U.S. patent application number 14/735762 was filed with the patent office on 2015-10-01 for composition with improved cleanliness for lubrication of steam and gas turbine systems.
The applicant listed for this patent is The Lubrizol Corporation. Invention is credited to Allan R. Barber, Betsy J. Butke.
Application Number | 20150275123 14/735762 |
Document ID | / |
Family ID | 45558813 |
Filed Date | 2015-10-01 |
United States Patent
Application |
20150275123 |
Kind Code |
A1 |
Butke; Betsy J. ; et
al. |
October 1, 2015 |
COMPOSITION WITH IMPROVED CLEANLINESS FOR LUBRICATION OF STEAM AND
GAS TURBINE SYSTEMS
Abstract
The present invention relates to the use of an additive
composition that contains the combination of two specific types of
antioxidants with one or more of four specific types of dispersants
in a Group II and/or Group III base oil-containing lubricating
composition. The lubricating composition of the present invention
provides improved cleanliness in steam and gas turbine systems. The
invention further relates to the process to make the novel additive
composition and its use in industrial fluids.
Inventors: |
Butke; Betsy J.; (Mentor,
OH) ; Barber; Allan R.; (Belper, GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Lubrizol Corporation |
Wickliffe |
OH |
US |
|
|
Family ID: |
45558813 |
Appl. No.: |
14/735762 |
Filed: |
June 10, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13978225 |
Jul 3, 2013 |
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PCT/US12/20580 |
Jan 9, 2012 |
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14735762 |
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61431572 |
Jan 11, 2011 |
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Current U.S.
Class: |
508/192 ;
508/287; 508/562; 508/563 |
Current CPC
Class: |
C10M 2215/223 20130101;
C10M 2209/103 20130101; C10M 2215/064 20130101; C10M 2217/043
20130101; C10M 2219/044 20130101; C10M 2215/02 20130101; C10M
169/044 20130101; C10N 2030/04 20130101; C10M 2207/281 20130101;
C10N 2040/135 20200501; C10M 2223/043 20130101; C10N 2040/12
20130101; C10M 2219/084 20130101; C10M 141/08 20130101; C10M
2215/042 20130101; C10M 2209/084 20130101; C10M 2203/1025 20130101;
C10M 133/44 20130101; C10M 2217/04 20130101; C10M 2219/106
20130101; C10M 169/04 20130101; C10M 2219/082 20130101; C10M
2207/125 20130101; C10N 2030/08 20130101; C10M 2215/28 20130101;
C10M 2203/1025 20130101; C10N 2020/02 20130101; C10M 2215/28
20130101; C10N 2060/14 20130101; C10M 2203/1025 20130101; C10N
2020/02 20130101; C10M 2215/28 20130101; C10N 2060/14 20130101 |
International
Class: |
C10M 141/08 20060101
C10M141/08 |
Claims
1. A lubricating oil composition comprising: a) an oil of
lubricating viscosity comprising a Group II base oil, a Group III
base oil, or combinations thereof; b) an antioxidant component
comprising: (i) an alkylated diphenylamine, and (ii) a substituted
hydrocarbyl mono-sulfide; c) a dispersant component comprising at
least one of: (i) a polyetheramine, (ii) a borated succinimide
dispersant, (iii) a non-borated succinimide dispersant, and (iv) a
Mannich reaction product of a dialkylamine, an aldehyde and a
hydrocarbyl substituted phenol and d) optionally one or more
additional additives; wherein component b) is present in the
overall composition from 0.4 to 0.9 parts by weight; and wherein
the substituted hydrocarbyl mono-sulfides are represented by the
formula: ##STR00012## wherein R.sup.3 is a saturated or unsaturated
branched or linear alkyl group with about 10 to about 15 carbon
atoms; R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are independently
hydrogen or alkyl containing about 1 to about 3 carbon atoms;
wherein: (I) the dispersant component comprises a polyetheramine
derived from the reaction of a mixture of alcohols containing from
10 to 15 carbon atoms, an alkoxylate and an amine; wherein the
antioxidant component is present in the overall composition at less
than 0.865 parts by weight; wherein the composition is free of
N-alkyl sarcosines; wherein the composition contains less than 0.1
parts by weight of fatty carboxylic acids; and wherein the
dispersant component is present in the overall composition from
0.07 to 0.4 parts by weight; (II) the dispersant component
comprises a borated succinimide dispersant derived from
polyisobutylene having a number average molecular weight from 500
to 3000 and polyethylenepolyamines; wherein the dispersant
component is present in the overall composition from 0.07 to less
than 0.4 parts by weight; (III) the dispersant component comprises
a non-borated succinimide dispersant derived from polyisobutylene
having a number average molecular weight from 500 to 3000 and
polyethylenepolyamines; wherein the composition contains less than
0.1 parts by weight of fatty carboxylic acids; and wherein the
dispersant component is present in the overall composition from
0.06 to 0.35 parts by weight; or (IV) the dispersant component
comprises a Mannich reaction product derived from the reaction of a
dialkylamine, formaldehyde, and a polyisobutylene substituted
phenol where the polyisobutylene has a number average molecular
weight from 500 to 3000; and wherein the dispersant component is
present in the overall composition from 0.07 to 0.44 parts by
weight.
2. The composition of claim 1 wherein component d) comprises a rust
inhibitor, a metal deactivator, a demulsifier, an antifoam agent,
or combinations thereof.
3. The composition of claim 2 wherein the rust inhibitor comprises
an amine phosphate, a fatty carboxylic acid or ester thereof, an
ester of a nitrogen-containing carboxylic acid, an ammonium
sulfonate, an imidazoline, or combinations thereof; wherein the
metal deactivator comprises a triazole, a tolyltriazole, a
thiadiazole, or combinations thereof; wherein the demulsifier
comprises a polyether; and wherein the antifoam comprises an
acrylate copolymer.
4. The composition of claim 1, wherein the alkylated diphenylamine
is represented by the formula: ##STR00013## wherein R.sup.1 and
R.sup.2 are independently a hydrogen or an alkyl group containing
about 5 to 20 carbon atoms; or a linear or branched alkyl group
containing 1 to 24 carbon atoms and q and r are each independently
0, 1, 2, or 3, provided that the sum of q and r is at least
one.
5. The composition of claim 1, wherein the substituted hydrocarbyl
monosulfide is n-dodecyl 2-hydroxyethyl sulfide,
1-(tert-dodecylthio)-2-propanol, or mixtures thereof.
6. The lubricating composition of claim 2, wherein the metal
deactivator is selected from the group comprising hydrocarbyl
substituted benzotriazole, 5-methylbenzotriazole and mixtures
thereof.
7. The composition of claim 1, wherein the additive components b)
to d) are in the range about 0 to about 13 parts by weight of the
overall composition.
8. The composition of claim 1 wherein: (I) the dispersant component
comprises a polyetheramine derived from the reaction of a mixture
of alcohols containing from 10 to 18 carbon atoms, an alkoxylate
and an amine; wherein the antioxidant component is present in the
overall composition at less than 0.865 parts by weight; wherein the
composition is free of N-alkyl sarcosines; wherein the composition
contains less than 0.1 parts by weight of fatty carboxylic acids;
and wherein the dispersant component is present in the overall
composition from 0.07 to 0.4 parts by weight.
9. The composition of claim 1 wherein: (II) the dispersant
component comprises a borated succinimide dispersant derived from
polyisobutylene having a number average molecular weight from 500
to 3000 and polyethylenepolyamines; wherein the dispersant
component is present in the overall composition from 0.07 to less
than 0.4 parts by weight.
10. The composition of claim 1 wherein: (III) the dispersant
component comprises a non-borated succinimide dispersant derived
from polyisobutylene having a number average molecular weight from
500 to 3000 and polyethylenepolyamines; wherein the composition
contains less than 0.1 parts by weight of fatty carboxylic acids;
and wherein the dispersant component is present in the overall
composition from 0.06 to 0.35 parts by weight.
11. The composition of claim 1 wherein: (IV) the dispersant
component comprises a Mannich reaction product derived from the
reaction of a dialkylamine, formaldehyde, and a polyisobutylene
substituted phenol where the polyisobutylene has a number average
molecular weight from 500 to 3000; and wherein the dispersant
component is present in the overall composition from 0.07 to 0.44
parts by weight.
