阅读说明：本技术 含磷抗磨添加剂 (Phosphorus-containing antiwear additive ) 是由 W·R·S·巴顿 P·E·亚当斯 D·J·萨科曼多 J·卡西尔 于 2018-10-01 设计创作，主要内容包括：提供一种用于制备磷酸的经羟基取代的二酯的盐的方法,包含：(a)使磷化剂与一元醇并且与丙二醇反应,其中一元醇:丙二醇的摩尔比大于约4:1,并且其中采用过量的所述磷化剂以使得由此形成的产物混合物含有磷酸官能度；以及(b)使步骤(a)的产物混合物与胺反应。产物适用作抗磨剂。(There is provided a process for preparing a salt of a hydroxy-substituted diester of phosphoric acid, comprising: (a) reacting a phosphating agent with a monohydric alcohol and with propylene glycol, wherein the molar ratio of monohydric alcohol to propylene glycol is greater than about 4:1, and wherein the phosphating agent is employed in excess such that the product mixture formed thereby contains phosphate functionality; and (b) reacting the product mixture of step (a) with an amine. The product is suitable for use as an antiwear agent.)

1. A process for preparing a salt of a hydroxy-substituted (di) ester of phosphoric acid comprising:

(a) reacting a phosphating agent with a monohydric alcohol and with propylene glycol, wherein the molar ratio of monohydric alcohol to propylene glycol is greater than about 4:1, whereby the product mixture formed thereby contains phosphate functionality; and

(b) reacting the product mixture of step (a) with an amine comprising at least one primary or at least one secondary alkyl amine.

2. The method of claim 1, wherein the phosphating agent comprises phosphorus pentoxide.

3. The method of claim 1 or claim 2, wherein the monohydric alcohol has from about 4 to about 20 carbon atoms.

4. The method of any one of claims 1-3, wherein the monohydric alcohol comprises 2-ethylhexanol.

5. The method of any one of claims 1-4, wherein the propylene glycol comprises 1, 2-propanediol.

6. The method of any one of claims 1 to 5, wherein the molar ratio of monohydric alcohol to propylene glycol is about 8:2, or about 5.5:1 to about 7: 1.

7. The process of any one of claims 1 to 6 wherein the molar ratio of monohydric alcohol to propylene glycol is from about 8.4:1.6 to about 8.9: 1.1.

8. The method of any one of claims 1-7, wherein the phosphating agent comprises phosphorus pentoxide,and per 1 mole of said phosphorus pentoxide (as P)₂O₅Calculated) from about 2.5 to about 3.5 or from about 2.5 to about 3.0 moles of total monohydric alcohol plus propylene glycol.

9. The process of claim 8 wherein about 3.0 total monohydric alcohols plus propylene glycol are reacted per 1 mole of initial charge of phosphorus pentoxide.

10. The process of any one of claims 1 to 9, wherein the reaction of step (a) is carried out at about 40 ℃ to about 90 ℃.

11. The process of any one of claims 1 to 10, wherein the product mixture prepared by step (a) is substantially free of materials containing dimeric or oligomeric moieties derived from dimerization or oligomerization of alkylene oxides.

12. The method of any one of claims 1-11, wherein the amine comprises at least one primary alkyl amine having from about 6 to about 18 carbon atoms.

13. The method of any one of claims 1 to 12, wherein the amine comprises at least one secondary amine having from about 10 to about 22 carbon atoms.

14. A product prepared by the method of any one of claims 1 to 13.

15. An industrial lubricant comprising the product of claim 14, wherein the industrial lubricant is a grease, a metal working fluid, an industrial gear lubricant, a hydraulic oil, a turbine oil, a cycle oil, or a refrigerant.

16. A lubricant comprising an oil of lubricating viscosity and the product of claim 14.

17. A method for lubricating a gear, axle, transaxle, or transmission comprising supplying thereto the lubricant of claim 16.

18. The method of claim 17, wherein the gear is a hypoid gear.

19. A method of lubricating an engine comprising supplying thereto the lubricant of claim 16.

20. Use of the method according to any one of claims 1 to 13 for the preparation of an antiwear agent.

21. Use of the product of claim 14 to impart antiwear properties to a lubricant composition.

Technical Field

The disclosed technology relates to antiwear agents and lubricating compositions thereof, as well as improved methods for making antiwear agents. The invention further provides a method of lubricating a driveline device or a grease application by employing a lubricating composition containing an antiwear agent. The lubricating composition is also suitable for use in engine oils, industrial lubrication and metal working applications.

Background

Driveline power transmission devices, such as gears or transmissions, particularly axle fluids and Manual Transmission Fluids (MTF), and grease applications exhibit highly challenging technical problems and solutions for meeting multiple, but often conflicting, lubrication requirements while providing durability and cleanliness.

The need to provide chemicals that meet modern lubrication requirements, provide thermal oxidation stability and cleanliness, and have non-objectionable odors has driven the development of new antiwear chemicals for such applications as gear oils. Many current phosphorus antiwear or extreme pressure additives contain sulfur. The presence of sulfur in antiwear or extreme pressure additives becomes less desirable due to increased environmental concerns. In addition, many sulfur-containing antiwear or extreme pressure additives release volatile sulfur species, creating lubricating compositions containing antiwear or extreme pressure additives with odors that may also be harmful to the environment or release emissions that may be above the emissions specified by increasingly stringent health and safety regulations.

FOR example, THE ring-to-pin ratio (ring to pin ratio) OF some light HYPOID gears has changed from 5.86 to 1 to 4.45 to 1. due to these ring-to-pin ratio changes, some previously effective anti-wear or extreme pressure additives have not met THE ASTM 6121Standard test METHOD (ASTM D6121STANDARDTEST METHOD EVA L A TION OF THE THIE L OAD CARRYING CAPACITY OF L UBRICANTS UNDEDICTION OF L OW SPEED AND HIGH TOUE USED FOR FIN FINA L HYPOID DRIVE AX L ES) to evaluate THE load carrying capacity OF lubricants USED in THE final HYPOID DRIVE shaft under low speed and high TORQUE conditions.

Disclosure of Invention

It has been surprisingly found that the properties of the salts of hydroxy-substituted (di) esters of phosphoric acid ("phosphate salts") vary with the type and amount of alkylene polyol used to prepare the salts under ASTM D6121. Specifically, phosphates prepared with low levels of propylene glycol perform unexpectedly better than phosphates prepared with other types of alkylene polyols, and even better than phosphates prepared with high levels of propylene glycol. Accordingly, the disclosed technology provides a process for preparing a salt of a hydroxy-substituted (di) ester of phosphoric acid comprising: (a) reacting a phosphating agent with a monohydric alcohol and with propylene glycol, wherein the molar ratio of monohydric alcohol to propylene glycol is greater than about 4:1, whereby the product mixture formed thereby contains phosphate functionality (i.e., not all P-OH groups are esterified); and (b) reacting the product mixture of step (a) with an amine. In one embodiment, the amine comprises at least one primary alkyl amine or at least one secondary alkyl amine. In one embodiment, an excess of phosphating agent may be employed.

