U.S. patent application number 16/427859 was filed with the patent office on 2019-12-12 for non-zinc-based antiwear compositions, hydraulic oil compositions, and methods of using the same.
The applicant listed for this patent is ExxonMobil Research and Engineering Company. Invention is credited to Kevin J. Buzdygon, Kathleen K. Cooper, Rajeev Kumar, Flory K. Wong.
Application Number | 20190376000 16/427859 |
Document ID | / |
Family ID | 66999912 |
Filed Date | 2019-12-12 |
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United States Patent
Application |
20190376000 |
Kind Code |
A1 |
Buzdygon; Kevin J. ; et
al. |
December 12, 2019 |
NON-ZINC-BASED ANTIWEAR COMPOSITIONS, HYDRAULIC OIL COMPOSITIONS,
AND METHODS OF USING THE SAME
Abstract
The present disclosure provides an antiwear composition
including molybdenum dithiocarbamate and an additional antiwear
agent including at least one non-zinc-based antiwear additive. The
present disclosure further provides a lubricating composition or
hydraulic oil that includes at least one lubricating base oil and
an antiwear composition (such as, a non-zinc-based or substantially
zinc-free antiwear agent) including an effective amount of
molybdenum dithiocarbamate. The disclosure also provides methods of
making and using the same.
Inventors: |
Buzdygon; Kevin J.;
(Wilmington, DE) ; Wong; Flory K.; (Voorhees,
NJ) ; Kumar; Rajeev; (Bryn Mawr, PA) ; Cooper;
Kathleen K.; (South River, NJ) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ExxonMobil Research and Engineering Company |
Annandale |
NJ |
US |
|
|
Family ID: |
66999912 |
Appl. No.: |
16/427859 |
Filed: |
May 31, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62683257 |
Jun 11, 2018 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 2219/068 20130101;
C10N 2010/12 20130101; C10M 169/04 20130101; C10M 155/00 20130101;
C10M 2223/04 20130101; C10M 2229/00 20130101; C10N 2030/40
20200501; C10N 2040/08 20130101; C10M 135/18 20130101; C10M
2223/047 20130101; C10N 2030/06 20130101; C10M 2219/068 20130101;
C10N 2010/12 20130101 |
International
Class: |
C10M 169/04 20060101
C10M169/04; C10M 155/00 20060101 C10M155/00 |
Claims
1. An antiwear composition comprising: an effective amount of
molybdenum dithiocarbamate; and an effective amount of at least one
non-zinc-based antiwear agent.
2. The antiwear composition of claim 1, wherein the antiwear agent
includes at least one of a phosphorous-based antiwear agent, alkyl
phosphate or ester thereof, dialkyl dithiophosphate ester, a
phosphate-based antiwear agent, salts thereof, or a combination
thereof.
3. The antiwear composition of claim 1, wherein the composition is
substantially zinc free.
4. A hydraulic oil composition comprising: at least one lubricating
base oil; and an antiwear composition comprising an effective
amount of molybdenum dithiocarbamate.
5. The composition of claim 4, wherein the effective amount of the
molybdenum dithiocarbamate is no greater than about 0.75 wt. %.
6. The composition of claim 4, wherein the lubricating base oil or
oils comprise at least one of: a Group I oil, a Group II oil, a
Group III oil, a Group IV oil, a Group V oil, a gas-to-liquid oil,
a polyalphaolefin, or combinations thereof.
7. The composition of claim 4, wherein the lubricating base oil or
oils include at least one of: at least one Group I oil; at least
one Group III oil, or a combination thereof.
8. The composition of claim 4, further comprising at least one of a
dispersant, an additional antiwear agent, a corrosion inhibitor, a
rust inhibitor, a detergent, an anti-seizure agent, an antifoam
agent or defoamant, a wax modifier, a metal deactivator/passivator,
an extreme pressure additive, an antioxidant, a viscosity index
improver, a viscosity improver/modifier, a seal compatibility
agent, a pour point depressant, a friction modifier, a lubricity
agent, an anti-staining agent, a dye or colorant/chromophoric
agent, a demulsifier, a wetting agent, an oxidation inhibitor, a
tackiness agent, a colorant, a detergent stabilizer, or
combinations thereof.
9. The composition of claim 4, wherein the hydraulic oil
composition is substantially zinc free.
10. The composition of claim 4, wherein the hydraulic oil
composition has reduced wear in at least one of a hydraulic motor,
a hydraulic pump, at least a portion of a hydraulic system, or a
combination thereof, relative to a hydraulic oil composition that
includes a non-zinc-based or zinc-free antiwear composition without
molybdenum dithiocarbamate.
11. The composition of claim 4, wherein the hydraulic oil
composition provides acceptable wear in the Rexroth Fluid Test
Axial Piston Unit Closed Loop test for at least one of a hydraulic
pump, a hydraulic motor, at least a portion of a hydraulic system,
or a combination thereof.
12. A method of making a hydraulic oil composition with improved
antiwear activity for at least one of a hydraulic pump, a hydraulic
motor, at least a portion of a hydraulic system, or a combination
thereof compared to a hydraulic oil composition that includes a
non-zinc-based or zinc-free antiwear composition without molybdenum
dithiocarbamate, the method comprising mixing: at least one
lubricating base oil; and an antiwear composition comprising an
effective amount of molybdenum dithiocarbamate.
13. The method of claim 12, wherein the effective amount of the
molybdenum dithiocarbamate is no greater than about 0.75 wt. %.
14. The method of claim 12, wherein at least one of: the
lubricating base oil or oils comprises at least one of: a Group I
oil, a Group II oil, a Group III oil, a Group IV oil, a Group V
oil, a gas-to-liquid oil, a polyalphaolefin, or combinations
thereof; the composition further comprises at least one of a
dispersant, an additional antiwear agent, a corrosion inhibitor, a
rust inhibitor, a detergent, an anti-seizure agent, an antifoam
agent or defoamant, a wax modifier, a metal deactivator/passivator,
an extreme pressure additive, an antioxidant, a viscosity index
improver, a viscosity improver/modifier, a seal compatibility
agent, a pour point depressant, a friction modifier, a lubricity
agent, an anti-staining agent, a dye or colorant/chromophoric
agent, a demulsifier, a wetting agent, an oxidation inhibitor, a
gelling agent, a tackiness agent, a colorant, a detergent
stabilizer, or combinations thereof; or a combination thereof.
15. A hydraulic oil composition produced according to claim 12.
16. A method for lubricating at least one of a hydraulic motor
requiring a hydraulic oil composition, a hydraulic pump requiring
the hydraulic oil composition, at least a portion of a hydraulic
system requiring the hydraulic oil composition, or a combination
thereof, the method comprising: supplying the hydraulic motor,
pump, the portion of the hydraulic system, or a combination
thereof, with a hydraulic oil composition comprising: at least one
lubricating base oil; and an antiwear composition comprising an
effective amount of molybdenum dithiocarbamate.
17. The method of claim 16, wherein the effective amount of the
molybdenum dithiocarbamate is no greater than about 0.75 wt. %.
18. The method of claim 16, wherein at least one of: the
lubricating base oil or oils comprises at least one of: a Group I
oil, a Group II oil, a Group III oil, a Group IV oil, a Group V
oil, a gas-to-liquid oil, a polyalphaolefin, or combinations
thereof; the composition further comprises at least one of a
dispersant, an additional antiwear agent, a corrosion inhibitor, a
rust inhibitor, a detergent, an anti-seizure agent, an antifoam
agent or defoamant, a wax modifier, a metal deactivator/passivator,
an extreme pressure additive, an antioxidant, a viscosity index
improver, a viscosity improver/modifier, a seal compatibility
agent, a pour point depressant, a friction modifier, a lubricity
agent, an anti-staining agent, a dye or colorant/chromophoric
agent, a demulsifier, a wetting agent, an oxidation inhibitor, a
gelling agent, a tackiness agent, a colorant, a detergent
stabilizer, or combinations thereof; or a combination thereof.
19. The method of claim 16, wherein the lubricating base oil or
oils includes at least one of: at least one Group I oil, at least
one Group III oil, or a combination thereof.
20. The method of claim 16, wherein at least one of: the antiwear
composition is substantially zinc free; the hydraulic oil
composition is substantially zinc-free composition; the hydraulic
oil composition has reduced wear in at least one of a hydraulic
motor, a hydraulic pump, at least a portion of a hydraulic system,
or a combination thereof, relative to a hydraulic oil composition
that includes a non-zinc-based or zinc-free antiwear composition
without molybdenum dithiocarbamate; the hydraulic oil composition
provides acceptable wear in (e.g., the hydraulic oil composition
passes) the Rexroth Fluid Test Axial Piston Unit Closed Loop test
for at least one of a hydraulic pump, a hydraulic motor, at least a
portion of a hydraulic system, or a combination thereof; or a
combination thereof.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional
Application Ser. No. 62/683,257 filed Jun. 11, 2018 which is herein
incorporated by reference in its entirety.
FIELD
[0002] The present disclosure relates to antiwear additive, a
lubricating composition including the same, and methods of using
the same. In particular, the disclosure relates to lubricating
hydraulic compositions comprising a non-zinc-based or substantially
zinc-free antiwear additive/composition, and methods of lubricating
a hydraulic system (e.g., hydraulic pump and/or motor) by using the
same.
BACKGROUND
[0003] Hydraulic systems (which may include a pump(s), a motor(s)
and ancillary systems) can be comprised of copper alloys which are
susceptible to corrosion, which can inhibit robustness of the
system. Maintaining lubricant and system compatibility enhances the
equipment life and productivity.
[0004] Drivers for next generation hydraulic lubricants include
long life oil with reduced operational costs and environmental
footprint. Lubricants that meet these characteristics must also
comply with the latest equipment designs. Hydraulic equipment
strategies and equipment evolution for some original equipment
manufacturers (OEMs), include the move to higher pressures and
temperatures than previously utilized. One outcome from this
evolution is the need for improved mechanical strength and
stability of componentry of hydraulic systems. Some OEMs, e.g.
Bosch Rexroth AG, use proprietary strategies to case harden the
metallic surface of hydraulic system components in order for the
system(s) to operate at higher pressures and temperatures.
[0005] Designing lubricants that protect these modified surfaces
has been challenging, and some hydraulic equipment companies, e.g.,
Bosch Rexroth AG, advise their customers that only approved oils
should be utilized in their equipment. For example, the Bosch
Rexroth AG Fluid Test Axial Piston Unit Closed Loop (RFT-APU-CL)
test is a hydraulic pump/motor test that utilizes high stress
laboratory conditions and requires hydraulic oil/fluid with robust
antiware activity. The test consists of a break-in test, swivel
cycle test, and a corner power test. The RFT-APU-CL test utilizes a
A4VG045EP hydraulic pump and a A6VM060EP hydraulic motor that
includes case hardened material.
[0006] While the hydraulic oil or fluid market includes
zinc-containing products and non-zinc-based or zinc-free containing
products, it is believed that the RFT-APU-CL test may favor
zinc-based antiwear additives, such as zinc dithiophosphate (ZDP)
or zinc dialkyl dithiophosphates (ZDDP). In fact, while many
zinc-based hydraulic fluids have apparently passed the RFT-APU-CL
test and are approved by Bosch Rexroth AG, the inventors are
unaware of a zinc-free antiwear additive that has yet gained full
approval by Bosch Rexroth AG. That is, currently known non-zinc
based antiwear additives generally have higher motor piston wear in
the RFT-APU-CL test. The reasons for the differential efficacy of
zinc-based and zinc-free antiwear additives is not known.
[0007] However, many owner/operators of hydraulic equipment, would
prefer for personal or environmental reasons, and is sometimes
required by local legislation, to utilize a zinc-free or
non-zinc-based hydraulic fluid/oil with robust antiwear
activity--i.e., a non-zinc-based or substantially zinc-free
antiwear additive that has antiwear activity that is comparable to
zinc-based or zinc-containing antiwear additives. Thus, there is a
need for hydraulic fluid/oil comprising a non-zinc-based or
substantially zinc-free antiwear additive with good antiwear
properties (i.e., good antiwear activity as determined by the
RFT-APU-CL test) that is available for hydraulic applications, e.g.
for use in Bosch Rexroth AG hydraulic equipment.
SUMMARY
[0008] The present disclosure provides a substantially zinc-free or
non-zinc-based antiwear additive/composition and lubricating
compositions, such as a hydraulic oil composition, including the
same, both of which have a surprising and unexpected robust
lubricating properties (e.g. under the Bosch Rexroth AG Fluid Test
Axial Piston Unit Closed Loop (RFT-APU-CL) test), and methods of
making and using the same.
[0009] Therefore, an aspect of the present disclosure includes an
antiwear composition (e.g., a non-zinc-based antiwear composition)
comprising: an effective amount of molybdenum dithiocarbamate; and
an effective amount of at least one non-zinc-based or zinc-free
antiwear agent. In an embodiment, the non-zinc-based or zinc-free
antiwear agent includes at least one of a phosphorous-based
antiwear agent, alkyl phosphate or ester thereof, dialkyl
dithiophosphate ester, a phosphate-based antiwear agent, salts
thereof, or a combination thereof. In any aspect or embodiments
described herein, the antiwear composition is a substantially
zinc-free antiwear composition or non-zinc-based antiwear
composition. For example, the antiwear composition may be
zinc-free.
[0010] In some embodiments, the antiwear composition includes
dialkyl dithiophosphate ester.
[0011] In certain embodiments, the antiwear composition is
substantially zinc free (e.g., the antiwear composition may include
zinc as a minor impurity).
[0012] A further aspect of the present disclosure includes a
hydraulic oil composition comprising: at least one lubricating base
oil; and an antiwear composition (such as, a non-zinc-based
antiwear composition or an antiwear composition that is
substantially zinc free [e.g., an antiwear composition that may
include zinc as a minor impurity] and/or an effective amount of an
antiwear composition) comprising an effective amount of molybdenum
dithiocarbamate. In any aspect or embodiments described herein, the
antiwear composition may be zinc-free.
[0013] In some embodiments, the effective amount of the molybdenum
dithiocarbamate is no greater than about 0.75 wt. % (e.g., from
about 0.001 wt. % to about 0.6 wt. % or from about 0.01 wt. % to
about 0.5 wt. %).
[0014] In certain embodiments, the lubricating base oil or oils
comprises at least one of: a Group I oil, a Group II oil, a Group
III oil, a Group IV oil, a Group V oil, a gas-to-liquid oil, a
polyalphaolefin, or combinations thereof.
[0015] In further embodiments, the lubricating base oil or oils
include at least one of: at least one Group I oil; at least one
Group III oil, or a combination thereof.
[0016] In another embodiment, the hydraulic oil composition further
comprises at least one of a dispersant, an additional antiwear
agent (e.g., a non-zinc-based or zinc-free antiwear agent), a
corrosion inhibitor, a rust inhibitor, a detergent, an anti-seizure
agent, an antifoam agent or defoamant, a wax modifier, a metal
deactivator/passivator, an extreme pressure additive, an
antioxidant, a viscosity index improver, a viscosity
improver/modifier, a seal compatibility agent, a pour point
depressant, a friction modifier, a lubricity agent, an
anti-staining agent, a dye or colorant/chromophoric agent, a
demulsifier, a wetting agent, an oxidation inhibitor, a tackiness
agent, a colorant, a detergent stabilizer, or combinations
thereof.
[0017] In other embodiments, the hydraulic oil composition is
substantially zinc-free (e.g., the hydraulic oil composition may
include zinc as a minor impurity). In any aspect or embodiment
described herein, the hydraulic oil composition is a substantially
zinc-free hydraulic oil composition. For example, the hydraulic oil
composition may be zinc-free.
[0018] In yet further embodiments, the hydraulic oil composition
has reduced wear in at least one of a hydraulic motor, a hydraulic
pump, at least a portion of a hydraulic system, or a combination
thereof, relative to a hydraulic oil composition that includes a
substantially zinc-free antiwear composition or a non-zinc-based
antiwear composition without molybdenum dithiocarbamate.
[0019] In particular embodiments, the hydraulic oil composition
provides acceptable wear in (e.g., the hydraulic oil composition
passes) the Rexroth Fluid Test Axial Piston Unit Closed Loop test
for at least one of a hydraulic pump, a hydraulic motor, at least a
portion of a hydraulic system, or a combination thereof.
[0020] Another aspect of the present disclosure includes a method
of making a hydraulic oil composition with improved antiwear
activity for at least one of a hydraulic pump, a hydraulic motor,
at least a portion of a hydraulic system, or a combination thereof
compared to a hydraulic oil composition that includes a
substantially zinc-free or non-zinc-based antiwear composition
without molybdenum dithiocarbamate, the method comprising mixing:
at least one lubricating base oil; and an antiwear composition
(such as, a non-zinc-based or an antiwear composition that is
substantially zinc free [e.g., the antiwear composition may include
zinc as a minor impurity] and/or an effective amount of an antiwear
composition) comprising an effective amount of molybdenum
dithiocarbamate.
[0021] In some embodiments, the effective amount of the molybdenum
dithiocarbamate is no greater than about 0.75 wt. % (e.g., from
about 0.001 wt. % to about 0.6 wt. % or from about 0.01 wt. % to
about 0.5 wt. %).
[0022] In certain embodiments, at least one of: (1) the lubricating
base oil or oils comprises at least one of: a Group I oil, a Group
II oil, a Group III oil, a Group IV oil, a Group V oil, a
gas-to-liquid oil, a polyalphaolefin, or combinations thereof, (2)
the composition further comprises at least one of a dispersant, an
additional antiwear agent (e.g., a non-zinc-based or zing-free
antiwear agent), a corrosion inhibitor, a rust inhibitor, a
detergent, an anti-seizure agent, an antifoam agent or defoamant, a
wax modifier, a metal deactivator/passivator, an extreme pressure
additive, an antioxidant, a viscosity index improver, a viscosity
improver/modifier, a seal compatibility agent, a pour point
depressant, a friction modifier, a lubricity agent, an
anti-staining agent, a dye or colorant/chromophoric agent, a
demulsifier, a wetting agent, an oxidation inhibitor, a gelling
agent, a tackiness agent, a colorant, a detergent stabilizer, or
combinations thereof; or (3) a combination thereof.
[0023] An aspect of the present disclosure includes a hydraulic oil
composition produced according to the method of making the
hydraulic oil/fluid of the present disclosure.
[0024] An additional aspect of the present disclosure includes a
method for lubricating at least one of a hydraulic motor requiring
a hydraulic oil composition, a hydraulic pump requiring the
hydraulic oil composition, at least a portion of a hydraulic system
requiring the hydraulic oil composition, or a combination thereof,
the method comprising: supplying the hydraulic motor, pump, the
portion of the hydraulic system, or a combination thereof, with a
hydraulic oil composition comprising: at least one lubricating base
oil; and an antiwear composition (e.g., a non-zinc-based or
substantially zinc-free antiwear composition) comprising an
effective amount of molybdenum dithiocarbamate.
[0025] In some embodiments, the effective amount of the molybdenum
dithiocarbamate is no greater than about 0.75 wt. % (e.g., from
about 0.001 wt. % to about 0.6 wt. % or from about 0.01 wt. % to
about 0.5 wt. %).
[0026] In further embodiments, at least one of: (1) the lubricating
base oil or oils comprises at least one of: a Group I oil, a Group
II oil, a Group III oil, a Group IV oil, a Group V oil, a
gas-to-liquid oil, a polyalphaolefin, or combinations thereof, (2)
the composition further comprises at least one of a dispersant, an
additional antiwear agent (e.g., a non-zinc-based or zinc-free
antiwear agent), a corrosion inhibitor, a rust inhibitor, a
detergent, an anti-seizure agent, an antifoam agent or defoamant, a
wax modifier, a metal deactivator/passivator, an extreme pressure
additive, an antioxidant, a viscosity index improver, a viscosity
improver/modifier, a seal compatibility agent, a pour point
depressant, a friction modifier, a lubricity agent, an
anti-staining agent, a dye or colorant/chromophoric agent, a
demulsifier, a wetting agent, an oxidation inhibitor, a gelling
agent, a tackiness agent, a colorant, a detergent stabilizer, or
combinations thereof; or (3) a combination thereof.
[0027] In other embodiments, the lubricating base oil or oils
includes at least one of: at least one Group I oil, at least one
Group III oil, or a combination thereof.
[0028] In other embodiments, at least one of: (1) the antiwear
composition is substantially zinc free [e.g., the antiwear
composition may include zinc as a minor impurity] the hydraulic oil
composition is substantially zinc-free composition (e.g., the
hydraulic oil may include zinc as a minor impurity); (2) the
hydraulic oil composition has reduced wear in at least one of a
hydraulic motor, a hydraulic pump, at least a portion of a
hydraulic system, or a combination thereof, relative to a hydraulic
oil composition that includes a substantially zinc-free antiwear
composition or a non-zinc-base antiwear composition without
molybdenum dithiocarbamate; (3) the hydraulic oil composition
provides acceptable wear in (e.g., the hydraulic oil composition
passes) the Rexroth Fluid Test Axial Piston Unit Closed Loop test
for at least one of a hydraulic pump, a hydraulic motor, at least a
portion of a hydraulic system, or a combination thereof; or (4) a
combination thereof.
[0029] Where applicable or not specifically disclaimed, any one of
the embodiments described herein are contemplated to be able to
combine with any other one or more embodiments or aspects, even
though the embodiments are described under different aspects of the
disclosure. These and other embodiments are disclosed or are
understood to be encompassed by, the following Detailed
Description, including Examples herein.
DETAILED DESCRIPTION
[0030] The present disclosure relates, in part, to the surprising
and unexpected discovery of a non-zinc-based or substantially
zinc-free antiwear additive/composition that provides robust
antwear activity in the Bosch Rexroth AG Fluid Test Axial Piston
Unit Closed Loop (RFT-APU-CL) test, which heretofore has been
achieved primarily by zinc-based antiwear compositions.
[0031] The following is a detailed description provided to aid
those skilled in the art in practicing the present disclosure.
Those of ordinary skill in the art may make modifications and
variations in the embodiments described herein without departing
from the spirit or scope of the present disclosure. Unless
otherwise defined, all technical and scientific terms used herein
have the same meaning as commonly understood by one of ordinary
skill in the art to which this disclosure belongs. The terminology
used in the description of the disclosure herein is for describing
particular embodiments only and is not intended to be limiting of
the disclosure. All publications, patent applications, patents,
figures and other references mentioned herein are expressly
incorporated by reference in their entirety.
[0032] It was surprising and unexpectedly discovered that a
non-zinc-based antiwear composition could provide a robust antiwear
activity in hydraulic systems, such as in Bosch Rexroth AG
hydraulic systems, which to date has been primarily achieved with
antiwear compositions comprising at least one of zinc
dithiophosphate (ZDP) and zinc dialkyl dithiophosphates (ZDDP).
[0033] As such, an aspect of the present disclosure provides an
antiwear composition (e.g., a non-zinc-based antiwear composition)
comprising: an effective amount of molybdenum dithiocarbamate. The
antiwear composition of the present disclosure may further include
at least one additional antiwear agent (e.g., an effective amount
of an additional antiwear agent). The additional antiwear agent may
be at least one non-zinc-based or zinc-free antiwear agent. For
example, the non-zinc-based zinc-free antiwear agent may includes
at least one of a phosphorous-based antiwear agent, alkyl phosphate
or ester thereof, dialkyl dithiophosphate ester, a phosphate-based
antiwear agent, salts thereof, or a combination thereof. Another
aspect of the disclosure provides a hydraulic fluid that includes
at least one base oil; and a non-zinc-based or substantially
zinc-free antiwear composition/additive of the present
disclosure--i.e., an antiwear composition that includes an
effective amount of molybdenum dithiocarbamate. It should be noted
that the antiwear composition and lubricating compositions of the
present disclosure may be utilized in any application that would
benefit from the advantages and benefits described herein, e.g.,
the antiwear composition (e.g., a non-zinc-based antiwear
composition comprising an effective amount of molybdenum
dithiocarbamate and an effective amount of at least one additional
non-zinc-based or zinc-free antiwear agent (e.g., at least one
antiwear agent selected from the group consisting of a
phosphorous-based antiwear agent, alkyl phosphate or ester thereof,
dialkyl dithiophosphate ester, a phosphate-based antiwear agent,
salts thereof, or a combination thereof) may be utilized as or be
included in an industrial fluid, hydraulic fluid, turbine oil, or
circulating oil.
[0034] The following terms may have meanings ascribed to them
below, unless specified otherwise. However, it should be understood
that other meanings that are known or understood by those having
ordinary skill in the art are also possible, and within the scope
of the present disclosure. In the case of conflict, the present
specification, including definitions, will control. In addition,
the materials, methods, and examples are illustrative only and not
intended to be limiting.
[0035] As used herein, the terms "non-zinc-based" and
"substantially zinc-free", should be understood to mean that zinc
has not been added (e.g., ZDP, ZDDP, or derivatives thereof) to the
composition to which it is referring, and thus, zinc (if present)
may be present within the composition only as a minor impurity
(e.g, at trace amounts). For example, the non-zinc-based or
substantially zinc-free antiwear composition does not include ZDP,
ZDDP, or derivatives thereof.
[0036] As used herein, the term "lubricating oil" or "lubricating
composition" may refer to a lubricating oil or fluid, such as a
hydraulic oil or fluid, or an antiwear composition, unless their
context indicates otherwise.
[0037] As used herein, the term "effective" is used to describe an
amount of a compound, composition or component which, when used
within the context of its intended use, effects an intended result.
The term effective subsumes all other effective amount or effective
concentration terms, which are otherwise described or used in the
present application.
[0038] The articles "a", "an", and "the" as used herein and in the
appended claims are used herein to refer to one or to more than one
(i.e., to at least one) of the grammatical object of the article
unless the context clearly indicates otherwise. By way of example,
"an element" means one element or more than one element.
[0039] The phrase "and/or," as used herein in the specification and
in the claims, should be understood to mean "either or both" of the
elements so conjoined, i.e., elements that are conjunctively
present in some cases and disjunctively present in other cases.
Multiple elements listed with "and/or" should be construed in the
same fashion, i.e., "one or more" of the elements so conjoined.
Other elements may optionally be present other than the elements
specifically identified by the "and/or" clause, whether related or
unrelated to those elements specifically identified. Thus, as a
non-limiting example, a reference to "A and/or B", when used in
conjunction with open-ended language such as "comprising" can
refer, in one embodiment, to A only (optionally including elements
other than B); in another embodiment, to B only (optionally
including elements other than A); in yet another embodiment, to
both A and B (optionally including other elements); etc.
[0040] As used herein in the specification and in the claims, "or"
should be understood to have the same meaning as "and/or" as
defined above. For example, when separating items in a list, "or"
or "and/or" shall be interpreted as being inclusive, i.e., the
inclusion of at least one, but also including more than one, of a
number or list of elements, and, optionally, additional unlisted
items. Only terms clearly indicated to the contrary, such as "only
one of" or "exactly one of," or, when used in the claims,
"consisting of," will refer to the inclusion of exactly one element
of a number or list of elements. In general, the term "or" as used
herein shall only be interpreted as indicating exclusive
alternatives (i.e., "one or the other but not both") when preceded
by terms of exclusivity, such as "either," "one of," "only one of,"
or "exactly one of."
[0041] As used herein in the specification and in the claims, the
phrase "at least one," in reference to a list of one or more
elements, should be understood to mean at least one element
selected from anyone or more of the elements in the list of
elements, but not necessarily including at least one of each and
every element specifically listed within the list of elements and
not excluding any combinations of elements in the list of elements.
This definition also allows that elements may optionally be present
other than the elements specifically identified within the list of
elements to which the phrase "at least one" refers, whether related
or unrelated to those elements specifically identified. Thus, as a
nonlimiting example, "at least one of A and B" (or, equivalently,
"at least one of A or B," or, equivalently "at least one of A
and/or B") can refer, in one embodiment, to at least one,
optionally including more than one, A, with no B present (and
optionally including elements other than B); in another embodiment,
to at least one, optionally including more than one, B, with no A
present (and optionally including elements other than A); in yet
another embodiment, to at least one, optionally including more than
one, A, and at least one, optionally including more than one, B
(and optionally including other elements); etc.
[0042] In the claims, as well as in the specification above, all
transitional phrases such as "comprising," "including," "carrying,"
"having," "containing," "involving," "holding," "composed of," and
the like are to be understood to be open-ended, i.e., to mean
including but not limited to. Only the transitional phrases
"consisting of" and "consisting essentially of" shall be closed or
semi-closed transitional phrases, respectively, as set forth in the
United States Patent Office Manual of Patent Examining Procedures,
Section 2111.03.
[0043] As used herein in the specification and in the claims, the
phrase "at least one," in reference to a list of one or more
elements, should be understood to mean at least one element
selected from anyone or more of the elements in the list of
elements, but not necessarily including at least one of each and
every element specifically listed within the list of elements and
not excluding any combinations of elements in the list of elements.
This definition also allows that elements may optionally be present
other than the elements specifically identified within the list of
elements to which the phrase "at least one" refers, whether related
or unrelated to those elements specifically identified. Thus, as a
non-limiting example, "at least one of A and B" (or, equivalently,
"at least one of A or B," or, equivalently "at least one of A
and/or B") can refer, in one embodiment, to at least one,
optionally including more than one, A, with no B present (and
optionally including elements other than B); in another embodiment,
to at least one, optionally including more than one, B, with no A
present (and optionally including elements other than A); in yet
another embodiment, to at least one, optionally including more than
one, A, and at least one, optionally including more than one, B
(and optionally including other elements); etc.
[0044] It should also be understood that, in certain methods
described herein that include more than one step or act, the order
of the steps or acts of the method is not necessarily limited to
the order in which the steps or acts of the method are recited
unless the context indicates otherwise.