12. A process to prepare a lubricating oil composition comprising
the steps of: (I) mixing together: a) an oil of lubricating
viscosity comprising a Group II base oil, a group III base oil, or
combinations thereof; b) an antioxidant component comprising: (i)
an alkylated diphenylamine, and (ii) a substituted hydrocarbyl
mono-sulfide; c) a dispersant component comprising at least one of:
(i) a polyetheramine, (ii) a borated succinimide dispersant, (iii)
a non-borated succinimide dispersant, and (iv) a Mannich reaction
product of a dialkylamine, an aldehyde and a hydrocarbyl
substituted phenol; and d) optionally other additives; wherein
component b) is present in the overall composition from 0.4 to 0.9
parts by weight; and wherein the substituted hydrocarbyl
mono-sulfides are represented by the formula: ##STR00014## wherein
R.sup.3 is a saturated or unsaturated branched or linear alkyl
group with about 10 to about 15 carbon atoms; R.sup.4, R.sup.5,
R.sup.6 and R.sup.7 are independently hydrogen or alkyl containing
about 1 to about 3 carbon atoms; wherein: (I) the dispersant
component comprises a polyetheramine derived from the reaction of a
mixture of alcohols containing from 10 to 18 carbon atoms, an
alkoxylate and an amine; wherein the antioxidant component is
present in the overall composition at less than 0.865 parts by
weight; wherein the composition is free of N-alkyl sarcosines;
wherein the composition contains less than 0.1 parts by weight of
fatty carboxylic acids; and wherein the dispersant component is
present in the overall composition from 0.07 to 0.4 parts by
weight; (II) the dispersant component comprises a borated
succinimide dispersant derived from polyisobutylene having a number
average molecular weight from 500 to 3000 and
polyethylenepolyamines; wherein the dispersant component is present
in the overall composition from 0.07 to less than 0.4 parts by
weight; (III) the dispersant component comprises a non-borated
succinimide dispersant derived from polyisobutylene having a number
average molecular weight from 500 to 3000 and
polyethylenepolyamines; wherein the composition contains less than
0.1 parts by weight of fatty carboxylic acids; and wherein the
dispersant component is present in the overall composition from
0.06 to 0.35 parts by weight; or (IV) the dispersant component
comprises a Mannich reaction product derived from the reaction of a
dialkylamine, formaldehyde, and a polyisobutylene substituted
phenol where the polyisobutylene has a number average molecular
weight from 500 to 3000; and wherein the dispersant component is
present in the overall composition from 0.07 to 0.44 parts by
weight.
13. The process of claim 12, wherein the antioxidant package is in
the range of 0.05 to 13 parts by weight of the overall composition;
the dispersant component is in the range of 0.05 to 10 parts by
weight of the overall composition; the optional additives, when
present, are present from 0.001 to 10 parts by weight of the
overall composition; and the balance is made up of the oil of
lubricating viscosity.
14. The process of claim 12 wherein: (I) the dispersant component
comprises a polyetheramine derived from the reaction of a mixture
of alcohols containing from 10 to 18 carbon atoms, an alkoxylate
and an amine; wherein the antioxidant component is present in the
overall composition at less than 0.865 parts by weight; wherein the
composition is free of N-alkyl sarcosines; wherein the composition
contains less than 0.1 parts by weight of fatty carboxylic acids;
and wherein the dispersant component is present in the overall
composition from 0.07 to 0.4 parts by weight.
15. The process of claim 12 wherein: (II) the dispersant component
comprises a borated succinimide dispersant derived from
polyisobutylene having a number average molecular weight from 500
to 3000 and polyethylenepolyamines; wherein the dispersant
component is present in the overall composition from 0.07 to less
than 0.4 parts by weight.
16. The process of claim 12 wherein: (III) the dispersant component
comprises a non-borated succinimide dispersant derived from
polyisobutylene having a number average molecular weight from 500
to 3000 and polyethylenepolyamines; wherein the composition
contains less than 0.1 parts by weight of fatty carboxylic acids;
and wherein the dispersant component is present in the overall
composition from 0.06 to 0.35 parts by weight.
17. The process of claim 12 wherein: (IV) the dispersant component
comprises a Mannich reaction product derived from the reaction of a
dialkylamine, formaldehyde, and a polyisobutylene substituted
phenol where the polyisobutylene has a number average molecular
weight from 500 to 3000; and wherein the dispersant component is
present in the overall composition from 0.07 to 0.44 parts by
weight.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to the use of an additive
composition that contains the combination of two specific types of
antioxidants with one or more of four specific types of dispersants
in a Group II and/or Group III base oil-containing lubricating
composition. The lubricating composition of the present invention
provides improved cleanliness in steam and gas turbine systems. The
invention further relates to the process to make the novel additive
composition and its use in industrial fluids.
BACKGROUND OF THE INVENTION
[0002] Varnish is a well known and recognized problem in the
lubricant industry and in the area of power generation and
gas-turbine applications is becoming of greater and greater
concern. Turbine design is moving to systems that provide more
power from smaller equipment, leading to tighter clearances,
extended drain intervals, and so more stress and harsher conditions
on both the equipment and the lubricant used in its operation. The
best fluids will meet these challenges and keep the system free of
varnish and other deposits. In addition turbine oils are
increasingly being formulated with Group II and Group III oils
instead of Group I base oils.
[0003] These new base oils are much less polar than Group I oils,
and additive formulations that worked well in Group I base oils
often fail to provide the desired performance when used in Group II
and Group III oils. Coupled with the design and operation changes
discussed above, there is a need to tailor the additive mixture for
optimum performance in Group II and/or Group III base oils.
[0004] Group II and Group III oils are more highly refined than
Group I oils. Group I oils tend to have higher aromatic and
unsaturated components, which are more susceptible to oxidation
than other species found in the oils. Indeed, these new groups of
oils were developed in part to try and provide improved oxidation
stability. While this does provide improved oxidative stability for
the base oil itself, they also end up having poorer solvency
compared to Group I oils. With this reduced solvency, oxidation
by-products, from the oil itself or other sources, that would have
remained dissolved in Group I based fluids often drop out of Group
II or Group III based fluids, forming varnish on the surfaces of
the equipment.
[0005] In addition, many power generation turbines in today's
market are peaking units, meaning they only operate at times of
peak demand. During the regular periods of down time in this type
of equipment, when the system lubricant cools, solvency decreases
allowing polar materials and varnish to come out of solution and
deposit on metal surfaces.
[0006] In addition to oxidation and the by-products it produces,
static discharge, micro-dieseling, incompatibility, and
contamination are also root causes of varnish. Incompatibility is a
particular concern with Group II and Group III oils as some
additives that are compatible with Group I oils are not compatible
with Group II and Group III oils.
[0007] Furthermore, Group I based fluids tend to follow gradual
oxidation rates that can be monitored over time, giving operators a
reliable means of determining the remaining service life of a
fluid. In contrast, Group II and Group III based fluids may go from
normal oxidation levels and operation to failure mode very quickly
with little or no indication before hand. This added complication
further increases the need for Group II and Group III based fluids
that provide reliable performance in these high cost systems that
cannot afford unplanned downtime and equipment damage caused by
spent lubricant.
[0008] Formulating a fluid with the required amount of oxidative
stability and resistance to formation of deposits is a challenge.
The primary types of additives used to control oxidation are
phenols and amines, both of which react at high temperatures,
forming oxidation products that contribute to system deposits and
varnish. Thus it is critical to find the proper balance of
oxidation inhibitor and dispersant components for the specific
application and base fluid involved, allowing for significantly
improved lubricant life, and so equipment life and operation time.
Dispersants frequently cause oil and water to emulsify, so the
choice of the right dispersant must allow the fluid to maintain
good demulsibility as required for proper turbine operation.
Emulsified water reduces lubricant film formation and promotes rust
and oxidation. Fluids that emulsify are not widely accepted in the
marketplace.
[0009] The formulation of lubricating compositions for steam and
gas turbine systems has been complicated by the growing use of API
Group II and Group III base oils which has led to increasing
varnish formation in some power generating turbines. There is a
need for turbine lubricants that allow the use of Group II and
Group III base oils while providing long service life, that avoid
the varnish problems that can lead to disruptions in equipment
operation and unplanned downtime.
[0010] It would be desirable for these lubricating oil compositions
to be capable of imparting acceptable levels of rust and/or
oxidation inhibition without the formation of unwanted deposits
that increase the viscosity of the fluid. Furthermore, it would be
desirable for these lubricating oil compositions to control and
prevent the formation of filter plugging deposits and/or sludge in
industrial fluids.
SUMMARY OF THE INVENTION
[0011] The invention provides Group II and Group III base oil
formulated lubricating compositions for steam and gas turbine
systems that provide balanced performance in modern turbine
systems. The invention further provides a method of making such
compositions and methods of using them in the operation of steam
and gas turbine systems.
[0012] The invention provides a lubricating oil composition made up
of: (a) an oil of lubricating viscosity that includes a Group II
base oil, a Group III base oil, or combinations thereof; (b) an
antioxidant component; and (c) a dispersant component. The
antioxidant component includes: (i) an alkylated diphenylamine, and
(ii) a substituted hydrocarbyl mono-sulfide. The dispersant
component includes: (i) a polyetheramine; (ii) a borated
succinimide dispersant; (iii) a non-borated succinimide dispersant;
(iv) a Mannich reaction product of a dialkylamine, an aldehyde and
a hydrocarbyl substituted phenol; or any combination thereof. The
compositions of the present invention may also include one or more
additional additives.