The disclosed technology also provides the use of the above method to prepare an antiwear agent.

The disclosed technology also provides products made by the above methods, as well as lubricants comprising an oil of lubricating viscosity and the products so made. The technology also provides a method for lubricating a gear, axle, or transmission, the method comprising supplying such a lubricant thereto.

The disclosed technology also provides a composition comprising a primary or secondary alkyl amine salt of a phosphorus-containing composition comprising at least some molecules represented by the formula

Wherein R is an alkyl group having from 4 to 20 carbon atoms, each Q is a methyl group, and each X is independently R or H or an R 'OH group, wherein R' is derived from propylene glycol, with the proviso that at least one X is H, further with the proviso that the composition is substantially free of materials containing dimeric or oligomeric moieties derived from the dimerization or oligomerization of alkylene oxides.

The disclosed technology also provides for the use of the product as described herein to impart antiwear properties to a lubricant composition.

Detailed Description

Various preferred features and embodiments will be described below by way of non-limiting illustration.

The disclosed technology provides a method for preparing a salt of a hydroxy-substituted (di) ester of phosphoric acid, comprising: (a) reacting a phosphating agent with a monohydric alcohol and with propylene glycol, wherein the molar ratio of monohydric alcohol to propylene glycol is greater than about 4:1, and wherein the phosphating agent is employed in an excess such that the product mixture formed thereby contains phosphate functionality; and (b) reacting the product mixture of step (a) with an amine.

The phosphating agent that may be employed is typically phosphorus pentoxide or a reactive equivalent thereof. Phosphorus pentoxide is commonly referred to as P₂O₅It is its empirical formula, even though it is believed that it is at least partially composed of more complex molecules, such as P₄O₁₀And (4) forming. Both species have phosphorus in their +5 oxidation state. Other phosphorus species that may be used include polyphosphoric acid and phosphorus trihaloxide, such as phosphorus oxychloride.

The phosphating agent reacts with monohydric alcohols and with propylene glycol. The monohydric alcohol may typically have a hydrocarbyl group of 1 to 30 carbon atoms, or typically a hydrocarbyl group of 4 to 20 carbon atoms, such as 6 to 18 or 6 to 12 or 6 to 10 or 12 to 18 or 14 to 18 carbon atoms. The monohydric alcohols may be straight or branched chain; it may likewise be saturated or unsaturated.

As used in this specification, 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 a carbon atom directly attached to the rest of the molecule (in the case of an alcohol, directly attached to the-OH group of the alcohol) and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include:

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

substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfinyl);

hetero substituents, that is, substituents that, while having a predominantly hydrocarbon character in the context of this invention, contain elements 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 atoms, oxygen atoms, and nitrogen atoms. 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.

Suitable monohydric alcohols include the various isomers of octanol, such as, in particular, 2-ethylhexanol. Other examples of suitable alcohols include butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, octadecenol (oleyl alcohol), nonadecanol, eicosanol, and mixtures thereof. Examples of suitable alcohols include, for example, 4-methyl-2-pentanol, 2-ethylhexanol, isooctanol, and mixtures thereof.

Examples of commercially available alcohols include oxon by Monsanto7911、Oxo7900 and Oxo1100, 1100; of ICI79; of Condea (now Sasol)1620、610 and810; of Afton corporation610 and810; of Shell AG79、911 and25L of Condea Augusta, Milan125; of Henkel KGaA (now Cognis)Andand of Ugine Kuhlmann7-11 and91。

the phosphating agent also reacts with propylene glycol. In one notable embodiment, the propylene glycol comprises 1, 2-propanediol.

The relative amounts of monohydric alcohol and propylene glycol are selected so that the molar ratio of monohydric alcohol to propylene glycol is greater than 4:1, or in other embodiments 8:2, or about 5.5:1 to about 7: 1. In yet other embodiments, the molar ratio of monohydric alcohol to propylene glycol may be from about 8.4:1.6 to about 8.9: 1.1. If expressed on an equivalent basis, a 1:1 molar ratio of monohydric alcohol to glycol would correspond to a 1:2 ratio of-OH groups. Thus, when approximately equal molar amounts of monohydric alcohol and propylene glycol are used, more hydroxyl groups will be contributed by the glycol than by the monohydric alcohol.

In such total amounts, the monohydric alcohol and propylene glycol are reacted with a phosphating agent (which may alternatively be referred to as a phosphating agent) such that the product mixture thus formed contains phosphate functionality. That is, the phosphating agent is not completely converted to its ester form, but retains at least a portion of the P — OH acidic functionality, if desired, by using a sufficient amount of phosphating agent compared to an equivalent amount of alcohol and polyol. Specifically, in certain embodiments, the phosphating agent (which may include phosphorus pentoxide) may be reacted with monohydric alcohol and propylene glycol at a ratio of 1 to 3 or 1 to 2.5 (or 1.25 to 2 or 1.5 to 2.5 or 2.5 to 3.5) moles of hydroxyl groups per 1 mole of phosphorus from the phosphating agent. In other embodiments, the phosphating agent may be reacted with the monohydric alcohol and propylene glycol in a ratio of 1 to 1.75 moles of the combined monohydric alcohol plus propylene glycol per phosphorus atom of the phosphating agent. If the phosphating agent is regarded as phosphorus pentoxide P₂O₅Such that there are two P atoms per mole of phosphating agent, this ratio can be expressed as 2 to 3.5 moles (alcohol + polyol)/mole P₂O₅. In other embodiments, 2.5 to 3.5 or 2.5 to 3.0 moles of total alcohol and polyol per mole of phosphorus pentoxide may be used. In yet other embodiments, 3.0 moles of total alcohol and polyol per mole of phosphorus pentoxide may be used. (this assumes that phosphorus pentaoxide has the formula P₂O₅Rather than P as an alternative₄O₁₀(ii) a An appropriate ratio corresponding to either equation can be readily calculated. ) The number of alcoholic OH groups/P atoms may also depend on the relative amounts of monoalcohol and diol (or higher alcohols) employed. For example, if the molar ratio of monoalcohol to diol is 1:1, then there will be 1.5 OH groups per mole of total alcohol, the above range of 1 to 1.75 moles of alcohol per P atomWill correspond to 1.5 to 2.625 OH groups per P atom.

In an oversimplified schematic, the reaction of the phosphating agent with one or more alcohols may be represented as follows:

3ROH+P₂O₅→(RO)₂P(＝O)OH+RO-P(＝O)(OH)₂

where ROH represents a monohydric alcohol or part of propylene glycol, or both R groups may together represent the propylene moiety of propylene glycol. As will be seen below, residual phosphoric acid acidic functional groups may react at least partially with amines.

The phosphating agent may be mixed with the monohydric alcohol and propylene glycol and reacted with the monohydric alcohol and propylene glycol in any order. In certain embodiments, the total feed of phosphating agent is reacted with the total feed of monohydric alcohol plus propylene glycol in a single mixture.