[0045] Unless specifically stated or obvious from context, as used
herein, the term "about" or "approximately" is understood as within
a range of normal tolerance in the art, for example within 2
standard deviations of the mean. About can be understood as within
10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, or
0.01% of the stated value. Unless otherwise clear from context, all
numerical values provided herein can be modified by the term
"about."
[0046] Any compositions or methods provided herein can be combined
with one or more of any of the other compositions and methods
provided herein.
[0047] Ranges provided herein are understood to be shorthand for
all of the values within the range. For example, a range of 1 to 50
is understood to include any number, combination of numbers, or
sub-range from the group consisting 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,
11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27,
28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44,
45, 46, 47, 48, 49, or 50.
[0048] Reference will now be made in detail to exemplary
embodiments of the disclosure. While the disclosure will be
described in conjunction with the exemplary embodiments, it will be
understood that it is not intended to limit the disclosure to those
embodiments. To the contrary, it is intended to cover alternatives,
modifications, and equivalents as may be included within the spirit
and scope of the disclosure as defined by the appended claims.
[0049] It should however be noted that the antiwear and lubricating
compositions of the present disclosure may be utilized in or as
industrial fluids, hydraulic fluids, turbine oils, or circulating
oils.
Compositions of the Present Disclosure
[0050] An aspect of the present disclosure provides a
non-zinc-based antiwear composition (e.g., a non-zinc-based
antiwear composition) comprising an effective amount of molybdenum
dithiocarbamate. In any aspect or embodiment described herein, the
antiwear composition may further include an effective amount of at
least one additional antiwear agent (e.g., 1, 2, 3, 4, 5, or more),
such as a non-zinc-based or zinc-free antiwear agent (e.g., at
least one antiwear agent selected from the group consisting of a
phosphorous-based antiwear agent, alkyl phosphate or ester thereof,
dialkyl dithiophosphate ester, a phosphate-based antiwear agent,
salts thereof, or a combination thereof). In certain embodiments,
the antiwear composition includes dialkyl dithiophosphate ester. In
any aspect or embodiment described herein, the antiwear composition
of the present disclosure provides robust antiwear activity, e.g.
as determined by the RFT-APU-CL test, in a hydraulic motor, a
hydraulic pump, or both, as compared presently known non-zinc-based
or zinc-free antiwear compositions without molybdenum
dithiocarbamate.
[0051] The effective amount of molybdenum dithiocarbamate in the
antiwear composition may be about 5 wt. % to about 70 wt. % of the
antiwear composition. For example, the dithiocarbamate may be
present in the antiwear composition in an amount of about 5 to
about 70 wt. %, about 5 to about 65 wt. %, about 5 to about 60 wt.
%, about 5 to about 55 wt. %, about 5 to about 50 wt. %, about 5 to
about 45 wt. %, about 5 to about 40 wt. %, about 5 to about 35 wt.
%, about 5 to about 30 wt. %, about 5 to about 25 wt. %, about 5 to
about 20 wt. %, about 5 to about 15 wt. %, about 7.5 to about 70
wt. %, about 7.5 to about 65 wt. %, about 7.5 to about 60 wt. %,
about 7.5 to about 55 wt. %, about 7.5 to about 50 wt. %, about 7.5
to about 45 wt. %, about 7.5 to about 40 wt. %, about 7.5 to about
35 wt. %, about 7.5 to about 30 wt. %, about 7.5 to about 25 wt. %,
about 7.5 to about 20 wt. %, about 10 to about 70 wt. %, about 10
to about 65 wt. %, about 10 to about 60 wt. %, about 10 to about 55
wt. %, about 10 to about 50 wt. %, about 10 to about 45 wt. %,
about 10 to about 40 wt. %, about 10 to about 35 wt. %, about 10 to
about 30 wt. %, about 10 to about 25 wt. %, about 15 to about 70
wt. %, about 15 to about 65 wt. %, about 15 to about 60 wt. %,
about 15 to about 55 wt. %, about 15 to about 50 wt. %, about 15 to
about 45 wt. %, about 15 to about 40 wt. %, about 15 to about 35
wt. %, about 15 to about 30 wt. %, about 15 to about 25 wt. %,
about 20 to about 70 wt. %, about 20 to about 65 wt. %, about 20 to
about 60 wt. %, about 20 to about 55 wt. %, about 20 to about 50
wt. %, about 20 to about 45 wt. %, about 20 to about 40 wt. %,
about 20 to about 35 wt. %, about 20 to about 30 wt. %, about 25 to
about 70 wt. %, about 25 to about 65 wt. %, about 25 to about 60
wt. %, about 25 to about 55 wt. %, about 25 to about 50 wt. %,
about 25 to about 45 wt. %, about 25 to about 40 wt. %, about 25 to
about 35 wt. %, about 35 to about 70 wt. %, about 35 to about 65
wt. %, about 35 to about 60 wt. %, about 35 to about 55 wt. %,
about 35 to about 50 wt. %, about 35 to about 45 wt. %, about 45 to
about 70 wt. %, about 45 to about 65 wt. %, about 45 to about 60
wt. %, about 45 to about 55 wt. %, about 55 to about 70 wt. %, or
about 55 to about 65 wt. %.
[0052] In certain embodiments, the antiwear composition of the
present disclosure is substantially zinc free. The antiwear
composition may have zinc as a minor impurity. In certain
embodiments, the antiwear composition does not include ZDP, ZDDP,
or derivatives thereof.
[0053] A further aspect of the present disclosure includes a
hydraulic oil composition comprising: at least one lubricating base
oil (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more); and an
effective amount of a non-zinc-based antiwear composition (such as,
a substantially zinc free) comprising an effective amount of
molybdenum dithiocarbamate (e.g., no greater than about 0.75 wt. %
of the hydraulic oil composition). For example, molybdenum
dithiocarbamate may be present in the hydraulic oil composition in
an amount .ltoreq.about 0.75 wt. %, .ltoreq.about 0.65 wt. %,
.ltoreq.about 0.6 wt. %, .ltoreq.about 0.5 wt. %, .ltoreq.about 0.4
wt. %, .ltoreq.about 0.3 wt. %, .ltoreq.about 0.2 wt. %,
.ltoreq.about 0.175 wt. %, .ltoreq.about 0.1.5 wt. %, about 0.001
to about 0.75 wt. %, about 0.001 to about 0.65 wt. %, about 0.001
to about 0.6 wt. %, about 0.001 to about 0.5 wt. %, about 0.001 to
about 0.4 wt. %, about 0.001 to about 0.3 wt. %, about 0.001 to
about 0.2 wt. %, about 0.001 to about 0.175 wt. %, about 0.001 to
about 0.15 wt. %, about 0.01 to about 0.75 wt. %, about 0.01 to
about 0.65 wt. %, about 0.01 to about 0.6 wt. %, about 0.01 to
about 0.5 wt. %, about 0.01 to about 0.4 wt. %, about 0.01 to about
0.3 wt. %, about 0.01 to about 0.2 wt. %, about 0.01 to about 0.175
wt. %, about 0.05 to about 0.75 wt. %, about 0.05 to about 0.65 wt.
%, about 0.05 to about 0.6 wt. %, about 0.05 to about 0.5 wt. %,
about 0.05 to about 0.4 wt. %, about 0.05 to about 0.3 wt. %, about
0.05 to about 0.2 wt. %, about 0.05 to about 0.175 wt. %, about
0.05 to about 0.15 wt. %, about 0.2 to about 0.75 wt. %, about 0.2
to about 0.65 wt. %, about 0.2 to about 0.6 wt. %, about 0.2 to
about 0.5 wt. %, about 0.3 to about 0.75 wt. %, about 0.3 to about
0.65 wt. %, or about 0.5 to about 0.75 wt. %.
[0054] In any aspect or embodiment described herein, the
lubricating base oil or oils may comprise at least one of: at least
one Group I oil, at least one Group II oil, at least one Group III
oil, at least one Group IV oil, at least one Group V oil, at least
one gas-to-liquid oil, at least one polyalphaolefin, or
combinations thereof. For example, the lubricating base oil or oils
may include at least one of: at least one Group I oil (e.g., 1, 2,
3, 4, 5, or more); at least one Group III oil (e.g., 1, 2, 3, 4, 5,
6, 7, 8, or more), or a combination thereof.
[0055] The hydraulic oil composition may further comprise at least
one performance additive. For example, the lubricating oil or
hydraulic oil/fluid composition of the present disclosure may
further comprise at least of a dispersant, an additional antiwear
agent (e.g. a non-zinc-based or zinc-free antiwear agent), a
corrosion inhibitor, a rust inhibitor, a detergent, an anti-seizure
agent, an antifoam agent or defoamant, a wax modifier, a metal
deactivator/passivator, an extreme pressure additive, an
antioxidant, a viscosity index improver, a viscosity
improver/modifier, a seal compatibility agent, a pour point
depressant, a friction modifier, a lubricity agent, an
anti-staining agent, a dye or colorant/chromophoric agent, a
demulsifier, a wetting agent, an oxidation inhibitor, a tackiness
agent, a colorant, a detergent stabilizer, or combinations thereof.
Thus, the antiwear composition of the hydraulic oil composition may
further comprise at least one additional antiwear agent that
includes at least one of a phosphorous-based antiwear agent, alkyl
phosphate or ester thereof, dialkyl dithiophosphate ester, a
phosphate-based antiwear agent, salts thereof, or a combination
thereof. Exemplary performance additives that may be utilized in
the present disclosure are described in greater detail below.
[0056] The hydraulic oil composition of the present disclosure may
be substantially free of zinc. For example, the hydraulic
composition of the present disclosure may not have zinc added, but
it could be present as a minor impurity. In certain embodiments,
the hydraulic oil composition is zinc-free.
[0057] As discussed above and demonstrated below in the Examples,
the hydraulic oil composition of the present disclosure provides
robust antiwear activity in hydraulic systems as demonstrated by
the surprising and unexpected ability to reduce wear in at least
one of a hydraulic motor, a hydraulic pump, at least a portion of a
hydraulic system, or a combination thereof, relative to a hydraulic
oil composition that include a non-zinc-based antiwear composition
(e.g., a substantially zinc-free or zinc-free antiwear agent)
without molybdenum dithiocarbamate. In particular, the hydraulic
oil composition of the present disclosure provides acceptable wear
in (i.e., the hydraulic oil composition passes) the Rexroth Fluid
Test Axial Piston Unit Closed Loop test for at least one of a
hydraulic pump, a hydraulic motor, at least a portion of a
hydraulic system, or a combination thereof, because of the
surprisingly robust antiwear activity of molybdenum
dithiocarbamate, as demonstrated in the Examples below.
Base Oil(s)
[0058] Groups I, II, III, IV and V are broad base oil stock
categories, the characteristics of which are summarized in Table 1
below, developed and defined by the American Petroleum Institute
(API Publication 1509; www.API.org) to create guidelines for
lubricant base oils. Group I base stocks have a viscosity index of
between about 80 to about 120 and contain greater than about 0.03%
sulfur and/or less than about 90% saturates. Group II base stocks
have a viscosity index of between about 80 to about 120, and
contain less than or equal to about 0.03% sulfur and greater than
or equal to about 90% saturates. Group III stocks have a viscosity
index greater than about 120 and contain less than or equal to
about 0.03% sulfur and greater than about 90% saturates. Group IV
includes polyalphaolefins (PAO). Group V base stock includes base
stocks not included in Groups I-IV.
TABLE-US-00001 TABLE 1 Properties of Base Oil Groups Base Oil
Properties Saturates Sulfur Viscosity Index Group I <90 and/or
>0.03% and .gtoreq.80 and <120 Group II .gtoreq.90 and
.ltoreq.0.03% and .gtoreq.80 and <120 Group III .gtoreq.90 and
.ltoreq.0.03% and .gtoreq.120 Group IV polyalphaolefins (PAO) Group
V All other base oil stocks not included in Groups I, II, III or
IV
[0059] Natural oils include animal oils, vegetable oils (castor oil
and lard oil, for example), and mineral oils. Animal and vegetable
oils possessing favorable thermal oxidative stability can be used.
Of the natural oils, mineral oils are preferred. Mineral oils vary
widely as to their crude source, for example, as to whether they
are paraffinic, naphthenic, or mixed paraffinic-naphthenic. Oils
derived from coal or shale are also useful. Natural oils vary also
as to the method used for their production and purification, for
example, their distillation range and whether they are straight run
or cracked, hydrorefined, or solvent extracted.
[0060] Group II and/or Group III hydroprocessed or hydrocracked
base stocks are also well known base stock oils.
[0061] Synthetic oils include hydrocarbon oil. Hydrocarbon oils
include oils such as polymerized and interpolymerized olefins
(polybutylenes, polypropylenes, propylene isobutylene copolymers,
ethylene-olefin copolymers, and ethylene-alphaolefin copolymers,
for example). Polyalphaolefin (PAO) oil base stocks are commonly
used synthetic hydrocarbon oil. By way of example, PAOs derived
from C.sub.8, C.sub.10, C.sub.12, C.sub.14 olefins or mixtures
thereof may be utilized. See U.S. Pat. Nos. 4,956,122; 4,827,064;
and 4,827,073.
[0062] The average molecular weights of the PAOs, which are known
materials and generally available on a major commercial scale from
suppliers such as ExxonMobil Chemical Company, Chevron Phillips
Chemical Company, BP, and others, can vary from about 250 to about
3,000, although PAO's may be made in viscosities up to about 150
cSt (100.degree. C.). The PAOs are typically comprised of
relatively low molecular weight hydrogenated polymers or oligomers
of alphaolefins which include, but are not limited to, C.sub.2 to
about C.sub.32 alphaolefins with the C.sub.8 to about C.sub.16
alphaolefins, such as 1-octene, 1-decene, 1-dodecene and the like.
For example, the polyalphaolefins can be poly-1-octene,
poly-1-decene, poly-1-dodecene, a combination thereof, or mixed
olefin-derived polyolefins. However, the dimers of higher olefins
in the range of C.sub.12 to C.sub.18 may be used to provide low
viscosity base stocks of acceptably low volatility. Depending on
the viscosity grade and the starting oligomer, the PAOs may be
predominantly dimers, trimers and tetramers of the starting
olefins, with minor amounts of the lower and/or higher oligomers,
having a viscosity range of 1.5 cSt to 12 cSt. PAO fluids of
particular use may include 3 cSt, 3.4 cSt, and/or 3.6 cSt and
combinations thereof. Mixtures of PAO fluids having a viscosity
range of 1.5 cSt to approximately 150 cSt or more may be used if
desired. Unless indicated otherwise, all viscosities cited herein
are measured at 100.degree. C.
[0063] The PAO fluids may be conveniently made by the
polymerization of an alphaolefin in the presence of a
polymerization catalyst such as the Friedel-Crafts catalysts
including, for example, aluminum trichloride, boron trifluoride or
complexes of boron trifluoride with water, alcohols such as
ethanol, propanol or butanol, carboxylic acids or esters such as
ethyl acetate or ethyl propionate. For example the methods
disclosed by U.S. Pat. No. 4,149,178 or 3,382,291 may be
conveniently used herein. Other descriptions of PAO synthesis are
found in the following U.S. Pat. Nos. 3,742,082; 3,769,363;
3,876,720; 4,239,930; 4,367,352; 4,413,156; 4,434,408; 4,910,355;
4,956,122; and 5,068,487. The dimers of the C.sub.14 to C.sub.18
olefins are described in U.S. Pat. No. 4,218,330.
[0064] Other useful lubricant oil base stocks include wax isomerate
base stocks and base oils, comprising hydroisomerized waxy stocks
(e.g. waxy stocks such as gas oils, slack waxes, fuels hydrocracker
bottoms, etc.), hydroisomerized Fischer-Tropsch waxes,
Gas-to-Liquids (GTL) base stocks and base oils, and other wax
isomerate hydroisomerized base stocks and base oils, or mixtures
thereof. Fischer-Tropsch waxes, the high boiling point residues of
Fischer-Tropsch synthesis, are highly paraffinic hydrocarbons with
very low sulfur content. The hydroprocessing used for the
production of such base stocks may use an amorphous
hydrocracking/hydroisomerization catalyst, such as one of the
specialized lube hydrocracking (LHDC) catalysts or a crystalline
hydrocracking/hydroisomerization catalyst, such as a zeolitic
catalyst. For example, one useful catalyst is ZSM-48 as described
in U.S. Pat. No. 5,075,269, the disclosure of which is incorporated
herein by reference in its entirety. Processes for making
hydrocracked/hydroisomerized distillates and
hydrocracked/hydroisomerized waxes are described, for example, in
U.S. Pat. Nos. 2,817,693; 4,975,177; 4,921,594 and 4,897,178 as
well as in British Patent Nos. 1,429,494; 1,350,257; 1,440,230 and
1,390,359. Each of the aforementioned patents is incorporated
herein in their entirety. Particularly favorable processes are
described in European Patent Application Nos. 464546 and 464547,
also incorporated herein by reference. Processes using
Fischer-Tropsch wax feeds are described in U.S. Pat. Nos. 4,594,172
and 4,943,672, the disclosures of which are incorporated herein by
reference in their entirety.
[0065] Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived
base oils, and other wax-derived hydroisomerized (wax isomerate)
base oils may be used in the present disclosure, and may have
kinematic viscosities at 100.degree. C. of about 2 cSt to about 50
cSt, e.g. about 2 cSt to about 30 cSt or about 3 cSt to about 25
cSt, as exemplified by GTL 4 with kinematic viscosity of about 4.0
cSt at 100.degree. C. and a viscosity index of about 141. These
Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base
oils, and other wax-derived hydroisomerized base oils may have
useful pour points of about -20.degree. C. or lower, and under some
conditions may have advantageous pour points of about -25.degree.
C. or lower, with useful pour points of about -30.degree. C. to
about -40.degree. C. or lower. Useful compositions of
Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base
oils, and wax-derived hydroisomerized base oils are recited in U.S.
Pat. Nos. 6,080,301; 6,090,989, and 6,165,949 for example, and are
incorporated herein in their entirety by reference.
[0066] The hydrocarbyl aromatics can be used as a base oil or base
oil component and can be any hydrocarbyl molecule in which at least
about 5% of its weight is derived from an aromatic moiety, such as
a benzenoid moiety or naphthenoid moiety, or their derivatives.
These hydrocarbyl aromatics include alkyl benzenes, alkyl
naphthalenes, alkyl biphenyls, alkyl diphenyl oxides, alkyl
naphthols, alkyl diphenyl sulfides, alkylated bis-phenol A,
alkylated thiodiphenol, and the like. The aromatic can be
mono-alkylated, dialkylated, polyalkylated, and the like. The
aromatic can be mono- or poly-functionalized. The hydrocarbyl
groups can also be comprised of mixtures of alkyl groups, alkenyl
groups, alkynyl, cycloalkyl groups, cycloalkenyl groups and other
related hydrocarbyl groups. The hydrocarbyl groups can range from
about C.sub.6 up to about C.sub.60 with a range of about C.sub.8 to
about C.sub.20 often being preferred. A mixture of hydrocarbyl
groups may be utilized, and up to about three such substituents may
be present. The hydrocarbyl group can optionally contain sulfur,
oxygen, and/or nitrogen containing substituents. The aromatic group
can also be derived from natural (petroleum) sources, provided at
least about 5% of the molecule is comprised of an above-type
aromatic moiety. In certain embodiments, the viscosity at
100.degree. C. is approximately 2 cSt to about 50 cSt, e.g.
approximately 3 cSt to about 20 cSt for the hydrocarbyl aromatic
component. In one embodiment, an alkyl naphthalene where the alkyl
group is primarily comprised of 1-hexadecene is used. Other
alkylates of aromatics can be advantageously used. Naphthalene or
methyl naphthalene, for example, can be alkylated with olefins such
as octene, decene, dodecene, tetradecene or higher, mixtures of
similar olefins, and the like. Alkylated naphthalene and analogues
may also comprise compositions with isomeric distribution of
alkylating groups on the alpha and beta carbon positions of the
ring structure. Distribution of groups on the alpha and beta
positions of a naphthalene ring may range from 100:1 to 1:100, more
often 50:1 to 1:50 Useful concentrations of hydrocarbyl aromatic in
a lubricant oil composition can be about 2% to about 25%, e.g.
about 4% to about 20% or about 4% to about 15%, depending on the
application.
[0067] Alkylated aromatics such as the hydrocarbyl aromatics of the
present disclosure may be produced by well-known Friedel-Crafts
alkylation of aromatic compounds. See Friedel-Crafts and Related
Reactions, Olah, G. A. (ed.), Inter-science Publishers, New York,
1963. For example, an aromatic compound, such as benzene or
naphthalene, is alkylated by an olefin, alkyl halide or alcohol in
the presence of a Friedel-Crafts catalyst. See Friedel-Crafts and
Related Reactions, Vol. 2, part 1, chapters 14, 17, and 18, See
Olah, G. A. (ed.), Inter-science Publishers, New York, 1964. Many
homogeneous or heterogeneous, solid catalysts are known to one
skilled in the art. The choice of catalyst depends on the
reactivity of the starting materials and product quality
requirements. For example, strong acids such as AlCl.sub.3,
BF.sub.3, or HF may be used. In some cases, milder catalysts such
as FeCl.sub.3 or SnCl.sub.4 are preferred. Newer alkylation
technology uses zeolites or solid super acids.
[0068] Esters comprise a useful base stock. Additive solvency and
seal compatibility characteristics may be secured by the use of
esters such as the esters of dibasic acids with monoalkanols and
the polyol esters of monocarboxylic acids. Esters of the former
type include, for example, the esters of dicarboxylic acids such as
phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic
acid, maleic acid, azelaic acid, suberic acid, sebacic acid,
fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl
malonic acid, alkenyl malonic acid, etc., with a variety of
alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol,
2-ethylhexyl alcohol, etc. Specific examples of these types of
esters include dibutyl adipate, di(2-ethylhexyl) sebacate,
di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate,
diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl
sebacate, etc.
[0069] Particularly useful synthetic esters are those which are
obtained by reacting one or more polyhydric alcohols, such as
hindered poly ols (including the neopentyl polyols, e.g., neopentyl
glycol, trimethylol ethane, 2-methyl-2-propyl-1,3-propanediol,
trimethylol propane, pentaerythritol and dipentaerythritol) with
alkanoic acids containing at least about 4 carbon atoms, e.g.
C.sub.5 to C.sub.30 acids such as saturated straight chain fatty
acids including caprylic acid, capric acid, lauric acid, myristic
acid, palmitic acid, stearic acid, arachic acid, and behenic acid,
or the corresponding branched chain fatty acids or unsaturated
fatty acids such as oleic acid, or mixtures of any of these
materials.
[0070] Suitable synthetic ester components include the esters of
trimethylol propane, trimethylol butane, trimethylol ethane,
pentaerythritol and/or dipentaerythritol with one or more
monocarboxylic acids containing from about 5 to about 10 carbon
atoms. These esters are widely available commercially, for example,
the Mobil P-41 and P-51 esters of ExxonMobil Chemical Company
(Irving, Tex., USA).
[0071] Also useful are esters derived from renewable material, such
as coconut, palm, rapeseed, soy, sunflower and the like. These
esters may be monoesters, di-esters, polyol esters, complex esters,
or mixtures thereof. These esters are widely available
commercially, for example, the Mobil P-51 ester of ExxonMobil
Chemical Company (Irving, Tex., USA).
[0072] Turbine oil formulations containing renewable esters are
contemplated by the present disclosure. For such formulations, the
renewable content of the ester is typically greater than about 70
weight percent, preferably more than about 80 weight percent and
most preferably more than about 90 weight percent.
[0073] Other useful fluids of lubricating viscosity include
non-conventional or unconventional base stocks that have been
processed, e.g. catalytically, or synthesized to provide high
performance lubrication characteristics.
[0074] Non-conventional or unconventional base stocks/base oils
include one or more of a mixture of base stock(s) derived from one
or more Gas-to-Liquids (GTL) materials, as well as
isomerate/isodewaxate base stock(s) derived from natural wax or
waxy feeds, mineral and or non-mineral oil waxy feed stocks such as
slack waxes, natural waxes, and waxy stocks such as gas oils, waxy
fuels hydrocracker bottoms, waxy raffinate, hydrocrackate, thermal
crackates, or other mineral, mineral oil, or even non-petroleum oil
derived waxy materials such as waxy materials received from coal
liquefaction or shale oil, and mixtures of such base stocks.
[0075] GTL materials are materials that are derived via one or more
synthesis, combination, transformation, rearrangement, and/or
degradation/deconstructive processes from gaseous carbon-containing
compounds, hydrogen-containing compounds and/or elements as feed
stocks such as hydrogen, carbon dioxide, carbon monoxide, water,
methane, ethane, ethylene, acetylene, propane, propylene, propyne,
butane, butylenes, and butynes. GTL base stocks and/or base oils
are GTL materials of lubricating viscosity that are generally
derived from hydrocarbons; for example, waxy synthesized
hydrocarbons, that are themselves derived from simpler gaseous
carbon-containing compounds, hydrogen-containing compounds and/or
elements as feed stocks. GTL base stock(s) and/or base oil(s)
include oils boiling in the lube oil boiling range (1)
separated/fractionated from synthesized GTL materials such as, for
example, by distillation and subsequently subjected to a final wax
processing step which involves either or both of a catalytic
dewaxing process, or a solvent dewaxing process, to produce lube
oils of reduced/low pour point; (2) synthesized wax isomerates,
comprising, for example, hydrodewaxed or hydroisomerized cat and/or
solvent dewaxed synthesized wax or waxy hydrocarbons; (3)
hydrodewaxed or hydroisomerized cat and/or solvent dewaxed
Fischer-Tropsch (F-T) material (i.e., hydrocarbons, waxy
hydrocarbons, waxes and possible analogous oxygenates); such as
hydrodewaxed or hydroisomerized/followed by cat and/or solvent
dewaxing dewaxed F-T waxy hydrocarbons, or hydrodewaxed or
hydroisomerized/followed by cat (or solvent) dewaxing dewaxed, F-T
waxes, or mixtures thereof.
[0076] GTL base stock(s) and/or base oil(s) derived from GTL
materials, especially, hydrodewaxed or hydroisomerized/followed by
cat and/or solvent dewaxed wax or waxy feed, preferably F-T
material derived base stock(s) and/or base oil(s), are
characterized typically as having kinematic viscosities at
100.degree. C. of from about 2 mm.sup.2/s to about 50 mm.sup.2/s
(ASTM D445). They are further characterized typically as having
pour points of -5.degree. C. to about -40.degree. C. or lower (ASTM
D97). They are also characterized typically as having viscosity
indices of about 80 to about 140 or greater (ASTM D2270).
[0077] In addition, the GTL base stock(s) and/or base oil(s) are
typically highly paraffinic (>90% saturates), and may contain
mixtures of monocycloparaffins and multicycloparaffins in
combination with non-cyclic isoparaffins. The ratio of the
naphthenic (i.e., cycloparaffin) content in such combinations
varies with the catalyst and temperature used. Further, GTL base
stock(s) and/or base oil(s) typically have very low sulfur and
nitrogen content, generally containing less than about 10 ppm, and
more typically less than about 5 ppm of each of these elements. The
sulfur and nitrogen content of GTL base stock(s) and/or base oil(s)
obtained from F-T material, especially F-T wax, is essentially nil.
In addition, the absence of phosphorus and aromatics make this
materially especially suitable for the formulation of low SAP
products.
[0078] The term GTL base stock and/or base oil and/or wax isomerate
base stock and/or base oil is to be understood as embracing
individual fractions of such materials of wide viscosity range as
recovered in the production process, mixtures of two or more of
such fractions, as well as mixtures of one or two or more low
viscosity fractions with one, two or more higher viscosity
fractions to produce a blend wherein the blend exhibits a target
kinematic viscosity.
[0079] The GTL material, from which the GTL base stock(s) and/or
base oil(s) is/are derived is preferably an F-T material (i.e.,
hydrocarbons, waxy hydrocarbons, wax).
[0080] Base oils for use in the formulated lubricating oils useful
in the present disclosure are any of the variety of oils
corresponding to API Group I, Group II, Group III, Group IV, and
Group V oils and mixtures thereof, e.g. API Group II oil may be
utilized in the compositions of the present disclosure.
[0081] The base oil constitutes the major component of the
lubricating or hydraulic oil/fluid composition of the present
disclosure and can be present in an amount ranging from about 80 to
about 99.8 weight percent, e.g. from about 90 to about 99.5 weight
percent or from about 95 to about 99 weight percent, based on the
total weight of the composition. The base oil may be selected from
any of the synthetic or natural oils typically used as lubricating
oils for industrial oils and turbomachines. The base oil
conveniently has a kinematic viscosity, according to ASTM standards
(e.g., ASTM D445 or ASTM D7042), of about 7 cSt to about 46 cSt (or
mm.sup.2/s) at 40.degree. C. and preferably of about 10 cSt to
about 32 cSt (or mm2/s) at 40.degree. C., often from about 15 cSt
to about 22 cSt. Mixtures of synthetic and natural base oils may be
used if desired. Bi-modal, tri-modal, and additional combinations
of mixtures of Group I, II, III, IV, and/or V base stocks may be
used if desired.
[0082] The co-base stock component is present in an amount
sufficient for providing solubility, compatibility and dispersancy
of polar additives in the lubricating oil. The co-base stock
component is present in the lubricating oils of the disclosure in
an amount from about 1 to about 99 weight percent, e.g. from about
5 to about 95 weight percent or from about 10 to about 90 weight
percent.
[0083] Table 2 below summarizes useful and preferred amounts of
illustrative lubricating base oils in accordance with this
disclosure.
