阅读说明：本技术 用高焦磷酸酯含量的润滑剂润滑机械装置的方法 (Method for lubricating a mechanical device with a lubricant having a high pyrophosphate content ) 是由 B·B·菲利皮尼 S·帕特尔森 W·R·S·巴顿 于 2018-04-25 设计创作，主要内容包括：提供一种润滑剂组合物,其含有具有润滑粘度的油和基本上无硫的烷基磷酸酯胺盐,其中至少30摩尔％的磷原子处于烷基焦磷酸酯盐结构中,以及常规含磷抗磨添加剂和甘油酯中的任一者或两者。在所述磷酸酯胺盐中,至少80摩尔％的烷基通常为具有3至12个碳原子的仲烷基。还提供通过采用所述润滑剂组合物在机械装置中在宽温度范围内改进磨损的方法。(A lubricant composition is provided comprising an oil of lubricating viscosity and a substantially sulfur-free alkyl phosphate amine salt wherein at least 30 mole% of the phosphorus atoms are in the alkyl pyrophosphate salt structure, and either or both of a conventional phosphorus-containing antiwear additive and a glycerol ester. In the amine phosphate salt, at least 80 mole% of the alkyl groups are typically secondary alkyl groups having 3 to 12 carbon atoms. Also provided are methods of improving wear in a mechanical device over a wide temperature range by employing the lubricant compositions.)

1. a lubricant composition comprising

a. An oil of lubricating viscosity;

b. An antiwear additive comprising a substantially sulfur-free alkyl phosphate amine salt wherein at least about 30 mole percent of the phosphorus atoms are in the alkyl pyrophosphate salt structure and at least about 80 mole percent of the alkyl groups are secondary alkyl groups having from about 3 to about 12 carbon atoms; and

c. At least one of the following:

i. A hydrocarbyl amine salt of an alkyl phosphate ester,

A glyceride, and

A mixture of (i) and (ii).

2. The lubricant composition of claim 1 wherein said antiwear additive is present in about 0.01 to about 5 weight percent of said composition.

3. The lubricant composition of claim 1 or 2 wherein said antiwear additive is present in said lubricant composition in an amount to deliver a phosphorus content of at least 200ppm to 2000 ppm.

4. A lubricant composition as set forth in any one of claims 1-3 wherein said sulfur-free alkyl phosphate amine salt comprises a material represented by formula (I) or (II):

Wherein each R¹Independently is a secondary alkyl group having from about 4 to about 12 carbon atoms, and each R²Independently is hydrogen or a hydrocarbyl or ester-containing group, and at least one R²The group is a hydrocarbyl or an ester-containing group;

OR wherein the-OH group is-OR¹Radical substitution, OR in which one OR more-OR¹The radicals being replaced by-OH groups, or in which R is¹The groups are replaced by phosphorus-containing groups.

5. The lubricant composition of any one of claims 1 to 4, wherein the glyceride is glycerol monooleate or borated glycerol monooleate.

6. A lubricant composition according to any one of claims 1 to 5 wherein the glyceride is present at least 0.01 wt%.

7. The lubricant composition of any one of claims 1 to 6 wherein the glyceride is present at 0.01 to 1 wt%.

8. The lubricant composition of any one of claims 1 to 6 wherein the glyceride is present at 1 to 3 wt%.

9. The lubricant composition of any one of claims 1 to 8 wherein the alkyl phosphoric acid of the hydrocarbylamine salt of alkyl phosphate ester is a dialkyl dithiophosphoric acid.

10. The lubricant composition of any one of claims 1 to 9, wherein the hydrocarbyl amine in the hydrocarbyl amine salt of an alkyl phosphate ester is C₈To C₂₀An alkyl amine.

11. A lubricant composition as set forth in any one of claims 1 through 10 wherein said hydrocarbyl amine salt of alkyl phosphate is present from 0.3 to 2 weight percent.

12. Lubricant combination according to any of claims 1 to 11Wherein the oil of lubricating viscosity has a kinematic viscosity at 100 ℃ of from about 1.5 to about 7.5 millimeters as determined by ASTM D445²In seconds.

13. The lubricant composition of any one of claims 1 to 12 wherein said oil of lubricating viscosity comprises a polyalphaolefin having a kinematic viscosity at 100 ℃ of from about 1.5 to about 7.5 as determined by ASTM D445.

14. The lubricant composition of any one of claims 1 through 13 wherein the lubricant composition has a kinematic viscosity at 100 ℃ of from about 3 to about 7.5 as determined by ASTM D445.

15. A method of improving wear in a mechanical device, comprising supplying the lubricant composition of any of claims 1-14 to the mechanical device, and operating the mechanical device.

16. The method of claim 15, wherein the mechanical device comprises a shaft.

17. The method of claim 15, wherein the mechanical device includes a bearing.

18. The method of claim 15, wherein the mechanical device comprises a hypoid gear.

19. The method of any one of claims 15 to 18, wherein the method comprises the step of operating the mechanical device at a temperature between about 40 ℃ to about 160 ℃.

Background

The disclosed technology relates to lubricant compositions containing an oil of lubricating viscosity and a substantially sulfur-free alkyl phosphate amine salt wherein at least 30 mole% of the phosphorus atoms are in the alkyl pyrophosphate ester salt structure, and either or both of conventional phosphorus-containing anti-wear additives and glycerol esters, and methods of improving gear, shaft and bearing wear in mechanical devices over a wide temperature range by employing the lubricant compositions.

