U.S. patent application number 14/690588 was filed with the patent office on 2015-08-13 for antiwear composition and method of lubricating driveline device.
The applicant listed for this patent is The Lubrizol Corporation. Invention is credited to Mark R. Baker, Vera M. Marsic, Morey N. Najman.
Application Number | 20150225667 14/690588 |
Document ID | / |
Family ID | 49670983 |
Filed Date | 2015-08-13 |
United States Patent
Application |
20150225667 |
Kind Code |
A1 |
Najman; Morey N. ; et
al. |
August 13, 2015 |
ANTIWEAR COMPOSITION AND METHOD OF LUBRICATING DRIVELINE DEVICE
Abstract
The present invention relates to an antiwear agent and
lubricating compositions thereof. The invention further provides
for a method of lubricating a driveline device application by
employing a lubricating composition containing the antiwear
agent.
Inventors: |
Najman; Morey N.; (Midland,
MI) ; Baker; Mark R.; (Midland, MI) ; Marsic;
Vera M.; (Mentor, OH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Lubrizol Corporation |
Wickliffe |
OH |
US |
|
|
Family ID: |
49670983 |
Appl. No.: |
14/690588 |
Filed: |
April 20, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13959982 |
Aug 6, 2013 |
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14690588 |
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13390790 |
May 8, 2012 |
8951943 |
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PCT/US2010/045145 |
Aug 11, 2010 |
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13959982 |
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61234722 |
Aug 18, 2009 |
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Current U.S.
Class: |
508/192 ;
508/273; 508/434; 508/437 |
Current CPC
Class: |
C10M 2215/223 20130101;
C10M 2207/289 20130101; C10N 2040/04 20130101; C10N 2030/54
20200501; C10M 2207/282 20130101; C10M 2219/08 20130101; C10N
2030/76 20200501; C10M 141/10 20130101; C10M 2223/043 20130101;
C10M 2223/047 20130101; C10M 2215/28 20130101; C10M 2223/049
20130101; C10N 2030/06 20130101; C10M 161/00 20130101; C10N 2030/10
20130101; C10M 2219/106 20130101 |
International
Class: |
C10M 161/00 20060101
C10M161/00 |
Claims
1. 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) 0.01 wt % to 3 wt % of a derivative
of a hydroxycarboxylic acid, wherein the derivative of a
hydroxycarboxylic acid is represented by the formula: ##STR00004##
wherein n=2, m=1, or n and m both equal 2, or n=3, m=1; X is an
aliphatic or alicyclic group, or an aliphatic or alicyclic group
containing an oxygen atom in the carbon chain, or a substituted
group of the foregoing types, said group containing up to 6 carbon
atoms and having n+m available points of attachment; each Y is
independently --O--; and each R and R.sup.1 are independently
hydrogen or a hydrocarbyl group, provided that at least one R or
R.sup.1 group is a hydrocarbyl group; each R.sup.2 is independently
hydrogen, a hydrocarbyl group or an acyl group, further provided
that at least one --OR.sup.2 group is located on a carbon atom
within X that is .alpha. or .beta. to at least one of the
--C(O)--Y--R groups, and (b) 0.05 wt % to 2 wt % of a phosphorus
compound, wherein the phosphorus compound is an amine salt of a
phosphate hydrocarbon ester represented by the formula:
##STR00005## wherein R.sup.3 and R.sup.4 are independently hydrogen
or hydrocarbon containing 8 to 18 carbon atoms, with the proviso
that at least one is a hydrocarbon group; and R.sup.5, R.sup.6,
R.sup.7 and R.sup.8 independently hydrogen or a hydrocarbyl group,
with the proviso that at least one is a hydrocarbyl group.
2. The method of claim 1, wherein the hydroxy-carboxylic acid is
tartaric acid or citric acid.
3. The method of claim 1, wherein the hydroxy-carboxylic acid is
present at 0.01 wt % to 1 wt % of the lubricating composition.
4. The method of claim 1, wherein the hydroxy-carboxylic acid is
present at 0.1 wt % to 0.2 wt % of the lubricating composition.
5. The method of claim 1, wherein the phosphorus compound is a
mixture of an amine salt of a phosphate hydrocarbon ester, and a
phosphite having at least one hydrocarbyl group with 4 or more
carbon atoms.
6. The method of claim 5, wherein the phosphite is a
mono-hydrocarbyl substituted phosphite, a di-hydrocarbyl
substituted phosphite, or a tri-hydrocarbyl substituted
phosphite.