The phosphating agent may itself also be introduced in a single portion into the reaction mixture, or it may be introduced in multiple portions. Thus, in one embodiment, a reaction product (or intermediate) is prepared in which a portion of the phosphating agent is reacted with the monohydric alcohol and propylene glycol and thereafter a second feed of phosphating agent is added.

The reaction product from the phosphating agent with the monohydric alcohol and propylene glycol will be a mixture of separate substances, and the specific detailed composition will depend to some extent on the order of addition of the reactants. However, the reaction mixture will generally contain at least some molecules represented by formula (I) or (II)

Wherein R is an alkyl or hydrocarbyl group provided by a monohydric alcohol, R 'is an alkylene group provided by an alkylene glycol, and each X is independently R or H or an-R' OH group, with the proviso that at least one X is H. In the case where the alkylene glycol is 1, 2-propanediol, the corresponding structure may be represented by:

(allowing any orientation of the propylene glycol moiety; methyl groups may be on other carbon atoms instead.)

Variable amounts of products represented by other structures, such as partially esterified species, or fully esterified species, can be present:

including cyclic esters, such as:

and others containing more than one unit derived from propylene glycol in the ring, as well as substances having a P-O-P bond (pyrophosphates). There will also likely be some longer chain species with higher degrees of condensation, for example:

wherein R is an alkyl group having from 4 to 20 carbon atoms, each Q is a methyl group, and each X is independently R or H or an R 'OH group, wherein R' is derived from propylene glycol, with the proviso that at least one X is H, further with the proviso that the composition is substantially free of materials containing dimeric or oligomeric moieties derived from the dimerization or oligomerization of alkylene oxides.

However, the product of the reaction as described herein will likely contain little or no material containing (ether type) alkylene oxide dimers or oligomers or alkylene glycol (or glycol) dimers or oligomers (initiated by phosphoric acid). Such dimeric or oligomeric species may be formed when alkylene oxides are used in place of the alkylene glycols of the present technology. The present technology provides materials characterized by relatively small amounts of "alkylene oxide" (or "ether-type") dimers or oligomers, and are therefore particularly useful in providing antiwear properties when converted to amine salts as described below. In certain embodiments, the reaction product is substantially free of materials containing dimeric or oligomeric moieties derived from the dimerization or oligomerization of alkylene oxides. By "substantially free" it is meant that materials containing such dimeric or oligomeric moieties may constitute less than 5 wt.%, or less than 1 wt.%, or less than 0.1 wt.%, or 0.01 to 0.05 wt.% of the total phosphorus-containing material.

The reaction of the phosphating agent with the monohydric alcohol and propylene glycol may be effected by reacting a mixture of the reactants at 40 ℃ to 110 ℃, or 40 ℃ to 90 ℃ for 1 to 10, or 2 to 8, or 3 to 5 hours. The process may be carried out at reduced pressure, atmospheric pressure or above atmospheric pressure. Any water of reaction may be removed by distillation or purging with an inert gas.

The product or intermediate prepared from the reaction of the phosphating agent with monohydric alcohol and propylene glycol is further reacted with an amine to form a mixture of materials characterized as comprising one or more amine salts; it may also contain substances characterized by the presence of a P-N bond. The product comprises amine salts of primary, secondary, tertiary amines or mixtures thereof. In one embodiment, the primary amine comprises a tertiary-aliphatic primary amine. In one embodiment, the amine is not an aromatic amine, and in another embodiment, it does not contain an amine nitrogen within the heterocyclic ring. In one embodiment, the amine is an alkylamine, such as a dialkylamine or a monoalkylamine. A suitable dialkylamine (i.e., secondary amine) can be bis-2-ethylhexylamine. A suitable monoalkylamine (i.e., primary amine) may be 2-ethylhexylamine. In certain embodiments, the amine comprises at least one primary alkyl amine or at least one secondary alkyl amine. In one embodiment, the amine comprises at least one primary alkyl amine having from 6 to 18 carbon atoms. As mentioned above, proper selection of the amine can ensure that the product has relatively low toxicity.

Examples of suitable primary amines include ethylamine, propylamine, butylamine, 2-ethylhexylamine, octylamine, and dodecylamine, and 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 (products available from Aksu Chemicals, Chicago, Illinois) such as Armeen C, Armeen O L, Armeen T, Armeen HT, Armeen S andarmeen SD, wherein the letter designation relates to a fatty group, such as cocoyl, oleyl, tallow, or stearyl.

Examples of suitable secondary amines include dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, bis-2-ethylhexylamine, methylethylamine, ethylbutylamine, N-methyl-1-amino-cyclohexane, N-methyl-1-methyl-N-butyl-amine, N-methyl-N-butyl,2C and ethylpentanamine. The secondary amine may be a cyclic amine such as piperidine, piperazine, and morpholine. Examples of the tertiary amines include tri-n-butylamine, tri-n-octylamine, tri-decylamine, tri-laurylamine, tri-hexadecylamine and dimethyloleylamine ()DMOD)。

In one embodiment, the amines are in the form of a mixture. Examples of suitable mixtures of amines include (i) amines having 11 to 14 carbon atoms in the tertiary alkyl primary group (i.e., primary amines having 11 to 14 carbon atoms in the tertiary alkyl group), (ii) amines having 14 to 18 carbon atoms in the tertiary alkyl primary group (i.e., primary amines having 14 to 18 carbon atoms in the tertiary alkyl group), or (iii) amines having 18 to 22 carbon atoms in the tertiary alkyl primary group (i.e., primary amines having 18 to 22 carbon atoms in the tertiary alkyl 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) are mixtures of C11 to C14 tertiary alkyl primary amines and C18 to C22 tertiary alkyl primary amines, respectively.

In certain embodiments, the amine will comprise at least one secondary amine having a total of 10 to 22 carbon atoms, or 12 to 20, or 14 to 18, or 16 carbon atoms. In certain embodiments, the secondary amine will contain two alkyl groups each having from 5 to 11 carbon atoms, or from 6 to 10, or from 7 to 9 carbon atoms. An example is bis-2-ethylhexylamine.

Other exemplary amines include α -methylbenzylamine, tert-butylamine, tert-octylamine, and combinations thereof.

In certain embodiments, the amount of amine used to prepare the mixture of the disclosed technology will be that amount necessary to neutralize (theoretically) all or substantially all of the acidity of the phosphorus product described above, e.g., 90-100% or 92-98% or about 95% acidity. In one embodiment, as an example, the amount of acidity of the phosphorus product can be determined by titration with a bromophenol blue indicator, and the amount of amine employed can be 95% of the amount of acidity determined to be present on an equivalents basis. The amount of acidity can be expressed as total acid number TAN (ASTM D663 or 664 or 974), if desired.

In certain embodiments, the amine salt will comprise a mixture of substances that will include some molecules represented by the somewhat idealized structure of formula (III).