Driveline power transmission devices, such as gears or transmissions, present extremely challenging technical problems and solutions to meet a variety and often conflicting lubrication requirements while providing durability and cleanliness.

the motivation for developing new antiwear chemicals for such applications as gear and shaft oils is the desire to provide chemicals that meet modern lubrication requirements, including low viscosity fluids, low temperature durability, and improved performance over a wider temperature range.

The disclosed technology provides one or more of the above-described advantages.

disclosure of Invention

One aspect of the disclosed technology relates to a lubricant composition containing an oil of lubricating viscosity; a sulfur-free antiwear additive and at least one of: hydrocarbyl amine salts of alkyl phosphate esters, glycerol esters, and mixtures thereof.

The sulfur-free antiwear additive may comprise a substantially sulfur-free alkyl phosphate amine salt wherein at least about 30 mole percent of the phosphorus atoms are in the alkyl pyrophosphate salt structure and at least about 80 mole percent of the alkyl groups are secondary alkyl groups having from about 3 to about 12 carbon atoms.

The sulfur-free antiwear additive may be present in the lubricant composition in an amount from about 0.01 to about 5 percent by weight of the composition, or in some embodiments, in an amount to deliver a phosphorus content of at least 200ppm to 2000ppm to the composition.

In embodiments, the glyceride in the lubricant composition may be glycerol monooleate or borated glycerol monooleate. The glyceride may be present in the lubricant composition at least 0.01 wt%, or for example, 0.01 to 1 wt%. In another embodiment, the glyceride may be present in the lubricant composition at 1 to 3 wt%.

The alkyl phosphoric acid of the hydrocarbyl amine salt of an alkyl phosphate ester may be a dialkyl dithiophosphoric acid. The hydrocarbyl amine in the hydrocarbyl amine salt of the alkyl phosphate ester may be C₈To C₂₀An alkyl amine.

In some embodiments, the hydrocarbyl amine salt of an alkyl phosphate ester may be present from 0.3 to 2 weight percent.

In some embodiments, the kinematic viscosity at 100 ℃ of the oil of lubricating viscosity in the lubricant composition as obtained by ASTM D445 may be from about 1.5 to about 7.5 millimeters²In seconds. In some embodiments, the oil of lubricating viscosity may be or include a polyalphaolefin having a kinematic viscosity at 100 ℃ of from about 1.5 to about 7.5 as determined by ASTM D445.

Another aspect of the disclosed technology relates to a method of improving wear in a mechanical device. The method may comprise supplying the lubricant composition as mentioned to a mechanical device, and operating the mechanical device.

The mechanical device may be or include, for example, a shaft, a bearing, or a hypoid gear.

Detailed Description

Various preferred features and embodiments will be described hereinafter by way of non-limiting illustration. One aspect of the present invention is a lubricant composition containing (a) an oil of lubricating viscosity, (b) a substantially sulfur-free phosphate amine salt antiwear additive, and (c) a hydrocarbyl amine salt of an alkyl phosphate, a glycerol ester, or a mixture thereof.

(a) Oil of lubricating viscosity

One component of the disclosed technology is an oil of lubricating viscosity, also known as a base oil. The Base Oil may be selected from any of group I-V Base oils from American Petroleum Institute (API) guide for Base Oil interchange (API) (2011)

i, II th and group III are mineral oil base stocks. Other recognized base oil classes may be used even if the API has no formal identification: group II + which refers to group II materials having a viscosity index of 110-119 and lower volatility than other group II oils; and group III + which refers to group III materials having a viscosity index greater than or equal to 130. Oils of lubricating viscosity may include natural or synthetic oils, and mixtures thereof. Mixtures of mineral and synthetic oils may be used, such as polyalphaolefin oils and/or polyester oils.

In one embodiment, the oil of lubricating viscosity has a kinematic viscosity at 100 ℃ of 1.5 to 7.5, or 2 to 7, or 2.5 to 6.5, or 3 to 6 millimeters as determined by ASTM D445²In seconds. In one embodiment, the oil of lubricating viscosity comprises a polyalphaolefin having a kinematic viscosity at 100 ℃ of 1.5 to 7.5, or any of the other aforementioned ranges, as obtained by ASTM D445.

(b) Substantially sulfur-free alkyl phosphate amine salt antiwear additives

As further described, the lubricants of the disclosed technology will comprise substantially sulfur-free amine salts of alkyl phosphate esters. In this salt composition, at least 30 mole percent of the phosphorus atoms are in the alkyl pyrophosphate structure, rather than the orthophosphate (or monomeric phosphate) structure. The percentage of phosphorus atoms in the pyrophosphate structure may be 30 to 100 mole%, or 40 to 90%, or 50 to 80%, or 55 to 70%, or 55 to 65%. The remaining amount of phosphorus atoms may be in the orthophosphate structure or may be composed in part of unreacted phosphoric acid or other phosphorus species. In one embodiment, up to 60 or up to 50 mole% of the phosphorus atoms are in the mono-or dialkyl orthophosphate salt structure.

