unsulfurized metal salt.

[0087] In step (b) _s the neutral or overbased salt of a sulfurized alkyl-substiiuted hydroxyaromatic composition is reacted with an effective amount of an. aldehyde and a primary and/or secondary monoamine compound having at least one active hydrogen and under reaction conditions sufficient to provide a post-treated salt of the suifurized alkyi- substituted hydroxyaromatic composition having at least about 70% reduced content, by combined mass, of the unsulfurized alkyi-substituted hydroxyaromaiic compound and its unsulfurized metal salt, compared to the content, by combined mass, of the unsulfurized alkyi-substituted hydroxyaromatic compound and its unsulfurized metal salt present in the non-post-treated salt of a suifurized alkyi-substituted hydroxyaromatic composition,

[0088] Suitable aldehydes include formaldehyde, aldehydes having the formula wherein R' is a branched or linear Q to Cio alkyl radical, C ₃ io C _t eycloaikyl radical, C ₆ to Ciij aryl radical, C? to C20 alkaryl radical, or a C? to <¼ø aralkyl radical, and the like and mixtures thereof. In one embodiment, the aldehyde is a non-enoHzable aldehyde,

[0089] Representative examples of aliphatic aldehydes for use herein include, but are not limited to, formaldehyde, acetaldehyde, propionalde-hyde, butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde and the like.

(009OJ Representative examples of aromatic aldehydes for use herein include, but are not limited to, benzaidehyde, aikyibenzaldehyde such as para-tolualdehyde, hydroxybenzaldehyde and the like.

(0091 J Also useful are formaldehyde producing reagents, such aqueous formaldehyde solutions such as formal in solutions, formaldehyde oligomers, e.g. trioxane, or polymers of formaldehyde, such as paraformaldehyde. In one preferred embodiment, the aldehyde is paraformaldehyde used,

{O092J In general, an effective amount of aldehyde present in step (b) ranges from about 1 molar equivalents to about 15 molar equivalents per equivalent of the unsulfurized alkyl-substituted hydroxyaromatic compound and its unsulfurized metal salt present in the neutral or overbased salt of a sui&rized alkyl-substituted hydroxyaromatic composition. In one embodiment, the amount of aldehyde present in step (b) is from about 1 molar equivalents to about 10 equivalents per equivalent of the unsulfurized alkyl-substituted hydroxyaromatic compound and its unsulfurized metal salt present in the neutral or overbased salt of a sulfurked alkyl-substituted hydroxyaromatic composition. |0Θ93| Suitable amine compounds are primary or secondary monoamines having at least one active hydrogen. In one embodiment, a suitable primary monoamine compound for use herein is represented by the formula HNRR.', where one of the radicals R or R ^! is hydrogen and the other radical is a C1 -C30 hvdrocarbvi radical. Examples of such C\-C^ hvdrocarbvi radicals include, but are not limited to, a straight or branched, substituted or unsubstituted C1-C30 alkyl radical, a substituted or unsubstituted 03-030 cycloalkyl radical, a substituted or unsubstituted C Cjo cycloalkylalkyl radical, a substituted or unsubstituted C3- Cyj cycloalkenyl radical, a substituted or unsubstituted C5-C30 aryl radical, and a substituted or unsubstituted C5-C30 arylaikyi radical; a substituted or unsubstituted Cj to C¾ alcohol radical; a substituted or unsubstituted Or to C20 alkoxy radical and the like,

p)894] Representative examples of alkyl radicals for use herein include, by way of example, a straight or branched alkyl chain radical containing carbon and hydrogen atoms of from 1 to about 30 carbon atoms and preferably from I to about 6 carbon atoms with or without uttsaturation, to the rest of the molecule, e.g., methyl, ethyl, n-propyl, 1 -methylethyl (tsopropyi), n-butyi, n-pentyl, etc., and the like.

{0695J Representative examples of cycloalkyl radicals tor use herein include, by way of example, a substituted or unsubstituted nort-aroniatlc mono or raulttcyclic ring system of about 3 to about 30 carbon atoms such as, for example, cyclopropyi, cyclobutyl, cydopentyl, eyclohexyl, perhydronapththyl, adamaniyi and norbornyl groups, bridged cyclic groups or sprirobicyciic groups, e.g., spiro-(4,4)-non~2-yl and the like,

f9090f Representative examples of cycloalkylalkyl radicals for use herein include, by ^¬ way of example, a substituted or unsubstituted cyclic ring-containing radical containing from about 3 to about 30 carbon atoms directly attached to the aikyl group which are then attached to the main structure of the monomer at any carbon from the alkyl group that results in the creation of a stable structure such as, for example, cyclopropytmethyl. cyclobutyleihy!, cyclopentylethyl and the like.

fOG97| Representative examples of cycloaikenyl radicals for use herein include, by way of example, a substituted or unsubstituted cyclic ring-containing radical containing from about 3 to about 30 carbon atoms with at least one carbon-carbon double bond such as, for example, cyclopropenyi, cyclobutenyi, cyc!opentenyl and the like,

(0098] Representative examples of aryl radicals for use herein include, by way of example, a substituted or unsubstituted monoaromatic or polyaromatic radical containing from about 5 to about 30 carbon atoms such as, for example, phenyl, naphthyl, tetrahydronapthyl, indenyt, biphenyl and the like,

[0099] Representative examples of arylalkyl radicals for use herein include, by way of example, a substituied or unsubstituted aryl group as defined herein directly bonded to an a!kyl group as defined herein, e.g., -CH2C H5, -CjHsCgHs and the like,

[00100] Representative examples of alcohol radicals for use herein include, by way of example, an -OH group attached via carbon linkage to the rest of the molecule, i.e., of the general formula ~ R ² OH, wherein R ² is an alkyl, cycloaikyl, cycloalkylaikyi, cycloaikenyl, aryl or an arylalkyl as defined herein and the OH group is attached to any carbon atom.

fOOlOl J Representative examples of alkoxy radicals for use herein include, by way of example, an alky! grou as defined herein attached via oxygen linkage to the rest of the molecule, i.e., of the general formula -OR ^' ', wherein R is an alkyl, cycloaikyl, cycloalkyialkyl, cycloaikenyl aryi or an arylalkyl as defined herein, e.g., ~QC¾, -OQ>Hs, or -O Hs, and the like,

[00102] The substituents in the 'substituted alky!', 'substituted cycloa kyl', 'substituted cycloalkylalky , 'substituted cycloaikenyl ^* , 'substituted aryl', 'substituted arylalkyl ^* , 'substituted alcohol*, and 'substituted alkoxy' may be the same or different and include one or more substituents such as hydrogen, hydroxy, halogen, carboxyl oxo (~0), ihio(— S), substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, and the like.

(00! 3) Suitable primary monoamine compounds of the formula H RR ¹ include, but are not limited to, alkyfammes such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butyiamine, isobutylamine, sec-butyiamine, tert-butylamme, pentylamine, hexylamine, heptylamine, oetylamme, nonylamine decylamine, undecylamine, dodecyiamine, tetradecylamine, hexadodecylamine, stearylamme, octadecylamine, eicosylaraine, and the like; cycloalk [amines such as cyclopentylamtne, cyc ohexyS mine, and the like; arylamines such as aniline, benzylamine, 2-aminotoluene, 3-ammotoluene, 4- aminotoluene, and the tike; alkanoiamines such as metb^oiamine, cthanolamine, and the like; alkoxyamines such as 2,4-dimethyianiHne, 2,3-dimethy!aniline, 2,5-dimethylani!ine, 2,6- dimethylaniline, 3,4-dimethyiamiiiie, 3,5-dimethylaniIii.e, 2,4,5-trimeihyianiline, 2,4,6- trimethylani!ine, 3,4,5,0~tetrameihylamline ₅ 2,4,5,6-tetramethylanUine, 2,3,5,6- tetramethylaniime, 2-ethyi~3-hexyfaniline, 2-ethyi-4-hexylaniline, 2-ethyl-5-hexylani.ine, 2- ethyl-6-hexylaniline, 3-ethyl-4-hexylaniline, 3-ethyl-5-hexylam!ine _f 3-ethyl-2-hexylaniline, 4- ethyl-2 iexy]aniline _? 5-ethyl-2-hexylaiiiHne, 6-ethyl-2-hexylaiiiline, 4-ethy!-3-hexylaniline, 5- ethyl-3-hexyianiline, 3,4,6-triethy.!toluene, 2-methoxyaniline, 3-tnethoxyaniline, 4- methoxyaniline, 2-methoxy-3-methylaniHn , 2-methox -4-methy!aaiUne, 2~raethoxy-5- methylaniline, 2-raethoxy-0-met ylaniline. 3-niethox -2-raethy3aniline, 3-methoxy-4- methylaniline, 3-methoxy-5-methylaniime, 3-methoxy-6-methyIanil.ine _f 4-methoxy ^« 2 ^« meihylanilme, 4-meihoxy-3-methylaniline, 2-ethoxyaniline, S-ethoxyaniiine, 4-ethoxyaniiine, 4~methoxy~5-meihyianiHne, 4-methoxy-6-methyla!iilme, 2-methoxy-3~ethylaniiine _> 2- meraoxy-4-ethylaniIioe, 2-methoxy-5-ethylaniHne _> 2-methoxy-6~elfty!a Une _i 3-methoxy-2- ethylaniline, 3-methoxy-4-ethylanilme, 3-meihoxy~5~emylaniiine _J 3-methoxy-0-eth.ylan.iine, 4-methoxy-2-ethyIaniHne, 4- ethoxy-3-ethyianiline _} 2-methoxy-2 _! 3 _} 4-trimethylamline _I 3- methoxy-2,4,S-triraethylaniline, 4-methoxy-2 _s 3 _i 5-triraethylaniime, and the like and mixtures thereof