TABLE-US-00002 TABLE 2 Useful and Preferred Amounts of Illustrative
Lubricating Base Oils Approximate Approximate wt % wt %
Illustrative Base Oils (Useful) (Preferred) Mineral Oil API Group
I, II/II+ 0-100 3-95 Naphthenic 0-100 3-95 API Group III/III+ = GTL
0-100 3-95 API Group IV PAO 0-100 3-95 API Group V (examples listed
below): 0-100 3-95 Ethylene-propylene copolymer (EPC) 0-100 3-95
Polyol Esters 0-100 3-95 Phosphate Esters 0-100 3-95 Phthalate
Esters 0-100 3-95 Dibasic Esters e.g. Adipate 0-100 3-95 Carbonate
Esters 0-100 3-95 Trimellitate Esters 0-100 3-95 Oil Soluble
Polyalkylene Glycols 0-100 3-95 Polyalkylene Glycols 0-100 3-95
Alkylated Naphthalenes 0-100 3-95 Viscobase Fluids 0-100 3-95
Olefin-esters (e.g. Ketjenlube) 0-100 3-95 Linear or Branched
Alkylbenzenes 0-100 3-95 TME-based esters 0-100 3-95 Polyethers
0-100 3-95 2 Ethylhexanoic acid ester 0-100 3-95 PMA/PAO
co-oligomers 0-100 3-95 Alkylated Diphenyl Oxide (ADPO) 0-100 3-95
Alkylated Sulfurized Diphenyl Oxide 0-100 3-95 (ASDPO) Bisphenol
Sulfide Ether (BPSE) 0-100 3-95 (C16,C20) 3-phenylpropionate 0-100
3-95 Hexyl 2-(decyloxy)benzoate 0-100 3-95 Diheptyl
N-octylsuccinate 0-100 3-95
Performance Additives.
[0084] The lubricating composition of the present disclosure may
further comprise at least one performance additive (i.e., a
lubricating oil performance additive). For example, the lubricating
composition may include at least one of a dispersant, an additional
detergent, a corrosion inhibitor, a rust inhibitor, a metal
deactivator, an additional antiwear agent (e.g., an additional
non-zinc-base antiwear agent), an extreme pressure additive, an
anti-seizure agent, a wax modifier, a viscosity index improver, a
viscosity modifier/improver, a seal compatibility agent, an
additional friction modifier, a lubricity agent, an anti-staining
agent, a dye or colorant/chromophoric agent, a demulsifier, an
emulsifier, a pour point depressant, a wetting agent, a tackiness
agent, a colorant, an antioxidants, an oxidation inhibitor, or a
combination thereof. The presence or absence of these lubricating
oil performance additives does not adversely affect the lubricating
compositions of the present disclosure. For a review of many
commonly used additives, see Klamann in Lubricants and Related
Products, Verlag Chemie, Deerfield Beach, Fla.; ISBN 0 89573 177 0.
Reference is also made to "Lubricant Additives" by M. W. Ranney,
published by Noyes Data Corporation of Parkridge, N.J. (1973) and
"Lubricant Additives: Chemistry and Applications" edited by L. R.
Rudnick, published by CRC Press of Boca Raton, Fla. (2009).
[0085] The additives useful in this disclosure do not have to be
soluble in the lubricating oils. Insoluble additives in oil can be
dispersed in the lubricating oils of this disclosure.
[0086] The types and quantities of performance additives used in
combination with the present disclosure in lubricant compositions
are not limited by the examples shown herein as illustrations.
[0087] As such, in any aspect or embodiment described herein, the
composition further comprises at least one of a dispersant, an
additional antiwear agent (e.g., a non-zinc-based or zinc-free
antiwear agent), a corrosion inhibitor, a rust inhibitor, an
additional detergent, an anti-seizure agent, an antifoam agent or
defoamant, a wax modifier, a metal deactivator/passivator, an
extreme pressure additive, an antioxidant, a viscosity index
improver, a viscosity improver/modifier, a seal compatibility
agent, a pour point depressant, a friction modifier, a lubricity
agent, an anti-staining agent, a dye or colorant/chromophoric
agent, a demulsifier, a wetting agent, an oxidation inhibitor, a
tackiness agent, a colorant, a detergent stabilizer, or
combinations thereof. In any aspect or embodiment described herein,
the dispersant includes succinimide-type dispersant. The dispersant
may be present in an amount of .ltoreq.about 1.5 wt. %,
.ltoreq.about 1.25 wt. %, or about 1 wt. %. For example, the
dispersant may be present in an amount of about 0.1 to about 1.5
wt. %, about 0.1 to about 1.25 wt. %, about 0.1 to about 1 wt. %,
about 0.1 to about 0.5 wt. %, about 0.25 to about 1.5 wt. %, about
0.25 to about 1.25 wt. %, about 0.5 to about 1 wt. %, about 0.5 to
about 1.5 wt. %, about 0.5 to about 1.25 wt. %, about 0.5 to about
1 wt. %, about 0.75 to about 1.5 wt. %, about 0.75 to about 1.25
wt. %, or about 1 to about 1.5 wt. %.
[0088] Unless specified otherwise, the performance additive or
performance additives listed above are present in a total amount
equal to or less than about 10 wt %, equal to or less than about
9.5 wt %, equal to or less than about 9 wt %, equal to or less than
about 8.5 wt %, equal to or less than about 8 wt %, equal to or
less than about 7.5 wt %, equal to or less than about 7 wt %, equal
to or less than about 6.5 wt %, equal to or less than about 6 wt %,
equal to or less than about 5.5 wt %, equal to or less than about 5
wt %, equal to or less than about 4.5 wt %, equal to or less than
about 4 wt %, equal to or less than about 3.5 wt %, equal to or
less than about 3 wt %, equal to or less than about 2.5 wt %, equal
to or less than about 2 wt %, equal to or less than about 1.5 wt %,
or equal to or less than about 0.5 wt %. For example, the
performance additive or performance additives are present in a
total amount of about 0.1 to about 10 wt %, about 0.1 to about 9 wt
%, about 0.1 to about 8 wt %, about 0.1 to about 7 wt %, about 0.1
to about 6 wt %, about 0.1 to about 5 wt %, about 0.1 to about 4 wt
%, about 0.1 to about 3 wt %, about 0.1 to about 2 wt %, about 0.1
to about 1 wt %, about 0.5 to about 10 wt %, about 0.5 to about 9
wt %, about 0.5 to about 8 wt %, about 0.5 to about 7 wt %, about
0.5 to about 6 wt %, about 0.5 to about 5 wt %, about 0.5 to about
4 wt %, about 0.5 to about 3 wt %, about 0.5 to about 2 wt %, about
1 to about 10 wt %, about 1 to about 9 wt %, about 1 to about 8 wt
%, about 1 to about 7 wt %, about 1 to about 6 wt %, about 1 to
about 5 wt %, about 1 to about 4 wt %, about 1 to about 3 wt %,
about 2 to about 10 wt %, about 2 to about 9 wt %, about 2 to about
8 wt %, about 2 to about 7 wt %, about 2 to about 6 wt %, about 2
to about 5 wt %, about 2 to about 4 wt %, about 3 to about 10 wt %,
about 3 to about 9 wt %, about 3 to about 8 wt %, about 3 to about
7 wt %, about 3 to about 6 wt %, about 3 to about 5 wt %, about 4
to about 10 wt %, about 4 to about 9 wt %, about 4 to about 8 wt %,
about 4 to about 7 wt %, about 4 to about 6 wt %, about 5 to about
10 wt %, about 5 to about 9 wt %, about 5 to about 8 wt %, about 5
to about 7 wt %, about 6 to about 10 wt %, about 6 to about 9 wt %,
about 6 to about 8 wt %, about 7 to about 10 wt %, about 7 to about
9 wt %, or about 8 to about 10 wt %.
Viscosity Improver(s) or Modifier(s).
[0089] The viscosity improver, viscosity modifier, or Viscosity
Index (VI) modifier increases the viscosity of the lubricating
composition at elevated temperatures, thereby increasing film
thickness, and having limited effects on the viscosity of the
lubricating composition at low temperatures. In certain
embodiments, the lubricating composition comprises at least one
viscosity improver (e.g., 1, 2, 3, 4, 5, 6, or more viscosity
improver(s)). Any viscosity improver that is known or that becomes
known in the art may be utilized in the lubricating composition of
the present disclosure. Exemplary viscosity improvers include high
molecular weight hydrocarbons, polyesters and viscosity index
improver dispersants that function as both a viscosity index
improver and a dispersant. The molecular weight of these polymers
can range from about 1,000 to about 1,500,000 (e.g., about 20,000
to about 1,200,000 or about 50,000 to about 1,000,000). In a
particular embodiment, the molecular weights of these polymers can
range from about 1,000 to about 1,000,000 (e.g., about 1,200 to
about 500,000 or about 1,200 to about 5,000).
[0090] In certain embodiments, the viscosity improver is at least
one of linear or star-shaped polymers of methacrylate, linear or
star-shaped copolymers of methacrylate, butadiene, olefins,
alkylated styrenes, polyisobutylene, polymethacrylate (e.g.,
copolymers of various chain length alkyl methacrylates), copolymers
of ethylene and propylene, hydrogenated block copolymers of styrene
and isoprene, or combinations thereof. For example, the viscosity
improver may include styrene-isoprene or styrene-butadiene based
polymers of about 50,000 to about 200,000 molecular weight.
[0091] Olefin copolymers are commercially available from Chevron
Oronite Company LLC under the trade designation "PARATONE.RTM."
(such as "PARATONE.RTM. 8921" and "PARATONE.RTM. 8941"); from Afton
Chemical Corporation under the trade designation "HiTEC.RTM." (such
as "HiTEC.RTM. 5850B"); and from The Lubrizol Corporation under the
trade designation "Lubrizol.RTM. 7067C". Hydrogenated polyisoprene
star polymers are commercially available from Infineum
International Limited, e.g., under the trade designation "SV200"
and "SV600". Hydrogenated diene-styrene block copolymers are
commercially available from Infineum International Limited, e.g.,
under the trade designation "SV 50".
[0092] The polymethacrylate or polyacrylate polymers can be linear
polymers which are available from Evnoik Industries under the trade
designation "Viscoplex.RTM." (e.g., Viscoplex 6-954) or star
polymers which are available from Lubrizol Corporation under the
trade designation Asteric.TM. (e.g., Lubrizol 87708 and Lubrizol
87725).
[0093] Illustrative vinyl aromatic-containing polymers useful in
the present disclosure may be derived predominantly from vinyl
aromatic hydrocarbon monomer. Illustrative vinyl
aromatic-containing copolymers useful in the present disclosure may
be represented by the following formula:
A-B,
wherein: [0094] A is a polymeric block derived predominantly from
vinyl aromatic hydrocarbon monomer, and [0095] B is a polymeric
block derived predominantly from conjugated diene monomer.
[0096] Although their presence is not required to obtain the
benefit of the composition of the present disclosure, viscosity
modifiers may be used in an amount of less than about 10 weight
percent (e.g. less than about 7 weight percent or less than about 4
weight percent). In certain embodiments, the viscosity improver is
present in an amount less than 2 weight percent, less than about 1
weight percent, or less than about 0.5 weight percent, based on the
total weight of the lubricating composition. Viscosity modifiers
are generally added as concentrates, in large amounts of diluent
oil.
[0097] As used herein, the viscosity modifier concentrations are
given on an "as delivered" basis. The active polymer may be
delivered with a diluent oil. The "as delivered" viscosity modifier
may contain from about 20 weight percent to about 75 weight percent
of an active polymer for polymethacrylate or polyacrylate polymers,
or from about 8 weight percent to about 20 weight percent of an
active polymer for olefin copolymers, hydrogenated polyisoprene
star polymers, or hydrogenated diene-styrene block copolymers, in
the "as delivered" polymer concentrate.
Antioxidant(s).
[0098] In certain embodiments, the lubricating composition
comprises at least one antioxidant (e.g., 1, 2, 3, 4, 5, 6, or more
antioxidant(s)). The antioxidant(s) may be added to retard the
oxidative degradation of base oils during service. Such degradation
may result in deposits on metal surfaces, the presence of sludge,
or a viscosity increase in the lubricant. One skilled in the art
knows a wide variety of oxidation inhibitors that are useful in
lubricating oil compositions. See, Klamann in Lubricants and
Related Products, op cite, and U.S. Pat. Nos. 4,798,684 and
5,084,197, for example. Any antioxidant that is known or that
becomes known in the art may be utilized in the lubricating
composition of the present disclosure.
[0099] Two general types of oxidation inhibitors are those that
react with the initiators, peroxy radicals, and hydroperoxides to
form inactive compounds, and those that decompose these materials
to form less active compounds. Examples are hindered (alkylated)
phenols, e.g. 6-di(tert-butyl)-4-methylphenol
[2,6-di(tert-butyl)-p-cresol, DBPC], and aromatic amines, e.g.
N-phenyl-.alpha.-naphthalamine. These oxidation inhibitors are used
in turbine, circulation, and hydraulic oils that are intended for
extended service.
[0100] The antioxidant or antioxidants may be present in an amount
equal to or less than about 6 wt %, equal to or less than about
5.75 wt %, equal to or less than about 5.5 wt %, equal to or less
than about 5.25 wt %, equal to or less than about 5 wt %, equal to
or less than about 4.75 wt %, equal to or less than about 4.5 wt %,
equal to or less than about 4.25 wt %, equal to or less than about
4 wt %, equal to or less than about 3.75 wt %, equal to or less
than about 3.5 wt %, equal to or less than about 3.25 wt %, equal
to or less than about 3 wt %, equal to or less than about 2.75 wt
%, equal to or less than about 2.5 wt %, equal to or less than
about 2.25 wt %, equal to or less than about 2 wt %, equal to or
less than about 1.75 wt %, equal to or less than about 1.5 wt %,
equal to or less than about 1.25 wt %, equal to or less than about
1 wt %, equal to or less than about 0.75 wt %, equal to or less
than about 0.50 wt %, or equal to or less than about 0.25 wt % on
an as-received basis. For example, the antioxidant or antioxidants
may be present in an amount of about 0.1 wt % to about 6 wt %,
about 0.1 wt % to about 5 wt %, about 0.1 wt % to about 4 wt %,
about 0.1 wt % to about 3 wt %, about 0.1 wt % to about 2 wt %,
about 0.1 wt % to about 1.5 wt %, about 0.1 wt % to about 1 wt %,
about 0.1 wt % to about 0.75 wt %, about 0.1 wt % to about 0.5 wt
%, about 0.2 wt % to about 6 wt %, about 0.2 wt % to about 5 wt %,
about 0.2 wt % to about 4 wt %, about 0.2 wt % to about 3 wt %,
about 0.2 wt % to about 2 wt %, about 0.2 wt % to about 1.5 wt %,
about 0.2 wt % to about 1 wt %, about 0.2 wt % to about 0.75 wt %,
about 0.2 wt % to about 0.5 wt %, about 0.3 wt % to about 6 wt %,
about 0.3 wt % to about 5 wt %, about 0.3 wt % to about 4 wt %,
about 0.3 wt % to about 3 wt %, about 0.3 wt % to about 2 wt %,
about 0.3 wt % to about 1.5 wt %, about 0.3 wt % to about 1 wt %,
about 0.3 wt % to about 0.75 wt %, about 0.3 wt % to about 0.5 wt
%, about 0.5 wt % to about 6 wt %, about 0.5 wt % to about 5 wt %,
about 0.5 wt % to about 4 wt %, about 0.5 wt % to about 3 wt %,
about 0.5 wt % to about 2 wt %, about 0.5 wt % to about 1.5 wt %,
about 0.5 wt % to about 1 wt %, about 0.5 wt % to about 0.75 wt %,
about 0.5 wt % to about 0.5 wt %, about 1 wt % to about 6 wt %,
about 1 wt % to about 5 wt %, about 1 wt % to about 4 wt %, about 1
wt % to about 3 wt %, about 2 wt % to about 6 wt %, about 2 wt % to
about 5 wt %, about 2 wt % to about 4 wt %, about 3 wt % to about 6
wt %, about 3 wt % to about 5 wt %, about 4 wt % to about 6 wt %,
or about 5 wt % to about 6 wt % on an as-received basis. In an
embodiment, the antioxidant include at least one of a food-grade
phenolic antioxidant, a food-grade aminic antioxidant, or a
combination thereof.
[0101] The below discussion of phenolic antioxidants is presented
only by way of example, and is not limiting on the type of phenolic
antioxidants that can be utilized in the lubricating composition of
the present disclosure.
[0102] Useful antioxidants include hindered phenols. These phenolic
antioxidants may be ashless (metal-free) phenolic compounds or
neutral or basic metal salts of certain phenolic compounds. In an
embodiment, the phenolic antioxidant compounds or compounds are
hindered phenolics which are the ones which contain a sterically
hindered hydroxyl group, such as those that are derivatives of
dihydroxy aryl compounds in which the hydroxyl groups are in the o-
or p-position to each other. In certain embodiments, the phenolic
antioxidant or antioxidants are hindered phenols substituted with
C6+ alkyl groups and the alkylene coupled derivatives of these
hindered phenols. Examples of phenolic materials of this type
2-t-butyl-4-heptyl phenol; 2-t-butyl-4-octyl phenol;
2-t-butyl-4-dodecyl phenol; 2,6-di-t-butyl-4-heptyl phenol;
2,6-di-t-butyl-4-dodecyl phenol; 2-methyl-6-t-butyl-4-heptyl
phenol; and 2-methyl-6-t-butyl-4-dodecyl phenol. Other useful
hindered mono-phenolic antioxidants may include for example
hindered 2,6-di-alkyl-phenolic proprionic ester derivatives.
Bis-phenolic antioxidants may also be advantageously used in
combination with the composition of the present disclosure.
Examples of ortho-coupled phenols include:
2,2'-bis(4-heptyl-6-t-butyl-phenol);
2,2'-bis(4-octyl-6-t-butyl-phenol); and
2,2'-bis(4-dodecyl-6-t-butyl-phenol). Para-coupled bisphenols
include for example 4,4'-bis(2,6-di-t-butyl phenol) and
4,4'-methylene-bis(2,6-di-t-butyl phenol).
[0103] Further examples of phenol-based antioxidants include
2-t-butylphenol, 2-t-butyl-4-methylphenol,
2-t-butyl-5-methylphenol, 2,4-di-t-butylphenol,
2,4-dimethyl-6-t-butylphenol, 2-t-butyl-4-methoxyphenol,
3-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone (manufactured
by the Kawaguchi Kagaku Co. under trade designation "Antage DBH"),
2,6-di-t-butylphenol and 2,6-di-t-butyl-4-alkylphenols such as
2,6-di-t-butyl-4-methylphenol and 2,6-di-t-butyl-4-ethylphenol;
2,6-di-t-butyl-4-alkoxyphenols such as
2,6-di-t-butyl-4-methoxyphenol and 2,6-di-t-butyl-4-ethoxyphenol,
3,5-di-t-butyl-4-hydroxybenzylmercaptoocty-1 acetate,
alkyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionates such as
n-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (manufactured
by the Yoshitomi Seiyaku Co. under the trade designation "Yonox
SS"), n-dodecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate and
2'-ethylhexyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate;
2,6-di-t-butyl-alpha-dimethylamino-p-cresol,
2,2'-methylenebis(4-alkyl-6-t-butylphenol) compounds such as
2,2'-methylenebis(4-methyl-6-t-butylphe-nol) (manufactured by the
Kawaguchi Kagaku Co. under the trade designation "Antage W-400")
and 2,2'-methylenebis(4-ethyl-6-t-butylphenol) (manufactured by the
Kawaguchi Kagaku Co. under the trade designation "Antage W-500");
bisphenols such as 4,4'-butylidenebis(3-methyl-6-t-butyl-phenol)
(manufactured by the Kawaguchi Kagaku Co. under the trade
designation "Antage W-300"), and
4,4'-methylenebis(2,6-di-t-butylphenol) (manufactured by Laporte
Performance Chemicals under the trade designation "Ionox
220AH").
[0104] Other examples of phenol-based antioxidants include
4,4'-bis(2,6-di-t-butylphenol), 2,2-(di-p-hydroxyphenyl)propane
(Bisphenol A), 2,2-bis(3,5-di-t-butyl-4-hydroxyphenyl)propane,
4,4'-cyclohexylidenebis(2,6-di-t-butylphenol), hexamethylene glycol
bis[3, (3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by
the Ciba Specialty Chemicals Co. under the trade designation
"Irganox L109"), triethylene glycol
bis[3-(3-t-butyl-4-hydrox-y-5-methylphenyl)propionate]
(manufactured by the Yoshitomi Seiyaku Co. under the trade
designation "Tominox 917"),
2,2'-thio[diethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
(manufactured by the Ciba Speciality Chemicals Co. under the trade
designation "Irganox L115"),
3,9-bis{1,1-dimethyl-2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)-propionylo-
-xy]ethyl}2,4, 8, 10-tetraoxaspiro[5,5]undecane (manufactured by
the Sumitomo Kagaku Co. under the trade designation "Sumilizer
GA80") and 4,4'-thiobis(3-methyl-6-t-butylphenol) (manufactured by
the Kawaguchi Kagaku Co. under the trade designation "Antage RC"),
2,2'-thiobis(4,6-di-t-butylresorcinol); polyphenols, such as
tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionato]methane
(manufactured by the Ciba Speciality Chemicals Co. under the trade
designation "Irganox L101"),
1,1,3-tris(2-methyl-4-hydroxy-5-t-butylpheny-1)butane (manufactured
by the Yoshitomi Seiyaku Co. under the trade designation "Yoshinox
930"),
1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene
(manufactured by Ciba Speciality Chemicals under the trade
designation "Irganox 330"),
bis[3,3'-bis(4'-hydroxy-3'-t-butylpheny-1)butyric acid] glycol
ester,
2-(3',5'-di-t-butyl-4-hydroxyphenyl)-methyl-4-(2'',4''-di-t-butyl-3''-hyd-
roxyphenyl)methyl-6-t-butylphenol and
2,6-bis(2'-hydroxy-3'-t-butyl-5'-methylbenzyl)-4-methylphenol; and
phenol/aldehyde condensates, such as the condensates of
p-t-butylphenol and formaldehyde and the condensates of
p-t-butylphenol and acetaldehyde.
[0105] The phenolic antioxidant or phenolic type antioxidant
include sulfurized and non-sulfurized phenolic antioxidants.
Phenolic antioxidants include compounds having one or more than one
hydroxyl group bound to an aromatic ring which may itself be
mononuclear (e.g., benzyl) or poly-nuclear (e.g., naphthyl and
spiro aromatic compounds). Thus, phenol type antioxidants include
phenol per se, catechol, resorcinol, hydroquinone, naphthol, etc.,
as well as alkyl or alkenyl and sulfurized alkyl or alkenyl
derivatives thereof, and bisphenol type compounds including such
bi-phenol compounds linked by alkylene bridges sulfuric bridges or
oxygen bridges. Alkyl phenols may include mono- and poly-alkyl or
alkenyl phenols, the alkyl or alkenyl group containing from about 3
to about 100 carbons (e.g., about 4 to about 50 carbons) and
sulfurized derivatives thereof. The number of alkyl or alkenyl
groups present in the aromatic ring may range from 1 up to the
available unsatisfied valences of the aromatic ring remaining after
counting the number of hydroxyl groups bound to the aromatic
ring.
[0106] For example, the phenolic antioxidant may be represented by
the following formula:
(R).sub.x--Ar--(OH).sub.y,
wherein: [0107] Ar is selected from the group consisting of:
##STR00001##
[0108] wherein: [0109] R is a C.sub.3-C.sub.100 alkyl or alkenyl
group, a sulfur substituted alkyl or alkenyl group (e.g., a
C.sub.4-C.sub.50 alkyl or alkenyl group or sulfur substituted alkyl
or alkenyl group, a C.sub.3-C.sub.100 alkyl or sulfur substituted
alkyl group, or a C.sub.4-C.sub.50 alkyl group); [0110] W is a
C.sub.1-C.sub.100 alkylene or sulfur substituted alkylene group
(e.g., a C.sub.2-C.sub.50 alkylene or sulfur substituted alkylene
group or a C.sub.2-C.sub.2 alkylene or sulfur substituted alkylene
group); y is at least 1 to up to the available valences of Ar;
[0111] x ranges from 0 to up to the available valances of Ar-y;
[0112] z ranges from 1 to 10; [0113] n ranges from 0 to 20; [0114]
m is 0 to 4; and [0115] p is 0 or 1.
[0116] In certain embodiments, at least one of: R is
C.sub.4-C.sub.50 alkyl group, W is a C.sub.2-C.sub.20 alkylene or
sulfur substituted alkylene group, y ranges from 1 to 3, x ranges
from 0 to 3, z ranges from 1 to 4, n ranges from 0 to 5, p is 0, or
a combination thereof.
[0117] In particular embodiments, the phenolic antioxidant include
hindered phenolics and phenolic esters that contain a sterically
hindered hydroxyl group. For example, the phenolic antioxidant can
include derivatives of dihydroxy aryl compounds in which the
hydroxyl groups are in the o- or p-position to each other. The
phenolic antioxidant may include the hindered phenols substituted
with C.sub.1+ alkyl groups and the alkylene coupled derivatives of
these hindered phenols, such as: 2-t-butyl-4-heptyl phenol;
2-t-butyl-4-octyl phenol; 2-t-butyl-4-dodecyl phenol;
2,6-di-t-butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol;
2-methyl-6-t-butyl-4-heptyl phenol; 2-methyl-6-t-butyl-4-dodecyl
phenol; 2,6-di-t-butyl-4 methyl phenol; 2,6-di-t-butyl-4-ethyl
phenol; 2,6-di-t-butyl 4 alkoxy phenol; and/or
##STR00002##
[0118] In certain embodiments, the phenolic type antioxidant is at
least one of Ethanox.RTM. 4710, Irganox.RTM. 1076, Irganox.RTM.
L1035, Irganox.RTM. 1010, Irganox.RTM. L109, Irganox.RTM. L118,
Irganox.RTM. L135, or a combination thereof.
[0119] The phenolic antioxidant or antioxidants may be present in
an amount of about 0.05 wt % to about 3 wt %, about 0.05 wt % to
about 2.5 wt %, about 0.05 wt % to about 2 wt %, about 0.05 wt % to
about 1.5 wt %, about 0.05 wt % to about 1 wt %, about 0.05 wt % to
about 0.75 wt %, about 0.05 wt % to about 0.5 wt %, about 0.05 wt %
to about 0.3 wt %, about 0.1 wt % to about 3 wt %, about 0.1 wt %
to about 2.5 wt %, about 0.1 wt % to about 2 wt %, about 0.1 wt %
to about 1.5 wt %, about 0.1 wt % to about 1 wt %, about 0.1 wt %
to about 0.75 wt %, about 0.1 wt % to about 0.5 wt %, about 0.1 wt
% to about 0.3 wt %, about 0.5 wt % to about 3 wt %, about 0.5 wt %
to about 2.5 wt %, about 0.5 wt % to about 2 wt %, about 0.5 wt %
to about 1.5 wt %, about 0.5 wt % to about 1 wt %, about 1 wt % to
about 3 wt %, about 1 wt % to about 2.5 wt %, about 1 wt % to about
2 wt %, about 1 wt % to about 1.75 wt %, about 1 wt % to about 1.5
wt %, about 1.5 wt % to about 3 wt %, about 1.5 wt % to about 2.5
wt %, about 1.5 wt % to about 2 wt %, about 2 wt % to about 3 wt %,
about 2 wt % to about 2.5 wt %, or about 2.5 wt % to about 3 wt %,
on an as-received basis.
[0120] Effective amounts of one or more catalytic antioxidants may
be used. The catalytic antioxidants comprise an effective amount of
a) one or more oil soluble polymetal organic compounds; and,
effective amounts of b) one or more substituted
N,N'-diaryl-o-phenylenediamine compounds or c) one or more hindered
phenol compounds; or a combination of both b) and c). Catalytic
antioxidants are more fully described in U.S. Pat. No. 8,048,833,
which is incorporated herein by reference in its entirety.
[0121] Non-phenolic oxidation inhibitors that may be used in the
composition of the present disclosure include aromatic amine
antioxidants, which may be used either as such or in combination
with phenolic antioxidants.
[0122] An exemplary aromatic amine antioxidant include alkylated
and non-alkylated aromatic amines, such as aromatic monoamines of
the formula
R.sup.1R.sup.2R.sup.3N,
wherein: [0123] R.sup.1 is an aliphatic, aromatic or substituted
aromatic group; [0124] R.sup.2 is an aromatic or a substituted
aromatic group; [0125] R.sup.3 is H, alkyl, aryl or
R.sup.4S(O).sub.XR.sup.5; [0126] R.sup.4 is an alkylene,
alkenylene, or aralkylene group; [0127] R.sup.5 is a higher alkyl
group, or an alkenyl, aryl, or alkaryl group; and [0128] x is 0, 1
or 2.
[0129] The aliphatic group R.sup.1 may contain from 1 to about 20
carbon atoms (e.g. from about 6 to 12 carbon atoms). The aliphatic
group may be a saturated aliphatic group. In certain embodiments,
both R.sup.1 and R.sup.2 are aromatic or substituted aromatic
groups, and the aromatic group may be a fused ring aromatic group
such as naphthyl. Aromatic groups R.sup.1 and R.sup.2 may be joined
together with other groups such as S.
[0130] The aminic antioxidant may be an aromatic amine antioxidant,
such as an phenyl-.alpha.-naphthyl amine (e.g., Irganox.RTM. L06)
which is described by the following chemical structure:
##STR00003##
wherein: [0131] R.sup.z is hydrogen or a C.sub.1 to C.sub.14 linear
or C.sub.3 to C.sub.14 branched alkyl group; and [0132] n is an
integer ranging from 1 to 5 (e.g. 1).
[0133] In certain embodiments, at least one of: R.sup.z is C.sub.1
to C.sub.10 linear or C.sub.3 to C.sub.10 branched alkyl group; n
is 1; or a combination thereof,
[0134] In another embodiment, R.sup.z is a linear or branched
C.sub.6 to C.sub.8.