Substantially sulfur-free alkyl phosphate amine salts, as present in the pyrophosphate form (sometimes referred to as the POP structure), may be represented in part by the following formulas (I) and/or (II):

Formula (I) represents a semi-neutralized phosphonium salt; formula (II) representsA fully neutralized salt. It is believed that both of the hydroxyl hydrogen atoms of the first formed phosphate ester structure are sufficiently acidic to be neutralized by the amine such that formula (II) may predominate if a stoichiometrically sufficient amount of amine is present. The degree of actual neutralization, i.e., the degree of salination of the-OH groups of the phosphorus ester, can be from 50% to 100%, or from 80% to 99%, or from 90% to 98%, or from 93% to 97%, or about 95%, which can be determined or calculated based on the amount of amine added to the phosphate ester mixture. Variants of these materials may also exist, such as variants of formula (I) OR formula (II) in which the-OH group in (I) is replaced by another-OR¹radical substitution, OR in which one OR more-OR¹The radicals being replaced by-OH groups, or in which R is¹The radicals being replaced by phosphorus-containing groups, i.e. containing a third phosphorus structure in place of the terminal R¹Those of the group. Illustrative variant structures may include the following:

The structures of formulas (I) and (II) are shown to be completely sulfur-free species because the phosphorus atom is bonded to oxygen rather than a sulfur atom. However, it is possible that a small mole fraction of the O atoms may be replaced by S atoms, such as 0 to 5%, or 0.1 to 4%, or 0.2 to 3%, or 0.5 to 2%.

These pyrophosphate salts can be distinguished from orthophosphoric acid ester salts of the general structure

Which optionally may also be present in the amounts as indicated above.

In the formulae (I) and (II), each R¹Independently an alkyl group having 3 to 12 carbon atoms. In certain embodiments, at least 80 mole%, or at least 85, 90, 95, or 99% of the alkyl groups will be secondary alkyl groups. In some embodiments, the alkyl group will have from 4 to 12 carbon atoms, or from 5 to 10, or from 6 to 8 carbon atoms. Such groups include 2-butyl, 2-pentyl, 3-methyl-2-butyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methyl-2-pentylAnd other such secondary groups having 6, 7, 8, 9, 10, 11 or 12 carbon atoms and isomers thereof. In some embodiments, the alkyl group will have a methyl branch alpha to the group, an example being 4-methyl-2-pentyl (also known as 4-methylpent-2-yl).

Such alkyl groups (including cycloalkyl groups) will typically be reacted with phosphorus pentoxide (referred to herein as P) via the corresponding alcohol or alcohols₂O₅Although it is recognized that a more likely structure may be represented by P₄O₁₀Represented by (a) to provide. Generally, for each mole of P₂O₅2 to 3.1 moles of alcohol will be provided to provide a mixture of partial esters, including mono-and diesters of orthophosphoric acid ester structures and diesters of pyrophosphoric acid ester structures:

In certain embodiments, for each mole of P₂O₅2.5 to 3 moles of alcohol, or 2.2 to 2.8 moles/mole, or even 2.2 to 2.4 moles/mole may be provided. 2.5 to 3 (or 2.2-2.8 or 2.2-2.4) moles of alcohol are generally available for reaction with P₂O₅Reacted (i.e., included in the reaction mixture), but typically the actual reaction will consume less than 3 moles/mole. Thus, the alkylphosphate amine salt may be prepared by reacting phosphorus pentoxide with a secondary alcohol having 4 to 12 carbon atoms, and reacting the product thereof with an amine, as described in additional detail below.

Reaction conditions and reactants may be selected which will favor the formation of esters of the pyrophosphate structure and will be relatively unfavorable for the formation of mono-and diesters of orthophosphoric esters. It was found that the formation of the pyrophosphate structure was favored by using a secondary alcohol instead of a primary alcohol. Advantageous synthesis temperatures include 30 to 60 ℃, or 35 to 50 ℃, or 40 to 50 ℃, or 30 to 40 ℃, or about 35 ℃, and in some embodiments, the reaction temperature may be 50-60 ℃. Subsequent heating at 60 to 80 ℃ or about 70 ℃ after initial mixing of the components may be desirable. It may be desirable to avoid overheating of the reaction mixture or to stop heating once the reaction is substantially complete, particularly at temperatures of 60 ℃ or higher; this is for the fieldas will be apparent to those skilled in the art. In certain embodiments, the reaction temperature will not exceed 62 ℃ or 61 ℃ or 60 ℃. Favorable conditions may also include the exclusion of excess water. The progress of the reaction and the relative amounts of the various phosphorus species can be determined by spectroscopic means known to those skilled in the art, including infrared spectroscopy and³¹P or¹H NMR spectroscopy.

Although the phosphate ester can be separated from the ortho ester if necessary, the reaction mixture can also be used without separation of the components and may be commercially preferred.

Amine component-reacting the pyrophosphate phosphate or the mixture of phosphates with an amine to form an amine salt. The amine may be represented by R² ₃N represents, wherein each R²Independently is hydrogen or a hydrocarbyl group or an ester-containing group or an ether-containing group, with the proviso that at least one R²The radicals being hydrocarbon radicals or ester-containing or ether-containing radicals (i.e. not being NH)₃). Suitable hydrocarbyl amines include primary amines having 1 to 18 carbon atoms, or 3 to 12 or 4 to 10 carbon atoms, such as methylamine, ethylamine, propylamine, isopropylamine, butylamine and isomers thereof, pentylamine and isomers thereof, hexylamine and isomers thereof, heptylamine and isomers thereof, octylamine and isomers thereof, such as isooctylamine and 2-ethylhexylamine, and higher amines. Other primary amines include dodecylamine, fatty amines such as n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine and oleylamine. Other useful fatty amines include commercially available fatty amines, e.g.Amines (available from Aksu chemical Co., Chicago, Ill.) such asC、O、OL、T、HT、S andSD, wherein the letter designation refers to a fatty group such as coco, oleyl, tallow, or stearyl.