[0013] The invention further provides for compositions that further
include: (i) a rust inhibitor, for example an amine phosphate, a
fatty carboxylic acid or ester thereof, an ester of a
nitrogen-containing carboxylic acid, an ammonium sulfonate, or an
imidazoline; (ii) a metal deactivator, for example a triazole, a
tolyltriazole, a thiadiazole, or combinations thereof; (iii) a
demulsifier, for example a polyether; (iv) an antifoam agent, for
example an acrylate copolymer; or any combinations thereof.
[0014] The invention further provides for compositions that include
a substituted hydrocarbyl mono-sulfide. In other embodiments the
invention provides for compositions essentially free or even free
of substituted hydrocarbyl mono-sulfides.
[0015] The invention provides for the compositions described above
where the dispersant component includes a polyetheramine derived
from the reaction of a mixture of alcohols containing from 10 to 18
carbon atoms, an alkylene oxide and an amine; wherein the
antioxidant component is present in the overall composition at less
than 0.865 parts by weight; wherein the composition is free of
N-alkyl sarcosines; wherein the composition contains less than 0.1
parts by weight of fatty carboxylic acids; and wherein the
dispersant component is present in the overall composition from
0.07 to 0.4 parts by weight.
[0016] The invention provides for the compositions described above
where the dispersant component includes a borated succinimide
dispersant derived from polyisobutylene having a number average
molecular weight from 500 to 3000 and polyethylenepolyamines;
wherein the dispersant component is present in the overall
composition from 0.07 to less than 0.4 parts by weight.
[0017] The invention provides for the compositions described above
where the dispersant component includes a non-borated succinimide
dispersant derived from polyisobutylene having a number average
molecular weight from 500 to 3000 and polyethylenepolyamines;
wherein the composition contains less than 0.1 parts by weight of
fatty carboxylic acids; and wherein the dispersant component is
present in the overall composition from 0.06 to 0.35 parts by
weight.
[0018] The invention provides for the compositions described above
where the dispersant component includes a Mannich reaction product
derived from the reaction of a dialkylamine, formaldehyde, and a
polyisobutylene substituted phenol where the polyisobutylene has a
number average molecular weight from 500 to 3000; and wherein the
dispersant component is present in the overall composition from
0.07 to 0.44 parts by weight.
[0019] The process of the invention, wherein the antioxidant
package is in the range of 0.05 to 13 parts be weight of the
overall composition; the dispersant component is in the range of
0.05 to 10 parts be weight of the overall composition; the optional
additives, when present, are present from 0.001 to 10 parts be
weight of the overall composition; and the balance is made up of
the oil of lubricating viscosity.
[0020] The invention provides for a process of making the
lubricating compositions described herein including the steps of
mixing together the components described above, and further
described below.
[0021] The invention further provides a lubricating oil composition
that is capable of preventing filter plugging deposits and
sludge.
DETAILED DESCRIPTION OF THE INVENTION
[0022] Various features and embodiments of the invention will be
described below by way of non-limiting illustration. Unless
otherwise noted, the part by weight (pbw) values provided herein
for various components described below are in regards to
compositions that contain 100 pbw base oil. However the pbw values
may, in some embodiments, instead be treated as percent by weight
values relative to an overall composition.
[0023] The invention provides a lubricating oil composition made up
of: (a) an oil of lubricating viscosity that includes a Group II
base oil, a Group III base oil, or combinations thereof; (b) an
antioxidant component; and (c) a dispersant component. The
antioxidant component includes: (i) an alkylated diphenylamine, and
(ii) a substituted hydrocarbyl mono-sulfide. The dispersant
component includes: (i) a polyetheramine; (ii) a borated
succinimide dispersant; (iii) a non-borated succinimide dispersant;
(iv) a Mannich reaction product of a dialkylamine, an aldehyde and
a hydrocarbyl substituted phenol; or any combination thereof. The
compositions of the present invention may also include one or more
additional additives.
The Oil of Lubricating Viscosity
[0024] One component of the compositions of the invention is an oil
of lubricating viscosity, which can be present in a major amount,
for a lubricant composition, or in a concentrate forming amount,
for a concentrate. Suitable oils include natural and synthetic
lubricating oils and mixtures thereof. In a fully formulated
lubricant, the oil of lubricating viscosity is generally present in
a major amount (i.e. an amount greater than 50 percent by weight).
Typically, the oil of lubricating viscosity is present in an amount
of 75 to 95 percent by weight, and often greater than 80 percent by
weight of the overall composition. The base oil component generally
makes up 100 parts by weight (pbw) of the overall composition with
the pbw ranges for the other components being provided with this
100 pbw of base oil in mind. In other embodiments the pbw ranges of
the various components, including the base oils, are provided such
that the total of the pbw of all components is 100. The pbw ranges
provided for the various components described below may be taken
either way.
[0025] The lubricating oil component of the present invention
includes a Group II or Group III base oil, or a combination
thereof. These are classifications established by the API (American
Petroleum Institute). Group III oils contain <0.03 percent
sulfur and >90 percent saturates and have a viscosity index of
>120. Group II oils have a viscosity index of 80 to 120 and
contain <0.03 percent sulfur and >90 percent saturates. The
oil can also be derived from the hydroisomerization of wax, such as
slack wax or a Fischer-Tropsch synthesized wax. Such
"Gas-to-Liquid" oils are typically characterized as Group III.
[0026] The compositions of the present invention may include some
amount of Group I base oils, and even Group IV and Group V base
oils. Polyalphaolefins are categorized as Group IV. Group V
encompasses "all others". However, in some embodiments the
lubricating oil component of the invention contains no more than
20, 10, 5, or even 1 percent by weight Group I base oil. These
limits may also apply to Group IV or Group V base oils. In other
embodiments the lubricating oil present in the compositions of the
invention is at least 60, 70, 80, 90, or even 95 percent by weight
Group II and/or Group III base oil. In some embodiments the
lubricating oil present in the compositions of the invention is
essentially only Group II and/or Group III base oil, where small
amounts of other types of base oils may be present but not in
amounts that significantly impact the properties or performance of
the overall composition.
[0027] The oil of lubricating viscosity may be present in the range
from 60 to 99.9, from 88.5 to 99.6, from 96.9 to 99.5, or from 98.2
to 99.4 weight percent of the lubricating oil composition. Each oil
of lubricating viscosity described above may be used alone or as
mixtures of one or more thereof.
The Antioxidant Component
[0028] The antioxidant component includes: (i) an alkylated
diphenylamine, and (ii) a substituted hydrocarbyl mono-sulfide.
[0029] The alkylated diphenylamines suitable for use in the
invention may be represented by the formula:
##STR00001##
wherein R.sup.1 and R.sup.2 are independently a hydrogen or an
alkyl group containing about 5 to 20 carbon atoms; or a linear or
branched alkyl group containing 1 to 24 carbon atoms and q and r
are each independently 0, 1, 2, or 3, provided that the sum of q
and r is at least one. In some embodiments R.sup.1 and R.sup.2 are
independently hydrogen or alkyl groups containing 1 to 24, 4 to 20,
5 to 16, or 6 to 12 or even 10 carbon atoms. In any of the
embodiments described above, each R.sup.1 and R.sup.2 may be a
linear alkyl group, a branched alkyl group, or even an arylalkyl
group.
[0030] In some embodiments the alkylated diphenylamines of the
invention are bis-nonylated diphenylamine and bis-octylated
diphenylamine.
[0031] The alkylated diphenylamines are present in a range from
0.02 to 4, from 0.03 to 2.5, or from 0.05 to 1.5 pbw of the overall
lubricating composition. In some embodiments the alkylated
diphenylamines are present in a range from 0.01, 0.05, 0.10, 0.15,
0.20, 0.25, 0.3, or even 0.35 up to 1.0, 0.9, 0.8, 0.75, 0.7, or
even 0.6 pbw of the overall lubricating composition. In still other
embodiments the alkylated diphenylamines may be present from 0.35
or 0.375 up to 0.51, 0.75, 0.775 or 0.1 pbw of the overall
lubricating composition, or even 0.375 pbw. The alkylated
diphenylamines may be used alone or in mixtures thereof.
[0032] The substituted hydrocarbyl mono-sulfides suitable for use
in the invention may be represented by the formula:
##STR00002##
wherein R.sup.3 is a saturated or unsaturated branched or linear
alkyl group with about 8 to about 20 carbon atoms; R.sup.4,
R.sup.5, R.sup.6 and R.sup.7 are independently hydrogen or alkyl
containing about 1 to about 3 carbon atoms, or even 1 to 2 carbon
atoms. In some embodiments R.sup.3 contains from 8 to 20, 9 to 17,
10 to 15 or even 11 to 13 carbon atoms. R.sup.3 can be branched or
linear, but in some embodiments is branched.
