阅读说明：本技术 噁唑啉改性分散剂 (Oxazoline modified dispersant ) 是由 阿图罗·卡兰扎 姜胜 约翰·洛佩尔 于 2020-01-10 设计创作，主要内容包括：本公开涉及具有分散剂特性的<Image he="59" wi="59" file="DDA0002362363670000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>唑啉改性的润滑添加剂和包含这种分散剂润滑添加剂的润滑油组合物。本公开还涉及包含本公开的添加剂的润滑剂组合物用于改善发动机润滑剂组合物的烟尘或污泥处理特征同时提供稳健和一致的摩擦性能的用途。(The disclosure relates to compositions having dispersant properties Oxazoline-modified lubricant additives and lubricating oil compositions containing such dispersant lubricant additives. The present disclosure also relates to the use of a lubricant composition comprising the additives of the present disclosure to improve soot or sludge handling characteristics of an engine lubricant composition while providing robust and consistent tribological properties.)

1. A lubricant dispersant, comprising:

a reaction product of a hydrocarbyl-substituted succinamide or succinimide dispersant and an oxazoline or oxazoline derivative to form the lubricant dispersant having one or more pendant hydrocarbyl amide groups;

wherein the hydrocarbyl-substituted succinamide or succinimide dispersant is derived from a hydrocarbyl-substituted acylating agent reacted with a polyalkylene polyamine; and

wherein the hydrocarbyl substituent of the succinamide or succinimide dispersant is a linear or branched hydrocarbyl group having a number average molecular weight of about 250 to about 5,000 as measured by GPC using polystyrene as a calibration standard.

2. The lubricant dispersant of claim 1, wherein the oxazoline or the oxazoline derivative includes a pendant hydrocarbyl group in one or a combination of oxazoline ring positions 2,4, 5; or wherein the oxazoline or the oxazoline derivative is selected from the group consisting of 2-ethyl-2-oxazoline; 2-methyl-2-oxazoline; 2-benzyl-4, 4-dimethyl-2-oxazoline; 2-ethyl-4, 4-dimethyl-2-oxazoline; 2,4, 4-trimethyl-2-oxazoline; 4, 4-dimethyl-2-oxazoline; 2- (2, 6-dimethoxyphenyl) -4, 4-dimethyl-2-oxazoline; 2-phenyl-2-oxazoline; 2- [1- (hydroxymethyl) ethyl ] oxazoline; mixtures thereof and derivatives thereof.

3. The lubricant dispersant of claim 1, wherein the acylating agent is selected from the group consisting of maleic anhydride, maleic acid, malic acid, tartaric acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, ethylmaleic anhydride, dimethylmaleic anhydride, methylmaleic acid, dimethylmaleic acid, hexylmaleic acid, and combinations thereof; or wherein the one or more side chain hydrocarbyl amide groups extend from an amine moiety provided by the polyalkylene polyamine.

4. The lubricant dispersant of claim 1, wherein the hydrocarbyl substituent is derived from one or more of ethylene, propylene, isopropene, butene, isobutene, octane, hexane, decene, pentene, isopentene, neopentene, or combinations thereof; or wherein the hydrocarbyl substituent is derived from an olefin copolymer; or wherein the hydrocarbyl substituent of the succinamide or the succinimide is a linear or branched hydrocarbyl group having a number average molecular weight of from about 250 to about 3,000 as measured by GPC using polystyrene as a calibration standard.

5. The lubricant dispersant of claim 1 wherein the polyalkylene polyamine is selected from the group consisting of a mixture of polyethylene polyamines having an average of 5 to 7 nitrogen atoms, triethylene tetramine, tetraethylene pentamine, and combinations thereof; or wherein the reaction product is the hydrocarbyl-substituted succinimide and has a ratio of pendant amide groups to imide groups of from about 0.5: 1 to about 5: 1.

6. The lubricant dispersant of claim 2 wherein the hydrocarbyl side group is selected from the group consisting of C1 to C32 hydrocarbyl, substituted or unsubstituted aromatic, substituted or unsubstituted heterocyclic aromatic, hydroxyalkyl, and mixtures thereof.

7. The lubricant dispersant of claim 3, wherein the amine moiety is a primary amine moiety, a secondary amine moiety, or a combination thereof; or further comprises a molar ratio of about 0.33: 1 to about 6: 1 molar equivalents of said oxazoline or said oxazoline derivative to said amine moieties provided by said polyalkylene polyamine reactant.

8. The lubricant dispersant of claim 2 wherein the olefin copolymer is obtained from ethylene and one or more C3 to C10 α olefins.

9. The lubricant dispersant of claim 2 wherein said polyalkylene polyamine has the formula

Wherein

Each R and R' is independently a divalent C1-C6 alkylene linking group;

R₁and R₂Each independently hydrogen, C1-C6 alkyl, or together with the nitrogen atom to which they are attached form a 5-or 6-membered ring, optionally fused with one or more aromatic or non-aromatic rings; and

n is an integer from 0 to 8.

10. A lubricant composition, comprising:

a base oil of lubricating viscosity;

a dispersant derived from a hydrocarbyl-substituted succinamide or succinimide reacted with an oxazoline or oxazoline derivative, the dispersant having one or more pendant hydrocarbyl amide groups extending from an amine portion thereof;

wherein the hydrocarbyl-substituted succinamide or succinimide is derived from a hydrocarbyl-substituted succinic anhydride or acid reacted with a polyalkylene polyamine that provides the one or more amine moieties; and

wherein the hydrocarbyl substituent of the succinamide or succinimide is a straight or branched chain hydrocarbyl group having a number average molecular weight of from about 250 to about 5,000 as measured by GPC using polystyrene as a calibration standard.

11. The lubricant composition of claim 10, wherein the oxazoline or the oxazoline derivative includes a pendant hydrocarbyl group in one or a combination of oxazoline ring positions 2,4, 5; or wherein the oxazoline or the oxazoline derivative is selected from the group consisting of 2-ethyl-2-oxazoline; 2-methyl-2-oxazoline; 2-benzyl-4, 4-dimethyl-2-oxazoline; 2-ethyl-4, 4-dimethyl-2-oxazoline; 2,4, 4-trimethyl-2-oxazoline; 4, 4-dimethyl-2-oxazoline; 2- (2, 6-dimethoxyphenyl) -4, 4-dimethyl-2-oxazoline; 2-phenyl-2-oxazoline; 2- [1- (hydroxymethyl) ethyl ] oxazoline; mixtures thereof and derivatives thereof.

12. The lubricant composition of claim 10, wherein the hydrocarbyl-substituted succinic anhydride or acid is hydrocarbyl-substituted maleic anhydride, maleic acid, malic acid, tartaric acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, ethylmaleic anhydride, dimethylmaleic anhydride, methylmaleic acid, dimethylmaleic acid, hexylmaleic acid, or a combination thereof; or wherein the amine moieties provided by the polyalkylene polyamine are selected from one of primary amines, secondary amines, or combinations thereof; or wherein the hydrocarbyl substituent is a linear or branched hydrocarbyl group having a number average molecular weight of from about 250 to about 3,000 as measured by GPC using polystyrene as a calibration standard; or wherein the polyalkylene polyamine is selected from the group consisting of mixtures of polyethylene polyamines having an average number of nitrogen atoms of from 5 to 7, triethylene tetramine, tetraethylene pentamine, and combinations thereof; or wherein the dispersant is the hydrocarbyl-substituted succinimide and the side chain amide groups to imide groups ratio is from 0.5: 1 to 5: 1; or wherein the hydrocarbyl substituent of the dispersant is derived from one or more of ethylene, propylene, isopropene, butene, isobutylene, octane, hexane, decene, pentene, isopentene, neopentene, or combinations thereof; or wherein the hydrocarbyl substituent of the dispersant is an olefin copolymer.

13. The lubricant composition of claim 12 wherein the hydrocarbyl side group is selected from C1 to C32 hydrocarbyl groups, substituted or unsubstituted aromatic groups, substituted or unsubstituted heterocyclic aromatic groups, hydroxyalkyl groups, and mixtures thereof, or wherein the olefin copolymer is obtained from ethylene and one or more C3 to C10 α olefins.

14. The lubricant composition of claim 12, further comprising a molar ratio of about 0.33: 1 to about 6: 1 molar equivalents of oxazoline or oxazoline derivative to amine moieties provided by the polyalkylene polyamine reactant.

15. The lubricant composition of claim 12, wherein the polyalkylene polyamine has the formula:

wherein

Each R and R' is independently a divalent C1-C6 alkylene linking group;

R₁and R₂Each independently hydrogen, C1-C6 alkyl, or together with the nitrogen atom to which they are attached form a 5-or 6-membered ring, optionally fused with one or more aromatic or non-aromatic rings; and

n is an integer from 0 to 8.

Technical Field

The present disclosure relates to oxazoline-modified lubricating additives, such as dispersants and/or dispersant viscosity index modifiers, and lubricating oil compositions containing such additives. The present disclosure also relates to methods or uses of lubricant compositions comprising the additives herein to provide dispersancy while also improving the tribological properties of the lubricant.

Background

Engine oils contain a number of additives to provide various functions to the lubricant. Dispersants or dispersant viscosity modifiers are one additive in formulating lubricants that aid in suspending deposited precursors, soot, sludge or other contaminants that may degrade the performance of the lubricant over time. In many cases, the dispersant or dispersant viscosity modifier contains a nitrogen moiety that aids in dispersion and/or provides other functions, such as antiwear or viscosity modification. For example, typical dispersants include the reaction product of polyisobutylene with maleic anhydride to form polyisobutylene succinic anhydride (PIBSA). The PIBSA is then reacted with various nitrogen-containing compounds to form dispersants or dispersant viscosity modifiers. Other common dispersants are formed by reacting an olefin copolymer with maleic anhydride to form an olefin copolymer succinic anhydride (e.g., ethylene/propylene succinic anhydride or EPSA). The copolymer may also be reacted with various nitrogen compounds to form a functionalized dispersant or dispersant viscosity modifier. However, in some cases, the primary and/or secondary amines typically used in dispersant functionalization tend to be incompatible with engine elastomer seals and/or affect the tribological properties of the lubricant. In the past, various borates, anhydrides, and carboxylic acids have been used to attenuate the effect of unprotected amines, but the use of such additional lubricant components tends to complicate lubricant formulation and is undesirable.

Disclosure of Invention

In one aspect, the present disclosure relates to a lubricant dispersant comprising the reaction product of a hydrocarbyl-substituted succinamide or succinimide dispersant and an oxazoline or oxazoline derivative to form a lubricant dispersant having one or more pendant hydrocarbyl amide groups. The hydrocarbyl-substituted succinamide or succinimide dispersants are derived from a hydrocarbyl-substituted acylating agent reacted with a polyalkylene polyamine. The hydrocarbyl substituent of the succinamide or succinimide dispersant is a linear or branched hydrocarbyl group having a number average molecular weight of from about 250 to about 5,000 as measured by GPC using polystyrene as a calibration standard.

In the foregoing embodiments, the oxazoline or oxazoline derivative may include a pendant hydrocarbyl group in one or a combination of oxazoline ring positions 2,4, 5. In any of the preceding embodiments, the hydrocarbyl pendant group may be selected from C1 to C32 hydrocarbyl groups, substituted or unsubstituted aromatic, substituted or unsubstituted heterocyclic aromatic, hydroxyalkyl groups, and mixtures thereof. In any of the preceding embodiments, the oxazoline or oxazoline derivative may be selected from 2-ethyl-2-oxazoline; 2-methyl-2-oxazoline; 2-benzyl-4, 4-dimethyl-2-oxazoline; 2-ethyl-4, 4-dimethyl-2-oxazoline; 2,4, 4-trimethyl-2-oxazoline; 4, 4-dimethyl-2-oxazoline; 2- (2, 6-dimethoxyphenyl) -4, 4-dimethyl-2-oxazoline; 2-phenyl-2-oxazoline; 2- [1- (hydroxymethyl) ethyl ] oxazoline; mixtures thereof and derivatives thereof.

In any of the preceding embodiments, the acylating agent may be selected from the group consisting of maleic anhydride, maleic acid, malic acid, tartaric acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, ethylmaleic anhydride, dimethylmaleic anhydride, methylmaleic acid, dimethylmaleic acid, hexylmaleic acid, and combinations thereof.

In any of the preceding embodiments, the one or more pendant hydrocarbyl amide groups extend from an amine moiety provided by the polyalkylene polyamine. In any of the preceding embodiments, the amine moiety can be a primary amine moiety, a secondary amine moiety, or a combination thereof. In any of the preceding embodiments, the dispersant may comprise a molar ratio of about 0.33: 1 to about 6: 1 molar equivalents of oxazoline or oxazoline derivative to the amine moieties provided by the polyalkylene polyamine reactant.

In any of the preceding embodiments, the hydrocarbyl substituent may be derived from one or more of ethylene, propylene, isopropene, butene, isobutene, octane, hexane, decene, pentene, isopentene, neopentene, and combinations thereof. In any of the preceding embodiments, the hydrocarbyl substituent may be derived from an olefin copolymer. In any of the preceding embodiments, the olefin copolymer may be from ethylene and one or more C3 to C10_αAn olefin is obtained. In any of the preceding embodiments, the hydrocarbyl substituent of the succinamide or succinimideMay be a linear or branched hydrocarbon group having a number average molecular weight of from about 250 to about 3,000 as measured by GPC using polystyrene as a calibration standard. In any of the preceding embodiments, the polyalkylene polyamine may have the formula

Wherein each R and R' is independently a divalent C1 to C6 alkylene linking group, and each R₁And R₂Independently hydrogen, C1 to C6 alkyl or together with the nitrogen atom to which they are attached form a5 or 6 membered ring, optionally fused to one or more aromatic or non-aromatic rings; n is an integer between 0 and 8. In any of the preceding embodiments, the polyalkylene polyamine may be selected from the group consisting of mixtures of polyethylene polyamines having an average of 5 to 7 nitrogen atoms, triethylene tetramine, tetraethylene pentamine, and combinations thereof. In any of the preceding embodiments, the reaction product may be a hydrocarbyl-substituted succinimide, and may have a ratio of pendant amide groups to imide groups of about 0.5: 1 to about 5: 1.