7. The method of claim 5, wherein the phosphite having at least one
hydrocarbyl group with 4 or more carbon atoms is represented by the
formulae: ##STR00006## wherein at least two of R.sup.9, R.sup.10
and R.sup.11 may be a hydrocarbyl group containing at least 4
carbon atoms and the other may be hydrogen or a hydrocarbyl
group.
8. The method of claim 1, wherein the phosphorus compound is
present at 0.1 wt % to 1 wt % of the lubricating composition.
9. The method of claim 1, wherein the phosphorus compound is
present at 0.2 wt % to 0.4 wt % of the lubricating composition.
10. The method of claim 1 further comprising 0.1 wt % to 5 wt % of
a borated polyisobutylene succinimide, or a dimercaptothiadiazole
derivative of a polyisobutylene succinimide.
11. The method of claim 1, wherein (a) the derivative of a
hydroxycarboxylic acid is present at 0.01 wt % to 1 wt % of the
lubricating composition; and (b) wherein the phosphorus compound is
present at 0.05 wt % to 2 wt % of the lubricating composition.
12. The method of claim 1, wherein (a) the derivative of a
hydroxycarboxylic acid is present at 0.05 wt % to 0.5 wt % of the
lubricating composition; and (b) wherein the phosphorus compound is
present at 0.1 wt % to 1 wt % of the lubricating composition.
Description
FIELD OF INVENTION
[0001] The present invention relates to an antiwear agent and
lubricating compositions thereof. The invention further provides
for a method of lubricating a driveline device by employing a
lubricating composition described herein.
BACKGROUND OF THE INVENTION
[0002] One of the important parameters influencing durability or
wear resistance of devices employing a lubricating composition 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 of the sulphur-containing antiwear or
extreme pressure additives evolve volatile sulphur species,
resulting in lubricating compositions containing antiwear or
extreme pressure additives having an odour, which may also be
detrimental to the environment or evolve emissions that may be
higher than increasingly tighter health and safety legislation
specifies.
[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 at least one of (i) limited extreme
pressure and antiwear performance over a wide range of operating
conditions, (ii) limited oxidative stability, (iii) form deposits,
or (iv) cause corrosion (for example copper 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] International publication WO 2008/070307 discloses malonate
esters suitable as antiwear agents.
[0009] International Patent application WO U.S. Ser. No. 09/036,623
(Filed Mar. 10, 2009 by Najman) discloses a driveline device
lubricated with a composition containing a derivative of a
hydroxycarboxylic acid and 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.
[0010] 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.
[0011] 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
[0012] The inventors of 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
wear), and (vi) deposit control. Wear may include reduced rippling,
ridging and scoring. The wear may be observed on a ring and/or
pinion of a driveline device.
[0013] In one embodiment the invention provides 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 selected from the group consisting of an amine salt of a
phosphate hydrocarbon ester, a phosphite having at least one
hydrocarbyl group with 4 or more carbon atoms, and mixtures
thereof. In one embodiment the phosphorus compound is a mixture of
an amine salt of a phosphate hydrocarbon ester, and a phosphite
having at least one hydrocarbyl group with 4 or more carbon
atoms.
[0014] 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) a derivative of a hydroxycarboxylic acid, and
(b) a phosphorus compound selected from the group consisting of an
amine salt of a phosphate hydrocarbon ester, a phosphite having at
least one hydrocarbyl group with 4 or more carbon atoms, having at
least one hydrocarbyl group with 4 or more carbon atoms, and
mixtures thereof.
[0015] In one embodiment the derivatives of hydroxycarboxylic acid
include imides, di-esters, di-amides, ester-amides derivatives of
tartaric acid.
[0016] In one embodiment the phosphorus compound may be an amine
salt of a phosphate hydrocarbon ester, or mixtures thereof.
[0017] In one embodiment the lubricating composition disclosed
herein contains
[0018] (a) the derivative of a hydroxycarboxylic acid present at
0.01 wt % to 3 wt %, or 0.01 wt % to 1 wt %, or 0.05 wt % to 0.5 wt
%, or 0.1 wt % to 0.2 wt % (typically 0.05 wt % to 0.5 wt %) of the
lubricating composition; and
[0019] (b) the phosphorus compound present at 0.01 wt % to 5 wt %,
or 0.05 wt % to 2 wt %, or 0.1 wt % to 1 wt %, or 0.2 wt % to 0.4
wt % (typically 0.1 wt % to 1 wt %) of the lubricating
composition.