Secondary amines which may be used include dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, methylethylamine, ethylbutylamine, bis-2-ethylhexylamine, N-methyl-1-amino-cyclohexane, N-methyl-1-methyl-N-hexylamine, N-methyl-N-butyl-ethyl-amine, N-methyl,2C and ethylpentanamine. The secondary amine may be a cyclic amine such as piperidine, piperazine, and morpholine.

Suitable tertiary amines include tri-n-butylamine, tri-n-octylamine, tri-decylamine, tri-laurylamine, tri-hexadecylamine, and dimethyloleylamine ()DMOD). Triisodecylamine or tridecylamine and isomers thereof may be used.

Examples of mixtures of amines include (i) amines having 11 to 14 carbon atoms on the tertiary alkyl primary group, (ii) amines having 14 to 18 carbon atoms on the tertiary alkyl primary group, or (iii) amines having 18 to 22 carbon atoms on the tertiary alkyl primary group. Other examples of tertiary alkyl primary amines include tert-butylamine, tert-hexylamine, tert-octylamine (e.g., 1-dimethylhexylamine), tert-decylamine (e.g., 1-dimethyloctylamine), tert-dodecylamine, tert-tetradecylamine, tert-hexadecylamine, tert-octadecylamine, tert-tetracosylamine, and tert-octacosylamine. In one embodiment, useful amine mixtures include "81R "or"JMT”。81R andJMT (both of which are Rohm)&Haas) manufactured and sold) can be a mixture of C11 to C14 tertiary alkyl primary amines and C18 to C22 tertiary alkyl primary amines, respectively.

Ester-containing amines-in other embodiments, the amine can be an ester-containing amine such as an N-hydrocarbyl-substituted γ -or δ -amino (thio) ester, which is thus a secondary amine. One or both of the O atoms of the ester group may be replaced by sulfur, although sulfur atoms may generally be absent. The N-substituted gamma-amino ester can be represented by

And N-substituted delta-amino esters can be represented by

One or more additional substituents or groups may also be present at the α, β, γ, or δ positions of the amino ester. In one embodiment, such substituents are absent. In another embodiment, a substituent is present at the beta position, thus in certain embodiments, yielding a set of materials represented by the formula

R and R⁴Is defined as follows; x is O or S (O in one embodiment), and R⁵Can be hydrogen, hydrocarbyl or substituted by-C (═ O) -R⁶A group of the formula (I), wherein R⁶Is hydrogen, alkylor-X' -R⁷Wherein X' is O or S, and R⁷Is a hydrocarbon group having 1 to 30 carbon atoms. That is, the substituent at the β -position of the chain may comprise an ester, thioester, carbonyl, or hydrocarbyl group. When R is⁵is-C (═ O) -R⁶when, the structure can be represented by

will be understood to encompass similar structures of δ -amino esters; this may be for example such that,

It is apparent that when R is⁶is-X' -R⁷When the material will be a substituted succinate or thioester. In particular, in one embodiment, the material may be a methyl succinic diester with an amine substitution on the methyl group. R⁴And R⁷The groups may be the same or different; in certain embodiments, they may independently have 1 to 30 or 1 to 18 carbon atoms, as described below for R⁴The method is as follows. In certain embodiments, the materials may be represented by the following structures

In certain embodiments, the material will be or will comprise a dihydrocarbyl 2- ((hydrocarbyl) -aminomethylsuccinate (which may also be referred to as a dihydrocarbyl 2- ((hydrocarbyl) aminomethylsuccinate).

In the above structure, the hydrocarbyl substituent R on the amine nitrogen may comprise a hydrocarbyl group having at least 3 carbon atoms and having a branch at the 1 or 2 (i.e., alpha or beta) position of the hydrocarbyl chain (not to be confused with the alpha or beta position of the above ester group). Such branched hydrocarbyl radicals R may be represented by the partial formula

Wherein the bond on the right represents the attachment of a nitrogen atomAnd (4) point. In this partial structure, n is 0 or 1, R¹Is hydrogen or a hydrocarbyl radical, R²And R³May independently be a hydrocarbon group or together may form a carboxyl structure. The hydrocarbyl group may be aliphatic, cycloaliphatic or aromatic or mixtures thereof. When n is 0, the branch is at the 1 or alpha position of the group. When n is 1, the branch is at the 2 or beta position. If above R⁴Is methyl, then in some embodiments n may be 0.

Of course, branches may be present at both the 1 and 2 positions. Attachment to a cyclic structure is considered to be a branch:

(1-or type of. alpha. branched chain)

Thus, a branched hydrocarbyl substituent R on the amine nitrogen may include such groups as isopropyl, cyclopropyl, sec-butyl, isobutyl, tert-butyl, 1-ethylpropyl, 1, 2-dimethylpropyl, neopentyl, cyclohexyl, 4-heptyl, 2-ethyl-1-hexyl (commonly referred to as 2-ethylhexyl), tert-octyl (e.g., 1, 1-dimethyl-1-hexyl), 4-heptyl, 2-propylheptyl, adamantyl, and α -methylbenzyl.

in the above structure, R as part of the alcohol residue⁴May have from 1 to 30 or from 1 to 18 or from 1 to 12 or from 2 to 8 carbon atoms. It may be a hydrocarbyl group or a hydrocarbyl group. It may be aliphatic, cycloaliphatic, branched aliphatic or aromatic. In certain embodiments, R⁴The group can be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, cyclohexyl, isooctyl or 2-ethylhexyl. If R is⁴Is methyl, then the R group as a hydrocarbyl substituent on the nitrogen may typically have a branch at the 1-position. In other embodiments, R⁴The group may be an ether-containing group. For example, it may be an ether-containing group or a polyether-containing group, which may contain, for example, 2 to 120 carbon atoms and an oxygen atom representing ether functionality.

