U.S. patent application number 12/920628 was filed with the patent office on 2011-07-21 for antiwear composition and method of lubricating driveline device.
This patent application is currently assigned to THE LUBRIZOL CORPORATION. Invention is credited to Morey N. Najman.
Application Number | 20110177988 12/920628 |
Document ID | / |
Family ID | 43034284 |
Filed Date | 2011-07-21 |
United States Patent
Application |
20110177988 |
Kind Code |
A1 |
Najman; Morey N. |
July 21, 2011 |
Antiwear Composition and Method of Lubricating Driveline Device
Abstract
The present invention relates to a method of driveline device by
supplying to the driveline device a lubricating composition
containing an oil of lubricating viscosity and an antiwear package,
wherein the antiwear package includes: (a) derivatives of a
carboxylic acid (typically a hydroxycarboxylic acid); and (b) a
phosphorus compound. The invention further provides lubricating
compositions containing an oil of lubricating viscosity and an
antiwear package, wherein the antiwear package includes (a)
derivatives of a carboxylic acid (typically a hydroxycarboxylic
acid); and (b) an amine or metal salt of a phosphorus compound that
is either (i) a hydroxy-substituted di-ester of (thio)phosphoric
acid, or (ii) a phosphorylated hydroxy-substituted di- or tri-ester
of (thio)phosphoric acid.
Inventors: |
Najman; Morey N.; (Lakewood,
OH) |
Assignee: |
THE LUBRIZOL CORPORATION
WICKLIFFE
OH
|
Family ID: |
43034284 |
Appl. No.: |
12/920628 |
Filed: |
March 10, 2009 |
PCT Filed: |
March 10, 2009 |
PCT NO: |
PCT/US09/36623 |
371 Date: |
March 23, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61037843 |
Mar 19, 2008 |
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Current U.S.
Class: |
508/272 ;
508/306; 508/423; 508/425 |
Current CPC
Class: |
C10M 2207/282 20130101;
C10N 2040/042 20200501; C10M 2207/283 20130101; C10M 2215/082
20130101; C10M 2219/08 20130101; C10M 2219/022 20130101; C10N
2040/044 20200501; C10M 2205/04 20130101; C10M 2223/042 20130101;
C10M 2223/045 20130101; C10M 2207/34 20130101; C10M 2205/0285
20130101; C10M 141/10 20130101; C10M 2219/106 20130101; C10M
2205/02 20130101; C10M 2205/026 20130101; C10M 2207/289 20130101;
C10M 2203/1006 20130101; C10N 2040/04 20130101; C10M 2209/084
20130101; C10M 2223/043 20130101; C10M 2215/08 20130101; C10N
2030/06 20130101; C10N 2030/42 20200501; C10N 2060/14 20130101;
C10M 2215/086 20130101; C10M 2205/02 20130101; C10M 2209/086
20130101; C10M 2205/04 20130101; C10M 2209/086 20130101 |
Class at
Publication: |
508/272 ;
508/423; 508/425; 508/306 |
International
Class: |
C10M 137/06 20060101
C10M137/06; C10M 137/08 20060101 C10M137/08; C10M 135/36 20060101
C10M135/36; C10M 145/32 20060101 C10M145/32; C10M 137/10 20060101
C10M137/10 |
Claims
1-25. (canceled)
26. A method for lubricating a driveline device comprising
supplying to the mechanical a device a lubricating composition
comprising an oil of lubricating viscosity and an antiwear package,
wherein the antiwear package comprises: (a) a derivative of a
hydroxycarboxylic acid; and (b) a phosphorus compound.
27. The method of claim 26, wherein the phosphorus compound is an
amine or metal salt of a phosphorus compound that is either: (i) a
hydroxy-substituted di-ester of (thio)phosphoric acid, or (ii) a
phosphorylated hydroxy-substituted di- or tri-ester of
(thio)phosphoric acid.
28. The method of claim 26, wherein the phosphorus compound is an
amine or metal salt of a phosphorus compound.
29. The method of claim 26, wherein the phosphorus compound is a
hydroxy-substituted di-ester of (thio)phosphoric acid.
30. The method of claim 28, wherein the amine or metal salt of a
phosphorus compound is a phosphorylated hydroxy-substituted di- or
tri-ester of (thio)phosphoric acid.
31. The method of claim 26, wherein the derivative of a
hydroxycarboxylic acid is selected from the group consisting of
imides, di-esters, di-amides, di-imides, ester-amides,
ester-imides, imide-amides.
32. The method of claim 26, wherein the derivative of a
hydroxycarboxylic acid is selected from the group consisting of
imides, di-esters, di-amides, and ester-amides.
33. The method of claim 26, wherein the derivative of a
hydroxycarboxylic acid is derived from tartaric acid.
34. The method of claim 26, wherein the derivative of a
hydroxycarboxylic acid is derived from citric acid.
35. The method of claim 26, wherein the antiwear package is present
at 0.05 wt % to 5 wt % of the lubricating composition.
36. The method of claim 26, wherein the derivative of a
hydroxycarboxylic acid is present 0.025 to 2.5 wt % of the
lubricating composition.
37. The method of claim 26, wherein the phosphorus compound is
present at 0.05 to 2.5 wt % of the lubricating composition.
38. The method of claim 26, wherein the lubricating composition has
a sulphur-content of 0.4 wt % to 5 wt % of the lubricating
composition.
39. The method of claim 26, wherein the driveline device is a
manual transmission or a gear, a gearbox, an axle gear, or an
automatic transmission.
40. The method of claim 26, wherein the lubricating composition
further comprises an organo-sulphide, or mixtures thereof.
41. The method of claim 40, wherein the organo-sulphide comprises
at least one of a polysulphide, thiadiazole compound, or mixtures
thereof.
42. The method of claim 26, wherein the lubricating composition
further comprises a viscosity modifier selected from the group
consisting of polyisobutenes, polymethacrylates, polyacrylates,
esters of maleic anhydride-styrene copolymers, esters of maleic
anhydride-olefin copolymers, and mixtures thereof.
43. The method of claim 42, wherein the viscosity modifier is a
polymethacrylate.
44. The method of claim 42, wherein the viscosity modifier is
present at greater than 12 wt % to 55 wt %, of the lubricating
composition.
Description
FIELD OF INVENTION
[0001] The invention provides a lubricating composition containing
an antiwear package. The invention further relates to a method of
lubricating a mechanical device by lubricating the device with the
lubricating composition.
BACKGROUND OF THE INVENTION
[0002] Lubricants for driveline power transmitting devices (such as
gears or transmissions), especially axle fluids, automatic
transmission fluids (ATFs), and manual transmission fluids (MTFs)),
present highly challenging technological problems and solutions for
satisfying the multiple and often conflicting lubricating
requirements, whilst providing durability and cleanliness. One of
the important parameters influencing durability is the
effectiveness of phosphorus antiwear or extreme pressure additives
at providing devices with appropriate protection under various
conditions of load and speed. However, many of the phosphorus
antiwear or extreme pressure additives contain sulphur. Due to
increasing environmental concerns, the presence of sulphur in
antiwear or extreme pressure additives is becoming less desirable.
In addition, many lubricating compositions containing antiwear or
extreme pressure additives evolve volatile sulphur species
resulting in an odour and potential detriment to health and the
environment.
[0003] A lubricating composition having the correct balance of
phosphorus antiwear or extreme pressure additives provides
driveline power transmitting devices with prolonged life and
efficiency with controlled deposit formation and oxidation
stability. However, many of the antiwear or extreme pressure
additives employed have limited oxidative stability, form deposits,
or increase corrosion. In addition, many phosphorus antiwear or
extreme pressure additives typically contain sulphur, which results
in an odorous lubricating composition containing the phosphorus
antiwear or extreme pressure additives. A number of references
disclosing antiwear chemistry are discussed below.
[0004] U.S. Pat. No. 5,338,470 discloses alkylated citric acid
derivatives obtained as a reaction product of citric acid and an
alkyl alcohol or amine. The alkylated citric acid derivative is
effective as an antiwear agent and friction modifier.
[0005] U.S. Pat. No. 4,237,022 discloses tartrimides useful as
additives in lubricants and fuels for effective reduction in squeal
and friction as well as improvement in fuel economy.
[0006] U.S. Pat. No. 4,952,328 discloses lubricating oil
compositions for internal combustion engines, comprising (A) oil of
lubricating viscosity, (B) a carboxylic derivative produced by
reacting a succinic acylating agent with certain amines, and (C) a
basic alkali metal salt of sulphonic or carboxylic acid.
[0007] U.S. Pat. No. 4,326,972 discloses lubricant compositions for
improving fuel economy of internal combustion engines. The
composition includes a specific sulphurised composition (based on
an ester of a carboxylic acid) and a basic alkali metal
sulphonate.
[0008] U.S. Patent Application 60/862,534 (PCT/US07/082057)
discloses malonate esters suitable as antiwear agents.
[0009] International Publication WO 2005/087904 discloses
lubricants containing hydroxy carboxylic acid and hydroxy
polycarboxylic acid esters in combination with
phosphorus-containing additives. The phosphorus-containing
additives include zinc dihydrocarbyldithiophosphates and/or neutral
phosphorus compounds, such as trilauryl phosphate or
triphenylphosphorothionate. The lubricants are useful in engine
lubricants.
[0010] International Publication WO 2006/044411 discloses a
low-sulphur, low-phosphorus, low-ash lubricant composition
containing a tartrate ester, or amide having 1 to 150 carbon atoms
per ester or amide group. The lubricant composition is suitable for
lubricating an internal combustion engine.
