U.S. patent application number 12/529369 was filed with the patent office on 2010-04-22 for additive concentrate and a method of lubricating transmissions.
Invention is credited to Susie Hurley, James L. Sumiejski.
Application Number | 20100099593 12/529369 |
Document ID | / |
Family ID | 39709018 |
Filed Date | 2010-04-22 |
United States Patent
Application |
20100099593 |
Kind Code |
A1 |
Hurley; Susie ; et
al. |
April 22, 2010 |
Additive Concentrate and a Method of Lubricating Transmissions
Abstract
The present invention relates to an additive concentrate
comprising a friction modifier, a corrosion inhibitor, and an oil
of lubricating viscosity. The invention further provides a method
for lubricating a transmission using the additive concentrate.
Inventors: |
Hurley; Susie; (Duffield,
GB) ; Sumiejski; James L.; (Mentor, OH) |
Correspondence
Address: |
THE LUBRIZOL CORPORATION;ATTN: DOCKET CLERK, PATENT DEPT.
29400 LAKELAND BLVD.
WICKLIFFE
OH
44092
US
|
Family ID: |
39709018 |
Appl. No.: |
12/529369 |
Filed: |
March 11, 2008 |
PCT Filed: |
March 11, 2008 |
PCT NO: |
PCT/US08/56477 |
371 Date: |
December 14, 2009 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
60895240 |
Mar 16, 2007 |
|
|
|
Current U.S.
Class: |
508/555 |
Current CPC
Class: |
C10M 2215/02 20130101;
C10N 2070/02 20200501; C10M 2215/04 20130101; C10M 133/16 20130101;
C10M 2215/023 20130101; C10M 2215/08 20130101; C10M 133/48
20130101; C10M 141/06 20130101; C10N 2040/045 20200501; C10N
2040/042 20200501; C10M 2215/041 20130101; C10M 2215/042 20130101;
C10M 2215/225 20130101; C10M 2215/0806 20130101; C10M 2215/0425
20130101; C10M 2215/2203 20130101; C10N 2040/044 20200501; C10N
2030/06 20130101; C10M 133/06 20130101; C10M 133/08 20130101; C10M
2215/082 20130101; C10M 133/04 20130101; C10N 2030/76 20200501 |
Class at
Publication: |
508/555 |
International
Class: |
C10M 133/16 20060101
C10M133/16 |
Claims
1-13. (canceled)
14. A method of lubricating a transmission by supplying to the
transmission a lubricating composition further treated with an
additive concentrate comprising: (a) 4 wt % to 67 wt % of a static
friction reducing friction modifier; (b) 0 wt % to 10 wt %, or 0.1
wt % to 5 wt % of a corrosion inhibitor; (c) 3 wt % to 96 wt % of
an oil of lubricating viscosity; and (d) 0 wt % to 20 wt % of other
performance additives, wherein the static friction reducing
friction modifier is an amide represented by the formula
R.sup.1R.sup.2N--C(O)R.sup.3, wherein R.sup.1 and R.sup.2 are each
independently hydrocarbyl groups of at least 6 carbon atoms and
R.sup.3 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.
15. The method of claim 14, wherein the additive concentrate
contains the static friction reducing friction modifier at 10 wt %
to 50 wt %.
16. The method of claim 14, wherein the additive concentrate
contains the static friction reducing friction modifier at 20 wt %
to 40 wt %.
17. The method of claim 14, wherein the additive concentrate
contains the corrosion inhibitor at 0.1 wt % to 5 wt %.
18. The method of claim 14, wherein the additive concentrate
contains the corrosion inhibitor at 0.2 wt % to 3 wt %.
19. The method of claim 14, wherein the additive concentrate is
supplied to the transmission as a service-fill top treat.
20. The method of claim 14, wherein the additive concentrate is
supplied to the transmission as a service-fill top treat at 0.1 wt
% to 30 wt %.
21. The method of claim 14, wherein the additive concentrate is
supplied to the transmission as a service-fill top treat at 1 wt %
to 15 wt %.
22. A method of lubricating a transmission containing a lubricant
comprising supplying to the lubricant within the transmission an
additive concentrate comprising: (a) 4 wt % to 67 wt % of a static
friction reducing friction modifier; (b) 0 wt % to 10 wt %, or 0.1
wt % to 5 wt % of a corrosion inhibitor; (c) 3 wt % to 96 wt % of
an oil of lubricating viscosity; and (d) 0 wt % to 20 wt % of other
performance additives, wherein the static friction reducing
friction modifier is an amide represented by the formula
R.sup.1R.sup.2N--C(O)R.sup.3, wherein R.sup.1 and R.sup.2 are each
independently hydrocarbyl groups of at least 6 carbon atoms and
R.sup.3 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.
23. An additive concentrate comprising: (a) 4 wt % to 67 wt % of a
static friction reducing friction modifier; (b) 0 wt % to 10 wt %,
or 0.1 wt % to 5 wt % of a corrosion inhibitor; (c) 3 wt % to 96 wt
% of an oil of lubricating viscosity; and (d) 0 wt % to 20 wt % of
other performance additives, wherein the static friction reducing
friction modifier is an amide represented by the formula
R.sup.1R.sup.2N--C(O)R.sup.3, wherein R.sup.1 and R.sup.2 are each
independently hydrocarbyl groups of at least 6 carbon atoms and
R.sup.3 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.
24. A method of lubricating a transmission by supplying to the
transmission a lubricating composition further treated with an
additive concentrate comprising: (a) 4 wt % to 67 wt % of a static
friction reducing friction modifier; (b) 0 wt % to 10 wt %, or 0.1
wt % to 5 wt % of a corrosion inhibitor; (c) 3 wt % to 96 wt % of
an oil of lubricating viscosity; and (d) 0 wt % to 20 wt % of other
performance additives, wherein the static friction reducing
modifier comprises a tertiary amine, wherein the amine contains
three substituent hydrocarbyl groups, two of which are alkyl
groups, and the amine is represented by the formula:
R.sup.4R.sup.5NR.sup.6 wherein R.sup.4 and R.sup.5 are each
independently an alkyl group of at least 6 carbon atoms and R.sup.6
is a polyhydroxyl-containing alkyl group or a
polyhydroxyl-containing alkoxyalkyl group.
25. A method of lubricating a transmission by supplying to the
transmission a lubricating composition further treated with an
additive concentrate comprising: (a) 4 wt % to 67 wt % of a static
friction reducing friction modifier; (b) 0 wt % to 10 wt %, or 0.1
wt % to 5 wt % of a corrosion inhibitor; (c) 3 wt % to 96 wt % of
an oil of lubricating viscosity; and (d) 0 wt % to 20 wt % of other
performance additives, wherein the static friction reducing
modifier comprises an amine, wherein the amine is secondary or
tertiary amine being represented by the formula:
R.sup.7R.sup.8NR.sup.9 wherein R.sup.7 and R.sup.8 are each
independently an alkyl group of at least 6 carbon atoms and R.sup.9
is a hydroxyl-containing alkyl group, a hydroxyl-containing
alkoxyalkyl group, an amine-containing alkyl group, a hydrocarbyl
group, or hydrogen, provided that when R.sup.9 is H, then at least
one of R.sup.7 and R.sup.8 is an alkyl group of 8 to 16 carbon
atoms.