[0033] In some embodiments the substituted hydrocarbyl monosulfides
include n-dodecyl-2-hydroxyethyl sulfide,
1-(tert-dodecylthio)-2-propanol, or combinations thereof. In some
embodiments the substituted hydrocarbyl monosulfide is
1-(tert-dodecylthio)-2-propanol.
[0034] The substituted hydrocarbyl monosulfides may be present in
the range from 0.02 to 4, 0.03 to 2.5, or 0.05 to 1.5 pbw of the
lubricating oil composition. In some embodiments the substituted
hydrocarbyl monosulfides are present in a range from 0.01, 0.03,
0.05, or even 0.08 up to 1.0, 0.8, 0.5, 0.3 or 0.1 pbw of the
overall lubricating composition. In still other embodiments the
substituted hydrocarbyl monosulfides may be present from 0.08 up to
0.1, or even at 0.09 pbw of the overall lubricating composition.
The substituted hydrocarbyl monosulfides may be used alone or
mixtures thereof.
[0035] The antioxidant package may optionally include sterically
hindered phenols represented by the formula:
##STR00003##
wherein R.sup.8 and R.sup.9 are independently branched or linear
alkyl groups containing about 1 to about 24, preferably about 4 to
about 18, and most preferably from about 4 to about 12 carbon
atoms.
[0036] R.sup.8 and R.sup.9 may be either a straight or branched
chain, branched is preferred. Preferably the phenol is butyl
substituted containing two t-butyl groups. When the t-butyl groups
occupy the 2,6-positions, the phenol is sterically hindered. q is
hydrogen or hydrocarbyl. Examples of suitable hydrocarbyl groups
include but are not limited to 2-ethylhexyl or n-butyl ester,
dodecyl or mixtures thereof.
[0037] Other optional sterically hindered phenols suitable for the
invention include but are not limited to those represented by the
formulae:
##STR00004##
wherein R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15
are either straight or branched chain and contain about 4 to about
18, preferably from about 4 to about 12 carbon atoms. Preferably
the phenol is butyl substituted.
[0038] R.sup.16 and R.sup.17 are independently hydrogen, an
arylalkyl group or a linear or branched alkyl group. R.sup.16 and
R.sup.17 are preferably in the para position. The arylalkyl or
alkyl groups contain about 1 to about 15, preferably about 1 to
about 10, and most preferably about 1 to about 5 carbon atoms. The
bridging group Y includes but is not limited to --CH.sub.2--
(methylene bridge) or --CH.sub.2OCH.sub.2-- (ether bridge).
[0039] Examples of methylene-bridged sterically hindered phenols
include but are not limited to 4,4'-methylenebis(6-tert-butyl
o-cresol), 4,4'-methylenebis(2-tert-amyl-o-cresol),
2,2'-methylenebis(4-methyl-6-tert-butylphenol),
4,4'-methylenebis(2,6-di-tertbutylphenol) or mixtures thereof.
[0040] In one embodiment the antioxidant is a hindered
ester-substituted phenol represented by the formula:
##STR00005##
wherein R.sup.18, R.sup.19 and R.sup.20 are straight or branched
alkyl group containing about 2 to about 22, preferably about 2 to
about 18, more preferably about 4 to about 8 carbon atoms. Specific
examples include but are not limited to alkyl groups such as
2-ethylhexyl or n-butyl ester, dodecyl or mixtures thereof.
[0041] The sterically hindered phenols are present in the range
from 0 to 13, from 0.02 to 4, from 0.03 to 2.5, or from 0.05 to 1.5
pbw of the lubricating oil composition. The sterically hindered
phenols may be used alone or in combination. In some embodiments
the compositions of the invention are essentially free or even free
of sterically hindered phenols.
[0042] In some embodiments the antioxidant component, whether it
contains one antioxidant or a mixture of two or more antioxidants,
may be present in the overall composition from 0.05 to 13 pbw, or
from 0.1 to 0.4 pbw, or from 0.05, 0.1, 0.2, or 0.3 up to 13, 0.9,
0.75, 0.6, or 0.5 pbw. In some embodiments the antioxidant
component is even present from 0.4 up to 0.9 or 0.5 pbw. In other
embodiments the antioxidant component is present from 0.45, 0.465,
or even 0.60 up to 0.87, 0.865, 0.70 or 0.65 pbw.
The Dispersant Component
[0043] The dispersant component includes: (i) a polyetheramine;
(ii) a borated succinimide dispersant; (iii) a non-borated
succinimide dispersant; (iv) a Mannich reaction product of a
dialkylamine, an aldehyde and a hydrocarbyl substituted phenol; or
any combination thereof. In some embodiments the dispersant
component is present from 0.05 to 0.5 pbw of the overall
composition.
[0044] Polyetheramines of the invention include compounds having
two or more consecutive ether groups and at least one primary,
secondary or tertiary amino group where the amine nitrogen has some
basicity. The polyetheramines of this invention include
poly(oxyalkylene) amines having a sufficient number of repeating
oxyalkylene units to render the poly(oxyalkylene)amine soluble in a
base oil while allowing acceptable performance in ASTM D1401
(Standard Test Method for Water Separability of Petroleum Oils and
Synthetic Fluids) test. Generally, poly(oxyalkylene)amines having
at least about 5 oxyalkylene units are suitable for use in the
present invention. Poly(oxyalkylene)amines can include:
hydrocarbylpoly(oxyalkylene)amines,
hydrocarbylpoly(oxyalkylene)polyamines, and derivatives of
polyhydric alcohols having at least two poly(oxyalkylene)amine
and/or poly(oxyalkylene)polyamine chains on the molecule of the
derivative. In one embodiment, the poly(oxyalkylene)amine for use
in the invention is represented by the formula
R--O-(AO).sub.m--R.sup.1--N--R.sup.2R.sup.3 wherein R is a
hydrocarbyl group of 1 to 50 carbon atoms, or about 8 to about 30
carbon atoms; A is an alkylene group having 2 to 18 carbon atoms or
2 to 6 carbon atoms; m is a number from 1 to 50; R.sup.1 is an
alkylene group having 2 to 18 carbon atoms or 2 to 6 carbon atoms;
and R.sup.2 and R.sup.3 are independently hydrogen, a hydrocarbyl
group or --[R.sup.4N(R.sup.5)].sub.nR.sup.6 wherein R.sup.4 is an
alkylene group having 2 to 6 carbon atoms, R.sup.5 and R.sup.6 are
independently hydrogen or a hydrocarbyl group, and n is a number
from 1 to 7.
[0045] In another embodiment, the poly(oxyalkylene)amine of the
present invention can be represented by the formula:
RO[CH.sub.2CH(CH.sub.2CH.sub.3)O].sub.mCH.sub.2CH.sub.2CH.sub.2NH.sub.2
wherein R is an aliphatic group or alkyl-substituted phenyl group
of 8 to 30 carbon atoms; and m is a number from 12 to 30. In yet
another embodiment, the poly(oxyalkylene)amine of the present
invention can be represented by the formula:
CH.sub.3CH(CH.sub.3)[CH.sub.2CH(CH.sub.3)].sub.2CH(CH.sub.3)CH.sub.2CH.su-
b.2O--[CH.sub.2CH(CH.sub.2CH.sub.3)O].sub.mCH.sub.2CH.sub.2CH.sub.2NH.sub.-
2 wherein m is a number from about 16 to about 28.
Poly(oxyalkylene)amines of the present invention can have a
molecular weight in the range from about 300 to about 5,000.
[0046] The polyetheramines of the present invention can be prepared
by initially condensing an alcohol or alkylphenol with an alkylene
oxide, mixture of alkylene oxides or with several alkylene oxides
in sequential fashion in a 1:1-50 mole ratio of hydric compound to
alkylene oxide to form a polyether intermediate. U.S. Pat. Nos.
5,112,364 and 5,264,006 provide reaction conditions for preparing a
polyether intermediate.
[0047] The alcohols can be monohydric or polyhydric, linear or
branched, saturated or unsaturated and having 1 to 50 carbon atoms,
or from 8 to 30 carbon atoms, or from 10 to 16 carbon atoms.
Branched alcohols of the present invention can include Guerbet
alcohols, as described in U.S. Pat. No. 5,264,006, which generally
contain between 12 and 40 carbon atoms and can be represented by
the formula R--CH(CH.sub.2CH.sub.2R)CH.sub.2OH where R is a
hydrocarbyl group. In one embodiment, the alkyl group of the
alkylphenols can be 1 to 50 carbon atoms, or 2 to 24 carbon atoms,
or 10 to 20 carbon atoms.
[0048] In one embodiment, the alkylene oxides include
1,2-epoxyalkanes having 2 to 18 carbon atoms, or 2 to 6 carbon
atoms. In yet another embodiment, the alkylene oxides can be
ethylene oxide, propylene oxide and butylene oxide. Especially
useful is propylene oxide, butylene oxide, or a mixture thereof.
The number of alkylene oxide derived units in the polyether
intermediate can be 1-50, or 12-30, or 16-28.