Wherein A and A' are independently H or methyl; each R and R' group is independently a hydrocarbyl group; each R' is independently R, H or hydroxyalkyl; y is independently R 'or a group represented by RO (R' O) P (O) O-CH (A ') CH (A) - (e.g., RO (R' O) P (O) O-CH)₂CH(CH₃) -) according to the formula (I); x is 0 to 3, with the proviso that when x ═ 0, R' is hydroxyalkyl; and m and n are both positive non-zero integers, provided that the sum of (m + n) is equal to 4. In one embodiment, x ═ 0 and each R' is independently R, H or hydroxyalkyl.

It is apparent that the anionic moiety of formula (III) on the left is a representation of the anion derived from a substance of formula (I), (Ia), (II) or (Ha), and each of the foregoing representations and descriptions relating to those formulae will also apply to the anionic moiety of formula (III). Likewise, the cationic moiety of formula (III) on the right is representative of the cation derived from an amine as described above.

In some embodiments, amine esters may be used to prepare salts. Amine esters can be prepared by mixing itaconic acid with an alcohol and an amine. Suitable amines for use in forming the amine ester include the amines described above. The amine ester is then added to the product or intermediate prepared from the reaction of the phosphating agent with monohydric alcohol and propylene glycol to form the amine salt of the phosphate ester.

It is known that some of the substances described above may interact in the final formulation so that the components of the final formulation may be different from those initially added. For example, metal ions (e.g., of a detergent) can migrate to other acidic or anionic sites of other molecules, such as the products described above. 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 technology, which encompasses compositions prepared by blending the above-described components.

The amine salt compositions described above will generally be used in lubricant compositions. The amount will generally be an amount suitable to provide anti-wear properties to the lubricant. Such amounts may typically be 0.3 to 3 wt%, or 0.5 to 1 wt%, or greater than 1 to 1.9 wt%, or 1.1 to 1.8 wt%, or 1.2 to 1.8 wt%, or 1.3 to 1.7 wt%, or even 1.44 to 1.62 wt% in certain embodiments.

Oil of lubricating viscosity

One of the components of the lubricant composition is an oil of lubricating viscosity. These include natural and synthetic oils of lubricating viscosity, oils derived from hydrocracking, hydrogenation, and hydrofinishing, and unrefined, refined, and rerefined oils and mixtures thereof.

In one embodiment, the base oil comprises poly α olefins including PAO-2, PAO-4, PAO-5, PAO-6, PAO-7, or PAO-8.

Oils of lubricating viscosity may also be defined as specified in the American Petroleum Institute (API) guide for Base Oil Interchangeability (Base Oil interchange Guidelines).

Group IV all poly α olefins (PAO)

Group V not including all other substances in groups I, II, III or IV

Even if the API is not formally identified, other recognized base oil classes can be used, group II + referring to group II materials having a viscosity index of 110-119 and lower volatility than other group II oils, and group III + referring to group III materials having a viscosity index greater than or equal to 130.

In one embodiment, the oil of lubricating viscosity comprises an API group I, group II, group III, group IV, group V, group VI base oil or mixtures thereof, and in another embodiment comprises an API group II, group III, group IV base oil or mixtures thereof. In another embodiment, the oil of lubricating viscosity is a group III or group IV base oil, and in another embodiment is a group IV base oil.

The amount of oil of lubricating viscosity present is typically the remainder remaining after subtracting the compounds of the present technology and other listed components (such as friction modifiers, conventional phosphorus antiwear and/or extreme pressure agents, organo-sulfides and other performance additives) from about 100 weight percent. In one embodiment, the lubricating composition is in the form of a concentrate and/or a fully formulated lubricant. If the phosphorus-containing additive and any other performance additives are in the form of a concentrate (which may be combined with additional oils to form, in whole or in part, a finished lubricant), the ratio of the sum of the components of the lubricating composition to the oil of lubricating viscosity and/or to the diluent oil comprises a range of 1:99 to about 99:1 (by weight) or 80:20 to 10:90 (by weight).

In one embodiment, the kinematic viscosity of the oil of lubricating viscosity is 3 to 7.5, or 3.6 to 6, or 3.5 to 5mm at 100 ℃ by ASTM D445²In one embodiment, the oil of lubricating viscosity comprises a poly α -olefin having a kinematic viscosity at 100 ℃ of 3 to 7.5 by ASTM D445, or any of the other aforementioned ranges.

The lubricant formulation may contain a viscosity modifier (which is sometimes counted as part of the oil component of lubricating viscosity). Viscosity Modifiers (VM) and Dispersant Viscosity Modifiers (DVM) are well known. Examples of VMs and DVMs may include polymethacrylates, polyacrylates, polyolefins, styrene-maleic ester copolymers, and similar polymeric materials including homopolymers, copolymers, and graft copolymers. The DVM may comprise a nitrogen-containing methacrylate polymer, such as a nitrogen-containing methacrylate polymer derived from methyl methacrylate and dimethylaminopropylamine.

Examples of commercially available VMs, DVMs, and chemical classes thereof may include the following: polyisobutenes (e.g.Indopol from BP Amoco)^TMOr Parapol from Exxonmobil (Exxonmobil)^TM) Olefin copolymers (e.g., L ubizol from lubon, L ubizol)^TM7060. 7065 and 7067, and L ucant from Mitsui^TMHC-2000L and HC-600), hydrogenated styrene-diene copolymers (e.g., Shellvis from Shell)^TM40 and 50 of the total weight of the composition,and from Luborun Inc7308 and 7318); styrene/maleate copolymers as dispersant copolymers (e.g. from Luborun Corp.)3702 and 3715); polymethacrylates, some of which have dispersant properties (e.g., Viscoplex from RohMax)^TMThose of the series, Hitec from Afton (Afton)^TMViscosity modifiers, and those from Luborun7702、7727、7725、7720C and7723) (ii) a Olefin-grafted polymethacrylate polymers (e.g., Viscoplex from RohMax^TM2-500 and 2-600); and hydrogenated polyisoprene star polymers (e.g., Shellvis from Shell)^TM200 and 260). Viscosity modifiers that can be used are described in U.S. Pat. nos. 5,157,088, 5,256,752, and 5,395,539. Other viscosity modifiers include olefin-maleic anhydride ester copolymers, as disclosed in PCT publication WO 2010/014655. The VM and/or DVM may be used in the functional fluid at a concentration of up to 20 wt% or even up to 60 wt% or 70 wt%. Concentrations of 1 to 12 wt% or 3 to 10 wt% may also be used.