100104] In another embodiment, a suitable secondary monoamine compound for use herein is represented by the formula HNRR , where R and R arc the same or different and arc Cj-C¾i! hydrocarhyl radicals, Examples of such hydrocarbyl radicals for R and R ^! of the secondary monoamine compound can be any of the hydrocarbyl radicals discussed above for the primary monoamine compounds. Suitable secondary monoamine compounds of the formula HNRR ¹ include, hut are not limited to, diaikyiamines such as dimethylamme, diethylamine, methylethylamine, di-n -propylamine, dusopropylamine, diisobutyiarnine, di* sec-butylamine, di-teit-bittyiamine, dipentylarmne, dihexylamme, and the like, dicycloamines such as dicyclopentylamine, dicye!ohexylamme, and the like; diarykraines such as dipheny!amine, and the like; dialkanoiamines such as diethanolamine, di-n-p.ropanolamme _f diisopropanolamine. and the like, N-alkylalkanolamines such as N-meihyiethanokmine. - ehtylethano lamine and the like and mixtures thereof. [ Ol Sj In general, an effective amount of the monoamine compound present in step (h) ranges from about 1 molar equivalents to about 15 equivalents per equivalent of the unsulfurized aikyl -substituted hydroxyaromatic compound and its unsulfurized meta! salt present in the neutral or overbased salt of a sulfurized alkyl-substitufe hydroxyaromatic composition, in one embodiment, the amount of monoamine compound present sn step (b) is from about 1 molar equivalents to about 10 equivalents per equivalent of the unsulfurized aikyi-substituted hydroxyaromatic compound and its unsulfurized metal salt present in the neutral or overbased salt of a sulfurized alkyl-substituted hydroxyaromatic composition. O01O6{ In one embodiment, an effective amount of aldehyde and the monoamine compound present in ste (b) is a molar ratio of aldehyde to the monoamine compound ranging from about 1 : 1 to about 5:1.

[00107} in one embodiment, the reaction is carried out employing a molar ratio of the neutral or overbased salt of a sulfurized alkyi-substituted hydroxyaromatic composition to aldehyde to monoamine compound ranging from about I ;! : 1 to about 1 : 10:10.

[00108} As one skilled in the art will readily appreciate, the reaction conditions will necessarily depend on the reaetants employed and their respective effective amount, in one embodiment, suitable reaction conditions include a temperature ranging from about 70°C to about \ WC and time period for the reaction ranging from about 30 minutes to about 14 hour,

[0810 j If desired, step (b) can be carried out in the presence of a suitable solvent, which can be recovered from the reaction product. Suitable solvents include organic solvents such as, for example, aromatic hydrocarbon solvents such as toluene, benzene, and the like, alcohol solvents such as methanol, ethanoi, deeylalcohol, 2 -ethyl hexanol and the like, and mixtures thereof. If desired, the reaction may be carried out in a mineral lubricating oil and the resulting product is recovered as a lubricating oil concentrate,

[00110] The reaction of the neutral or overbased sai of a sulfurized alkyl- substituted hydroxyaromatic composition with an effective amount of aldehyde and primary and/or secondary monoamine compound having at least one active hydrogen is carried out under reaction conditions sufficient to provide a post-treated salt of the sulfurized alkyl-subsiituied hydrox aromatic composition having at least about 70% reduced content, by combined mass, of the unsuifurized alkyl-substituted hydroxvaromatic compound and its unsuifurized metal salt, compared to the content, by combined mass, of the unsuHurized alkyl-substituted hydroxyaromaiic compound and its unsuifurized metai salt present in the non-post-treated salt of a sulfurized alky 1 -substituted hydroxyaromatic composition. In one embodiment, the reaction of the neutral or overbased salt of a sulfurized alkyl-substituted hydroxyaromatic composition with an effective amount of aldehyde and primary and/or secondary monoamine compound having at least one active hydrogen is carried out unde reaction conditions sufficient to provide a post-treated salt of the sulfurized alkyl-substituted hydroxvaromatic composition having at least about 75% reduced content, by combined mass, of the unsuifurized alkyl-substituted hydroxyaromatic compound and its unsuifurized metal salt.

[0011 i f In one embodiment, the reaction of the neutral or overbased salt of a sulfurized alkyl-substituted hydroxyaromatic composition with an effective amount of aldehyde and primary and/or secondary monoamine compound having at least one active hydrogen is carried out under reaction conditions sufficient to provide a post-treated sait of the sulfurized alkyl-substituted hydroxyaromatic composition having at least about S0% reduced content, by combined mass, of the unsuifurized alkyl-substituted hydroxyaromatic compound and its unsuifurized metal sait. In one embodiment, the reaction of the neutral or overbased salt of a sulfurized aikyl-substituted hydroxyaromaiic composition with an effective amount of aldehyde and primary and/or secondary monoamine compound having at least one active hydrogen is carried out under reaction conditions sufficient to provide a post-treated salt of the sulfurized alkyi-subsiitiued hydroxyaromatic composition having at least about 85% reduced content, by combined mass, of the unsuifurized alkyl-substituted hydroxyaromatic compound and its unsuifurized metal salt,

[00112] In one embodiment, the reaction of the neutral or overbased salt of a sulfurized alkyl-substituted hydroxyaromatic composition with an effective amount of aldehyde and primary and/or secondary monoamine compound having at least one active hydrogen is carried out under reaction conditions sufficient to provide a post-treated salt of the sulfurized alkyl-substituted hydroxyaromatic composition having at least about 90% reduced content, by combined mass, of the unsuifurized a!kyl -substituted hydroxyaromatic compound and its unsuifurized metal salt, in one embodiment, the reaction of the neutral or overbased salt of a sulfurized alkyl-substituted hydroxyaromatic composition with an effective amoimf of aldehyde and primary and or secondary monoamine compound having at least one active hydrogen is carried out under reaction conditions sufficient to provide a post-treated salt of the sulfurized alkyl*substituted hydroxyaromatic composition having at least about 95% reduced content, by combined mass, of the unsuifurized alkyl-substituted hydroxyaromatic compound and its unsuifurized metal salt. In one embodiment, the reaction of the neutral or overbased salt of a sulfurized alkyl-substituted hydroxyaromaiic composition with an effective amount of aldehyde and primary and/or secondary monoamine compound having at least one active hydrogen is carried out under reaction conditions sufficient to provide a post- treated salt of the siUfurised alkyl-substituted hydroxyaromatic composition having 100% reduced content, by combined mass, of the unsu!furizcd alkyl-substituted hydroxyaromatic compound and its unsulfurized metal salt,