[0049] The polyether intermediates can be converted to
polyetheramines by several methods. The polyether intermediate can
be converted to a polyetheramine by a reductive amination with
ammonia, a primary amine or a polyamine as described in U.S. Pat.
Nos. 5,112,364 and 5,752,991. In one embodiment, the polyether
intermediate can be converted to a polyetheramine via an addition
reaction of the polyether to acrylonitrile to form a nitrile which
is then hydrogenated to form the polyetheramine. U.S. Pat. No.
5,264,006 provides reaction conditions for the cyanoethylation of
the polyether with acrylonitrile and the subsequent hydrogenation
to form the polyetheramine. In yet another embodiment, the
polyether intermediate or poly(oxyalkylene) alcohol is converted to
the corresponding poly(oxyalkylene) chloride via a suitable
chlorinating agent followed by displacement of chlorine with
ammonia, a primary or secondary amine, or a polyamine as described
in U.S. Pat. No. 4,247,301.
[0050] In some embodiments the polyetheramine of the present
invention is derived from the reaction of a mixture of alcohols
containing from 10 to 18 carbon atoms, an alkoxylate and an
amine.
[0051] In some embodiments the compositions of the present
invention include a polyetheramine dispersant where the
polyetheramine is present in the overall composition from 0.07 to
0.6 pbw, or from 0.09 to 0.5 pbw.
[0052] In addition, in some of these embodiments, (i) the
antioxidant component is present in the overall composition at less
than 0.865 pbw; (ii) the composition is free of N-alkyl sarcosines;
(iii) the composition contains less than 0.15 pbw of fatty
carboxylic acids; or any combination thereof.
[0053] Another type of dispersant, which can be used in the
invention, is a succinimide. Succinimide dispersants are well known
in the field of lubricants and include primarily what are sometimes
referred to as "ashless" dispersants because they do not contain
ash-forming metals and they do not normally contribute any ash
forming metals when added to a lubricant. Succinimide dispersants
are the reaction product of a hydrocarbyl substituted succinic
acylating agent and an amine containing at least one hydrogen
attached to a nitrogen atom. The term "succinic acylating agent"
refers to a hydrocarbon-substituted succinic acid or succinic
acid-producing compound (which term also encompasses the acid
itself). Such materials typically include hydrocarbyl-substituted
succinic acids, anhydrides, esters (including half esters) and
halides.
[0054] Succinic based dispersants have a wide variety of chemical
structures including typically structures such as:
##STR00006##
[0055] In the above structure, each R.sup.1 is independently a
hydrocarbyl group, which may be bound to multiple succinimide
groups, typically a polyolefin-derived group having a number
average molecular weight (Mn) of 500 or 700 to 10,000. Typically
the hydrocarbyl group is an alkyl group, frequently a
polyisobutylene group derived from polyisobutylene with a Mn of 500
or 700 to 5000, or 1500 or 2000 to 5000. Alternatively expressed,
the R.sup.1 groups can contain 40 to 500 carbon atoms or at least
50 to 300 carbon atoms, e.g., aliphatic carbon atoms. The R.sup.2
are alkylene groups, commonly ethylene (C.sub.2H.sub.4) groups.
Such molecules are commonly derived from reaction of an alkenyl
acylating agent with a polyamine, and a wide variety of linkages
between the two moieties is possible beside the simple imide
structure shown above, including a variety of amides and quaternary
ammonium salts. Succinimide dispersants are more fully described in
U.S. Pat. Nos. 4,234,435, 3,172,892, and 6,165,235.
[0056] The polyalkenes from which the substituent groups are
derived are typically homopolymers and interpolymers of
polymerizable olefin monomers of 2 to 16 carbon atoms; usually 2 to
6 carbon atoms.
[0057] The olefin monomers from which the polyalkenes are derived
are polymerizable olefin monomers characterized by the presence of
one or more ethylenically unsaturated groups (i.e.,
>C.dbd.C<); that is, they are mono-olefinic monomers such as
ethylene, propylene, 1-butene, isobutene, and 1-octene or
polyolefinic monomers (usually diolefinic monomers) such as
1,3-butadiene, and isoprene. These olefin monomers are usually
polymerizable terminal olefins; that is, olefins characterized by
the presence in their structure of the group >C.dbd.CH.sub.2.
Relatively small amounts of non-hydrocarbon substituents can be
included in the polyolefin, provided that such substituents do not
substantially interfere with formation of the substituted succinic
acid acylating agents. Each R.sup.1 group may contain one or more
reactive groups, i.e. succinic groups.
[0058] The amines which are reacted with the succinic acylating
agents to form the carboxylic dispersant composition can be
monoamines or polyamines. In either case they will be characterized
by the formula R.sup.4R.sup.5NH wherein R.sup.4 and R.sup.5 are
each independently hydrogen, hydrocarbon, amino-substituted
hydrocarbon, hydroxy-substituted hydrocarbon, alkoxy-substituted
hydrocarbon, amino, carbamyl, thiocarbamyl, guanyl, or acylimidoyl
groups provided that no more than one of R.sup.4 and R.sup.5 is
hydrogen. In all cases, therefore, they will be characterized by
the presence within their structure of at least one H--N<group.
Therefore, they have at least one primary (i.e., H.sub.2N--) or
secondary amino (i.e., H--N<) group. Examples of monoamines
include ethylamine, diethylamine, n-butylamine, di-n-butylamine,
allylamine, isobutylamine, cocoamine, stearylamine, laurylamine,
methyllaurylamine, oleylamine, N-methyl-octylamine, dodecylamine,
and octadecylamine.
[0059] The polyamines from which the dispersant is derived include
principally alkylene amines conforming, for the most part, to the
formula
##STR00007##
wherein t is an integer typically less than 10, A is hydrogen or a
hydrocarbyl group typically having up to 30 carbon atoms, and the
alkylene group is typically an alkylene group having less than 8
carbon atoms. The alkylene amines include principally, ethylene
amines, hexylene amines, heptylene amines, octylene amines, other
polymethylene amines. They are exemplified specifically by:
ethylene diamine, diethylene triamine, triethylene tetramine,
propylene diamine, decamethylene diamine, octamethylene diamine,
di(heptamethylene) triamine, tripropylene tetramine, tetraethylene
pentamine, trimethylene diamine, pentaethylene hexamine,
di(-trimethylene) triamine. Higher homologues such as are obtained
by condensing two or more of the above-illustrated alkylene amines
likewise are useful. Tetraethylene pentamine is particularly
useful.
[0060] The ethylene amines, also referred to as polyethylene
polyamines, are especially useful. They are described in some
detail under the heading "Ethylene Amines" in Encyclopedia of
Chemical Technology, Kirk and Othmer, Vol. 5, pp. 898-905,
Interscience Publishers, New York (1950).
[0061] Hydroxyalkyl-substituted alkylene amines, i.e., alkylene
amines having one or more hydroxyalkyl substituents on the nitrogen
atoms, likewise are useful. Examples of such amines include
N-(2-hydroxyethyl)ethylene diamine,
N,N'-bis(2-hydroxyethyl)-ethylene diamine,
1-(2-hydroxyethyl)piperazine, monohydroxy-propyl)-piperazine,
di-hydroxypropyl-substituted tetraethylene pentamine,
N-(3-hydroxypropyl)-tetra-methylene diamine, and
2-heptadecyl-1-(2-hydroxyethyl)-imidazoline.
[0062] Higher homologues, such as are obtained by condensation of
the above-illustrated alkylene amines or hydroxy alkyl-substituted
alkylene amines through amino radicals or through hydroxy radicals,
are likewise useful. Condensed polyamines are formed by a
condensation reaction between at least one hydroxy compound with at
least one polyamine reactant containing at least one primary or
secondary amino group and are described in U.S. Pat. No. 5,230,714
(Steckel).
[0063] The succinimide dispersant is referred to as such since it
normally contains nitrogen largely in the form of imide
functionality, although it may be in the form of amine salts,
amides, imidazolines as well as mixtures thereof. To prepare the
succinimide dispersant, one or more of the succinic acid-producing
compounds and one or more of the amines are heated, typically with
removal of water, optionally in the presence of a normally liquid,
substantially inert organic liquid solvent/diluent at an elevated
temperature, generally in the range of 80.degree. C. up to the
decomposition point of the mixture or the product; typically
100.degree. C. to 300.degree. C.
[0064] The succinic acylating agent and the amine (or organic
hydroxy compound, or mixture thereof) are typically reacted in
amounts sufficient to provide at least one-half equivalent, per
equivalent of acid-producing compound, of the amine (or hydroxy
compound, as the case may be). Generally, the maximum amount of
amine present will be about 2 moles of amine per equivalent of
succinic acylating agent. For the purposes of this invention, an
equivalent of the amine is that amount of the amine corresponding
to the total weight of amine divided by the total number of
nitrogen atoms present. The number of equivalents of succinic
acid-producing compound will vary with the number of succinic
groups present therein, and generally, there are two equivalents of
acylating reagent for each succinic group in the acylating
reagents. Additional details and examples of the procedures for
preparing the succinimide detergents of the present invention are
included in, for example, U.S. Pat. Nos. 3,172,892; 3,219,666;
3,272,746; 4,234,435; 6,440,905 and 6,165,235.