In addition to the phosphorus salt compositions described above, the lubricant formulations may also contain one or more conventional phosphorus antiwear and/or extreme pressure agents. Alternatively, the lubricant formulation may be free of such conventional agents. Conventional phosphorus antiwear and/or extreme pressure agents may be present in amounts of 0 wt% to 10 wt%, 0 wt% to 8 wt%, 0 wt% to 6 wt%, 0.05 wt% to 2.5 wt%, 1 wt% to 2 wt%, and 0.05 wt% to 4 wt% of the lubricating composition. Suitable agents include those described in U.S. Pat. No. 3,197,405; see, e.g., examples 1 through 25 thereof. For automotive gear oils, the phosphate content may be 200 to 3,000ppm, 500 to 2,000ppm, or 1,000 to 1,800ppm of the lubricating composition. For manual transmission fluids, the phosphate content may be 500 to 1,000ppm, 400 to 1,500ppm, or 450 to 1,250ppm of the lubricating composition. For axle lubricants, the phosphate content may be 400 to 3,000ppm, 500 to 2,000ppm, or 1,000 to 1,800ppm of the total lubricating composition.

Conventional phosphorus antiwear agents may include nonionic phosphorus compounds, amine salts of phosphorus compounds other than those disclosed above (e.g., amine salts of mixtures of monoalkyl and dialkyl phosphate esters), ammonium salts of phosphorus compounds other than those disclosed above, metal dialkyl dithiophosphates, metal dialkyl phosphates, or mixtures thereof. In one embodiment, the conventional phosphorus antiwear or extreme pressure agent is selected from the group consisting of: nonionic phosphorus compounds, metal dialkyldithiophosphates, metal dialkylphosphates, and mixtures thereof.

In one embodiment, the conventional phosphorus antiwear agent comprises a metal dialkyldithiophosphate. The alkyl group of the dialkyldithiophosphate may be straight or branched chain and may contain 2 to 20 carbon atoms, provided that the total number of carbons is sufficient to render the metal dialkyldithiophosphate oil soluble. The metal of the metal dithiophosphate typically comprises a monovalent or divalent metal. Examples of suitable metals include sodium, potassium, copper, calcium, magnesium, barium or zinc. In one embodiment, the phosphorus-containing acid, salt or ester is a zinc dialkyldithiophosphate. Examples of suitable zinc dialkylphosphates (commonly referred to as ZDDP, ZDP or ZDTP) include zinc di (2-methylpropyl) dithiophosphate, zinc di (pentyl) dithiophosphate, zinc di (1, 3-dimethylbutyl) dithiophosphate, zinc di- (heptyl) dithiophosphate, zinc di- (octyl) dithiophosphate, zinc di- (2-ethylhexyl) dithiophosphate, zinc di- (nonyl) dithiophosphate, zinc di- (decyl) dithiophosphate, zinc di- (dodecyl) dithiophosphate, zinc di- (dodecylphenyl) dithiophosphate, zinc di (heptylphenyl) dithiophosphate, and mixtures of alcohols, ZDDP prepared from methylpropyl and pentanol, 2-ethylhexyl and isopropanol, or 4-methyl-2-pentyl and isopropanol; or mixtures thereof.

In one embodiment, the conventional phosphorus antiwear agent comprises a metal hydrocarbyl phosphate or a metal dihydrocarbyl phosphate. The hydrocarbyl group of the metal dialkylphosphate includes a linear or branched alkyl group, a cyclic alkyl group, a linear or branched alkenyl group, an aryl group, or an aralkyl group. In one embodiment, the hydrocarbyl group of the metal dialkylphosphate is an oil soluble alkyl group. The alkyl group typically includes from about 1 to about 40, or from about 4 to about 20, or from about 6 to about 16 carbon atoms. Examples of suitable hydrocarbyl or alkyl groups are listed in WO2008/094759, paragraphs 0069 to 0076.

In one embodiment, the metal hydrocarbyl phosphate or metal dihydrocarbyl phosphate comprises a metal salt of a mono-alkyl phosphate, and in another embodiment, a metal salt of a di-alkyl phosphate. In one embodiment, the metal of the metal hydrocarbyl or metal dihydrocarbyl phosphate is a monovalent metal, in another embodiment the metal is divalent, and in another embodiment the metal is trivalent. The metal of the metal hydrocarbyl or metal dihydrocarbyl phosphate may include aluminum, calcium, magnesium, strontium, chromium, iron, cobalt, nickel, zinc, tin, manganese, silver, or mixtures thereof. In one embodiment, the metal is zinc.

In one embodiment, the lubricating composition further comprises an extreme pressure agent. Suitable extreme pressure agents include organo-sulfides. In one embodiment, the organo-sulfides comprise at least one of a polysulfide, a thiadiazole compound, or a mixture thereof. In various embodiments, the organo-sulfides are present in a range of 0 wt.% to 10 wt.%, 0.01 wt.% to 10 wt.%, 0.1 wt.% to 8 wt.%, 0.25 wt.% to 6 wt.%, 2 wt.% to 5 wt.%, or 3 wt.% to 5 wt.% of the lubricating composition. For automotive gear oils, the sulfur content may be 100 to 40,000ppm, 200 to 30,000ppm, or 300 to 25,000ppm of the lubricating composition. For manual transmission fluids, the sulfur content may be 500 to 5,000ppm, 1,500 to 4,000ppm, 2,500 to 3,000ppm of the lubricating composition. For axle lubricants, the sulfur content may be 5,000 to 40,000ppm, 10,000 to 30,000ppm, or 12,000 to 25,000ppm of the total lubricating composition.

Examples of thiadiazoles include 2, 5-dimercapto-1, 3, 4-thiadiazole or oligomers thereof, hydrocarbyl substituted 2, 5-dimercapto-1, 3, 4-thiadiazole, hydrocarbylthio substituted 2, 5-dimercapto-1, 3, 4-thiadiazole or oligomers thereof. Oligomers of hydrocarbyl-substituted 2, 5-dimercapto-1, 3, 4-thiadiazoles are typically formed by forming sulfur-sulfur bonds between 2, 5-dimercapto-1, 3, 4-thiadiazole units to form oligomers having two or more of said thiadiazole units. Other examples of thiadiazole compounds can be found in WO2008/094759, paragraphs 0088 to 0090.

The organosulfide may alternatively be a polysulfide. In one embodiment, at least about 50 weight percent of the polysulfide molecules are a mixture of trisulfide or tetrasulfide compounds. In other embodiments, at least about 55 wt.%, or at least about 60 wt.% of the polysulfide molecules are a mixture of trisulfide or tetrasulfide compounds. Polysulfides include sulfurized organic polysulfides derived from oils, fatty acids or esters, olefins, or polyolefins.

Oils that may be sulfurized include natural or synthetic oils such as mineral oil, lard oil, carboxylic acid esters derived from aliphatic alcohols and fatty acids or aliphatic carboxylic acids (e.g., myristoleate and oleyl oleate), and synthetic unsaturated esters or glycerides.

Fatty acids include those containing from 8 to 30, or from 12 to 24 carbon atoms. Examples of fatty acids include oleic acid, linoleic acid, linolenic acid, and pine oil. Sulfurized fatty acid esters prepared from mixed unsaturated fatty acid esters, such as obtained from animal fats and vegetable oils, including pine oil, linseed oil, soybean oil, rapeseed oil, and fish oil.