[00113] Lubricating Oil Composition

[00114} Another embodiment of the present invention is directed to a lubricating oil composition containing at least (a) a major amount of an oil of lubricating viscosity; and (b) at least one post-treated salt of a sulfurized alky! -substituted hydroxyaromatic composition which is a reaction product of (i) a salt of a sulfurized alkyl-substituted hydroxyaromatic composition, wherein the alkyl-substituted hydroxyaromatic compound is derived from alkyiatton of a hydroxyaromatic compound with one or more olefins comprising C<> to Cis oligomers of monomers selected from propylene, butylene or mixtures thereof, (ii) a source of an aldehyde and (iii) a primary and/or secondary monoamine compound having at least one active hydrogen,

[00115] Another embodiment of the present invention is directed to a lubricating oil composition containing at leasi (a) a major amount of an oil of lubricating viscosity; and (b) at least one post-treated salt of a sulfurized alkyl-substituted hydroxyaromatic composition having a reduced content, by combined mass, of an utisulfurized alkyl-substituted hydroxyaromatic compound and its unsulfurized metal salt, the post-treated salt of a siilfurized alkylhydroxyaromatic composition being produced by a process comprising: fOOl 16J (t) providing a salt of a sulfurized alkyl-substituted hydroxyaromatic composition containing an unsulfurized alkyl-substituted hydroxyaromatic compound and its unsulfurized metal salt; wherein the alkyl-substituted hydroxyaromatic compound is derived from alky!ation of a hydroxyaromatic compound with one or more olefins comprising C to Cjg oligomers of monomers selected from propylene, butylene or mixtures thereof; and

100117) (ii) reacting the sa!t of a sulfurized alkyl-substituted hydroxyaromatic composition with an effective amount of an aldehyde and a primary and/or secondary monoamine compound having at least one active hydrogen and under reaction conditions sufficient to provide a post-treated salt of the sulfurized alkyl-substituted hydroxyaromatic composition having at least about 70% reduced content, by combined mass, of the unsulfurized alkyl-substituted hydroxyaromatic compound and its unsulfurized metal salt compared to the content, by combined mass, of the unsulfurized alkyl-substituted hydroxyaromatic compound and its unsulfurized metal salt present in the non-post-treated salt of a sulfurized. alkyl-substituted hydroxyaromatic composition.

[00118] Generally, a post-treated salt of the sulfurized alkyl-substituted hydroxyaromatic composition of this invention will be present in the lubricating oil compositions in an amount of about amount of about 0,01 to about 10 wt. %, based on the total weight of the lubricating oil composition, in one embodiment a post-treated salt of the sulfurized alkyl-substituted hydroxyaromatic composition of this invention will be present in the lubricating oii compositions in an amount of about amount of about 0,01 to about 3 wt. %, based on the total weight of the lubricating oil composition. [00119] The oil of lubricating viscosity for use in the lubricating oil compositions of this invention, also referred to as a base oil, is typically present in a major amount, e.g., an amount of greater than 50 wt. %, or greater than about 70 wt %, or from about SO to about 99.5 wt. % or from about 85 to about 98 wt. %, based on the total weight of the composition. The expression "base oil" as used herein shall be understood to mean a base stock or blend of base stocks which is a lubricant component thai is produced by a single manufacturer to the same specifications (independent of feed source or manufacturer's location); that meets the same manufacturer's specification; and that is identified by a unique formula, product identification number, or both. The base oil for use herein can be any presently known or later-discovered oil of lubricating viscosity used in formulating lubricating oil compositions for any and all such applications, e.g., engine oils, marine cylinder oils, functional fluids such as hydraulic oils, gear oils, transmission fluids, etc. Additionally, the base oils for use herein can optionally contain viscosity index improvers, e.g., polymeric alkyimethacryiates; olefimc copolymers, e.g., an ethylene-propylene copolymer or a styrene-butadiene copolymer; and the like and mixtures thereof.

[00120] As one skilled to the art would readily appreciate, the viscosity of the base oil is dependent upon the application. Accordingly, the viscosity of a base oil for use herein will ordinarily range from about 2 to about 2000 centistokes (cSt) at 100° Centigrade i°C), Generally, individually the base oils used as engine oils will have a kinematic viscosity range at KXFC of about 2 cSt to about 30 cSt, or from about 3 cSt to about 16 cSt, or from about 4 cSt to about 12 cSt and will be selected or blended depending on the desired end use and the additives in the finished oil to give the desired grade of engine oil, e.g., a lubricating oil composition having an SAE Viscosity Grade of OW, 0W-20, OW-30, QW-40, OW-50, OW-60, 5W, 5W-20, 5W-30, 5W-40, SW-50, 5W-60, 10 W, 1 OW-20, 1 OW-30, IOW-40, 10W-50, 15 W, 15W-20, 15W-30 or 15W-40. Oils used as gear oils can have viscosities ranging from about 2 cSt to about 2000 cSt at 100°C, The kinematic viscosity of the base oils or the lubricating oil compositions disclosed herein can be measured according to ASTM D 445, which is incorporated herein by reference.

[00121] Base stocks may be manufactured using a variety of different processes including, but not limited to, distillation, solvent refining, hydrogen processing, oligomerization, esterification, and rerefining. Rerefmed stock shall be substantially free from materials introduced through manufacturing, contamination, or previous use. The base oil of the lubricating oil compositions of this invention may be any natural or synthetic lubricating base oil. Suitable hydrocarbon synthetic oils include, but are not limited to, oils prepai'ed from the polymerization of ethylene or from the polymerization of 1 -olefins to provide polymers such as po!yalphaoleiln or PAO oils, or from hydrocarbon synthesis procedures using carbon monoxide and hydrogen gases such as in a Fischer-Tropseh process, For example, a suitable base oil is one that comprises little, if any, heavy fraction; e.g., little, if any, lube oil fraction of viscosity 20 cSt or higher at 100°C.

1001221 The base oil may be derived from natural lubricating oils, synthetic lubricating oils or mixtures thereof. Suitable base oil includes base stocks obtained by isomerization of synthetic wax and slack wax, as well as hydrocracked base stocks produced by hydrocracking (rather than solvent extracting) the aromatic and polar components of the crude. Suitable base oils include those in all API categories I, IE, III, IV and V as defined i API Publication 1509,, 14th Edition, Addendum l _f Dec 1998. Group IV base oils are polyalphaoiefins (PAD). Group V base oils include all other base oils not included in Group I, Π, ΪΪΙ, or IV. Although Group ΪΙ, ΙΠ and IV base oils are preferred for use in ibis invention, these base oils may be prepared by combining one or more of Group I, ϊϊ, 10, IV and V base stocks or base oils. f00123j Useful natural oils include mineral lubricating oils such as, for example, liquid petroleum oils, solvent-treated or acid-treated mineral lubricating oils of the paraffimc, naphthenie or mixed paraffinic-naphthenic types, oils derived from coal or shale, animal oils, vegetable oils (e.g., rapeseed oils, castor oils and lard oil), and the like.

[00124] Useful synthetic lubricating oils include, but are not limited to, hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and mtejrpotyowrized olefins, e.g., polybuty!enes, polypropyienes, propyiene-isobutyiene copolymers, chlorinated poiybutytenes, po!y(l-hexenes), poly(i-octenes), poly(l-decenes} _> and the like and mixtures thereof; aiky!benzenes such as dodecylbenzenes, tetradecyibenzenes, dinonylbenzenes, ώ(2- ethylhexyl)¾;rtzenes, and th like; polyphenyls such as biphenyis, terphenyis, alkylated polyphenyls, and the like; alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivative, analogs and homologs thereof and the like.

[00125} ihtT useful synthetic lubricating oils include, but are not limited to, oils made by polymerizing olefins of less than 5 carbon atoms such as ethylene, propylene, butylenes, isobutene, pentene, and mixtures thereof. Methods of preparing such polymer oils are well known to those skilled in the art.

{00126J Additional useful synthetic hydrocarbon oils include liquid polymers of alpha olefins having the proper viscosity. Especially useful synthetic hydrocarbon oils are the hydrogenated liquid oligomers of (¾ to C alpha olefins such as, for example, 1-decene iri er.