[0065] In some embodiments the compositions of the invention
include a non-borated succinimide dispersant derived from
polyisobutylene having a number average molecular weight from 500
to 3000 and polyethylenepolyamines.
[0066] In such embodiments the non-borated succinimide dispersant
may be present in the overall composition from 0.06 to 0.35 pbw, or
from 0.05, 0.06, 0.055, 0.065, or even 0.057 up to 0.5, 0.35, 0.33,
0.325, or even 0.285 pbw. In some embodiments the non-borated
succinimide dispersant is present from 0.057 to 0.285 pbw. In other
embodiments the non-borated succinimide dispersant is present from
0.057 to 0.325 pbw.
[0067] In some of these embodiments the composition contains less
than 0.1 pbw of fatty carboxylic acids.
[0068] In some embodiments the succinimide dispersants above may be
borated. Borated dispersants are well-known materials and can be
prepared by treating one or more of dispersants described above
with a borating agent such as boric acid. Typical conditions
include heating the dispersant with boric acid at 100 to 150
degrees C. The dispersants may also be treated by reaction with
maleic anhydride as described in PCT application US99/23940 filed
13 Oct. 1999.
[0069] In some embodiments the compositions of the invention
include a borated succinimide dispersant derived from
polyisobutylene having a number average molecular weight from 500
to 3000 and polyethylenepolyamines.
[0070] In such embodiments the borated succinimide dispersant may
be present in the overall composition from 0.07 to 0.4 pbw, or from
0.05, 0.07, or even 0.067 up to 0.5, 0.4, 0.35 or even 0.335
pbw.
[0071] In some of these embodiments the composition contains less
than 0.1 pbw of fatty carboxylic acids.
[0072] The dispersant of the invention can be a Mannich dispersant.
Mannich dispersants are the reaction product of a
hydrocarbyl-substituted phenol, an aldehyde, and an amine or
ammonia, but in this invention generally a dialkylamine. The
hydrocarbyl substituent of the hydrocarbyl-substituted phenol can
have 10 to 400 carbon atoms, in another instance 30 to 180 carbon
atoms, and in a further instance 10 or 40 to 110 carbon atoms. This
hydrocarbyl substituent can be derived from an olefin or a
polyolefin. Useful olefins include alpha-olefins, such as 1-decene,
which are commercially available.
[0073] The polyolefins which can form the hydrocarbyl substituent
can be prepared by polymerizing olefin monomers by well known
polymerization methods and are also commercially available. The
olefin monomers include monoolefins, including monoolefins having 2
to 10 carbon atoms such as ethylene, propylene, 1-butene,
isobutylene, and 1-decene. An especially useful monoolefin source
is a C.sub.4 refinery stream having a 35 to 75 weight percent
butene content and a 30 to 60 weight percent isobutene content.
Useful olefin monomers also include diolefins such as isoprene and
1,3-butadiene. Olefin monomers can also include mixtures of two or
more monoolefins, of two or more diolefins, or of one or more
monoolefins and one or more diolefins. Useful polyolefins include
polyisobutylenes having a number average molecular weight of 140 to
5000, in another instance of 400 to 2500, and in a further instance
of 140 or 500 to 1500. The polyisobutylene can have a vinylidene
double bond content of 5 to 69 percent, in a second instance of 50
to 69 percent, and in a third instance of 50 to 95 percent. The
polyolefin can be a homopolymer prepared from a single olefin
monomer or a copolymer prepared from a mixture of two or more
olefin monomers. Also possible as the hydrocarbyl substituent
source are mixtures of two or more homopolymers, two or more
copolymers, or one or more homopolymers and one or more
copolymers.
[0074] The hydrocarbyl-substituted phenol can be prepared by
alkylating phenol with an olefin or polyolefin described above,
such as a polyisobutylene or polypropylene, using well-known
alkylation methods.
[0075] The aldehyde used to form the Mannich dispersant can have 1
to 10 carbon atoms, and is generally formaldehyde or a reactive
equivalent thereof such as formalin or paraformaldehyde.
[0076] The amine used to form the Mannich dispersant can be a
monoamine or a polyamine, including alkanolamines having one or
more hydroxyl groups. Useful amines include ethanolamine,
diethanolamine, methylamine, dimethylamine, ethylenediamine,
dimethylaminopropylamine, diethylenetriamine and
2-(2-amino-ethylamino) ethanol. The Mannich dispersant can be
prepared by reacting a hydrocarbyl-substituted phenol, an aldehyde,
and an amine as described in U.S. Pat. No. 5,697,988. In one
embodiment of this invention the Mannich reaction product is
prepared from an alkylphenol derived from a polyisobutylene,
formaldehyde, and an amine that is a primary monoamine, a secondary
monoamine, or an alkylenediamine, in particular, ethylenediamine or
dimethylamine. In some embodiments the Mannich is prepared from a
dialkylamine or a dialkenylamine.
[0077] The Mannich reaction product of the present invention can be
prepared by reacting the alkyl-substituted hydroxyaromatic
compound, aldehyde and polyamine by well known methods including
the method described in U.S. Pat. No. 5,876,468.
[0078] The Mannich reaction product can be prepared by well known
methods generally involving reacting the hydrocarbyl substituted
hydroxy aromatic compound, an aldehyde and an amine at temperatures
between 50 to 200.degree. C. in the presence of a solvent or
diluent while removing reaction water as described in U.S. Pat. No.
5,876,468.
[0079] In some embodiments the compositions of the present
invention contain a Mannich reaction product derived from the
reaction of a dialkylamine, formaldehyde, and a polyisobutylene
substituted phenol where the polyisobutylene has a number average
molecular weight from 500 to 3000. The Mannich dispersant may be
present in the overall composition from 0.07 to 0.44 pbw, from
0.05, 0.07, or even 0.088 up to 0.5, 0.45, or even 0.44 pbw.
Additional Additives
[0080] Optionally the lubricating compositions of the invention
include one or more additional additives, which may be selected
from the group including: a foam inhibitor, a demulsifier, a pour
point depressant, or mixtures thereof. The optional additives are
present in the range from 0.0005 to 1.3, from 0.00075 to 0.5, from
0.001 to 0.4, or from 0.0015 to 0.3 pbw of the lubricating oil
composition. The optional additives may be used alone or mixtures
thereof.
[0081] Antifoams, also known as foam inhibitors, are known in the
art and include but are not limited to organic silicones and
non-silicon foam inhibitors. Examples of organic silicones include
dimethyl silicone and polysiloxanes. Examples of non-silicon foam
inhibitors include but are not limited to poly(ethyl acrylate),
poly(2-ethylhexylacrylate), copolymers of ethyl acrylate and
2-ethylhexy acrylate and optionally vinyl acetate, poly vinyl
acetate, polyethers, polyacrylates and mixtures thereof. In some
embodiments the antifoam is a polyacrylate. Antifoams may be
present in the composition from 0.001 to 0.012 or 0.004 pbw or even
0.001 to 0.003.
[0082] Demulsifiers are known in the art and include but are not
limited to derivatives of propylene oxide, ethylene oxide,
polyoxyalkylene alcohols, alkyl amines, amino alcohols, diamines or
polyamines reacted sequentially with ethylene oxide or substituted
ethylene oxides or mixtures thereof. Examples of demulsifiers
include polyethylene glycols, polyethylene oxides, polypropylene
oxides, (ethylene oxide-propylene oxide) polymers and mixtures
thereof. In some embodiments the demulsifiers is a polyether.
Demulsifiers may be present in the composition from 0.002 to 0.012
pbw.
[0083] Pour point depressants are known in the art and include but
are not limited to esters of maleic anhydride-styrene copolymers,
polymethacrylates; polyacrylates; polyacrylamides; condensation
products of haloparaffin waxes and aromatic compounds; vinyl
carboxylate polymers; and terpolymers of dialkyl fumarates, vinyl
esters of fatty acids, ethylene-vinyl acetate copolymers, alkyl
phenol formaldehyde condensation resins, alkyl vinyl ethers and
mixtures thereof.
[0084] The compositions of the invention may also include a rust
inhibitor. Suitable rust inhibitors include hydrocarbyl amine salts
of alkylphosphoric acid, hydrocarbyl amine salts of
dialkyldithiophosphoric acid, hydrocarbyl amine salts of
hydrocarbyl aryl sulphonic acid, fatty carboxylic acids or esters
thereof, an ester of a nitrogen-containing carboxylic acid, an
ammonium sulfonate, an imidazoline, or any combination thereof; or
mixtures thereof.