In another aspect, the present disclosure relates to a lubricant composition comprising a base oil of lubricating viscosity and a dispersant derived from a hydrocarbyl-substituted succinamide or succinimide reacted with an oxazoline or oxazoline derivative, and wherein the dispersant has one or more pendant hydrocarbyl amide groups extending from an amine portion thereof. The hydrocarbyl-substituted succinamides or succinimides are derived from a hydrocarbyl-substituted succinic anhydride or acid reacted with a polyalkylene polyamine that provides one or more amine moieties. The hydrocarbyl substituent of the succinamide or succinimide is a straight or branched chain hydrocarbyl group having a number average molecular weight of from about 250 to about 5,000 as measured by GPC using polystyrene as a calibration standard.

In any of the preceding embodiments, the oxazoline or oxazoline derivative may include a pendant hydrocarbyl group in one or a combination of oxazoline ring positions 2,4, 5. In any of the preceding embodiments, the hydrocarbyl pendant group may be selected from C1 to C32 hydrocarbyl groups, substituted or unsubstituted aromatic, substituted or unsubstituted heterocyclic aromatic, hydroxyalkyl groups, and mixtures thereof. In any of the preceding embodiments, the oxazoline or oxazoline derivative may be selected from 2-ethyl-2-oxazoline; 2-methyl-2-oxazoline; 2-benzyl-4, 4-dimethyl-2-oxazoline; 2-ethyl-4, 4-dimethyl-2-oxazoline; 2,4, 4-trimethyl-2-oxazoline; 4, 4-dimethyl-2-oxazoline; 2- (2, 6-dimethoxyphenyl) -4, 4-dimethyl-2-oxazoline; 2-phenyl-2-oxazoline; 2- [1- (hydroxymethyl) ethyl ] oxazoline; mixtures thereof and derivatives thereof.

In any of the preceding embodiments, the hydrocarbyl-substituted succinic anhydride or acid may be hydrocarbyl-substituted maleic anhydride, maleic acid, malic acid, tartaric acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, ethylmaleic anhydride, dimethylmaleic anhydride, methylmaleic acid, dimethylmaleic acid, hexylmaleic acid, or a combination thereof. In any of the preceding embodiments, the amine moiety provided by the polyalkylene polyamine may be selected from one of a primary amine, a secondary amine, or a combination thereof. In any of the preceding embodiments, the dispersant further comprises a molar ratio of about 0.33: 1 to about 6: 1 molar equivalents of oxazoline or oxazoline derivative to the amine moieties provided by the polyalkylene polyamine reactant.

In any of the preceding embodiments, the hydrocarbyl substituent may be a straight or branched chain hydrocarbyl group having a number average molecular weight of from about 250 to about 3,000 as measured by GPC using polystyrene as a calibration standard. In any of the preceding embodiments, the polyalkylene polyamine may have the formula

Wherein each R and R' is independently a divalent C1 to C6 alkylene linking group, and each R₁And R₂Independently hydrogen, C1 to C6 alkyl or together with the nitrogen atom to which they are attached form a5 or 6 membered ring, optionally fused to one or more aromatic or non-aromatic rings; n is an integer between 0 and 8. In any of the preceding embodiments, the polyalkylene polyamine may be selected from the group consisting of mixtures of polyethylene polyamines having an average of 5 to 7 nitrogen atoms, triethylene tetramine, tetraethylene pentamine, and combinations thereof. In any of the preceding embodiments, dispersingThe dispersant may be a hydrocarbyl-substituted succinimide, and may have a ratio of pendant amide groups to imide groups of from 0.5: 1 to 5: 1 in any of the foregoing embodiments, the hydrocarbyl substituent of the dispersant may be derived from one or more of ethylene, propylene, isopropene, butene, isobutene, octane, hexane, decene, pentene, isopentene, neopentene, or combinations thereof.

In another aspect, the present disclosure relates to a method of use or use of any embodiment of the above-described lubricant additive or lubricant composition to provide dispersancy and provide robust and consistent boundary friction. In any embodiment, the method or use can provide robust and consistent boundary friction regardless of the processing rate of the additive, the oxazoline capping agent, and/or the molar equivalents of oxazoline moieties to amine moieties.

Drawings

FIG. 1 is a graph showing the dispersant performance of an example dispersant at about 0.665 weight percent in a lubricating oil; and

FIG. 2 is a graph comparing boundary friction of lubricants including dispersants with different types of nitrogen capping agents.

Detailed Description

Lubricant additives and lubricating oil compositions comprising such additives are described herein. In one approach, the lubricant additive may include a dispersant or dispersant viscosity modifier post-treated with an oxazoline moiety to provide good dispersancy while providing improved and consistent tribological properties. In one method or embodiment, the dispersant or dispersant viscosity modifier herein may be a succinamide or succinimide compound or polymer reacted or post-treated with an oxazoline or oxazoline derivative to form the lubricant additive of the present invention, which includes one or more pendant or side chain hydrocarbyl amide groups. This post-treatment may be applied to dispersant additives, dispersant viscosity modifier additives, and the like, depending on the desired application or use. For ease of discussion, dispersant additives will be used throughout this disclosure for simplicity, but this discussion also applies to dispersant viscosity modifier additives, dispersant viscosity index improvers, or other nitrogen or amine functionalized additives that may require more robust tribological properties as well as dispersant function of the additive.

As described in the background, lubricants or engine oils typically include a number of additives. Dispersants are common additives in engine oils for dispersing sludge, carbon, soot, oxidation products and other deposit precursors. Such additives help keep engine components clean, extend engine life, and help maintain proper emissions and good fuel economy. In some methods, the dispersant accomplishes this task by inhibiting particle-to-particle aggregation. Thus, as the amount of dispersant in a lubricant composition increases, the soot and sludge handling performance of the lubricant generally improves, but in some cases increasing the amount of these additives can adversely affect other properties of the fluid. In another aspect, described herein are lubricant additives having dispersant properties, and lubricating oils comprising such additives, having one or more of the following: comparable (or better) dispersant performance, improved tribological properties, and at the same time more robust or consistent tribological performance, regardless of the treatment rate, the type of amine post-treatment moiety, and/or the molar equivalents between the amine post-treatment moiety and the primary/secondary amines of the dispersant.

In one aspect, the lubricant additive is the reaction product of a hydrocarbyl-substituted succinamide or succinimide dispersant and an oxazoline or oxazoline derivative to form a lubricant dispersant having one or more side chain hydrocarbyl amide groups that cap primary and/or secondary amines on the dispersant molecule. the hydrocarbyl-substituted succinamide or succinimide dispersant is derived from a hydrocarbyl-substituted acylating agent reacted with a polyalkylene polyamine. the hydrocarbyl substituent of the succinamide or succinimide dispersant is a linear or branched hydrocarbyl group having a number average molecular weight of from about 250 to about 5,000, as measured by GPC using polystyrene as a calibration benchmark (in other methods, from about 250 to about 3,000.) in some embodiments, the linear or branched hydrocarbyl group is derived from ethylene, propylene, isopropene, butylene, isobutylene, octane, hexane, decene, pentene, isopentene, neopentene, and combinations thereof, or in other embodiments, the linear or branched hydrocarbyl group is derived from a linear or branched hydrocarbyl group derived from ethylene, propylene, isopropenyl, butylene, isobutylene, octane, hexane, decene, pentene, isopentene, neopentene, and combinations thereof, or in other embodiments, the branched chain hydrocarbyl-terminated olefin dispersant is a branched chain hydrocarbyl-terminated ethylene-terminated primary amine dispersant or oxazoline-terminated or oxazoline derivative, and/or a branched chain hydrocarbyl-terminated oxazoline-terminated olefin dispersant is provided herein.

Also disclosed herein is a method or use of the chemical modification of oxazoline or oxazoline derivatives as lubricant additives, which unexpectedly provides more robust tribological properties as well as dispersant properties of the additives. The present disclosure provides a method of capping exposed primary and/or secondary amines by a post-treatment reaction with an oxazoline or oxazoline derivative. It has also been demonstrated that unexpected improvements in dispersibility and improved tribological properties at low treat rate performance can also be achieved in certain applications when the amine is capped with certain oxazolines. As described below, a variety of oxazoline derivatives are compatible with the present disclosure. Each component will be described further below, starting with the oxazoline post-treatment component first, then the dispersant molecule, and finally the amine-functional component.

Oxazoline post-treatment:

in one aspect, the lubricious additive herein is post-treated or reacted with an oxazoline-derived capping agent, such as an oxazoline of formula I or a derivative thereof

Wherein R is₁-R₃Each independently selected from the group consisting of: hydrogen, halo, nitro, cyano, C₁To C₃₂Aliphatic, phenyl, naphthyl, 3-7 membered heterocyclyl, 5-6 membered heteroaryl, and wherein said C₁To C₃₂Up to 5 carbons of the aliphatic group may be independently and optionally replaced by a divalent group selected from: -O-, -NH-, -N (C)_1-4Alkyl) -, -C (O) O-, -C (O) NH-, -C (O) N (C)₁₄Alkyl) -. In some embodiments or methods, each R is₁-R₃May be independently and optionally substituted with up to three substituents selected from: c₁To C₆Alkyl, phenyl, naphthyl, 3-7 membered heterocyclyl, 5-6 membered heteroaryl, halo, nitro and cyano. In other aspects, R₂Is hydrogen, halo or C_1-4An alkyl group.

In another embodiment, R₁Selected from the group consisting of: halo, nitro, cyano, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-heptyl, 2-ethylhexyl, phenyl, furyl, thienyl, 2H-pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, 1,3, 4-thiadiazolyl, 2H-pyranyl, 4-H-pyranyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazolyl, pyrazinyl and 1,3, 5-triazinyl, optionally substituted with up to three substituents selected from the group consisting of C, nitro, cyano, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-heptyl, 2-ethylhexyl, phenyl, furyl, thienyl, pyrrolyl₁To C₆Alkyl, phenyl, halo, nitro and cyano.

In some methods, R₁Is ethyl or phenyl, or R₁Possibly hydrogen. In other methods, R₂Is hydrogen. In some other embodiments, R₃Is hydrogen. In some further embodiments, R₃And R₂Are all hydrogen. In a further embodiment, R₁Is ethyl or phenyl, and R₃And R₂Are all hydrogen.

In other methods or embodiments, the oxazoline or derivative thereof suitable for use as an end-capping agent herein may be selected from the group consisting of 2-phenyl-2-oxazoline; 2-ethyl-2-oxazoline; 2-methyl-2-oxazoline; 2-benzyl-4, 4-dimethyl-2-oxazoline; 2-ethyl-4, 4-dimethyl-2-oxazoline; 2,4, 4-trimethyl-2-oxazoline; 4, 4-dimethyl-2-oxazoline; 2- (2, 6-dimethoxyphenyl) -4, 4-dimethyl-2-oxazoline; 2- [1- (hydroxymethyl) ethyl]An oxazoline; mixtures thereof and derivatives thereof. In yet other methods or embodiments, the oxazoline or derivative thereof includes a pendant group at positions 2,4, and 5 (or any combination thereof), or a combination thereof, where the pendant group is selected fromFrom heterocycles, aromatics, C₁To C₃₂And mixtures thereof.

In some optional methods, the capping ratio of the primary and/or secondary amines of the lubricating additives herein can be from about 5% to about 100%, in other methods from about 5% to about 70%, from about 5% to about 50%, and in yet other methods from about 7% to about 35% capping. In these optional methods, the capping ratio can range from at least about 5%, at least about 10%, at least about 20%, at least about 30%, at least about 40%, or at least about 50% and not greater than about 100%, not greater than about 90%, not greater than about 80%, not greater than about 70%, or not greater than about 60%. As used herein, the optional capping ratio is the percentage of primary or secondary amines that have been capped or post-treated with at least oxazoline or a derivative thereof. In some processes, the molar ratio of oxazoline or derivative thereof to active amine (i.e., primary and/or secondary amine) is from about 9: 1 to about 0.33: 1, and in other processes from about 0.33: 1 to about 6: 1; from about 3: 1 to about 1: 1 in other processes; and in yet other methods from about 3: 1 to about 1.5: 1. In another method, the molar ratio of oxazoline or derivative thereof to active amine is about 1: 1. The percentage of capping in the alternative method is determined by measuring the nitrogen concentration (from the amine or secondary amine) of the additive before and after the capping reaction using known nitrogen measurement techniques.

In some methods, the reaction product described herein is a hydrocarbyl-substituted succinimide, and when capped with an oxazoline or oxazoline derivative of formula I, as described above, the ratio of amide groups to imide groups is from about 0.5: 1 to about 5: 1.

Hydrocarbyl-substituted succinamide or succinimide dispersants:

the hydrocarbyl-substituted succinamides or succinimides of the present disclosure are derived from a hydrocarbyl-substituted acylating agent reacted with a polyalkylene polyamine the hydrocarbyl substituent of the succinimide or succinamide is a linear or branched hydrocarbyl group having a number average molecular weight of from about 250 to about 10,000 as measured by GPC using polystyrene as a calibration standard as discussed in more detail below the linear or branched hydrocarbyl group may be derived from, for example, polyisobutylene (or other olefin) or olefin copolymers obtained from an olefin ethylene and one or more C3 to C10 α olefins.

In one embodiment, the hydrocarbyl-substituted polycarboxylic acid or anhydride may be prepared by first reacting the double bond on the hydrocarbyl terminal group with an acylating agent (e.g., maleic acid or maleic anhydride) by a thermal ene reaction and/or a halogenated condensation to form the hydrocarbyl-substituted succinic acid or anhydride, see, for example, U.S. patent 7,897,696, U.S. Pat. No. 3,3,361,673, and U.S. Pat. No. 3,676,089, which are incorporated herein by reference. Alternatively, hydrocarbyl-substituted polycarboxylic acids or anhydrides (e.g., hydrocarbyl-substituted succinic anhydrides) can be prepared by reacting chlorinated polyolefins with maleic anhydride, as described, for example, in U.S. Pat. No. 3,172,892, the disclosure of which is also incorporated by reference. Further discussion of hydrocarbyl-substituted succinic anhydrides may be found in, for example, US 4,234,435; the disclosures of which are incorporated by reference, are found in US5,620,486 and US5,393,309. The reaction temperature for forming the hydrocarbyl-substituted succinic acid or anhydride is from about 100 ℃ to about 250 ℃. This reaction is often promoted by the addition of chlorine. Alkenyl succinimides or succinamides in which the succinic group contains a hydrocarbyl substituent containing at least 4 carbon atoms can be used in the present disclosure and are described, for example, in US3,172,892; US3,202,678; US3,216,936; US3,219,666; US3,254,025; US3,272,746; US 4,234,435; US 4,613,341; and US5,575,823, the disclosures of all of which are hereby incorporated by reference.