In another embodiment, R⁴May be a hydroxyalkyl group or a polyhydroxyalkyl group having 2 to 12 carbon atoms. Such materials may be based on glycols, such as ethylene glycol or propylene glycol, where one of the hydroxyl groups may react to form an ester linkage, leaving an unesterified alkyl group. Another example of a material may be glycerol, which may leave one or two hydroxyl groups after condensation. Other polyhydroxy materials include pentaerythritol and trimethylolpropane. Optionally, one or more hydroxyl groups may react to form an ester or thioester. In one embodiment, R⁴One or more of the hydroxyl groups within may be condensed or attached with additional groups so as to form a bridging species.

In one embodiment, the amine can be represented by the following structure

wherein R is⁶And R⁷Independently is an alkyl group having from 1 to about 6 carbon atoms and R⁸And R⁹Independently an alkyl group having from 1 to about 12 carbon atoms.

the N-hydrocarbyl-substituted γ amino ester or γ -aminothioester materials disclosed herein can be prepared by the michael addition of a primary amine, typically having a branched hydrocarbyl group as described above, with an ethylenically unsaturated ester or thioester of the type described above. In this case, the ethylenic unsaturation will be between the β and γ carbon atoms of the ester. Thus, for example, the reaction can be carried out as follows

Wherein the X and R groups are as defined above. In one embodiment, the ethylenically unsaturated ester can be an ester of itaconic acid. In this structure, n can be 0 or 1, R¹Can be hydrogen or a hydrocarbyl radical, R²And R³Can independently be a hydrocarbon group or together form a carbocyclic ring structure, X is O or S, R⁴May be a hydrocarbon group having 1 to 30 carbon atoms, and R⁵Can be hydrogen, hydrocarbyl or substituted by-C (═ O) -R⁶A group of the formula (I), whichIn R⁶Is hydrogen, alkyl or-X' -R⁷Wherein X' is O or S, and R⁷is a hydrocarbon group having 1 to 30 carbon atoms.

In one embodiment, the amine reactant is not a tertiary hydrocarbyl (e.g., tertiary alkyl) primary amine, i.e., n is not zero and R is¹、R²And R³Each is a hydrocarbyl group.

The amines that can be reacted to form the above michael addition products can be primary amines, such that the resulting product will be a secondary amine having a branched R substituent as described above and a nitrogen also attached to the rest of the molecule.

The N-hydrocarbyl substituted δ -amino ester or δ -aminothioester materials disclosed herein can be prepared by reductive amination of esters of 5-oxo substituted carboxylic acids or 5-oxo substituted thiocarboxylic acids. They may also be prepared by amination of esters of 5-halogen-substituted carboxylic acids or 5-halogen-substituted thiocarboxylic acids, or by reductive amination of esters of 2-amino-substituted adipic acid, or by alkylation of esters of 2-amino-adipic acid.

Additional details of N-substituted γ -amino esters and details of their synthesis can be found in WO2014/074335 to Lubrizol (Lubrizol) at 5.15.5.4.2014. Additional details of N-substituted δ -amino esters and details of their synthesis can be found in PCT application PCT/US2015/027958 filed on 28.4.2015 and US61/989306 filed on 6.5.2015.

Any type of amine will react to neutralize one or more acidic groups on the phospholipid component, which will comprise the pyrophosphate esters described above as well as any orthophosphate esters that may be present.

amount of amine salt

The substantially sulfur-free amine salt of an alkyl phosphate ester may be present in the lubricant composition in an amount of 0.01 to 5 weight percent. This amount refers to the total amount of the one or more amine phosphate salts of any structure of both orthophosphoric acid esters and pyrophosphates (it being understood that at least 30 mole percent of the phosphorus atoms are in the alkyl pyrophosphate salt structure). From this, the amount of the phosphate amine salt in the pyrophosphate structure can be easily calculated. Alternative amounts of the amine salt of an alkylphosphate may be 0.2 to 3 wt%, or 0.2 to 1.2 wt%, or 0.5 to 2 wt%, or 0.6 to 1.7 wt%, or 0.6 to 1.5 wt%, or 0.7 to 1.2 wt%. The amount may be suitable to provide phosphorus to the lubricant formulation in an amount of 200 to 3000 parts per million by weight (ppm), or 400 to 2000ppm, or 300 to 2000, or 600 to 1500ppm, or 700 to 1100ppm, or 900 to 1900, or 1100 to 1800 ppm.

Activation temperatureThe sulfur-free alkylphosphate amine salt antiwear additive of the lubricant composition will provide antiwear performance over a wider temperature range than current conventional antiwear components. As used herein, activation temperature means the temperature at which the antiwear additive reacts with the iron-containing surface and forms a protective tribofilm. The activation temperature can be measured by running a number of four-ball tests at different temperatures and analyzing the end of the test part by surface analysis techniques, or by recording the pass results for runs at different temperatures. The four ball test is a test used to assess the wear characteristics of a lubricating fluid. The four ball test was run according to ASTM D4172 and involved rotating the steel ball on three clamped ball tops at a rate of 1200rpm at 40kg force at 75 ℃ for 60 minutes to get an average wear track result. Generally, average wear trace results of 0.6mm and below are considered acceptable results. Passing results in a four ball test at a given temperature indicate that the antiwear additive is active at that temperature. The activation temperature of the additive will be from 25 ℃ to about 105 ℃, or from about 35 ℃ to 100 ℃, or from 40 ℃ to about 90 ℃. When used in combination with additional antiwear agents other than the phosphate amine salt antiwear additive compounds of the present invention, the activation temperature may be additionally extended by 25 ℃ to 175 ℃, or 25 ℃ to 160 ℃.