SUMMARY OF THE INVENTION
[0011] The inventors of the this invention have discovered that a
lubricating composition and method as disclosed herein is capable
of providing acceptable levels of at least one of (i) sulphur
(typically reducing or preventing emissions from waste oil), (ii)
fuel economy/efficiency (typically improving fuel
economy/efficiency), (iii) oxidation control (typically reducing or
preventing oxidation), (iv) friction performance, (v) wear and/or
extreme pressure performance (typically reducing or preventing),
and (vi) deposit control.
[0012] In one embodiment the invention provides a lubricating
composition comprising an oil of lubricating viscosity and an
antiwear package, wherein the antiwear package comprises: [0013]
(a) a derivative of a hydroxycarboxylic acid; and [0014] (b) an
amine or metal salt of a phosphorus compound, wherein the metal
salt contains a mono-valent metal (such as sodium, lithium or
potassium).
[0015] In one embodiment the invention provides a lubricating
composition comprising an oil of lubricating viscosity and an
antiwear package, wherein the antiwear package comprises: [0016]
(a) a derivative of a hydroxycarboxylic acid; and [0017] (b) an
amine salt of a phosphorus compound (may also be referred to as an
ashless salt of a phosphorus compound).
[0018] In one embodiment the invention provides a lubricating
composition comprising an oil of lubricating viscosity and an
antiwear package, wherein the antiwear package comprises: [0019]
(a) a derivative of a hydroxycarboxylic acid; and [0020] (b) an
amine or metal salt of a phosphorus compound that is either (i) a
hydroxy-substituted di-ester of (thio)phosphoric acid, or (ii) a
phosphorylated hydroxy-substituted di- or tri-ester of
(thio)phosphoric acid.
[0021] In one embodiment the invention provides a lubricating
composition comprising an oil of lubricating viscosity and an
antiwear package, wherein the antiwear package comprises: [0022]
(a) an antiwear agent which may be represented by a compound of
Formula (1a) and/or (1b):
##STR00001##
[0022] wherein
[0023] n' is 0 to 10 for Formula (1b), and 1 to 10 for Formula
(1a);
[0024] p is 1 to 5;
[0025] Y and Y' are independently O, >NH, >NR.sup.3, or an
imide group formed by taking together both Y and Y' groups in (1b)
or two Y groups in (1a) and forming a R.sup.1--N< group between
two >C.dbd.O groups;
[0026] X is independently --CH.sub.2--, >CHR.sup.4 or
>CR.sup.4R.sup.5, >CHOR.sup.6, or
>C(CO.sub.2R.sup.6).sub.2, --CH.sub.3, --CH.sub.2R.sup.4 or
CHR.sup.4R.sup.5, --CH.sub.2OR.sup.6, or
--CH(CO.sub.2R.sup.6).sub.2, .ident.C--R.sup.6 (where .ident.equals
three valences, and may only apply to Formula (1a)) or mixtures
thereof to fulfill the valence of Formula (1a) and/or (1b)
(typically the compound of Formula (1a) or (1b) has at least one X
that is hydroxyl-containing (i.e., >CHOR.sup.6, wherein R.sup.6
is hydrogen));
[0027] R.sup.1 and R.sup.2 are independently hydrocarbyl groups,
typically containing 1 to 150 carbon atoms;
[0028] R.sup.3 is a hydrocarbyl group;
[0029] R.sup.4 and R.sup.5 are independently keto-containing groups
(such as acyl groups), ester groups or hydrocarbyl groups; and
[0030] R.sup.6 is independently hydrogen or a hydrocarbyl group,
typically containing 1 to 150 carbon atoms; and [0031] (b) an amine
or metal salt of a phosphorus compound that may be either (i) a
hydroxy-substituted di-ester of (thio)phosphoric acid, or (ii) a
phosphorylated hydroxy-substituted di- or tri-ester of
(thio)phosphoric acid.
[0032] When X is hydroxyl-containing, the compound Formula (1a)
and/or (1b) may be derived from hydroxycarboxylic acids such as
tartaric acid, citric acid, or mixtures thereof.
[0033] When X is not hydroxyl-containing, the compound Formula (1a)
and/or (1b) may be derived from malonic acid, oxalic acid,
chlorophenyl malonic acid, or mixtures thereof.
[0034] In one embodiment the invention provides a method for
lubricating a driveline device comprising supplying to the
driveline device a lubricating composition comprising an oil of
lubricating viscosity and an antiwear package, wherein the antiwear
package comprises a compound of Formula (1a) and/or (1b) (as
defined above) and a phosphorus compound (for example, a phosphorus
acid or an ester thereof or a salt thereof or the salt of an ester
thereof). Typically the phosphorus compound is oil-soluble.
[0035] In one embodiment the invention provides a lubricating
composition comprising an oil of lubricating viscosity and an
antiwear package, wherein the antiwear package comprises: [0036]
(a) a derivative of a hydroxycarboxylic acid, wherein the
hydroxycarboxylic acid is tartaric acid; and [0037] (b) an amine or
metal salt of a phosphorus compound that may be (i) a
hydroxy-substituted di-ester of (thio)phosphoric acid, or (ii) a
phosphorylated hydroxy-substituted di- or tri-ester of
(thio)phosphoric acid.
[0038] In one embodiment the derivatives of hydroxycarboxylic acid
include imide, di-esters, di-amides, ester-amide derivatives of
tartaric acid.
[0039] In different embodiments the lubricating compositions
disclosed herein contain 0 ppm to 500 ppm, or 5 ppm to 300 ppm, or
20 ppm to 250 ppm of molybdenum.
[0040] In one embodiment the invention provides a method for
lubricating a mechanical device (typically a driveline device)
comprising supplying to the mechanical a device a lubricating
composition as disclosed herein.
[0041] In one embodiment the invention provides a method for
lubricating a driveline device comprising supplying to the
mechanical a device a lubricating composition comprising an oil of
lubricating viscosity and an antiwear package, wherein the antiwear
package comprises: [0042] (a) a derivative of a hydroxycarboxylic
acid, typically the hydroxycarboxylic acid is tartaric acid; and
[0043] (b) a phosphorus compound (typically, an amine or metal salt
of a phosphorus compound that may be either (i) a
hydroxy-substituted di-ester of (thio)phosphoric acid, or (ii) a
phosphorylated hydroxy-substituted di- or tri-ester of
(thio)phosphoric acid).
[0044] The lubricating compositions disclosed herein may have a
sulphur-content of greater than 0.3 wt %, or 0.4 wt % to 5 wt %, or
0.5 wt % to 3 wt %, 0.8 wt % to 2.5 wt %, or 1 wt % to 2 wt % of
the lubricating composition.
[0045] In one embodiment the invention provides for the use of a
lubricating composition as disclosed herein for providing
acceptable levels of at least one of (i) phosphorus emissions, (ii)
sulphur emissions, (iii) fuel economy/efficiency, (iv) oxidation
control, (v) friction performance, (vi) wear and/or extreme
pressure performance (typically reducing or preventing), and (vii)
deposit control.
DETAILED DESCRIPTION OF THE INVENTION
[0046] The present invention provides a lubricating composition and
a method for lubricating a mechanical device as disclosed above.
Typically the mechanical device is a driveline device (including a
gear or transmission).
Antiwear Package
[0047] The antiwear package includes two antiwear agents as
disclosed above.
[0048] The antiwear package typically includes (i) a derivative of
a hydroxycarboxylic acid, and (ii) a phosphorus compound (typically
an ashless phosphorus compound). The phosphorus compound may
include an amine or metal salt of a phosphorus compound that may be
either (i) a hydroxy-substituted di-ester of (thio)phosphoric acid,
or (ii) a phosphorylated hydroxy-substituted di- or tri-ester of
(thio)phosphoric acid.
[0049] The antiwear package may be present at 0.01 wt % to 10 wt %,
or 0.05 wt % to 10 wt %, or 0.05 wt % to 5 wt % of the lubricating
composition.
[0050] The derivative of a hydroxycarboxylic acid (or the antiwear
agent represented by a compound of Formula (1a) and/or (1b)) may be
present at 0.005 wt % to 10 wt %, or 0.025 to 5 wt %, or 0.25 to
2.5 wt % of the lubricating composition.
[0051] The phosphorus compound may be present at 0.005 wt % to 10
wt %, or 0.025 to 5 wt %, or 0.05 to 2.5 wt % of the lubricating
composition.
Derivative of a Hydroxycarboxylic Acid
[0052] In one embodiment one antiwear agent derived from Formula
(1a) and/or (1b) includes a derivative of a hydroxycarboxylic acid.
The derivative of a hydroxycarboxylic acid, typically a tartrate,
may also function as rust and corrosion inhibitors, friction
modifiers, antiwear agents and demulsifiers. In one embodiment the
derivative of a hydroxycarboxylic acid may also have friction
modifying properties.
[0053] In one embodiment the derivative of a hydroxycarboxylic acid
may be ashless (i.e., do not contain metal in amounts greater than
those associated with contaminant amounts).
[0054] Derivatives of the hydroxycarboxylic acid include imides,
di-esters, di-amides, di-imides (applicable for tetra-acids and
higher), ester-amides, ester-imides (applicable for tri-acids and
higher, such as citric acid), imide-amides (applicable for
tri-acids and higher, such as citric acid). In one embodiment the
antiwear agent includes imides, di-esters, di-amides, or
ester-amides.
[0055] In one embodiment the antiwear agent may be derived from at
least one of a hydroxy-carboxylic acid di-ester, a
hydroxy-carboxylic acid di-amide, a hydroxy-carboxylic acid
di-imide, a hydroxy-carboxylic acid ester-amide, a
hydroxy-carboxylic acid ester-imide, and a hydroxy-carboxylic acid
imide-amide. In one embodiment the antiwear agent may be derived
from at least one of the group consisting of a hydroxy-carboxylic
acid di-ester, a hydroxy-carboxylic acid di-amide, and a
hydroxy-carboxylic acid ester-amide.