189127) Another class of useful synthetic lubricating oils include, but are not limited to, alkylene oxide polymers, i.e., homopolymers, nterpoiymere, and derivatives thereof where the terminal hydroxy! groups have been modified by, for example, esterification or eiherifieation. These oils are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and phenyl ethers of these polyoxyaikylene polymers (e.g., methyl poly propylene glycol ether having an average molecular weight of 1 ,000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropyleiie glycol having a molecular weight of 1 ,000-1 ,500, etc.) or mono- and polycarboxyiic esters thereof such as. for example, the acetic esters, mixed fatty acid esters, or the Co oxo acid diester of tetraethylene glycol,

1061 8} Yet another class of useful synthetic lubricating oils include, but are not limited to, the esters of dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyi succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acids, alkyl malonic acids, alkenyi malonic acids, etc., with a variety of alcohols, e.g., butyl alcohol, hexyl alcohol dodecyi alcohol, 2 ^» ethythexyl alcohol, ethylene glycol, di ethylene glycol monoether, propylene glycol, etc. Specific examples of these esters include dibutyl adipate, di(2-ethy!hexyl)sebacate, di-n-hexyi fumarate, dioctyl sebacate, dtisooctyl azeiate, diisodecyl azeiate, 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.

[00129] Esters useful as synthetic oils also include, but are not limited to, those made from carboxyiic acids having from about 5 to about 12 carbon atoms with alcohols, e.g., methanol, ethanoi, etc., polyols and polyol ethers such as neopentyl glycol, trimeihyiol propane, pentaerythritoJ, dipentaeiythrito!, iripentaerythritol, and the like,

[0 130] Silicon-based oils such as, for example, polyaikyl-, polyaryl-, po!yaikoxy- or poiyaryloxy-si !oxane oils and silicate oils, comprise another useful class of synthetic lubricating oils. Specifk examples of these include, but are not limited to, tetraethyl silicate, tetra-isopropyl silicate, teira-(2-ethy[hexyl) silicate, tetra-(4-methyI-hexyi)siiicate, tetra-(p- tert-buty I phenyl )siiicate, hexyi-(4-mcthyl-2-pentoxy)disUoxane, poly(methyl)siloxanes _s poiy(methylphenyl)siloxanes, and the tike. Still yet other useful synthetic lubricating oils include, but are not limited to, liquid esters of phosphorous containing acids, e.g., tricresyl phosphate, trioctyi phosphate, diethyl ester of decaae phosphionic acid, etc., polymeric tetrahydrofuraiis and the like,

[ΘΘ131] The lubricating oil may be derived from unrefined, refined and rerefmed oils, either natural, synthetic or mixtures of two or more of any of these of the type disclosed hereinabove. Unrefined oils are those obtained directly from a natural or synthetic sourc (e.g., coal, shale, or tar sands bitumen) without f urther purification or treatment. Examples of unrefined oils include, but are not limited to, a shale oil obtained directly from retorting operations, a petroleum oil obtained directl from distillation or an ester oil obtained directly from an esierification process, each of which is then used without further treatment. 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. These purification techniques are known to those of skill in the art and include, for example, solvent extractions, secondary distillation, acid or base extraction, filtration, percolation, hydrotreating, dewaxing, etc. Rerefined oils are obtained by treating used oils in processes similar to those used to obtain refined oils. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products,

[89132] Lubricating oil base stocks derived from the hydroisomerization of wax may aiso be used, either alone or in combination with the aforesaid natural and/or synthetic base stocks. Such wax isomerate oil is produced by the hydroisomerization of natural or synthetic waxes or mixtures thereof over a hydroisomerization catalyst.

[001.33 Natural waxes are typically the slack waxes recovered by the solvent dewaxing of mineral oils; synthetic waxes are typical iy the wax produced by the Fischer- Tropsch process.

[00134] The lubricating oil compositions of the present invention may also contain other conventional additives that can impart or improve any desirable property of the lubricating oil composition in which these additives are dispersed or dissolved, Any additive known to a person of ordinary skill in the art may be used in the lubricating oil compositions disclosed herein. Some suitable additives have been described in Mortier et ai, ₅ "Chemistry and Technology of Lubricants," 2nd Edition, London, Springer, (1996); aid Leslie R. Rudnick, "Lubricant Additives: Chemistry and Applications," New York, Marcel Dekl er (2003), both of which are incorporated herein by reference, For example, the lubricating oil compositions can be blended with antioxidants, anti-wear agents, detergents such as metal detergen s, rust inhibitors, de-hazing agents, demidsifying agents, metal deactivating agents, friction modifiers, pour point depressants, antifoaming agents, co-solvents, package compatibilisers, corrosion-inhibitors, ashless dispefsants, dyes, extreme pressure agents and the like and mixtures thereof A variety of the additives are known and commercially available. These additives, or their analogous compounds, can be employed for the preparation of the lubricating oil compositions of the invention by the usual blending procedures.

(00135J In genera!, the concentration of each of the additives in the lubricating oil composition, when used, may range from about 0,001 wt % to about 10 wt %, from about 0.01 wt, % to about 5 wt. %, or from about 0.1 wt. % to about 2.5 wt % _} based on the total weight of the lubricating oil composition. Further, the total amount of the additives in the lubricating oil composition may range from about 0.00! wt. % to about 20 wt. %, from about 0.01 wt, % to about 10 wt, %„ or from about 0, 1 wt, % to about 5 wt, %, based on the total weight of the lubricating oil composition.

[00136J The lubricating oil composition disclosed herein can contain one or more antioxidants that can reduce or prevent the oxidation of the base oil. Any antioxidant known by a person of ordinary skill in the art may be used in the lubricating oil composition. Non- liraiting examples of suitable antioxidants include amine-based antioxidants (e.g., alkyi diphenylamines such as bis-nonylated diphenylamine, bis-octylated dipheny!amine, and octyiated butylated diphen lamine. phenyl -a-naphthyjamine, a!ky! or arylalkyl substituted phenyl-a-naphthylamme, alkylated p-phenyleae diamines, ieti-mneihyi-diaminodiphenylamine and the like), phenolic antioxidants (e.g., 2-tert-butyl phenol, 4-methyl ^» 2,6~di-tert-butylphenol, 2,4,6 ri-tert-buryIphenoI, 2,6-di-tert-butyl-p-creso!, 2,6-di-tert-butyJphenoi, 4,4'- meihylenebis-(2,6-di~tert-butylphenol), 4,4'-thiobis(6-di-iert-butyl-o-cresoi) and the like), sulfur-based antioxidants (e.g., dilaury{-3,3'-tModipropionate, sulfurized phenolic antioxidants and the Hke), phosphorous-based antioxidants (e.g., phosphites and the like), zinc dithiophosphaie, oil-soluble copper compounds and combinations thereof. The amount of the antioxidant may vary from about 0.01 wt, % to about 10 wt %, from about 0.05 wt. % to about 5 wt, %, or from about 0.1 wt, % to about 3 wt. %, based on the total weight of the lubricating oil composition. Some suitable antioxidants have been described in Leslie R, Rudnick, "Lubricant Additives: Chemistry and Applications," New York, Marcel Dekker, Chapter I, pages 1-28 (2003), which is incorporated herein by reference.

[00137] The lubricating oil composition disclosed herein can contain one or more ashless dispersant compounds to maintain in suspension insoluble materials resulting from oxidation during use, thus preventing sludge flocculation and precipitation or deposition on metal parts. Dispersants may also function to reduce changes in lubricating oil viscosity by preventing the growth of large contaminant particles in the lubricant Any dispersant known by a person of ordinary skill in the art may be used in the lubricating oil composition. An ashless dispersant generally comprises an oil soluble poiymeric hydrocarbon backbone having functional groups that are capable of associating with particles to he dispersed.

[00138] In one embodiment, an ashless dispersant is one or more basic nitrogen- containing ashless dispersants. Nitrogen-containing basic ashless (metal-free) dispersants contribute to the base number or BN (as can be measured by ASTM D 2896-1 1) of a lubricating oil composition to which they are added, without introducing additional sulfated ash. Basic nitrogen-containing ashless dispersants useful in this invention include bydrocarbyi succinimides; hydrocarbyl succinamides; mixed ester/amides of hydrocarbyl- substituted succinic acids formed by reacting a hydroearbyl-substituted succinic acylating agent stepwise or with a mixture of alcohols and amines, and or with amino alcohols; Mannich condensation products of hydrocarbyl-substituted phenols, formaldehyde and poiyamines; and amine dispersants formed by reacting high moiecular weight aliphatic or aiicycHc halides with amines, such as polyalkylene poiyamines. Mixtures of such dispersants can also be used.