[0020] 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.
[0021] In different embodiments 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.
[0022] 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 wear reducing or preventing), and
(vii) deposit control.
DETAILED DESCRIPTION OF THE INVENTION
[0023] The present invention provides a lubricating composition;
and a method for lubricating a driveline device as disclosed
above.
Compound Derived from Hydroxy-Carboxylic Acid
[0024] The invention provides a lubricating composition containing
a compound derived from a hydroxy-carboxylic acid. The compound
derived from a hydroxy-carboxylic acid may be represented by the
formula:
##STR00001##
wherein n and m may be independently integers of 1 to 5; X may be
an aliphatic or alicyclic group, or an aliphatic or alicyclic group
containing an oxygen atom in the carbon chain, or a substituted
group of the foregoing types, said group containing up to 6 carbon
atoms and having n+m available points of attachment; each Y may be
independently --O--, or >NR.sup.1 or two Ys together may
represent the nitrogen of an imide structure R--N< formed
between two carbonyl groups; and each R and R.sup.1 may be
independently hydrogen or a hydrocarbyl group, provided that at
least one R or R.sup.1 group is a hydrocarbyl group; each R.sup.2
may be independently hydrogen, a hydrocarbyl group or an acyl
group, further provided that at least one --OR.sup.2 group is
located on a carbon atom within X that is .alpha. or .beta. to at
least one of the --C(O)--Y--R groups.
[0025] The compound derived from the hydroxy-carboxylic acid may be
derived from glycolic acid (n and m both equal 1), malic acid (n=2,
m=1), tartaric acid (n and m both equal 2), citric acid (n=3, m=1),
or mixtures thereof. In one embodiment the compound derived from
the hydroxy-carboxylic acid may be derived from tartaric acid or
citric acid. In one embodiment the compound derived from the
hydroxy-carboxylic acid may be derived from tartaric acid.
[0026] The compound derived from the hydroxy-carboxylic acid may be
an amide, ester or imide derivative of a hydroxy-carboxylic acid,
or mixtures thereof. In one embodiment the compound derived from
the hydroxy-carboxylic acid may be an amide, ester or imide
derivative of a hydroxy-carboxylic acid. For example the compound
derived from the hydroxy-carboxylic acid may an ester or imide of
tartaric acid, or the compound derived from the hydroxy-carboxylic
acid may an ester or imide of citric acid.
[0027] In one embodiment the compound derived from the
hydroxy-carboxylic acid may be 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
mono-imide, a hydroxy-carboxylic acid ester-amide, a
hydroxy-carboxylic acid ester-imide, and a hydroxy-carboxylic acid
imide-amide. In one embodiment the amide, ester or imide derivative
of a hydroxy-carboxylic acid may derived from at least one of the
group consisting of a hydroxy-carboxylic acid di-ester, a
hydroxy-carboxylic acid di-amide, a hydroxy-carboxylic acid
mono-imide, and a hydroxy-carboxylic acid ester-amide.
[0028] Each R, R.sup.1 and R.sup.2 group of the compound derived
from the hydroxy-carboxylic acid may be a linear or branched alkyl
group each having 1 to 150, or 8 to 30, or 8 to 20 carbon atoms.
The ester derivatives of the hydroxy-carboxylic acid may be formed
by the reaction of an alcohol with hydroxy-carboxylic acid. The
alcohol includes both monohydric alcohols and polyhydric alcohols.
The carbon atoms of the alcohol may be linear chains, branched
chains, or mixtures thereof.
[0029] Examples of a suitable branched alcohol include
2-ethylhexanol, iso-tridecanol, iso-octyl alcohol, Guerbet
alcohols, or mixtures thereof
[0030] 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 8 to 20 carbon atoms.
[0031] In one embodiment the imide derivatives of a
hydroxy-carboxylic acid may be tartrimides, typically containing 8
to 20 carbon atoms. Amines used to prepare imides may include alkyl
amines (such as n-hexylamine (caproylamine), n-octylamine
(caprylylamine), n-decylamine (caprylamine), n-dodecylamine
(laurylamine), n-tetradecylamine (myristylamine),
n-pentadecylamine, n-hexadecylamine (palmitylamine), margarylamine,
n-octadecylamine (stearylamine)), unsaturated amines (such as
dodecenylamine, myristoleylamine, palmitoleylamine, oleylamine, and
linoleylamine), or etheramines (such as those identified as
SURFAM.TM. P14AB (branched C14), SURFAM.TM. P16A (linear C16), and
SURFAM.TM. P17AB (branched C17)). 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.