Polysulfides may also be derived from olefins, which are derived from a wide range of alkenes (typically having one or more double bonds). In one embodiment, the olefin contains 3 to 30 carbon atoms. In other embodiments, the olefin contains from 3 to 16, or from 3 to 9 carbon atoms. In one embodiment, the sulfurized olefin includes olefins derived from propylene, isobutylene, pentene, or mixtures thereof. In another embodiment, the polysulfide comprises a polyolefin derived from the polymerization of an olefin as described above by known techniques. In one embodiment, the polysulfides include dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenols, sulfurized dipentene, sulfurized dicyclopentadiene, sulfurized terpene, and sulfurized Diels-Alder (Diels-Alder) adduct; a phosphosulfurized hydrocarbon.

In one embodiment, the lubricating composition further comprises a friction modifier. In various embodiments, the friction modifier is present in an amount of 0 wt% to 7 wt%, 0.1 wt% to 6 wt%, 0.25 wt% to 5 wt%, or 0.5 wt% to 5 wt% of the lubricating composition.

Friction modifiers include fatty amines, borated glycerol esters, fatty acid amides, non-borated fatty epoxides, alkoxylated fatty amines, borated alkoxylated fatty amines, metal salts of fatty acids, fatty imidazolines, metal alkyl salicylates (which may also be referred to as detergents), metal sulfonates (which may also be referred to as detergents), condensation products of carboxylic acids or polyalkylene polyamines, or amides of hydroxyalkyl compounds. In one embodiment, the friction modifier comprises a fatty acid ester of glycerol. The fatty acid may contain from 6 to 24 or from 8 to 18 carbon atoms. In one embodiment, the friction modifier may comprise the product of isostearic acid and tetraethylenepentamine. A more detailed list of possible friction modifiers is found in WO2008/094759, paragraphs 0100 to 0113.

The compositions of the present invention optionally further comprise at least one other performance additive. Other performance additives include metal deactivators, detergents, dispersants, borated dispersants, antioxidants, corrosion inhibitors, foam inhibitors, demulsifiers, pour point depressants, seal swell agents, and mixtures thereof. Foam inhibitors phosphorus compounds that may be suitable for use in the present technology may tend to produce enhanced foam formation, particularly in some embodiments when the phosphorus compound is present at higher concentrations, such as 0.5 wt% or greater, or 1.0 wt% or greater, for example 1.1 wt% to 3 wt%. In various embodiments, the total combined amount of the other performance additive compounds is present at 0 wt% to 25 wt%, about 0.1 wt% to 15 wt%, or 0.5 wt% to 10 wt% of the lubricating composition. Although one or more of the other performance additives may be present, the other performance additives are typically present in different amounts relative to each other.

Antioxidants include molybdenum compounds such as molybdenum dithiocarbamates, sulfurized olefins, hindered phenols, amine compounds such as alkylated diphenylamines (typically di-nonyldiphenylamines, octyldiphenylamines, or di-octyldiphenylamines).

The cleaning agents include neutral or overbased detergents, newtonian or non-newtonian, alkaline earth or transition metal salts with one or more of the following: phenates, sulfurized phenates, sulfonates, carboxylic acids, phosphoric acids, mono-and/or dithiophosphoric acids, salicins, alkyl salicylates, and salixarates.

Dispersants include N-substituted long chain alkenyl succinimides as well as Mannich condensation products and post-treated forms thereof. Post-treatment dispersants include those that react with: urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds and phosphorus compounds. In one embodiment, the dispersant comprises a borated polyisobutylene succinimide. Typically, the number average molecular weight of the polyisobutylene is in the range of about 450 to 5000 or 550 to 2500. In various embodiments, the dispersant is present in an amount of 0 wt% to 10 wt%, 0.01 wt% to 10 wt%, or 0.1 wt% to 5 wt% of the lubricating composition.

Corrosion inhibitors include octylamine octanoate, condensation products of dodecenylsuccinic acid or anhydride, condensation products of fatty acids (such as oleic acid) with polyamines, or thiadiazole compounds described above. Metal deactivators include derivatives of benzotriazole (typically tolyltriazole), 1,2, 4-triazole, benzimidazole, 2-alkyldithiobenzimidazole or 2-alkyldithiobenzothiazole.

The foam inhibitor comprises a copolymer of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate. Demulsifiers include trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers. Pour point depressants include esters of maleic anhydride-styrene, polymethacrylates, polyacrylates, or polyacrylamides. The sealing swelling agent comprises Exxon Neoton-37^TM(FN 1380) and Exxon Mineral Seal Oil^TM(FN 3200)。

In one embodiment, the lubricating composition described herein may be a grease, and such compositions will typically further comprise a grease thickener. Grease thickeners include materials derived from: (i) inorganic powders, such as clay, organo-clay, bentonite, fumed silica, calcite, carbon black, pigments, copper phthalocyanine or mixtures thereof; (ii) carboxylic acids and/or esters (e.g., monocarboxylic or polycarboxylic acids and/or esters thereof); (iii) a polyurea or diurea; or (iv) mixtures thereof. A detailed description of specific grease thickeners is found in WO2008/094759, paragraphs 0135 to 0145. The grease composition may also contain one or more metal deactivators, antioxidants, antiwear agents, rust/corrosion inhibitors, viscosity modifiers, extreme pressure agents (as described above), or mixtures of two or more thereof.

Method and application

In one embodiment, the disclosed technology provides for the use of the lubricating composition disclosed herein in gears and transmissions to impart at least one of antiwear properties, extreme pressure properties, acceptable deposit control, acceptable oxidation stability, and reduced odor.

In one embodiment, the component is a driveline component comprising at least one of: a transmission, a manual transmission, a gear, a gearbox, a wheel axle gear, an automatic transmission, a dual clutch transmission, or a combination thereof. In another embodiment, the transmission may be an automatic transmission or a Dual Clutch Transmission (DCT). Additional exemplary automatic transmissions include, but are not limited to, Continuously Variable Transmissions (CVTs), continuously variable transmissions (IVTs), friction ring transmissions, continuously slipping torque transfer clutches (CSTCCs), and step automatic transmissions.

Alternatively, the transmission may be a Manual Transmission (MT) or a gear. In yet another embodiment, the component may be an agricultural tractor or an off-highway vehicle component that incorporates at least one of a wet brake, a transmission, a hydraulic system, a final drive, a power take-off system, or a combination thereof.

In various embodiments, the lubricating composition can have a composition as described in table 1. The weight percentages (wt%) shown in table 1 below are based on active material.

TABLE 1

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

The phosphate ester salts may also be used in industrial lubricant compositions, such as greases, metal working fluids, industrial gear lubricants, hydraulic oils, turbine oils, cycle oils, or refrigerants. Such lubricant compositions are well known in the art.