Description
FIELD OF INVENTION
[0001] The present invention relates to an additive concentrate
comprising a friction modifier, a corrosion inhibitor, and an oil
of lubricating viscosity. The invention further provides a method
for lubricating a transmission using the additive concentrate.
BACKGROUND OF THE INVENTION
[0002] Driveline transmissions especially automatic transmission
fluids (ATFs), present highly challenging technological problems
and solutions for satisfying the multiple and often conflicting
lubricating and power transmitting requirements of modern automatic
transmissions (including continuously variable transmissions of
various types). Many additive components are typically included in
an ATF, providing such performance characteristics as lubrication,
dispersancy, friction control (for clutches), antiwear performance,
anti-shudder performance, anti-corrosion and anti-oxidation
performance. However, over periods of use, the additive components
are consumed which can detrimentally damage transmissions. For
example a transmission may experience increased shudder,
chattering, or squawking (a vibration oscillation of a clutch that
may be audible). Reducing the impact of shudder, chattering, or
squawking has been achieved by employing friction modifiers such as
those defined in U.S. Pat. Nos. 3,156,653, 3,070,546, 3,275,559,
and 5,750,476; and U.S. Patent Applications 60/725,360 (now WO
2007/044820), 2005/0250655, and 2003/0220208.
[0003] U.S. Pat. Nos. 3,156,653; and 3,070,546 both disclose
lubricating compositions containing a carboxy amide. The
lubricating compositions are suitable for reducing squawking or
chattering.
[0004] U.S. Pat. No. 3,275,559 discloses an automatic transmission
with suppressed squawking by employing a lubricating composition
containing an N-alkyl alkylene diamine.
[0005] U.S. Pat. No. 5,750,476 discloses improving anti-shudder
durability of a power transmission by employing a lubricating
composition containing an anti-shudder improving effective amount
of (a) an isomerised alkenyl succinimide, and (b) an oil-soluble
phosphorus-containing compound.
[0006] US Patent Application 2003/0220208 discloses a lubricating
composition containing an additive combination of (i) an
oil-soluble fatty acid ester of a polyhydric alcohol and (ii) an
oil-soluble fatty acid amide. The lubricating composition is useful
for the reduction of brake and clutch noise.
[0007] US Patent Application 2005/0250655 discloses a lubricating
composition containing a 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.
[0008] U.S. Patent Application 60/725,360 (filed on Oct. 11, 2005,
inventors Bartley, Lahiri, Baker and Tipton), now WO 2007/044820,
discloses a reaction product of a hydroxyalkyl compound with an
acylating agent or an amine. The resultant product may be an amide
represented by the formula R.sup.1R.sup.2N--C(O)R.sup.3, wherein
R.sup.1 and R.sup.2 are each independently hydrocarbyl groups of at
least 6 carbon atoms and R.sup.3 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.
[0009] Overcoming shudder, chattering, or squawking is typically
achieved by replacing the transmissions' fluid (typically a factory
fill fluid) with a replacement fluid. However, this results in
excessive repair cost due to the difficulty of changing the fluid
and increased waste lubricant. Thus it would be desirable to
lubricate a transmission lubricant capable of minimising noise,
shudder, chattering, or squawking, whilst also not adversely
affecting the frictional balance and clutch holding capacity, nor
increasing lubricant waste. The present invention provides a means
of overcoming shudder, chattering, or squawking whilst at the same
time minimising at least one of the cost, time, and waste involved
in a conventional fluid replacement.
SUMMARY OF THE INVENTION
[0010] In one embodiment the invention provides an additive
concentrate comprising:
[0011] (a) 4 wt % to 67 wt % of a static friction reducing friction
modifier;
[0012] (b) 0 wt % to 10 wt %, or 0.1 wt % to 5 wt % of a corrosion
inhibitor;
[0013] (c) 3 wt % to 96 wt % of an oil of lubricating viscosity;
and
[0014] (d) 0 wt % to 20 wt % of other performance additives.
[0015] In one embodiment the invention provides a method of
lubricating a transmission by supplying to the transmission a
lubricating composition further treated with an additive
concentrate comprising:
[0016] (a) 4 wt % to 67 wt % of a static friction reducing friction
modifier;
[0017] (b) 0 wt % to 10 wt %, or 0.1 wt % to 5 wt % of a corrosion
inhibitor;
[0018] (c) 3 wt % to 96 wt % of an oil of lubricating viscosity;
and
[0019] (d) 0 wt % to 20 wt % of other performance additives.
[0020] In one embodiment the invention provides a method of
lubricating a transmission containing a lubricant comprising
supplying to the lubricant within the transmission an additive
concentrate comprising:
[0021] (a) 4 wt % to 67 wt % of a static friction reducing friction
modifier;
[0022] (b) 0 wt % to 10 wt %, or 0.1 wt % to 5 wt % of a corrosion
inhibitor;
[0023] (c) 3 wt % to 96 wt % of an oil of lubricating viscosity;
and
[0024] (d) 0 wt % to 20 wt % of other performance additives.
[0025] In one embodiment the invention provides an additive
concentrate comprising:
[0026] (a) 4 wt % to 67 wt % of a friction modifier with a
co-efficient of friction of greater than 0.09;
[0027] (b) 0 wt % to 10 wt %, or 0.1 wt % to 5 wt % of a corrosion
inhibitor;
[0028] (c) 3 wt % to 96 wt % of an oil of lubricating viscosity;
and
[0029] (d) 0 wt % to 20 wt % of other performance additives.
[0030] In one embodiment the invention provides a method of
lubricating a transmission by supplying to the transmission a
lubricating composition further treated with an additive
concentrate comprising:
[0031] (a) 4 wt % to 67 wt % of a friction modifier with a
co-efficient of friction of greater than 0.09;
[0032] (b) 0 wt % to 10 wt %, or 0.1 wt % to 5 wt % of a corrosion
inhibitor;
[0033] (c) 3 wt % to 96 wt % of an oil of lubricating viscosity;
and
[0034] (d) 0 wt % to 20 wt % of other performance additives.
[0035] In one embodiment the invention provides a method of
lubricating a transmission containing a lubricant comprising
supplying to the lubricant within the transmission an additive
concentrate comprising:
[0036] (a) 4 wt % to 67 wt % of a friction modifier with a
co-efficient of friction of greater than 0.09;
[0037] (b) 0 wt % to 10 wt %, or 0.1 wt % to 5 wt % of a corrosion
inhibitor;
[0038] (c) 3 wt % to 96 wt % of an oil of lubricating viscosity;
and
[0039] (d) 0 wt % to 20 wt % of other performance additives.
[0040] In one embodiment the invention provides for the use of the
additive concentrate described herein as a top treat package to
diminish squawk in a transmission.