[00139] Representative examples of ashless dispersants include, but are not limited to, amines, alcohols, amides, or ester polar moieties attached to the polymer backbones via bridging groups. An ashless dispersant ma be, for example, selected from oil soluble salts, esters, ammo-esters, amides, imides, and oxazolines of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides; thiocarboxy!ate derivatives of long chain hydrocarbons, long chain aliphatic hydrocarbons having a polyamine attached directly thereto; and Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine,

100140] CarboxyHc dispersants are reaction products of carboxyHc acylating agents (acids, anhydrides, esters, etc.) comprising at least about 34 and preferably at least about 54 carbon atoms with nitrogen containing compounds (such as amines), organic hydroxy compounds (such as aliphatic compounds including monohydric and polyhydric alcohois, or aromatic compounds including phenols and naphthois), and/or basic inorganic materials. These reaction products include iniides, amides, and esters,

[00141] Succinimide dispereants ar a type of carboxylic dispersant. They are produced by reacting hydrocarbyl -substituted succinic acylating agent with organic hydroxy compounds, or with amines comprising at least one hydrogen atom attached to a nitrogen atom, or with a mixture of the hydroxy compounds and amines. The term "succinic acylating agent" refers to a hydrocarbon-substituted succinic acid or a succinic acid-producing compound, the latter encompasses the acid itself. Such materials typically include hydrocarbyl-substimted succinic acids, anhydrides, esters (including half esters) and halides, (00142! Succimc-based dispereants have a wide variety of chemical structures. One class of succinic-based dispersants may be represented by the formula;

wherein each R ¹ is independently a hydrocarby! group, such as a poiyoiefm-dcrived group. TypicalJy the hydrocarby! group is an aikyl group, such as a polyisobuty! group. Alternatively expressed, the R ^f groups can contain about 40 to about 500 carbon atoms, and these atoms may be present in aliphatic forms. ² is an a!kylene group, commonly an ethylene (C2H4) group. Examples of suecinim e dispersants include those described in, for example, U.S. Patent Nos. 3,172,892, ,234,435 and 6,165,235. {00143} The pofyaikenes from which the substituent groups are derived are typically homopolymers and mierpolyraers of polymcrizab!e olefin monomers of 2 to about 16 carbon atoms, and usually 2 to 6 carton atoms. The amines which are reacted with the succinic acylating agents to form the carboxylie dispersant composition can be monoamines or polyamines,

[09144] Succinimide dispersants are referred to as such since they normally contain nitrogen largely in the form of imide functionality, although the amide functionality may be in the form of amine salts, amides, imidazolines as well as mixtures thereof To prepare a succinimide dispersant* one or more succinic acid-producing compounds and one or more amines are heated and typically water is removed, optionally in the presence of a substantially inert organic liquid solvent/diluent. The reaction temperature can range from about 80 ^e C up to the decomposition temperature of the mixture or the product, which typically falls between about lOOT to about 30Q°C. Additional details and examples of procedures for preparing the succinimide dispersants of the present invention include those described in, for example, U.S. Patent Nos, 3,172,892, 3,219,666, 3,272,746, 4,234,435, 6,165,235 and 6,440,905.

(001 5) Suitable ashless dispersants may also include amine dispersants, which are reaction products of relatively high molecular weight aliphatic halides and amines, preferably polyalkylene polyamines. Examples of such amine dispersants include those described in, for example, U.S. Patent Nos. 3,275,554, 3,438,757, 3,454,555 and 3,565,804.

[00146] Suitable ashless dispersants may further include "Martnich dispersants," which are reaction products of alkyl phenols in which the alkyl group contains at Least about 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyaraines). Examples of such dispersants include those described in, for example, U.S. Patent Nos. 3,036,003, 3,586,629, 3,591,598 and 3,980,569.

j 001 7] Suitable ashless dispersants may also be post-treated ashless dispersants such as post-treated sueeinimides, e.g., rx>st-treatment processes involving borate or ethylene carbonate as disclosed in, for example, U.S. Patent Nos. 4,612,132 and 4,746,446; and the like as well as other post-treatment processes. The carbonate-treated alkenyl succinimide is a polybutene succinimide derived from polvbulcnes having a molecular weight of about 450 to about 3000, preferably from about 900 to about 2500, more preferably from about 1300 to about 2400, and most preferably from about 2000 to about 2400, as well as mixtures of these molecular weights. Preferably, it is prepared by reacting, under reactive conditions, a mixture of a polybutene succinic acid derivative, m unsaturated acidic reagent copolymer of an unsaturated acidic reagent and an olefin, and a polyamine, such as disclosed in U.S. Patent No. 5,716,912, the contents of which are incorporated herein by reference.

100148] Suitable ashless dispersants may also be polymeric, which are itrterpoiymers of oil-solubilizing monomers such as decyl methacrylate, vinyl deeyl ether and high molecular weight olefins with monomers containing polar substitutes. Examples of polymeric dispersants include those described in, for example, U.S. Patent Nos. 3,329,658; 3,449,250 and 3,666,730.

[00.1493 ** *>ne preferred embodiment of the present invention, an ashless dispersant for us in the lubricating oil composition is a bis-succinimide derived from a polyisobutenyi group having a number average molecular weight of about 700 to about 2300, The dtspersant(s) for use in the lubricating oil compositions of the present invention are preferably non-polymeric (e g,, are mono- or bis-succinimides).

[001501 T¾ ^e lubricating oil composition disclosed herein can contain m additional detergent Any compound or a mixture of compounds that can. reduce or slow the build up of engine deposits can be used as a detergent. Non-limiting examples of suitable metal detergent include sulfurized or unsuifurized alkyl or alkenyl phenates, alkyl or alkenyl aromatic sulfonates, borated sulfonates, sulfurized or unsulfurized metal salts of multi-hydroxy alkyl or alkenyl aromatic compounds, alkyl or alkenyl hydroxy aromatic sulfonates, sulfurized or unsulfurized alkyl or alkenyl ttaphtbenates, metal salts of alkanoic acids, metal salts of an alkyl or alkenyl multiacid, and chemical and physical mixtures ihercof. Other non-limiting examples of suitable metal detergents include metal sulfonates, salicylates, phosphonates, thiophosphonates and combinations thereof. The metal can be any metal suitable for making sulfonate, salicylate or phosphonate detergents. Non-limiting examples of suitable metals include alkali metals, alkaline metals and transition metals. In some embodiments, the metal is Ca, Mg, Ba, , Na, Li or the like.

((H) 151 ] Generally, the amount of the detergent additive can be less than 10,000 ppm, less than 1000 ppm, less than 100 ppm, or less than 10 ppm, based on the total weight of the lubricating oil composition. In some embodiments, the amount of the detergent is from about 0.001 wt. % to about 5 wt %, from about 0.05 wt % to abou 3 wt %, or from about 0,1 wt. % to about 1 wt, %, based on the total weight of the lubricating oil composition. Some suitable detergents have been described in Mortier et a!., "Chemistry and Technology of Lubricants," 2nd Edition, London, Springer, Chapter 3, pages 75-85 (1996); and Leslie . Rudnick, "Lubricant Additives; Chemistry and Applications," New York, Marcel Defcker, Chapter 4, pages 113-136 (2003), both of which are incorporated herein by reference.

[00152 J The lubricating oil composition disclosed herein can contain one or more friction modifiers that can lower the friction between moving parts. Any friction modifier known by a person of ordinary skill in the art may be used in the lubricating oil composition. Non-limiting examples of suitable friction modifiers include fatty earboxy!ic acids; derivatives (e.g.. alcohol, esters, borated esters, amides, metal salts and the like) of fatty carboxylic acid; mono-, di~ or tri-alkyl substituted phosphoric acids or phosphonic acids; derivatives (e.g., esters, amides, metal salts and the like) of mono-, di- or tri-alkyl substituted phosphoric acids or phosphonic acids; mono-, di- or tri-alkyl substituted amines; mono- or di- alkyl substituted amides and combinations thereof, in some embodiments examples of friction modifiers include, but are not limited to, alkoxylated fatty amines; borated fatty epoxides; fatty phosphites, fatty epoxides, fatty amines, borated alkoxylated fatty amines, metal salts of fatty acids, fatty acid amides, glycerol esters, borated glycerol esters; and fatty imidazolines as disclosed in U.S. Patent No. 6372,696, the contents of which are incorporated by reference herein; friction modifiers obtained from a reaction product of a C4 to€75, or a Cs to€24, or a C<, t C20. fatty acid ester and a nitrogen-containing compound selected from the group consisting of ammonia, and an alkanolamine and the like and mixtures thereof. The amount of the friction modifier may vary from about 0.01 wt. % to about 10 t. %. from about 0.05 wt. % to about 5 wt. %, or from about 0.1 wt. % to about 3 wt. %. based on the total weight of the lubricating oil composition. Some suitable friction modifiers have been described in Mortier et al. _s "Chemistry and Technology of Lubricants,' ¹ 2nd Edition, London, Springer, Chapter 6, pages 183-187 (1996); and Leslie R, Rudnick, "Lubricant Additives: Chemistry and Applications," New York, Marcel Dekker, Chapters 6 and 7, pages 171-222 (2003), both of which are incorporated herein by reference,