[0135] In certain embodiments, the aromatic amine antioxidant can
have at least 6 carbon atoms substituted with an alkyl groups.
Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl,
and decyl. In an embodiments, the aliphatic groups will not contain
more than about 14 carbon atoms. Additional amine antioxidants
include diphenylamines, phenyl naphthylamines, phenothiazines,
imidodibenzyls, and diphenyl phenylene diamines. In a particular
embodiment, a mixture of two or more (e.g., 2, 3, 4, 5, or more)
aromatic amine antioxidants are present in the lubricating
composition. Polymeric amine antioxidants can also be used.
Particular examples of aromatic amine antioxidants useful in the
composition of the present disclosure include:
p,p'-dioctyldiphenylamine; t-octylphenyl-alpha-naphthylamine;
phenyl-alphanaphthylamine; and
p-octylphenyl-alpha-naphthylamine.
[0136] Further examples of amine-based antioxidants include
dialkyldiphenylamines, such as p,p'-dioctyldiphenylamine
(manufactured by the Seiko Kagaku Co. under the trade designation
"Nonflex OD-3"), p,p'-di-alpha-methylbenzyl-diphenylamine and
N-p-butylphenyl-N-p'-octylphenylamine; monoalkyldiphenylamines,
such as mono-t-butyldiphenylamine, and monooctyldiphenylamine;
bis(dialkylphenyl)amines such as di(2,4-diethylphenyl)amine and
di(2-ethyl-4-nonylphenyl)amine; alkylphenyl-1-naphthylamines, such
as octylphenyl-1-naphthylamine and
N-t-dodecylphenyl-1-naphthylamine; arylnaphthylamines, such as
1-naphthylamine, phenyl-1-naphthylamine, phenyl-2-naphthylamine,
N-hexylphenyl-2-naphthylamine and N-octylphenyl-2-naphthylamine,
phenylenediamines such as N,N'-diisopropyl-p-phenylenediamine and
N,N'-diphenyl-p-phenylenediamine, and phenothiazines such as
phenothiazine (manufactured by the Hodogaya Kagaku Co.:
Phenothiazine) and 3,7-dioctylphenothiazine.
[0137] A sulfur-containing antioxidant may be any and every
antioxidant containing sulfur, for example, including dialkyl
thiodipropionates such as dilauryl thiodipropionate and distearyl
thiodipropionate, dialkyldithiocarbamic acid derivatives (excluding
metal salts), bis(3,5-di-t-butyl-4-hydroxybenzyl)sulfide,
mercaptobenzothiazole, reaction products of phosphorus pentoxide
and olefins, and dicetyl sulfide. For example, the
sulfur-containing antioxidant is a dialkyl thiodipropionate, such
as dilauryl thiodipropionate and distearyl thiodipropionate.
[0138] Additional examples of sulphur-based antioxidants include
dialkylsulphides, such as didodecylsulphide and
dioctadecylsulphide; thiodipropionic acid esters, such as didodecyl
thiodipropionate, dioctadecyl thiodipropionate, dimyristyl
thiodipropionate and dodecyloctadecyl thiodipropionate, and
2-mercaptobenzimidazole. In an embodiment, the antioxidant is a
sulfurized alkyl phenols, or an alkali or alkaline earth metal salt
thereof.
[0139] In certain embodiments, the lubricating composition includes
at least one aminic antioxidant (e.g., 1, 2, 3, 4, 5, or more)
present in an amount equal to or less than about 6 wt %, equal to
or less than about 5.75 wt %, equal to or less than about 5.5 wt %,
equal to or less than about 5.25 wt %, equal to or less than about
5 wt %, equal to or less than about 4.75 wt %, equal to or less
than about 4.5 wt %, equal to or less than about 4.25 wt %, equal
to or less than about 4 wt %, equal to or less than about 3.75 wt
%, equal to or less than about 3.5 wt %, equal to or less than
about 3.25 wt %, equal to or less than about 3 wt %, equal to or
less than about 2.75 wt %, equal to or less than about 2.5 wt %,
equal to or less than about 2.25 wt %, equal to or less than about
2 wt %, equal to or less than about 1.75 wt %, equal to or less
than about 1.5 wt %, equal to or less than about 1.25 wt %, equal
to or less than about 1 wt %, equal to or less than about 0.75 wt
%, equal to or less than about 0.50 wt %, or equal to or less than
about 0.25 wt % on an as-received basis. For example, the aminic
antioxidant or antioxidants may be present in an amount of about
0.1 wt % to about 6 wt %, about 0.1 wt % to about 5 wt %, about 0.1
wt % to about 4 wt %, about 0.1 wt % to about 3 wt %, about 0.1 wt
% to about 2 wt %, about 0.1 wt % to about 1.5 wt %, about 0.1 wt %
to about 1 wt %, about 0.1 wt % to about 0.75 wt %, about 0.1 wt %
to about 0.5 wt %, about 0.2 wt % to about 6 wt %, about 0.2 wt %
to about 5 wt %, about 0.2 wt % to about 4 wt %, about 0.2 wt % to
about 3 wt %, about 0.2 wt % to about 2 wt %, about 0.2 wt % to
about 1.5 wt %, about 0.2 wt % to about 1 wt %, about 0.2 wt % to
about 0.75 wt %, about 0.2 wt % to about 0.5 wt %, about 0.3 wt %
to about 6 wt %, about 0.3 wt % to about 5 wt %, about 0.3 wt % to
about 4 wt %, about 0.3 wt % to about 3 wt %, about 0.3 wt % to
about 2 wt %, about 0.3 wt % to about 1.5 wt %, about 0.3 wt % to
about 1 wt %, about 0.3 wt % to about 0.75 wt %, about 0.3 wt % to
about 0.5 wt %, about 0.5 wt % to about 6 wt %, about 0.5 wt % to
about 5 wt %, about 0.5 wt % to about 4 wt %, about 0.5 wt % to
about 3 wt %, about 0.5 wt % to about 2 wt %, about 0.5 wt % to
about 1.5 wt %, about 0.5 wt % to about 1 wt %, about 0.5 wt % to
about 0.75 wt %, about 0.5 wt % to about 0.5 wt %, about 1 wt % to
about 6 wt %, about 1 wt % to about 5 wt %, about 1 wt % to about 4
wt %, about 1 wt % to about 3 wt %, about 2 wt % to about 6 wt %,
about 2 wt % to about 5 wt %, about 2 wt % to about 4 wt %, about 3
wt % to about 6 wt %, about 3 wt % to about 5 wt %, about 4 wt % to
about 6 wt %, or about 5 wt % to about 6 wt % on an as-received
basis.
[0140] Other oxidation inhibitors that have proven useful in
lubricating compositions are chlorinated aliphatic hydrocarbons
such as chlorinated wax; organic sulfides and polysulfides such as
benzyl disulfide, bis(chlorobenzyl)disulfide, dibutyl tetrasulfide,
sulfurized methyl ester of oleic acid, sulfurized alkylphenol,
sulfurized dipentene, and sulfurized terpene; phosphosulfurized
hydrocarbons such as the reaction product of a phosphorus sulfide
with turpentine or methyl oleate, phosphorus esters including
principally dihydrocarbon and trihydrocarbon phosphites such as
dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite,
pentylphenyl phosphite, dipentylphenyl phosphite, tridecyl
phosphite, distearyl phosphite, dimethyl naphthyl phosphite, oleyl
4-pentylphenyl phosphite, polypropylene (molecular weight
500)-substituted phenyl phosphite, diisobutyl-substituted phenyl
phosphite; metal thiocarbamates, such as zinc
dioctyldithiocarbamate, and barium heptylphenyl dithiocarbamate;
Group II metal phosphorodithioates such as zinc
dicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate,
barium di(heptylphenyl)(phosphorodithioate, cadmium
dinonylphosphorodithioate, and the reaction of phosphorus
pentasulfide with an equimolar mixture of isopropyl alcohol,
4-methyl-2-pentanol, and n-hexyl alcohol.
[0141] Another class of antioxidants which may be used in the
lubricating oil compositions disclosed herein are oil soluble
copper compounds. Any oil soluble suitable copper compound may be
blended into the lubricating composition. Examples of suitable
copper antioxidants include copper dihydrocarbyl thio- or
dithio-phosphates and copper salts of carboxylic acid (naturally
occurring or synthetic). Other suitable copper salts include copper
dithiacarbamates, sulphonates, phenates, and acetylacetonates.
Basic, neutral, or acidic copper Cu(I) and or Cu(II) salts derived
from alkenyl succinic acids or anhydrides are known to be
particularly useful.
[0142] In an embodiment, the antioxidants includes hindered
phenols, arylamines, or a combination thereof. These antioxidants
may be used individually by type or in combination with one
another.
Pour Point Depressant(s).
[0143] In other embodiments, the lubricating composition comprises
at least one pour point depressant or a lube oil flow improver.
Pour point depressant may be added to lower the minimum temperature
at which the fluid will flow or can be poured. Any pour point
depressant or lube oil flow improved that is known or that becomes
known in the art may be utilized in the lubricating composition of
the present disclosure. In certain embodiments, the pour point
depressant includes at least one (e.g., 1, 2, 3, 4, or more) pour
point depressant or lube oil flow improver, such as at least one of
alkylated naphthalenes polymethacrylates (e.g., copolymers of
various chain length alkyl methacrylates), polyacrylates,
polyarylamides, condensation products of haloparaffin waxes and
aromatic compounds, vinyl carboxylate polymers, terpolymers of
dialkylfumarates, vinyl esters of fatty acids, allyl vinyl ethers,
or combinations thereof. U.S. Pat. Nos. 1,815,022; 2,015,748;
2,191,498; 2,387,501; 2,655, 479; 2,666,746; 2,721,877; 2,721,878;
and 3,250,715 describe useful pour point depressants and/or the
preparation thereof. The pour point depressant or depressants may
be present in an amount equal to or less than about 5 wt %, for
example about 0.01 to about 1.5 wt %. For example, the pour point
depressant or depressants may be present in an amount equal to or
less than about 5 wt %, equal to or less than about 4.75 wt %,
equal to or less than about 4.5 wt %, equal to or less than about
4.25 wt %, equal to or less than about 4 wt %, equal to or less
than about 3.75 wt %, equal to or less than about 3.5 wt %, equal
to or less than about 3.25 wt %, equal to or less than about 3 wt
%, equal to or less than about 2.75 wt %, equal to or less than
about 2.5 wt %, equal to or less than about 2.25 wt %, equal to or
less than about 2 wt %, equal to or less than about 1.75 wt %,
equal to or less than about 1.5 wt %, equal to or less than about
1.25 wt %, equal to or less than about 1 wt %, equal to or less
than about 0.75 wt %, equal to or less than about 0.50 wt %, or
equal to or less than about 0.25 wt % of the lubricating
composition. For example, the pour point depressant or depressants
may be present in an amount of about 0.1 wt % to about 5 wt %,
about 0.1 wt % to about 4 wt %, about 0.1 wt % to about 3 wt %,
about 0.1 wt % to about 2 wt %, about 0.1 wt % to about 1.5 wt %,
about 0.1 wt % to about 1 wt %, about 0.1 wt % to about 0.75 wt %,
about 0.1 wt % to about 0.5 wt %, about 0.2 wt % to about 5 wt %,
about 0.2 wt % to about 4 wt %, about 0.2 wt % to about 3 wt %,
about 0.2 wt % to about 2 wt %, about 0.2 wt % to about 1.5 wt %,
about 0.2 wt % to about 1 wt %, about 0.2 wt % to about 0.75 wt %,
about 0.2 wt % to about 0.5 wt %, about 0.3 wt % to about 5 wt %,
about 0.3 wt % to about 4 wt %, about 0.3 wt % to about 3 wt %,
about 0.3 wt % to about 2 wt %, about 0.3 wt % to about 1.5 wt %,
about 0.3 wt % to about 1 wt %, about 0.3 wt % to about 0.75 wt %,
about 0.3 wt % to about 0.5 wt %, about 0.5 wt % to about 5 wt %,
about 0.5 wt % to about 4 wt %, about 0.5 wt % to about 3 wt %,
about 0.5 wt % to about 2 wt %, about 0.5 wt % to about 1.5 wt %,
about 0.5 wt % to about 1 wt %, about 0.5 wt % to about 0.75 wt %,
about 0.5 wt % to about 0.5 wt %, about 1 wt % to about 5 wt %,
about 1 wt % to about 4 wt %, about 1 wt % to about 3 wt %, about 2
wt % to about 5 wt %, about 2 wt % to about 4 wt %, or about 3 wt %
to about 5 wt % of the lubricating composition.
Seal Compatibility Agent(s).
[0144] In other embodiments, the lubricating composition comprises
at least one (e.g., 1, 2, 3, 4, or more) seal compatibility agent.
The seal compatibility agent(s) may be added to help swell
elastomeric seals by causing a chemical reaction in the fluid or
physical change in the elastomer. Any seal compatibility agent that
is known or that becomes know may be utilized in the lubricating
composition of the present disclosure. For example, the seal
compatibility agent or agents may include at least one of organic
phosphates, aromatic esters, aromatic hydrocarbons, esters (e.g.
butylbenzyl phthalate), polybutenyl succinic anhydride, or
sulfolane-type seal swell agents (e.g. Lubrizol 730-type seal swell
additives), or combinations thereof. Although their presence is not
required to obtain the benefit of the present disclosure, seal
compatibility additives may be present in an amount of zero to
about 3 weight percent (e.g., about 0.01 to about 2 weight percent)
of the lubricating composition.
Antifoam Agent(s).
[0145] In other embodiments, the lubricating composition comprises
at least one (e.g., 1, 2, 3, 4, or more) antifoam agent. The
antifoam agent(s) may be added to retard the formation of stable
foams. Any antifoam agent that is known or that becomes know may be
utilized in the lubricating composition of the present disclosure.
Foam inhibitors include polymers of alkyl methacrylate especially
useful poly alkyl acrylate polymers where alkyl may be understood
to be methyl, ethyl propyl, isopropyl, butyl, or iso butyl and
polymers of dimethylsilicone which form materials called
dimethylsiloxane polymers in the viscosity range of 100 cSt to
100,000 cSt. Silicone polymers, which have been post reacted with
various carbon containing moieties, are the most widely used
defoamers. Organic polymers are sometimes used as defoamers
although much higher concentrations are required.
[0146] Antifoam agents are commercially available and may be used
in conventional minor amounts along with other additives such as
demulsifiers. Although their presence is not required to obtain the
benefit of the present disclosure, the antifoam agent or agents may
be present in a combined amount less than 1 weight percent (e.g.
less than 0.1 weight percent) of the lubricating composition.
Demulsifier(s).
[0147] In other embodiments, the lubricating composition comprises
at least one (e.g., 1, 2, 3, 4, or more) demulsifier. The
demulsifier may be added to separate emulsions (e.g.,
water-in-oil). Any demulsifier that is known or that becomes know
may be utilized in the lubricating composition of the present
disclosure. An illustrative demulsifying component is described in
EP-A-330,522. This exemplary demulsifying agent is obtained by
reacting an alkylene oxide with an adduct obtained by reaction of a
bis-epoxide with a polyhydric alcohol. Demulsifiers are
commercially available and may be used in conventional minor
amounts along with other additives such as antifoam agents.
Although their presence is not required to obtain the benefit of
the present disclosure, the emulsifier or emulsifiers may be
present a combined amount less than 1 weight percent (e.g. less
than 0.1 weight percent).
[0148] In certain embodiments, the demulsifying agent includes at
least one of alkoxylated phenols, phenol-formaldehyde resins,
synthetic alkylaryl sulfonates (such as metallic dinonylnaphthalene
sulfonates), or a combination thereof. In an embodiment, a
demulsifing agent is a predominant amount of a water-soluble
polyoxyalkylene glycol having a pre-selected molecular weight of
any value in the range of between about 450 and about 5000 or more.
In an embodiment, the water soluble polyoxyalkylene glycol
demulsifier may also be one produced from alkoxylation of n-butanol
with a mixture of alkylene oxides to form a random alkoxylated
product.
[0149] Polyoxyalkylene glycols useful in the present disclosure may
be produced by a well-known process for preparing polyalkylene
oxide having hydroxyl end-groups by subjecting an alcohol or a
glycol ether and one or more alkylene oxide monomers, such as
ethylene oxide, butylene oxide, or propylene oxide, to form block
copolymers in addition polymerization, while employing a strong
base, such as potassium hydroxide as a catalyst. In such a process,
the polymerization is commonly carried out under a catalytic
concentration of about 0.3 to about 1.0% by mole of potassium
hydroxide to the monomer(s) and at high temperature of about
100.degree. C. to about 160.degree. C. It is well known that the
catalyst potassium hydroxide is, for the most part, bonded to the
chain-end of the produced polyalkylene oxide in a form of alkoxide
in the polymer solution so obtained.
[0150] The soluble polyoxyalkylene glycol emulsifier(s) useful in
the compositions of the present disclosure may also be one produced
from alkoxylation of n-butanol with a mixture of alkylene oxides to
form a random alkoxylated product.
Corrosion Inhibitor or Anti-Rust Additive.
[0151] In other embodiments, the lubricating composition comprises
at least one (e.g. 1, 2, 3, 4, or more) corrosion inhibitor or
anti-rust additive. The corrosion inhibitor or anti-rust additive
may be added to protect lubricated metal surfaces against chemical
attack by water or other contaminants. A wide variety of corrosion
inhibitors are commercially available, and any corrosion inhibitor
or anti-rust additive that is known or that becomes know may be
utilized in the lubricating composition of the present disclosure.
In an embodiment, the corrosion inhibitor can be a polar compound
that wets the metal surface protecting it with a film of oil. In
another embodiment, the anti-rust additive may absorb water by
incorporating it in a water-in-oil emulsion so that only the oil
touches the surface. In yet a further embodiment, the corrosion
inhibitor chemically adheres to the metal to produce a non-reactive
surface. In certain embodiments, the anti-rust additive or
corrosion inhibitor is at least one zinc dithiophosphates, metal
phenolates, basic metal sulfonates, a fatty acid, a fatty acid
mixture, amines, or a combination thereof.
[0152] Antirust additives may include (short-chain) alkenyl
succinic acids, partial esters thereof and nitrogen-containing
derivatives thereof; and synthetic alkarylsulfonates, such as metal
dinonylnaphthalene sulfonates. Antirust agents include, for
example, monocarboxylic acids which have from 8 to 30 carbon atoms,
alkyl or alkenyl succinates or partial esters thereof,
hydroxy-fatty acids, which have from 12 to 30 carbon atoms and
derivatives thereof, sarcosines which have from 8 to 24 carbon
atoms and derivatives thereof, amino acids and derivatives thereof,
naphthenic acid and derivatives thereof, lanolin fatty acid,
mercapto-fatty acids, and/or paraffin oxides.
[0153] Examples of monocarboxylic acids (C8-C30), include, for
example, caprylic acid, pelargonic acid, decanoic acid, undecanoic
acid, lauric acid, myristic acid, palmitic acid, stearic acid,
arachic acid, behenic acid, cerotic acid, montanic acid, melissic
acid, oleic acid, docosanic acid, erucic acid, eicosenic acid, beef
tallow fatty acid, soy bean fatty acid, coconut oil fatty acid,
linolic acid, linoleic acid, tall oil fatty acid, 12-hydroxystearic
acid, laurylsarcosinic acid, myritsylsarcosinic acid,
palmitylsarcosinic acid, stearylsarcosinic acid, oleylsarcosinic
acid, alkylated (C8-C20) phenoxyacetic acids, lanolin fatty acid,
and C8-C24 mercapto-fatty acids.
[0154] Examples of polybasic carboxylic acids include, for example,
the alkenyl (C10-C100) succinic acids indicated in CAS No.
27859-58-1 and ester derivatives thereof, dimer acid,
N-acyl-N-alkyloxyalkyl aspartic acid esters (U.S. Pat. No.
5,275,749).
[0155] Examples of the alkylamines that function as antirust
additives or as reaction products with the above carboxylates to
give amides and the like are represented by primary amines, such as
laurylamine, coconut-amine, n-tridecylamine, myristylamine,
n-pentadecylamine, palmitylamine, n-heptadecylamine, stearylamine,
n-nonadecylamine, n-eicosylamine, n-heneicosylamine,
n-docosylamine, n-tricosylamine, n-pentacosylamine, oleylamine,
beef tallow-amine, hydrogenated beef tallow-amine and soy
bean-amine. Examples of the secondary amines include dilaurylamine,
di-coconut-amine, di-n-tridecylamine, dimyristylamine,
di-n-pentadecylamine, dipalmitylamine, di-n-pentadecylamine,
distearylamine, di-n-nonadecylamine, di-n-eicosylamine,
di-n-heneicosylamine, di-n-docosylamine, di-n-tricosylamine,
di-n-pentacosyl-amine, dioleylamine, di-beef tallow-amine,
di-hydrogenated beef tallow-amine and di-soy bean-amine.
[0156] Examples of the aforementioned N-alkylpolyalkyenediamines
include: ethylenediamines, such as laurylethylenediamine, coconut
ethylenediamine, n-tridecylethylenediamine-,
myristylethylenediamine, n-pentadecylethylenediamine,
palmitylethylenediamine, n-heptadecylethylenediamine,
stearylethylenediamine, n-nonadecylethylenediamine,
n-eicosylethylenediamine, n-heneicosylethylenediamine,
n-docosylethylendiamine, n-tricosylethylenediamine,
n-pentacosylethylenediamine, oleylethylenediamine, beef
tallow-ethylenediamine, hydrogenated beef tallow-ethylenediamine
and soy bean-ethylenediamine; propylenediamines such as
laurylpropylenediamine, coconut propylenediamine,
n-tridecylpropylenediamine, myristylpropylenediamine,
n-pentadecylpropylenediamine, palmitylpropylenediamine,
n-heptadecylpropylenediamine, stearylpropylenediamine,
n-nonadecylpropylenediamine, n-eicosylpropylenediamine,
n-heneicosylpropylenediamine, n-docosylpropylendiamine,
n-tricosylpropylenediamine, n-pentacosylpropylenediamine,
diethylene triamine (DETA) or triethylene tetramine (TETA),
oleylpropylenediamine, beef tallow-propylenediamine, hydrogenated
beef tallow-propylenediamine and soy bean-propylenediamine;
butylenediamines such as laurylbutylenediamine, coconut
butylenediamine, n-tridecylbutylenediamine-,
myristylbutylenediamine, n-pentadecylbutylenediamine,
stearylbutylenediamine, n-eicosylbutylenediamine,
n-heneicosylbutylenediamine, n-docosylbutylendiamine,
n-tricosylbutylenediamine, n-pentacosylbutylenediamine,
oleylbutylenediamine, beef tallow-butylenediamine, hydrogenated
beef tallow-butylenediamine and soy bean butylenediamine; and
pentylenediamines such as laurylpentylenediamine, coconut
pentylenediamine, myristylpentylenediamine,
palmitylpentylenediamine, stearylpentylenediamine,
oleyl-pentylenediamine, beef tallow-pentylenediamine, hydrogenated
beef tallow-pentylenediamine and soy bean pentylenediamine.
[0157] The corrosion inhibitor or anti-rust additive may be present
in an amount equal to or less than about 5 wt %, for example about
0.01 to 5 wt %, on an as-received basis. For example, the corrosion
inhibitor may be present in an amount equal to or less than 4 wt %,
equal or less than 3 wt %, equal to or less than 2 wt %, or equal
to or less than 1 wt % on an as-received basis. By way of further
example, the corrosion inhibitor may be present in an amount of
about 0.01 to about 5 wt %, about 0.01 to about 4 wt %, about 0.01
to about 3 wt %, about 0.01 to about 2 wt %, about 0.05 to about 5
wt %, about 0.05 to about 4 wt %, about 0.05 to about 3 wt %, about
0.05 to about 2 wt %, about 0.1 to about 5 wt %, about 0.1 to about
4 wt %, about 0.1 to about 3 wt %, about 0.1 to about 2 wt %, about
1 to about 5 wt %, about 1 to about 4 wt %, about 1 to about 3 wt
%, about 2 to about 5 wt %, about 2 to about 4 wt %, or about 3 to
about 5 wt %, on an as-received basis.
Metal Passivator(s), Deactivator(s) and Corrosion Inhibitor(s).
[0158] This type of component includes
2,5-dimercapto-1,3,4-thiadiazoles and derivatives thereof,
mercaptobenzothiazoles, alkyltriazoles and benzotriazoles. Examples
of dibasic acids useful as anti-corrosion agents, other than
sebacic acids, which may be used in the present disclosure, are
adipic acid, azelaic acid, dodecanedioic acid, 3-methyladipic acid,
3-nitrophthalic acid, 1,10-decanedicarboxylic acid, and fumaric
acid. The anti-corrosion combination is a straight or
branch-chained, saturated or unsaturated monocarboxylic acid or
ester thereof which may optionally be sulphurized in an amount up
to 35% by weight. In an embodiment, the acid is a C4 to C22
straight chain unsaturated monocarboxylic acid. The monocarboxylic
acid may be a sulphurized oleic acid. However, other suitable
materials are oleic acid itself, valeric acid and erucic acid. A
component of the anti-corrosion combination is a triazole as
previously defined. In an embodiment, the triazole is
tolylotriazole, which may be included in the compositions of the
disclosure include triazoles, thiazoles and certain diamine
compounds which are useful as metal deactivators or metal
passivators. Examples include triazole, benzotriazole and
substituted benzotriazoles, such as alkyl substituted derivatives.
The alkyl substituent may contain up to 1.5 carbon atoms, e.g. up
to 8 carbon atoms. The triazoles may contain other substituents on
the aromatic ring such as halogens, nitro, amino, mercapto, etc.
Examples of suitable compounds are benzotriazole and the
tolyltriazoles, ethylbenzotriazoles, hexylbenzotriazoles,
octylbenzotriazoles, chlorobenzotriazoles and nitrobenzotriazoles.
In a particular embodiment, the compound is benzotriazole and/or
tolyltriazole.
[0159] Illustrative substituents include, for example, alkyl that
is straight or branched chain, for example, methyl, ethyl,
n-propyl, iso-propyl, n-butyl, sec-butyl, n-pentyl, n-hexyl,
n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-dodecyl,
n-tetradecyl, n-hexadecyl, n-octadecyl or n-eicosyl; alkenyl that
is straight or branched chain, for example, prop-2-enyl,
but-2-enyl, 2-methyl-prop-2-enyl, pent-2-enyl, hexa-2,4-dienyl,
dec-10-enyl or eicos-2-enyl; cycloalkyl that is, for example,
cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, adamantyl or
cyclododecyl; aralkyl that is, for example, benzyl, 2-phenylethyl,
benzhydryl or naphthylmethyl; aryl that is, for example, phenyl or
naphthyl; heterocyclic group that is, for example, a morpholine,
pyrrolidine, piperidine or a perhydroazepine ring; alkylene
moieties that include, for example, methylene, ethylene, 1:2- or
1:3-propylene, 1:4-butylene, 1:6-hexylene, 1:8-octylene,
1:10-decylene and 1:12-dodecylene.
[0160] Illustrative arylene moieties include, for example,
phenylene and naphthylene. 1-(or 4)-(dimethylaminomethyl) triazole,
1-(or 4)-(diethylaminomethyl) triazole, 1-(or
4)-(di-isopropylaminomethyl) triazole, 1-(or
4)-(di-n-butylaminomethyl) triazole, 1-(or
4)-(di-n-hexylaminomethyl) triazole, 1-(or
4)-(di-isooctylaminomethyl) triazole, 1-(or
4)-(di-(2-ethylhexyl)aminomethyl) triazole, 1-(or
4)-(di-n-decylaminomethyl) triazole, 1-(or
4)-(di-n-dodecylaminomethyl) triazole, 1-(or
4)-(di-n-octadecylaminomethyl) triazole, 1-(or
4)-(di-n-eicosylaminomethyl) triazole, 1-(or
4)-[di-(prop-2'-enyl)aminomethyl] triazole, 1-(or
4)-[di-(but-2'-enyl)aminomethyl] triazole, 1-(or
4)-[di-(eicos-2'-enyl)aminomethyl] triazole, 1-(or
4)-(di-cyclohexylaminomethyl) triazole, 1-(or
4)-(di-benzylaminomethyl) triazole, 1-(or 4)-(di-phenylaminomethyl)
triazole, 1-(or 4)-(4'-morpholinomethyl) triazole, 1-(or
4)-(1'-pyrrolidinomethyl) triazole, 1-(or 4)-(1'-piperidinomethyl)
triazole, 1-(or 4)-(1'-perhydoroazepinomethyl) triazole, 1-(or
4)-(2',2''-dihydroxyethy)aminomethyl]triazole, 1-(or
4)-(dibutoxypropyl-aminomethyl) triazole, 1-(or
4)-(dibutylthiopropyl-aminomethyl) triazole, 1-(or
4)-(di-butylaminopropyl-aminomethyl) triazole,
1-(or-4)-(1-methanomine)-N,N-bis(2-ethylhexyl)-methyl
benzotriazole, N,N-bis-(1- or 4-triazolylmethyl) laurylamine,
N,N-bis-(1- or 4-triazolylmethyl) oleylamine, N,N-bis-(1- or
4-triazolylmethyl) ethanolamine and N,N,N',N'-tetra(1- or
4-triazolylmethyl) ethylene diamine.