DETAILED DESCRIPTION OF THE INVENTION
[0041] The present invention provides an additive concentrate and a
method for lubricating a transmission as disclosed above.
[0042] The additive concentrate is typically added as a top treat.
The top treat may be added to the transmission as a service-fill or
factory-fill. Typically the top treat may be added to the
transmission as a service-fill.
[0043] The additive concentrate may contain the static friction
reducing friction modifier at 4 wt % to 67 wt %, or 10 wt % to 50
wt %, or 20 wt % to 40 wt %.
[0044] The additive concentrate may contain the corrosion inhibitor
at 0 wt % to 10 wt %, or 0.1 wt % to 5 wt %, or 0.2 wt % to 3 wt
%.
[0045] The additive concentrate may contain the oil of lubricating
viscosity at 3 wt % to 96 wt %, or 33 wt % to 89 wt %, or 47 wt %
to 77.8 wt %.
[0046] The additive concentrate may contain the total of other
performance additives at 0 wt % to 20 wt %, or 1 wt % to 12 wt %,
or 2 wt % to 10 wt %.
[0047] The additive concentrate may be added to a transmission at a
treat rate of 0.1 wt % to 30 wt %, or 1 wt % to 15 wt %.
Static Friction Reducing Friction Modifiers
[0048] The static friction reducing friction modifier may also be
described as a friction modifier with a co-efficient of friction of
greater than 0.09. The static friction is expressed in term of
.mu.T or the stabilized static coefficient from the SAE#2 test
procedure. The test procedure is described in the Japanese
Automobile Standard, JASO M-348-95, "Test method for friction
property of automatic transmission fluids".
[0049] The static friction reducing friction modifier may also be
described as a friction modifier of the type described in PCT
Publication WO 2004/007652 A1. Typically static friction reducing
friction modifiers are characterised by their ability to provide a
positive slope in a friction versus speed curve whilst maintaining
a high static coefficient of friction.
[0050] In one embodiment the static friction reducing friction
modifier may be 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, now
WO 2007/044820. The friction modifier disclosed in U.S. Patent
Application 60/725,360 may be an amide represented by the formula
R.sup.1R.sup.2N--C(O)R.sup.3, wherein R.sup.1 and R.sup.2 are each
independently hydrocarbyl groups of at least 6 carbon atoms and
R.sup.3 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.
[0051] In one embodiment the static friction reducing friction
modifier may be 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. The number of carbon atoms
may range from 6 to 30, or 8 to 20. 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.
[0052] In one embodiment the static friction reducing friction
modifier may be a polyol ester as described in U.S. Pat. No.
5,750,476 column 8, line 40 to column 9, line 28.
[0053] In one embodiment the static friction reducing friction
modifier may be 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.
[0054] In one embodiment the friction modifier may be a
hydroxylamine compound as defined in column 37, line 19, to column
39, line 38 of U.S. Pat. No. 5,534,170. Optionally the
hydroxylamine may be borated as such products are described in
column 39, line 39 to column 40 line 8 of U.S. Pat. No.
5,534,170.
[0055] In one embodiment the static friction reducing friction
modifier comprises one or more of a hydroxy-amide, a hydroxy amide
mono- or di-ester, a hydroxy oxazoline, a hydroxy oxazoline ester,
an oxazoline diester, a tri-ester amide, or mixtures thereof.
[0056] In one embodiment the static friction reducing modifier is
an amide represented by the formula R.sup.1R.sup.2N--C(O)R.sup.3,
wherein R.sup.1 and R.sup.2 are each independently hydrocarbyl
groups of at least 6 carbon atoms and R.sup.3 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.
[0057] In one embodiment the static friction reducing modifier is
other than an amide represented by the formula
R.sup.1R.sup.2N--C(O)R.sup.3, wherein R.sup.1 and R.sup.2 are each
independently hydrocarbyl groups of at least 6 carbon atoms and
R.sup.3 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.
[0058] In one embodiment the static friction reducing modifier is a
tertiary amine. The amine will contain three substituent
hydrocarbyl groups, two of which are alkyl groups. The amine is
represented by the formula
R.sup.4R.sup.5NR.sup.6
wherein R.sup.4 and R.sup.5 are each independently an alkyl group
of at least 6 carbon atoms (e.g., 8 to 20 carbon atoms or 10 to 18
or 12 to 16) and R.sup.6 is a polyhydroxyl-containing alkyl group
or a polyhydroxyl-containing alkoxyalkyl group.
[0059] In one embodiment the amine comprises a product of
di-cocoalkyl amine or homologous amines. Di-cocoalkyl amine (or
di-cocoamine) is a secondary amine in which two of the R groups in
the above formula are predominantly C.sub.12 groups, derived from
coconut oil and the remaining R group is H.
[0060] In one embodiment, R.sup.6 is a polyol-containing alkyl
group (that is, a group containing 2 or more hydroxy groups) or a
group containing one or more hydroxy groups and one or more amine
groups. For instance, R.sup.6 may be --CH.sub.2--CHOH--CH.sub.2OH
or a homologue thereof, containing, for example, 3 to 8 carbon
atoms or 3 to 6 carbon atoms or 3 to 4 carbon atoms, and 2, 3, 4 or
more hydroxy groups (normally no more than one hydroxy group per
carbon atom). A typical resulting product may thus be represented
by
R.sup.4R.sup.5N--CH.sub.2--CHOH--CH.sub.2OH
[0061] or homologues thereof, where R.sup.4 and R.sup.5 are, as
described above, independently alkyl groups of 8 to 20 carbon
atoms. Such products may be obtained by the reaction of a dialkyl
amine with an epoxide or chlorohydroxy compound. In particular,
reaction of a secondary amine with glycidol (2,3-epoxy-1-propanol)
or "chloroglycerine" (that is, 3-chloropropane-1,2-diol) may be
effective under conditions as described above. Such materials based
on the reaction of dicocoamine with one or more moles of glycidol
or chloroglycerine are particularly useful in providing
friction-modifying performance. If reaction is with multiple moles
of glycidol or chloroglycerine, or other epoxyalkanols or
chlorodiols, a dimeric or oligomeric ether-containing group, that
is, a hydroxyl-substituted alkoxyalkyl group, may result.
[0062] In one embodiment the static friction reducing modifier may
be described as a compound comprising a core portion comprising 3
to 8 carbon atoms, (e.g, 3 to 6, or 3 carbon atoms), said core
portion being substituted by: (i) at least two hydroxy groups, or
at least one hydroxy group and at least one alkoxy group of 1 to 4
carbon atoms wherein said alkoxy group is further substituted by at
least one hydroxy group or another such alkoxy group; and (ii) at
least one amino group, the nitrogen atom thereof bearing two
hydrocarbyl groups, each such hydrocarbyl group independently
having 6 to 30 carbon atoms.