100153] The lubricating oil composition disclosed herein can contain one or more anti- wear agents that can reduce friction and excessive war. Any anti-wear agent known by a person of ordinary skill in the art may be used in the lubricating oil composition. Non- limiting examples of suitable anti-wear agents include zinc dithiophosphate, metal (e.g., Pb, Sb, Mo and the like) salts of dithiophosphates. metal (e.g., Zn, Pb, Sb, Mo and the like) salts of dithiocarbamates, metal (e.g., Zn, Pb, Sb and the like) salts of fatty acids, boron compounds, phosphate esters, phosphite esters, amine salts of phosphoric acid esters or thiophosphoric acid esters, reaction products of dicyclopentadiene and thiophosphoric acids and combinations thereof. The amount of the anti-wear agent may vary from about 0.01 wt % to about 5 wt. %, from about 0,05 wt. % to about 3 wt, %, or from about 0, 1 wt, % to about 1 wt %, based on the total weight of the lubricating oil composition. Some suitable anti-wear agents have been described in Leslie R. Rudnick, "Lubricant Additives: Chemistry and Applications," New York, Marcel Dekker, Chapter 8, pages 223-258 (2003), which is incorporated herein by reference.

f 00154} In certain embodiments, the anti-wear agent is or comprises a dihydrocarbyl dithiophosphate metal salt, such as zinc dialkyl dithiophosphate compounds. The metal of the dihydrocarbyl dithiophosphate metal salt may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. In some embodiments, the metal is zinc. n other embodiments, the alkyl group of the dihydrocarbyl dithiophosphate metal salt has from about 3 to about 22 carbon atoms, from about 3 t about 18 carbon atoms, from about 3 to about 12 carbon atoms, or from about 3 to about 8 carbon atoms. In further embodiments, the alkyl group is linear or branched,

fOOtSSj The amount of the dihydrocarbyl dithiophosphate metal salt including the zinc dialkyl dithiophosphate salts in the lubricating oil compositio disclosed herein is measured by its phosphoais content. In some embodiments, the phosphorus content of the lubricating oil composition disclosed herein is fro about 0,01 t % to about 0, 12 wt, %, from about 0.1 wt. % to about 0.10 wt. %, or from about 0.2 wt. % to about 0.8 wt. %, based on the total weight of the lubricating oil composition,

[001561 T e lubricating oil composition disclosed herein can contain one or more foam inhibitors or anti-foam inhibitors that can break up foams in oils. Any foam inhibitor or anti- foam known by a person of ordinary skill in the art may be used in the lubricating oil composition. Non-limiting examples of suitable foam inhibitors or anti-foam inhibitors include silicone oils or poiydimethyJsiloxanes, iluorosi!icones, alkoxyiated aliphatic acids, po!yethers (e.g., polyethylene glycols), branched polyvinyl ethers, alkyl acrylate polymers, alkyl methaeryiate polymers, polyalkoxyamines and combinations thereof. In some embodiments, the ibam inhibitors or anti-foam inhibitors comprises glycerol monostearate, polyglycol pahnitate, a trialkyl monothiophosphate, an ester of sulfonated rieinoieic acid, benzoylacetone, methyl salicylate, glycerol raonooleate, or glycerol dioleate. The amount of the foam inhibitors or anti-foam inhibitors may vary from about 0.01 wt. % to about 5 wt, %, from about 0.05 wt. % to about 3 wt. %, or from about 0.1 wt % to about 1 wt. % based on the total weight of the lubricating oil composition. Some suitable foam inhibitors or anti- foam inhibitors have been described in Moitier ct al., Theaustry and Technology of

Lubricants," 2nd Edition, London, Springer, Chapter 6, pages 190-193 (1996), which is incorporated herein by reference.

{00157] The lubricating oil composition disclosed herein can contain one or more pour point depressants that can lower the pour point of the lubricating oii composition. Any pour point depressant know by a person of ordinary skill in the art may be used in the lubricating oil composition. Non-limiting examples of suitable pom- point depressants include polyraethaerylates, alkyt acrylate polymers, aikyl methacrylate polymers, di(tetra*parafftn phenol)phthaIate, condensates of tetra-paraffm phenol, condensates of a chlorinated paraffin with naphthalene and combinations thereof. In some embodiments, the pour point depressant comprises an ethylene-vinyl acetate copolymer, a condensate of chlorinated paraffin and phenol, poiyaikyl stymie or the like. The amount of the pour point depressant may vary from about 0,01 wt, % to about 10 wt, %, from about 0,05 wt, % to about 5 wt %, or from about 0.1 wt. % to about 3 wt. %, based on the total weight of the lubricating oil composition, Some suitable pour point depressants have been described in Mortier et al. _} "Chemistry and Technology of Lubricants," 2nd Edition, London. Springer, Chapter 6, pages 187-1 S9 (1 96); and Leslie R. Rudmck, "Lubricant Additives: Chemistry and Applications," New York, Marcel Dekker, Chapter 1 1 , pages 329-354 (2003), both of which are incorporated herein by reference,

[00158] The lubricating oil composition disclosed herein can contain one or more demulsifiers that can promote oil -water separation in lubricating oil compositions that are exposed to water or steam. Any demulsifier known by a person of ordinary skill in the art may be used in the lubricating oil composition. Non-limiting examples of suitable demuisifiers include anionic surfactants (e.g., alkyl-naphifialene sulfonates, aikyl benzene sulfonates and the like), nonionic alkoxylated alky! phenol resins, polymers of alkylene oxides (e.g., polyethylene oxide, polypropylene oxide, block copolymers of ethylene oxide, propylene oxide and the like), esters of oil soluble acids, polyoxyethylene sorbitan ester and combinations thereof. The amount of the demutsifier may vary from about 0.01 wt. % to about 10 wt, %, from about 0,05 wt. % to about 5 wt. %, or from about 0.1 wt. % to about 3 wi %, based on the total weight of the lubricating oil composition. Some suitable demuisifiers have been described in Mortier ei at., "Chemistry and Technology of Lubricants." 2nd Edition, London, Springer, Chapter 6, pages 190-193 (1996), which is incorporated herein by reference.