[0032] US Patent Applications U.S. 60/939,949 (filed May 24, 2007)
and U.S. 60/939,952 (filed May 24, 2007) disclose in more detail
useful hydroxycarboxylic acid compounds for the present
invention.
[0033] Canadian Patent 1 183 125; 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 useful
examples of suitable tartaric acid derivatives.
[0034] The compound derived from the hydroxy-carboxylic acid may be
present at 0.01 wt % to 3 wt %, or 0.01 wt % to 1 wt %, or 0.05 wt
% to 0.5 wt %, or 0.1 wt % to 0.2 wt % of the lubricating
composition.
Phosphorus Compound
[0035] The phosphorus compound may be selected from the group
consisting of an amine salt of a phosphate hydrocarbon ester, a
phosphite having at least one hydrocarbyl group with 4 or more
carbon atoms, having at least one hydrocarbyl group with 4 or more
carbon atoms, and mixtures thereof.
[0036] In one embodiment the phosphorus compound is sulphur-free
i.e., the phosphorus compound is not a thiophosphite, nor a
thiophosphate.
[0037] The phosphorus compound may be present at 0.01 wt % to 5 wt
%, or 0.05 wt % to 2 wt %, or 0.1 wt % to 1 wt %, or 0.2 wt % to
0.4 wt % of the lubricating composition. The amount of phosphorus
provided to the lubricating composition by the phosphorus compound
may, in certain embodiments, be 0.001 to 0.5 wt %, or 0.005 to 0.2
wt %, or 0.01 to 0.1 wt % or 0.02 to 0.04 wt %.
Amine Salt of a Phosphate Hydrocarbon Ester
[0038] In one embodiment the lubricating composition contains a
phosphorus compound that may be an amine salt of a phosphate
hydrocarbon ester (i.e., an amine salt of a hydrocarbon ester of
phosphoric acid). The amine salt of a phosphate hydrocarbon ester
may be derived from an amine salt of a phosphate. The amine salt of
the phosphate hydrocarbon ester may be represented by the
formula:
##STR00002##
wherein R.sup.3 and R.sup.4 may be independently hydrogen or
hydrocarbon typically containing 4 to 40, or 6 to 30, or 6 to 18,
or 8 to 18 carbon atoms, with the proviso that at least one is a
hydrocarbon group; and R.sup.5, R.sup.6, R.sup.7 and R.sup.8 may be
independently hydrogen or a hydrocarbyl group, with the proviso
that at least one is a hydrocarbyl group.
[0039] The hydrocarbon groups of R.sup.3 and/or R.sup.4 may be
linear, branched, or cyclic.
[0040] Examples of a hydrocarbon group for R.sup.3 and/or R.sup.4
include straight-chain or branched alkyl groups include methyl,
ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,
undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,
heptadecyl and octadecyl.
[0041] Examples of a cyclic hydrocarbon group for R.sup.3 and/or
R.sup.4 include cyclopentyl, cyclohexyl, cycloheptyl,
methylcyclopentyl, dimethylcyclopentyl, methylcyclopentyl,
dimethylcyclopentyl, methylethylcyclopentyl, diethyl-cyclopentyl,
methylcyclohexyl, dimethylcyclohexyl, methylethylcyclohexyl,
diethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl,
methylethyl-cycloheptyl, and diethylcycloheptyl.
[0042] In one embodiment the phosphate may be an amine salt of a
mixture of monoalkyl and dialkyl phosphoric acid esters. The
monoalkyl and dialkyl groups may be linear or branched.
[0043] The amine salt of a phosphate hydrocarbon ester may be
derived from an amine such as a primary amine, a secondary amine, a
tertiary amine, or mixtures thereof. The amine may be aliphatic, or
cyclic, aromatic or non-aromatic, typically aliphatic. In one
embodiment the amine includes an aliphatic amine such as a
tertiary-aliphatic primary amine.
[0044] Examples of suitable primary amines include ethylamine,
propylamine, butylamine, 2-ethylhexylamine,
bis-(2-ethylhexyl)amine, 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.
[0045] Examples of suitable secondary amines include dimethylamine,
diethylamine, dipropylamine, dibutylamine, diamylamine,
dihexylamine, diheptylamine, methylethylamine, ethylbutylamine,
N-methyl-1-amino-cyclohexane, Armeen.RTM. 2C and ethylamylamine.