[0056] Examples of a suitable a hydroxycarboxylic acid include
citric acid, tartaric acid, malic acid (or hydroxy-succinic acid),
lactic acid, oxalic acid, glycolic acid, hydroxy-propionic acid,
hydroxyglutaric acid, or mixtures thereof. In one embodiment the
antiwear agent may be derived from tartaric acid, citric acid,
hydroxy-succinic acid, dihydroxy mono-acids, mono-hydroxy diacids,
or mixtures thereof. In one embodiment the antiwear agent includes
a compound derived from tartaric acid.
[0057] US Patent Application 2005/198894 discloses suitable
hydroxycarboxylic acid compounds, and methods of preparing the
same.
[0058] Canadian Patent 1183125; US Patent Publication numbers
2006/0183647 and US-2006-0079413; U.S. Patent Application No.
60/867,402; and British Patent 2 105 743 A, all disclose examples
of suitable tartaric acid derivatives.
[0059] A detailed description of methods for preparing suitable
tartrimides (by reacting tartaric acid with a primary amine) is
disclosed in U.S. Pat. No. 4,237,022.
[0060] In one embodiment the antiwear agent includes imide,
di-esters, di-amides, ester-amide derivatives of tartaric acid.
[0061] In one embodiment the antiwear agent may be represented by a
compound of Formula (1a) and/or (1b) as defined above: wherein
[0062] n' is 0 to 10, 0 to 6, or 0 to 4 for Formula (1b), and for
Formula (1a) 1 to 4, or 1 to 2;
[0063] p is 1 to 5, or 1 to 2, or 1;
[0064] Y and Y' are independently --O--, >NH, >NR.sup.3, or
an imide group formed by taking together both Y and Y' groups and
forming a R.sup.1--N< group between two >C=O groups;
[0065] X is independently --CH.sub.2--, >CHR.sup.4 or
>CR.sup.4R.sup.5, >CHOR.sup.6, or
>C(CO.sub.2R.sup.6).sub.2, --CH.sub.3, --CH.sub.2R.sup.4 or
CHR.sup.4R.sup.5, --CH.sub.2OR.sup.6, or
--CH(CO.sub.2R.sup.6).sub.2, .ident.C--R.sup.6 (where .ident.
equals three valences, and may only apply to Formula (1a)) or
mixtures thereof to fulfill the valence of Formula (1a) and/or (1b)
(typically the compound of Formula (1a) or (1b) has at least one X
that is hydroxyl-containing (i.e., >CHOR.sup.6, wherein R.sup.6
is hydrogen));
[0066] R.sup.1 and R.sup.2 are independently hydrocarbyl groups,
typically containing 1 to 150, 4 to 30, or 6 to 20, or 10 to 20, or
11 to 18 carbon atoms;
[0067] R.sup.3 is a hydrocarbyl group;
[0068] R.sup.4 and R.sup.5 are independently keto-containing groups
(such as acyl groups), ester groups or hydrocarbyl groups; and
[0069] R.sup.6 is independently hydrogen or a hydrocarbyl group,
typically containing 1 to 150, or 4 to 30 carbon atoms.
[0070] In one embodiment the di-esters, di-amides, di-imides
(applicable for tetra-acids and higher), ester-amide, ester-imide
(applicable for tri-acids and higher, such as citric acid),
imide-amide (applicable for tri-acids and higher, such as citric
acid) compounds may be derived from a compound of Formula (1a)
and/or (1b). In one embodiment the di-esters, di-amides,
ester-amide, compounds may be derived from a compound of Formula
(1a) and/or (1b).
[0071] In one embodiment the compound of Formula (1b) contains an
imide group. The imide group is typically formed by taking together
the Y and Y' groups and forming a R.sup.1--N< group between two
>C.dbd.O groups.
[0072] In one embodiment the compound of Formula (1a) and/or (1b)
has n, X, and R', R.sup.2 and R.sup.6 defined as follows: n is 1 to
2, X is >CHOR.sup.6; and R.sup.1, and R.sup.2 are independently
hydrocarbyl groups containing 4 to 30 carbon atoms, and R.sup.6 is
independently hydrogen or a hydrocarbyl group containing 4 to 30
carbon atoms.
[0073] In one embodiment Y and Y' are both --O--.
[0074] In one embodiment the compound of Formula (1a) and/or (1b)
has n, X, Y, Y' and R', R.sup.2 and R.sup.6 defined as follows: n
is 1 to 2, X is >CHOR.sup.6; Y and Y' are both --O--, and
R.sup.1, and R.sup.2 are independently hydrocarbyl groups
containing 4 to 30 carbon atoms, and R.sup.6 is independently
hydrogen or a hydrocarbyl group containing 4 to 30 carbon
atoms.
[0075] The di-esters, di-amides, di-imides (applicable for
tetra-acids and higher), ester-amide, ester-imide (applicable for
tri-acids and higher, such as citric acid), imide-amide (applicable
for tri-acids and higher, such as citric acid) compounds of Formula
(1a) and/or (1b) may be prepared by reacting a dicarboxylic acid
(such as tartaric acid), with an amine or alcohol, optionally in
the presence of a known esterification catalyst. The amine or
alcohol typically has sufficient carbon atoms to fulfill the
requirements of R.sup.1 and/or R.sup.2 as defined in Formula (1a)
and/or (1b).
[0076] In one embodiment R.sup.1 and R.sup.2 may be independently
linear or branched hydrocarbyl groups. In one embodiment the
hydrocarbyl groups may be branched. In one embodiment the
hydrocarbyl groups may be linear. The R.sup.1 and R.sup.2 may be
incorporated into Formula (1a) and/or (1b) by either an amine or an
alcohol. The alcohol includes both monohydric alcohol and
polyhydric alcohol.
[0077] In one embodiment the antiwear agent may be derived from a
compound of Formula (1b).
[0078] Examples of a suitable branched alcohol include
2-ethylhexanol, isotridecanol, Guerbet alcohols, or mixtures
thereof.
[0079] Examples of a monohydric alcohol include methanol, ethanol,
propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol,
decanol, undecanol, dodecanol, tridecanol, tetradecanol,
pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol,
eicosanol, or mixtures thereof. In one embodiment the monohydric
alcohol contains 5 to 20 carbon atoms.
[0080] The alcohol includes either a monohydric alcohol or a
polyhydric alcohol. Examples of a suitable polyhydric alcohol
include ethylene glycol, propylene glycol, 1,3-butylene glycol,
2,3-butylene glycol, 1,5-pentane diol, 1,6-hexane diol, glycerol,
sorbitol, pentaerythritol, trimethylolpropane, starch, glucose,
sucrose, methylglucoside, or mixtures thereof. In one embodiment
the polyhydric alcohol may be used in a mixture along with a
monohydric alcohol. Typically, in such a combination the monohydric
alcohol constitutes at least 60 mole percent, or at least 90 mole
percent of the mixture.
[0081] In one embodiment the antiwear agent may be derived from
tartaric acid. The tartaric acid used for preparing the tartrates
of the invention may be commercially available (for instance
obtained from Sargent Welch), and it is likely to exist in one or
more isomeric forms such as d-tartaric acid, 1-tartaric acid,
d,l-tartaric acid (racemic mixture) or mesotartaric acid, often
depending on the source (natural) or method of synthesis (e.g. from
maleic acid). These derivatives may also be prepared from
functional equivalents to the diacid readily apparent to those
skilled in the art, such as esters, acid chlorides, or
anhydrides.
[0082] When the compound of Formula (1a) and/or (1b) is derived
from tartaric acid, resultant tartrates may be solid, semi-solid,
or oil depending on the particular alcohol used in preparing the
tartrate. For use as additives in oleaginous compositions including
lubricating and fuel compositions the tartrates are advantageously
soluble and/or stably dispersible in such oleaginous compositions.
For example, compositions intended for use in oils are typically
oil-soluble and/or stably dispersible in an oil in which they are
to be used. The term "oil-soluble" as used in this specification
and appended claims does not necessarily mean that all the
compositions in question are miscible or soluble in all proportions
in all oils. Rather, it is intended to mean that the composition is
soluble in an oil (e.g., mineral oil, or synthetic oil) in which it
is intended to function to an extent which permits the solution to
exhibit one or more of the desired properties. Similarly, it is not
necessary that such "solutions" be true solutions in the strict
physical or chemical sense. They may instead be micro-emulsions or
colloidal dispersions which, for the purpose of this invention,
exhibit properties sufficiently close to those of true solutions to
be, for practical purposes, interchangeable with them within the
context of this invention.
Amine or Metal Salt of a Phosphorus Compound
[0083] As used herein the term "(thio)phosphoric" means either a
sulphur-containing phosphoric acid or a sulphur-free phosphoric
acid.
[0084] In one embodiment an amine or metal salt of a phosphorus
compound may be either (i) a hydroxy-substituted di-ester of
(thio)phosphoric acid, or (ii) a phosphorylated hydroxy-substituted
di- or tri-ester of (thio)phosphoric acid.
[0085] In one embodiment the amine or metal salt of a phosphorus
compound is sulphur-free.
[0086] The amine or metal salt of a sulphur-free phosphorus
compound may be represented Formula (2):
##STR00002##
wherein
[0087] A and A' are independently H, or a hydrocarbyl group
containing 1 to 30 carbon atoms;
[0088] each R and R'' group are independently a hydrocarbyl
group;
[0089] each R' is independently R, H, or a hydroxyalkyl group;
[0090] Y is independently R', or a group represented by
RO(R'O)P(O)--CH(A')CH(A)- (such as
RO(R')P(O)--CH.sub.2CH(CH.sub.3)--);
[0091] x' ranges from 0 to 1 (in one embodiment when x'=0, R' is a
hydroxyalkyl group); and
[0092] m and n are both positive non-zero integers, with the
proviso that the sum of (m+n) is equal to 4;
[0093] M is a metal ion;
[0094] t is an integer varying from 1 to 4 (or 1 to 2); and
[0095] q and e are fractions, whose total provides complete valence
to satisfy t, with the proviso that q is in the range of 0.1 to 1.5
(or 0.1 to 1), and e is in the range of 0 to 0.9.