[0085] Suitable hydrocarbyl amine salts of alkylphosphoric acid of
the invention are represented by the following formula:
##STR00008##
wherein R.sup.21 and R.sup.22 are independently hydrogen, alkyl
chains or hydrocarbyl, preferably at least one of R.sup.21 and
R.sup.22 are hydrocarbyl. R.sup.21 and R.sup.22 contain about 4 to
about 30, preferably about 8 to about 25, more preferably about 10
to about 20, and most preferably about 13 to about 19 carbon atoms.
R.sup.23, R.sup.24 and R.sup.25 are independently hydrogen, alkyl
branched or linear alkyl chains with about 1 to about 30,
preferably about 4 to about 24, even more preferably about 6 to
about 20, and most preferably about 10 to about 16 carbon atoms.
R.sup.23, R.sup.24 and R.sup.25 are independently hydrogen, alkyl
branched or linear alkyl chains, preferably at least one, and most
preferably two of R.sup.23, R.sup.24 and R.sup.25 are hydrogen.
[0086] Examples of alkyl groups suitable for R.sup.23, R.sup.24 and
R.sup.25 include but are not limited to butyl, sec butyl, isobutyl,
tert-butyl, pentyl, n-hexyl, sec hexyl, n-octyl, 2-ethyl, hexyl,
decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,
hexadecyl, heptadecyl, octadecyl, octadecenyl, nonodecyl, eicosyl
or mixtures thereof.
[0087] In one embodiment the hydrocarbyl amine salt of an
alkylphosphoric acid is the reaction product of a C.sub.14 to
C.sub.18 alkylated phosphoric acid with Primene 81R (produced and
sold by Rohm & Haas) which is a mixture of C.sub.11 to C.sub.14
tertiary alkyl primary amines.
[0088] Hydrocarbyl amine salts of dialkyldithiophosphoric acid of
the invention used in the rust inhibitor package are represented by
the formula:
##STR00009##
wherein R.sup.26 and R.sup.27 are independently branched or linear
alkyl groups. R.sup.26 and R.sup.27 contain about 3 to about 30,
preferably about 4 to about 25, more preferably about 5 to about
20, and most preferably about 6 to about 19 carbon atoms. R.sup.23,
R.sup.24 and R.sup.25 are as described above.
[0089] Examples of hydrocarbyl amine salts of
dialkyldithiophosphoric acid of the invention include but are not
limited to the reaction product(s) of heptylated or octylated or
nonylated dithiophosphoric acids with ethylene diamine, morpholine
or Primene 81R or mixtures thereof.
[0090] Suitable hydrocarbyl amine salts of hydrocarbyl aryl
sulphonic acids used in the rust inhibitor package of the invention
are represented by the formula:
##STR00010##
wherein Cy is a benzene or naphthalene ring. R.sup.28 is a
hydrocarbyl group with about 4 to about 30, preferably about 6 to
about 25, more preferably about 8 to about 20 carbon atoms. z is
independently 1, 2, 3, or 4 and most preferably z is 1 or 2.
R.sup.23, R.sup.24 and R.sup.25 are as described above.
[0091] Examples of hydrocarbyl amine salts of hydrocarbyl aryl
sulphonic acid of the invention include but are not limited to the
ethylene diamine salt of dinonyl naphthalene sulphonic acid.
[0092] Examples of suitable fatty carboxylic acids or esters
thereof include glycerol monooleate and oleic acid. An example of a
suitable ester of a nitrogen-containing carboxylic acid includes
oleyl sarcosine.
[0093] The rust inhibitors may be present in the range from
0.02-0.2, from 0.03 to 0.15, from 0.04 to 0.12, or from 0.05 to 0.1
pbw of the lubricating oil composition. The rust inhibitors of the
invention may be used alone or in mixtures thereof.
[0094] The lubricating compositions of the invention may also
include a metal deactivator. Metal deactivators are used to
neutralise the catalytic effect of metal for promoting oxidation in
lubricating oil. Suitable metal deactivators include but are not
limited to triazoles, tolyltriazoles, a thiadiazole, or
combinations thereof, as well as derivatives thereof. Examples
include derivatives of benzotriazoles, benzimidazole,
2-alkyldithiobenzimidazoles, 2-alkyldithiobenzothiazoles,
2-(N,N'-dialkyldithio-carbamoyl)benzothiazoles,
2,5-bis(alkyl-dithio)-1,3,4-thiadiazoles,
2,5-bis(N,N'-dialkyldithiocarbamoyl)-1,3,4-thiadiazoles,
2-alkyldithio-5-mercapto thiadiazoles or mixtures thereof.
[0095] In some embodiments the metal deactivator is a hydrocarbyl
substituted benzotriazole compound. The benzotriazole compounds
with hydrocarbyl substitutions include at least one of the
following ring positions 1- or 2- or 4- or 5- or 6- or
7-benzotriazoles. The hydrocarbyl groups contain about 1 to about
30, preferably about 1 to about 15, more preferably about 1 to
about 7 carbon atoms, and most preferably the metal deactivator is
5-methylbenzotriazole used alone or mixtures thereof.
[0096] In some embodiments the lubricating compositions on the
invention include a substituted triazole, and may be a substituted
benzotriazole. In some of these embodiments the hydrocarbyl group
linked to one of the nitrogen atoms in the triazole ring does not
contain any oxygen atoms.
[0097] In some embodiments the substituted triazole has a single
hydrocarbyl group linked to a nitrogen atom on the triazole ring.
In some embodiments the substituted triazole contains an aryl group
linked and a single hydrocarbyl group linked to a nitrogen atom on
the triazole ring.
[0098] In some embodiments the substituted triazole may be
represented by the following formulas:
##STR00011##
or a combination thereof; where, for both formula X and formula XI:
n is an integer from 0 to 4; --R is a hydrocarbyl group; --Y is
--R.sup.1 or --(R.sup.2).sub.m--NR.sup.3R.sup.3 where --R.sup.1 is
a hydrocarbyl group, --R.sup.2-- is a hydrocarbylene group, m is 0
or 1 or 2, and each --R.sup.3 is independently hydrogen or a
hydrocarbyl group, so long as the --R.sup.1, --R.sup.2--, and
--R.sup.3 overall contain from 7 or even 9 to 40 carbon atoms
combined. In some embodiments the substituted triazole of the
invention is represented by Formula (X).
[0099] In some embodiments: n may be from 0 or 1 up to 4, 3, 2 or
1; R may be a hydrocarbyl group and may contain from 1 to 50 carbon
atoms, or from 1 or 2 up to 40, 30, 20, 18 or even 8 carbon atoms,
and in some embodiments contains 1 or 2 carbon atoms; within Y, m
may be 0 or 1 or 2 and in some embodiments 1 or 2; R.sup.1 may be a
hydrocarbyl group and may contain from 1, 6, 10 or 12 up to 40, 30,
20, or even 18 carbon atoms; R.sup.2 may be a hydrocarbylene group
and may contain from 1, 6, 10 or 12 up to 40, 30, 20, 18, or even 8
carbon atoms or even 1 to 8 carbon atoms and in some embodiments
contains 1 carbon atom; R.sup.3 may be hydrogen or a hydrocarbyl
group and may contain from 1, 6, 10 or 12 up to 40, 30, 20, 18, or
even 8 carbon atoms or even 1 to 8 carbon atoms and in some
embodiments contains 8 carbon atoms, so long as Y contains from 8
to 40 carbon atoms.
[0100] In some embodiments --Y is --R.sup.1, --R.sup.2--NHH,
--R.sup.2--NHR.sup.3, --R.sup.2--NR.sup.3R.sup.3 where the various
R groups can have any of definitions provided above again so long
as the Y group contains overall 6 or 7 or even 9 up to 40 carbon
atoms.
[0101] In some embodiments all of the hydrocarbyl groups described
above are free of oxygen atoms. In some embodiments all of the
hydrocarbyl groups described above are free of all heteroatoms and
are purely alkyl groups except for a single nitrogen atom present
in the Y group.
[0102] The substituted triazole of the invention may be prepared by
condensing a basic triazole via its acidic --NH group with an
aldehyde and an amine. In some embodiments the substituted triazole
is the reaction product of a triazole, an aldehyde and an amine.
Suitable triazoles that may be used to prepare the substituted
triazole of the invention include benzotriazole, while suitable
aldehydes include formaldehyde and reactive equivalents like
formalin, while suitable amines include primary or secondary
amines. In some embodiments the amines are secondary amines and
further are branched amines. In still further embodiments the
amines are beta-branched amines, for examples bis-2-ethylhexyl
amine.
[0103] The metal deactivators may be present in the range from
0.001 to 0.1, from 0.01 to 0.04 or from 0.015 to 0.03 pbw of the
lubricating oil composition. Metal deactivators may also be present
in the composition from 0.002 or 0.004 to 0.02 pbw. The metal
deactivator may be used alone or mixtures thereof.