|00159j The lubricating oil composition disclosed herein can contain one or more corrosion inhibitors that can reduce corrosion, Any corrosion inhibitor known by a person of ordinary skill in the art may be used in the lubricating oil composition. Non-limiting examples of suitable corrosion inhibitor include half esters o amides of dodecylsuccimc acid, phosphate esters, thiophospbates, alky! imidazolines, sarcosines and combinations thereof The amount of the corrosion inhibitor may vary from about 0.01 wt. % to about 5 wt. %, from about 0.05 wt, % to about 3 wt, %, or from about 0.1 wt, % to about 1 wt, %, based on the total weight of the lubricating oil composition. Some suitable corrosion inhibitors have been described in Mortier et ah, "Chemistry and Technology of Lubricants," 2nd Edition, London, Springer, Chapter 6, pages 193-1 6 (1996), which is incorporated herein by reference. |00160| The lubricating oil composition disclosed herein can contain one or more extreme pressure (BP) agents that can prevent sliding metal surfaces from seizing under conditions of extreme pressure, An extreme pressure agent known by a person of ordinary ski!! in. the art may be used in the lubricating oil composition. Generally, the extreme pressure agent is a compound that can combine chemically with a metal to form a surface film that prevents the welding of asperities in opposing metal surfaces under high loads. Non- limiting examples of suitable extreme pressure agents include sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, folly or partially esterifkd esters of trivalerit or pentavaleni acids of phosphorus, sulfurized olefins, dihydroearbyl polysulfldes, sulfurized Diels-Alder adducts, sulfurized dicyclopentadiene, sulfurized or co-sulfurked mixtures of fatty acid esters and monounsaturated olefins, eo-sulfurized blends of fatty acid, fatty acid ester and alpha-oiefin, functionally-substituted dihydroearbyl polysulfldes, ink- aldehydes, thia*ketones, epithio compounds, sulfur-containing ac tal derivatives, co- sulfurized blends of terpens and acyclic olefins, and polysulftde olefin products, amine salts of phosphoric acid esters or ihiophosphoric acid esters and combinations thereof. The amount of the extreme pressure agent may vary from about 0.01 wt, % to about 5 wt %, from about 0.05 wt, % to about 3 wt. %, or from about 0,1 wt, % to about 1 wt. %, based on the total weight of the lubricating oil composition. Some suitable extreme pressure agents have been described in Leslie R, udnick, "Lubricant Additives: Chemistry and Applications," New York, Marcel Dekker, Chapter 8, pages 223-258 (2003), which is incorporated herein by reference. (00161 ] The lubricating oil composition disclosed herein can contain one or more rust inhibitors that cart inhibit the corrosion of ferrous metal surfaces. Any rust inhibitor known by a person of ordinary skill in the art may be used in the lubricating oil composition. Non- limiting examples of suitable rust inhibitors include nonionic poiyoxyaikyiene agents, e.g., polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonyhphenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene octyl stearyl ether, polyoxyethylene oley! ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol monooleate, and polyethylene glycol monooleate; stearic acid and other fatty acids; dkarboxyiic acids; metal soaps; fatty acid amine salts; metal salts of heavy sulfonic acid; partial carboxylie acid ester of polyhydric alcohol; phosphoric esters; (short-chain) alkenyl succinic acids; partial esters thereof and nitrogen-containing derivatives thereof; synthetic a!karyisulfonates, e.g., metal dinonylnaphthalene sulfonates; and the like and mixtures thereof. The amount of the rust inhibitor may vary from about 0.01 wt. % to about 10 wt. %, from about 0.05 wi. % to about 5 wt, %, or from about 0.1 wt. % to about 3 wt, %, based on the total weight of the lubricating oil composition.

[00162] The lubricating oil composition disclosed herein ca contain one or more multifunctional additives. Non-limiting examples of suitable multifunctional additives include sulfurized oxymolybdenum dithiocarbamate, sulfurized oxymolybdenum organophosphorodithioate, oxymolybdenum monoglyeeride, oxymolybdenum diethylate amide, amine-molybdenum complex compound, and sulfur-containing molybdenum complex compound. {(101631 The lubricating oil composition disclosed herein can contain one or more viscosity Index improvers. Non-limiting examples of suitable viscosity index improvers include polymethacrylate type polymers, ethylene-propylene copolymers, siyrene-isoprene copolymers, hydrated siyrene-isoprene copolymers, polyisobutylene, and dispersant type Viscosity index improvers,

[001.64] The lubricating oil composition disclosed herein can contain one or more metal deactivators. Non-limiting examples of suitable metal deactivators include disalicylidene propylenediamine, triazok derivatives, thiadiazole derivatives, and mereaptobenzimidazoles.

[00165] If desired, the lubricant additives may be provided as an additive package or concentrate in which the additives are incorporated into a substantially inert, normally liquid organic diluent such as, for example, mineral oil, naphtha, benzene, toluene or xylene to form an additive concentrate. These concentrates usually contain from about 20% to about 80% by weight of such diluent. Typically, a neutral oil having a viscosity of about 4 to about 8.5 cSt at 100°C and preferably about 4 to about 6 cSt at 100°C will be used as the diluent, though synthetic oils, as well as other organic liquids which are compatible with the additives and finished lubricating oil can also be used. The additive package will typically contain one or more of the various additives, referred to above, in the desired amounts and ratios to facilitate direct combination with the requisite amount of the oil of lubricating viscosity.

[0016 1 fa t present invention, the sulfated ash content of the total lubricating oii composition is less than 5 wt %. less than 4 wt %, less than 3 wf. %, less than 2 wt. %, or less than i wt. %, as measured according to ASTM D874-07. (001671 The lubricating oil composition disclosed herein may be suitable for use as motor oils (or engine oils or crankcase oils), trunk piston engine oils, marine oils, transmission fluids, gear oils, power steering fluids, shock absorber fluids, brake fluids, hydraulic fluids and/or greases,

[001681 In one embodiment, the lubricating oil composition disclosed herein is a motor or engine oil. Such a motor oil composition may be used to lubricate all major moving parts in any reciprocating internal combustion engine, reciprocating compressors and in steam engines of crankcase design. In automotive applications, the motor oil composition may also be used to cool hot engine parts, keep the engine free of rust and deposits, and seal the rings and valves against leakage of combustion gases. The motor oil composition may comprise a base oil, a post-treated salt of a sulfurized aikyi-subsiituted hydroxyaromatic composition disclosed herein, and one or more optional additives.

( 01691 In one embodiment, the lubricating oi! composition disclosed herein is a gear oil for either automotive or industrial applications. The gear oil composition may be used to lubricate gears, rear axles, automotive transmissions, final drive axles, accessories in agricultural and construction equipment, gear housings and enclosed chain drives. The gear oil composition may comprise a base oil, a post-treated salt of a sulfurized alkyi-substituted hydroxyaromatic composition disclosed herein, and one or more optional additives

{00170} In one embodiment, the lubricating oil composition disclosed herein is a transmission fluid, The transmission fluid composition may be used in either automatic transmission or manual transmission to reduce transmission losses. The transmission fluid composition may comprise a base oil, a post-treated salt of a sulfurized alkyl-substituted hydroxyaromatic composition disclosed herein, and one or more optional additives.

J0017I I In one embodiment, the lubricating oil composition disclosed herein is a grease used in various appiications where extended lubrication is required and where oil would not be retained, e.g., on a vertical shaft. The grease composition may comprise a base oil, a post- treated salt of a sulfurized alkyl-substituted hydroxyaromatic composition disclosed herein, one or more optional additives and a thickener.

fOOl 72) The following non-limiting examples are illustrative of the present invention. fG0l73j The concentration of free unsuliurized alkyl-substituted hydroxyaromatic compound and its unsulfurized metal salts in the post-treated salt of the sulfurized alkyl- substituted hydroxyaromatic composition as disclosed herein and exemplified below, as well as lubricants and oil additives containing salts of the sulfurized alkyl-substituted hydroxyaromatic composition is determined by reverse phase High Performance Liquid Chromatography (HPLC). In the HPLC method, samples were prepared for analysis by weighing accurately 80 to 120 mg of sample into a 10 ml volumetric flask, diluting to the level mark with methylene chloride, and mixing until the sample is fully dissolved.

(001741 The HPLC system used in the HPLC method included a HPLC pump, a thermostatted HPLC column compartment, HPLC fluorescence detector, and PC-based chromatograph data acquisition system. The particular system described is based on an Agilent 1200 HPLC with ChemStation software. The HPLC column was a Phenomenex Luna C8(2) 150 x 4.6mm 5μ«ι ΙΟθΑ, P/N 00F4249E0.

[0 175] The following system settings were used in performing the analyses: [00176] Pump flow = 1.0 ml/mm

[001773 Maximum pressure - 200 bars

{00178] Fluorescence wavelength: 225 excitation 313 emission : Gain∞ 9

[00179] Column Thermostat temperature = 25°C

[00180] Injection Size = ^: 1 Τ of diluted sample

[00181] Eiution type: Gradient, reverse phase

[00182] Gradient: 0-7 rain 85/15 methano!/water switching to 100% methanol linear gradient,

[00183} Run time: 17 minutes

[00184] The resulting chromatograph typically contains several peaks. Peaks due to the free unsulfurized alky! -substituted hydroxyaromatic compound and its unsulfurized metal saits, which convert to free un-sulfurized hydroxyaiOmadc compound under these conditions, elute together at early retention times; whereas peaks due to sulf rized salts of aikyl- substituted hydroxyaromatic compositions typically elute at longer retention times. For purposes of quantitation, the area of the single largest peak of the free unsulfurized alkyl- substituted hydroxyaromatic compound and its unsulfurized metal salts was measured, and then that area was used to determine the concentration of the total free unsulfurized alkyl- substituted hydroxyaromatic compound and its unsulfurized metal salt species. The assumption is tha the speciation of a!kyl-substituted hydroxyaromatic compounds does not change; if something does change the speciation of the aikyl-substituted hydroxyaromatic compounds, then recalibratton is necessary. (00185] The area of the chosen peak is compared to a calibration curve to arrive at the wt-% of free alkylphenol and free unsuifurized salts of alkylphenols. The calibration curve was developed using the same peak in the chromatography obtained for the free unsulfurized alkylhydroxyaromatic compound used to make the phenate product.