The secondary amines may be cyclic amines such as piperidine,
piperazine and morpholine.
[0046] Examples of tertiary amines include tri-n-butylamine,
tri-n-octylamine, tri-decylamine, tri-laurylamine,
tri-hexadecylamine, and dimethyloleylamine (Armeen.RTM. DMOD).
[0047] In one embodiment the amines are in the form of a mixture.
Examples of suitable mixtures of amines include (i) a tertiary
alkyl primary amine with 11 to 14 carbon atoms, (ii) a tertiary
alkyl primary amine with 14 to 18 carbon atoms, or (iii) a tertiary
alkyl primary amine with 18 to 22 carbon atoms. 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.
[0048] In one embodiment a useful mixture of amines is
"Primene.RTM. 81R" or "Primene.RTM. JMT." Primene.RTM. 81R and
Primene.RTM. JMT (both produced and sold by Rohm & Haas) are
mixtures of C11 to C14 tertiary alkyl primary amines and C18 to C22
tertiary alkyl primary amines respectively.
[0049] The amine salt of a phosphate hydrocarbon ester may be
prepared as is described in U.S. Pat. No. 6,468,946. Column 10,
lines 15 to 63 describes phosphoric acid esters formed by reaction
of phosphorus compounds, followed by reaction with an amine to form
an amine salt of a phosphate hydrocarbon ester. Column 10, line 64,
to column 12, line 23, describes preparative examples of reactions
between phosphorus pentoxide with an alcohol (having 4 to 13 carbon
atoms), followed by a reaction with an amine (typically
Primene.RTM. 81-R) to form an amine salt of a phosphate hydrocarbon
ester.
Phosphite
[0050] In one embodiment the lubricating composition contains a
phosphite having at least one hydrocarbyl group with 4 or more
carbon atoms. In one embodiment the lubricating composition
contains a phosphite having at least one hydrocarbyl group with 8
or more, or 12 or more carbon atoms. Typical ranges for the number
of carbon atoms on the hydrocarbyl group include 4 to 30, or 10 to
24, or 12 to 22, or 14 to 20, or 16 to 18. The phosphite may be a
mono-hydrocarbyl substituted phosphite, a di-hydrocarbyl
substituted phosphite, or a tri-hydrocarbyl substituted
phosphite.
[0051] The phosphite having at least one hydrocarbyl group with 4
or more carbon atoms may be represented by the formulae:
##STR00003##
wherein at least one or two of R.sup.9, R.sup.10 and R.sup.11 may
be a hydrocarbyl group containing at least 4 carbon atoms and the
other may be hydrogen or a hydrocarbyl group. In one embodiment two
or more of R.sup.9, R.sup.10 and R.sup.11 are hydrocarbyl groups.
The hydrocarbyl groups may be alkyl, cycloalkyl, aryl, acyclic or
mixtures thereof. In the formula with all thee groups R.sup.9,
R.sup.10 and R.sup.11, the compound may be a tri-hydrocarbyl
substituted phosphite i.e., R.sup.9, R.sup.10 and R.sup.11 are all
hydrocarbyl groups.
[0052] Alkyl groups may be linear or branched, typically linear,
and saturated or unsaturated, typically saturated. Examples of
alkyl groups for R.sup.9, R.sup.10 and R.sup.11 include butyl,
hexyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl,
tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,
octadecenyl, nonodecyl, eicosyl or mixtures thereof.
[0053] Alkyl groups may be linear or branched, typically linear,
and saturated or unsaturated, typically saturated. Examples of
alkyl groups for R.sup.9, R.sup.10 and R.sup.11 include butyl,
hexyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl,
tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,
octadecenyl, nonodecyl, eicosyl or mixtures thereof. In one
embodiment the alkyl groups R.sup.9 and R.sup.10 have 4 carbon
atoms (typically n-butyl).
[0054] The amine salt of a phosphate hydrocarbon ester and/or, a
phosphite having at least one hydrocarbyl group with 4 or more
carbon atoms may in one embodiment be in a mixture with one or more
of phosphorus acid, phosphoric acid, polyphosphoric acid, a
trialkyl phosphate or trialkyl thiophosphate. For instance the
amine salt of a phosphate hydrocarbon ester and/or, a phosphite
having at least one hydrocarbyl group with 4 or more carbon atoms
may in one embodiment be in a mixture with phosphoric acid.