In hydrocarbyl-substituted polycarboxylic acids or anhydrides, such as alkenyl succinic acids or anhydrides, the succinic moiety: the ratio of hydrocarbyl backbone is from about 0.8: 1 to about 2: 1, or from about 1: 1 to about 1.8: 1, or from about 1.2: 1 to about 1.5: 1.

The acylating agent of the above process is an unsaturated substituted or unsubstituted organic acid or anhydride, such as a maleic or fumaric reactant of the general formula:

wherein X and X 'are the same or different, provided that at least one of X and X' is a group capable of reacting to esterify an alcohol, form an amide or amine salt with ammonia or an amine, form a metal salt with a reactive metal or substantially react with a metal compound, or otherwise function as an acylating agent. Typically, X and/or X' are-OH, -O-hydrocarbyl, -NH₂And X' together may be-O-to form an anhydride. In some embodiments, X and X' are such that both carboxyl functional groups can enter the acylation reaction.

Maleic anhydride is a suitable acylating agent. Other suitable acylating agents include electron deficient olefins such as monophenyl maleic anhydride; monomethyl maleic anhydride, dimethyl maleic anhydride, N-phenyl maleimide and other substituted maleimides; an isomaleimide; fumaric acid, maleic acid and fumaric acid alkylhydrogen esters, fumaric acid and maleic acid dialkyl esters, fumaric acid and maleic acid; and maleic nitrile and fumaric nitrile.

In some processes, the molar ratio of maleic anhydride (or other acylating agent) to ethylenically unsaturated hydrocarbon or polyolefin can vary widely. For example, and in some embodiments, it may vary from about 6: 1 to about 1: 6, or from about 5: 1 to about 1: 5, or from about 3: 1 to about 1: 3, and in yet other processes, maleic anhydride may be used in stoichiometric excess to force the reaction to completion. If desired, unreacted maleic anhydride can be removed by vacuum distillation.

The hydrocarbyl substituents can include olefins such as, but not limited to, linear α olefins, branched α olefins, polymers and copolymers of lower olefins the olefins can be selected from ethylene, propylene, isopropene, butenes, such as isobutylene, 1-octane, 1-hexene, 1-decene, n-pentene, isopentene, and/or neopentenes, and the like.

Hydrocarbyl substituents are also made from olefin terpolymers. Useful products can be made from: ethylene-C_3-12α olefin-C_5-12A non-conjugated diene terpolymer; such as ethylene-propylene-1, 4-hexadiene terpolymers; ethylene propylene-1, 5-cyclooctadiene terpolymer; ethylene-propylene norbornene terpolymers, and the like.

In one method or embodiment, the hydrocarbyl substituent may be derived from a butene polymer, such as a polymer of isobutylene. In some embodiments, suitable polyisobutylenes for preparing the polycarboxylic acids or polycarboxylic anhydrides of the present disclosure may include those that comprise at least about 20% (e.g., at least 50% and as another example at least 70%) of the more reactive methylvinylidene isomer. Suitable polyisobutenes include polyisobutenes prepared using BF3 catalysts. The preparation of such polyisobutenes in which the methylvinylidene isomer constitutes a high percentage of the total composition is described in U.S. Pat. Nos. 4,152,499 and 4,605,808, the disclosures of which are hereby incorporated by reference.

In another embodiment, the hydrocarbyl substituent is derived from ethylene and one or more C₃To C₁₀α olefin-derived olefin copolymer, the one or more C₃To C₁₀α the olefin may be, for example, C₃Or C₄A carbon atom. Copolymers of ethylene and propylene or ethylene and butene are possible.

More complex polymer matrices, often referred to as interpolymers, can be prepared using at least three monomers. For example, the monomers can be ethylene, propylene, and a third monomer typically used to prepare the interpolymer matrix is a polyene monomer selected from the group consisting of non-conjugated dienes and trienes. The non-conjugated diene component is a component having 5 to 14 carbon atoms in the chain. Preferably, the diene monomer is characterized by the presence of a vinyl group in its structure and may include cyclic and bicyclic compounds. Representative dienes include 1, 4-hexadiene, 1, 4-cyclohexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 1, 5-heptadiene, and 1, 6-octadiene. Mixtures of more than one diene can be used to prepare the interpolymers. A preferred non-conjugated diene for use in preparing the terpolymer or interpolymer matrix is 1, 4-hexadiene.

The triene component has at least two non-conjugated double bonds and up to about 30 carbon atoms in the chain. Typical trienes used to prepare the interpolymers of the present invention are 1-isopropylidene-3 a, 4,7, 7 a-tetrahydroindene, 1-isopropylidene dicyclopentadiene, dihydro-isopropyldicyclopentadiene and 2- (2-methylene-4-methyl-3-pentenyl) [2.2.1] bicyclo-5-heptene.

The ethylene-propylene or higher α -olefin copolymer may be composed of about 15 to 80 mole percent ethylene and about 85 to 20 mole percent C₃To C₁₀α -olefins, wherein the preferred molar ratio is about 35 to 75 mole% ethylene and about 65 to 25 mole% C₃To C₁₀α -olefins, the more preferred proportions being about 50 to 70 mol% ethylene and 50 to 30 mol% C₃To C₁₀α -olefin, and most preferably in a ratio of 55 to 65 mole percent ethylene and 45 to 35 mole percent C₃To C₁₀α -olefins.

Terpolymer variants of the foregoing polymers may contain from about 0.1 to 10 mole percent of a non-conjugated diene or triene.

In some processes, the terms polymer and copolymer are generally used to encompass ethylene copolymers, terpolymers, or interpolymers. These materials may contain minor amounts of other olefin monomers, as long as the basic properties of the copolymer are not substantially altered.

In some processes or embodiments, the number average molecular weight of the hydrocarbyl substituent may be from about 250 to about 10,000; in other methods, from about 250 to about 5,000; in other methods, from about 300 to about 5,000; in other methods, from about 300 to about 3,000; in other methods, from about 300 to about 2500; in other methods, from about 750 to about 2500; in other methods, from about 600 to 1,500; in a further method, from about 600 to about 1300; or from about 1,300 to about 2,700 as determined by Gel Permeation Chromatography (GPC) using polystyrene as a calibration standard. In yet other methods, the number average molecular weight of the hydrocarbyl substituent can range from at least about 250, at least about 300, at least about 600, at least about 900, or at least about 1.000 and not more than 5,000; not more than 4,000; no more than about 3,000; not more than 2,500; no more than about 1,500 or no more than about 1,000.

The number average molecular weight (Mn) of any of the embodiments herein can be determined using an instrument such as a Gel Permeation Chromatography (GPC) instrument available from Waters (Waters) and data processed using software such as Waters Empower software) Wherein the column temperature is about 40 ℃, unstable HP L C grade Tetrahydrofuran (THF) can be used as a solvent, the flow rate is 1.0m L/min GPC instruments can be calibrated with commercially available Polystyrene (PS) standards with narrow molecular weight distribution in the range of 500-380,000g/mol for samples with a mass of less than 500g/mol, calibration curves can be extrapolated, samples and PS standards can be dissolved in THF and prepared at concentrations of 0.1 to 0.5 wt.%, and without filtration, using GPC measurements are also described in US5,266,223, which is incorporated herein by reference, GPC methods additionally provide molecular weight distribution information, see for example w.yau, j.j.kirkland d.d.by Modern size exclusion liquid Chromatography (model sizeExclusion L acquired Chromatography), John, william, ny, incorporated herein by sond, which is also incorporated herein.

Nitrogen or amine functionalization:

the above-mentioned hydrocarbyl-substituted polycarboxylic acids or anhydrides are nitrogen or amine functionalized (and then post-treated with an oxazoline or oxazoline derivative, also as described above). In one method or embodiment, the lubricant additive may be a dispersant or dispersant viscosity modifier, such as an amine-functionalized hydrocarbyl-substituted polycarboxylic acid or anhydride (e.g., a hydrocarbyl-substituted succinimide or a hydrocarbyl succinimide).

In one method or embodiment, the hydrocarbyl-substituted polycarboxylic acid or anhydride is functionalized with a polyalkylene polyamine, such as an amine-containing polyalkylene polyamine of the following formula III:

wherein each R and R' is independently a divalent C₁To C₆An alkylene linker; each R₄And R₅Independently hydrogen, C1 to C6 alkyl or together with the nitrogen atom to which they are attached form a5 or 6 membered ring, optionally fused to one or more aromatic or non-aromatic rings, n is an integer between 0 and 8.

Amine functionalization of hydrocarbyl-substituted polycarboxylic acids or anhydrides is well known in the art and can be achieved by reacting a hydrocarbyl-substituted polycarboxylic acid or anhydride with a nitrogen source, such as a polyamine having at least one basic nitrogen. The conversion of alkenylsuccinic acids or anhydrides to succinimides is described in U.S. Pat. No. 3,215,707 and U.S. Pat. No. 4,234,435, which are incorporated herein by reference. Suitable nitrogen sources include polyamines, polyalkylene polyamines and mixtures thereof. The polyalkylene polyamine may include a mixture of polyethylene polyamines having an average of 5 to 7 nitrogen atoms, triethylene tetramine (TETA), tetraethylene pentamine (TEPA), and combinations thereof.

In some processes, non-limiting exemplary polyamines can include ethylenediamine, propylenediamine, butylenediamine, Diethylenetriamine (DETA), triethylenetetramine (TETA), Pentaethylenehexamine (PEHA), aminoethylpiperazine, Tetraethylenepentamine (TEPA), N-methyl-1, 3-propanediamine, N' -dimethyl-1, 3-propanediamine, aminoguanidine bicarbonate (AGBC), and heavy polyamines such as E100 heavy amine bottoms. Heavy polyamines may comprise a mixture of polyalkylenepolyamines having a minor amount of lower polyamine oligomers (e.g., TEPA and PEHA), but the major oligomers have an average of 5 or more nitrogen atoms per molecule, in other processes, an average of seven or more nitrogen atoms (and in yet other processes an average of 5-7 nitrogen atoms), two or more primary amines, and more extensive branching than conventional polyamine mixtures. Other non-limiting polyamines that can be used to prepare the hydrocarbyl-substituted succinimide dispersants are disclosed in U.S. patent 6,548,458, the disclosure of which is fully incorporated herein by reference. In some methods, the polyamine used in the dispersant-forming reaction is selected from the group consisting of triethylenetetramine, tetraethylenepentamine, E100 heavy amine bottoms, and combinations thereof. In a preferred embodiment, the polyamine may be Tetraethylenepentamine (TEPA).

In one embodiment, the reaction between the hydrocarbyl-substituted polycarboxylic acid or polycarboxylic anhydride and the alkylene polyamine to form the dispersant may be carried out by: the components are mixed and the mixture is heated to a temperature high enough to cause the reaction to occur but not so high as to cause decomposition of the reactants or products, or the anhydride may be heated to the reaction temperature and the polyamine added over an extended period. Useful temperatures are from about 100 ℃ to about 250 ℃. Exemplary results may be obtained by conducting the reaction at a temperature sufficiently high to distill off water formed in the reaction.

In one embodiment, the amine comprises one or more primary or secondary amine groups. In some cases, the polyalkylene polyamine can have at least three nitrogen atoms and about 4 to 20 carbon atoms. One or more oxygen atoms may also be present in the polyamine. Several polyamines can be used to prepare the dispersant. In addition to the above nitrogen sources, non-limiting exemplary polyamines can include aminoguanidine bicarbonate (AGBC), Ethylenediamine (EDA), N-methylpropanediamine, Diethylenetriamine (DETA), Pentaethylenehexamine (PEHA), or other heavy polyamines. Some heavy polyamines may comprise a mixture of polyalkylene polyamines with minor amounts of lower polyamine oligomers (e.g., TEPA and PEHA), but major polyamine oligomers have seven or more nitrogen atoms per molecule, two or more primary amines, and more extensive branching than conventional polyamine mixtures. Other non-limiting polyamines that can be used to prepare the dispersant are disclosed in U.S. patent 6,548,458, the disclosure of which is incorporated herein by reference in its entirety.

Other examples of suitable polyalkylene polyamines include, but are not limited to, propylene diamine, isopropyl diamine, butylene diamine, pentylene diamine, hexylene diamine, dipropylene triamine, dimethylaminopropylamine, diisopropyltriamine, dibutylamine, di-sec-butyltriamine, tripropylene tetramine, triisobutylene tetramine, pentaethylene hexamine, and mixtures thereof.

A particularly suitable group of polyalkylene polyamines may contain from about 2 to about 12 nitrogen atoms and from about 2 to about 24 carbon atoms. The alkylene groups of such polyalkylene polyamines may contain from about 2 to about 6 carbon atoms, more preferably from about 2 to about 4 carbon atoms. Many polyamines suitable for use in the present invention are commercially available, others can be prepared by methods well known in the art. For example, methods for preparing amines and reactions thereof are described in Sidgewick, "The organic chemistry of Nitrogen", Clarendon Press, Oxford, 1966; noller's "Chemistry of organic Compounds," Saunders, Philadelphia, second edition, 1957; and Kirk-Othmer, "Encyclopedia of Chemical Technology," second edition, especially volume 2, pages 99-116, each of which is incorporated herein by reference.

Other amines useful in forming the dispersant include alkanolamines containing one or more hydroxyl groups, such as 2- (2-aminoethylamino) ethanol, aminoalkyl substituted heterocycles, such as 1- (3-aminopropyl) imidazole and 4- (3-aminopropyl) morpholine, condensates of polyamines with polyhydroxy compounds, such as polyethylene polyamine condensate with tris (hydroxymethyl) aminomethane, as described in U.S. Pat. No. 5,653,152, or mixtures thereof.