[0063] In one embodiment the static friction reducing modifier is a
secondary or tertiary amine. The amine will contain at least two
substituent hydrocarbyl groups, for example, alkyl groups. The
amine is represented by the formula
R.sup.7R.sup.8NR.sup.9
wherein R.sup.7 and R.sup.8 are each independently an alkyl group
of at least 6 carbon atoms (e.g., 8 to 20 carbon atoms or 10 to 18
or 12 to 16) and R.sup.9 is a hydroxyl-containing alkyl group, a
hydroxyl-containing alkoxyalkyl group, an amine-containing alkyl
group, a hydrocarbyl group, or hydrogen, provided that when R.sup.9
is H, then at least one of R.sup.7 and R.sup.8 is an alkyl group of
8 to 16 carbon atoms such as, for instance, 10 to 16 carbon atoms
or 12 to 14 carbon atoms. In certain embodiments both of R.sup.7
and R.sup.8 are alkyl groups of 8 to 16, or 10 to 16, or 12 to 14
carbon atoms. A commercial example of such an amine is Armeen
2C.TM., which is a secondary amine where the two alkyl groups are
believed to be predominately C.sub.12 to C.sub.14.
[0064] In one embodiment the amine comprises di-cocoalkyl amine or
homologous amines. Di-cocoalkyl amine (or di-cocoamine) is a
secondary amine in which two of the R groups in the above formula
are predominantly C.sub.12 groups, derived from coconut oil and the
remaining R group is H. In another embodiment the amine may be
Armeen HTL8.TM., which is believed to be a secondary amine with
mixed alkyl groups comprising 2-ethylhexyl groups (C8) and
hydrogenated tallow groups (largely C16-18).
[0065] In another embodiment, R.sup.9 in the above structure is
--CH.sub.2--CHOH--R.sup.10, where R.sup.10 is hydrogen or an alkyl
group, e.g., a methyl group or an alkyl group of 1 to 26 carbon
atoms, or 6 to 20 carbon atoms, or 12 to 18 carbon atoms, or 14 to
16 carbon atoms, or 14 carbon atoms. Such materials can be prepared
by reaction of a secondary amine such as di-cocoalkylamine with an
epoxide, such as propylene oxide (in the case where R.sup.10 is
methyl). The resulting products can thus, more specifically, be
represented by the structure
R.sup.7R.sup.8N--CH.sub.2--CHOH--CH.sub.3
where R.sup.7 and R.sup.8 are, as described above, independently
alkyl groups of 8 to 20 carbon atoms. The reaction of the dialkyl
amine and the epoxide can be effected by reaction under pressure in
the presence of a basic catalyst. In another embodiment, R.sup.9 is
an aminopropyl groups such as
--CH.sub.2--CH.sub.2--CH.sub.2--NH.sub.2, and the resulting product
can be prepared by reaction of a secondary amine such as
dicocoalkyl amine with acrylonitrile followed by a reduction.
[0066] In another embodiment, R.sup.9 can be a polyol-containing
alkyl group (that is, a group containing 2 or more hydroxy groups)
or a group containing one or more hydroxy groups and one or more
amine groups. For instance, R.sup.9 may be
--CH.sub.2--CHOH--CH.sub.2OH or a homologue thereof, containing,
for example, 3 to 8 carbon atoms or 3 to 6 carbon atoms or 3 to 4
carbon atoms, and 2, 3, 4 or more hydroxy groups (normally no more
than one hydroxy group per carbon atom). A typical resulting
product may thus be represented by
R.sup.7R.sup.8N--CH.sub.2--CHOH--CH.sub.2OH
or homologues thereof, where R.sup.7 and R.sup.8 are, as described
above, independently alkyl groups of 8 to 20 carbon atoms. Such
products may be obtained by the reaction of a dialkyl amine with an
epoxide or chlorohydroxy compound. In particular, reaction of a
secondary amine with glycidol (2,3-epoxy-1-propanol) or
"chloroglycerine" (that is, 3-chloropropane-1,2-diol) may be
effective under conditions as described above. Such materials based
on the reaction of dicocoamine with one or more moles of glycidol
or chloroglycerine are particularly useful in providing
friction-modifying performance. If reaction is with multiple moles
of glycidol or chloroglycerine, or other epoxyalkanols or
chlorodiols, a dimeric or oligomeric ether-containing group, that
is, a hydroxyl-substituted alkoxyalkyl group, may result.
[0067] In certain embodiments, thus, the amine may be a tertiary
amine, that is, in which R.sup.9 is other than hydrogen. If all
three groups R.sup.7, R.sup.8, and R.sup.9 are alkyl groups, then
R.sup.9 may also be an alkyl group of at least 6 carbon atoms
(e.g., 8 to 20 carbon atoms or 10 to 18 or 12 to 16).
Corrosion Inhibitor
[0068] The lubricating composition may further comprise a corrosion
inhibitor or mixtures thereof. In one embodiment the corrosion
inhibitor also exhibits antiwear properties.
[0069] The corrosion inhibitors of the invention include
benzotriazoles (typically tolyltriazole),
2-alkyldithiobenzimidazoles or 2-alkyldithio benzothiazoles,
1,2,4-triazoles, benzimidazoles, octylamine octanoate, condensation
products of dodecenyl succinic acid or anhydride,
dimercaptothiadiazoles and reactive equivalents thereof, or
mixtures thereof.
[0070] The corrosion inhibitor may comprise at least one of a
dimercaptothiadiazole, 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 are
commonly utilised, with 2,5-dimercapto-[1,3,4]-thiadiazole most
commonly utilised due to availability. In several 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.
[0071] In one embodiment, the thiazole compound may be the reaction
product of a phenol with an aldehyde and a dimercaptothiadiazole.
The phenol may be an alkyl phenol wherein the alkyl group contains
at least about 6, e.g., 6 to 24, or 6, or 7, to 12 carbon atoms.
The aldehyde may be an aldehyde containing 1 to 7 carbon atoms or
an aldehyde synthon, such as formaldehyde. In one embodiment, the
aldehyde is formaldehyde or paraformaldehyde. The aldehyde, phenol
and dimercaptothiadiazole are typically reacted by mixing them at a
temperature up to about 150.degree. C. such as 50.degree. C. to
130.degree. C., in molar ratios of 0.5 to 2 moles of phenol and 0.5
to 2 moles of aldehyde per mole of dimercaptothiadiazole. In one
embodiment, the three reagents are reacted in equal molar amounts.
The product may be described as an
alkylhydroxyphenylmethylthio-substituted [1,3,4]-thiadiazole; the
alkyl moiety may be, among others, hexyl, heptyl, octyl, or
nonyl.
[0072] Useful thiadiazole compounds thus may include
2-alkyldithio-5-mercapto-[1,3,4]-thiadiazoles,
2,5-bis(alkyldithio)-[1,3,4]-thiadiazoles,
2-alkyl-hydroxyphenylmethylthio-5-mercapto-[1,3,4]-thiadiazoles,
and mixtures thereof.