[0161] The metal deactivating agents which can be used in the
lubricating compositon of the present disclosure includes, for
example, benzotriazole and the 4-alkylbenzotriazoles such as
4-methylbenzotriazole and 4-ethylbenzotriazole;
5-alkylbenzotriazoles such as 5-methylbenzotriazole,
5-ethylbenzotriazole; 1-alkylbenzotriazoles such as
1-dioctylauainomethyl-2,3-benzotriazole; benzotriazole derivatives
such as the 1-alkyltolutriazoles, for example,
1-dioctylaminomethyl-2,3-t-olutriazole; benzimidazole and
benzimidazole derivatives such as 2-(alkyldithio)-benzimidazoles,
for example, such as 2-(octyldithio)-benzimidazole,
2-(decyldithio)benzimidazole and 2-(dodecyldithio)-benzimidazole;
2-(alkyldithio)-toluimidazoles such as
2-(octyldithio)-toluimidazole, 2-(decyldithio)-toluimidazole and
2-(dodecyldithio)-toluimidazole; indazole and indazole derivatives
of toluimidazoles such as 4-alkylindazole, 5-alkylindazole;
benzothiazole, 2-mercaptobenzothiazole derivatives (manufactured by
the Chiyoda Kagaku Co. under the trade designation "Thiolite
B-3100") and 2-(alkyldithio)benzothiazoles such as
2-(hexyldithio)benzothiazole and 2-(octyldithio)benzothiazole;
2-(alkyl-dithio)toluthiazoles such as 2-(benzyldithio)toluthiazole
and 2-(octyldithio)toluthiazole,
2-(N,N-dialkyldithiocarbamyl)benzothiazoles such as
2-(N,N-diethyldithiocarbamyl)benzothiazole,
2-(N,N-dibutyldithiocarbamyl)-benzotriazole and
2-N,N-dihexyl-dithiocarbamyl)benzotriazole; benzothiazole
derivatives of 2-(N,N-dialkyldithiocarbamyl)toluthiazoles such as
2-(N,N-diethyldithiocarbamyl)toluthiazole,
2-(N,N-dibutyldithiocarbamyl)toluthiazole,
2-(N,N-dihexyl-dithiocarbamyl)-toluthiazole;
2-(alkyldithio)benzoxazoles such as 2-(octyldithio)benzoxazo-le,
2-(decyldithio)-benzoxazole and 2-(dodecyldithio)benzoxazole;
benzoxazole derivatives of 2-(alkyldithio)toluoxazoles such as
2-(octyldithio)toluoxazole, 2-(decyldithio)toluoxazole,
2-(dodecyldithio)toluoxazole;
2,5-bis(alkyldithio)-1,3,4-thiadiazoles such as
2,5-bis(heptyldithio)-1,3,4-thiadiazole, 2,5-bis-(nonyldithio)-1,
3,4-thiadiazole, 2,5-bis(dodecyldithio)-1,3,4-thiadiazole and
2,5-bis-(octadecyldithio)-1,3,4-thiadiazole;
2,5-bis(N,N-dialkyl-dithioca-rbamyl)-1,3,4-thiadiazoles such as
2,5-bis(N,N-diethyldithiocarbamyl)-1,3,-4-thiadiazole,
2,5-bis(N,N-dibutyldithiocarbamyl)-1,3,4-thiadiazole and
2,5-bis(N,N-dioctyldithiocarbamyl)1,3,4-thiadiazole; thiadiazole
derivatives of
2-N,N-dialkyldithiocarbamyl-5-mercapto-1,3,4-thiadiazoles such as
2-N,N-dibutyldithiocarbamyl-5-mercapto-1,3,4-thiadiazole and
2-N,N-dioctyl-dithiocarbamyl-5-mercapto-1,3,4-thiadiazole, and
triazole derivatives of 1-alkyl-2,4-triazoles such as
1-dioctylaminomethyl-2,4-triazole; or concentrates and/or mixtures
thereof.
[0162] Although their presence is not required to obtain the
benefit of the present disclosure, the metal deactivator(s) and
corrosion inhibitor(s) may be present from zero to about 1% by
weight (e.g. from 0.01% to about 0.5% by weight) of the total
lubricating composition.
Additional Antiwear Additive(s) or Inhibitor(s).
[0163] In certain embodiments, the lubricating composition
comprises at least one (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or more)
antiwear additive or wear inhibitor. In other embodiments, the
antiwear composition of the present disclosure comprises at least
one additional antiwear additive or wear inhibitor. Any antiwear
additive that is known or that becomes known may be utilized in the
lubricating composition of the present disclosure or the antiwear
composition of the present disclosure. The antiwear additive may be
an alkyldithiophosphate(s), dialkyldithiophosphate, aryl
phosphate(s), tri-butyl phosphate, and/or phosphite(s). The
antiwear additive(s) may be essentially free of metals, or they may
contain metal salts.
[0164] In certain embodiments, the antiwear additive is a phosphate
ester or salt thereof. A phosphate ester or salt may be a
monohydrocarbyl, dihydrocarbyl or a trihydrocarbyl phosphate,
wherein each hydrocarbyl group is saturated. In an embodiment, each
hydrocarbyl group independently contains from about 8 to about 30,
or from about 12 up to about 28, or from about 14 up to about 24,
or from about 14 up to about 18 carbons atoms. In an embodiment,
the hydrocarbyl groups are alkyl groups. Examples of hydrocarbyl
groups include at least one of tridecyl, tetradecyl, pentadecyl,
hexadecyl, heptadecyl, octadecyl groups, and mixtures thereof.
[0165] A phosphate ester or salt is a phosphorus acid ester
prepared by reacting at least one (e.g., 1, 2, 3, 4, or more)
phosphorus acid or anhydride with a saturated alcohol. The
phosphorus acid or anhydride can be an inorganic phosphorus
reagent, such as phosphorus pentoxide, phosphorus trioxide,
phosphorus tetroxide, phosphorous acid, phosphoric acid, phosphorus
halide, lower phosphorus esters, or a phosphorus sulfide, including
phosphorus pentasulfide, and the like. Lower phosphorus acid esters
may contain from 1 to about 7 carbon atoms in each ester group.
Alcohols used to prepare the phosphorus acid esters or salts.
Examples of commercially available alcohols and alcohol mixtures
include Alfol 1218 (a mixture of synthetic, primary, straight-chain
alcohols containing 12 to 18 carbon atoms); Alfol 20+ alcohols
(mixtures of C18-C28 primary alcohols having mostly C20 alcohols as
determined by GLC (gas-liquid-chromatography)); and Alfol22+
alcohols (C18-C28 primary alcohols containing primarily C22
alcohols). Alfol alcohols are available from, e.g., Continental Oil
Company. Another example of a commercially available alcohol
mixture is Adol 60 (about 75% by weight of a straight chain C22
primary alcohol, about 15% of a C20 primary alcohol, and about 8%
of C18 and C24 alcohols). The Adol alcohols are marketed by Ashland
Chemical.
[0166] The antiwear additive may include at least one (e.g., a
mixture of) monohydric fatty alcohol. For example, a mixture of
monohydric fatty alcohols derived from naturally occurring
triglycerides and ranging in chain length from C8 to C18 may be
utilized as an antiwear additive. A variety of monohydric fatty
alcohol mixtures are available from Procter & Gamble Company.
These mixtures contain various amounts of fatty alcohols containing
12, 14, 16, or 18 carbon atoms. For example, CO-1214 is a fatty
alcohol mixture containing 0.5% of C10 alcohol, 66.0% of C12
alcohol, 26.0% of C14 alcohol and 6.5% of C16 alcohol.
[0167] Another group of commercially available alcohol mixtures
include the "Neodol" products available from Shell Chemical Co. For
example, Neodol 23 is a mixture of C12 and C13 alcohols; Neodol 25
is a mixture of C12 to C15 alcohols; and Neodol 45 is a mixture of
C14 to C15 linear alcohols. The phosphate contains from about 14 to
about 18 carbon atoms in each hydrocarbyl group. The hydrocarbyl
groups of the phosphate may be derived from a mixture of fatty
alcohols having from about 14 up to about 18 carbon atoms. The
hydrocarbyl phosphate may also be derived from a fatty vicinal
diol. Fatty vicinal diols include, but not limited to, those
available from Ashland Oil under the general trade designation Adol
114 and Adol 158. The former is derived from a straight chain alpha
olefin fraction of C11-C14, and the latter is derived from a
C15-C18 fraction.
[0168] Phosphate salts may be prepared by reacting an acidic
phosphate ester with an amine compound or a metallic base to form
an amine or a metal salt. The amines may be monoamines or
polyamines. Useful amines include those amines disclosed in U.S.
Pat. No. 4,234,435.
[0169] Illustrative monoamines may contain a hydrocarbyl group,
which contains from 1 to about 30 carbon atoms, or from 1 to about
12, or from 1 to about 6. Examples of primary monoamines useful in
the present disclosure include methylamine, ethylamine,
propylamine, butylamine, cyclopentylamine, cyclohexylamine,
octylamine, dodecylamine, allylamine, cocoamine, stearylamine, and
laurylamine. Examples of secondary monoamines include
dimethylamine, diethylamine, dipropylamine, dibutylamine,
dicyclopentylamine, dicyclohexylamine, methylbutylamine,
ethylhexylamine, etc.
[0170] An amine may be a fatty (C8-C30) amine which includes
n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine,
n-hexadecylamine, n-octadecylamine, oleyamine, etc. Also useful
fatty amines include commercially available fatty amines, such as
"Armeen" amines (products available from Akzo Chemicals, Chicago,
Ill.), e.g. 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.
[0171] Other useful amines include primary ether amines, such as
those represented by the formula:
R''(OR').times.NH.sub.2,
wherein: [0172] R' is a divalent alkylene group having about 2 to
about 6 carbon atoms; [0173] x is a number from one to about 150,
or from about one to about five, or one; and [0174] R'' is a
hydrocarbyl group of about 5 to about 150 carbon atoms.
[0175] An exemplary or illustrative ether amine is available under
the name SURFAM.RTM. amines produced and marketed by Mars Chemical
Company, Atlanta, Ga. Additional exemplary ether amines include
those identified as SURFAM P14B (decyloxypropylamine), SURFAM P16A
(linear C16), and SURFAM P17B (tridecyloxypropylamine). The carbon
chain lengths (i.e., C14, etc.) of the SURFAM ether amines
described above and used hereinafter are approximate and include
the oxygen ether linkage.
[0176] A further illustrative amine is a tertiary-aliphatic primary
amine. For example, the aliphatic group, such as an alkyl group,
contains from about 4 to about 30, or from about 6 to about 24, or
from about 8 to about 22 carbon atoms. Usually the tertiary alkyl
primary amines are monoamines the alkyl group is a hydrocarbyl
group containing from one to about 27 carbon atoms. Such amines are
illustrated by tert-butylamine, tert-hexylamine,
1-methyl-1-amino-cyclohexane, tert-octylamine, tert-decylamine,
tert-dodecylamine, tert-tetradecylamine, tert-hexadecylamine,
tert-octadecylamine, tert-tetracosanylamine, tert-octacosanylamine,
and combinations thereof. Mixtures of tertiary aliphatic amines may
also be used in preparing the phosphate salt. Illustrative of amine
mixtures of this type are "Primene 81R", which is a mixture of
C11-C14 tertiary alkyl primary amines, and "Primene JMT", which is
a similar mixture of C18-C22 tertiary alkyl primary amines (both
are available from Rohm and Haas Company). The tertiary aliphatic
primary amines and methods for their preparation are known to those
of ordinary skill in the art.
[0177] Another illustrative amine is a heterocyclic polyamine. The
heterocyclic polyamines include aziridines, azetidines, azolidines,
tetra- and dihydropyridines, pyrroles, indoles, piperidines,
imidazoles, di- and tetra-hydroimidazoles, piperazines, isoindoles,
purines, morpholines, thiomorpholines, N-aminoalkylmorpholines,
N-aminoalkylthiomorpholines, N-aminoalkyl-piperazines,
N,N'-diaminoalkylpiperazines, azepines, azocines, azonines,
azecines and tetra-, di- and perhydro derivatives of each of the
above, and mixtures of two or more (e.g., 2, 3, 4, 5, 6, or more)
of these heterocyclic amines. In certain embodiments, the
heterocyclic amines are saturated 5- and 6-membered heterocyclic
amines containing only nitrogen, oxygen and/or sulfur in the hetero
ring, especially the piperidines, piperazines, thiomorpholines,
morpholines, pyrrolidines, and the like. Piperidine, aminoalkyl
substituted piperidines, piperazine, aminoalkyl substituted
piperazines, morpholine, aminoalkyl substituted morpholines,
pyrrolidine, and aminoalkyl-substituted pyrrolidines, are
especially preferred. Usually the aminoalkyl substituents are
substituted on a nitrogen atom forming part of the hetero ring.
Specific examples of such heterocyclic amines include
N-aminopropylmorpholine, N-aminoethylpiperazine, and
N,N'-diaminoethylpiperazine. Hydroxy heterocyclic polyamines are
also useful. Examples include N-(2-hydroxyethyl)cyclohexylamine,
3-hydroxycyclopentylamine, parahydroxyaniline,
N-hydroxyethylpiperazine, and the like.
[0178] The metal salts of the phosphorus acid esters may be
prepared by the reaction of a metal base with the acidic phosphorus
ester. The metal base may be any metal compound capable of forming
a metal salt. Examples of metal bases include metal oxides,
hydroxides, carbonates, sulfates, borates, or the like. The metals
of the metal base include Group IA, IIA, IB through VIIB, and VIII
metals (CAS version of the Periodic Table of the Elements). These
metals include the alkali metals, alkaline earth metals and
transition metals. In an embodiment, the metal is a Group IIA
metal, such as calcium or magnesium, Group IIB metal or a Group
VIIB metal, such as manganese. In particular embodiments, the metal
is magnesium, calcium or manganese. Examples of metal compounds
which may be reacted with the phosphorus acid include copper
hydroxide, copper oxide, etc.
[0179] The lubricating composition of the present disclosure also
may include a fatty imidazoline or a reaction product of a fatty
carboxylic acid and at least one polyamine. The fatty imidazoline
has fatty substituents containing from 8 to about 30, or from about
12 to about 24 carbon atoms. The substituent may be saturated or
unsaturated, for example, heptadeceneyl derived olyel groups. In a
particular embodiment, the substituents are saturated. In one
aspect, the fatty imidazoline may be prepared by reacting a fatty
carboxylic acid with a polyalkylenepolyamine. The fatty carboxylic
acids are can be mixtures of straight and branched chain fatty
carboxylic acids containing about 8 to about 30 carbon atoms, or
from about 12 to about 24, or from about 16 to about 18. Carboxylic
acids include the polycarboxylic acids or carboxylic acids or
anhydrides having from 2 to about 4 carbonyl groups, (e.g. 2
carbonyl groups). The polycarboxylic acids include succinic acids
and anhydrides and Diels-Alder reaction products of unsaturated
monocarboxylic acids with unsaturated carboxylic acids (such as
acrylic, methacrylic, maleic, fumaric, crotonic and itaconic
acids). In particular embodiments, the fatty carboxylic acids are
fatty monocarboxylic acids, having from about 8 to about 30, (e.g.
about 12 to about 24 carbon atoms), such as octanoic, oleic,
stearic, linoleic, dodecanoic, and tall oil acids. In an
embodiment, the fatty carboxylic acid is stearic acid. The fatty
carboxylic acid or acids are reacted with at least one polyamine.
The polyamines may be aliphatic, cycloaliphatic, heterocyclic or
aromatic. Examples of the polyamines include alkylene polyamines
and heterocyclic polyamines.
[0180] The antiwear additive according to the present disclosure
has very high effectiveness when used in low concentrations and is
free of chlorine. For the neutralization of the phosphoric esters,
the latter are taken and the corresponding amine slowly added with
stirring. The resulting heat of neutralization is removed by
cooling. The antiwear additive according to the present disclosure
can be incorporated into the respective base liquid with the aid of
fatty substances (e.g., tall oil fatty acid, oleic acid, etc.) as
solubilizers. The base liquids used are napthenic or paraffinic
base oils, synthetic oils (e.g., polyglycols, mixed polyglycols),
polyolefins, carboxylic esters, etc.
[0181] In further embodiments, the lubricating compositions of the
present disclosure can contain at least one phosphorus containing
antiwear additive. Examples of such additives are amine phosphate
antiwear additives such as that known under the trade name IRGALUBE
349 and/or triphenyl phosphorothionate antiwear additives, such as
that known under the trade name IRGALUBE TPPT. Such amine
phosphates may be present in an amount of from about 0.01 to about
2% (e.g. about 0.2 to about 1.5%) by weight of the lubricant
composition, while such phosphorothionates are suitably present in
an amount of from about 0.01 to about 3% (e.g., about 0.5 to about
1.5%) by weight of the lubricating composition. A mixture of an
amine phosphate and phosphorothionate may be employed.
[0182] Neutral organic phosphates may be present in an amount from
zero to about 4% (e.g., about 0.1 to about 2.5%) by weight of the
lubricating composition. The above amine phosphates can be mixed
together to form a single component capable of delivering antiwear
performance. The neutral organic phosphate is also a conventional
ingredient of lubricating oils.
[0183] Phosphates for use in the present disclosure include
phosphates, acid phosphates, phosphites, and acid phosphites. The
phosphates include triaryl phosphates, trialkyl phosphates,
trialkylaryl phosphates, triarylalkyl phosphates, trialkenyl
phosphates, or combinations thereof As specific examples of these,
referred to are triphenyl phosphate, tricresyl phosphate,
benzyldiphenyl phosphate, ethyldiphenyl phosphate, tributyl
phosphate, ethyldibutyl phosphate, cresyldiphenyl phosphate,
dicresylphenyl phosphate, ethylphenyldiphenyl phosphate,
diethylphenylphenyl phosphate, propylphenyldiphenyl phosphate,
dipropylphenylphenyl phosphate, triethylphenyl phosphate,
tripropylphenyl phosphate, butylphenyldiphenyl phosphate,
dibutylphenylphenyl phosphate, tributylphenyl phosphate, trihexyl
phosphate, tri(2-ethylhexyl) phosphate, tridecyl phosphate,
trilauryl phosphate, trimyristyl phosphate, tripalmityl phosphate,
tristearyl phosphate, trioleyl phosphate, or combinations
thereof.
[0184] The acid phosphates include, for example, 2-ethylhexyl acid
phosphate, ethyl acid phosphate, butyl acid phosphate, oleyl acid
phosphate, tetracosyl acid phosphate, isodecyl acid phosphate,
lauryl acid phosphate, tridecyl acid phosphate, stearyl acid
phosphate, isostearyl acid phosphate, or combinations thereof.
[0185] The phosphites include, for example, triethyl phosphite,
tributyl phosphite, triphenyl phosphite, tricresyl phosphite,
tri(nonylphenyl) phosphite, tri(2-ethylhexyl) phosphite, tridecyl
phosphite, trilauryl phosphite, triisooctyl phosphite,
diphenylisodecyl phosphite, tristearyl phosphite, trioleyl
phosphite, or combinations thereof.
[0186] The acid phosphites include, for example, dibutyl
hydrogenphosphite, dilauryl hydrogenphosphite, dioleyl
hydrogenphosphite, distearyl hydrogenphosphite, diphenyl
hydrogenphosphite, or combinations thereof.
[0187] Amines that form amine salts with such phosphates include,
for example, mono-substituted amines, di-substituted amines and
tri-substituted amines. Examples of the mono-substituted amines
include butylamine, pentylamine, hexylamine, cyclohexylamine,
octylamine, laurylamine, stearylamine, oleylamine and benzylamine;
and those of the di-substituted amines include dibutylamine,
dipentylamine, dihexylamine, dicyclohexylamine, dioctylamine,
dilaurylamine, distearylamine, dioleylamine, dibenzylamine, stearyl
monoethanolamine, decyl monoethanolamine, hexyl monopropanolamine,
benzyl monoethanolamine, phenyl monoethanolamine, and tolyl
monopropanolamine. Examples of tri-substituted amines include
tributylamine, tripentylamine, trihexylamine, tricyclohexylamine,
trioctylamine, trilaurylamine, tristearylamine, trioleylamine,
tribenzylamine, dioleyl monoethanolamine, dilauryl
monopropanolamine, dioctyl monoethanolamine, dihexyl
monopropanolamine, dibutyl monopropanolamine, oleyl diethanolamine,
stearyl dipropanolamine, lauryl diethanolamine, octyl
dipropanolamine, butyl diethanolamine, benzyl diethanolamine,
phenyl diethanolamine, tolyl dipropanolamine, xylyl diethanolamine,
triethanolamine, and tripropanolamine. Phosphates or their amine
salts are added to the base oil in an amount from zero to about 5%
by weight, (e.g. from about 0.1 to about 2% by weight) relative to
the total weight of the lubricating composition.
[0188] Illustrative carboxylic acids to be reacted with amines
include, for example, aliphatic carboxylic acids, dicarboxylic
acids (dibasic acids), aromatic carboxylic acids, or combinations
thereof. The aliphatic carboxylic acids have from 8 to 30 carbon
atoms, and may be saturated or unsaturated, and linear or branched.
Specific examples of the aliphatic carboxylic acids include
pelargonic acid, lauric acid, tridecanoic acid, myristic acid,
palmitic acid, stearic acid, isostearic acid, eicosanoic acid,
behenic acid, triacontanoic acid, caproleic acid, undecylenic acid,
oleic acid, linolenic acid, erucic acid, linoleic acid, or
combinations thereof. Specific examples of the dicarboxylic acids
include octadecylsuccinic acid, octadecenylsuccinic acid, adipic
acid, azelaic acid, sebacic acid, or combinations thereof. One
example of the aromatic carboxylic acids is salicylic acid.
Illustrative amines to be reacted with carboxylic acids include,
for example, polyalkylene-polyamines, such as diethylenetriamine,
triethylenetetramine, tetraethylenepentamine,
pentaethylenehexamine, hexaethyleneheptamine,
heptaethyleneoctamine, dipropylenetriamine,
tetrapropylenepentamine, hexabutyleneheptamine, or combinations
thereof; and alkanolamines, such as monoethanolamine and
diethanolamine. Of these, preferred are a combination of isostearic
acid, tetraethylenepentamine, or combinations thereof; and a
combination of oleic acid and diethanolamine. Reaction products of
carboxylic acids and amines may be added to the base oil in an
amount of from zero to about 5% by weight (e.g. from about 0.03 to
about 3% by weight) relative to the total weight of the lubricating
composition.
[0189] Other illustrative antiwear additives include phosphites,
thiophosphites, phosphates, and thiophosphates, including mixed
materials having, for instance, one or two sulfur atoms, i.e.,
monothio- or dithio compounds. 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 primarily composed of carbon and
hydrogen atoms and is attached to the remainder of the molecule
through a carbon atom and does not exclude the presence of other
atoms or groups in a proportion insufficient to detract from the
molecule having a predominantly hydrocarbon character. 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. A more detailed definition
of the terms "hydrocarbyl substituent" or "hydrocarbyl group," is
described in U.S. Pat. No. 6,583,092.
[0190] Specific examples of some phosphites and thiophosphites
within the scope of the disclosure include phosphorous acid, mono-,
di- or tri-thiophosphorous acid, mono-, di- or tri-propyl phosphite
or mono-, di- or tri-thiophosphite; mono-, di- or tri-butyl
phosphite or mono-, di- or tri-thiophosphite; mono-, di- or
tri-amyl phosphite or mono-, di- or tri-thiophosphite; mono-, di-
or tri-hexyl phosphite; or mono-, di- or tri-thiophosphite; mono-,
di- or tri-phenyl phosphite; or mono-, di- or tri-thiophosphite;
mono-, di- or tri-tolyl phosphite; or mono-, di- or
tri-thiophosphite; mono-, di- or tri-cresyl phosphite; or mono-,
di- or tri-thiophosphite; dibutyl phenyl phosphite; or mono-, di-
or tri-phosphite; amyl dicresyl phosphite; or mono-, di- or
tri-thiophosphite, and any of the above with substituted groups,
such as chlorophenyl or chlorobutyl.
[0191] Specific examples of the phosphates and thiophosphates
within the scope of the disclosure include phosphoric acid, mono-,
di-, or tri-thiophosphoric acid, mono-, di-, or tri-propyl
phosphate or mono-, di-, or tri-thiophosphate; mono-, di-, or
tri-butyl phosphate or mono-, di-, or tri-thiophosphate; mono-,
di-, or tri-amyl phosphate or mono-, di-, or tri-thiophosphate;
mono-, di-, or tri-hexyl phosphate or mono-, di-, or
tri-thiophosphate; mono-, di-, or tri-phenyl phosphate or mono-,
di-, or tri-thiophosphate; mono-, di-, or tritolyl phosphate or
mono-, di-, or trithiophosphate; mono-, di-, or tri-cresyl
phosphate or mono-, di-, or tri-thiophosphate; dibutyl phenyl
phosphate or mono-, di-, or tri-phosphate, amyl dicresyl phosphate
or mono-, di-, or tri-thiophosphate, and any of the above with
substituted groups, such as chlorophenyl or chlorobutyl.
[0192] These phosphorus compounds may be prepared by well-known
reactions. For example, the reaction of an alcohol or a phenol with
phosphorus trichloride or by a transesterification reaction.
Alcohols and phenols can be reacted with phosphorus pentoxide to
provide a mixture of an alkyl or aryl phosphoric acid and a dialkyl
or diaryl phosphoric acid. Alkyl phosphates can also be prepared by
the oxidation of the corresponding phosphites. Thiophosphates can
be prepared by the reaction of phosphites with elemental sulfur. In
any case, the reaction can be conducted with moderate heating.
Moreover, various phosphorus esters can be prepared by reaction
using other phosphorus esters as starting materials. Thus, medium
chain (C9 to C22) phosphorus esters have been prepared by reaction
of dimethylphosphite with a mixture of medium-chain alcohols by
means of a thermal transesterification or an acid- or
base-catalyzed transesterification. See, for example, U.S. Pat. No.
4,652,416. Most such materials are also commercially available; for
instance, triphenyl phosphite is available from Albright and Wilson
as Duraphos TPP.TM.; di-n-butyl hydrogen phosphite from Albright
and Wilson as Duraphos DBHP.TM.; and triphenylthiophosphate from
Ciba Specialty Chemicals as Irgalube TPPT.TM..
[0193] Examples of esters of the dialkylphosphorodithioic acids
include esters obtained by reaction of the dialkyl
phosphorodithioic acid with an alpha, beta-unsaturated carboxylic
acid (e.g., methyl acrylate) and, optionally an alkylene oxide such
as propylene oxide.
[0194] One or more of the above-identified metal dithiophosphates
may be used from about zero to about 2% by weight (e.g., from about
0.1 to about 1% by weight) based on the weight of the total
composition.
[0195] The hydrocarbyl in the dithiophosphate may be alkyl,
cycloalkyl, aralkyl or alkaryl groups, or a substantially
hydrocarbon group of similar structure. Illustrative alkyl groups
include isopropyl, isobutyl, n-butyl, sec-butyl, the various amyl
groups, n-hexyl, methylisobutyl, heptyl, 2-ethylhexyl, diisobutyl,
isooctyl, nonyl, behenyl, decyl, dodecyl, tridecyl, etc.
Illustrative lower alkylphenyl groups include butylphenyl,
amylphenyl, heptylphenyl, etc. Cycloalkyl groups likewise are
useful and these include chiefly cyclohexyl and the lower
alkyl-cyclohexyl radicals. Many substituted hydrocarbon groups may
also be used, e.g., chloropentyl, dichlorophenyl, and
dichlorodecyl.
[0196] The phosphorodithioic acids from which the metal salts
useful in this disclosure are prepared are well known. Examples of
dihydrocarbylphosphorodithioic acids and metal salts, and processes
for preparing such acids and salts are found in, for example U.S.
Pat. Nos. 4,263,150; 4,289,635; 4,308,154; and 4,417,990. These
patents are hereby incorporated by reference.
[0197] The phosphorodithioic acids may be prepared by the reaction
of a phosphorus sulfide with an alcohol or phenol or mixtures of
alcohols. An exemplary reaction involves four moles of the alcohol
or phenol and one mole of phosphorus pentasulfide, and may be
carried out within the temperature range from about 50.degree. C.
to about 200.degree. C. Thus, the preparation of O,O-di-n-hexyl
phosphorodithioic acid involves the reaction of a mole of
phosphorus pentasulfide with four moles of n-hexyl alcohol at about
100.degree. C. for about two hours. Hydrogen sulfide is liberated
and the residue is the desired acid. The preparation of the metal
salts of these acids may be effected by reaction with metal
compounds as well known in the art.
[0198] The metal salts of dihydrocarbyldithiophosphates, which are
useful in the present disclosure, include those salts containing
Group I metals, Group II metals, aluminum, lead, tin, molybdenum,
manganese, cobalt, and nickel. The Group II metals, aluminum, tin,
iron, cobalt, lead, molybdenum, manganese, nickel and copper are
among the preferred metals. Copper is especially useful metals.
Examples of metal compounds which may be reacted with the acid
include lithium oxide, lithium hydroxide, sodium hydroxide, sodium
carbonate, potassium hydroxide, potassium carbonate, silver oxide,
magnesium oxide, magnesium hydroxide, calcium oxide, strontium
hydroxide, cadmium oxide, cadmium hydroxide, barium oxide, aluminum
oxide, iron carbonate, copper hydroxide, lead hydroxide, tin
butylate, cobalt hydroxide, nickel hydroxide, nickel carbonate, and
the like.
[0199] In some instances, the incorporation of certain ingredients
such as small amounts of the metal acetate or acetic acid in
conjunction with the metal reactant will facilitate the reaction
and result in an improved product.
[0200] Especially useful metal phosphorodithloates can be prepared
from phosphorodithloic acids, which in turn are prepared by the
reaction of phosphorus pentasulfide with mixtures of alcohols. In
addition, the use of such mixtures enables the utilization of less
expensive alcohols, which individually may not yield oil-soluble
phosphorodithioic acids. Thus, a mixture of isopropyl and
hexylalcohols can be used to produce a very effective, oil-soluble
metal phosphorodithioate. For the same reason mixtures of
phosphorodithioic acids can be reacted with the metal compounds to
form less expensive, oil-soluble salts.