The reaction of a nitrogen source, such as a polyamine, with a hydrocarbyl-substituted polycarboxylic acid or anhydride produces a mono-, di-, tri-, or other succinimide, depending on the charge ratio of the nitrogen source and the hydrocarbyl-substituted polycarboxylic acid or anhydride. The charge ratio between the hydrocarbyl-substituted polycarboxylic acid or anhydride and the nitrogen source is from about 1: 1 to about 3.2: 1, or from about 2.5: 1 to about 3: 1, or from about 2.9: 1 to about 3: 1, or from about 1.6: 1 to about 2.5: 1, or from about 1.6: 1 to about 2: 1, or from about 1.6: 1 to about 1.8: 1, from about 1.3: 1 to about 1.8: 1, from about 1.4: 1 to about 1.8: 1, or from about 1: 6 to about 1.8: 1.

Definition of

For the purposes of this disclosure, chemical elements are identified according to the periodic table of the elements, CAS edition, Handbook of chemistry and Physics, 75 th edition. In addition, the general principles of Organic Chemistry are described in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausolato: 1999, and "March's advanced organic chemistry", 5th ed., ed.: smith, m.b. and March, j., John Wiley & Sons, new york: 2001, the entire contents of which are incorporated herein by reference.

As used herein, the term "effective concentration" refers to the concentration of dispersant necessary for the base oil to exhibit newtonian behavior, which indicates that the soot particles in the base oil are well dispersed.

The term "olefin copolymer" as used herein refers to random and/or block polymers composed of two or more different types of monomers, wherein all monomers contain at least one olefin (carbon-carbon double bond).

As described herein, a compound may be optionally substituted with one or more substituents, such as those generally described above, or as exemplified by particular classes, subclasses, and species of the disclosure.

The term "substantial amount" as used herein is understood to mean an amount greater than or equal to 50 wt%, for example from about 80 wt% to about 98 wt%, relative to the total weight of the composition. Furthermore, the term "minor amount" as used herein is understood to mean an amount of less than 50 wt.%, relative to the total weight of the composition.

The term "hydrocarbyl group" as used herein is used in its ordinary sense as is well known to those skilled in the art. In particular, it refers to a group having a carbon atom directly attached to the rest of the molecule and having a predominantly hydrocarbon character. Examples of hydrocarbyl groups include: (1) hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents and aromatic, aliphatic and alicyclic substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form an alicyclic radical); (2) substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of the description herein, do not alter the predominantly hydrocarbon substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, amino, alkylamino, and sulfoxy); (3) hetero substituents, that is, substituents that, while having a predominantly hydrocarbon character, contain atoms other than carbon in a ring or chain otherwise composed of carbon atoms in the context of this specification. Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents such as pyridyl, furyl, thienyl and imidazolyl. Generally, for every ten carbon atoms in the hydrocarbyl group, no more than two, or as another example, no more than one, non-hydrocarbon substituent is present; in some embodiments, there are no non-hydrocarbon substituents in the hydrocarbyl group.

As used herein, the term "aliphatic" includes the terms alkyl, alkenyl, alkynyl, each of which is optionally substituted as described below.

As used herein, an "alkyl" group refers to a saturated aliphatic hydrocarbon group containing 1 to 12 (e.g., 1 to 8,1 to 6, or 1 to 4) carbon atoms. The alkyl group may be linear or branched. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, isobutyl, n-pentyl, n-heptyl, or 2-ethylhexyl. Alkyl groups may be substituted (i.e., optionally substituted) with one or more substituents such as: halogen, phosphoric acid, cycloaliphatic radicals [ e.g. cycloalkyl or cycloalkenyl]Heterocycloaliphatic [ e.g. heterocycloalkyl or heterocycloalkenyl ]]Aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl [ e.g. (aliphatic) carbonyl, (cycloaliphatic) carbonyl or (heterocycloaliphatic) carbonyl]Nitro, cyano, acylamino [ e.g. (cycloalkylalkyl) carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl) carbonylamino, (heterocycloalkylalkyl) carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminoAlkylcarbonyl or heteroarylaminocarbonyl]Amino group [ e.g. aliphatic amino group, cycloaliphatic amino group or heterocycloaliphatic amino group]Sulfonyl [ e.g. aliphatic-SO₂-]Sulfinyl, thio, sulfoxy, urea, thiourea, sulfamoyl, sulfonamide, pendant oxy, carboxyl, carbamoyl, cycloaliphatic oxy, heterocycloaliphatic oxy, aryloxy, heteroaryloxy, aralkoxy, heteroaralkoxy, alkoxycarbonyl, alkylcarbonyloxy or hydroxyl. Without limitation, some examples of substituted alkyl groups include carboxyalkyl (e.g., HOOC-alkyl, alkoxycarbonylalkyl, and alkylcarbonyloxyalkyl), cyanoalkyl, hydroxyalkyl, alkoxyalkyl, acylalkyl, aralkyl, (alkoxyaryl) alkyl, (sulfonylamino) alkyl (e.g., (alkyl-SO)₂-amino) alkyl), aminoalkyl, amidoalkyl, (cycloaliphatic) alkyl or haloalkyl.

As used herein, an "alkenyl" group refers to an aliphatic carbon group containing 2-8 (e.g., 2-12, 2-6, or 2-4) carbon atoms and at least one double bond. Like alkyl, alkenyl groups may be straight or branched. Examples of alkenyl groups include, but are not limited to, allyl, isopropenyl, 2-butenyl, and 2-hexenyl. Alkenyl groups may be optionally substituted with one or more substituents such as: halogen, phosphoric acid, cycloaliphatic radicals [ e.g. cycloalkyl or cycloalkenyl]Heterocycloaliphatic [ e.g. heterocycloalkyl or heterocycloalkenyl ]]Aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl [ e.g. (aliphatic) carbonyl, (cycloaliphatic) carbonyl or (heterocycloaliphatic) carbonyl]Nitro, cyano, acylamino [ e.g. (cycloalkylalkyl) carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl) carbonylamino, (heterocycloalkylalkyl) carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl or heteroarylaminocarbonyl]Amino group [ e.g., aliphatic amino group, cycloaliphatic amino group, heterocyclic aliphatic amino group or aliphatic sulfonylamino group]Sulfonyl [ e.g. alkyl-SO)₂-, cycloaliphatic-SO₂-or aryl-SO₂Small sulfinyl, thio, sulfoxy radicalsUrea, thiourea, sulfamoyl, sulfonamide, pendant oxy, carboxyl, carbamoyl, cycloaliphatic oxy, heterocycloaliphatic oxy, aryloxy, heteroaryloxy, aralkoxy, heteroarylalkoxy, alkoxycarbonyl, alkylcarbonyloxy or hydroxyl. Without limitation, some examples of substituted alkenyl groups include cyanoalkenyl, alkoxyalkenyl, acylalkenyl, hydroxyalkenyl, aralkenyl, (alkoxyaryl) alkenyl, (sulfonylamino) alkenyl (e.g., (alkyl-SO)₂-amino) alkenyl), aminoalkenyl, amidoalkenyl, (cycloaliphatic) alkenyl, or haloalkenyl.

As used herein, "alkynyl" refers to an aliphatic carbon group containing 2 to 8 (e.g., 2 to 12, 2 to 6, or 2 to 4) carbon atoms and having at least one triple bond. The alkyl group may be linear or branched. Examples of alkynyl groups include, but are not limited to, propargyl and butynyl. Alkynyl groups may be optionally substituted with one or more substituents such as: aroyl, heteroaroyl, alkoxy, cycloalkyloxy, heterocycloalkoxy, aryloxy, heteroaryloxy, aralkoxy, nitro, carboxyl, cyano, halo, hydroxy, sulfo, mercapto, thio [ e.g. aliphatic or cycloaliphatic thio ]]Sulfinyl [ e.g. aliphatic sulfinyl or cycloaliphatic sulfinyl]Sulfonyl [ e.g. aliphatic-SO₂-, aliphatic amino-SO₂-or cycloaliphatic-SO₂Small acylamino groups [ e.g. aminocarbonyl, alkylaminocarbonyl, alkylcarbonylamino, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, cycloalkylcarbonylamino, arylaminocarbonyl, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl) carbonylamino, (cycloalkylalkyl) carbonylamino, heteroaralkylcarbonylamino, heteroarylcarbonylamino or heteroarylaminocarbonyl]Urea, thiourea, sulfamoyl, sulfonamide, alkoxycarbonyl, alkylcarbonyloxy, cycloaliphatic, heterocycloaliphatic, aryl, heteroaryl, acyl [ e.g. (cycloaliphatic) carbonyl or (heterocycloaliphatic) carbonyl]Amino [ e.g. aliphatic amino]A sulfoxy group, a pendant oxy group, a carboxyl group, a carbamoyl group, a (cycloaliphatic) oxy group, a (heterocycloaliphatic) oxy group or a (heteroaryl) alkoxy group.

As used hereinBy "amino" is meant-NR^XR^YWherein R is^XAnd R^YEach of which is independently hydrogen, alkyl, cycloalkyl, (cycloalkyl) alkyl, aryl, aralkyl, heterocycloalkyl, (heterocycloalkyl) alkyl, heteroaryl, carboxy, thio, sulfinyl, sulfonyl, (alkyl) carbonyl, (cycloalkyl) carbonyl, ((cycloalkyl) alkyl) carbonyl, arylcarbonyl, (aralkyl) carbonyl, (heterocycloalkyl) carbonyl, ((heterocycloalkyl) alkyl) carbonyl, (heteroaryl) carbonyl, or (heteroaralkyl) carbonyl, each of which is defined herein and optionally substituted. Examples of the amino group include an alkylamino group, a dialkylamino group, or an arylamino group. When the term "amino" is not a terminal group (e.g., alkylcarbonylamino), it is represented by-NR^X-represents. R^XHave the same meaning as defined above.

As used herein, a "cycloalkyl" group refers to a saturated carbocyclic monocyclic or bicyclic (fused or bridged) ring of 3 to 10 (e.g., 5 to 10) carbon atoms. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, cycloheptyl, octahydro-indenyl, decahydronaphthyl, bicyclo [3.2.1] octyl, bicyclo [2.2.2] octyl, bicyclo [3.3.1] nonyl, bicyclo [3.3.2] decyl, bicyclo [2.2.2] octyl, adamantyl or ((aminocarbonyl) cycloalkyl.

As used herein, a "heterocycloalkyl" group refers to a 3-10 membered mono-or bicyclic (fused or bridged) (e.g., 5-to 10-membered mono-or bicyclic) saturated ring structure in which one or more ring atoms is a heteroatom (e.g., N, O, S or a combination thereof). Examples of heterocycloalkyl include piperidinyl, piperazinyl, tetrahydropyranyl, tetrahydrofuranyl, 1, 4-dioxolanyl, 1, 4-dithianyl, 1, 3-dioxolanyl, oxazolidinyl, isoxazolidinyl, morpholinyl, thiomorpholinyl, octahydrobenzofuranyl, octahydrochromenyl, octahydrothiochromenyl, octahydroindolyl, octahydropyridinyl, decahydroquinolinyl, octahydrobenzo [ b ] thienyl, 2-oxa-bicyclo [2.2.2] octyl, 1-aza-bicyclo [2.2.2] octyl, 3-aza-bicyclo [3.2.1] octyl, and 2, 6-dioxa-tricyclo [3.3.1.0] nonyl. Monocyclic heterocycloalkyl groups can be fused with a phenyl moiety to form a structure, such as tetrahydroisoquinoline, which would be classified as heteroaryl.

As used herein, "heteroaryl" refers to a monocyclic, bicyclic, or tricyclic ring system having 4 to 15 ring atoms, wherein one or more of the ring atoms is a heteroatom (e.g., N, O, S or a combination thereof), and wherein the monocyclic ring system is aromatic, or at least one ring in the bicyclic or tricyclic ring system is aromatic. Heteroaryl includes benzo-fused ring systems having 2 to 3 rings. For example, benzo-fused groups include benzo fused to one or two 4-to 8-membered heterocyclic aliphatic moieties (e.g., indolizinyl, indolyl, isoindolyl, 3H-indolyl, indolinyl, benzo [ b ] furanyl, benzo [ b ] thienyl, quinolinyl, or isoquinolinyl). Some examples of heteroaryl groups are pyridyl, 1H-indazolyl, furyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, imidazolyl, tetrazolyl, benzofuryl, isoquinolyl, benzothiazolyl, xanthene, thioxanthene, phenothiazine, indoline, benzo [1, 3] dioxole, benzo [ b ] furyl, benzo [ b ] thienyl, indazolyl, benzimidazolyl, benzothiazolyl, furyl, cinnolinyl, quinolyl, quinazolinyl, cinnolinyl, phthaloyl (phthaloyl), quinazolinyl, quinoxalyl, isoquinolyl, 4H-quinolizinyl (4H-quinolizyl), benzo-1, 2, 5-thiadiazolyl, or 1, 8-naphthyridinyl (1, 8-naphthyridinyl).

Monocyclic heteroaryl includes, without limitation, furyl, thienyl, 2H-pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, 1,3, 4-thiadiazolyl, 2H-pyranyl, 4-H-pyranyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazolyl, pyrazinyl or 1,3, 5-triazinyl. Monocyclic heteroaryls are numbered according to standard chemical nomenclature.

Bicyclic heteroaryls include, without limitation, indolizinyl, indolyl, isoindolyl, 3H-indolyl, indolinyl, benzo [ b ] furanyl, benzo [ b ] thienyl, quinolinyl, isoquinolinyl, indolizinyl, isoindolyl, indolyl, benzo [ b ] furanyl, benzo [ b ] thienyl, indazolyl, benzimidazolyl, benzothiazolyl, purinyl, 4H-quinolizinyl, quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 1, 8-naphthyridinyl, or pteridinyl (pteridyl). Bicyclic heteroaryls are numbered according to standard chemical nomenclature.