(c) Additional alkyl phosphate antiwear agent。

The lubricant composition optionally additionally contains at least one additional antiwear agent in the form of a hydrocarbyl amine salt of an alkyl phosphate ester. Suitable hydrocarbylamine salts of alkyl phosphate esters include salts of dialkyldithiophosphoric acids represented by the formula:

Wherein R is²⁶And R²⁷Independently hydrogen or a hydrocarbyl group, such as alkyl; for phosphoric esters, R²⁶And R²⁷At least one of which will be a hydrocarbyl group. R²⁶And R²⁷May contain 3 or 4 to 30, or 8 to 25, or 10 to 20, or 13 to 19 carbon atoms. R²³、R²⁴And R²⁵May independently be hydrogen or a hydrocarbyl group such as an alkyl branched or straight alkyl chain having 1 to 30, or 4 to 24, or 6 to 20, or 10 to 16 carbon atoms. These R²³、R²⁴And R²⁵The group may be a branched or straight chain group, and in certain embodiments, R²³、R²⁴and R²⁵At least one or alternatively both of which are hydrogen. Is suitable for R²³、R²⁴And R²⁵Examples of alkyl groups of (a) include butyl, sec-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, sec-hexyl, n-octyl, 2-ethylhexyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonadecyl, eicosyl, and mixtures thereof.

in one embodiment, the hydrocarbyl amine salt of an alkyl phosphate is C₁₄To C₁₈Alkylated phosphoric acids with as C₁₁To C₁₄Primene 81R of a mixture of tertiary alkyl primary amines^TM(manufactured and sold by Rohm and Haas). Other amines that may be used include alkylalkanolamines, dialkanolamines, trialkanolamines such as triethanolamine, and borated amines as described below.

Thus, the amine salt used as this component in the present invention may comprise C of a mono-or dialkyl phosphate₈To C₂₀An alkylamine salt, or a mixture thereof. Those skilled in the art will appreciate that the amine salt of a thiophosphate ester will typically comprise a mixture of various individual chemicals. It will be understood by those skilled in the art that reference herein to "amine salts of phosphorus compounds" as used in the description of component (b) herein encompasses mixtures of such compounds as may be prepared by the syntheses described.

The amount of additional antiwear agent in the lubricant may be from 0.3 to 2 wt.%, or from 0.4 to 1.9, or from 0.5 to 1.8, or from 0.7 to 1.7 wt.%. The amount in the concentrate will be proportionally higher. The amount of the amine salt may also be an amount that contributes 0.03 to 0.2 wt.% phosphorus to the lubricant composition, or alternatively 0.08 to 0.17, or 0.11 to 0.17 wt.%.

(c) A glyceride.

The lubricant composition may also include a glyceride or a borated glyceride. Glycerides that may be used in the present invention are glycerides of fatty acids, such as fatty acids having from about 8 to about 22 carbon atoms, preferably from about 12 to about 20 carbon atoms. Examples of fatty acids that can be used to prepare the esters are isostearic acid, oleic acid, stearic acid, linoleic acid, and the like. The ester may be a mono-, di-or triester of a fatty ester. Glyceryl monooleate and glyceryl tallow fatty acid ester are known commercial materials. It is well recognized that glycerides are actually mixtures of mono-and diesters. Particularly suitable are mixtures of mono-and diesters containing at least 40% of monoglycerides. Preferably, the mixture of mono-and diesters of glycerol contains from about 40 to about 60 weight percent monoester. For example, commercial glycerol monooleate contains a mixture of about 45% to about 55% by weight monoester and 55% to about 45% monoester. Glycerol monooleate in its commercially available mixture is preferred.

The borated glycerides useful in the present invention are prepared by reacting fatty acid esters of glycerol with boric acid and removing the water. Preferably, the boric acid and fatty acid ester are reacted such that each boron will react with 1.5 to about 2.5 hydroxyl groups present in the mixture.

The reaction may be carried out at a temperature in the range of about 60 ℃ to about 135 ℃ in the absence or presence of any suitable organic solvent such as methanol, benzene, xylene, toluene, and the like.

if present, the amount of glyceride may be 0.01 to 3 wt%, or 0.01 to 1 wt%, or 1 to 3 wt%. In some embodiments, the glycerides may be present from 0.05 to 2.5 wt%, or from 0.1 to 2 wt%. In some embodiments, glycerol may be present from 0.05 to 0.9%, or from 0.1 to 0.8%, or from 0.2 to 0.6%. In some embodiments, the glycerides may be present from 1.25 to 2.75 wt%, or from 1.5 to 2.5 wt%.