In one embodiment, a lubricant may be used in the grease. The grease may have a composition comprising an oil of lubricating viscosity as described above, a grease thickener and from 0.001 wt% to 15 wt% of a phosphate salt. In other embodiments, the phosphate ester salt may be present in the lubricant at 0.01 wt.% to 5 wt.% or 0.002 to 2 wt.%, based on the total weight of the lubricant composition.

In one embodiment, the grease may also be a sulfonate grease. Such greases are known in the art. In another embodiment, the sulfonate grease may be a calcium sulfonate grease prepared by overbasing neutral calcium sulfonate to form amorphous calcium carbonate and then converting it to calcite or vaterite, or a mixture thereof.

The grease thickener may be any grease thickener known in the art. Suitable grease thickeners include, but are not limited to, metal salts of carboxylic acids, metal soap grease thickeners, mixed base soaps, complex soaps, non-soap grease thickeners, metal salts of such acid-functionalized oils, polyurea and diurea grease thickeners, or calcium sulfonate grease thickeners. Other suitable grease thickeners include polymeric thickeners such as polytetrafluoroethylene, polystyrene, and olefin polymers. Inorganic grease thickeners may also be used. Exemplary inorganic thickeners include clays, organo-clays, silica, calcium carbonate, carbon black, pigments, or copper phthalocyanines. Other thickeners include urea derivatives, such as polyureas or diureas. Specific examples of greases include those outlined in table 2 below.

TABLE 2

Treating the grease additive package with 2 to 5 wt% of the grease composition.

In various embodiments, the techniques provide engine oil lubricating compositions that may be employed in internal combustion engines. The internal combustion engine may be spark ignition or compression ignition. The internal combustion engine may be a 2-stroke or a 4-stroke engine. The internal combustion engine may be a passenger car engine, a light duty diesel engine, a heavy duty diesel engine, a motorcycle engine or a 2-stroke or 4-stroke marine diesel engine. Typically, the internal combustion engine may be a passenger car engine or a heavy duty diesel internal combustion engine.

The lubricant composition for an internal combustion engine may be applied to any engine lubricant regardless of the content of sulfur, phosphorus or sulfated ash (ASTM D-874). The lubricating composition can be characterized as having at least one of: (i) a sulfur content of 0.2 wt.% to 0.4 wt.% or less, (ii) a phosphorus content of 0.08 wt.% to 0.15 wt.%, and (iii) a sulfated ash content of 0.5 wt.% to 1.5 wt.% or less. The lubricating composition can also be characterized as having (i) a sulfur content of 0.5 wt.% or less, (ii) a phosphorus content of 0.1 wt.% or less, and (iii) a sulfated ash content of 0.5 wt.% to 1.5 wt.% or less. In yet another embodiment, the lubricating composition can be characterized as having a sulfated ash content of 0.5 wt.% to 1.2 wt.%. Specific examples of engine lubricants include those summarized in table 3 (weight percentages based on active material).

TABLE 3

Examples of the invention

Example 1 was prepared.4-methyl-2-pentanol (550g) and 1, 2-propanediol (58.5g) (molar ratio 0.7:0.1) were mixed in a reaction flask and heated to 70 ℃ under a slow stream of nitrogen with stirring. Phosphorus pentoxide (290.5g) was added in several increments with stirring while maintaining the temperature between 75 and 80 ℃. After the phosphorus pentoxide addition was complete, the reaction mixture was heated to 90 ℃ and held at this temperature for 2 hours, then cooled to 48 ℃. Approximately half of the reaction mixture was taken for further reaction. Bis-2-ethylhexylamine ("amine 1") (447.2g) was added dropwise to this amount over 1.5 hours. The resulting mixture was heated to 75 ℃ and held at this temperature for 3 hours. The reaction product was used without further purification.

Example 2 was prepared.For this example, the same procedure as in preparative example 1 was repeated except that the molar ratio of 4-methyl-2-pentanol to 1, 2-propanediol was 0.5: 0.1.

Example 3 was prepared.For this example, the phosphorus compound was prepared by mixing 2-ethylhexanol and 1, 2-propanediol (molar ratio 0.5:0.1) in a reaction flask and heating to 70 ℃ with stirring under a gentle stream of nitrogen. Phosphorus pentoxide was added in several increments with stirring. After the phosphorus pentoxide addition was complete, the reaction mixture was heated to 90 ℃ and held at this temperature for 6 hours. Additional phosphorus pentoxide was added in several increments over 1.5 hours. The reaction mixture was heated to 80 deg.CStirred for 3 hours and filtered. The filtrate was heated to 45 ℃ under a gentle stream of nitrogen.

In a separate vessel, itaconic acid, 2-ethylhexanol, and α -methylbenzylamine were mixed to form an amine ester ("amine 2").

Example 4 was prepared.Preparative example 4 was prepared in the same manner as preparative example 3, except that tert-butylamine ("amine 3") was used to prepare the amine ester. The amine ester is then added to the phosphorus compound to form an amine phosphate salt.

Example 5 was prepared.For this example, the same procedure as in preparation example 4 was repeated, but 4-methyl-2-pentanol was used instead of 2-ethylhexanol. The molar ratio of 4-methyl-2-pentanol to 1, 2-propanediol is 0.5: 0.1.

Example 6 was prepared.For this example, the same procedure as for preparation example 3 was repeated except that 4-methyl-2-pentanol was used instead of 2-ethylhexanol in the preparation of the phosphorus compound and tert-octylamine was used to prepare an amine ester ("amine 4"). The molar ratio of 4-methyl-2-pentanol to 1, 2-propanediol was kept at 0.5: 0.1.

Example 7 was prepared.2-ethylhexanol (400g) and 1, 2-propanediol (42.4g) (ratio 0.5:0.1) were mixed in a reaction flask and heated to 70 ℃ with stirring under a gentle stream of nitrogen. Phosphorus pentoxide (171.6g) was added in several increments with stirring while maintaining the temperature between 75 and 80 ℃. After the phosphorus pentoxide addition was complete, the reaction mixture was heated to 90 ℃ and held at this temperature for 2 hours, then cooled to 48 ℃. Taking about half of the reaction mixture for further reaction; bis-2-ethylhexylamine (232.2g) was added dropwise to this amount over 1.5 hours. The resulting mixture was heated to 75 ℃ and maintained at this temperature for 3 hours. The reaction product was used without further purification.

Comparative example 1-no propylene glycol.Isooctyl alcohol (b), (b)8) (700g) placed in a reaction flask and heated to 30 ℃ under a gentle stream of nitrogen with stirring. Addition of the pentoxide in several increments under stirringDiphosphorus (253.3g) was converted while maintaining the temperature at 65 ℃. After the addition of phosphorus pentoxide was completed, the reaction mixture was heated to 90 ℃ and held at this temperature for 2-3 hours, and then cooled to 50 ℃. 2-ethylhexylamine (472.9g) was added dropwise over 1.5 hours. The resulting mixture was heated to 75 ℃ and held at this temperature for 3 hours. The reaction product was used without further purification.