Lubricating oil composition

The novel lubricant additives described herein, such as novel dispersants, dispersant viscosity index improvers, dispersant viscosity modifiers, or other lubricant dispersants, can be incorporated into a large amount of base oil in combination with one or more other additives to produce a lubricating oil composition having a robust and reduced boundary coefficient of friction. The lubricating oil compositions herein may comprise from about 0.1 wt.% to about 10 wt.%, or from about 1 wt.% to about 8 wt.%, or from about 3 wt.% to about 10 wt.%, or from about 1 wt.% to about 6 wt.%, or from about 2 wt.% to about 4 wt.%, of the dispersant of the present invention, based on the weight of the lubricant composition. In some embodiments, the lubricant composition utilizes a mixed dispersant system in combination with one or more other additives. In other methods, the lubricating oil formulation can comprise the dispersant herein in an amount of at least about 0.1 wt.%, at least about 0.5 wt.%, at least about 1 wt.%, at least about 2 wt.%, or at least about 4 wt.%, and at most 10 wt.%, at most 8 wt.%, at most 6 wt.%, or at most 5 wt.%.

Base oil

The base oil or base oil of lubricating viscosity used in the lubricating oil compositions herein can be selected from any suitable base oil. Examples include Base oils in class I-V as specified in the American Petroleum Institute (API) guide for Base Oil Interchangeability (API) Base Oil interchange Guidelines. The five base oils are as follows:

TABLE 1

I, II th and group III are mineral oil process feedstocks. Group IV base oils contain true synthetic molecular species (truesynthetic molecular specie) which are produced by the polymerization of olefinically unsaturated hydrocarbons. Many group V base oils are also true synthetic products and may contain diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers and/or polyphenyl ethers, and the like, but may also be naturally occurring oils, such as vegetable oils. It should be noted that although group III base oils are derived from mineral oils, the rigorous processing experienced by these fluids makes their physical properties very similar to some real composites, such as PAOs. Accordingly, oils derived from group III base oils may be referred to in the industry as synthetic fluids.

The base oil used in the disclosed lubricating oil compositions can be a mineral oil, an animal oil, a vegetable oil, a synthetic oil, or mixtures thereof. Suitable oils may be derived from hydrocracking, hydrogenation, hydrofinishing, unrefined, refined and re-refined oils, and mixtures thereof.

Unrefined oils are those derived from a natural, mineral, or synthetic source with little or no further purification treatment. Refined oils are similar to unrefined oils except that they have been treated in one or more purification steps, which may result in an improvement in one or more properties. Examples of suitable purification techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Oils refined to edible quality may or may not be suitable. Edible oils may also be referred to as white oils. In some embodiments, the lubricating oil composition is free of edible or white oil.

Rerefined oils are also known as reclaimed or reprocessed oils. These oils are obtained similarly to refined oils, using the same or similar processes. Typically these oils are additionally processed by techniques directed to the removal of spent additives and oil breakdown products.

The mineral oil may comprise oil obtained by drilling or from plants and animals or any mixture thereof. For example, the oils may include, but are not limited to, castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic, or mixed paraffinic-naphthenic types. The oil may be partially or fully hydrogenated if desired. Oils derived from coal or shale may also be suitable.

Useful synthetic lubricating oils can include hydrocarbon oils such as polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene isobutylene copolymers), poly (1-hexenes), poly (1-octenes), terpolymers or oligomers of 1-decenes, such as poly (1-decene), which are commonly referred to as α -olefins, and mixtures thereof, alkyl-benzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di- (2-ethylhexyl) -benzenes), polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls), diphenylalkanes, alkylated diphenylethers, and alkylated diphenylsulfides, as well as derivatives, analogs, and homologs thereof, or mixtures thereof.

Other synthetic lubricating oils contain polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl ester of decane phosphionic acid), or polymeric tetrahydrofurans. Synthetic oils may be produced by Fischer-Tropsch reactions (Fischer-Tropsch reactions) and may typically be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil may be prepared by a fischer-tropsch gas-liquid synthesis step, as well as other natural gas synthesis oils.

The bulk of the base oil included in the lubricating composition may be selected from the group consisting of: group I, group II, group III, group IV, group V, and combinations of two or more of the foregoing, and wherein the bulk base oil is not a base oil resulting from providing an additive component or viscosity index improver in the composition. In another embodiment, the bulk of the base oil included in the lubricating composition may be selected from the group consisting of: group II, group III, group IV, group V, and combinations of two or more of the foregoing, and wherein the bulk base oil is not a base oil resulting from providing an additive component or viscosity index improver in the composition.

In the compositions herein, the amount of oil of lubricating viscosity may be the balance remaining after subtracting the sum of the amounts of performance additives from 100 wt%. For example, oil of lubricating viscosity that may be present in the finished fluid may be in a "major amount," such as greater than about 50 wt.%, greater than about 60 wt.%, greater than about 70 wt.%, greater than about 80 wt.%, greater than about 85 wt.%, greater than about 90 wt.%, or greater than about 95 wt.%.

In some processes, preferred base oils or base oils of lubricating viscosity have less than about 25ppm sulfur, a viscosity index greater than about 120, and a kinematic viscosity at about 100 ℃ of about 2 to about 8 cSt. In other methods, the base oil of lubricating viscosity has less than about 25ppm sulfur, a viscosity index greater than 120, and a kinematic viscosity at 100 ℃ of about 4 cSt. The base oil may have a C of greater than 40%, greater than 45%, greater than 50%, greater than 55%, or greater than 90%_P(paraffinic carbon content). The base oil may have a C of less than 5%, less than 3%, or less than 1%_A(aromatic carbon content). The base oil may have a C of less than 60%, less than 55%, less than 50%, or less than 50% and greater than 30%_N(naphthenic carbon content). The base oil can have a ratio of 1-ring naphthenes to 2-6-ring naphthenes of less than 2 or less than 1.5 or less than 1.

Other optional additives for lubricating oils are described below.

Detergent composition

The lubricant composition may optionally further comprise one or more neutral, low alkaline or high alkaline detergents and mixtures thereof.

Suitable detergent bases include: phenates, sulphur-containing phenates, sulphonates, calixarenes (calixarates), salicylates (salixarates), salicylates, carboxylic acids, phosphoric acids, monothiophosphoric and/or dithiophosphoric acids, alkylphenols, sulphur-coupled alkylphenol compounds or methylene-bridged phenols. Suitable detergents and methods for their preparation are described in more detail in a number of patent publications, including U.S. Pat. No. 7,732,390 and the references cited therein. The detergent matrix may be salted with an alkali metal or alkaline earth metal such as (but not limited to) the following: calcium, magnesium, potassium, sodium, lithium, barium, zinc or mixtures thereof.

Suitable detergents may comprise alkali or alkaline earth metal salts of petroleum sulphonic acid and long chain mono or dialkyl aryl sulphonic acids, for example calcium or magnesium salts, wherein the aryl groups are benzyl, tolyl and xylyl. Examples of other suitable detergents include, but are not limited to, the low base/neutral and high base forms of the following detergents: calcium phenate, sulfur-containing calcium phenate, calcium sulfonate, calixate, calcium salicylate, calcium carboxylate, calcium phosphate, calcium monothiophosphate and/or calcium dithiophosphate, calcium alkylphenol, sulfur-coupled alkylphenol calcium compounds, methylene-bridged calcium phenate, magnesium phenate, sulfur-containing magnesium phenate, magnesium sulfonate, calixate, magnesium salicylate, magnesium carboxylate, magnesium phosphate, magnesium monothiophosphate and/or magnesium dithiophosphate, magnesium alkylphenol, sulfur-coupled alkylphenol magnesium compounds, methylene-bridged magnesium phenate, sodium phenate, sulfur-containing sodium phenate, sodium sulfonate, sodium calixate, sodium salicylate, sodium carboxylate, sodium phosphate, sodium monothiophosphate and/or sodium dithiophosphate, sodium alkylphenol, sulfur-coupled alkylphenol sodium compounds, or methylene-bridged sodium phenate.

The detergent may be present at about 0 wt% to about 10 wt%, or about 0.1 wt% to about 8 wt%, or about 1 wt% to about 4 wt%, or greater than about 4 wt% to about 8 wt%. In other methods, the metal may be provided to the lubricating oil composition in an amount to provide about 450 to about 2200ppm of the metal in the lubricating oil composition and a soap content of about 0.4 to about 1.5 wt.% in the lubricating oil composition. In other methods, the amount of detergent is such as to provide from about 450 to about 2200ppm of metal to the lubricating oil composition and to provide a soap content in the lubricant composition of from about 0.4 to about 0.7 wt.%.

Overbased detergent additives are well known in the art and may be alkali metal or alkaline earth metal overbased detergent additives. Such detergent additives may be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas. The substrate is typically an acid, for example, an acid such as an aliphatic-substituted sulfonic acid, an aliphatic-substituted formic acid, or an aliphatic-substituted phenol.

The term "overbased" refers to metal salts, for example, of sulfonic acids, carboxylic acids, salicylic acid, and/or phenols, wherein the amount of metal present is in excess of the stoichiometric amount. The salt may have a conversion level of over 100% (i.e., it may include more than 100% of the theoretical amount of metal required to convert the acid to its "normal", "neutral" salt). The expression "metal ratio" is often abbreviated MR and is used to denote the ratio of the total stoichiometric amount of metal in the overbased salt to the stoichiometric amount of metal in the neutral salt, according to known chemical reactivity and stoichiometry. In normal or neutral salts, MR is one, and in overbased salts MR is greater than one. It is commonly referred to as an overbased, superbased or superbased salt, and may be a salt of an organic sulfuric acid, carboxylic acid or phenol.

As used herein, the term "TBN" is used to denote the total base number in mg KOH/g as measured by the ASTM D2896 method. The overbased detergent of the lubricating oil composition may have a Total Base Number (TBN) of greater than about 200mg KOH/g or greater, or about 250mg KOH/g or greater, or about 350mg KOH/g or greater, or about 375mg KOH/g or greater, or about 400mg KOH/g or greater. The metal to substrate ratio of the overbased detergent may be 1.1: 1, or 2: 1, or 4: 1, or 5: 1, or 7: 1, or 10: 1.

Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenates, overbased calcium-containing phenates, overbased calcium sulfonates, overbased calixarenols, overbased calcium salicylates, overbased calcium carboxylates, overbased calcium phosphates, overbased mono-and/or calcium dithiophosphates, overbased calcium alkylphenols, overbased sulfur-coupled calcium alkylphenolates, overbased calcium methylene-bridged phenates, overbased magnesium sulfur-containing phenates, overbased magnesium sulfonates, overbased calixarenols, overbased magnesium salicylates, overbased magnesium carboxylates, overbased magnesium phosphates, overbased mono-and/or magnesium dithiophosphates, overbased magnesium alkylphenols, overbased sulfur-coupled magnesium alkylphenolates compounds, or overbased magnesium methylene-bridged phenates.

The overbased detergent may comprise at least 97.5 wt.% of the total detergent in the lubricating oil composition. In some embodiments, at least 96 wt.%, or at least 94 wt.%, or at least 92 wt.%, or at least 90 wt.%, or at least 88 wt.%, or at least 80 wt.% of the total detergents in the lubricating oil composition are overbased detergents.

The TBN of the low alkaline/neutral detergent is at most 175mg KOH/g, or at most 150mg KOH/g. The low alkaline/neutral detergent may comprise a calcium or magnesium containing detergent. Examples of suitable low alkaline/neutral detergents include, but are not limited to, calcium sulfonate, calcium phenate, calcium salicylate, magnesium sulfonate, magnesium phenate, and magnesium salicylate. In some embodiments, the low alkaline/neutral detergent is a calcium-containing detergent or a mixture of magnesium-containing detergents.

The low-alkaline/neutral detergent may comprise at least 2.5 wt.% of the total detergent in the lubricating oil composition. In some embodiments, at least 4 wt.%, or at least 6 wt.%, or at least 8 wt.%, or at least 10 wt.%, or at least 12 wt.%, or at least 20 wt.% of the total detergents in the lubricating oil composition are low-alkaline/neutral detergents that may optionally be low-alkaline/neutral calcium-containing detergents. In certain embodiments, the one or more low-alkalinity/neutral detergents provide from about 50 to about 1000ppm by weight of calcium or magnesium to the lubricating oil composition, based on the total weight of the lubricating oil composition. In some embodiments, the one or more low-alkaline/neutral calcium-containing detergents provide 75 to less than 800ppm, or 100 to 600ppm, or 125 to 500ppm by weight calcium or magnesium to the lubricant composition based on the total weight of the lubricant composition.

Phosphorus-containing compound

The lubricant compositions herein may comprise one or more phosphorus-containing compounds that may impart antiwear benefits to the fluid. The one or more phosphorus-containing compounds are present in the lubricating oil composition in an amount in the range of from about 0 wt.% to about 15 wt.%, or from about 0.01 wt.% to about 10 wt.%, or from about 0.05 wt.% to about 5 wt.%, or from about 0.1 wt.% to about 3 wt.% of the lubricating oil composition. The phosphorus-containing compound may provide up to 5000ppm phosphorus, or from about 50 to about 5000ppm phosphorus, or from about 300 to about 1500ppm phosphorus, or up to 600ppm phosphorus, or up to 900ppm phosphorus to the lubricant composition. The one or more phosphorus-containing compounds include metal-containing phosphorus-containing compounds and/or ashless phosphorus-containing compounds. Examples of suitable phosphorus-containing compounds include, but are not limited to, thiophosphates, dithiophosphates, metal phosphates, metal thiophosphates, metal dithiophosphates, phosphates, phosphate esters, phosphite salts, phosphonate salts, phosphorus-containing carboxylic acid esters, ethers, or amide salts thereof, and mixtures thereof. Phosphorus-containing antiwear agents are more fully described in european patent 0612839. It should be noted that the terms phosphonate and phosphite are often used interchangeably in the lubricant industry. For example, dibutyl hydrogen phosphonate is commonly referred to as dibutyl hydrogen phosphite. It is within the scope of the present invention for the lubricant composition of the present invention to include a phosphorus-containing compound that may be referred to as a phosphite or phosphonate.

In any of the above phosphorus-containing compounds, the compound can have from about 5 to about 20 weight percent phosphorus, or from about 5 to about 15 weight percent phosphorus, or from about 8 to about 16 weight percent phosphorus, or from about 6 to about 9 weight percent phosphorus.