[0073] Examples of suitable thiadiazole compounds include
2-octyldithio-5-mercapto-1,3,4-thiadiazole,
2-nonyldithio-5-mercapto-1,3,4-thiadiazole,
2-dodecydithio-5-mercapto-1,3,4-thiadiazole,
2,5-dimercapto-1,3-4-thiadiazole (e.g.,
2,5-bis(alkyl-dithio)-1,3,4-thiadiazoles) include
2,5-bis(tert-octyldithio)-1,3,4-thiadiazole
2,5-bis(tert-nonyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-decyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-undecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-dodecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-tridecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-tetradecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-pentadecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-hexadecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-heptadecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-octadecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-nonadecyldithio)-1,3,4-thiadiazole or
2,5-bis(tert-eicosyldithio)-1,3,4-thiadiazole, or oligomers
thereof. In one embodiment the hydrocarbyl-substituted
2,5-dimercapto-1,3-4-thiadiazole comprises 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.
Oils of Lubricating Viscosity
[0074] 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 and re-refined oils and mixtures thereof.
[0075] Unrefined oils are those obtained directly from a natural or
synthetic source generally without (or with little) further
purification treatment.
[0076] Refined oils are similar to the unrefined oils except they
have been further treated in one or more purification steps to
improve one or more properties. Purification techniques are known
in the art and include solvent extraction, secondary distillation,
acid or base extraction, filtration, and percolation.
[0077] Re-refined oils are also known as reclaimed or reprocessed
oils, and are obtained by processes similar to those used to obtain
refined oils and often are additionally processed by techniques
directed to removal of spent additives and oil breakdown
products.
[0078] Natural oils useful in making the inventive lubricants
include animal oils (e.g., lard oil), vegetable oils (e.g., castor
oil), mineral lubricating oils such as liquid petroleum oils and
solvent-treated or acid-treated mineral lubricating oils of the
paraffinic, naphthenic or mixed paraffinic-naphthenic types and
oils derived from coal or shale or mixtures thereof.
[0079] Synthetic lubricating oils are useful and include
hydrocarbon oils such as polymerised and interpolymerised olefins
(e.g., polybutylenes, polypropylenes, propyleneisobutylene
copolymers); poly(1-hexenes), poly(1-octenes), poly(1-decenes), and
mixtures thereof; alkyl-benzenes (e.g. dodecylbenzenes,
tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes);
polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls);
alkylated diphenyl ethers and alkylated diphenyl sulphides and the
derivatives, analogs and homologs thereof or mixtures thereof.
[0080] Other synthetic lubricating oils include polyol esters (such
as Prolube.RTM.3970), diesters, liquid esters of
phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl
phosphate, and the diethyl ester of decane phosphonic acid), or
polymeric tetrahydrofurans. Synthetic oils may 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.
[0081] Oils of lubricating viscosity may also be defined as
specified in the American Petroleum Institute (API) Base Oil
Interchangeability Guidelines. The five base oil groups are as
follows: Group I (sulphur content >0.03 wt %, and/or <90 wt %
saturates, viscosity index 80-120); Group II (sulphur content
<0.03 wt %, and >90 wt % saturates, viscosity index 80-120);
Group III (sulphur content <0.03 wt %, and >90 wt %
saturates, viscosity index >120); Group IV (all polyalphaolefins
(PAOs)); and Group V (all others not included in Groups I, II, III,
or IV). The oil of lubricating viscosity comprises an API Group I,
Group II, Group III, Group IV, Group V oil or mixtures thereof. In
one embodiment the oil of lubricating viscosity may be an API Group
I, Group II, Group III, Group IV oil or mixtures thereof. In one
embodiment the oil of lubricating viscosity may be an API Group II,
Group III or Group IV oil or mixtures thereof. In one embodiment
the oil of lubricating viscosity may be an API Group II or Group
III oil or mixtures thereof.
[0082] In one embodiment the oil of lubricating viscosity is other
than a white oil base stock.
[0083] The amount of the oil of lubricating viscosity present is
typically the balance remaining after subtracting from 100 wt % the
sum of the static friction reducing friction modifier, the
corrosion inhibitor and the other performance additives (described
below).
[0084] The lubricating composition may be in the form of a
concentrate and/or a fully formulated lubricant. If the composition
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 components (a), (b) and (d) to the oil of
lubricating viscosity (c) 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
[0085] The composition of the invention optionally further includes
at least one other performance additive. The other performance
additives include detergents, viscosity index improvers (also
referred to as viscosity modifiers), antiwear agents, friction
modifiers other than the static reducing friction modifier of the
invention, friction stabilising agents, antioxidants, dispersants,
foam inhibitors, demulsifiers, pour point depressants, seal
swelling agents and mixtures thereof.
Antiwear Agent
[0086] The antiwear agent may be a phosphorus-containing acid,
salt, or ester, or mixtures thereof.
[0087] The antiwear agent may be metal-containing or metal free
(prior to being mixed with other components).
[0088] The antiwear agent may be derived from a phosphoric acid,
phosphorous acid, thiophosphoric acid, thiophosphorous acid, or
mixtures thereof.
[0089] The antiwear agent may include (i) a non-ionic phosphorus
compound; (ii) an amine salt of a phosphorus compound; (iii) an
ammonium salt of a phosphorus compound; (iv) a monovalent metal
salt of a phosphorus compound, such as a metal
dialkyldithiophosphate or a metal dialkylphosphate; or (v) mixtures
of (i), (ii), (iii) or (iv).
[0090] In one embodiment the antiwear agent comprises a metal
dialkyldithiophosphate or a metal dialkylphosphate. The alkyl
groups of the dialkyldithiophosphate and/or the dialkylphosphate
may be linear or branched containing 2 to 20 carbon atoms, provided
that the total number of carbons is sufficient to make the metal
dialkyldithiophosphate or phosphate oil soluble. The metal of the
metal dialkyldithiophosphate and/or dialkylphosphate typically
includes monovalent or divalent metals. Examples of suitable metals
include sodium, potassium, copper, calcium, magnesium, barium or
zinc. In one embodiment the antiwear agent is a zinc
dialkyldithiophosphate. In one embodiment the antiwear agent is a
zinc dialkylphosphate.
[0091] Examples of a suitable zinc dialkyldithiophosphate (often
referred to as ZDDP, ZDP or ZDTP) include zinc di-(amyl)
dithiophosphate, zinc di-(1,3-dimethylbutyl) dithiophosphate, zinc
di-(heptyl) dithiophosphate, zinc di-(octyl) dithiophosphate
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. In one embodiment the zinc
dialkyldithiophosphate comprises a mixed alkyl ZDDP compound,
wherein the alkyl groups include 2-methylpropyl and amyl. In one
embodiment the zinc dialkyldithiophosphate comprises a mixed alkyl
ZDDP compound, wherein one alkyl group comprises isopropyl and at
least one of 1,3-dimethylbutyl, 2-ethylhexyl and iso-octyl.
[0092] In one embodiment the antiwear agent is other than metal
dialkyldithiophosphate.