[0201] The mixtures of alcohols may be mixtures of different
primary alcohols, mixtures of different secondary alcohols, or
mixtures of primary and secondary alcohols. Examples of useful
mixtures include: n-butanol and n-octanol; n-pentanol and
2-ethyl-1-hexanol; isobutanol and n-hexanol; isobutanol and isoamyl
alcohol; isopropanol and 2-methyl-4-pentanol; isopropanol and
sec-butyl alcohol; isopropanol and isooctyl alcohol; and the
like.
[0202] Organic triesters of phosphorus acids are also employed in
lubricants. Exemplary esters include triarylphosphates, trialkyl
phosphates, neutral alkylaryl phosphates, alkoxyalkyl phosphates,
triaryl phosphite, trialkylphosphite, neutral alkyl aryl
phosphites, neutral phosphonate esters and neutral phosphine oxide
esters. In one embodiment, the long chain dialkyl phosphonate
esters are used. For example, the dimethyl-, diethyl-, and/or
dipropyl-oleyl phohphonates can be used. Neutral acids of
phosphorus acids are the triesters rather than an acid (HO-P) or a
salt of an acid.
[0203] Any C4 to C8 alkyl or higher phosphate ester may be employed
in the disclosure. For example, tributyl phosphate (TBP) and tri
isooctal phosphate (TOF) can be used. The specific triphosphate
ester or combination of esters can easily be selected by one
skilled in the art to adjust the density, viscosity, etc., of the
formulated fluid. Mixed esters, such as dibutyl octyl phosphate or
the like may be employed rather than a mixture of two or more
trialkyl phosphates.
[0204] A trialkyl phosphate is often useful to adjust the specific
gravity of the formulation, but it is desirable that the specific
trialkyl phosphate be a liquid at low temperatures. Consequently, a
mixed ester containing at least one partially alkylated with a C3
to C4 alkyl group is very desirable, for example, 4-isopropylphenyl
diphenyl phosphate or 3-butylphenyl diphenyl phosphate. Even more
desirable is a triaryl phosphate produced by partially alkylating
phenol with butylene or propylene to form a mixed phenol which is
then reacted with phosphorus oxychloride as taught in U.S. Pat. No.
3,576,923.
[0205] Any mixed triaryl phosphate (TAP) esters may be used as
cresyl diphenyl phosphate, tricresyl phosphate, mixed xylyl cresyl
phosphates, lower alkylphenyl/phenyl phosphates, such as mixed
isopropylphenyl/phenyl phosphates, t-butylphenyl phenyl phosphates.
These esters are used extensively as plasticizers, functional
fluids, gasoline additives, flame-retardant additives and the
like.
Extreme Pressure Agent(s).
[0206] In other embodiments, the lubricating composition comprises
at least one extreme pressure agent. Any extreme pressure agent
that is known or that becomes know may be utilized in the
lubricating composition of the present disclosure. In certain
embodiments, the extreme pressure agent includes at least two
(e.g., 2, 3, 4, or more) extreme pressure agents.
[0207] The extreme pressure agents can be at least one sulfur-based
extreme pressure agents, such as sulfides, sulfoxides, sulfones,
thiophosphinates, thiocarbonates, sulfurized fats and oils,
sulfurized olefins, the like, or combinations thereof; at least one
phosphorus-based extreme pressure agents, such as phosphoric acid
esters (e.g., tricresyl phosphate (TCP) and the like), phosphorous
acid esters, phosphoric acid ester amine salts, phosphorous acid
ester amine salts, the like, or combinations thereof; halogen-based
extreme pressure agents, such as chlorinated hydrocarbons, the
like, or combinations thereof; organometallic extreme pressure
agents, such as thiophosphoric acid salts thiocarbamic acid salts,
or combinations thereof; and the like.
[0208] The phosphoric acid ester, thiophosphoric acid ester, and
amine salts thereof functions to enhance the lubricating
performances, and can be selected from known compounds
conventionally employed as extreme pressure agents. For example,
phosphoric acid esters, a thiophosphoric acid ester, or an amine
salt thereof which has an alkyl group, an alkenyl group, an
alkylaryl group, or an aralkyl group, any of which contains
approximately 3 to 30 carbon atoms, may be employed.
[0209] Examples of the phosphoric acid esters include aliphatic
phosphoric acid esters such as triisopropyl phosphate, tributyl
phosphate, ethyl dibutyl phosphate, trihexyl phosphate,
tri-2-ethylhexyl phosphate, trilauryl phosphate, tristearyl
phosphate, and trioleyl phosphate; and aromatic phosphoric acid
esters such as benzyl phenyl phosphate, allyl diphenyl phosphate,
triphenyl phosphate, tricresyl phosphate, ethyl diphenyl phosphate,
cresyl diphenyl phosphate, dicresyl phenyl phosphate, ethylphenyl
diphenyl phosphate, diethylphenyl phenyl phosphate, propylphenyl
diphenyl phosphate, dipropylphenyl phenyl phosphate, triethylphenyl
phosphate, tripropylphenyl phosphate, butylphenyl diphenyl
phosphate, dibutylphenyl phenyl phosphate, and tributylphenyl
phosphate. In an embodiment, the phosphoric acid ester is a
trialkylphenyl phosphate.
[0210] Examples of the thiophosphoric acid esters include aliphatic
thiophosphoric acid esters such as triisopropyl thiophosphate,
tributyl thiophosphate, ethyl dibutyl thiophosphate, trihexyl
thiophosphate, tri-2-ethylhexyl thiophosphate, trilauryl
thiophosphate, tristearyl thiophosphate, and trioleyl
thiophosphate; and aromatic thiophosphoric acid esters such as
benzyl phenyl thiophosphate, allyl diphenyl thiophosphate,
triphenyl thiophosphate, tricresyl thiophosphate, ethyl diphenyl
thiophosphate, cresyl diphenyl thiophosphate, dicresyl phenyl
thiophosphate, ethylphenyl diphenyl thiophosphate, diethylphenyl
phenyl thiophosphate, propylphenyl diphenyl thiophosphate,
dipropylphenyl phenyl thiophosphate, triethylphenyl thiophosphate,
tripropylphenyl thiophosphate, butylphenyl diphenyl thiophosphate,
dibutylphenyl phenyl thiophosphate, and tributylphenyl
thiophosphate. In an embodiment, the thiophosphoric acid ester is a
trialkylphenyl thiophosphate.
[0211] Also employable are amine salts of the above-mentioned
phosphates and thiophosphates. Amine salts of acidic alkyl or aryl
esters of the phosphoric acid and thiophosphoric acid are also
employable. In an embodiment, the amine salt is an amine salt of
trialkylphenyl phosphate or an amine salt of alkyl phosphate.
[0212] One or any combination of the compounds selected from the
group consisting of a phosphoric acid ester, a thiophosphoric acid
ester, and an amine salt thereof may be used.
[0213] The phosphorus acid ester and/or its amine salt function to
enhance the lubricating performance of the composition, and can be
selected from known compounds conventionally employed as extreme
pressure agents. For example, the extreme pressure agent can be a
phosphorus acid ester or an amine salt thereof, which has an alkyl
group, an alkenyl group, an alkylaryl group, or an aralkyl group,
any of which contains approximately 3 to 30 carbon atoms.
[0214] Examples of phosphorus acid esters that may be used includes
aliphatic phosphorus acid esters, such as triisopropyl phosphite,
tributyl phosphite, ethyl dibutyl phosphite, trihexyl phosphite,
tri-2-ethylhexylphosphite, trilauryl phosphite, tristearyl
phosphite, and trioleyl phosphite; and aromatic phosphorus acid
esters such as benzyl phenyl phosphite, allyl diphenylphosphite,
triphenyl phosphite, tricresyl phosphite, ethyl diphenyl phosphite,
tributyl phosphite, ethyl dibutyl phosphite, cresyl diphenyl
phosphite, dicresyl phenyl phosphite, ethylphenyl diphenyl
phosphite, diethylphenyl phenyl phosphite, propylphenyl diphenyl
phosphite, dipropylphenyl phenyl phosphite, triethylphenyl
phosphite, tripropylphenyl phosphite, butylphenyl diphenyl
phosphite, dibutylphenyl phenyl phosphite, and tributylphenyl
phosphite. Also favorably employed are dilauryl phosphite, dioleyl
phosphite, dialkyl phosphites, and diphenyl phosphite. In certain
embodiments, the phosphorus acid ester is a dialkyl phosphite or a
trialkyl phosphite.
[0215] The phosphate salt may be derived from a polyamine, such as
alkoxylated diamines, fatty polyamine diamines, alkylenepolyamines,
hydroxy containing polyamines, condensed polyamines arylpolyamines,
and heterocyclic polyamines. Examples of these amines include
Ethoduomeen T/13 and T/20, which are ethylene oxide condensation
products of N-tallowtrimethylenediamine containing 3 and 10 moles
of ethylene oxide per mole of diamine, respectively.
[0216] In another embodiment, the polyamine is a fatty diamine. The
fatty diamine may include mono- or dialkyl, symmetrical or
asymmetrical ethylene diamines, propane diamines (1,2 or 1,3), and
polyamine analogs of the above. Suitable commercial fatty
polyamines are Duomeen C (N-coco-1,3-diaminopropane), Duomeen S
(N-soya-1,3-diaminopropane), Duomeen T
(N-tallow-1,3-diaminopropane), and Duomeen O
(N-oleyl-1,3-diaminopropane). "Duomeens" are commercially available
from Armak Chemical Co., Chicago, Ill.
[0217] Such alkylenepolyamines include methylenepolyamines,
ethylenepolyamines, butylenepolyamines, propylenepolyamines,
pentylenepolyamines, etc. The higher homologs and related
heterocyclic amines, such as piperazines and N-amino
alkyl-substituted piperazines, are also included. Specific examples
of such polyamines are ethylenediamine, triethylenetetramine,
tris-(2-aminoethyl)amine, propylenediamine, trimethylenediamine,
tripropylenetetramine, tetraethylenepentamine,
hexaethyleneheptamine, pentaethylenehexamine, etc. Higher homologs
obtained by condensing two or more of the above-noted
alkyleneamines are similarly useful as are mixtures of two or more
of the aforedescribed polyamines.
[0218] In one embodiment the polyamine is an ethylenepolyamine.
Such polyamines are described in detail under the heading Ethylene
Amines in Kirk Othmer's "Encyclopedia of Chemical Technology", 2nd
Edition, Vol. 7, pages 22-37, Interscience Publishers, New York
(1965). Ethylenepolyamines can be a complex mixture of
polyalkylenepolyamines, including cyclic condensation products.
[0219] Other useful types of polyamine mixtures are those resulting
from stripping of the above-described polyamine mixtures to leave,
as residue, what is often termed "polyamine bottoms". The
alkylenepolyamine bottoms can be characterized as having less than
2%, usually less than 1% (by weight) material boiling below about
200.degree. C. An exemplary sample of such ethylene polyamine
bottoms obtained from the Dow Chemical Company of Freeport, Tex.
designated "E-100". These alkylenepolyamine bottoms include cyclic
condensation products, such as piperazine, and higher analogs of
diethylenetriamine, triethylenetetramine and the like. These
alkylenepolyamine bottoms can be reacted solely with the acylating
agent or they can be used with other amines, polyamines, or
mixtures thereof. Another useful polyamine is a condensation
reaction between at least one hydroxy compound with at least one
polyamine reactant containing at least one primary or secondary
amino group. In an embodiment, the hydroxy compounds are alcohols
and amines. The polyhydric alcohols are described below. In one
embodiment, the hydroxy compounds are polyhydric amines. Polyhydric
amines include any of the above-described monoamines reacted with
an alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene
oxide, etc.) having from two to about 20 carbon atoms, or from two
to about four. Examples of polyhydric amines include
tri-(hydroxypropyl)amine, tris-(hydroxymethyl)amino methane,
2-amino-2-methyl-1,3-propanediol,
N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, and
N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine. IN an
embodiment, the polyhydric amin is tris(hydroxymethyl)aminomethane
(THAM).
[0220] Polyamines which react with the polyhydric alcohol or amine
to form the condensation products or condensed amines, are
described above. In an embodiment, the polyamine include at least
one of triethylenetetramine (TETA), tetraethylenepentamine (TEPA),
pentaethylenehexamine (PEHA), and mixtures of polyamines, such as
the above-described "amine bottoms".
[0221] In some embodiments, the extreme pressure additive or
additives includes sulphur-based extreme pressure additives, such
as dialkyl sulphides, dibenzyl sulphide, dialkyl polysulphides,
dibenzyl disulphide, alkyl mercaptans, dibenzothiophene,
2,2'-dithiobis(benzothiazole), or combinations thereof
phosphorus-based extreme pressure additives, such as trialkyl
phosphates, triaryl phosphates, trialkyl phosphonates, trialkyl
phosphites, triaryl phosphites, dialkylhydrozine phosphites, or
combinations thereof and/or phosphorus- and sulphur-based extreme
pressure additives, such as dialkylthiophosphoric acid, trialkyl
thiophosphate esters, acidic thiophosphate esters, trialkyl
trithiophosphates, or combinations thereof. Extreme pressure
additives can be used individually or in the form of mixtures,
conveniently in an amount within the range from zero to about 2% by
weight of the lubricating composition.
Dispersant(s).
[0222] In other embodiments, the lubricating composition comprises
at least one dispersant. During machine operation, oil-insoluble
oxidation byproducts are produced. The dispersant may be added to
help keep these byproducts in solution, thus diminishing their
deposition on metal surfaces. Any dispersant that is known or that
becomes know may be utilized in the lubricating composition of the
present disclosure. In certain embodiments, the dispersant includes
at least two (e.g., 2, 3, 4, or more) dispersants.
[0223] In some embodiments, the dispersants is ashless or
ash-forming in nature. In an embodiment, the dispersant is an
ashless. So called ashless are organic materials that form
substantially no ash upon combustion. For example,
non-metal-containing or borated metal-free dispersants are
considered ashless. In contrast, metal-containing detergents form
ash upon combustion.
[0224] Suitable dispersants may contain a polar group attached to a
relatively high molecular weight hydrocarbon chain (e.g., about 50
to about 400 carbon atoms). In certain embodiments, the polar group
contains at least one element of nitrogen, oxygen, or
phosphorus.
[0225] A particularly useful class of dispersants are the
(poly)alkenylsuccinic derivatives, which may be produced by the
reaction of a long chain hydrocarbyl substituted succinic compound,
e.g. a hydrocarbyl substituted succinic anhydride, with a
polyhydroxy or polyamino compound. The long chain hydrocarbyl group
constituting the oleophilic portion of the molecule, which confers
solubility in the oil, is normally a polyisobutylene group. Many
examples of this type of dispersant are well known commercially and
in the literature. Exemplary U.S. patents describing such
dispersants are U.S. Pat. Nos. 3,172,892; 3,2145,707; 3,219,666;
3,316,177; 3,341,542; 3,444,170; 3,454,607; 3,541,012; 3,630,904;
3,632,511; 3,787,374 and 4,234,435. Other types of dispersant are
described in U.S. Pat. Nos. 3,036,003; 3,200,107; 3,254,025;
3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,413,347; 3,697,574;
3,725,277; 3,725,480; 3,726,882; 4,454,059; 3,329,658; 3,449,250;
3,519,565; 3,666,730; 3,687,849; 3,702,300; 4,100,082; 5,705,458. A
further description of dispersants may be found, for example, in
European Patent Application No. 471 071, to which reference is made
for this purpose.
[0226] Hydrocarbyl-substituted succinic acid and
hydrocarbyl-substituted succinic anhydride derivatives are useful
dispersants. In particular, succinimide, succinate esters, or
succinate ester amides prepared by the reaction of a
hydrocarbon-substituted succinic acid compound (e.g., a
hydrocarbon-substituted succinic acid compound having at least 50
carbon atoms in the hydrocarbon substituent) with at least one
equivalent of an alkylene amine are particularly useful.
[0227] Succinimides are formed by the condensation reaction between
hydrocarbyl substituted succinic anhydrides and amines. Molar
ratios can vary depending on the polyamine. For example, the molar
ratio of hydrocarbyl substituted succinic anhydride to TEPA can
vary from about 1:1 to about 5:1. Representative examples are shown
in U.S. Pat. Nos. 3,087,936; 3,172,892; 3,219,666; 3,272,746;
3,322,670; and 3,652,616, 3,948,800; and Canada Patent No.
1,094,044.
[0228] Succinate esters may be formed by the condensation reaction
between hydrocarbyl substituted succinic anhydrides and alcohols or
polyols. Molar ratios can vary depending on the alcohol or polyol
used. For example, the condensation product of a hydrocarbyl
substituted succinic anhydride and pentaerythritol is a useful
dispersant.
[0229] Succinate ester amides may be formed by condensation
reaction between hydrocarbyl substituted succinic anhydrides and
alkanol amines. For example, suitable alkanol amines include
ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines
and polyalkenylpolyamines, such as polyethylene polyamines. One
example is propoxylated hexamethylenediamine. Representative
examples are shown in U.S. Pat. No. 4,426,305.
[0230] The molecular weight of the hydrocarbyl substituted succinic
anhydrides used in the preceding paragraphs can range between about
800 and about 2,500 or more. The above products can be post-reacted
with various reagents such as sulfur, oxygen, formaldehyde,
carboxylic acids, such as oleic acid. The above products can also
be post reacted with boron compounds, such as boric acid, borate
esters or highly borated dispersants, to form borated dispersants,
which may have from about 0.1 to about 5 moles of boron per mole of
dispersant reaction product.
[0231] Mannich base dispersants are made from the reaction of
alkylphenols, formaldehyde, and amines. See U.S. Pat. No.
4,767,551, which is incorporated herein by reference. Process aids
and catalysts, such as oleic acid and sulfonic acids, can also be
part of the reaction mixture. Molecular weights of the alkylphenols
may range from about 800 to about 2,500. Representative examples
are shown in U.S. Pat. Nos. 3,697,574; 3,703,536; 3,704,308;
3,751,365; 3,756,953; 3,798,165; and 3,803,039.
[0232] High molecular weight aliphatic acid modified Mannich
condensation products useful in this disclosure can be prepared
from high molecular weight alkyl-substituted hydroxyaromatics or
HNR.sub.2 group-containing reactants, wherein each R is
independently selected from hydrogen, C1-C18 alkyl, aryl, alkenyl,
alkaryl group.
[0233] Hydrocarbyl substituted amine ashless dispersant additives
are well known to one skilled in the art; see, for example, U.S.
Pat. Nos. 3,275,554; 3,438,757; 3,565,804; 3,755,433, 3,822,209,
and 5,084,197.
[0234] In certain embodiments, the dispersants include borated
and/or non-borated succinimides, including those derivatives from
mono-succinimides, bis-succinimides, and/or mixtures of mono- and
bis-succinimides, wherein the hydrocarbyl succinimide is derived
from a hydrocarbylene group such as polyisobutylene having a Mn of
from about 500 to about 5000, or from about 1000 to about 3000, or
about 1000 to about 2000, or a mixture of such hydrocarbylene
groups, often with high terminal vinylic groups. Other dispersants
include succinic acid-esters and amides,
alkylphenol-polyamine-coupled Mannich adducts, their capped
derivatives, and other related components.
[0235] Polymethacrylate or polyacrylate derivatives are another
class of dispersants. These dispersants may be prepared by reacting
a nitrogen containing monomer and a methacrylic or acrylic acid
esters containing about 5 to about 25 carbon atoms in the ester
group. Representative examples are shown in U.S. Pat. Nos.
2,100,993, and 6,323,164. Polymethacrylate and polyacrylate
dispersants may be used as multifunctional viscosity modifiers. The
lower molecular weight versions can be used as lubricant
dispersants or fuel detergents.
[0236] Illustrative dispersants useful in this disclosure include
those derived from polyalkenyl-substituted mono- or dicarboxylic
acid, anhydride or ester, wherein the polyalkenyl moiety has an
average molecular weight of at least about 900 and from greater
than 1.3 to 1.7 (e.g. from greater than 1.3 to 1.6 or from greater
than 1.3 to 1.5) functional groups (mono- or dicarboxylic acid
producing moieties) per polyalkenyl moiety (a medium functionality
dispersant). Functionality (F) can be determined according to the
following formula:
F=(SAP.times.Mn)/((112,200.times.A.I.)-(SAP.times.98)),
wherein: [0237] SAP is the saponification number (i.e., the number
of milligrams of KOH consumed in the complete neutralization of the
acid groups in one gram of the succinic-containing reaction
product, as determined according to ASTM D94); [0238] Mn is the
number average molecular weight of the starting olefin polymer; and
[0239] A.I. is the percent active ingredient of the
succinic-containing reaction product (the remainder being unreacted
olefin polymer, succinic anhydride and diluent).
[0240] The polyalkenyl moiety of the dispersant may have a number
average molecular weight of at least about 900 or suitably at least
about 1500, such as between about 1800 and about 3000 (e.g. between
about 2000 and about 2800, from about 2100 to about 2500, or from
about 2200 to about 2400). The molecular weight of a dispersant is
generally expressed in terms of the molecular weight of the
polyalkenyl moiety. This is because the precise molecular weight
range of the dispersant depends on numerous parameters including
the type of polymer used to derive the dispersant, the number of
functional groups, and the type of nucleophilic group employed.
[0241] Polymer molecular weight, specifically Mn, can be determined
by various known techniques. One convenient method is gel
permeation chromatography (GPC), which additionally provides
molecular weight distribution information (see W. W. Yau, J. J.
Kirkland and D. D. Bly, "Modern Size Exclusion Liquid
Chromatography", John Wiley and Sons, New York, 1979). Another
useful method for determining molecular weight, particularly for
lower molecular weight polymers, is vapor pressure osmometry (e.g.,
ASTM D3592).
[0242] In an embodiment, the polyalkenyl moiety in a dispersant has
a narrow molecular weight distribution (MWD), also referred to as
polydispersity, as determined by the ratio of weight average
molecular weight (Mw) to number average molecular weight (Mn).
Polymers having a Mw/Mn of less than 2.2 (e.g. less than 2.0) are
most desirable. Suitable polymers have a polydispersity of from
about 1.5 to 2.1 (e.g. from about 1.6 to about 1.8).
[0243] Suitable polyalkenes employed in the formation of the
dispersants include homopolymers, interpolymers or lower molecular
weight hydrocarbons. One family of such polymers comprise polymers
of ethylene and/or at least one C3 to C26 alpha-olefin having the
formula:
H.sub.2C=CHR.sup.6,
wherein R.sup.6 is a straight or branched chain alkyl radical
comprising 1 to 26 carbon atoms and wherein the polymer contains
carbon-to-carbon unsaturation, and a high degree of terminal
ethenylidene unsaturation. In an embodiment, such polymers comprise
interpolymers of ethylene and at least one alpha-olefin of the
above formula, wherein R.sup.6 is alkyl of from 1 to 18 carbon
atoms (e.g. from 1 to 8 carbon atoms or from 1 to 2 carbon
atoms).
[0244] Another useful class of polymers is polymers prepared by
cationic polymerization of monomers such as isobutene and styrene.
For example, the polymer(s) can be polyisobutenes obtained by
polymerization of a C4 refinery stream having a butene content of
35 to 75% by wt., and an isobutene content of 30 to 60% by wt.
Petroleum feestreams, such as Raffinate II, can be a source of
monomer for making poly-n-butenes. These feedstocks are disclosed
in the art such as in U.S. Pat. No. 4,952,739. Certain embodiments
utilize polyisobutylene prepared from a pure isobutylene stream or
a Raffinate I stream to prepare reactive isobutylene polymers with
terminal vinylidene olefins. Polyisobutene polymers that may be
employed may be based on a polymer chain of from about 1500 to
about 3000.
[0245] In yet further embodiments, the dispersant(s) are
non-polymeric (e.g., mono- or bis-succinimides). Such dispersants
can be prepared by conventional processes, such as those disclosed
in U.S. Patent Application Publication No. 2008/0020950, the
disclosure of which is incorporated herein by reference.
[0246] The dispersant(s) can be borated by conventional means, as
generally disclosed in U.S. Pat. Nos. 3,087,936, 3,254,025 and
5,430,105.
[0247] Dispersants may be used in an amount of zero to about 10
weight percent or about 0.01 to about 8 weight percent (e.g. about
0.1 to about 5 weight percent or about 0.5 to about 3 weight
percent). Or such dispersants may be used in an amount of zero to
about 8 weight percent (e.g. about 0.01 to about 5 weight percent
or about 0.1 to about 3 weight percent). On an active ingredient
basis, such additives may be used in an amount of zero to about 10
weight percent (e.g. about 0.3 to about 3 weight percent). The
hydrocarbon portion of the dispersant atoms can range from about
C60 to about C1000, or from about C70 to about C300, or from about
C70 to about C200. These dispersants may contain both neutral and
basic nitrogen, and mixtures thereof. Dispersants can be end-capped
by borates and/or cyclic carbonates. Nitrogen content in the
finished oil can vary from about zero to about 2000 ppm by weight
(e.g. from about 100 ppm by weight to about 1200 ppm by weight).
Basic nitrogen can vary from about zero to about 1000 ppm by weight
(e.g. from about 100 ppm by weight to about 600 ppm by weight).
[0248] Dispersants as described herein are beneficially useful with
the compositions of the present disclosure. Further, in one
embodiment, preparation of the compositions of the present
disclosure using one or more (e.g. 1, 2, 3, 4, or more) dispersants
is achieved by combining ingredients of the present disclosure,
plus optional base stocks and lubricant additives, in a mixture at
a temperature above the melting point of such ingredients,
particularly that of the one or more M-carboxylates (M=H, metal,
two or more metals, mixtures thereof).
[0249] As used herein, the dispersant concentrations are given on
an "as delivered" basis. The active dispersant may be delivered
with a process oil. The "as delivered" dispersant may contain from
about 20 weight percent to about 80 weight percent, or from about
40 weight percent to about 60 weight percent, of active dispersant
in the "as delivered" dispersant product.
Detergent(s).
[0250] In other embodiments, the lubricating composition comprises
at least one detergent. The detergent may be added to protect
lubricated metal surfaces against chemical attack by water or other
contaminants. Any detergent that is known or that becomes know may
be utilized in the lubricating composition of the present
disclosure. In certain embodiments, the detergent includes at least
two (e.g., 2, 3, 4, or more) detergents.
[0251] Illustrative detergents useful in this disclosure include,
for example, alkali metal detergents, alkaline earth metal
detergents, or mixtures of one or more alkali metal detergents and
one or more alkaline earth metal detergents. In an embodiment, the
detergent is an anionic material that contains a long chain
hydrophobic portion of the molecule and a smaller anionic or
oleophobic hydrophilic portion of the molecule. The anionic portion
of the detergent may be derived from an organic acid, such as a
sulfur-containing acid, carboxylic acid (e.g., salicylic acid),
phosphorus-containing acid, phenol, or mixtures thereof. The
counterion may be an alkaline earth or alkali metal. The detergent
can be overbased as described herein.
[0252] In other embodiments, the detergent is a metal salt of an
organic or inorganic acid, a metal salt of a phenol, or mixtures
thereof. The metal may be selected from an alkali metal, an
alkaline earth metal, and mixtures thereof. The organic or
inorganic acid may be selected from an aliphatic organic or
inorganic acid, a cycloaliphatic organic or inorganic acid, an
aromatic organic or inorganic acid, and mixtures thereof.
[0253] In certain embodiments, the metal is selected from an alkali
metal, an alkaline earth metal, and mixtures thereof. In another
embodiment, the metal is selected from calcium (Ca), magnesium
(Mg), and mixtures thereof.
[0254] The organic acid or inorganic acid may be selected from a
sulfur-containing acid, a carboxylic acid, a phosphorus-containing
acid, and mixtures thereof.
[0255] In a particular embodiment, the metal salt of an organic or
inorganic acid or the metal salt of a phenol comprises at least one
of calcium phenate, calcium sulfonate, calcium salicylate,
magnesium phenate, magnesium sulfonate, magnesium salicylate, an
overbased detergent, or mixtures thereof.
[0256] Salts that contain a substantially stochiometric amount of
the metal are described as neutral salts and have a total base
number (TBN, as measured by ASTM D2896) of from 0 to 80. Many
compositions are overbased, containing large amounts of a metal
base that is achieved by reacting an excess of a metal compound (a
metal hydroxide or oxide, for example) with an acidic gas (such as
carbon dioxide). Useful detergents can be neutral, mildly
overbased, or highly overbased. These detergents can be used in
mixtures of neutral, overbased, highly overbased calcium
salicylate, sulfonates, phenates and/or magnesium salicylate,
sulfonates, phenates. The TBN ranges can vary from low, medium to
high TBN products, including as low as 0 to as high as 600. In an
embodiment, the TBN delivered by the detergent is between 1 and 20
(e.g. between 1 and 12). Mixtures of low, medium, high TBN can be
used, along with mixtures of calcium and magnesium metal based
detergents, and including sulfonates, phenates, salicylates, and
carboxylates. A detergent mixture with a metal ratio of 1, in
conjunction with a detergent with a metal ratio of 2, and as high
as a detergent with a metal ratio of 5, can be used. Borated
detergents can also be used.
[0257] Alkaline earth phenates are another useful class of
detergent. These detergents can be made by reacting alkaline earth
metal hydroxide or oxide (CaO, Ca(OH)2, BaO, Ba(OH)2, MgO, Mg(OH)2,
for example) with an alkyl phenol or sulfurized alkylphenol. Useful
alkyl groups include straight chain or branched C1-C30 alkyl groups
(e.g. C4-C20 alkyl groups) or mixtures thereof. Examples of
suitable phenols include isobutylphenol, 2-ethylhexylphenol,
nonylphenol, dodecyl phenol, and the like. It should be noted that
starting alkylphenols may contain more than one alkyl substituent
that are each independently straight chain or branched and can be
used from about 0.5 to about 6 weight percent. When a
non-sulfurized alkylphenol is used, the sulfurized product may be
obtained by methods well known in the art. These methods include
heating a mixture of alkylphenol and sulfurizing agent (including
elemental sulfur, sulfur halides, such as sulfur dichloride, and
the like) and then reacting the sulfurized phenol with an alkaline
earth metal base.