The addition of the phosphorus-containing compound in combination with the dispersant described above to the lubricant composition unexpectedly imparts positive friction characteristics, such as a low coefficient of friction, to the lubricant composition. In some cases, the effect of the present invention is even more pronounced in cases where the phosphorus-containing compound itself imparts negative friction characteristics to the fluid. When these relatively poor friction reducing phosphorus-containing compounds are combined with the olefin copolymer dispersants described herein, the lubricant compositions have an improved, i.e., lower, coefficient of friction. That is, the dispersants herein tend to convert fluids containing phosphorus-containing compounds having relatively poor coefficients of friction into fluids having improved frictional properties.

This improvement in the friction performance of the lubricating composition containing the phosphorus-containing compound and olefin copolymer dispersant described herein is surprising, as the friction performance of the fluid is superior to phosphorus-containing compounds in combination with other types of dispersants, including polyisobutylene succinimide dispersants and olefin copolymer succinimide dispersants that do not have the specified characteristics of the copolymers described above.

One type of phosphorus-containing compound that imparts improved friction characteristics to the lubricating composition when combined with the dispersants herein is a metal dihydrocarbyl dithiophosphate compound, such as, but not limited to, a zinc dihydrocarbyl dithiophosphate compound (ZDDP). When the phosphorus-containing compound is a metallothiophosphate or metallodithiophosphate, such as ZDDP, it may comprise 5 to about 10 weight percent metal, about 6 to about 9 weight percent metal, about 8 to 18 weight percent sulfur, about 12 to about 18 weight percent sulfur, or about 8 to about 15 weight percent sulfur. Suitable metal dihydrocarbyl dithiophosphate salts may include dihydrocarbyl dithiophosphate metal salts where the metal may be an alkali metal, an alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, zirconium, zinc, or combinations thereof.

When the phosphorus-containing compound is a ZDDP, the alkyl groups on the ZDDP may be derived from primary alcohols, secondary alcohols, phenols, and/or mixtures thereof. For example, all alkyl groups of a ZDDP may be derived from a secondary alcohol, such as methyl isobutyl carbinol, or from a mixture of secondary alcohols, such as methyl isobutyl carbinol and isopropanol. In some cases, the alkyl group of ZDDP may be derived from a mixture of primary and secondary alcohols, such as 2-ethylhexanol, isobutanol, and isopropanol. For example, in one embodiment, about 20% of the alkyl groups are derived from 2-ethylhexanol, about 40% of the alkyl groups are derived from isobutanol, and about 40% of the alkyl groups are derived from isopropanol. In other embodiments, all alkyl groups on the ZDDP may be derived from primary alcohols, such as 2-ethylhexanol. The ZDDP can comprise about 6 to about 10 weight percent phosphorus, about 6 to about 9 weight percent zinc, and about 12 to about 18 weight percent sulfur.

Examples of such ZDDP's include, but are not limited to: o, O-di (C)_1-14-Alkyl) zinc dithiophosphate; zinc (mixed O, O-bis (sec-butyl and iso-octyl)) dithiophosphate; o, O-bis (branched and straight C)_3-8Alkyl) zinc dithiophosphate; zinc O, O-bis (2-ethylhexyl) dithiophosphate; zinc O, O-bis (mixed isobutyl and pentyl) dithiophosphate; mixing zinc O, O-bis (1, 3-dimethylbutyl and isopropyl) dithiophosphate; zinc O, O-diisooctyl dithiophosphate; zinc O, O-dibutyldithiophosphate; zinc O, O-bis (2-ethylhexyl with isobutyl and isopropyl) dithiophosphate; zinc O, O-bis (dodecylphenyl) dithiophosphate; zinc O, O-diisodecyl dithiophosphate; zinc O- (6-methylheptyl) -O- (1-methylpropyl) dithiophosphate; zinc O- (2-ethylhexyl) -O- (isobutyl) dithiophosphate; zinc O, O-diisopropyl dithiophosphate; zinc (mixed hexyl and isopropyl) dithiophosphate; zinc (mixed O- (2-ethylhexyl) and O-isopropyl) dithiophosphate; zinc O, O-dioctyldithiophosphate; zinc O, O-diamyl dithiophosphate; o- (2-methylbutyl)) -zinc O- (2-methylpropyl) dithiophosphate; and zinc O- (3-methylbutyl) -O- (2-methylpropyl) dithiophosphate.

The phosphorus-containing compound may have the formula:

wherein R in formula IV independently comprises 1 to 18 carbon atoms, or 2 to 12 carbon atoms, or about 3 to 8 carbon atoms. For example, R can be, for example, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, n-hexyl, isohexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl. The number of carbon atoms in each R group in the above formula is typically about 3 or greater, about 4 or greater, about 6 or greater, or about 8 or greater. Each R group may average 3 to 8 carbons. The total number of carbon atoms in the R group can be from 5 to about 72, or from 12 to about 32. In formula IV, a is a metal, such as aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, zirconium, zinc, or a combination thereof. When the phosphorus-containing compound has the structure shown in formula IV, the compound may have about 6 to about 9 weight percent phosphorus.

In some embodiments, the phosphorus-containing compounds of the present invention have the structure of formula IV, wherein a is zinc, and the compound provides 70 to 800ppm phosphorus to the lubricant composition.

It is understood in the art that a more precise representation of the sulfur-zinc coordination arrangement may be represented by the symmetrical arrangement shown below, and that the chemical structure of formula IV as used herein may be interchangeable with formula IV' shown below. It is also understood that the structures shown in formulas IV and IV' may exist as monomers, dimers, trimers or oligomers (e.g., tetramers).

The metal dihydrocarbyl dithiophosphates may be formed according to known techniques by first forming a dihydrocarbyl dithiophosphoric acid (DDPA), typically by one or moreAlcohols or phenols with P₂S₅And then neutralizing the formed DDPA with a metal compound such as zinc oxide. For example, DDPA can be prepared by reacting a mixture of primary and secondary alcohols with P₂S₅To prepare the compound. In this case, the DDPA includes alkyl groups derived from primary and secondary alcohols. Alternatively, multiple DDPAs may be prepared in which the alkyl group on one DDPA is derived entirely from a secondary alcohol and the alkyl group on another DDPA is derived entirely from a primary alcohol. The DDPAs are then mixed together to form a mixture of DDPAs having alkyl groups derived from primary and secondary alcohols.

For the preparation of the metal salts, any basic or neutral metal compound may be used, but oxides, hydroxides and carbonates are most commonly used. Commercial additives typically contain an excess of metal due to the use of an excess of basic metal compound in the neutralization reaction.

Another type of phosphorus-containing compound that imparts improved friction characteristics to the lubricating composition when combined with the olefin copolymer dispersants herein is an ashless (metal-free) phosphorus-containing compound.

In some embodiments, the ashless phosphorus-containing compound may be a dialkyl dithiophosphate, a pentyl phosphate, a diamyl phosphate, a dibutyl hydrogen phosphonate, a dimethyl octadecyl phosphonate, salts thereof, and mixtures thereof.

The ashless phosphorus-containing compound may have the formula:

wherein in formula V: r₁Is S or O; r₂is-OR ", -OH OR-R"; r₃is-OR ", -OH OR S R'" C (O) OH; r₄is-OR "; r' is C₁To C₃A branched or linear alkyl chain of (a); and R' is a C1 to C18 hydrocarbyl chain. When the phosphorus-containing compound has the structure shown in formula V, the compound may have about 8 to about 16 weight percent phosphorus.

In some embodiments, the lubricant composition comprises wherein R₁Is S; r₂is-OR "; r₃Is SR' COOH; r₄is-OR "; r' is C₃A branched alkyl chain; r' is C₄A phosphorus-containing compound of formula V; and wherein the phosphorus-containing compound is present in an amount to deliver 80 to 900ppm of phosphorus to the lubricant composition.

In another embodiment, the lubricant composition comprises wherein R₁Is O; r₂is-OH; r₃is-OR' OR-OH; r₄is-OR "; r' is C₅A phosphorus-containing compound of formula V; and wherein the phosphorus-containing compound is present in an amount to deliver 80 to 1500ppm of phosphorus to the lubricant composition.

In yet another embodiment, the lubricant composition comprises wherein R₁Is O; r₂Is OR "; r₃Is H; r₄is-OR "; r' is C₄A phosphorus-containing compound of formula V; and wherein the phosphorus-containing compound(s) is present in an amount to deliver 80 to 1550ppm phosphorus to the lubricant composition.

In other embodiments, the lubricant composition comprises wherein R₁Is O; r₂is-R "; r₃is-OCH₃or-OH; r₄is-OCH₃(ii) a R' is C₁₈A phosphorus-containing compound of formula V; and wherein the phosphorus-containing compound(s) is present in an amount to deliver 80 to 850ppm phosphorus to the lubricant composition.

Other antiwear Agents

The lubricant composition may also include other antiwear agents that are free of phosphorus compounds. Examples of such antiwear agents include borate esters, borate ester epoxides, thiocarbamate compounds including thiocarbamate, alkylene-coupled thiocarbamate and bis (S-alkyldithiocarbamoyl) disulfide, thiocarbamate amides, thiocarbamate ethers, alkylene-coupled thiocarbamate and bis (S-alkyldithiocarbamoyl) disulfide, and mixtures thereof, sulfurized olefins, tridecyl adipate, titanium compounds, and long chain derivatives of hydroxycarboxylic acids, such as tartrate derivatives, tartrimides, citrates, and mixtures thereof. A suitable thiocarbamate compound is molybdenum dithiocarbamate. Suitable tartrate derivatives or tartrimides may contain alkyl ester groups, wherein the total number of carbon atoms on the alkyl group may be at least 8. The tartrate derivative or the tartrimide may contain alkyl ester groups, wherein the total number of carbon atoms on the alkyl group may be at least 8. In one embodiment, the anti-wear agent may comprise a citrate ester. The additional antiwear agent may be present in a range including from about 0 wt% to about 15 wt%, or from about 0.01 wt% to about 10 wt%, or from about 0.05 wt% to about 5 wt%, or from about 0.1 wt% to about 3 wt% of the lubricating oil composition.

In some embodiments, the phosphorus-containing compound has a structure according to formula V and delivers from about 80 to about 4500ppm phosphorus to the lubricant composition. In other embodiments, the phosphorus-containing compound is present in an amount to deliver from about 150 to about 1500ppm phosphorus, or from about 300 to about 900ppm phosphorus, or from about 800 to 1600ppm phosphorus, or from about 900 to about 1800 ppm phosphorus to the lubricant composition.

Friction modifiers

The lubricating oil compositions herein may also optionally comprise one or more friction modifiers, for example, friction modifiers selected from organic ashless, nitrogen-free friction modifiers, organic ashless amine friction modifiers, inorganic friction modifiers, and mixtures thereof. Suitable friction modifiers may also include metal-containing as well as metal-free friction modifiers, and may include, but are not limited to: imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonates, metal-containing compounds, glycerides, borated glycerides, partial esters of glycerol such as monooleates, fatty esters of phosphites, fatty epoxides, sulfurized fatty compounds and olefins, sunflower oil, other naturally occurring vegetable or animal oils, dicarboxylic esters, esters or partial esters of polyhydric alcohols and one or more aliphatic or aromatic carboxylic acids, and the like. Friction modifiers may optionally be included in the lubricating oil compositions herein in the range of from about 0 wt.% to about 10 wt.%, or from about 0.01 wt.% to about 8 wt.%, or from about 0.1 wt.% to about 4 wt.%.

Suitable friction modifiers may contain hydrocarbyl groups selected from linear, branched or aromatic hydrocarbyl groups or mixtures thereof, and may be saturated or unsaturated. The hydrocarbyl group may be composed of carbon and hydrogen or heteroatoms, such as sulfur or oxygen. The hydrocarbyl group may range from about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long chain fatty acid ester. In another embodiment, the long chain fatty acid ester may be a mono-or di-ester or a (tri) glyceride. The friction modifier may be a long chain fatty amide, a long chain fatty amine, a long chain fatty ester, a long chain fatty epoxide derivative, or a long chain imidazoline.

Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free organic friction modifiers. Such friction modifiers may include esters formed by reacting carboxylic acids and anhydrides with alkanols, and typically include a polar terminal group (e.g., a carboxyl or hydroxyl group) covalently bonded to an oleophilic hydrocarbon chain. An example of an organic ashless, nitrogen-free friction modifier is generally known as Glycerol Monooleate (GMO), which may contain mono-, di-and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. patent 6,723,685, which is incorporated herein by reference in its entirety.

Amine-based friction modifiers may include amines or polyamines. The compounds may have linear, saturated or unsaturated hydrocarbon groups, or mixtures thereof, and may contain from about 12 to about 25 carbon atoms. Other examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds may have saturated or unsaturated linear hydrocarbon groups or mixtures thereof. Which may contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

The amines and amides can be used as such or in the form of adducts or reaction products with boron compounds, such as boron oxides, boron halides, metaborates, boric acid or monoalkyl borates, dialkyl borates or trialkyl borates. Other suitable friction modifiers are described in U.S. patent No. 6, 300, 291, which is incorporated herein by reference in its entirety.

Suitable friction modifiers include glycerol esters, fatty acids, glycerol monooleate, fatty alkyl tartrate derivativesAn organism, an imidazoline, an alkoxyamine, an alkyl fatty amine, an acylglycine, a cerium nanoparticle, a titanium-containing compound, a molybdenum-containing compound, and mixtures thereof. The titanium-containing compound may be the reaction product of a titanium alkoxide and neodecanoic acid. Cerium nanoparticles may be obtained from the reaction product of an organic cerium salt, a fatty acid, and an amine at a temperature of about 150 ℃ to about 250 ℃ in the substantial absence of water and an organic solvent. The cerium nanoparticles may have a particle size of less than about 10 nanometers. Suitable fatty acids may be those including C₁₀To C₃₀Fatty acids of saturated, monounsaturated or polyunsaturated carboxylic acids and amines selected from C₈To C₃₀Fatty amines of saturated or unsaturated amines.

In some methods, the friction modifier may be a glyceride having the formula:

wherein each R₂₀Independently selected from: h and-C (O) R '", wherein R'" can be a saturated or unsaturated alkyl group having 3 to 23 carbon atoms.

The friction modifier may also be an imidazoline having the formula

Wherein R is₂₁Is alkyl or alkenyl, having about 10 to about 30 carbon atoms, and R₂₂Is hydroxyalkyl, which means from about 2 to about 4 carbon atoms.