[0096] The amine salt of a sulphur-free phosphorus compound may be
represented by Formula (2a):
##STR00003##
wherein
[0097] A and A' are independently H, or a hydrocarbyl group
containing 1 to 30 carbon atoms;
[0098] each R and R'' group are independently a hydrocarbyl
group;
[0099] each R' is independently R, H, or a hydroxyalkyl group;
[0100] Y is independently R', or a group represented by
RO(R'O)P(O)--CH(A')CH(A)- (such as
RO(R'O)P(O)--CH.sub.2CH(CH.sub.3)--);
[0101] x' ranges from 0 to 1 (in one embodiment when x'=0, R' is a
hydroxyalkyl group);
[0102] m and n are both positive non-zero integers, with the
proviso that the sum of (m+n) is equal to 4.
[0103] In one embodiment the compound represented by Formula (2) or
Formula (2a) has x' equal to 1.
[0104] In one embodiment the compound represented by Formula (2) or
Formula (2a) has x' is equal to 0.
[0105] In one embodiment the compound represented by Formula (2) or
Formula (2a) has m equal to 2; and n equal to 2.
[0106] In one embodiment the compound represented by Formula (2) or
Formula (2a) has m equal to 3; and n equal to 1.
[0107] In one embodiment A and A' independently contain 1 to 10, or
2 to 6, or 2 to 4 carbon atoms.
[0108] In one embodiment R, R' and R'' all independently contain 1
to 30, or 1 to 20, or 4 to 20 carbon atoms. In one embodiment up to
half of the R' groups may be hydrogen.
[0109] In one embodiment R'' contains 8 to 26, or 10 to 20, or 13
to 19 carbon atoms.
[0110] The compound of Formula (2) or Formula (2a) includes amine
salts of a primary amine, a secondary amine, a tertiary amine, or
mixtures thereof. In one embodiment the primary amine includes a
tertiary-aliphatic primary amine.
[0111] Examples of suitable primary amines include ethylamine,
propylamine, butylamine, 2-ethylhexylamine, octylamine, and
dodecylamine, as well as such fatty amines as n-octylamine,
n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine,
n-octadecylamine and oleyamine. Other useful fatty amines include
commercially available fatty amines such as "Armeen.RTM." amines
(products available from Akzo Chemicals, Chicago, Ill.), such as
Armeen C, Armeen O, Armeen OL, Armeen T, Armeen HT, Armeen S and
Armeen SD, wherein the letter designation relates to the fatty
group, such as coco, oleyl, tallow, or stearyl groups.
[0112] Examples of suitable secondary amines include dimethylamine,
diethylamine, dipropylamine, dibutylamine, diamylamine,
dihexylamine, diheptylamine, methylethylamine, ethylbutylamine,
bis-2-ethylhexylamine, N-methyl-1-amino-cyclohexane, Armeen.RTM. 2C
and ethylamylamine. The secondary amines may be cyclic amines such
as piperidine, piperazine and morpholine.
[0113] Examples of tertiary amines include tri-n-butylamine,
tri-n-octylamine, tri-decylamine, tri-laurylamine,
tri-hexadecylamine, and dimethyloleylamine (Armeen.RTM. DMOD).
[0114] In one embodiment the amines may be in the form of a
mixture. Examples of suitable mixtures of amines include (i) an
amine with 11 to 14 carbon atoms on tertiary alkyl primary groups,
(ii) an amine with 14 to 18 carbon atoms on tertiary alkyl primary
groups, or (iii) an amine with 18 to 22 carbon atoms on tertiary
alkyl primary groups. Other examples of tertiary alkyl primary
amines include tert-butylamine, tert-hexylamine, tert-octylamine
(such as 1,1-dimethylhexylamine), tert-decylamine (such as
1,1-dimethyloctylamine), tertdodecylamine, tert-tetradecylamine,
tert-hexadecylamine, tert-octadecylamine, tert-tetracosanylamine,
and tert-octacosanylamine.
[0115] In one embodiment a useful mixture of amines includes
"Primene.RTM. 81R" or "Primene.RTM. JMT." Primene.RTM. 81R and
Primene.RTM. JMT (both produced and sold by Rohm & Haas) may be
mixtures of C11 to C14 tertiary alkyl primary amines and C 18 to
C22 tertiary alkyl primary amines respectively.
[0116] In one embodiment the metal ion of Formula (2) may be a
mono- or di-valent metal, or mixtures thereof. In one embodiment
the metal ion may be divalent.
[0117] In one embodiment the metal of the metal ion includes
lithium, sodium, potassium, calcium, magnesium, barium, copper,
nickel, tin or zinc.
[0118] In one embodiment the metal of the metal ion includes
lithium, sodium, calcium, magnesium, or zinc. In one embodiment the
metal of the metal ion may be zinc.
[0119] In one embodiment t is equal to 1, when the compound of
Formula (2) is an amine salt or a metal salt of a monovalent
metal.
[0120] In one embodiment t is equal to 2, when the compound of
Formula (2) is a metal salt of a divalent metal.
[0121] In one embodiment q is in the range of 0.5 to 1; and e is in
the range of 0 to 0.5.
[0122] In one embodiment the compound of Formula (2) is free of a
metal ion (e is equal to zero; and q is equal to one).
[0123] In one embodiment t is equal to 1, e is equal to 0, and q is
equal to 1.
Processes to Prepare Compound of Formula (2) and Formula (2a)
[0124] In one embodiment the sulphur-free amine salt of a
phosphorus compound obtained/obtainable by a process comprising:
reacting an amine with either (i) a hydroxy-substituted di-ester of
phosphoric acid, or (ii) a phosphorylated hydroxy-substituted di-
or tri-ester of phosphoric acid.
[0125] In one embodiment the salt of a hydroxy-substituted di-ester
of phosphoric acid may be prepared by a process comprising:
[0126] (i) reacting a phosphating agent (such as P.sub.2O.sub.5,
P.sub.4O.sub.10, or equivalents thereof) with an alcohol, to form a
mono- and/or di-phosphate ester;
[0127] (ii) reacting the phosphate ester with an alkylene oxide, to
form a hydroxy-substituted di-ester of phosphoric acid; and
[0128] (iii) salting the hydroxy-substituted di-ester of phosphoric
acid is reacted with an amine and/or metal.
[0129] In one embodiment the hydroxy-substituted di-ester of
phosphoric acid of (ii) may be further reacted at least once more,
by repeating step (i) above, with a phosphating agent (typically
forming a phosphorylated hydroxy-substituted di- or tri-ester of
phosphoric acid), before salting with an amine and/or metal (as in
step (iii) above).
[0130] In different embodiments, steps (i) and (ii) may be repeated
at least once more, optionally followed by step (i) before salting
with an amine and/or metal (as in step (iii) above). For example
the salts may be prepared by a process comprising performing the
steps (i),(ii), and (iii); or (i),(ii),(i), and (iii); or
(i),(ii),(i),(ii), and (iii); (i),(ii),(i),(ii),(i), and (iii), or
(i),(ii),(i),(ii),(i), (ii), and (iii), or
(i),(ii),(i),(ii),(i),(ii),(i) and (iii), or
(i),(ii),(i),(ii),(i),(ii),(i),(ii) and (iii), as defined
above.
[0131] In different embodiments the reaction product yields 1 wt %
to 99 wt %, or 20 wt % to 80 wt %, or 35 wt % to 75 wt %, of the
sulphur-free amine salt of a phosphorus compound of the
invention.
[0132] In different embodiments, the mole ratio in step (i) of the
mono-phosphate to di-phosphate includes ranges of 1:10 to 10:1, or
1:5 to 5:1, or 1:2 to 2:1, or 1:1.
[0133] In different embodiments, the mole ratio (based on the
amount of phosphorus) in step (i) of alkylene oxide to the mono-
and/or di-phosphate ester of step (i) includes ranges of 0.6:1 to
1.5:1, or 0.8:1 to 1.2:1.
[0134] In one embodiment alkylene oxide includes ethylene oxide,
propylene oxide or butylene oxide; and the mole ratio of alkylene
oxide to hydroxy-substituted di-ester of phosphoric acid in step
(ii) includes 1:1.
[0135] In one embodiment alkylene oxide includes C.sub.5 and higher
alkylene oxide; and the mole ratio of alkylene oxide to the
hydroxy-substituted di-ester of phosphoric acid in step (ii)
includes broader ranges because the alkylene oxides are less
volatile under reaction conditions.
[0136] The process described above in steps (i) to (iii), in
different embodiments may be carried out at a reaction temperature
in a range of 30.degree. C. to 140.degree. C., or 40.degree. C. to
110.degree. C., or 45.degree. C. to 90.degree. C.
[0137] The process may be carried out at reduced pressure,
atmospheric pressure or above atmospheric pressure. In one
embodiment the process may be carried out at atmospheric pressure
or above atmospheric pressure.
[0138] In one embodiment the process may be carried out in an inert
atmosphere. Examples of a suitable inert atmosphere include
nitrogen, argon, or mixtures thereof.
[0139] In different embodiments, the alkylene oxide contains 1 to
10, or 2 to 6, or 2 to 4 carbon atoms. In one embodiment the
alkylene oxide include ethylene oxide, propylene oxide, butylene
oxide, or mixtures thereof. In one embodiment the alkylene oxide
includes propylene oxide.
[0140] In different embodiments, the alcohol contains 1 to 30, or 4
to 24, or 8 to 18 carbon atoms.
[0141] The alcohol may be linear or branched.
[0142] The alcohol may be saturated or unsaturated.