Comparative example 2-no propylene glycol.For comparative example 2, a salt similar to that of preparation example 3 was prepared, but without propylene glycol, and tributylamine was used instead of α -methylbenzylamine to prepare the amine ester.

Comparative example 3-high propylene glycol content.Comparative example 3 is similar to preparation 1 except that high levels of propylene glycol are used. For comparative example 3, 4-methyl-2-pentanol and 1, 2-propanediol were mixed in a reaction flask in a ratio of 0.35 to 0.1.

Comparative example 4-conversion from 1, 2-diol.Comparative example 4 example 1 was prepared similarly except that 2-butyl-2-ethylpropane-1, 3-diol was used instead of 1, 2-propanediol. The ratio of 4-methyl-2-pentanol to 2-butyl-2-ethylpropane-1, 3-diol was 0.7: 0.1. In this example, 4-methyl-2-pentanol (422g) and 2-butyl-2-ethylpropane-1, 3-diol (95g) were mixed in a reaction flask and heated to 55 ℃ under a gentle stream of nitrogen with stirring. Phosphorus pentoxide (224.5g) was added in several increments with stirring while maintaining the temperature below 70 ℃ over 2 hours. After the phosphorus pentoxide addition was complete, the reaction mixture was heated to 85 ℃ and held at this temperature for 3 hours, and then cooled to room temperature. About 964g of the reaction mixture was taken for further reaction; to this amount 2-ethylhexylamine (398g) was added dropwise over 1.5 hours. The resulting mixture was heated to 85 ℃ and held at this temperature for 3 hours. The reaction product was then filtered using calcined diatomaceous earth.

Comparative example 5.

Comparative example 5 is similar to comparative example 4 except that 2, 3-butanediol (63g) was used. The amount of 4-methyl-2-pentanol was 500 g. To prepare the salt, 412.6g of bis-2-ethylhexylamine were used.

The materials of the preparation, comparison and control materials were used to prepare fully formulated lubricant compositions. Two sets of fully formulated lubricant compositions were prepared, one with a viscosity of 14cSt at 100 ℃ and one with a viscosity of 9cSt at 100 ℃. The lubricant compositions were formulated as shown in table 4 (weight percentages based on active).

TABLE 4

In the hypoid gear durability test, the wear performance of these fluids was evaluated using a light hypoid rear drive axle, with ASTM D6121 as the basis for setup, performance and evaluation tests. The test is a level 2 test. The light hypoid gear has a ring-to-pin ratio of 4.45 to 1.

Phase 1 was a 65 minute break-in phase, operating at high speed, low load, to allow gear adjustment before the endurance phase (phase 2) was run. In the regulation phase, the wheel speed is controlled to 682rpm, and the wheel torque is controlled to 508Nm per wheel (ring gear torque is controlled to 1016 Nm).

Stage 2 is a 24 hour durability stage for evaluating the ability of a lubricant to protect a gear from failure modes according to ASTM D6121. At this stage, the wheel speed is controlled to 124rpm, and the wheel torque is controlled to 2237Nm per wheel (ring gear torque is controlled to 4474 Nm).

Bulk oil temperature is measured by submerged thermocouples and allowed to warm to 135 ℃ without assistance during the conditioning phase and the oil temperature is maintained at 135 ℃ using water spray to the outside of the axle housing in both phase 1 and phase 2, the temperature of the axle sump is controlled with water spray the speed and torque ramp up smoothly over a few minutes (2-5) of the conditioning and testing steps, using an evaluator calibrated by the test monitoring center, following the evaluation procedure outlined in ASTM D6121, the test assembly is removed and evaluated, the pinion and ring gear risk ratings and pass/fail considerations are evaluated according to the API G L-5 specification.

The test results for the 14cSt lubricant composition are shown in table 5 below. All test results were at 24 hours unless otherwise indicated.

TABLE 5-14cSt Lubricant compositions

The results of the testing of the 9cSt lubricant composition are shown in table 6 below.

TABLE 6-9cSt Lubricant compositions

The results show that the material of the present technology provides improved performance compared to the comparative examples when measured using the hypoid gear wear test.

Thus, a process for preparing a salt of a hydroxy-substituted diester of phosphoric acid is disclosed. The process comprises (a) reacting a phosphating agent with a monohydric alcohol and with propylene glycol, wherein the molar ratio of monohydric alcohol to propylene glycol is greater than about 4:1, whereby the resulting product mixture thereby contains phosphate functionality; and (b) reacting the product mixture of step (a) with an amine comprising at least one primary or secondary alkyl amine. The phosphating agent may comprise phosphorus pentoxide.

In some embodiments, the monohydric alcohol has from about 4 to about 20 carbon atoms. In other embodiments, the monohydric alcohol comprises 2-ethylhexanol and in yet other embodiments, the propylene glycol comprises 1, 2-propylene glycol. The molar ratio of monohydric alcohol to propylene glycol may be about 8:2, or about 5.5:1 to about 7: 1. In yet other embodiments, the molar ratio of monohydric alcohol to propylene glycol may be from about 8.4:1.6 to about 8.9: 1.1.

In some embodiments, the phosphating agent comprises phosphorus pentoxide, and each 1 mole of phosphorus pentoxide (as P)₂O₅Calculated) from about 2.5 to about 35, or from about 2.5 to about 3.0 moles of total monohydric alcohol plus propylene glycol. In other embodiments, about 3.0 total monohydric alcohol plus propylene glycol are reacted per 1 mole of initial feed of phosphorus pentoxide.

The reaction of step (a) may be carried out at about 40 ℃ to about 110 ℃ or about 40 ℃ to about 90 ℃. The product mixture prepared by step (a) may be substantially free of materials containing dimeric or oligomeric moieties derived from the dimerization or oligomerization of alkylene oxides.

The amine can comprise at least one primary alkyl amine having from about 6 to about 18 carbon atoms. In some embodiments the amine comprises at least one secondary amine having from about 10 to about 22 carbon atoms.

The products produced by the process may be used in any industrial lubricant, such as greases, metal working fluids, industrial gear lubricants, hydraulic oils, turbine oils, cycle oils, or refrigerants.

In other embodiments, the product prepared by the described method may be added to a lubricant comprising an oil of lubricating viscosity. Methods for lubricating a driveline device, such as a gear, axle, transaxle, or transmission, are disclosed. The method includes supplying lubricant to a driveline device. In some embodiments, the gear is a hypoid gear. In other embodiments, a method of lubricating an engine is disclosed. The method includes supplying the engine with a lubricant.

The described process can be used to prepare an antiwear agent. Antiwear agents may be used to impart antiwear properties to the lubricant composition.

Each of the documents mentioned above is incorporated herein by reference. The mention of any document is not an admission that such document is entitled to antedate such document by virtue of prior art or constitutes common general knowledge of one of ordinary skill in any jurisdiction. Except by way of example, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material, reaction conditions, molecular weights, number of carbon atoms, and the like, are to be understood as 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 expression "consisting essentially of … …" is allowed to include substances that have no material impact on the basic and novel features of the composition under consideration.