Oils of Lubricating Viscosity
[0055] The lubricating composition comprises an oil of lubricating
viscosity. Such oils include natural and synthetic oils, oil
derived from hydrocracking, hydrogenation, and hydrofinishing,
unrefined, refined, re-refined oils or mixtures thereof. A more
detailed description of unrefined, refined and re-refined oils is
provided in International Publication WO2008/147704, paragraphs
[0054] to
[0056] A more detailed description of natural and synthetic
lubricating oils is described in paragraphs [0058] to [0059]
respectively of WO2008/147704. Synthetic oils may also be produced
by Fischer-Tropsch reactions and typically may be hydroisomerised
Fischer-Tropsch hydrocarbons or waxes. In one embodiment oils may
be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure
as well as other gas-to-liquid oils.
[0057] Oils of lubricating viscosity may also be defined as
specified in April 2008 version of "Appendix E--API Base Oil
Interchangeability Guidelines for Passenger Car Motor Oils and
Diesel Engine Oils", section 1.3 Sub-heading 1.3. "Base Stock
Catagories". In one embodiment the oil of lubricating viscosity may
be an API Group I, or Group II, or Group III, or Group IV oil. In
one embodiment the oil of lubricating viscosity may be an API Group
II or Group III oil. In one embodiment the oil of lubricating
viscosity may be a hydrocracked or severely hydrocracked base stock
and/or an API Group II or Group III oil.
[0058] 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 compound of the invention and the other
performance additives.
[0059] The lubricating composition may be in the form of a
concentrate and/or a fully formulated lubricant. If the lubricating
composition of the invention (comprising the additives disclosed
herein) is 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 of these additives 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.
Organo-Sulphide
[0060] 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.
[0061] In different embodiments, the organo-sulphide is present in
a range selected from the group consisting of 0 wt % to 10 wt %,
0.01 wt % to 10 wt %, 0.1 wt % to 8 wt %, and 0.25 wt % to 6 wt %;
of the lubricating composition.
Thiadiazole Compound
[0062] 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. These
thiadiazole compounds may also be used in the post treatment of
dispersants as mentioned below in the formation of a
dimercaptothiadiazole derivative of a polyisobutylene
succinimide.
[0063] 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]-thiadiazole. 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 are
commonly utilised. 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.
[0064] In one embodiment, the thiadiazole compound is 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
2-[5-heptyl-2-hydroxyphenylmethylthio]-5-mercapto-[1,3,4]-thiadiazole),
and mixtures thereof.
[0065] 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
[0066] In one embodiment at least 50 wt % of the polysulphide
molecules are a mixture of tri- or tetra-sulphides. In other
embodiments at least 55 wt %, or at least 60 wt % of the
polysulphide molecules are a mixture of tri- or
tetra-sulphides.
[0067] The polysulphide includes a sulphurised organic polysulphide
from oils, fatty acids or ester, olefins or polyolefins.
[0068] 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.
[0069] 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.
[0070] 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.
[0071] In one embodiment the polysulphide comprises a polyolefin
derived from polymerising by known techniques, an olefin as
described above.
[0072] 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.
Friction Modifier
[0073] In one embodiment the lubricating composition further
comprises a friction modifier. In different embodiments, the
friction modifier is present in a range selected from the group
consisting of 0 wt % to 5 wt %, 0.1 wt % to 4 wt %, 0.25 wt % to
3.5 wt %, 0.5 wt % to 2.5 wt %, and 1 wt % to 2.5 wt %, or 0.05 wt
% to 0.5 wt % of the lubricating composition.
[0074] 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.
[0075] In one embodiment the friction modifier includes a fatty
acid ester of glycerol. The final product 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 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 is 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 are
overbased calcium salts and basic oleic acid-zinc salt complexes
which can be represented by the general formula
Zn.sub.4Oleate.sub.6O. 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 is
the condensation product of a fatty acid with C8 to C24 atoms, and
a polyalkylene polyamine, and in particular, the product of
isostearic acid with tetraethylenepentamine.
[0076] 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 WO 2007/0044820 paragraphs 9,
and 20-22. The friction modifier disclosed in WO2007/044820
includes an amide represented by the formula
R.sup.12R.sup.13N--C(O)R.sup.14, wherein R.sup.12 and R.sup.13 are
each independently hydrocarbyl groups of at least 6 carbon atoms
and R.sup.14 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
72 and 73 of WO2007/044820). 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.