[0258] In some embodiments, the detergent is a metal salts of
carboxylic acids. These carboxylic acid detergents may be prepared
by reacting a basic metal compound with at least one carboxylic
acid and removing free water from the reaction product. These
compounds may be overbased to produce the desired TBN level.
Detergents made from salicylic acid are one class of detergents
derived from carboxylic acids. Useful salicylates include long
chain alkyl salicylates. One useful family of compositions is of
the formula:
##STR00004##
wherein: [0259] R is an alkyl group having about 1 to about 30
carbon atoms, n is an integer from 1 to 4, and [0260] M is an
alkaline earth metal.
[0261] In certain embodiments, the R group or groups are alkyl
chains of at least C11 (e.g. at least C13). R may be optionally
substituted with substituents that do not interfere with the
detergent's function. In an embodiment, the M is calcium,
magnesium, barium, or mixtures thereof. In a particular embodiment,
the M is calcium.
[0262] Hydrocarbyl-substituted salicylic acids may be prepared from
phenols by the Kolbe reaction (see U.S. Pat. No. 3,595,791). The
metal salts of the hydrocarbyl-substituted salicylic acids may be
prepared by double decomposition of a metal salt in a polar
solvent, such as water or alcohol.
[0263] Alkaline earth metal phosphates are also used as detergents
and are known in the art.
[0264] Detergents may be simple detergents or what is known as
hybrid or complex detergents. The latter detergents can provide the
properties of two detergents without the need to blend separate
materials. See U.S. Pat. No. 6,034,039.
[0265] In an embodiment, the detergent or detergents (e.g., 1, 2,
3, 4, or more detergents) includes calcium sulfonates, magnesium
sulfonates, calcium salicylates, magnesium salicylates, calcium
phenates, magnesium phenates, and other related components
(including borated detergents), or mixtures thereof. For example, a
mixture of detergents may include magnesium sulfonate and calcium
salicylate, magnesium sulfonate and calcium sulfonate, magnesium
sulfonate and calcium phenate, calcium phenate and calcium
salicylate, calcium phenate and calcium sulfonate, calcium phenate
and magnesium salicylate, or calcium phenate and magnesium phenate.
Overbased detergents may also be utilized in the lubricating
composition of the present disclosure.
[0266] Detergent concentration in the lubricating oils of this
disclosure can range from zero to about 6.0 weight percent (e.g.
zero to 5.0 weight percent or from about 0.01 weight percent to
about 3.0 weight percent) based on the total weight of the
lubricating oil.
[0267] As used herein, the detergent concentrations are given on an
"as delivered" basis. The active detergent may delivered with a
process oil. The "as delivered" detergent can contain from about 20
weight percent to about 100 weight percent, or from about 40 weight
percent to about 60 weight percent, of active detergent in the "as
delivered" detergent product.
Friction Modifier(s).
[0268] In other embodiments, the lubricating composition comprises
at least one (e.g., 1, 2, 3, 4, or more) friction modifier. A
friction modifier is any material or materials that can alter the
coefficient of friction of a surface lubricated by any lubricant or
fluid containing such material(s). Friction modifiers, also known
as friction reducers, or lubricity agents or oiliness agents, and
other such agents that change the ability of base oils, formulated
lubricant compositions, or functional fluids, to modify the
coefficient of friction of a lubricated surface may be effectively
used in combination with the base oils or lubricant compositions of
the present disclosure if desired. Friction modifiers that lower
the coefficient of friction are particularly advantageous in
combination with the base oils and lube compositions of this
disclosure. Any friction modifier that is known or that becomes
know may be utilized in the lubricating composition of the present
disclosure.
[0269] Friction modifiers may include, for example, organometallic
compounds or materials, or mixtures thereof. Illustrative
organometallic friction modifiers useful in the lubricating turbine
oil formulations of this disclosure include, for example,
molybdenum amine, molybdenum diamine, an organotungstenate, a
molybdenum dithiocarbamate, molybdenum dithiophosphates, molybdenum
amine complexes, molybdenum carboxylates, and the like, and
mixtures thereof. In an embodiment, tungsten-based compounds are
utilized.
[0270] Other illustrative friction modifiers useful in the
lubricating formulations of the present disclosure include, for
example, alkoxylated fatty acid esters, alkanolamides, polyol fatty
acid esters, borated glycerol fatty acid esters, fatty alcohol
ethers, and mixtures thereof.
[0271] Illustrative alkoxylated fatty acid esters include, for
example, polyoxyethylene stearate, fatty acid polyglycol ester, and
the like. These can include polyoxypropylene stearate,
polyoxybutylene stearate, polyoxyethylene isosterate,
polyoxypropylene isostearate, polyoxyethylene palmitate, and the
like.
[0272] Illustrative alkanolamides include, for example, lauric acid
diethylalkanolamide, palmic acid diethylalkanolamide, and the like.
These can include oleic acid diethyalkanolamide, stearic acid
diethylalkanolamide, oleic acid diethylalkanolamide,
polyethoxylated hydrocarbylamides, polypropoxylated
hydrocarbylamides, and the like.
[0273] Illustrative polyol fatty acid esters include, for example,
glycerol mono-oleate, saturated mono-, di-, and tri-glyceride
esters, glycerol mono-stearate, and the like. These can include
polyol esters, hydroxyl-containing polyol esters, and the like.
[0274] Illustrative borated glycerol fatty acid esters include, for
example, borated glycerol mono-oleate, borated saturated mono-,
di-, and tri-glyceride esters, borated glycerol mono-sterate, and
the like. In addition to glycerol polyols, these can include
trimethylolpropane, pentaerythritol, sorbitan, and the like. These
esters can be polyol monocarboxylate esters, polyol dicarboxylate
esters, and on occasion polyoltricarboxylate esters. In certain
embodiments, the friction modifier is glycerol mono-oleates,
glycerol dioleates, glycerol trioleates, glycerol monostearates,
glycerol distearates, and glycerol tristearates and the
corresponding glycerol monopalmitates, glycerol dipalmitates,
glycerol tripalmitates, or the respective isostearates, linoleates,
and the like, or combinations thereof. In an embodiment, the
friction modifier is a glycerol esters or mixtures containing any
of these. Ethoxylated, propoxylated, butoxylated fatty acid esters
of polyols, especially using glycerol as underlying polyol can be
utilized.
[0275] Illustrative fatty alcohol ethers include, for example,
stearyl ether, myristyl ether, and the like. Alcohols, including
those that have carbon numbers from C3 to C50, can be ethoxylated,
propoxylated, or butoxylated to form the corresponding fatty alkyl
ethers. The underlying alcohol portion can be, e.g., stearyl,
myristyl, C11-C13 hydrocarbon, oleyl, isosteryl, and the like.
[0276] Other friction modifiers could be optionally included in
addition to the fatty phosphites and fatty imidazolines. A useful
list of such other friction modifier additives is included in U.S.
Pat. No. 4,792,410. U.S. Pat. No. 5,110,488 discloses metal salts
of fatty acids and especially zinc salts, useful as friction
modifiers. Fatty acids are also useful friction modifiers. A list
of other suitable friction modifiers includes at least one of: (i)
fatty phosphonates; (ii) fatty acid amides; (iii) fatty epoxides;
(iv) borated fatty epoxides; (v) fatty amines; (vi) glycerol
esters; (vii) borated glycerol esters; (viii) alkoxylated fatty
amines; (ix) borated alkoxylated fatty amines; (x) metal salts of
fatty acids; (xi) sulfurized olefins; (xii) condensation products
of carboxylic acids or equivalents and polyalkylene-polyamines;
(xiii) metal salts of alkyl salicylates; (xiv) amine salts of
alkylphosphoric acids; (xv) fatty esters; (xvi) condensation
products of carboxylic acids; or equivalents with polyols and
mixtures thereof.
[0277] Representatives of each of these types of friction modifiers
are known and are commercially available. For instance, (i)
includes components of the formulas:
(RO)2PHO,
(RO)(HO)PHO, and
P(OR)(OR)(OR),
wherein, in these structures, the each "R" is conventionally
referred to as an alkyl group, but may also be hydrogen. It is, of
course, possible that the alkyl group is actually alkenyl and thus
the terms "alkyl" and "alkylated," as used herein, will embrace
other than saturated alkyl groups within the component. The
component should have sufficient hydrocarbyl groups to render it
substantially oleophilic. In some embodiments, the hydrocarbyl
groups are substantially un-branched. Many suitable such components
are available commercially and may be synthesized as described in
U.S. Pat. No. 4,752,416. In some embodiments, the component
contains 8 to 24 carbon atoms in each of the R groups. In other
embodiments, the component may be a fatty phosphite containing 12
to 22 carbon atoms in each of the fatty radicals, or 16 to 20
carbon atoms. In one embodiment the fatty phosphite can be formed
from oleyl groups, thus having 18 carbon atoms in each fatty
radical.
[0278] The (iv) borated fatty epoxides are 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 having the formula:
##STR00005##
wherein each of R.sup.7, R.sup.8, R.sup.9 and R.sup.19 is
independently hydrogen or an aliphatic radical, or any two thereof
together with the epoxy carbon atom or atoms to which they are
attached, form a cyclic radical. In an embodiment, the fatty
epoxide contains at least 8 carbon atoms.
[0279] The borated fatty epoxides can be characterized by the
method for their preparation which involves the reaction of two
materials. Reagent A can 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.4O.sub.7). In an embodiment, Reagent A is boric acid,
such as orthoboric acid. Reagent B can be at least one fatty
epoxide having the above formula. In the formula, each of the R
groups is most often hydrogen or an aliphatic radical with at least
one being a hydrocarbyl or aliphatic radical containing at least 6
carbon atoms. The molar ratio of reagent A to reagent B may be
about 1:0.25 to about 1:4 (e.g. about 1:1 to about 1:3 or about
1:2). The borated fatty epoxides can be prepared by merely blending
the two reagents and heating them at temperature of about
80.degree. C. to about 250.degree. C., such as about 100.degree. C.
to about 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.
[0280] The (iii) non-borated fatty epoxides, corresponding to
Reagent B above, are also useful as friction modifiers.
[0281] Borated amines are generally known from U.S. Pat. No.
4,622,158. Borated amine friction modifiers (including (ix) borated
alkoxylated fatty amines) can be prepared by the reaction of a
boron compounds, as described above, with the corresponding amines.
The amine can be a simple fatty amine or hydroxy containing
tertiary amines. The borated amines can be prepared by adding the
boron reactant, as described above, to an amine reactant and
heating the resulting mixture at about 50.degree. C. to about
300.degree. C. (e.g. about 100.degree. C. to about 250.degree. C.
or about 130.degree. C. to about 180.degree. C.) with stirring. The
reaction is continued until by-product water ceases to evolve from
the reaction mixture indicating completion of the reaction.
[0282] Among the amines useful in preparing the borated amines are
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. O/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.
Dihydroxyethyl tallowamine (commercially sold as ENT-12.TM.) is
included in these types of amines.
[0283] The (viii) alkoxylated fatty amines, and (v) fatty amines
themselves (such as oleylamine and dihydroxyethyl tallowamine) may
be useful as friction modifiers in this disclosure. Such amines are
commercially available.
[0284] Both borated and unborated fatty acid esters of glycerol can
be used as friction modifiers. The (vii) borated fatty acid esters
of glycerol are prepared by borating a fatty acid ester of glycerol
with boric acid with removal of the water of reaction. In an
embodiment, there is sufficient boron present such that each boron
will react with from 1.5 to 2.5 hydroxyl groups present in the
reaction mixture. The reaction may be carried out at a temperature
in the range of about 60.degree. C. to about 135.degree. C., in the
absence or presence of any suitable organic solvent, such as
methanol, benzene, xylenes, toluene, or oil.
[0285] The (vi) fatty acid esters of glycerol themselves can be
prepared by a variety of methods well known in the art. Many of
these esters, such as glycerol monooleate and glycerol tallowate,
are manufactured on a commercial scale. In a particular embodiment,
the esters are oil-soluble and prepared from C8 to C22 fatty acids
or mixtures thereof, such as are found in natural products and as
are described in greater detail below. In an embodiment, fatty acid
monoesters of glycerol used, although, mixtures of mono- and
diesters may be used. For example, commercial glycerol monooleate
may contain a mixture of 45% to 55% by weight monoester and 55% to
45% diester.
[0286] Fatty acids can be used in preparing the above glycerol
esters; they can also be used in preparing their (x) metal salts,
(ii) amides, and (xii) imidazolines, any of which can also be used
as friction modifiers. In an embodiment, the fatty acids are those
containing 10 to 24 carbon atoms, such as those containing 12 to 18
carbon atoms. The acids can be branched or straight-chain,
saturated or unsaturated. In some embodiments, the acids are
straight-chain acids. In other embodiments, the acids are branched.
Suitable acids include 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, coconut oil and Neat's foot oil.
In certain embodiments, the acid is oleic acid. In other
embodiments, the metal salts include zinc and calcium salts.
Examples are overbased calcium salts and basic oleic acid-zinc salt
complexes, such as zinc oleate, which can be represented by the
formula Zn.sub.4Oleate.sub.6O.sub.1. In an embodiment, the amides
are those prepared by condensation with ammonia or with primary or
secondary amines such as ethylamine and diethanolamine. Fatty
imidazolines are the cyclic condensation product of an acid with a
diamine or polyamine, such as a polyethylenepolyamine. The
imidazolines may be represented by the structure:
##STR00006##
wherein: R is an alkyl group; and R' is hydrogen or a hydrocarbyl
group or a substituted hydrocarbyl group, including
--(CH.sub.2CH.sub.2NH).sub.n-- groups, wherein n is an integer from
1 to 4. In an embodiment, the friction modifier is the condensation
product of a C10 to C24 fatty acid with a polyalkylene polyamine,
and in particular, the product of isostearic acid with
tetraethylenepentamine.
[0287] The condensation products of carboxylic acids and
polyalkyleneamines (xiii) may be imidazolines or amides. They may
be derived from any of the carboxylic acids described above and any
of the polyamines described herein.
[0288] Sulfurized olefins (xi) are well known commercial materials
used as friction modifiers. A particularly sulfurized olefin
utilized herein is one which is prepared in accordance with the
detailed teachings of U.S. Pat. Nos. 4,957,651 and 4,959,168.
Described therein is a co-sulfurized mixture of 2 or more reactants
selected from the group consisting of (1) at least one fatty acid
ester of a polyhydric alcohol, (2) at least one fatty acid, (3) at
least one olefin, and (4) at least one fatty acid ester of a
monohydric alcohol. Reactant (3), the olefin component, comprises
at least one olefin. This olefin is may be an aliphatic olefin,
which usually will contain 4 to 40 carbon atoms, e.g. from 8 to 36
carbon atoms. For example, terminal olefins, or alpha-olefins,
including those having from 12 to 20 carbon atoms, may be utilized.
Mixtures of these olefins are commercially available, and such
mixtures are contemplated for use in this disclosure. The
co-sulfurized mixture of two or more of the reactants, is prepared
by reacting the mixture of appropriate reactants with a source of
sulfur. The mixture to be sulfurized can contain about 10 to about
90 parts of Reactant (1), or about 0.1 to about 15 parts by weight
of Reactant (2); or about 10 to about 90 parts (e.g. about 15 to
about 60 parts or about 25 to about 35 parts) by weight of Reactant
(3), or about 10 to about 90 parts by weight of reactant (4). The
mixture, in the present disclosure, includes Reactant (3) and at
least one other member of the group of reactants identified as
Reactants (1), (2) and (4). The sulfurization reaction may be
effected at an elevated temperature with agitation and optionally
in an inert atmosphere and in the presence of an inert solvent. The
sulfurizing agents useful in the process of the present disclosure
include elemental sulfur, which maybe hydrogen sulfide, sulfur
halide plus sodium sulfide, and a mixture of hydrogen sulfide and
sulfur or sulfur dioxide. For example, about 0.5 to about 3 moles
of sulfur are employed per mole of olefinic bonds. Sulfurized
olefins may also include sulfurized oils, such as vegetable oil,
lard oil, oleic acid and olefin mixtures.
[0289] Metal salts of alkyl salicylates (xiii) include calcium and
other salts of long chain (e.g. C12 to C16) alkyl-substituted
salicylic acids.
[0290] Amine salts of alkylphosphoric acids (xiv) include salts of
oleyl and other long chain esters of phosphoric acid, with amines
as described below. Useful amines in this regard are
tertiary-aliphatic primary amines, sold under the tradename
Primene.TM..
[0291] In some embodiments, the friction modifier is a fatty acid
or fatty oil, a metal salt of a fatty acid, a fatty amide, a
sulfurized fatty oil or fatty acid, an alkyl phosphate, an alkyl
phosphate amine salt; a condensation product of a carboxylic acid
and a polyamine, a borated fatty epoxide, a fatty imidazoline, or
combinations thereof.
[0292] In other embodiments, the friction modifier may be the
condensation product of isostearic acid and tetraethylene
pentamine, the condensation product of isostearic acid and
1-[tris(hydroxymethyl)]methylamine, borated polytetradecyloxirane,
zinc oleate, hydroxylethyl-2-heptadecenyl imidazoline, dioleyl
hydrogen phosphate, C14-C18 alkyl phosphate or the amine salt
thereof, sulfurized vegetable oil, sulfurized lard oil, sulfurized
oleic acid, sulfurized olefins, oleyl amide, glycerol monooleate,
soybean oil, or mixtures thereof.
[0293] In still other embodiments, the friction modifier may be
glycerol monooleate, oleylamide, the reaction product of isostearic
acid and 2-amino-2-hydroxymethyl-1,3-propanediol, sorbitan
monooleate, 9-octadecenoic acid, isostearyl amide, isostearyl
monooleate or combinations thereof.
[0294] Although their presence is not required to obtain the
benefit of the present disclosure, friction modifiers may be
present in an amount from zero to about 2 wt % (e.g., about 0.01 wt
% to about 1.5 wt %) of the lubricating composition. These ranges
may apply to the amounts of individual friction modifier present in
the composition or to the total friction modifier component in the
compositions, which may include a mixture of two or more friction
modifiers.
[0295] Many friction modifiers tend to also act as emulsifiers.
This is often due to the fact that friction modifiers often have
non-polar fatty tails and polar head groups.
[0296] The lubricating composition of the present disclosure
exhibit desired properties, e.g., wear control, in the presence or
absence of a friction modifier.
[0297] Although their presence is not required to obtain the
benefit of this disclosure, the friction modifier or friction
modifiers may be present in an amount of about 0.01 weight percent
to about 5 weight percent (e.g. about 0.1 weight percent to about
2.5 weight percent, or about 0.1 weight percent to about 1.5 weight
percent, or about 0.1 weight percent to about 1 weight percent).
Concentrations of molybdenum-containing materials are often
described in terms of Mo metal concentration. Advantageous
concentrations of Mo may range from about 25 ppm to about 700 ppm
or more (e.g. about 50 to about 200 ppm). Friction modifiers of all
types may be used alone or in mixtures with the materials of this
disclosure. Often mixtures of two or more friction modifiers, or
mixtures of friction modifier(s) with alternate surface active
material(s), are also desirable.
Molybdenum-Containing Compounds (Friction Reducers).
[0298] Illustrative molybdenum-containing friction reducers useful
in the disclosure include, for example, an oil-soluble decomposable
organo molybdenum compound, such as Molyvan.TM. 855 which is an oil
soluble secondary diarylamine defined as substantially free of
active phosphorus and active sulfur. The Molyvan.TM. 855 is
described in Vanderbilt's Material Data and Safety Sheet as a
organomolybdenum compound having a density of 1.04 and viscosity at
100.degree. C. of 47.12 cSt. The organo molybdenum compounds may be
useful because of their superior solubility and effectiveness.
[0299] Another illustrative molybdenum-containing compound is
Molyvan.TM. L, which is sulfonated oxymolybdenum
dialkyldithiophosphate described in U.S. Pat. No. 5,055,174 hereby
incorporated by reference.
[0300] Molyvan.TM. A made by R. T. Vanderbilt Company, Inc., New
York, N.Y., USA, is also an illustrative molybdenum-containing
compound, which contains about 28.8 wt. % Mo, 31.6 wt. % C, 5.4 wt.
% H., and 25.9 wt. % S. Also useful are Molyvan.TM. 855,
Molyvan.TM. 822, Molyvan.TM. 856, and Molyvan.TM. 807.
[0301] Also useful is Sakura Lube.TM. 500, which is more soluble Mo
dithiocarbamate containing lubricant additive obtained from Asahi
Denki Corporation and comprised of about 20.2 wt. % Mo, 43.8 wt. %
C, 7.4 wt. % H, and 22.4 wt. % S. Sakura Lube.TM. 300, a low sulfur
molybdenum dithiophosphate having a molybdenum to sulfur ratio of
1:1.07, is a molybdenum-containing compound useful in this
disclosure.
[0302] Also useful is Molyvan.TM. 807, a mixture of about 50 wt. %
molybdenum ditridecyldithyocarbonate, and about 50 wt. % of an
aromatic oil having a specific gravity of about 38.4 SUS and
containing about 4.6 wt. % molybdenum, also manufactured by R. T.
Vanderbilt and marketed as an antioxidant and antiwear
additive.
[0303] Other sources are molybdenum Mo(Co).sub.6, and molybdenum
octoate, MoO(C.sub.7H.sub.15CO.sub.2).sub.2 containing about 8 wt-%
Mo marketed by Aldrich Chemical Company, Milwaukee, Wis. and
molybdenum naphthenethioctoate marketed by Shephard Chemical
Company, Cincinnati, Ohio.
[0304] Inorganic molybdenum compounds, such as molybdenum sulfide
and molybdenum oxide, are substantially less preferred than the
organic compounds as described in Molyvan.TM. 855, Molyvan.TM. 822,
Molyvan.TM. 856, and Molyvan.TM. 807.
[0305] Illustrative molybdenum-containing compounds useful in this
disclosure are disclosed, for example, in U.S. Patent Application
Publication No. 2003/0119682, which is incorporated herein by
reference.
[0306] Organo molybdenum-nitrogen complexes may also be included in
the formulations of the present disclosure. The term "organo
molybdenum nitrogen complexes" embraces the organo molybdenum
nitrogen complexes described in U.S. Pat. No. 4,889,647. The
complexes are reaction products of a fatty oil, dithanolamine and a
molybdenum source. Specific chemical structures have not been
assigned to the complexes. U.S. Pat. No. 4,889,647 reports an
infrared spectrum for an exemplary reaction product of that
disclosure; the spectrum identifies an ester carbonyl band at 1740
cm 1 and an amide carbonyl band at 1620 cm 1. The fatty oils are
glyceryl esters of higher fatty acids containing at least 12 carbon
atoms up to 22 carbon atoms or more. The molybdenum source is an
oxygen-containing compound such as ammonium molybdates, molybdenum
oxides and mixtures.
[0307] Other organo molybdenum complexes which can be used in the
present disclosure are tri nuclear molybdenum sulfur compounds
described in EP 1 040 115 and WO 99/31113, and the molybdenum
complexes described in U.S. Pat. No. 4,978,464.
[0308] Molybdenum-containing additives may be used in an amount of
from zero to about 5.0 percent by mass of the lubricating
composition. For example, the dosage may be up to about 3,000 ppm
by mass, such as from about about 100 ppm to about about 2,500 ppm
by mass, from about 300 to about 2,000 ppm by mass, or from about
300 to about 1,500 ppm by mass of molybdenum.
Borated Ester Compounds.
[0309] Illustrative boron-containing compounds useful in the
disclosure include, for example, a borate ester, a boric acid,
other boron compounds, such as a boron oxide. The boron compound is
hydrolytically stable and is utilized for improved antiwear, and
performs as a rust and corrosion inhibitor for copper bearings and
other metal engine components. The borated ester compound acts as
an inhibitor for corrosion of metal to prevent corrosion of either
ferrous or non-ferrous metals (e.g. copper, bronze, brass,
titanium, aluminum and the like) or both, present in concentrations
in which they are effective in inhibiting corrosion.
[0310] Patents describing techniques for making basic salts of
sulfonic, carboxylic acids and mixtures thereof include U.S. Pat.
Nos. 5,354,485; 2,501,731; 2,616,911; 2,777,874; 3,384,585;
3,320,162; 3,488,284; and 3,629,109. The disclosures of these
patents are incorporated herein by reference. Methods of preparing
borated overbased compositions are found in U.S. Pat. Nos.
4,744,920; 4,792,410; and PCT publication WO 88/03144. The
disclosures of these references are incorporated herein by
reference. The oil-soluble neutral or basic salts of alkali or
alkaline earth metals salts may also be reacted with a boron
compound.
[0311] An illustrative borate ester utilized in this disclosure is
manufactured by Exxon-Mobil USA under the product designation of
("MCP 1286") and MOBIL ADC700. Test data show the viscosity at
100.degree. C. using the D-445 method is 2.9 cSt; the viscosity at
40.degree. C. using the D-445 method is 11.9; the flash point using
the D-93 method is 146; the pour point using the D-97 method is
-69; and the percent boron as determined by the ICP method is 5.3%.
The borated ester (Vanlube.TM. 289), which is marketed as an
antiwear/antiscuff additive and friction reducer, is an exemplary
borate ester useful in the disclosure.
[0312] An illustrative borate ester useful in this disclosure is
the reaction product obtained by reacting about 1 mole fatty oil,
about 1.0 to 2.5 moles diethanolamine followed by subsequent
reaction with boric acid to yield about 0.1 to 3 percent boron by
mass. It is believed that the reaction products may include one or
both of the following two primary components, with the further
listed components being possible components when the reaction is
pushed toward full hydration:
##STR00007## [0313] where R.sub.1=H or C.sub.xH.sub.y where x=1 to
60, and y=3 to 121
##STR00008##
[0313] wherein Y represents a fatty oil residue. In an embodiment,
the fatty oils are glyceryl esters of higher fatty acids containing
at least 12 carbon atoms (e.g. 22 carbon atoms or more). Such
esters are commonly known as vegetable and animal oils. Vegetable
oils that may be used include oils derived from coconut, corn,
cottonseed, linseed, peanut, soybean and sunflower seed. Similarly,
animal fatty oils such as tallow may be used.
[0314] The source of boron is boric acid or materials that afford
boron and are capable of reacting with the intermediate reaction
product of fatty oil and diethanolamine to form a borate ester
composition.
[0315] While the above organoborate ester composition is
specifically discussed above, it should be understood that other
organoborate ester compositions should also function with similar
effect in the present disclosure, such as those set forth in U.S.
Patent Application Publication No. 2003/0119682, which is
incorporated herein by reference. In addition, dispersions of
borate salts, such as potassium borate, may also be useful.
[0316] Other illustrative organoborate compositions useful in this
disclosure are disclosed, for example, in U.S. Patent Application
Publication No. 2008/0261838, which is incorporated herein by
reference.
[0317] In addition, other illustrative oranoborate compositions
useful in this disclosure are disclosed, for example, U.S. Pat.
Nos. 4,478,732, 4,406,802, 4,568,472 on borated mixed hydroxyl
esters, alkoxylated amides, and amines; U.S. Pat. No. 4,298,486 on
borated hydroxyethyl imidazolines; U.S. Pat. No. 4,328,113 on
borated alkyl amines and alkyl diamines; U.S. Pat. No. 4,370,248 on
borated hydroxyl-containing esters, including GMO; U.S. Pat. No.
4,374,032 on borated hydroxyl-containing hydrocarbyl oxazolines;
U.S. Pat. No. 4,376,712 on borated sorbitan esters; U.S. Pat. No.
4,382,006 on borated ethoxylated amines; U.S. Pat. No. 4,389,322 on
ethoxylated amides and their borates; U.S. Pat. No. 4,472,289 on
hydrocarbyl vicinal diols and alcohols and ester mixtures and their
borates; U.S. Pat. No. 4,522,734 on borates of hydrolyzed
hydrocarbyl epoxides; U.S. Pat. No. 4,537,692 on etherdiamine
borates; U.S. Pat. No. 4,541,941 on mixtures containing vicinal
diols and hydroxyl substituted esters and their borates; U.S. Pat.
No. 4,594,171 on borated mixtures of various hydroxyl and/or
nitrogen containing borates; and U.S. Pat. No. 4,692,257 on various
borated alcohols/diols, all of which are incorporated herein by
reference.
[0318] Although their presence is not required to obtain the
benefit of this disclosure, boron-containing compounds may be
present in an amount of from zero to about 10.0% percent (e.g. from
about 0.01% to about 5% or from about 0.1% to about 3.0%) by weight
of the lubricating composition. An effective elemental boron range
of up to about 1000 ppm or less than about 1% elemental boron.
Thus, in an embodiment, a concentration of elemental boron is from
about 100 to about 1000 ppm (e.g. from about 100 to about 300
ppm).
[0319] When lubricating oil compositions contain one or more of the
additives discussed above, the additive(s) are blended into the
composition in an amount sufficient for it to perform its intended
function. Exemplary amounts of such additives useful in the present
disclosure are shown in Table 3 below.
[0320] It is noted that many of the additives are shipped from the
additive manufacturer as a concentrate, containing one or more
additives together, with a certain amount of base oil diluents.
Accordingly, the weight amounts in Table 3 below, as well as other
amounts mentioned herein, are directed to the amount of active
ingredient (that is the non-diluent portion of the ingredient). The
weight percent (wt %) indicated below is based on the total weight
of the lubricating oil composition.