In one embodiment, the lubricant composition contains (a) an oil of lubricating viscosity, (b) a substantially sulfur-free alkyl phosphate amine salt antiwear additive (i.e., a substantially sulfur-free alkyl phosphate amine salt as described herein), and (C) a hydrocarbyl amine salt of an alkyl phosphate (e.g., a C8 to C20 dialkyl dithiophosphate). In another embodiment, a lubricant composition contains (a) an oil of lubricating viscosity, (b) a substantially sulfur-free alkyl phosphate amine salt antiwear additive, and (c) a glycerol ester (e.g., glycerol monooleate). In further embodiments, the lubricant composition contains (a) an oil of lubricating viscosity, (b) a substantially sulfur-free alkyl phosphate amine salt antiwear additive, and (c) a mixture of a hydrocarbyl amine salt of an alkyl phosphate and a glycerol ester.

Optional Components

Other materials that may be present in the lubricant composition in their conventional amounts include, for example, detergents, viscosity modifiers, dispersants, antioxidants, tartrates, tartramides, and tartrimides, for example. Other additives that may optionally be used in their conventional amounts in the lubricant composition include, for example, pour point depressants, extreme pressure agents, dimercaptothiadiazole compounds, color stabilizers, and anti-foaming agents.

In one embodiment, the dynamic viscosity at 100 ℃ of the final lubricant composition containing the oil of lubricating viscosity, the substantially sulfur-free amine salt of an alkyl phosphate ester, and other optional additives as desired, as obtained by ASTM D445, can be 3 to 7.5 or 3.25 to 7, or 3.5 to 6.5, or 3.75 to 6 millimeters²In seconds. In some embodiments, the lubricant composition may have a kinematic viscosity at 100 ℃ of 5.5 to 7, or 5 to 6.5, or 5 to 6 millimeters as determined by ASTM D445²In seconds.

The disclosed technology provides a method of lubricating a mechanical device comprising supplying to the mechanical device a lubricant composition as described herein, i.e., a lubricant composition comprising: (a) an oil of lubricating viscosity, (b) a substantially sulfur-free alkyl phosphate amine salt antiwear additive, and (c) at least one of: (i) a hydrocarbyl amine salt of an alkyl phosphate, (ii) a glyceride, and (iii) mixtures thereof, and operating machinery.

The mechanical device may comprise a gear, such as in a gearbox (e.g., a manual transmission) or in an axle or differential of a vehicle, or in other driveline power transmission mechanisms. The mechanical device may also include a bearing. It is also applicable in engine lubricants, hydraulic oils, transmission fluids, tractor hydraulic oils, industrial lubricating oil applications, and lubricating greases. The lubricated gears may comprise hypoid gears, such as those in the rear drive shaft.

In an embodiment, a method of lubricating a mechanical device may include improving an antiwear protection temperature profile and a method of operating a mechanical device by supplying to the mechanical device a lubricant composition containing (a) an oil of lubricating viscosity, (b) a substantially sulfur-free alkyl amine phosphate salt antiwear additive, and (c) a hydrocarbyl amine salt of an alkyl phosphate. In such processes, an improvement in the anti-wear protection temperature profile is seen when the mechanical device is operated, for example, in a temperature range of about 40 ℃ to about 160 ℃, or about 55 ℃ to about 160 ℃.

In an embodiment, a method of lubricating a mechanical device may include improving an antiwear protection temperature profile and a method of operating a mechanical device by supplying to the mechanical device a lubricant composition containing (a) an oil of lubricating viscosity, (b) a substantially sulfur-free alkyl phosphate amine salt antiwear additive, and (c) a glycerol ester (e.g., 0.01 to 1 wt% glycerol ester). In such processes, an improvement in the wear protection temperature profile is seen when the mechanical device is operated, for example, in a temperature range of about 40 ℃ to about 160 ℃.

In an embodiment, a method of lubricating a mechanical device may include improving an antiwear protection temperature profile and a method of operating a mechanical device by supplying to the mechanical device a lubricant composition containing (a) an oil of lubricating viscosity, (b) a substantially sulfur-free alkyl amine phosphate salt antiwear additive, and (c) a mixture of a hydrocarbyl amine salt of an alkyl phosphate and a glycerol ester. In such processes, an improvement in the anti-wear protection temperature profile is seen when the mechanical device is operated, for example, in a temperature range of about 40 ℃ to about 160 ℃, or about 40 ℃ to about 135 ℃.

As used herein, the term "condensation product" is intended to encompass esters, amides, imides, and other such materials, which can be prepared by the condensation reaction of an acid or reactive equivalent of an acid (e.g., an acid halide, anhydride, or ester) with an alcohol or amine, whether or not the condensation reaction is actually performed to directly produce the product. Thus, for example, a particular ester may be prepared by a transesterification reaction rather than directly by a condensation reaction. The resulting product is still considered to be a condensation product.

Unless otherwise indicated, each chemical component is present in an amount based on the active chemical species, excluding any solvents or diluent oils that may typically be present in commercial materials. However, unless otherwise specified, each chemical species or composition referred to herein should be interpreted as a commercial grade material, which may contain isomers, by-products, derivatives, and other such materials as are commonly understood to be present in the commercial grade.

As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense as is well known to those skilled in the art. In particular, it refers to a group having carbon atoms directly attached to the rest of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include:

Hydrocarbon substituents, that is, aliphatic substituents (e.g., alkyl or alkenyl), alicyclic substituents (e.g., cycloalkyl, cycloalkenyl), and aromatic, aliphatic, and alicyclic substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed by another portion of the molecule (e.g., two substituents together form a ring);

Substituted hydrocarbon substituents, that is, substituents other than hydrocarbon groups containing substituents that do not alter the predominantly hydrocarbon nature in the context of this invention (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy); and

Hetero substituents, that is, substituents that, while having a predominantly hydrocarbon character in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms, and encompass substituents such as pyridyl, furyl, thienyl and imidazolyl. Heteroatoms include sulfur, oxygen, and nitrogen. Typically, no more than two or no more than one non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; alternatively, non-hydrocarbon substituents may not be present in the hydrocarbyl group.