[0077] In one embodiment the friction modifier includes a secondary
or tertiary amine being represented by the formula
R.sup.15R.sup.16NR.sup.17, wherein R.sup.15 and R.sup.16 are each
independently an alkyl group of at least 6 carbon atoms and
R.sup.17 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.
[0078] 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 WO 2008/014319.
[0079] 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.
[0080] 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.
[0081] 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.
[0082] In one embodiment the friction modifier includes an
alkoxylated amine e.g., an ethoxylated amine derived from 1.8%
Ethomeen.TM. T-12 and 0.90% Tomah.TM. 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.
[0083] 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.
[0084] 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.
[0085] 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.
[0086] In one embodiment the friction modifier includes an
alkylphosphonate mono- or di-ester sold commercially by Rhodia
under the trademark Duraphos.RTM. DMODP.
[0087] 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 are
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).
[0088] 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.40.sub.7), or orthoboric acid. Reagent B includes at
least one fatty epoxide. The molar ratio of reagent A to reagent B
is generally 1:0.25 to 1:4, or 1:1 to 1:3, or 1:1 to 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.
Other Performance Additive
[0089] 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.
[0090] In different embodiments, the total combined amount of the
other performance additive compounds is present in a range selected
from the group consisting of 0 wt % to 25 wt %, 0.1 wt % to 15 wt
%, and 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.
[0091] 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).
[0092] 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.
[0093] Dispersants are known and include for example an
N-substituted long chain alkenyl succinimide, a Mannich base, or
mixtures thereof. Examples of N-substituted long chain alkenyl
succinimides include polyisobutylene succinimide, wherein the
polyisobutylene from which the polyisobutylene succinic anhydride
is derived has a number average molecular weight in the range of
350 to 5000, or 500 to 3000, or 750 to 1150.
[0094] The dispersants may also be post-treated by conventional
methods by a reaction with any of a variety of agents. Among these
are boron compounds (such as boric acid), urea, thiourea,
dimercaptothiadiazoles, carbon disulphide, aldehydes, ketones,
carboxylic acids such as terephthalic acid, hydrocarbon-substituted
succinic anhydrides, maleic anhydride, nitriles, epoxides, and
phosphorus compounds. In one embodiment the post-treated dispersant
may be a borated dispersant such as a borated polyisobutylene
succinimide. In one embodiment the post-treated dispersant may be
made by reaction with a dimercaptothiadiazole (to form a dispersant
such as a dimercaptothiadiazole derivative of a polyisobutylene
succinimide).
[0095] In different embodiments, the dispersant is present in a
range selected from the group consisting of 0 wt % to 10 wt %, 0.01
wt % to 10 wt %, and 0.1 wt % to 5 wt %, of the lubricating
composition.
[0096] Viscosity modifiers include hydrogenated copolymers of
styrene-butadiene, ethylene-propylene copolymers, polyisobutenes,
hydrogenated styrene-isoprene polymers, hydrogenated isoprene
polymers, polymethacrylate acid esters, polyacrylate acid esters,
polyalkyl styrenes, alkenyl aryl conjugated diene copolymers,
polyolefins, polyalkylmethacrylates and esters of maleic
anhydride-styrene copolymers. 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; may also
be used in the composition of the invention.
[0097] 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,
benzimidazoles, 2-alkyldithiobenzimidazoles or
2-alkyldithiobenzothiazoles.
[0098] Foam inhibitors include for example 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
[0099] The method of the invention is useful for lubricating a
variety of driveline devices applications. 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 is a manual
transmission or a gear, a gearbox, or an axle gear.
[0100] The automatic transmission includes continuously variable
transmissions (CVT), infinitely variable transmissions (IVT),
Torroidal transmissions, continuously slipping torque converted
clutches (CSTCC), stepped automatic transmissions or dual clutch
transmissions (DCT).
[0101] In one embodiment the invention provides for the use of the
lubricating composition disclosed herein in gears and transmissions
to impart at least one of antiwear performance, extreme pressure
performance, acceptable deposit control, acceptable oxidation
stability and reduced odour.
[0102] 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. However, the amount of each
chemical component is presented exclusive of any solvent or diluent
oil, which may be customarily present in the commercial material,
unless otherwise indicated.
[0103] 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
[0104] Lubricant Example 1 (EX1) is a 80W-90 gear oil lubricant
containing 0.4 wt % of a Primene.RTM.81-R amine salt of oleyl
phosphate and 0.15 wt % of 2-ethylhexyl tartrate.