[0143] Examples of a suitable alcohol include hexanol, heptanol,
octanol, nonanol, dodecanol, dodecanol, tridecanol, tetradecanol,
pentadecanol, hexadecanol, heptadecanol, octadecanol, octadecenol
(oleyl alcohol), nonadecanol, eicosyl-alcohol, or mixtures thereof.
Examples of a suitable alcohol include for example,
4-methyl-2-pentanol, 2-ethylhexanol, isooctanol, or mixtures
thereof.
[0144] Examples of commercially available alcohols include
Alcohol.RTM. 7911, Oxo Alcohol.RTM. 7900 and Oxo Alcohol.RTM. 1100
of Monsanto; Alphanol.RTM. 79 of ICI; Nafol.RTM. 1620, Alfol.RTM.
610 and Alfol.RTM. 810 of Condea (now Sasol); Epal.RTM. 610 and
Epal.RTM. 810 of Ethyl Corporation; Linevol.RTM. 79, Linevol.RTM.
911 and Dobanol.RTM. 25 L of Shell AG; Lial.RTM. 125 of Condea
Augusta, Milan; Dehydad.RTM. and Lorol.RTM. of Henkel KGaA (now
Cognis) as well as Linopol.RTM. 7-11 and Acropol.RTM. 91 of Ugine
Kuhlmann.
[0145] Useful amines include amine salts of a primary amine, a
secondary amine, a tertiary amine, or mixtures thereof. A more
detailed description of useful amines is defined above.
AMINE SALTS OF PHOSPHORIC ACID: PREPARATIVE EXAMPLES
Preparative Example 1
[0146] Step A: Phosphorus pentoxide (219 g, about 1.54 mol) is
added slowly over a period of about 1.5 hours to a flask containing
isooctyl alcohol (about 602 g, about 4.63 mol) whilst stirring at
about 60.degree. C. to about 70.degree. C. in a nitrogen
atmosphere. The mixture is then heated to about 90.degree. C. and
held there for about 5 hours. The product is cooled. Analysis of
the product indicates a phosphorus content of about 11.6 wt %.
[0147] Step B: At temperature of about 50.degree. C., a flask
containing the product of Step A (about 760 g, about 2.71 mol based
on equivalent weight of 280 g/mol) stirring at (15-40.degree. C.)
mixed with a stoichiometric amount of propylene oxide (about 157.7
g, about 2.71 mol) dropwise via an addition funnel. The propylene
oxide is added over a period of about 1.5 hours, to form a mixture.
The mixture is then heated to 70.degree. C. and held for about 2
hours. The product is cooled. The product of Step B has a
phosphorus content of about 9.6 wt %.
[0148] Step C: The product of Step B (about 881.5 g, 2.73 mol P
based on % P=9.6) is heated to 50.degree. C. under nitrogen and
phosphorus pentoxide (129 g, 0.91 mol) is added in four equal
portions over about one hour. During the addition the temperature
is maintained between the range of about 55.degree. C. to about
70.degree. C., whilst vigorously stirring to provide a product that
is a homogeneous solid. The temperature is raised to about
80.degree. C.; and held for about 3 hours, to form a product. Upon
cooling the product contains 13.7 wt % of phosphorus
[0149] Step D: The product of Step C (about 706.7 g, about 2.24
mol) is heated to about 45.degree. C. in a nitrogen atmosphere in a
flask. Bis-(2-ethylhexyl)amine (about 596 g, about 2.47 mol) is
added dropwise via an addition funnel over a period of about 2
hours whilst controlling the temperature to be about 55.degree. C.
to about 60.degree. C. The flask is then heated to about 75.degree.
C. and held there for about 2 hours. Upon cooling the product of
Step D is light orange and has a phosphorus content of 7.7 wt
%.
Preparative Example 2
[0150] Preparative Example 2 is prepared employing a similar
procedure as Step A and Step B of Preparative Example 1. However,
for Step A, a stoichiometric amount of propylene oxide (209 g, 3.60
mol) is added to isooctyl phosphate acid (about 952 g, about 3.43
mol). The mixture is then heated to about 75.degree. C. for 4
hours. The resultant product of Step A has a phosphorus content of
about 9.65 wt %. For Step B, the product of Step A (about 208 g,
about 0.374 mol) is heated in the flask and bis-(2-ethylhexyl)amine
(about 97.5 g, about 0.404 mol) is added dropwise via an addition
funnel over a period of about 40 minutes. The reaction temperature
is then raised to about 75.degree. C. and held for about 5 hours.
The resultant product has a phosphorus content of about 6.6 wt
%.
Preparative Example 3
[0151] Preparative Example 3 is prepared in a similar procedure as
Preparative Example 1. However, step A of Preparative Example 3
reacts phosphorus pentoxide (about 189 g, about 1.33 mol),
methylamyl alcohol (about 408 g, about 4 mol). The phosphorus
pentoxide is added over a period of about 75 minutes and at a
temperature of about 60.degree. C. The product is then heated to
about 70.degree. C. and held for about 1.5 hours. The resultant
product has a phosphorus content of about 13.7 wt %. Step B is
carried out by reacting the product of Step A (171.7 g, 0.719 mol
based on equivalent weight of 240 g/mol), with about 1.1
equivalents of propylene oxide (about 46.0 g, about 0.791 mol). The
resultant product has a phosphorus content of about 10.96 wt %.
Step C is carried out by heating the product of Step B (about 200
g, about 0.71 mol) at about 60.degree. C. under a nitrogen
atmosphere and reacting with phosphorus pentoxide (about 33 g,
about 0.23 mol). The reaction exotherm reaches about 87.degree. C.
Upon cooling to about 65.degree. C., the flask is held at this
temperature for about 1.5 hours. The flask is then cooled to about
40.degree. C. followed by the dropwise addition over a period of
about 1.5 hours of bis-(2-ethylhexyl)amine (about 200 g, about 0.83
mol). The flask is then heated to about 75.degree. C. and held for
about 2 hours. The product has a phosphorus content of about 8.6 wt
%, and a nitrogen content of about 2.8 wt %.
Preparative Example 4
[0152] The process to prepare Preparative Example 4 is similar to
that of Preparative Example 2. However, for Step A, the flask
contains methylamyl phosphate acid (about 154.4 g, about 0.647 mol)
and at about 25.degree. C., under a nitrogen atmosphere,
1,2-epoxyhexadecane (about 163.0 g, about 0.679 mol) is added
dropwise via an addition funnel over a period of about 1.5 hours.
The mixture is then heated to about 75.degree. C. and held there
for about 4 hours. The product has a phosphorus content of about
6.7 wt %. The product of Step A is then heated to about 60.degree.
C., under a nitrogen atmosphere and phosphorus pentoxide (about 33
g, about 0.23 mol) is added in two portions over a period of about
1.5 hours. The temperature was held at about 75.degree. C. for
about 1.5 hours. The product is then heated to about 40.degree. C.
under nitrogen and bis-(2-ethylhexyl)amine (about 144.8 g, about
0.596 mol) was added dropwise via addition funnel over 1.5 hours.
The temperature is then increased to about 70.degree. C. and held
for a period of about 2 hours. The product has a phosphorus content
of about 6.6 wt %, and a nitrogen content of about 2.1 wt %.
Preparative Example 5
[0153] with Thiophosphoric Acid: Phosphorus pentoxide (144 grams)
is added in two portions one hour apart to 1176 grams of
hydroxypropyl O,O-di(4-methyl-2-pentyl)phosphorodithioate (prepared
by reacting di(4-methyl-2-pentyl)-phosphorodithioic acid with about
1.1 moles of propylene oxide at 54.degree. C. and removing excess
propylene oxide by vacuum stripping). The mixture is heated at
71.degree. C. for 6 hours to give an acidic intermediate (1320 g).
This intermediate is neutralised by adding 555 g of a
C.sub.12-14-alkyl amine over two hours at 49.degree. C. After
heating to 77.degree. C. the material is vacuum stripped to give
the product.
[0154] Preparative Examples 6 to 8
[0155] are prepared in a similar manner to Preparative Examples 2
to 4, except the bis-(2-ethylhexyl)amine is replaced with
C.sub.12-14 tertiary alkyl primary amine (Primene.RTM. 81R).
[0156] In one embodiment the amine or metal salt of a phosphorus
compound is an amine salt of a sulphur-containing phosphoric acid
as described in U.S. Pat. No. 3,197,405, for example, any one of
examples 1 to 25.
[0157] In one embodiment amine or metal salt of a phosphorus
compound is a sulphur-containing compound.
[0158] In one embodiment amine or metal salt of a phosphorus
compound is other than a sulphur-containing compound.
[0159] The amine salt of a sulphur-free phosphorus compound may be
a reaction product prepared from a dithiophosphoric acid reacting
with an epoxide or a glycol. This reaction product may be further
reacted with a phosphorus acid, anhydride, or lower ester (where
"lower" signifies 1 to 8, or 1 to 6, or 1 to 4, or 1 to 2 carbon
atoms in the alcohol-derived portion of the ester). The epoxide
includes an aliphatic epoxide or a styrene oxide. Examples of
useful epoxides include ethylene oxide, propylene oxide, butene
oxide, octene oxide, dodecene oxide, styrene oxide and the like. In
one embodiment the epoxide may be propylene oxide. The glycols
include aliphatic glycols having 1 to 12, or 2 to 6, or 2 to 3
carbon atoms. The resulting acids are then salted with amines.
[0160] The amine or metal salt of a phosphorus compound may be
present at 0.01 wt % to 10 wt %, or 0.1 wt % to 5 wt %, or 0.2 wt %
to 3 wt % of the lubricating composition.
[0161] In one embodiment the antiwear package further comprises
antiwear agents other than those disclosed above.
[0162] In one embodiment the antiwear package does not contain a
zinc dialkyldithiophosphate.