[0093] In one embodiment the antiwear agent comprises an ammonium
or amine salt of a phosphorus-containing acid or ester.
[0094] The amine salt of a phosphorus acid or ester includes
phosphoric acid esters and amine salts thereof;
dialkyldithiophosphoric acid esters and amine salts thereof; amine
salts of phosphites; and amine salts of phosphorus-containing
carboxylic esters, ethers, and amides; and mixtures thereof.
[0095] The amine salt of a phosphorus acid or ester may be used
alone or in combination. In one embodiment the amine salt of a
phosphorus compound is derived from an amine salt of a phosphorus
compound, or mixtures thereof.
[0096] In one embodiment the amine salt of a phosphorus acid or
ester includes a partial amine salt-partial metal salt compounds or
mixtures thereof. In one embodiment the amine salt of a phosphorus
acid or ester further comprises a sulphur atom in the molecule.
[0097] The amines which may be suitable for use as the amine salt
include primary amines, secondary amines, tertiary amines, and
mixtures thereof. The amines include those with at least one
hydrocarbyl group, or, in certain embodiments, two or three
hydrocarbyl groups. The hydrocarbyl groups may contain 2 to 30
carbon atoms, or in other embodiments 8 to 26, or 10 to 20, or 13
to 19 carbon atoms.
[0098] 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
O L, Armeen T, Armeen H T, Armeen S and Armeen S D, wherein the
letter designation relates to the fatty group, such as coco, oleyl,
tallow, or stearyl groups.
[0099] Examples of suitable secondary amines include dimethylamine,
diethylamine, dipropylamine, dibutylamine, diamylamine,
dihexylamine, diheptylamine, methylethylamine, ethylbutylamine,
di-cocoalkyl amine (or di-cocoamine) and ethylamylamine. The
secondary amines may be cyclic amines such as piperidine,
piperazine and morpholine.
[0100] The amine may also be a tertiary-aliphatic primary amine.
The aliphatic group in this case may be an alkyl group containing 2
to 30, or 6 to 26, or 8 to 24 carbon atoms. Tertiary alkyl amines
include monoamines such as tert-butylamine, tert-hexylamine,
1-methyl-1-amino-cyclohexane, tert-octylamine, tert-decylamine,
tertdodecylamine, tert-tetradecylamine, tert-hexadecylamine,
tert-octadecylamine, tert-tetracosanylamine, and
tert-octacosanylamine.
[0101] In one embodiment the amine salt of a phosphorus acid or
ester includes an amine with C11 to C14 tertiary alkyl primary
groups or mixtures thereof. In one embodiment the amine salt of a
phosphorus compound includes an amine with C14 to C18 tertiary
alkyl primary amines or mixtures thereof. In one embodiment the
amine salt of a phosphorus compound includes an amine with C18 to
C22 tertiary alkyl primary amines or mixtures thereof.
[0102] Mixtures of amines may also be used in the invention. In one
embodiment a useful mixture of amines is "Primene.RTM. 81R" and
"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.
[0103] In one embodiment the amine salt of a phosphorus acid or
ester is the reaction product of a C.sub.14 to C.sub.18 alkylated
phosphoric acid with Primene 81R.TM. (produced and sold by Rohm
& Haas) which is a mixture of C11 to C14 tertiary alkyl primary
amines.
[0104] Examples of the amine salt of a phosphorus acid or ester
include the reaction product(s) of isopropyl, methyl-amyl
(1,3-dimethylbutyl or mixtures thereof), 2-ethylhexyl, heptyl,
octyl or nonyl dithiophosphoric acids with ethylene diamine,
morpholine, or Primene 81R.TM., and mixtures thereof.
[0105] In one embodiment a dithiophosphoric acid may be reacted
with an epoxide or a glycol. This reaction product is 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 is propylene oxide. The glycols may be
aliphatic glycols having 1 to 12, or 2 to 6, or 2 to 3 carbon
atoms. The dithiophosphoric acids, glycols, epoxides, inorganic
phosphorus reagents and methods of reacting the same are described
in U.S. Pat. Nos. 3,197,405 and 3,544,465. The resulting acids may
then be salted with amines. An example of suitable dithiophosphoric
acid is prepared by adding phosphorus pentoxide (about 64 grams) at
58.degree. C. over a period of 45 minutes to 514 grams of
hydroxypropyl O,O-di(1,3-dimethylbutyl)phosphorodithioate (prepared
by reacting di(1,3-dimethylbutyl)-phosphorodithioic acid with 1.3
moles of propylene oxide at 25.degree. C.). The mixture is heated
at 75.degree. C. for 2.5 hours, mixed with a diatomaceous earth and
filtered at 70.degree. C. The filtrate contains 11.8% by weight
phosphorus, 15.2% by weight sulphur, and an acid number of 87
(bromophenol blue).
[0106] In one embodiment the antiwear agent comprises a non-ionic
phosphorus compound. Typically the non-ionic phosphorus compound
may have an oxidation of +3 or +5. The different embodiments
comprise phosphite ester, phosphate esters, or mixtures
thereof.
[0107] In one embodiment the antiwear agent comprises a non-ionic
phosphorus compound that is a hydrocarbyl phosphite. The
hydrocarbyl phosphite of the invention includes those represented
by the formula:
##STR00001##
wherein each R''' may be independently hydrogen or a hydrocarbyl
group, with the proviso that at least one of the R''' groups is
hydrocarbyl.
[0108] Each hydrocarbyl group of R''' may contain at least 2 or 4
carbon atoms. Typically, the combined total sum of carbon atoms
present on both R''' groups may be less than 45, less than 35 or
less than 25. Examples of suitable ranges for the number of carbon
atoms present on both R''' groups includes 2 to 40, 3 to 24 or 4 to
20. Examples of suitable hydrocarbyl groups include propyl, butyl,
pentyl, hexyl dodecyl, butadecyl, hexadecyl, or octadecyl groups.
Generally the hydrocarbyl phosphite is soluble or at least
dispersible in oil. In one embodiment the hydrocarbyl phosphite may
be di-butyl hydrogen phosphite or a C.sub.16-18 alkyl hydrogen
phosphite. A more detailed description of the non-ionic phosphorus
compound is found in column 9, line 48 to column 11, line 8 of U.S.
Pat. No. 6,103,673.
Other Friction Modifiers
[0109] Another friction modifier (i.e. other than component (a) of
the invention) may be present, including 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, condensation
products of carboxylic acids or polyalkylene-polyamines, or amides
of hydroxyalkyl compounds.
[0110] In one embodiment the other friction modifier may include 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.
[0111] When in the form of a metal salt, typically the metal may be
zinc or calcium and the products may be overbased. Examples are
overbased calcium salts and basic oleic acid-zinc salt complexes.