The friction modifier may also be an alkoxyamine comprising an N-aliphatic hydrocarbyl-substituted diethanolamine, wherein the N-aliphatic hydrocarbyl-substituent is at least one straight chain aliphatic hydrocarbyl group free of acetylenic unsaturation and having 14 to 20 carbon atoms.

The friction modifier may further be an alkyl fatty amine including an aliphatic primary fatty amine selected from the group consisting of n-hexylamine, n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-octadecylamine, and mixtures thereof;

the friction modifier may be an acylglycine and has the formula

Wherein R is₂₃Is a straight or branched, saturated, unsaturated or partially saturated hydrocarbon radical having from about 8 to about 22 carbon atoms, and R₂₄Is hydrogen, a hydrocarbon radical having 1 to 8 carbon atoms or C containing one or more heteroatoms₁To C₈A hydrocarbyl group.

Extreme pressure agent

The lubricant compositions of the present invention may also comprise at least one extreme pressure agent. The extreme pressure agent may comprise sulfur, and may comprise at least 12 wt.% sulfur. In some embodiments, the extreme pressure agent added to the lubricating oil is sufficient to provide at least 350ppm sulfur, 500ppm sulfur, 760ppm sulfur, from about 350 to about 2,000ppm sulfur, from about 2,000 to about 30,000ppm sulfur, or from about 2,000 to about 4,800ppm sulfur, or from about 4,000 to about 25,000ppm sulfur to the lubricant composition.

A wide variety of sulfur-containing extreme pressure agents are suitable and include sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, fully or partially esterified esters of phosphorous trivalent or pentavalent acids, sulfurized olefins (see, e.g., U.S. Pat. Nos. 2,995,569; 3,673,090; 3,703,504; 3,703,505; 3,796,661; 3,873,454; 4,119,549; 4,119,550; 4,147,640; 4,191,659; 4,240,958; 4,344,854; 4,472,306; and 4,711,736), dihydrocarbyl polysulfides (see, e.g., U.S. Pat. Nos. 2,237,625; 2,237,627; 2,527,948; 2,695,316; 3,022,351; 3,308,166; 3,392,201; 4,564,709; and British patent No. 1,162,334), functional group-substituted dihydrocarbyl polysulfides (see, e.g., U.S. Pat. Nos. 4,218,332), and polysulfide olefin products (see, e.g., U.S. Pat. No. 4,795,576). Other suitable examples include compounds selected from sulfurized olefins, sulfur-containing amino heterocycles, 5-dimercapto-1, 3, 4-thiadiazole, having a majority of S₃And S₄Polysulfides of sulfides, sulfurized fatty acids, sulfurized branched olefins, organic polysulfides, and mixtures thereofA sulfur compound.

In some embodiments, the extreme pressure agent is present in the lubricating composition in an amount up to about 3.0 wt.%, or up to about 5.0 wt.%. In other embodiments, the extreme pressure agent is present in an amount of about 0.05 wt.% to about 0.5 wt.%, based on the total lubricant composition. In other embodiments, the extreme pressure agent is present in an amount of about 0.1 wt.% to about 3.0 wt.%, based on the total lubricant composition. In other embodiments, the extreme pressure agent is present in an amount of about 0.6 to about 1 weight percent based on the total lubricant composition. In other embodiments, the detergent is present in an amount of about 1.0 wt.%, based on the total lubricant composition.

One class of suitable extreme pressure agents are polysulfides comprised of one or more compounds represented by the formula: r_a-S_x-R_bWherein R is_aAnd R_bIs a hydrocarbyl group, each hydrocarbyl group may contain from 1 to 18 and in other processes from 3 to 18 carbon atoms, and x may be in the range of from 2 to 8, typically in the range of from 2 to 5, especially 3. In certain methods, x is an integer from 3 to 5, wherein 30% to 60% of x is an integer of 3 or 4. The hydrocarbyl groups can be of widely different types, such as alkyl, cycloalkyl, alkenyl, aryl or aralkyl. Tertiary alkyl polysulfides, such as di-t-butyl trisulfide, and mixtures comprising di-t-butyl trisulfide (e.g., mixtures consisting essentially or entirely of tri-, tetra-, and pentasulfides) may be used. Examples of other useful dihydrocarbyl polysulfides include diamyl polysulfides, dinonyl polysulfides, dodecyl polysulfides and dibenzyl polysulfides.

Another suitable class of extreme pressure agents is sulfurized isobutylene, which is made by reacting an olefin, such as isobutylene, with sulfur. Sulfurized Isobutylene (SIB), particularly sulfurized polyisobutylene, typically has a sulfur content of about 10% to about 55%, desirably about 30% to about 50%, by weight. A variety of other olefins or unsaturated hydrocarbons, such as isobutylene dimers or trimers, may be used to form sulfurized olefin extreme pressure agents. Various processes for the preparation of sulfurized olefins have been disclosed in the prior art. See, for example, Myers' U.S. patent 3,471,404; U.S. patent 4,204,969 to Papay et al; zaweski et al, U.S. patent 4,954,274; united states patent numbers 4,966,720 to DeGonia et al; and Horodysky et al, U.S. patent 3,703,504, each of which is incorporated herein by reference.

The process for preparing sulfurized olefins, including the processes disclosed in the above patents, generally involves the formation of a material commonly referred to as an "adduct" in which the olefin is reacted with a sulfur halide, such as sulfur monochloride. The adduct is then reacted with a sulfur source to provide a sulfurized olefin. The quality of sulfurized olefins is typically measured by various physical properties including, for example, viscosity, sulfur content, halogen content, and copper corrosion test weight loss. Us patent 4,966,720 relates to sulfurized olefins used as extreme pressure additives in lubricating oils and to a two-step reaction for their preparation.

Antioxidant agent

Antioxidant compounds are known and include, for example, phenates, phenol sulfides, sulfurized olefins, phosphosulfurized terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, dinonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine), phenyl- α -naphthylamine, alkylated phenyl- α -naphthylamine, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, macroantioxidants, or mixtures thereof.

The hindered phenol antioxidant may contain a secondary butyl group and/or a tertiary butyl group as a steric hindering group. The phenolic group may be further substituted with a hydrocarbyl group and/or a bridging group attached to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2, 6-di-tert-butylphenol, 4-methyl-2, 6-di-tert-butylphenol, 4-ethyl-2, 6-di-tert-butylphenol, 4-propyl-2, 6-di-tert-butylphenol or 4-butyl-2, 6-di-tert-butylphenol or 4-dodecyl-2, 6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant may be an ester and may include, for example, Irganox, which is commercially available from BASF^TML-135 or derived from the addition product of 2, 6-di-tert-butylphenol and an alkyl acrylate, wherein the alkyl group may contain from about 1 to about 18, or from about 2 to about 12,or from about 2 to about 8, or from about 2 to about 6, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant can be an ester, and can include ETHANOK, commercially available from Jacob Corporation (Albemarle Corporation)^TM4716。

Useful antioxidants may include diarylamines and phenols. In one embodiment, the lubricating oil composition may contain a mixture of diarylamines and phenols such that the various antioxidants may be present in an amount sufficient to provide up to about 5 wt.%, based on the weight of the lubricant composition. In one embodiment, the antioxidant can be a mixture of about 0.3 to about 1.5 weight percent diarylamine and about 0.4 to about 2.5 weight percent phenol, based on the lubricant composition.

Examples of suitable olefins that may be sulfurized to form sulfurized olefins include propylene, butene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof, as well as dimers, trimers, and tetramers thereof, are particularly suitable olefins. Alternatively, the olefin may be a Diels-Alder adduct of a diene (e.g., 1, 3-butadiene) with an unsaturated ester (e.g., butyl acrylate).

Suitable fatty acids and esters thereof include triglycerides, oleic acid, linoleic acid, palmitoleic acid, or mixtures thereof.

One or more antioxidants may be present in the lubricating oil composition in the range of from about 0 wt.% to about 20 wt.%, or from about 0.1 wt.% to about 10 wt.%, or from about 1 wt.% to about 5 wt.%.

Boron-containing compounds

The lubricant compositions herein may optionally contain one or more boron-containing compounds. Examples of boron-containing compounds include borate esters, borated fatty amines, borated epoxides, borated detergents, and borated dispersants, such as borated succinimide dispersants, as disclosed in U.S. patent 5,883,057. The boron-containing compound, if present, should be used in an amount sufficient to provide a lubricant composition having a boron content of up to about 3000ppm, from about 5ppm to about 2000ppm, from about 15ppm to about 600ppm, from about 20ppm to about 400ppm, from about 70ppm to about 300 ppm.

Additional dispersant

Additional dispersants contained in the lubricant composition may include, but are not limited to, an oil soluble polymeric hydrocarbon backbone having functional groups capable of associating with the particles to be dispersed. Typically, the dispersant comprises an amine, alcohol, amide or ester polar moiety attached to the polymer backbone, typically via a bridging group. The dispersant may be selected from mannich dispersants as described in U.S. Pat. nos. 3,634,515, 3,697,574, and 3,736,357; ashless succinimide dispersants as described in U.S. Pat. nos. 4,234,435 and 4,636,322; amine dispersants as described in U.S. Pat. nos. 3,219,666, 3,565,804, and 5,633,326; koch dispersants as described in U.S. patent nos. 5,936,041, 5,643,859, and 5,627,259, and polyalkylene succinimide dispersants as described in U.S. patent No. 5,851,965; 5,853,434, respectively; and 5,792,729.

The additional dispersant may be derived from poly α -olefin (PAO) succinic anhydride, olefin maleic anhydride copolymer, as one example, the additional dispersant may be described as poly-pibsa.

If present, the additional dispersant may be used in an amount sufficient to provide up to about 10 wt.%, based on the final weight of the lubricating oil composition. Another amount of dispersant that may be used may be from about 0.1 wt.% to about 10 wt.%, or from about 3 wt.% to about 8 wt.%, or from about 1 wt.% to about 6 wt.%, based on the final weight of the lubricating oil composition.

Molybdenum-containing compound

The lubricating oil compositions herein may also optionally contain one or more molybdenum-containing compounds. The oil soluble molybdenum compound may have the functional properties of an antiwear agent, an antioxidant, a friction modifier, or a mixture thereof.

The oil-soluble molybdenum-containing compound may include molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum dithiophosphinates, amine salts of molybdenum-containing compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organo-molybdenum compounds, and/or mixtures thereof. Alternatively, the oil-soluble molybdenum-containing compound may include molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum dithiophosphinates, amine salts of molybdenum-containing compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organo-molybdenum compounds, and/or mixtures thereof. The molybdenum sulfide comprises molybdenum disulfide. The molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum-containing compound may be selected from the group consisting of: molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum-containing compounds, and mixtures thereof. In one embodiment, the oil soluble molybdenum compound may be a molybdenum dithiocarbamate.

Suitable examples of molybdenum compounds that may be used include the commercial materials sold under the trademark Vanderbilt Co., L td, available from Vanderbilt Inc822、A、2000 and855, and Sakura-L ube available from Adeka Corporation^TMS-165、S-200、S-300、S-310G、S-525、S-600、S-700 and S-710, and mixtures thereof. Suitable molybdenum components are described in U.S. patent nos. 5,650,381; U.S. patent numbers RE 37,363E 1; U.S. Pat. nos. RE 38,929E 1; and U.S. patent No. RE40,595E 1, which is incorporated herein by reference in its entirety.

Further, the molybdenum compound may be an acidic molybdenum compound. Comprising molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate and other alkali metal molybdates and other molybdenum salts, e.g. sodium hydrogen molybdate, MoOCl₄、MoO₂Br₂、Mo₂O₃Cl₆Molybdenum trioxide or similar acidic molybdenum compounds. Alternatively, the composition may provide molybdenum through a molybdenum/sulfur complex of a basic nitrogen compound, as described, for example, in U.S. patent No. 4,263,152; nos. 4,285,822; U.S. Pat. No. 4,283,295; 4,272,387 No; no. 4,265,773; nos. 4,261,843; nos. 4,259,195 and 4,259,194; and WO 94/06897, which are incorporated herein by reference in their entirety.

Another suitable class of organo-molybdenum compounds are trinuclear molybdenum compounds, e.g., of the formula Mo₃S_kL_nQ_zWherein S represents sulfur, L represents an independently selected ligand having an organic group in an amount sufficient to render the compound soluble or dispersible in oil, n is 1 to 4, k varies from 4 to 7, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z is in the range of 0 to 5 and comprises a non-stoichiometric value.

The oil-soluble molybdenum-containing compound may be present in an amount sufficient to provide about 0.5ppm to about 2000ppm, about 1ppm to about 700ppm, about 1ppm to about 550ppm, about 5ppm to about 300ppm, or about 20ppm to about 250ppm of molybdenum.

Transition metal-containing compound

The lubricant compositions herein may also optionally comprise a transition metal-containing compound or metalloid. Transition metals may include, but are not limited to: titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten, and the like. Suitable metalloids include, but are not limited to, boron, silicon, antimony, tellurium, and the like.

In one embodiment, the transition metal-containing compound may serve as an antiwear agent, a friction modifier, an antioxidant, a deposit control additive, or serve multiple functions. In one embodiment, the transition metal-containing compound may be an oil-soluble titanium compound, such as a titanium (IV) alkoxide. Titanium-containing compounds that can be used in the disclosed technology or to prepare the oil-soluble materials of the disclosed technology are various ti (IV) compounds, such as titanium (IV) oxide; titanium (IV) sulfide; titanium (IV) nitrate; titanium (IV) alkoxides, such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexanoate; and other titanium-containing compounds or complexes, including but not limited to titanium phenoxide; titanium carboxylates, such as titanium 2-ethyl-1-3-adipate or citrate or oleate; and (triethanolaminoate) titanium (IV) isopropoxide. Other forms of titanium contemplated within the disclosed technology include titanium phosphates, such as titanium dithiophosphates (e.g., titanium dialkyl dithiophosphates), and titanium sulfonates (e.g., titanium alkyl benzene sulfonates), or in general, reaction products of titanium compounds with various acidic materials to form salts (e.g., oil soluble salts). The titanium compounds can thus be derived in particular from organic acids, alcohols and diols. The Ti compound may also be present in a dimeric or oligomeric form, containing a Ti-O-Ti structure. Such titanium materials are commercially available or can be readily prepared by appropriate synthetic techniques that will be apparent to those skilled in the art. It is present in solid or liquid form at room temperature, depending on the specific compound. They may also be provided in the form of solutions in suitable inert solvents.