[0163] In one embodiment the antiwear package does not contain
antiwear agents other than those disclosed above.
[0164] Other antiwear agents include a non-ionic phosphorus
compound with phosphorus atoms having an oxidation state of +3, a
metal dialkyldithiophosphate, metal dialkylphosphate (typically a
zinc di dialkylphosphate), a metal dialkyldithiophosphate
(typically a zinc di dialkyldithiophosphate), or mixtures
thereof.
[0165] Examples of a suitable zinc dialkyldithiophosphate often
referred to as ZDDP, ZDP or ZDTP) include zinc
di-(2-methylpropyl)dithiophosphate/di-(amyl)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, or mixtures thereof.
[0166] Examples of a zinc dialkylphosphate include zinc
di-(2-methylpropyl)phosphate, zinc di-(amyl)phosphate, zinc
di-(1,3-dimethylbutyl)phosphate, zinc di-(heptyl)phosphate, zinc
di-(octyl)phosphate, zinc di-(2-ethylhexyl)phosphate, zinc
di-(nonyl)phosphate, zinc di-(decyl)phosphate, zinc
di-(dodecyl)phosphate, zinc di-(dodecylphenyl)phosphate, zinc
di-(heptylphenyl)phosphate, or mixtures thereof.
[0167] Examples of a non-ionic phosphorus compound with phosphorus
atoms having an oxidation state of +3 include a phosphite ester, or
mixtures thereof. A more detailed description of the non-ionic
phosphorus compound include column 9, line 48 to column 11, line 8
of U.S. Pat. No. 6,103,673
Organo-Sulphide
[0168] In one embodiment the lubricating composition further
comprises an organo-sulphide, or mixtures thereof. In one
embodiment the organo-sulphide comprises at least one of a
polysulphide, thiadiazole compound, or mixtures thereof.
[0169] In different embodiments, the organo-sulphide may be present
in a range of 0 wt % to 10 wt %, or 0.01 wt % to 10 wt %, or 0.1 wt
% to 8 wt %, or 0.25 wt % to 6 wt % of the lubricating
composition.
Thiadiazole Compound
[0170] Examples of a thiadiazole include
2,5-dimercapto-1,3,4-thiadiazole, or oligomers thereof, a
hydrocarbyl-substituted 2,5-dimercapto-1,3-4-thiadiazole, a
hydrocarbylthio-substituted 2,5-dimercapto-1,3-4-thiadiazole, or
oligomers thereof. The oligomers of hydrocarbyl-substituted
2,5-dimercapto-1,3-4-thiadiazole typically form by forming a
sulphur-sulphur bond between 2,5-dimercapto-1,3-4-thiadiazole units
to form oligomers of two or more of said thiadiazole units.
[0171] Examples of a suitable thiadiazole compound include at least
one of a dimercaptothiadiazole, 2,5-dimercapto-[1,3,4]-thiadiazole,
3,5-dimercapto-[1,2,4]-thiadiazole,
3,4-dimercapto-[1,2,5]-thiadiazole, or
4-5-dimercapto-[1,2,3]-thiadaizole. Typically readily available
materials such as 2,5-dimercapto-1,3,4-thiadiazole or a
hydrocarbyl-substituted 2,5-dimercapto-1,3-4-thiadiazole or a
hydrocarbylthio-substituted 2,5-dimercapto-1,3,4-thiadiazole may be
commonly utilised, with 2,5-dimercapto-[1,3,4]-thiadiazole most
commonly utilised due to availability. In different embodiments the
number of carbon atoms on the hydrocarbyl-substituent group
includes 1 to 30, 2 to 25, 4 to 20, 6 to 16, or 8 to 10.
[0172] In one embodiment, the thiadiazole compound may be the
reaction product of a phenol with an aldehyde and a
dimercaptothiadiazole. The phenol includes an alkyl phenol wherein
the alkyl group contains at least 6, e.g., 6 to 24, or 6 (or 7) to
12 carbon atoms. The aldehyde includes an aldehyde containing 1 to
7 carbon atoms or an aldehyde synthon, such as formaldehyde. Useful
thiadiazole compounds include
2-alkyldithio-5-mercapto-[1,3,4]-thiadiazoles,
2,5-bis(alkyldithio)-[1,3,4]-thiadiazoles,
2-alkylhydroxyphenylmethylthio-5- mercapto-[1,3,4]-thiadiazoles
(such as
245-heptyl-2-hydroxyphenylmethylthio]-5-mercapto-[1,3,4]-thiadiazole),
and mixtures thereof.
[0173] In one embodiment the thiadiazole compound includes at least
one of 2,5-bis(tert-octyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-nonyldithio)-1,3,4-thiadiazole, or
2,5-bis(tert-decyldithio)-1,3,4-thiadiazole.
Polysulphide
[0174] In one embodiment at least 50 wt % of the polysulphide
molecules may be a mixture of tri- or tetra-sulphides. In other
embodiments at least 55 wt %, or at least 60 wt % of the
polysulphide molecules may be a mixture of tri- or
tetra-sulphides.
[0175] The polysulphide includes a sulphurised organic polysulphide
from oils, fatty acids or ester, olefins or polyolefins.
[0176] Oils which may be sulfurized include natural or synthetic
oils such as mineral oils, lard oil, carboxylate esters derived
from aliphatic alcohols and fatty acids or aliphatic carboxylic
acids (e.g., myristyl oleate and oleyl oleate), and synthetic
unsaturated esters or glycerides.
[0177] Fatty acids include those that contain 8 to 30, or 12 to 24
carbon atoms. Examples of fatty acids include oleic, linoleic,
linolenic, and tall oil. Sulphurised fatty acid esters prepared
from mixed unsaturated fatty acid esters such as are obtained from
animal fats and vegetable oils, including tall oil, linseed oil,
soybean oil, rapeseed oil, and fish oil.
[0178] The polysulphide includes olefins derived from a wide range
of alkenes. The alkenes typically have one or more double bonds.
The olefins in one embodiment contain 3 to 30 carbon atoms. In
other embodiments, olefins contain 3 to 16, or 3 to 9 carbon atoms.
In one embodiment the sulphurised olefin includes an olefin derived
from propylene, isobutylene, pentene or mixtures thereof.
[0179] In one embodiment the polysulphide comprises a polyolefin
derived from polymerising by known techniques, an olefin as
described above.
[0180] In one embodiment the polysulphide includes dibutyl
tetrasulphide, sulphurised methyl ester of oleic acid, sulphurised
alkylphenol, sulphurised dipentene, sulphurised dicyclopentadiene,
sulphurised terpene, and sulphurised Diels-Alder adducts;
phosphosulphurised hydrocarbons.
Friction Modifier
[0181] In one embodiment the lubricating composition further
comprises a friction modifier. In different embodiments, the
friction modifier may be present at 0 wt % to 5 wt %, or 0.1 wt %
to 4 wt %, or 0.25 wt % to 3.5 wt %, or 0.5 wt % to 2.5 wt %, or 1
wt % to 2.5 wt %, or 0.05 wt % to 0.5 wt % of the lubricating
composition.
[0182] The friction modifier includes fatty amines, borated
glycerol esters, fatty acid amides, non-borated fatty epoxides,
borated fatty epoxides, alkoxylated fatty amines, borated
alkoxylated fatty amines, metal salts of fatty acids, fatty
imidazolines, metal salts of alkyl salicylates (may also be
referred to as a detergent), metal salts of sulphonates (may also
be referred to as a detergent), condensation products of carboxylic
acids or polyalkylene-polyamines, or amides of hydroxyalkyl
compounds.
[0183] In one embodiment the friction modifer is another type of
fatty acid derivative. In one embodiment the friction modifier
includes a fatty acid ester or partial ester of glycerol. Such a
friction modifier may be in the form of a metal salt, an amide, an
imidazoline, or mixtures thereof. The fatty acids may contain 6 to
24, or 8 to 18 carbon atoms. The fatty acids may be branched or
straight-chain, saturated or unsaturated. Suitable acids include
2-ethylhexanoic, decanoic, oleic, stearic, isostearic, palmitic,
myristic, palmitoleic, linoleic, lauric, and linolenic acids, and
the acids from the natural products tallow, palm oil, olive oil,
peanut oil, corn oil, and Neat's foot oil. In one embodiment the
fatty acid may be oleic acid. When in the form of a metal salt,
typically the metal includes zinc or calcium; and the products
include overbased and non-overbased products. Examples may be
overbased calcium salts and basic oleic acid-zinc salt complexes.
When in the form of an amide, the condensation product includes
those prepared with ammonia, or with primary or secondary amines
such as diethylamine and diethanolamine. When in the form of an
imidazoline, the condensation product of an acid with a diamine or
polyamine such as a polyethylenepolyamine. In one embodiment the
friction modifier may be the condensation product of a fatty acid
with C.sub.8 to C.sub.24 atoms, and a polyalkylene polyamine, and
in particular, the product of isostearic acid with
tetraethylenepentamine.
[0184] In one embodiment the friction modifier includes a secondary
or tertiary amine being represented by the formula
R.sup.aR.sup.bNR.sup.c, wherein R.sup.a and R.sup.b are each
independently an alkyl group of at least 6 carbon atoms and R.sup.c
is hydrogen, a hydrocarbyl group, a hydroxyl-containing alkyl
group, or an amine-containing alkyl group. A more detailed
description of the friction modifier is described in US Patent
Application 2005/037897 in paragraphs 8 and 19 to 22.