EXAMPLE 1

[(H) 186] Preparation of Mannich Post-Treated Sulfurized Calcium Phenate Composition,

[60187] 10 g of an overbased sulfurized calcium phenate composition (commercially available from Chevron Oronite Company LLC) having a TPP content of about 8 wt % was heated to about S0°C and transferred to a iOOmi two-neck round bottom flask. The temperature in the flask was maintained at about 80°C while 5ml o toluene solvent (approximately 50 wt. % equivalent of the phenate charge) was added to the composition, immediately after the addition of solvent, 5 molar equivalents of paraformaldehyde (based on molar equivalent of residual TPP) was added and then the mixture was held at 80°C for 10 minutes. Next, 5 molar equivalents of diethylamine (based on molar equivalent of residual TPP) was then slowly added and the reaction conditions were maintained at a temperature of 80°C for a reaction time of 4 hours. At the end of the reaction time, the solvent was distilled under vacuum. The distilled product had a residual total TPP content of 0.53 wt. %, which resulted in a 93.38% reduction. EXAMPLES 2 to 14 and COMPARATIVE EXAMPLES A and B

[00188 j The following examples were repeated ίη substantially the same manner as Example I using the reactants and reaction conditions as set fortii below in Table L In Exampie 5, the overbased suifurized calcium phenate composition was first quenched with 1 molar equivalent of acetic acid prior to the addition of the Mannich reagents. For the following examples, the source of formaldehyde was paraformaldehyde and the starting sulfur .ed calcium phenate composition was an overbased sulfurized calcium phenate composition having a TPP content of about 8.0 wt, %.

TABLE 1

EXAMPLES 15 to 25 and COMPARATIVE EXAMPLES C-E

(00189] The following examples were repeated in substantially the same manner as Example 1 using the reactants and reaction conditions as set forth below in Table 2, For the following examples the source of formaldehyde was either parafomiaidehyde (PF) or formalin (F) and the starting sulfurized calcium phenate composition was an overbased sulfurized calcium phenate composition having a TPP content of about 5.5 wt ¾.

TABLE 2

EXAMPLES 26 to 29

[00190] The following examples were repeated in substantially the same manner as Example 1 using the reaciants and reaction conditions as set forth below in Table 3, For each example, the source of formaldehyde was paraformaldehyde and the starting sulfurized calcium phcnate composition was not overbased and had a TPP content of about 2.8 wt. %.

TABLE 3

EXAMPLE 30

[00191 J Preparation of Man ich Post-Treated Tetrapropenyi Alkylphenol

[00192] To 150g of tetrapropenylphenol (TPP) in a 1 liter three neck round bottom ilask fitted with a magnetic siirrer, condenser and nitrogen inlet was added 500ml of anhydrous benzene. The solution was stirred vigorously under a nitrogen atmosphere at ambient temperature, and paraformaldehyde (I9.55g, 1.2eq) was added, followed by addition of diethyl amine (67.9ml, 1 ,2eq) over a 5 minute period. The reaction mixture was heated to 80°C for 4 hours, then cooled to ambient temperature. Ethyl acetate was then added (500ml) and the reaction mixiure was washed with 3 x 2G0«»I of IN HCl, dried over MgSO* and the solvent removed under reduced pressure,

{00193] The crude product was purified using flash column chromatography: ^! H NMR 6 0.2-1.9 (m, 31.9 H, CH3, CH2), S 2.51 (t, 4.0 H,CH2), § 3.7 (s, 2.0 II. CH2-N), 3 6.5 - 7.3 (m, 3.0 H, aromatic CH).

|00194j Testing

{001951 The objective of the study was to evaluate the ability of the mannich post- treated tetrapropeiiyi aikyiphenol of Example 30, to demonstrate or mimic biological activities consistent with agonism of natural estrogens,

[00196 Procedure

[001971 In accordance with OECD Guideline No. 440. the OECD principles of GLP, and U.S. EPA GLP Standards (40 CFR, Pat 160 and 792), the mamiich post-treated tetraprope yl aikyiphenol of Example 30 was administered orally by gavage to test groups of 6 ovariectomized female Crl:CD(SD) rats once daily for 3 consecutive days at 75, 250, 500, and 1000 mg/kg day. A positive control group ( 17a-ethyn lestradiol at 0.2 mg kg/day) and a vehicle control group (com oil) were also tested. Animals were euthanized by carbon dioxide inhalation approximately 24 hours following administration of the last dose, and a gross examination of the uterus was conducted; and uterine weights (wet and blotted) were recorded. [001981 Results:

(001991 Body Weights

[00200] Significant (p<0,05 or p<0.1 ) mean body weight losses were noted in the animals (250, 500, and ! 000 mg/kg/day treatment groups) treated with mannich post-treated tetrapropenyi aikylphenoi of Example 30 and the positive control animals (0.2 mg kg/day estradiol) compared to the mean body weight gains in the vehicle control animals over the treatment period,

1002011 Uterine Weights

[00202] As shown in Figure 1. there was no significant difference in mean blotted or wet uterine weights at any of the four treatment groups (75, 250. 500, and 1000 mg kg day) compared to the vehicle control group. Both mean blotted and wet uterine weights in the positive control grou were significantly increased (p<0.0i) compared to the vehicle control group. It is believed that TPP typically causes dose-dependent increase in uterine weights (1, 2, 3 and 7 fold at 75, 125, 250, and 500 mg/kg/day, respectively,

100203) Conclusion

[00204] OECD Guideline No. 440 (Uterotrophic Assay) indicates that a test should be considered positive if there is a statistical increase in uterine weight (p<0.05) when compared to vehicle control. Based on this guidance, the data suggests that the mannich post-treated tetrapropenyi aikylphenoi of Example 30 does not appear to demonstrate or mimic the biological activity consistent with agonists of natural estrogen in the Uterotrophic assay. EXAMPLE 31

100205] Preparation of Mannich Post Treated Sulfurized Calcium Phenate Composition,

{00206] A reactor containing 418.6 grams of overbased sulfurized calcium phenate composition (commercially available from Chevron Oronite Company LLC) having a total TPP content of 5,5 wt % was heated to a reaction temperature of 100°C and 12.6 grams of solid para-formaldehyde was added. This mixture was stirred 5 minutes and then 30.5 grams of di-ethylamioe was added over 3 minutes. The reaction mixture was held at I0Q°C for 5 hours. The reaction was stripped, by placed under vacuum (250 mm Hg) and heated to 130°C and held there for 30 minutes. The vacuum was broken with nitrogen, the reaction allowed to cool to approximately i 0(fC and the reactor contents isolated to afford 431.6 grams of crude product, A portion (214.9 grams ) of the crude product was filtered with the aid of filter aid (Ceiite) to afford 187.7 grams of final product with the following properties: TBN ~ 260; wt. % Total TPP - 0.3; wt.. %, % Ca - 9.2, wt. % Sulfur - 3.2, wt % C02 - 4.78, Volume % Sediment - 0.01, wt. % Nitrogen - 035, Viscosity - 504 cSt (100°C) as determined by ASTM D445-88.

[00207] Repeating the above reaction while varying the reaction temperature between SOT and 130°C; the hold time between 3.5 hrs and 6 hrs; the stripping temperature between 1 10°C and 130°C and stripping vacuum between 250 mm Hg and 350 Hg; afforded filtered final products with viscosities ranging from 389 cSt (110 ^e C) to 538 cSt (100°C). (ΘΘ208) It will be understood that various modifications may be made to the embodiments disclosed herein. Therefore the above description should not be construed as limiting, but merely as exemplifications of preferred embodiments. For example, the functions described above and impiemenied as the best mode for operating the present invention are for illustration purposes only. Other arrangements aid methods may be impiemented by those skilled in the art without departing from the scope and spirit of this invention. Moreover, those skilled in the art will envision other modifications within the scope and spirit of the claims appended hereto.