In one embodiment, titanium may be supplied as a Ti modified dispersant, such as a succinimide dispersant. Such materials can be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride (e.g., an alkenyl (or alkyl) succinic anhydride). The resulting titanate-succinate intermediate may be used as is, or may be reacted with any of a variety of materials, such as (a) polyamine succinimide/amide dispersants with free, condensable-NH functionality; (b) components of polyamine-based succinimide/amide dispersants, i.e., alkenyl- (or alkyl-) succinic anhydrides and polyamines, (c) hydroxyl-containing polyester dispersants prepared by the reaction of substituted succinic anhydrides with polyols, aminoalcohols, polyamines or mixtures thereof. Alternatively, the titanate-succinate intermediate may be reacted with other reagents such as alcohols, aminoalcohols, ether alcohols, polyether alcohols or polyols or fatty acids and the product thereof used directly to impart Ti to the lubricant, or additionally, reacted with succinic acid dispersants as described herein. For example, tetraisopropyl titanate may be reacted with polyisobutylene-substituted succinic anhydride at 140 ℃ to 150 ℃ for 5 to 6 hours to provide a titanium modified dispersant or intermediate. The resulting material may be further reacted with a succinimide dispersant derived from polyisobutylene-substituted succinic anhydride and a polyethylene polyamine to produce a titanium-modified succinimide dispersant.

Another titanium-containing compound may be titanium alkoxides and C₆To C₂₅A reaction product of a carboxylic acid. The reaction product may be represented by the formula:

wherein p + q is 4; q is in the range of 1 to 3; r₁₉Is an alkyl moiety having in the range of 1-8 carbon atoms; r₁₆Selected from hydrocarbyl groups containing about 6 to 25 carbon atoms; r₁₇And R₁₈The same or different and selected from hydrocarbyl groups containing from about 1 to 6 carbon atoms; or by the formula:

wherein in formula X, X is in the range of 0 to 3; r₁₆Selected from hydrocarbyl groups containing about 6 to 25 carbon atoms. R₁₇And R₁₈The same or different and selected from hydrocarbyl groups containing from about 1 to 6 carbon atoms; and/or R₁₉Is selected from H or C₆To C₂₅Carboxylic acid moieties. Suitable carboxylic acids may include, but are not limited to, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acidArachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexane carboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, and the like.

In one embodiment, the oil soluble titanium compound is present in the lubricating oil composition in an amount capable of providing from 0ppm to 3000ppm by weight titanium, or from 25ppm to about 1500ppm by weight titanium, or from about 35ppm to 500ppm by weight titanium, or from about 50ppm to about 300ppm by weight.

Viscosity index improver

Suitable additional viscosity index improvers can include polyolefins, olefin copolymers, ethylene/propylene copolymers, polyisobutylene, hydrogenated styrene-isoprene polymers, styrene/maleate copolymers, hydrogenated styrene/butadiene copolymers, hydrogenated isoprene polymers, α -olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenyl aryl conjugated diene copolymers, or mixtures thereof.

The lubricating oil compositions herein may also optionally contain one or more other dispersant viscosity index improvers in addition to or in place of the viscosity index improvers. Suitable viscosity index improvers may include functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with the reaction product of an acylating agent (e.g., maleic anhydride) and an amine; with amine functionalized polymethacrylates, or esterified maleic anhydride-styrene copolymers reacted with amines.

The total amount of other viscosity index improvers and/or dispersant viscosity index improvers may be from about 0 wt.% to about 20 wt.%, from about 0.1 wt.% to about 15 wt.%, from about 0.1 wt.% to about 12 wt.%, or from about 0.5 wt.% to about 10 wt.%, from about 3 wt.% to about 20 wt.%, from about 3 wt.% to about 15 wt.%, from about 5 wt.% to about 15 wt.%, or from about 5 wt.% to about 10 wt.% of the lubricating oil composition.

In some embodiments, the other viscosity index improver is a polyolefin or olefin copolymer having a number average molecular weight of from about 10,000 to about 500,000, from about 50,000 to about 200,000, or from about 50,000 to about 150,000. In some embodiments, the viscosity index improver is a hydrogenated styrene/butadiene copolymer having a number average molecular weight of from about 40,000 to about 500,000, from about 50,000 to about 200,000, or from about 50,000 to about 150,000. In some embodiments, the viscosity index improver is a polymethacrylate having a number average molecular weight of from about 10,000 to about 500,000, from about 50,000 to about 200,000, or from about 50,000 to about 150,000.

Other optional additives

Other additives may be selected to perform one or more functions required of the lubricating composition. In addition, one or more of the additives mentioned may be multifunctional and provide functions in addition to or different from those specified herein. The other additives may be additives other than the specified additives of the present disclosure and/or may comprise one or more of the following: metal deactivators, viscosity index improvers, detergents, ashless TBN accelerators, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, emulsifiers, pour point depressants, seal swelling agents, and mixtures thereof. Typically, a fully formulated lubricating oil will contain one or more of these additives.

Suitable metal deactivators may comprise, benzotriazole derivatives (typically tolyltriazole), dimercaptothiadiazole derivatives, 1, 2, 4-triazole, benzimidazole, 2-alkyldithiobenzimidazole or 2-alkyldithiobenzothiazole; a foam inhibitor comprising a copolymer of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; a demulsifier comprising a trialkyl phosphate, polyethylene glycol, polyethylene oxide, polypropylene oxide, and a (ethylene oxide-propylene oxide) polymer; a pour point depressant comprising an ester of maleic anhydride-styrene, polymethacrylate, polyacrylate, or polyacrylamide.

Suitable foam inhibitors include silicon-based compounds, such as silicones.

Suitable pour point depressants may comprise polymethyl methacrylate or mixtures thereof. The pour point depressant can be present in an amount sufficient to provide from about 0 wt.% to about 1 wt.%, from about 0.01 wt.% to about 0.5 wt.%, or from about 0.02 wt.% to about 0.04 wt.%, based on the final weight of the lubricating oil composition.

Other suitable corrosion inhibitors include long chain α, omega-dicarboxylic acids having a molecular weight in the range of about 600 to about 3000, and alkenyl succinic acids in which the alkenyl group contains about 10 or more carbon atoms, such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid.

If present, the rust inhibitor may be used in an amount sufficient to provide from about 0 wt.% to about 5 wt.%, from about 0.01 wt.% to about 3 wt.%, from about 0.1 wt.% to about 2 wt.%, based on the final weight of the lubricating oil composition.

The lubricant composition may also include a corrosion inhibitor (note that some of the other noted components may also have copper corrosion inhibiting properties). Suitable copper corrosion inhibitors include ether amines, polyethoxylated compounds such as ethoxylated amines and ethoxylated alcohols, imidazolines, monoalkyl and dialkyl thiadiazoles, and the like.

Thiazoles, triazoles and thiadiazoles may also be used in lubricants. Examples include benzotriazole, tolyltriazole, octyltriazole, decyltriazole, dodecyltriazole, 2-mercaptobenzotriazole, 2, 5-dimercapto-1, 3, 4-thiadiazole, 2-mercapto-5-hydrocarbylthio-1, 3, 4-thiadiazole, and 2-mercapto-5-hydrocarbylthio-1, 3, 4-thiadiazole. In one embodiment, the lubricant composition comprises a1, 3, 4-thiadiazole, such as a 2-hydrocarbyl dithio-5-mercapto-1, 3, 4-dithiadiazole.

Anti-foaming agents/surfactants may also be included in the fluids according to the present invention. Various agents are known for this purpose. Copolymers of ethyl acrylate and hexyl acrylate may be used, such as PC-1244 available from Solutia. In other embodiments, a silicone fluid, such as 4% DCF, may be included. Mixtures of anti-foaming agents may also be present in the lubricant composition. .

Suitable engine lubricants may include additive components within the ranges listed in table 2 with wide and narrower ranges. The base oil constitutes the remainder of the lubricant.

TABLE 2

The above percentages for each component represent the weight percent of each component, based on the weight of the total final lubricating oil composition. The remainder of the lubricating oil composition is comprised of one or more base oils. The additives used to formulate the compositions described herein can be blended into the base oil individually or in various sub-combinations. However, it may be suitable to blend all of the components simultaneously using an additive concentrate (i.e., additive plus diluent, such as a hydrocarbon solvent).

Fully formulated lubricants typically contain an additive package, commonly referred to as a dispersant/inhibitor package or DI package, which will supply the features required in the formulation. Suitable DI packages are described, for example, in U.S. patent nos. 5,204,012 and 6,034,040. The types of additives included in the additive package may be dispersants, seal swell agents, antioxidants, foam inhibitors, lubricants, rust inhibitors, corrosion inhibitors, demulsifiers, viscosity index improvers, and the like. Some of these components are well known to those skilled in the art and are typically used in conventional amounts with the additives and compositions described herein.

The additives used to formulate the compositions described herein can be blended into the base oil individually or in various sub-combinations. However, it may be suitable to blend all of the components simultaneously using an additive concentrate (i.e., additive plus diluent, such as a hydrocarbon solvent). When in the form of an additive concentrate, the use of the additive concentrate may take advantage of the mutual compatibility provided by the combination of ingredients. Furthermore, the use of a concentrate may reduce mixing time and may reduce the likelihood of mixing errors.

In a further embodiment, the present invention is directed to a method for lubricating an engine by lubricating the engine with the lubricant composition of any of the preceding embodiments. In a still further embodiment, the present invention relates to the use of a lubricant composition according to any one of the preceding embodiments for lubricating an engine and/or the use of a lubricant composition for achieving a reduced coefficient of friction and/or improved seal compatibility, as shown in the following table.

The lubricants, combinations of components, or individual components of the present description may be suitable for use as lubricants for various types of internal combustion engines. Suitable engine types may include, but are not limited to, heavy duty diesel engines, passenger cars, light duty diesel engines, medium speed diesel engines, or marine engines. The internal combustion engine may be a diesel fuel engine, a gasoline fuel engine, a natural gas fuel engine, a biofuel engine, a hybrid diesel/biofuel engine, a hybrid gasoline/biofuel engine, an ethanol fuel engine, a hybrid gasoline/ethanol fuel engine, a Compressed Natural Gas (CNG) fuel engine, or a mixture thereof. The diesel engine may be a compression ignition engine. The gasoline engine may be a spark ignition engine. Internal combustion engines may also be used in combination with electric or battery power sources. An engine so configured is commonly referred to as a hybrid engine. The internal combustion engine may be a 2-stroke, 4-stroke or rotary engine. Suitable internal combustion engines include marine diesel engines (e.g. inland ships), aviation piston engines, low load diesel engines and motorcycle, automotive, locomotive and truck engines.

The lubricating oil composition for an internal combustion engine may be suitable for use in any engine lubricant, regardless of the sulfur, phosphorus, or sulfated ash (ASTM D-874) content. In some methods, the sulfur content of the engine oil lubricant may be about 1 wt% or less, or about 0.8 wt% or less, or about 0.5 wt% or less, or about 0.3 wt% or less, or about 0.2 wt% or less. In one embodiment, the sulfur content may range from about 0.001 wt% to about 0.5 wt%, or from about 0.01 wt% to about 0.3 wt%. The phosphorus content of the engine oil lubricants herein may be about 0.2 wt% or less, or about 0.1 wt% or less, or about 0.085 wt% or less, or about 0.08 wt% or less, or even about 0.06 wt% or less, about 0.055 wt% or less, or about 0.05 wt% or less. In one embodiment, the phosphorus content may be from about 50ppm to about 1000ppm, or from about 325ppm to about 850ppm, or up to 600 ppm. The total sulfated ash content of the engine oil lubricants herein may be about 2 wt% or less, or about 1.5 wt% or less, or about 1.1 wt% or less, or about 1 wt% or less, or about 0.8 wt% or less, or about 0.5 wt% or less. In one embodiment, the sulfated ash content may be from about 0.05 wt% to about 0.9 wt%, or from about 0.1 wt% or from about 0.2 wt% to about 0.45 wt%.

Additionally, the lubricants of the present description may be adapted to meet one or more industry specification requirements, such as I L SACGF-3, GF-4, GF-5, GF-6, CK-4, FA-4, CJ-4, CI-4 Plus, CI-4, ACEA A1/B1, A2/B2, A3/B3, A3/B4, A5/B5, C1, C2, C3, C4, C5, E4/E6/E7/E9, Euro 5/6, SO D L-1, low SAPS, medium SAPS, or original equipment manufacturer specifications, such as Dexos^TM1、Dexos^TM2. MB approval 229.51/229.31, VW 502.00, 503.00/503.01, 504.00, 505.00, 506.00/506.01, 507.00, 508.00, 509.00, BMW L onglife-04, Porsche C30, Peugeot citron Automobiles B712290, B712296, B712297, B712300, B712302, B712312, B712007, B712008, Ford WSS-M2C153-H, WSS-M2C930-A, WSS-M2C945-A, WSS-M2C913A, WSS-M2C913-B, WSS-M2C913-C, GM 6094-M, ChryslerMS-6395, or any past or future passenger car motor oil or heavy duty diesel specification not mentioned hereinIn some embodiments, the amount of phosphorus in the finished fluid is 1000ppm or less, or 900ppm or less, or 800ppm or 600ppm or less for passenger car motor oil applications. In some embodiments, the amount of phosphorus in the finished fluid is 1200ppm or less, 1000ppm or less, or 900ppm or less, or 800ppm or less for heavy duty diesel applications.

In certain applications, the lubricants of the present disclosure may also be suitable for use in automatic transmission fluids, continuously variable transmission fluids, manual transmission fluids, gear oils, other fluids associated with powertrain components, off-road fluids, power steering fluids, fluids used in wind turbines, compressors, hydraulic fluids, skid fluids, and other industrial fluids. In some applications, these lubrication applications may include lubrication of gearboxes, power take-offs and clutches, rear axles, reduction gears, wet brakes, and hydraulic accessories.

Unless otherwise indicated or apparent from the context of the following examples and the entire disclosure that is discussed, all percentages, ratios, and parts mentioned in the disclosure are by weight.