TABLE-US-00003 TABLE 3 Exemplary Amounts of Industrial Lubricating
Oil Components Approximate Approximate Compound wt % (Useful) wt %
(Exemplary) Dispersant 0-20 0-3 Detergent 0-20 0-3 Friction
Modifier 0-5 .sup. 0-1.5 Antioxidant 0.1-5 0.1-3.sup. Pour Point
Depressant 0.0-5 0.01-1.5 (PPD) Antifoam Agent 0.0001-3 0.001-0.3
Demulsifier 0.001-3 0.001-0.15 Viscosity Modifier 0.1-10 0.1-1.sup.
(solid polymer basis) Antiwear 0.05-3 0.5-1.5 Inhibitor and
Antirust 0.01-5 0.01-2
[0321] The foregoing additives are all commercially available
materials. These additives may be added independently but are
usually precombined in packages which can be obtained from
suppliers of lubricant oil additives. Additive packages with a
variety of ingredients, proportions and characteristics are
available and selection of the appropriate package will take the
requisite use of the ultimate composition into account.
Methods of the Present Disclosure
[0322] Another aspect of the present disclosure includes a method
of making a hydraulic oil composition with improved antiwear
activity for at least one of a hydraulic pump, a hydraulic motor,
at least a portion of a hydraulic system, or a combination thereof
compared to a hydraulic oil composition that includes a
non-zinc-based antiwear composition. For example, the improved
antiwear activity for the hydraulic pump, the hydraulic motor, a
combination thereof, is compared to a hydraulic oil composition
that includes a non-zinc-ix) based antiwear composition that does
not include molybdenum dithiocarbamate. The method comprises
mixing: at least one lubricating base oil (e.g., 1, 2, 3, 4, 5, 6,
7, 8, 9, 10, or more); and an antiwear composition (e.g., an
effective amount of an antiwear composition) comprising an
effective amount of molybdenum dithiocarbamate. The antiwear
composition may be a non-zinc-based antiwear composition or a
substantially zinc-free antiwear composition. In certain
embodiments, the antiwear composition further includes at least one
additional antiwear agent (e.g., at least one non-zinc-based or
zinc-free antiwear agent), which may include at least one of a
phosphorous-based antiwear agent, alkyl phosphate or ester thereof,
dialkyl dithiophosphate ester, a phosphate-based antiwear agent,
salts thereof, or a combination thereof.
[0323] As described in greater detail above, the molybdenum
dithiocarbamate may be present in the hydraulic oil composition in
an amount no greater than about 0.75 wt. % (e.g., from about 0.001
wt. % to about 0.6 wt. % or from about 0.01 wt. % to about 0.5 wt.
%).
[0324] As discussed above, the lubricating base oil or oils may
include at least one of: at least one Group I oil, at least one
Group II oil, at least one Group III oil, at least one Group IV
oil, at least one Group V oil, at least one gas-to-liquid oil, at
least one polyalphaolefin, or a combination thereof. The method may
further comprise mixing at least one performance additive with the
antiwear composition and the base oil or oils. For example, the
lubricating composition may further comprise at least one of a
dispersant, an additional antiwear agent (e.g., a non-zinc-based or
zinc-free antiwear agent), a corrosion inhibitor, a rust inhibitor,
a detergent, an anti-seizure agent, an antifoam agent or defoamant,
a wax modifier, a metal deactivator/passivator, an extreme pressure
additive, an antioxidant, a viscosity index improver, a viscosity
improver/modifier, a seal compatibility agent, a pour point
depressant, a friction modifier, a lubricity agent, an
anti-staining agent, a dye or colorant/chromophoric agent, a
demulsifier, a wetting agent, an oxidation inhibitor, a gelling
agent, a tackiness agent, a colorant, a detergent stabilizer, or
combinations thereof, as described herein. For example, the
antiwear composition of the present disclosure may further include
at least one additional antiwear agent, such as at least one
non-zinc-based or zinc-free antiwear agent. The additional
non-zinc-based or zinc-free antiwear agent may include at least one
of a phosphorous-based antiwear agent, alkyl phosphate or ester
thereof, dialkyl dithiophosphate ester, a phosphate-based antiwear
agent, salts thereof, or a combination thereof.
[0325] An additional aspect of the present disclosure includes a
method for lubricating a hydraulic motor requiring a hydraulic oil
composition, a hydraulic pump requiring the hydraulic oil
composition, or both, the method comprising: supplying the
hydraulic motor, pump, or both with a hydraulic oil composition
comprising: at least one lubricating base oil; and an antiwear
composition (e.g., a non-zinc-based or substantially zinc-free
antiwear composition) comprising an effective amount of molybdenum
dithiocarbamate.
[0326] In some embodiments, the effective amount of the molybdenum
dithiocarbamate is no greater than about 0.75 wt. % (e.g., from
about 0.001 wt. % to about 0.6 wt. % or from about 0.01 wt. % to
about 0.5 wt. %).
[0327] In further embodiments, at least one of: (1) the lubricating
base oil or oils comprises at least one of: a Group I oil, a Group
II oil, a Group III oil, a Group IV oil, a Group V oil, a
gas-to-liquid oil, a polyalphaolefin, or combinations thereof; (2)
the composition further comprises at least one of a dispersant, an
additional antiwear agent (e.g., a non-zinc-based or zinc-free
antiwear agent), a corrosion inhibitor, a rust inhibitor, a
detergent, an anti-seizure agent, an antifoam agent or defoamant, a
wax modifier, a metal deactivator/passivator, an extreme pressure
additive, an antioxidant, a viscosity index improver, a viscosity
improver/modifier, a seal compatibility agent, a pour point
depressant, a friction modifier, a lubricity agent, an
anti-staining agent, a dye or colorant/chromophoric agent, a
demulsifier, a wetting agent, an oxidation inhibitor, a gelling
agent, a tackiness agent, a colorant, a detergent stabilizer, or
combinations thereof; or (3) a combination thereof.
[0328] In other embodiments, the lubricating base oil or oils
includes at least one of: at least one Group I oil, at least one
Group III oil, or a combination thereof.
[0329] In certain embodiments, the antiwear composition is
substantially zinc free. For example, zinc may be present in the
antiwear composition as a minor impurity. In other embodiments, the
hydraulic oil composition is substantially zinc-free. For example,
zinc may be present in the hydraulic oil/fluid as a minor
impurity.
[0330] The hydraulic oil composition of the present disclosure has
reduced wear in at least one of a hydraulic motor, a hydraulic
pump, at least a portion of a hydraulic system, or a combination
thereof, relative to a hydraulic oil composition that includes a
non-zinc-based antiwear composition or a zinc-free antiwear
composition without molybdenum dithiocarbamate.
[0331] The hydraulic oil composition provides acceptable wear in
(e.g., the hydraulic oil composition passes) the Rexroth Fluid Test
Axial Piston Unit Closed Loop test for at least one of a hydraulic
pump, a hydraulic motor, or both; or (4) a combination thereof.
INDUSTRIAL APPLICATION
[0332] The methods and lubricating composition of the present
disclosure may be suitable industrial fluids, hydraulic fluids,
turbine oils, circulating oils, or combinations thereof. In any
aspect or embodiments described herein, the lubricating composition
of the present disclosure is suitable for various mechanical
devices including industrial systems, hydraulic systems or
turbines. In any aspect or embodiments described herein, the
lubricating composition of the present disclosure is suitable for a
hydraulic system.
[0333] In any aspect and embodiment described herein, the methods
and compositions of the present disclosure are used in at least a
portion of a hydraulic system, a hydraulic pump, a hydraulic motor,
or a combination thereof. In any aspect or embodiments described
herein, the pump is a hydraulic piston pump, such as a vane pump.
In any aspect or embodiment described herein, the pump is a
hydraulic hybrid piston and vane pump.
Examples
[0334] The present disclosure is further illustrated by the
following examples which should not be construed as limiting. The
data below demonstrates that the antiwear and lubricating
compositions of the present disclosure provides the surprising and
unexpected improvement in antiwear activity under extreme
temperatures and pressures, as compared to lubricating compositions
with heretofore known non-zinc based antiwear additives. Those
skilled in the art will recognize that the present disclosure may
be practiced with variations on the disclosed structures,
materials, compositions and methods, and such variations are
regarded as within the ambit of the disclosure.
Example Formulations
[0335] The RFT-APU-CL test performed by Bosch Rexroth AG utilizes
an A4VG045EP hydraulic pump and a A6VM060EP hydraulic motor to
provide data representative of a hydrostatic transmission through a
break-in test, swivel cycle test, and a corner power test. The
suitability of the hydraulic oil/fluid is tested under high stress
conditions and the interaction between the fluid and component are
examined (component weight change, material compatibility, visual
inspection of the components and their surfaces, and the oil/fluid
throughout the test). The technical data of the hydraulic pump and
hydraulic motor are shown in Table 4 below and the operating
conditions of the break-in test, the swivel cycle test, and the
corner power test are shown in Table 5 below.
TABLE-US-00004 TABLE 4 Technical data for the A4VG045EP hydraulic
pump and the A6VM060EP hydraulic motor A4VG045EP A6VM060EP Data
Sheet 92004 91610 Operation Mode pump motor Nominal Volume 45
cm.sup.3 62 cm.sup.3 Maximum speed (at V.sub.g max) 4300 min.sup.-1
4450 min.sup.-1 Maximum pressure 500 bar 500 bar Control electric
electric
TABLE-US-00005 TABLE 5 Operating conditions of the break-in test,
swivel cycle test, and corner power test of the Bosch Rexroth AG
Fluid Test Axial Piston Unit Closed Loop test A4VG045EP A6VM060EP
Break-in Test Speed 2000 min.sup.-1 2000 min.sup.-1 Operating
Pressure 250 bar 250 bar Leckage Temperature 60.degree. C. at port
T Hydraulic Motor Operating Time 10 hours 10 hours Swivel Cycle
Test Speed 4000 min.sup.-1 4000 min.sup.-1 Operating Pressure 450
bar 450 bar Leckage Temperature 100.degree. C. at port T Hydraulic
Motor Operating Time 300 hours 300 hours Corner Power Test Speed
4000 min.sup.-1 4000 min.sup.-1 Operating Pressure 500 bar 500 bar
Leckage Temperature 100.degree. C. at port T Hydraulic Motore
Operating Time 200 hours 200 hours
[0336] Table 6 provides formulations of hydraulic oils using five
non-zinc based antiwear agents and RFT-APU-CL test results for each
of the example hydraulic oils. It was surprisingly discovered that
antiwear compositions including molybdenum dithiocarbamate had
robust antiwear activity (see Examples 3-4) as compared to
non-zinc-based antiwear agents without molybdenum dithiocarbamate
(see Examples 1 and 2). In particular, Examples 3-4 passed the A6
Motor portion of the test and were able to complete the test with
Examples 4 and 5 passing the A4 Motor portion of the test. In stark
contrast, Examples 1 and 2, not only fails the A6 Motor and A4 Pump
portions of the test, but also were unable to complete the
RFT-APU-CL test due to poor antiwear activity.
TABLE-US-00006 TABLE 6 Lubricating composition formulations and
Bosch Rexroth AG Fluid Test Axial Piston Unit Closed Loop test data
Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 RFT-APU- Overall Rating Failed Failed
Failed Passed Passed CL Test B-R test B-R test B-R test B-R test
B-R test Results* A6 Motor Rating Fail Fail Pass Pass Pass A4 Pump
Rating Not Not Fail Pass Pass completed completed ISO VG 32 32 32
32 46 Formulation Antiwear dialkyl 0.15 0.15 0.15 0.15 0.15
Composition dithiophosphate ester tri-butyl phosphate 0.25 moly 0.1
0.1 0.1 dithiocarbamate Base stocks, viscosity modifier, Balance
antioxidants, rust inhibitors, copper passivator, dispersant,
detergent, defoamant, demulsifier, and pour point depressant
typical of a zinc-free hydraulic oil
[0337] One skilled in the art appreciates that the antiwear
compositions of the examples include exemplary additional antiwear
agent(s) (i.e., in addition to molybdenum dithiocarbamate) and that
one skilled in the art would be able to select an appropriate
additional antiwear agent or agents based on the use of the
composition.
Specific Embodiments
[0338] An aspect of the present disclosure provides an antiwear
composition (e.g., a non-zinc-based antiwear composition)
comprising: an effective amount of molybdenum dithiocarbamate; and
an effective amount of at least one additional antiwear agent
(e.g., at least one non-zinc-based or zinc-free antiwear
agent).
[0339] In any aspect or embodiment described herein, the
additional, non-zinc-based, or zinc-free antiwear agent includes at
least one of a phosphorous-based antiwear agent, alkyl phosphate or
ester thereof, dialkyl dithiophosphate ester, a phosphate-based
antiwear agent, salts thereof, or a combination thereof.
[0340] In any aspect or embodiment described herein, the antiwear
composition includes dialkyl dithiophosphate ester.
[0341] In any aspect or embodiment described herein, the antiwear
composition is substantially zinc free (e.g., the antiwear
composition may include zinc as a minor impurity).
[0342] A further aspect of the present disclosure provides a
hydraulic oil composition comprising: at least one lubricating base
oil; and an antiwear composition (such as, a non-zinc-based
antiwear composition or an antiwear composition that is
substantially zinc free [e.g., an antiwear composition that may
include zinc as a minor impurity] and/or an effective amount of an
antiwear composition) comprising an effective amount of molybdenum
dithiocarbamate.
[0343] In any aspect or embodiment described herein, the effective
amount of the molybdenum dithiocarbamate is no greater than about
0.75 wt. % (e.g., from about 0.001 wt. % to about 0.6 wt. % or from
about 0.01 wt. % to about 0.5 wt. %).
[0344] In any aspect or embodiment described herein, the
lubricating base oil or oils comprises at least one of: a Group I
oil, a Group II oil, a Group III oil, a Group IV oil, a Group V
oil, a gas-to-liquid oil, a polyalphaolefin, or combinations
thereof.
[0345] In any aspect or embodiment described herein, the
lubricating base oil or oils include at least one of: at least one
Group I oil; at least one Group III oil, or a combination
thereof.
[0346] In any aspect or embodiment described herein, the hydraulic
oil composition further comprises at least one of a dispersant, an
additional antiwear agent (e.g., at least one non-zinc-based or
zinc-free antiwear agent), a corrosion inhibitor, a rust inhibitor,
a detergent, an anti-seizure agent, an antifoam agent or defoamant,
a wax modifier, a metal deactivator/passivator, an extreme pressure
additive, an antioxidant, a viscosity index improver, a viscosity
improver/modifier, a seal compatibility agent, a pour point
depressant, a friction modifier, a lubricity agent, an
anti-staining agent, a dye or colorant/chromophoric agent, a
demulsifier, a wetting agent, an oxidation inhibitor, a tackiness
agent, a colorant, a detergent stabilizer, or combinations
thereof.
[0347] In any aspect or embodiment described herein, the hydraulic
oil composition is substantially zinc-free (e.g., the hydraulic oil
composition may include zinc as a minor impurity).
[0348] In any aspect or embodiment described herein, the hydraulic
oil composition has reduced wear in at least one of a hydraulic
motor, a hydraulic pump, at least a portion of a hydraulic system,
or a combination thereof, relative to a hydraulic oil composition
that includes a non-zinc-based or zinc-free antiwear composition
without molybdenum dithiocarbamate.
[0349] In any aspect or embodiment described herein, the hydraulic
oil composition provides acceptable wear in (e.g., the hydraulic
oil composition passes) the Rexroth Fluid Test Axial Piston Unit
Closed Loop test for at least one of a hydraulic pump, a hydraulic
motor, at least a portion of a hydraulic system, or a combination
thereof.
[0350] Another aspect of the present disclosure provides a method
of making a hydraulic oil composition with improved antiwear
activity for at least one of a hydraulic pump, a hydraulic motor,
at least a portion of a hydraulic system, or a combination thereof,
compared to a hydraulic oil composition that includes a zinc-free
or non-zinc-based antiwear composition without molybdenum
dithiocarbamate, the method comprising mixing: at least one
lubricating base oil; and an antiwear composition (such as, a
non-zinc-based or an antiwear composition that is substantially
zinc free [e.g., the antiwear composition may include zinc as a
minor impurity] and/or an effective amount of an antiwear
composition) comprising an effective amount of molybdenum
dithiocarbamate.
[0351] In any aspect or embodiment described herein, the effective
amount of the molybdenum dithiocarbamate is no greater than about
0.75 wt. % (e.g., from about 0.001 wt. % to about 0.6 wt. % or from
about 0.01 wt. % to about 0.5 wt. %).
[0352] In any aspect or embodiment described herein, at least one
of: (1) the lubricating base oil or oils comprises at least one of:
a Group I oil, a Group II oil, a Group III oil, a Group IV oil, a
Group V oil, a gas-to-liquid oil, a polyalphaolefin, or
combinations thereof; (2) the composition further comprises at
least one of a dispersant, an additional antiwear agent (e.g., at
least one non-zinc-base or zinc-free antiwear agent), a corrosion
inhibitor, a rust inhibitor, a detergent, an anti-seizure agent, an
antifoam agent or defoamant, a wax modifier, a metal
deactivator/passivator, an extreme pressure additive, an
antioxidant, a viscosity index improver, a viscosity
improver/modifier, a seal compatibility agent, a pour point
depressant, a friction modifier, a lubricity agent, an
anti-staining agent, a dye or colorant/chromophoric agent, a
demulsifier, a wetting agent, an oxidation inhibitor, a gelling
agent, a tackiness agent, a colorant, a detergent stabilizer, or
combinations thereof; or (3) a combination thereof.
[0353] An aspect of the present disclosure provides a hydraulic oil
composition produced according to the method of making the
hydraulic oil/fluid of the present disclosure.
[0354] An additional aspect of the present disclosure provides a
method for lubricating at least one of a hydraulic motor requiring
a hydraulic oil composition, a hydraulic pump requiring the
hydraulic oil composition, at least a portion of a hydraulic system
requiring the hydraulic oil composition, or a combination thereof,
the method comprising: supplying the hydraulic motor, pump, a
portion of the hydraulic system, or a combination thereof with a
hydraulic oil composition comprising: at least one lubricating base
oil; and an antiwear composition (e.g., a non-zinc-based or
substantially zinc-free antiwear composition) comprising an
effective amount of molybdenum dithiocarbamate.
[0355] In any aspect or embodiment described herein, the effective
amount of the molybdenum dithiocarbamate is no greater than about
0.75 wt. % (e.g., from about 0.001 wt. % to about 0.6 wt. % or from
about 0.01 wt. % to about 0.5 wt. %).
[0356] In any aspect or embodiment described herein, at least one
of: (1) the lubricating base oil or oils comprises at least one of:
a Group I oil, a Group II oil, a Group III oil, a Group IV oil, a
Group V oil, a gas-to-liquid oil, a polyalphaolefin, or
combinations thereof; (2) the composition further comprises at
least one of a dispersant, an additional antiwear agent (e.g., at
least one non-zinc-based or zinc-free antiwear agent), a corrosion
inhibitor, a rust inhibitor, a detergent, an anti-seizure agent, an
antifoam agent or defoamant, a wax modifier, a metal
deactivator/passivator, an extreme pressure additive, an
antioxidant, a viscosity index improver, a viscosity
improver/modifier, a seal compatibility agent, a pour point
depressant, a friction modifier, a lubricity agent, an
anti-staining agent, a dye or colorant/chromophoric agent, a
demulsifier, a wetting agent, an oxidation inhibitor, a gelling
agent, a tackiness agent, a colorant, a detergent stabilizer, or
combinations thereof; or (3) a combination thereof.
[0357] In any aspect or embodiment described herein, the
lubricating base oil or oils includes at least one of: at least one
Group I oil, at least one Group III oil, or a combination
thereof.
[0358] In any aspect or embodiment described herein, at least one
of: (1) the antiwear composition is substantially zinc free [e.g.,
the antiwear composition may include zinc as a minor impurity] the
hydraulic oil composition is substantially zinc-free composition
(e.g., the hydraulic oil may include zinc as a minor impurity); (2)
the hydraulic oil composition has reduced wear in at least one of a
hydraulic motor, a hydraulic pump, at least a portion of a
hydraulic system, or a combination thereof, relative to a hydraulic
oil composition that includes a zinc-free or non-zinc-based
antiwear composition without molybdenum dithiocarbamate; (3) the
hydraulic oil composition provides acceptable wear in (e.g., the
hydraulic oil composition passes) the Rexroth Fluid Test Axial
Piston Unit Closed Loop test for at least one of a hydraulic pump,
a hydraulic motor, at least a portion of a hydraulic system, or a
combination thereof; or (4) a combination thereof.
[0359] In any aspect or embodiment described herein, the
substantially zinc-free antiwear composition or non-zinc-based
antiwear composition is zinc-free.
[0360] In any aspect or embodiment described herein, the hydraulic
oil composition is a substantially zinc-free hydraulic oil
composition.
[0361] In any aspect or embodiment described herein, the hydraulic
oil composition or substantially zinc-free hydraulic composition is
zinc-free.
EQUIVALENTS
[0362] Each documents referred to herein 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 all
percent values on weight percents and all ppm values are on a
weight to weight basis. 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, 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 disclosure can be used
together with ranges or amounts for any of the other elements.
[0363] Those skilled in the art will recognize, or be able to
ascertain using no more than routine experimentation, many
equivalents to the specific embodiments and methods described
herein. Such equivalents are intended to be encompassed by the
scope of the following claims.
[0364] It is understood that the detailed examples and embodiments
described herein are given by way of example for illustrative
purposes only, and are in no way considered to be limiting to the
disclosure. Various modifications or changes in light thereof will
be suggested to persons skilled in the art and are included within
the spirit and purview of this application and are considered
within the scope of the appended claims. For example, the relative
quantities of the ingredients may be varied to optimize the desired
effects, additional ingredients may be added, and/or similar
ingredients may be substituted for one or more of the ingredients
described. Additional advantageous features and functionalities
associated with the systems, methods, and processes of the present
disclosure will be apparent from the appended claims. Moreover,
those skilled in the art will recognize, or be able to ascertain
using no more than routine experimentation, many equivalents to the
specific embodiments of the disclosure described herein. Such
equivalents are intended to be encompassed by the following
claims.
PCT/EP Clauses:
[0365] 1. An antiwear composition (e.g., a non-zinc-based antiwear
composition) comprising: an effective amount of molybdenum
dithiocarbamate; and an effective amount of at least one
non-zinc-based antiwear agent.
[0366] 2. The antiwear composition of clause 1, wherein at least
one of: the antiwear agent includes at least one of a
phosphorous-based antiwear agent, alkyl phosphate or ester thereof,
dialkyl dithiophosphate ester, a phosphate-based antiwear agent,
salts thereof, or a combination thereof; the composition is
substantially zinc free (e.g., the antiwear composition may include
zinc as a minor impurity); or a combination thereof.
[0367] 3. A hydraulic oil composition comprising: at least one
lubricating base oil; and an antiwear composition (such as, a
non-zinc-based antiwear composition or an antiwear composition that
is substantially zinc free [e.g., an antiwear composition that may
include zinc as a minor impurity] and/or an effective amount of an
antiwear composition) comprising an effective amount of molybdenum
dithiocarbamate.
[0368] 4. The composition of clause 3, wherein the effective amount
of the molybdenum dithiocarbamate is no greater than about 0.75 wt.
% (e.g., from about 0.001 wt. % to about 0.6 wt. % or from about
0.01 wt. % to about 0.5 wt. %).
[0369] 5. The composition of clauses 3 or 4, wherein at least one
of: the lubricating base oil or oils comprise at least one of: a
Group I oil, a Group II oil, a Group III oil, a Group IV oil, a
Group V oil, a gas-to-liquid oil, a polyalphaolefin, or
combinations thereof; the composition further comprises at least
one of a dispersant, an additional antiwear agent, a corrosion
inhibitor, a rust inhibitor, a detergent, an anti-seizure agent, an
antifoam agent or defoamant, a wax modifier, a metal
deactivator/passivator, an extreme pressure additive, an
antioxidant, a viscosity index improver, a viscosity
improver/modifier, a seal compatibility agent, a pour point
depressant, a friction modifier, a lubricity agent, an
anti-staining agent, a dye or colorant/chromophoric agent, a
demulsifier, a wetting agent, an oxidation inhibitor, a tackiness
agent, a colorant, a detergent stabilizer, or combinations thereof;
or a combination thereof.
[0370] 6. The composition of any of clauses 3-5, wherein the
lubricating base oil or oils include at least one of: at least one
Group I oil; at least one Group III oil, or a combination
thereof.
[0371] 7. The composition of any of clauses 3-6, wherein the
hydraulic oil composition is substantially zinc-free (e.g., the
hydraulic oil composition may include zinc as a minor
impurity).
[0372] 8. The composition of any of clauses 3-7, wherein the
hydraulic oil composition has reduced wear in at least one of a
hydraulic motor, a hydraulic pump, at least a portion of a
hydraulic system, or a combination thereof, relative to a hydraulic
oil composition that includes a non-zinc-based or zinc-free
antiwear composition without molybdenum dithiocarbamate.
[0373] 9. The composition of any of clauses 3-8, wherein the
hydraulic oil composition provides acceptable wear in (e.g., the
hydraulic oil composition passes) the Rexroth Fluid Test Axial
Piston Unit Closed Loop test for at least one of a hydraulic pump,
a hydraulic motor, at least a portion of a hydraulic system, or a
combination thereof.
[0374] 10. A method of making a hydraulic oil composition with
improved antiwear activity for at least one of a hydraulic pump, a
hydraulic motor, at least a portion of a hydraulic system, or a
combination thereof compared to a hydraulic oil composition that
includes a non-zinc-based or zinc-free antiwear composition without
molybdenum dithiocarbamate, the method comprising mixing: at least
one lubricating base oil; and an antiwear composition (such as, a
non-zinc-based or an antiwear composition that is substantially
zinc free [e.g., the antiwear composition may include zinc as a
minor impurity] and/or an effective amount of an antiwear
composition) comprising an effective amount of molybdenum
dithiocarbamate.
[0375] 11. The method of clause 10, wherein at least one of: the
effective amount of the molybdenum dithiocarbamate is no greater
than about 0.75 wt. % (e.g., from about 0.001 wt. % to about 0.6
wt. % or from about 0.01 wt. % to about 0.5 wt. %); the lubricating
base oil or oils comprises at least one of: a Group I oil, a Group
II oil, a Group III oil, a Group IV oil, a Group V oil, a
gas-to-liquid oil, a polyalphaolefin, or combinations thereof; the
composition further comprises at least one of a dispersant, an
additional antiwear agent, a corrosion inhibitor, a rust inhibitor,
a detergent, an anti-seizure agent, an antifoam agent or defoamant,
a wax modifier, a metal deactivator/passivator, an extreme pressure
additive, an antioxidant, a viscosity index improver, a viscosity
improver/modifier, a seal compatibility agent, a pour point
depressant, a friction modifier, a lubricity agent, an
anti-staining agent, a dye or colorant/chromophoric agent, a
demulsifier, a wetting agent, an oxidation inhibitor, a gelling
agent, a tackiness agent, a colorant, a detergent stabilizer, or
combinations thereof; or a combination thereof.
[0376] 12. A hydraulic oil composition produced according to
clauses 10 or 11.
[0377] 13. A method for lubricating at least one of a hydraulic
motor requiring a hydraulic oil composition, a hydraulic pump
requiring the hydraulic oil composition, at least a portion of a
hydraulic system requiring the hydraulic oil composition, or a
combination thereof, the method comprising: supplying the hydraulic
motor, pump, the portion of the hydraulic system, or a combination
thereof, with a hydraulic oil composition comprising: at least one
lubricating base oil; and an antiwear composition (e.g., a
non-zinc-based or substantially zinc-free antiwear composition)
comprising an effective amount of molybdenum dithiocarbamate.
[0378] 14. The method of clause 13, wherein at least one of: the
effective amount of the molybdenum dithiocarbamate is no greater
than about 0.75 wt. % (e.g., from about 0.001 wt. % to about 0.6
wt. % or from about 0.01 wt. % to about 0.5 wt. %); the lubricating
base oil or oils comprises at least one of: a Group I oil, a Group
II oil, a Group III oil, a Group IV oil, a Group V oil, a
gas-to-liquid oil, a polyalphaolefin, or combinations thereof; the
composition further comprises at least one of a dispersant, an
additional antiwear agent, a corrosion inhibitor, a rust inhibitor,
a detergent, an anti-seizure agent, an antifoam agent or defoamant,
a wax modifier, a metal deactivator/passivator, an extreme pressure
additive, an antioxidant, a viscosity index improver, a viscosity
improver/modifier, a seal compatibility agent, a pour point
depressant, a friction modifier, a lubricity agent, an
anti-staining agent, a dye or colorant/chromophoric agent, a
demulsifier, a wetting agent, an oxidation inhibitor, a gelling
agent, a tackiness agent, a colorant, a detergent stabilizer, or
combinations thereof; or a combination thereof.
[0379] 15. The method of clauses 13 or 14, wherein at least one of:
the antiwear composition is substantially zinc free [e.g., the
antiwear composition may include zinc as a minor impurity]; the
hydraulic oil composition is substantially zinc-free composition
(e.g., the hydraulic oil may include zinc as a minor impurity); the
hydraulic oil composition has reduced wear in at least one of a
hydraulic motor, a hydraulic pump, at least a portion of a
hydraulic system, or a combination thereof, relative to a hydraulic
oil composition that includes a non-zinc-based or zinc-free
antiwear composition without molybdenum dithiocarbamate; the
hydraulic oil composition provides acceptable wear in (e.g., the
hydraulic oil composition passes) the Rexroth Fluid Test Axial
Piston Unit Closed Loop test for at least one of a hydraulic pump,
a hydraulic motor, at least a portion of a hydraulic system, or a
combination thereof or a combination thereof.
* * * * *
References