[0185] In one embodiment the friction modifier includes those
formed by the condensation of the hydroxyalkyl compound with an
acylating agent or an amine. A more detailed description of the
hydroxyalkyl compound is described in U.S. Patent Application
60/725,360 (filed on Oct. 11, 2005, inventors Bartley, Lahiri,
Baker and Tipton) in paragraphs 8, and 19-21. The friction modifier
disclosed in U.S. Patent Application 60/725,360 includes an amide
represented by the formula R.sup.dR.sup.dN--C(O)R.sup.f, wherein
R.sup.d and R.sup.e are each independently hydrocarbyl groups of at
least 6 carbon atoms and R.sup.f is a hydroxyalkyl group of 1 to 6
carbon atoms or a group formed by the condensation of said
hydroxyalkyl group, through a hydroxyl group thereof, with an
acylating agent. Preparative Examples are disclosed in Examples 1
and 2 (paragraphs 68 and 69 of U.S. Patent Application 60/725,360).
In one embodiment the amide of a hydroxylalkyl compound is prepared
by reacting glycolic acid, that is, hydroxyacetic acid,
HO--CH.sub.2--COOH with an amine.
[0186] In one embodiment the friction modifier includes a reaction
product of a di-cocoalkyl amine (or di-cocoamine) with glycolic
acid. The friction modifier includes compounds prepared in
Preparative Examples 1 and 2 of U.S. Patent Application
60/820,516.
[0187] In one embodiment the friction modifier includes those
derived from the reaction product of a carboxylic acid or a
reactive equivalent thereof with an aminoalcohol, wherein the
friction modifier contains at least two hydrocarbyl groups, each
containing at least 6 carbon atoms. An example of such a friction
modifier includes the reaction product of isostearic acid or an
alkyl succinic anhydride with tris-hydroxymethylaminomethane. A
more detailed description of such a friction modifier is disclosed
in US Patent Application 2003/22000 (or International Publication
WO04/007652) in paragraphs 8 and 9 to 14.
[0188] In one embodiment the friction modifier includes an
alkoxylated alcohol. A detailed description of suitable alkoxylated
alcohols is described in paragraphs 19 and 20 of US Patent
Application 2005/0101497. The alkoxylated amines are also described
in U.S. Pat. No. 5,641,732 in column 7, line 15 to column 9, line
25.
[0189] In one embodiment the friction modifier includes a hydroxyl
amine compound as defined in column 37, line 19, to column 39, line
38 of U.S. Pat. No. 5,534,170. Optionally the hydroxyl amine
includes borated as such products are described in column 39, line
39 to column 40 line 8 of U.S. Pat. No. 5,534,170.
[0190] In one embodiment the friction modifier includes an
alkoxylated amine e.g., an ethoxylated amine derived from 1.8%
Ethomeen T-12 and 0.90% Tomah PA-1 as described in Example E of
U.S. Pat. No. 5,703,023, column 28, lines 30 to 46. Other suitable
alkoxylated amine compounds include commercial alkoxylated fatty
amines known by the trademark "ETHOMEEN" and available from Akzo
Nobel. Representative examples of these ETHOMEEN.TM. materials is
ETHOMEEN.TM. C/12 (bis[2-hydroxyethyl]-coco-amine); ETHOMEEN.TM.
C/20 (polyoxyethylene[10]cocoamine); ETHOMEEN.TM. S/12
(bis[2-hydroxyethyl]soyamine); ETHOMEEN.TM. T/12
(bis[2-hydroxyethyl]-tallow-amine); ETHOMEEN.TM. T/15
(polyoxyethylene-[5]tallowamine); ETHOMEEN.TM. 0/12
(bis[2-hydroxyethyl]oleyl-amine); ETHOMEEN.TM. 18/12
(bis[2-hydroxyethyl]octadecylamine); and ETHOMEEN.TM. 18/25
(polyoxyethylene[15]octadecylamine). Fatty amines and ethoxylated
fatty amines are also described in U.S. Pat. No. 4,741,848.
[0191] In one embodiment the friction modifier includes a polyol
ester as described in U.S. Pat. No. 5,750,476 column 8, line 40 to
column 9, line 28.
[0192] In one embodiment the friction modifier includes a low
potency friction modifier as described in U.S. Pat. No. 5,840,662
in column 2, line 28 to column 3, line 26. U.S. Pat. No. 5,840,662
further discloses in column 3, line 48 to column 6, line 25
specific materials and methods of preparing the low potency
friction modifier.
[0193] In one embodiment the friction modifier includes a reaction
product of an isomerised alkenyl substituted succinic anhydride and
a polyamine as described in U.S. Pat. No. 5,840,663 in column 2,
lines 18 to 43. Specific embodiments of the friction modifier
described in U.S. Pat. No. 5,840,663 are further disclosed in
column 3, line 23 to column 4, line 35. Preparative examples are
further disclosed in column 4, line 45 to column 5, line 37 of U.S.
Pat. No. 5,840,663.
[0194] In one embodiment the friction modifier includes an
alkylphosphonate mono- or di-ester sold commercially by Rhodia
under the trademark Duraphos.RTM. DMODP.
[0195] In one embodiment the friction modifier includes a borated
fatty epoxide or alkylene oxide, known from Canadian Patent No.
1,188,704. These oil-soluble boron-containing compositions may be
prepared by reacting, at a temperature of 80.degree. C. to
250.degree. C., boric acid or boron trioxide with at least one
fatty epoxide or alkylene oxide. The fatty epoxide or alkylene
oxide typically contains at least 8 carbon atoms in the fatty
groups of the epoxide (or the alkylene groups of the alkylene
oxide).
[0196] The borated fatty epoxides include those characterised by
the method for their preparation which involves the reaction of two
materials. Reagent A includes boron trioxide or any of the various
forms of boric acid including metaboric acid (HBO.sub.2),
orthoboric acid (H.sub.3BO.sub.3) and tetraboric acid
(H.sub.2B.sub.4O.sub.7), or orthoboric acid. Reagent B includes at
least one fatty epoxide. The molar ratio of reagent A to reagent B
may be generally 1:0.25 to 1:4, or 1:1 to 1:3, or 1:2. The borated
fatty epoxides includes compounds prepared by blending the two
reagents and heating them at temperature of 80.degree. C. to
250.degree. C., or 100.degree. C. to 200.degree. C., for a period
of time sufficient for reaction to take place. If desired, the
reaction may be effected in the presence of a substantially inert,
normally liquid organic diluent. During the reaction, water is
evolved and may be removed by distillation.
Oils of Lubricating Viscosity
[0197] The lubricating oil composition includes natural or
synthetic oils of lubricating viscosity, oil derived from
hydrocracking, hydrogenation, hydrofinishing, and unrefined,
refined and re-refined oils and mixtures thereof.
[0198] Natural oils include animal oils, vegetable oils, mineral
oils and mixtures thereof. Synthetic oils include hydrocarbon oils,
silicon-based oils, and liquid esters of phosphorus-containing
acids. Synthetic oils may be produced by Fischer-Tropsch
gas-to-liquid synthetic procedure as well as other gas-to-liquid
oils. In one embodiment the composition of the present invention is
useful when employed in a gas-to-liquid oil. Often Fischer-Tropsch
hydrocarbons or waxes may be hydroisomerised.
[0199] In one embodiment the base oil comprises a polyalphaolefin
including a PAO-2, PAO-4, PAO-5, PAO-6, PAO-7 or PAO-8. The
polyalphaolefin in one embodiment is prepared from dodecene and in
another embodiment from decene.
[0200] In one embodiment the oil of lubricating viscosity is an
ester such as an adipate.
[0201] In one embodiment the oil of lubricating viscosity is at
least in-part a polymer (may also be referred to as a viscosity
modifier) including hydrogenated copolymers of styrene-butadiene,
ethylene-propylene copolymers, polyisobutenes, hydrogenated
styrene-isoprene polymers, hydrogenated isoprene polymers,
polymethacrylates, polyacrylates, polyalkyl styrenes, alkenyl aryl
conjugated diene copolymers, polyolefins, esters of maleic
anhydride-styrene copolymers, esters of maleic anhydride-olefin
copolymers, and mixtures thereof. In different embodiments the
polymer includes polyacrylates, polymethacrylates, and esters of
maleic anhydride-styrene copolymers, polyisobutenes or mixtures
thereof.
[0202] In one embodiment the lubricating composition contains an
oil of lubricating viscosity containing mixtures of a viscosity
modifier and an API Group III or IV base oil. In one embodiment the
lubricating composition contains a synthetic oil of lubricating
viscosity.
[0203] Oils of lubricating viscosity may also be defined as
specified in the American Petroleum Institute (API) Base Oil
Interchangeability Guidelines. In one embodiment the oil of
lubricating viscosity comprises an API Group I, II, III, IV, V, VI
base oil, or mixtures thereof, and in another embodiment API Group
II, III, IV base oil or mixtures thereof. In another embodiment the
oil of lubricating viscosity is a Group III or IV base oil and in
another embodiment a Group IV base oil.
[0204] The amount of the oil of lubricating viscosity present is
typically the balance remaining after subtracting from 100 wt % the
sum of the amount of the compounds of the present invention, the
friction modifier, the conventional phosphorus antiwear and/or
extreme pressure agent, the organo-sulphide, and the other
performance additives (described below).
[0205] In one embodiment the lubricating composition may be in the
form of a concentrate and/or a fully formulated lubricant. If the
antiwear package, and the other performance additives may be in the
form of a concentrate (which may be combined with additional oil to
form, in whole or in part, a finished lubricant), the ratio of the
components of the lubricating composition to the oil of lubricating
viscosity and/or to diluent oil include the ranges of 1:99 to 99:1
by weight, or 80:20 to 10:90 by weight.
Other Performance Additive
[0206] The composition of the invention optionally further includes
at least one other performance additive. The other performance
additives include metal deactivators, detergents, dispersants,
viscosity modifiers, dispersant viscosity modifiers, antioxidants,
corrosion inhibitors, foam inhibitors, demulsifiers, pour point
depressants, seal swelling agents, and mixtures thereof.