The zinc salt may be acidic, neutral or basic (overbased). These
salts may be prepared from the reaction of a zinc containing
reagent with a carboxylic acid or salt thereof. A useful method of
preparation of these salts is to react zinc oxide with a carboxylic
acid. Useful carboxylic acids include carboxylic acids of the
formula R.sup.1COOH where R.sup.1 is an aliphatic or alicyclic
hydrocarbon radical. In one embodiment R.sup.1 is a fatty group
such as stearyl, oleyl, linoleyl, palmityl, or mixtures thereof. In
one embodiment the zinc salt contains stoichiometric excess of zinc
over the amount needed to prepare a neutral salt. The stoichiometry
includes zinc present from 1.1 to 1.8 times the stoichiometric, or
1.3 to 1.6 times the stoichiometric amount of zinc. The zinc
carboxylates are known in the art and are described in U.S. Pat.
No. 3,367,869. Metal salts may also include calcium salts. Examples
may include overbased calcium salts.
[0112] When in the form of an amide, the condensation product may
be prepared with ammonia, or with primary or secondary amines such
as diethylamine and diethanolamine.
[0113] When in the form of an imidazoline, the cyclic condensation
product of a fatty acid ester of glycerol with a diamine or
polyamine such as a polyethylenepolyamine. In one embodiment the
other friction modifier is the condensation product of a C8 to C24
fatty acid with a polyalkylene polyamine, and in particular, the
product of isostearic acid with tetraethylenepentamine.
[0114] In one embodiment the other friction modifier may be an
alkoxylated alcohol. A detailed description of suitable
alkyoxylated 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.
[0115] In one embodiment the other friction modifier may be an
alkoxylated amine e.g., an ethoxylated amine derived from 1.79%
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]allow-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.
[0116] In one embodiment the other friction modifier may be 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.
[0117] In one embodiment the other friction modifier may be an
alkylphosphonate mono- or di-ester sold commercially by Rhodia
under the trademark Duraphos.RTM. DMODP.
[0118] In one embodiment the other friction modifier other may be a
borated fatty epoxide, known from Canadian Patent No. 1,188,704.
These oil-soluble boron-containing compositions are prepared by
reacting, at a temperature from 80.degree. C. to 250.degree. C.,
boric acid or boron trioxide with at least one fatty epoxide. The
fatty epoxide typically contains at least 8 carbon atoms in the
fatty groups of the epoxide.
[0119] The borated fatty epoxides may be characterised by the
method for their preparation which involves the reaction of two
materials. Reagent A may be 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). Boric acid, and especially orthoboric
acid. Reagent B may be 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 about 1:2. The borated fatty epoxides may be prepared by
merely blending the two reagents and heating them at temperature of
80.degree. to 250.degree. C., or 100.degree. 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.
Friction Stabilising Agents
[0120] In one embodiment the lubricating composition further
comprises a friction stabilising agent. Friction stabilising agents
include H.sub.3PO.sub.4, H.sub.3PO.sub.3 or mixtures thereof.
Typically H.sub.3PO.sub.4 is commercially available in 85%
solution.
Dispersant
[0121] In one embodiment the additive concentrate further comprises
a dispersant. The dispersant may be a succinimide dispersant (for
example N-substituted long chain alkenyl succinimides), a Mannich
dispersant, an ester-containing dispersant, a condensation product
of a fatty hydrocarbyl monocarboxylic acylating agent with an amine
or ammonia, an alkyl amino phenol dispersant, a hydrocarbyl-amine
dispersant, a polyether dispersant or a polyetheramine
dispersant.
[0122] In different embodiments the dispersant may be a
succinimide, succinic acid ester, or Mannich dispersant.
[0123] In several embodiments the N-substituted long chain alkenyl
succinimides contain an average of at least 8, or 30, or 35 up to
350, or to 200, or to 100 carbon atoms. In one embodiment, the long
chain alkenyl group is derived from a polyalkene characterised by
an M.sub.n (number average molecular weight) of at least 500.
Generally, the polyalkene is characterised by an M.sub.n of 500, or
700, or 800, or even 900 up to 5000, or to 2500, or to 2000, or
even to 1500 or 1200. In one embodiment the long chain alkenyl
group is derived form polyolefins. The polyolefins may be derived
from monomers including monoolefins having 2 to 10 carbon atoms
such as ethylene, propylene, 1-butene, isobutylene, and 1-decene.
An especially useful monoolefin source is a C.sub.4 refinery stream
having a 35 to 75 weight percent butene content and a 30 to weight
percent isobutene content. Useful polyolefins include
polyisobutylenes having a number average molecular weight of 400 to
5000, in another instance of 400 to 2500, and in a further instance
of 400 or 500 to 1500. The polyisobutylene may have a vinylidene
double bond content of 5 to 69%, in a second instance of 50 to 69%,
and in a third instance of 50 to 95%.
[0124] In one embodiment the succinimide dispersant comprises a
polyisobutylene-substituted succinimide, wherein the
polyisobutylene-substituent has a number average molecular weight
of 400 to 5000.
[0125] Succinimide dispersants and their methods of preparation are
more fully described in U.S. Pat. Nos. 4,234,435 and 3,172,892. The
succinimide dispersant may also be prepared by either direct
alkylation or chlorine-route.
[0126] Suitable ester-containing dispersants are typically high
molecular weight esters. These materials are described in more
detail in U.S. Pat. No. 3,381,022.
[0127] Mannich dispersants are the reaction product of a
hydrocarbyl-substituted phenol, an aldehyde, and an amine or
ammonia. The hydrocarbyl substituent of the hydrocarbyl-substituted
phenol may have 10 to 400 carbon atoms, in another instance 30 to
180 carbon atoms, and in a further instance 10 or 40 to 110 carbon
atoms. This hydrocarbyl substituent may be derived from an olefin
or a polyolefin. Useful olefins include alpha-olefins, such as
1-decene, which are commercially available.
[0128] Hydrocarbyl-amine dispersants are hydrocarbyl-substituted
amines. The hydrocarbyl-substituted amine may be formed by heating
a mixture of a chlorinated olefin or polyolefin such as a
chlorinated polyisobutylene with an amine such as ethylenediamine
in the presence of a base such as sodium carbonate as described in
U.S. Pat. No. 5,407,453.
[0129] Polyether dispersants include polyetheramines, polyether
amides, polyether carbamates, and polyether alcohols.
Polyetheramines and their methods of preparation are described in
greater detail in U.S. Pat. No. 6,458,172, columns 4 and 5.
[0130] In one embodiment the invention further comprises at least
one dispersant derived from polyisobutylene, an amine and zinc
oxide to form a polyisobutylene succinimide complex with zinc. The
polyisobutylene succinimide complex with zinc may be used alone or
in combination.
[0131] The dispersants may also be post-treated by conventional
methods by a reaction with any of a variety of agents. Among these
are boron, urea, thiourea, dimercaptothiadiazoles, carbon
disulphide, aldehydes, ketones, carboxylic acids,
hydrocarbon-substituted succinic anhydrides, maleic anhydride,
nitriles, epoxides, phosphorus compounds and/or metal
compounds.
[0132] In one embodiment the dispersant is a borated dispersant.