It is known that some of the materials described herein may interact in the final formulation such that the components in the final formulation may be different from the components initially added. For example, metal ions (e.g., of detergents) can migrate to other acidic or anionic sites of other molecules. The products formed thereby, including products formed when employing the compositions of the present invention in their intended use, may not be readily described. Nevertheless, all such modifications and reaction products are included within the scope of the present invention; the present invention encompasses compositions prepared by blending the above components.

The invention may be better understood with reference to the following examples.

Examples of the invention

Examples 1 to 6.Compositions having the characteristics of those compositions to be used in automotive axle lubricants were prepared. The composition contains the following components (provided on an oil-free basis).

Viscosity modifier	12.5％
		Dispersing agent	0.84％
Extreme pressure agent	4.6％
		Rust inhibitor	0.04％
Copper corrosion inhibitor	0.15％
		Friction modifiers	0.13％
Commercial antifoam agents	0.07％
		Substantially sulfur-free alkyl phosphate amine salt antiwear additive, additional antiwear agent, glycerol ester	the following table
Diluent oil	3.1％
		Polyalphaolefin (PAO) oils, as shown in the following Table	77.5％

The lubricant formulations of examples 1-6 were prepared as follows:

The lubricant formulations of examples 1-6 were subjected to a four ball wear test (ASTM D4172) in which a four ball tester was used to assess the wear characteristics of the lubricating fluid. The steel ball was rotated on the three clamped ball tops at a rate of 1200rpm under a force of 40kg at 75 ℃ for 60 minutes. The average wear track of the three clamped balls was then determined. Additional data was then obtained by running D4172 under non-standard conditions. The test speed, test duration and load were consistent with D4172, but the test oil temperature was varied as indicated in the table below. The lowest pass standard for D4172 is a wear track measurement of less than 0.6 mm.

Four ball wear results for final shaft fluids

All wear traces are reported in mm.

The wear track reported is the arithmetic mean of the wear track diameters of the three lower balls in the four-ball assembly.

Examples 7 to 10.A series of lubricating compositions having the same viscosity and two different phosphorus contents were prepared as follows. The compositions have the characteristics of those compositions that will be used as automotive gear lubricants. The composition contains the following components (provided on an oil-free basis).

The lubricant formulations of examples 7-10 were subjected to a hypoid gear durability test similar to ASTM D6121, known as Canadian (Canadian) L37, but run at 93 ℃ instead of the standard 135 ℃. The test used a light hypoid gear rear drive shaft. The test is a 2-stage steady state test typical for (but not necessarily identical to) ASTM D6121. Phase 1 was a 65 minute break-in phase, operating at high speed and low load to allow the gears to break-in before the durability phase. During this conditioning phase, the wheel speed of each wheel is controlled to 682rpm and the wheel torque is controlled to 508 Nm. Stage 2 is a 27 hour durability stage for evaluating the ability of a lubricant to protect a gear from failure modes evaluated according to ASTM D6121. The wheel speed of each wheel was controlled to 124rpm, and the wheel torque was controlled to 2237 Nm. The bulk oil temperature was measured via an immersion thermocouple and allowed to warm up without assistance during the conditioning phase and was limited to 93 ℃ using water spray to the outside of the axle housing during both phases of the test. The speed and torque ramped smoothly over 2-5 minutes between the conditioned and tested conditions. The test components are removed and rated by a rating machine calibrated by the test monitoring center according to the GL-5L-37 rating standard. The score of 10 is most preferable. The lowest pass standard according to ASTM D6121 is shown in parentheses.

The results show the same or improved wear performance, especially at low phosphorus content and lower temperatures.

each of the documents mentioned above is incorporated herein by reference, including any previous applications to which priority is claimed, whether or not specifically listed above. Reference to any document is not an admission that such document is entitled to antedate such document by virtue of prior art or constitutes common knowledge of one of ordinary skill in any jurisdiction. Except by way of example or where otherwise explicitly indicated, all numbers in this description specifying amounts of material, reaction conditions, molecular weights, number of carbon atoms, and so forth, are to be understood as optionally modified by the word "about". It is to be understood that the upper and lower amount, range, and ratio limits described herein may be independently combined. Similarly, the ranges and amounts for each element of the invention can be used in combination with the ranges or amounts for any of the other elements.

As used herein, the transitional term "comprising" synonymous with "including," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional unrecited elements or method steps. However, in each statement herein that "comprises," it is intended that the term also encompasses, as alternative embodiments, the phrases "consisting essentially of … …" and "consisting of … …," wherein "consisting of … …" excludes any elements or steps not specified and "consisting essentially of … …" permits the inclusion of additional, unrecited elements or steps that do not materially affect the basic or basic and novel characteristics of the composition or method under consideration. When applied to an element of a claim, the expression "consisting of … …" or "consisting essentially of … …" is intended to limit all matter of the type represented by the element, even though "comprising" exists elsewhere in the claims.

While certain representative embodiments and details have been shown for the purpose of illustrating the subject invention, it will be apparent to those skilled in this art that various changes and modifications can be made therein without departing from the scope of the subject invention. In this respect, the scope of the invention is limited only by the appended claims.