[0207] In different embodiments, the total combined amount of the
other performance additive compounds may be present at 0 wt % to 25
wt %, or 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, it is common for the other
performance additives to be present in different amounts relative
to each other.
[0208] Antioxidants include molybdenum compounds such as molybdenum
dithiocarbamates, sulphurised olefins, hindered phenols, aminic
compounds such as alkylated diphenylamines (typically di-nonyl
diphenylamine, octyl diphenylamine, or di-octyl diphenylamine), or
mixtures thereof.
[0209] Detergents include neutral or overbased detergents,
Newtonian or non-Newtonian, basic salts of alkali, alkaline earth
or transition metals with one or more of a phenate, a sulphurised
phenate, a sulphonate, a carboxylic acid, a phosphorus acid, a
mono- and/or a di-thiophosphoric acid, a saligenin, an
alkylsalicylate, and a salixarate mixtures.
[0210] Dispersants include N-substituted long chain alkenyl
succinimides, as well as Mannich condensation products as well as
post-treated versions thereof. Post-treated dispersants include
those by reaction with urea, thiourea, dimercaptothiadiazoles,
carbon disulphide, aldehydes, ketones, carboxylic acids,
hydrocarbon-substituted succinic anhydrides, nitriles, epoxides,
boron compounds, and phosphorus compounds, mixtures.
[0211] In one embodiment the dispersant is a borated dispersant,
typically a borated polyisobutylene succinimide. Typically the
number average molecular weight of the polyisobutylene ranges from
450 to 5000, or 550 to 2500. The borated dispersant may also have
friction performance.
[0212] In different embodiments, the dispersant may present at 0 wt
% to 10 wt %, or 0.01 wt % to 10 wt %, or 0.1 wt % to 5 wt %, of
the lubricating composition.
[0213] Viscosity modifiers include hydrogenated copolymers of
styrene-butadiene, ethylene-propylene copolymers, polyisobutenes,
hydrogenated styrene-isoprene polymers, hydrogenated isoprene
polymers, polymethacrylates, polyacrylates, polyalkyl styrenes,
hydrogenated alkenyl aryl conjugated diene copolymers, polyolefins,
esters of maleic anhydride-styrene copolymers, esters of maleic
anhydride-olefin copolymers, or mixtures thereof.
[0214] In one embodiment the viscosity modifier is other than
olefin copolymers, typically ethylene-propylene copolymers.
[0215] In one embodiment the viscosity modifier includes
polyisobutenes, polymethacrylates, polyacrylates, esters of maleic
anhydride-styrene copolymers, esters of maleic anhydride-olefin
copolymers, or mixtures thereof.
[0216] In one embodiment the viscosity modifier includes
polymethacrylates.
[0217] In different embodiments, the viscosity modifier may be
present at 0 wt % to 70 wt %, or 1 wt % to 65 wt %, or 5 wt % to 60
wt %, or greater than 12 wt % to 55 wt % of the lubricating
composition.
[0218] If viscosity modifiers with a low number average molecular
weight (i.e., 20,000 or less) are employed, higher treatment rates
are typically required. In some instances the treat rate may be
sufficiently high that the viscosity modifier becomes a significant
replacement for base oil (or the oil of lubricating viscosity). As
such the viscosity modifiers may be viewed as a synthetic base
stock, or as a component of the base oil.
[0219] Dispersant viscosity modifiers (often referred to as DVM)
include functionalised polyolefins, for example, ethylene-propylene
copolymers that have been functionalized with the reaction product
of maleic anhydride and an amine, a polymethacrylate functionalised
with an amine, or styrene-maleic anhydride copolymers reacted with
an amine; these may also be used in the composition of the
invention.
[0220] Corrosion inhibitors include octylamine octanoate,
condensation products of dodecenyl succinic acid or anhydride and a
fatty acid such as oleic acid with a polyamine, or a thiadiazole
compound described above. Metal deactivators include derivatives of
benzotriazoles (typically tolyltriazole), 1,2,4-triazoles,
2-alkyldithiobenzimidazoles, 2-alkyldithiobenzothiazoles, or
benzimidazoles.
[0221] Foam inhibitors include copolymers of ethyl acrylate and
2-ethylhexylacrylate 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. Seal swell agents include Exxon Necton-37.TM. (FN
1380) and Exxon Mineral Seal Oil (FN 3200).
Industrial Application
[0222] The method of the invention may be useful for lubricating a
variety of driveline devices. The driveline device comprises at
least one of a gear, a gearbox, an axle gear, a traction drive
transmission, an automatic transmission or a manual transmission.
In one embodiment the driveline device may be a manual transmission
or a gear, a gearbox, or an axle gear.
[0223] The automatic transmission includes continuously variable
transmissions (CVT), infinitely variable transmissions (IVT),
Toroidal transmissions, continuously slipping torque converted
clutches (CSTCC), stepped automatic transmissions or dual clutch
transmissions (DCT).
[0224] The following examples provide illustrations of the
invention. These examples are non-exhaustive and are not intended
to limit the scope of the invention.
EXAMPLES
[0225] Gear Oil Lubricants (CE1 to CE3 and EX1 to EX2): A series of
gear oil lubricants are prepared containing a blend of base oils
(40 wt % Yubase 4, 40 wt % polyalphaolefin, 10 wt % 2-ethylhexyl
adipate), and a gear oil concentrate. The gear oil concentrate once
blended comprises 1.2 wt % of borated dispersant (including
conventional amounts of diluent), 0.1 wt % of
2,5-bis(tert-nonyldithio)-1,3,4-thiadiazole, and 3 wt % of
sulphurised olefin. In addition the gear oil lubricants contain
components as summarised in the following below.
TABLE-US-00001 Isotridecyl Phosphorus Amount of Amount of Tartrate
Content THP (wt %) HP (wt %) (wt %) (ppm) CE1 0.59 0 0 500 CE2 0
0.63 0 500 EX1 0.59 0 1 500 EX2 0.63 1 500 CE3 0 0 1 0
Footnote:
[0226] THP is the product of Preparative Example 5. [0227] HP is a
Phosphoric Acid product from one of the Preparative Examples 1 to
4, or Preparative Examples 6 to 8 (see preparative examples
above).
[0228] The gear oils are tested for performance at high speed, low
torque, followed by low speed, high torque. The methodology is the
same as ASTM [0229] D6121. The results obtained are:
TABLE-US-00002 [0229] Types of Distress Measured on Ring and Pinion
Wear Rippling Ridging Pitting/Spalling Scoring CE1 Ring 7 8 5 9.9
10 Pinion 5 9 5 9.4 10 CE2 Ring 7 10 5 9.9 10 Pinion 6 9 5 9.7 10
EX1 Ring 7 10 9 9.9 10 Pinion 7 9 9 9.9 10 EX2 Ring 7 10 10 9.9 10
Pinion 7 8 9 9.9 10 CE3 Ring 6 10 5 9.7 10 Pinion 5 10 4 4 10
[0230] Overall the results indicate that the lubricating
composition of the invention is capable of providing a gear oil
with acceptable levels of wear performance, particularly for
ridging protection for both ring and pinion. In addition, the
lubricating composition of the invention is capable of providing a
gear oil with acceptable levels of wear protection whilst
maintaining protection against rippling and pitting/spalling.
[0231] It is known that some of the materials described above may
interact in the final formulation, so that the components of the
final formulation may be different from those that are initially
added. The products formed thereby, including the products formed
upon employing lubricant composition of the present invention in
its intended use, may not be susceptible of easy description.
Nevertheless, all such modifications and reaction products are
included within the scope of the present invention; the present
invention encompasses lubricant composition prepared by admixing
the components described above.
[0232] Each of the documents referred to above is incorporated
herein by reference. Except in the Examples, or where otherwise
explicitly indicated, all numerical quantities in this description
specifying amounts of materials, reaction conditions, molecular
weights, number of carbon atoms, and the like, are to be understood
as modified by the word "about." Unless otherwise indicated, each
chemical or composition referred to herein should be interpreted as
being a commercial grade material which may contain the isomers,
by-products, derivatives, and other such materials which are
normally understood to be present in the commercial grade. The
amount of each chemical component is presented inclusive of any
solvent or diluent oil, which may be customarily present in the
commercial material, unless otherwise indicated. It is to be
understood that the upper and lower amount, range, and ratio limits
set forth herein may be independently combined. Similarly, the
ranges and amounts for each element of the invention may be used
together with ranges or amounts for any of the other elements.
[0233] As used herein, the term "hydrocarbyl substituent" or
"hydrocarbyl group" is used in its ordinary sense, which is
well-known to those skilled in the art. Specifically, it refers to
a group having a carbon atom directly attached to the remainder of
the molecule and having predominantly hydrocarbon character.
Examples of hydrocarbyl groups include:
[0234] (i) hydrocarbon substituents, that is, aliphatic (e.g.,
alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl)
substituents, and aromatic-, aliphatic-, and alicyclic-substituted
aromatic substituents, as well as cyclic substituents wherein the
ring is completed through another portion of the molecule (e.g.,
two substituents together form a ring);
[0235] (ii) 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 sulphoxy);
[0236] (iii) hetero substituents, that is, substituents which,
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
[0237] (iv) heteroatoms include sulphur, oxygen, nitrogen, and
encompass substituents as pyridyl, furyl, thienyl and imidazolyl.
In general, no more than two, preferably no more than one,
non-hydrocarbon substituent will be present for every ten carbon
atoms in the hydrocarbyl group; typically, there will be no
non-hydrocarbon substituents in the hydrocarbyl group.
[0238] While the invention has been explained in relation to its
preferred embodiments, it is to be understood that various
modifications thereof will become apparent to those skilled in the
art upon reading the specification. Therefore, it is to be
understood that the invention disclosed herein is intended to cover
such modifications as fall within the scope of the appended
claims.
* * * * *