Typically the borated dispersant comprises a succinimide dispersant
which in turn comprises a polyisobutylene succinimide, wherein the
polyisobutylene has a number average molecular weight of 400 to
5000.
[0133] In one embodiment the dispersant is phosphorylated
dispersant, or a borated phosphorylated dispersant.
[0134] In one embodiment the dispersant may be prepared by heating
(i) a dispersant material described above (for example
N-substituted long chain alkenyl succinimides), (ii)
2,5-dimercapto-1,3,4-thiadiazole or a hydrocarbyl-substituted
2,5-dimercapto-1,3,4-thiadiazole, or oligomers thereof, (iii) a
borating agent, and (iv) optionally a dicarboxylic acid of an
aromatic compound selected from the group consisting of 1,3 diacids
and 1,4 diacids; or (v) optionally a phosphorus acid compound, said
heating being sufficient to provide a product of (i), (ii), (iii)
and optionally (iv) or (v), which is soluble in an oil of
lubricating viscosity. The dispersant prepared by heating is
described in more detail in US Patent Applications US04/027094 and
60/654,164 (now WO 2006/091387).
Antioxidants
[0135] In one embodiment the lubricating composition further
comprises an antioxidant. The antioxidant may be present in ranges
of 0 wt % to 10 wt %, 0.01 wt % to 5 wt %, or 0.05 wt % to 3 wt %
of the lubricating composition.
[0136] Suitable antioxidants include molybdenum compounds such as
molybdenum dithiocarbamates, sulphurised olefins, sulphides
(including hydroxylalkyl sulphides such as
1-(tert-dodecylthio)-2-propanol or tert-nonyl mercaptan reacted
with propylene oxide (mole ratio 1:1)), hindered phenols including
ester-substituted hindered phenols, aminic compounds such as
phenylalphanaphthylamines or alkylated diphenylamines (typically
nonyl diphenylamine, di-nonyl diphenylamine, octyl diphenylamine,
di-octyl diphenylamine), or mixtures thereof.
Viscosity Modifiers
[0137] In one embodiment the lubricating composition further
comprises a viscosity modifier or dispersant viscosity modifier
(also referred to as DVMs). The viscosity modifier may be present
at 0 wt % to 12 wt %, 0.1 wt % to 10 wt % or 1 wt % to 8 wt % of
the lubricating composition.
[0138] Viscosity modifiers include hydrogenated copolymers of
styrene-butadiene, ethylene-propylene copolymers, polyisobutenes,
hydrogenated styrene-isoprene polymers, hydrogenated isoprene
polymers, polymath-acrylates, polyacrylates, polyalkyl styrenes,
alkenyl aryl conjugated diene copolymers, polyolefins, and esters
of maleic anhydride-styrene copolymers.
[0139] Dispersant viscosity modifiers 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.
Detergents
[0140] In one embodiment the lubricating composition further
comprises a detergent 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 saligenin, an alkylsalicylate, and a salixarate.
The alkali metal includes sodium. The alkaline earth metal may be
calcium, magnesium or barium. In different embodiments the
detergent may be a magnesium sulphonate or a calcium
sulphonate.
[0141] Other optional components include foam inhibitors, including
polydimethyl siloxane, fluorosilicone, copolymers of ethyl acrylate
and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers
including trialkyl phosphates, polyethylene glycols, polyethylene
oxides, polypropylene oxides and (ethylene oxide-propylene oxide)
polymers; pour point depressants including esters of maleic
anhydride-styrene, polymethacrylates, polyacrylates or
polyacrylamides.
[0142] Seal swell agents including 3-(decyloxy)
tetrahydro-1,1-dioxide thiophene, decyloxysulpholane, phthalate
esters, Exxon Necton-37.TM. (FN 1380) and Exxon Mineral Seal Oil
(FN 3200) may also be present in the lubricating composition.
INDUSTRIAL APPLICATION
[0143] The method of the invention is useful for lubricating a
variety of transmissions including an automatic transmission or a
manual transmission. In one embodiment the mechanical device is an
automatic transmission.
[0144] 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).
[0145] 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
[0146] A conventional automatic transmission fluid is evaluated for
friction and squawk performance using a test methodology as defined
below. The conventional automatic transmission fluid is evaluated
as (i) a new fluid, (ii) a new fluid that is aged at 150.degree. C.
for 100 hours, and (iii) the aged fluid of (ii) is then aged for
100 hours at 150.degree. C. Fluid (iii) has therefore been aged for
a total of 200 hours at 150.degree. C.
[0147] The automatic transmission fluid is evaluated in a
ZF.RTM.-GK rig first utilising standard methods to evaluate
frictional performance, and then further evaluated for squawk
performance using the procedure set forth in ZF test procedure
"PVL44_Quietschversuche.sub.--6HP26E_V2.0.pv". The procedure
"PVL44_Quietschversuche.sub.--6HP26E_V2.0.pv" is available from ZF
Passau GmbH., Test Systems, Tittlinger Strasse 28, D-94034 Passau,
Germany. In order to obtain squawk performance data the GK-rig
employed is configured by addition of ZF Squawk Modifications,
including the addition of a data acquisition recorder capable of
recording squawk. The results obtained are:
TABLE-US-00001 Test Test Procedure Test Fluid Parameter(limit) Test
Result GWK Friction ATF with 12 wt % Slope (increase Increasing
Test of the top treat with speed) additive concentrate .mu.5 (0.110
to 0.109 of the invention added 0.113) GK E Clutch torque
oscillation < Squawk Test 50 Nm at p .ltoreq. 1.625N/mm.sup.2
100 Hrs ATF fluid with no Fail, >50 Nm at before run in top
treat additive 0.9 N/mm.sup.2 concentrate 100 Hrs ATF fluid with no
Fail, >50 Nm at after run in top treat additive 0.75 N/mm.sup.2
concentrate 200 Hrs ATF fluid with no Fail, >50 Nm at additional
aging top treat additive 0.5 N/mm.sup.2 at 150.degree. C.
concentrate Before ATF with 12 wt % Pass, no running in of the top
treat oscillation >50 Nm additive concentrate of the invention
added After ATF with 12 wt % Pass, no running in of the top treat
oscillation >50 Nm additive concentrate of the invention added
100 Hrs ATF with 12 wt % Pass, no additional aging of the top treat
oscillation >50 Nm at 150.degree. C. additive concentrate of the
invention added
[0148] Overall the data indicates that the automatic transmission
fluid treated with the additive concentrate as a top treat package
is capable of minimising noise, shudder, chattering, or squawking,
whilst also not adversely affecting the frictional balance and
clutch holding capacity, nor increasing lubricant waste. This
allows for the transmission to operate with appropriate frictional
performance and minimised noise, shudder, chatter or squawk.
[0149] 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: [0150] (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); [0151] (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); [0152]
(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 encompass substituents as
pyridyl, furyl, thienyl and imidazolyl. Heteroatoms include
sulphur, oxygen, nitrogen. 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.
[0153] 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.
[0154] 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. 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. 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.
[0155] 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.
* * * * *