[0105] Comparative Lubricant Example 1 (CLE1) is a gear oil
lubricant similar to EX1, except it does not contain the
tartrate.
[0106] Lubricant Example 2 (EX2) is a 80W-90 gear oil lubricant
containing 0.4 wt % of a dibutyl phosphite and 0.15 wt % of
2-ethylhexyl tartrate.
[0107] Comparative Lubricant Example 2 (CLE2) is a gear oil
lubricant similar to EX2, except it does not contain the
tartrate.
[0108] Comparative Lubricant Example 3 (CLE3) is a gear oil
lubricant similar to EX1, except it contains 0.15 wt % of 2-ethyl
hexyl tartrate and 0.18 wt % of an amine salt of a thiophosphate as
described by preparative examples 6 to 8 of International Patent
application WO U.S. Ser. No. 09/036,623 as described in paragraph
[0107] of said application.
[0109] Comparative Lubricant Example 4 (CLE4) is a gear oil
lubricant similar to EX1, except contains 0.18 wt % of an amine
salt of a phosphate as described by preparative examples 1 to 4 of
International Patent application WO U.S. Ser. No. 09/036,623 as
described in paragraphs [0099] to [0105] of said application.
[0110] Lubricant Example 3 (EX3) is an 80W-90 gear oil lubricant
containing 1 wt % of a Primene.RTM.81-R amine salt of oleyl
phosphate, 0.25 wt % of dibutyl phosphite, and 0.1 wt % of
2-ethylhexyl tartrate.
[0111] Lubricant Example 4 (EX4) is a 75W-90 gear oil lubricant
containing 0.8 wt % of a Primene.RTM.81-R amine salt of oleyl
phosphate, 0.5 wt % of dibutyl phosphite, and 0.2 wt % of
2-ethylhexyl tartrate.
[0112] Lubricants CLE1 to CLE4 and EX1 to EX4 are evaluated by the
methodologies of ASTM D6121-05a (the L-37 Gear Durability Test),
and L-42 Axle Shock Test method described in ASTM publication STP
512A. Typically better results in the L-42 test are for samples
with lower percent rating of ring and pinion scoring. Typically,
better results in the L-37 test are obtained for samples with
higher numbers.
[0113] The results obtained for EX1 and comparative examples CLE1,
CLE3 and CLE4 at the end of the L-42 test are as follows:
TABLE-US-00001 Pinion Pinion Ring Drive Ring Coast Drive Coast EX1
0 13 0 17 CLE1 0 21 0 29 CLE3 0 57 0 34 CLE4 0 92 0 66
[0114] The results of the L-42 test indicate that the composition
of the invention has reduced ring and pinion scoring compared to
similar compositions containing other antiwear additives. For
example the lubricating composition disclosed herein has improved
performance in the L-42 test over compositions similar to those
disclosed in International Patent application WO U.S. Ser. No.
09/036,623 (i.e., CLE3 and CLE4).
[0115] The results obtained for EX1 and comparative example CLE1 at
the end of the L-37 test are as follows:
TABLE-US-00002 Parameter Rated on Ring EX1 CLE1 Ring Wear Final
Wear Rating 8 7 Final Surface Fatigue Rippling 10 9 Final Surface
Fatigue Ridging 10 7 Final Surface Fatigue Pitting and 9.9 9.9
Spalling Merit Final Surface Fatigue Scoring 10 10 Pinion Wear
Final Wear Rating 8 6 Final Wear Rippling 9 8 Final Wear Ridging 10
7 Final Wear Scoring 9.9 9.6 Final Pitting and Spalling Merit 10
10
[0116] The results of the L-37 test indicate that the composition
of the invention has reduced wear, rippling, ridging and scoring
compared to similar compositions containing other antiwear
phosphorus additives.
[0117] Overall, the compositions of the invention have performance
benefits over comparative examples in 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.
[0118] 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.
[0119] 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." 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
[0120] 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: hydrocarbon substituents,
including aliphatic, alicyclic, and aromatic substituents;
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; and hetero substituents, that is, substituents which
similarly have a predominantly hydrocarbon character but contain
other than carbon in a ring or chain. A more detailed definition of
the term "hydrocarbyl substituent" or "hydrocarbyl group" is
described in paragraphs [0118] to [0119] of International
Publication WO2008147704.
[0121] As used herein the term "fatty" as in fatty acid (and other
expressions used herein) includes a hydrocarbyl chain containing 4
to 150, or 4 to 30, or 6 to 16 carbon atoms.
[0122] 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.
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