INDUSTRIAL APPLICATION
[0104] The invention further provides a process for the preparation
of lubricating oil compositions. The lubricating oil compositions
are prepared by the steps comprising: a) mixing and/or dissolving
in one another an antioxidant component that includes the
combination of an alkylated diphenylamine, and a substituted
hydrocarbyl mono-sulfide, a dispersant component which includes at
least one of a polyetheramine, a borated succinimide dispersant, a
non-borated succinimide dispersant, or a Mannich reaction product
of a dialkylamine, an aldehyde and a hydrocarbyl substituted
phenol. Optionally one or more additional additives may also be
mixed into the oil. The materials are mixed until the additives are
substantially or wholly dissolved, in some embodiments at elevated
temperatures in the range 40.degree. C. to 110.degree. C., or
50.degree. C. to 95.degree. C., or even 55.degree. C. to 85.degree.
C.; and for a period of time in the range 30 seconds to 24 hours, 2
minutes to 8 hours, or 5 minutes to 4 hours; and at pressures in
the range 700 mm of Hg to 2000 mm of Hg, 750 mm of Hg to 900 mm of
Hg, or 755 mm of Hg to 800 mm of Hg.
[0105] The order of addition of the additives is not overly
limited. The optional additives may be mixed in at the same time as
the other components or at a later time using any of the mixing
procedures described above.
[0106] In some embodiments a portion of oil or similar diluent is
present with the components and the components are mixed into the
oil. In other embodiments a minimal amount of oil or diluent is
present, other than that amount inherently present in the additive
from their means of production and preparation and additional base
oil is added after the component have been mixed. In any event the
described processes results in lubricating compositions.
[0107] In some embodiments the lubricating oil compositions may be
prepared from a concentrate comprising the steps of: a) mixing all
of the components described above with minimal oil and/or diluent
present, other than optionally some relatively small amount to
allow for reasonable handling properties. The resulting concentrate
may then be used in the preparation of a lubricating composition by
mixing the concentrate with an effective amount of base oil or
mixtures thereof resulting in a finished fluid. Optional additives
may be added to the concentrate or to the resulting final fluid.
These optional additives include any of those described above. In
some embodiments these optional additives include a foam inhibitor,
a demulsifier, a viscosity modifier, a pour point depressant, or
mixtures thereof, and may be added such that they are present in
the overall compositions in the range about 0, 0.01, 0.1 or even
0.25 or up to about 13, 10, 8 or even 6 pbw.
[0108] The compositions of the present invention may be used as
industrial fluids, hydraulic fluids, turbine oils and circulating
oils and combinations thereof. In some embodiments the compositions
are used in steam and gas turbine systems. The use of the
lubricating oil composition in such systems may prevent the
formation of filter plugging deposits and sludge in turbines, or
may provide at least one improved property selected from rust
inhibition, oxidation inhibition and mixtures thereof. The
invention further provides a lubricating oil composition that does
not substantially react with zinc and/or calcium which may also
prevent the formation of sludge and particulate material that
accumulates, plugging the fine filters.
[0109] The invention further provides a method of lubricating a
steam or gas turbine comprising the steps of supplying to said
turbine any of the lubricating compositions described herein.
[0110] The invention further provides a method of improving the
cleanliness of a steam or gas turbine comprising the steps of
supplying to said turbine any of the lubricating compositions
described herein. Operating the turbine with the described
lubricating composition will result in improved cleanliness
compared systems operated with conventional lubricants,
particularly those formulated in Group II and Group III oils.
Specific Embodiment
[0111] The invention will be further illustrated by the following
examples, which set forth particularly advantageous embodiments.
While the examples are provided to illustrate the invention, they
are not intended to limit it.
Comparative Example Set
[0112] Three comparative examples are prepared in order to better
demonstrate the effects of the compositions of the present
invention. These comparative examples are then included in each of
the example sets below. As with all of the examples below, other
additives are also present in the various formulations. While
differences between example formulations are noted, full
formulation details are not provided where they are not considered
critical to the results of the testing and/or where the specific
details are not believed to impact the results across samples.
[0113] Comparative Examples 1, 2 and 3 are each prepared in a blend
of Group III base oils. This same blend of Group III base oils is
used in the preparation of all of the examples described herein
unless otherwise noted. All the formulations provided below are
based on 100 pbw of the base oil. Comparative Examples 1, 2 and 3
also include a polyether demulsifier, an antiwear agent, an
antifoam, and a metal deactivator. Comparative Examples 1 and 2
contain the same polyether demulsifier while Comparative Example 3
contains a different polyether demulsifier. Comparative Example 1
contains no dispersant, 0.375 pbw alkylated diphenyl amine
antioxidant and 0.09 pbw substituted hydrocarbyl mono-sulfide.
Comparative Example 2 contains no dispersant, 0.51 pbw alkylated
diphenyl amine antioxidant, 0.09 pbw substituted hydrocarbyl
mono-sulfide, and 0.12 pbw of a sterically hindered phenol
antioxidant. Comparative Example 3 contains no dispersant, 0.775
pbw alkylated diphenyl amine antioxidant and 0.09 pbw substituted
hydrocarbyl mono-sulfide. The formulation details and test results
obtained for the comparative examples are included in the summary
table below for each of the example sets.
Example Set 1
[0114] A set of examples is prepared where the formulations contain
a polyetheramine dispersant. The tables below summarize these
formulations, including the comparative formulations described
above. Except for the differences noted in the tables and their
footnotes, the formulations of the listed examples are
substantially equivalent. The values in the tables are pbw.
TABLE-US-00001 TABLE 1-1 Details of Comparative Examples and
Examples 1-A to 1-E Comp Comp Comp Ex Ex Ex Ex Ex Component Ex
1.sup.1 Ex 2.sup.2 Ex 3.sup.3 1-A.sup.4 1-B.sup.5 1-C.sup.6
1-D.sup.7 1-E.sup.8 Base Oil Grp III Grp III Grp III Grp III Grp
III Grp II Grp II Grp III Alkylated 0.375 0.510 0.775 0.375 0.375
0.375 0.375 0.775 Diphenylamine Subst Mono- 0.09 0.09 0.09 0.09
0.09 0.09 0.09 0.09 Sulfide Polyetheramine 0.0 0.0 0.0 0.1 0.5 0.5
0.5 0.5 Dispersant Borated 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Succinimide Non-Borated 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Succinimide
Mannich 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Dispersant
.sup.1Comparative Example 1 also contains a polyether demulsifier,
an antiwear agent, an antifoam, and metal deactivator in
conventional amounts, referred to below as Additive Package I.
.sup.2Comparative Example 2 also contains Additive Package I.
.sup.3Comparative Example 3 contains the same additives and the
same amounts as those in Additive Package I except that the
specific polyether demulsifier is different from that used in the
other examples. This set of additives is referred to as Additive
Package II below. .sup.4Example 1-A also contains Additive Package
I. .sup.5Example 1-B also contains Additive Package I.
.sup.6Example 1-C also contains Additive Package I. .sup.7Example
1-D also contains Additive Package I. .sup.8Example 1-E also
contains Additive Package II.
TABLE-US-00002 TABLE 1-2 Details of Examples 1-F to 1-M Ex Ex Ex Ex
Ex Ex Ex Ex Component 1-F.sup.9 1-G.sup.10 1-H.sup.11 1-I.sup.12
1-J.sup.13 1-K.sup.14 1-L.sup.15 1-M.sup.16 Base Oil Blend Grp III
Grp III Grp III Grp III Grp III Grp III Grp III Grp II Alkylated
0.375 0.375 0.375 0.375 0.375 0.375 0.375 0.375 Diphenylamine Subst
Mono- 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.09 Sulfide
Polyetheramine 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.4 Dispersant Borated
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Succinimide Non-Borated 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 Succinimide Mannich 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 Dispersant .sup.9Example 1-F also contains Additive Package II,
as defined in Table 1-1 above. .sup.10Example 1-G contains the
polyether demulsifier and metal deactivator of Additive Package II
but does not contain the antiwear agent or the antifoam. This set
of additives is referred to as Additive Package III below. The
example also contains a fatty carboxylic acid. .sup.11Example 1-H
also contains Additive Package III and a fatty carboxylic ester.
.sup.12Example 1-I also contains Additive Package III and a
sarcosine corrosion inhibitor. .sup.13Example 1-J also contains
Additive Package III and a fatty carboxylic ester. .sup.14Example
1-K also contains Additive Package III and a sarcosine corrosion
inhibitor. .sup.15Example 1-L also contains Additive Package III
and a fatty carboxylic acid but in a smaller amount that used in
Example 1-G. .sup.16Example 1-M also contains Additive Package
I.
[0115] These examples are evaluated using ASTM D1401 to evaluate
each sample's water separability performance and an internal
thermal stability test.
[0116] For ASTM D1401, the test procedure involves a sample
containing about 40 ml of the composition of the invention and
about 40 ml of distilled water where the sample is stirred for
about 5 minutes at about 54.degree. C. in a graduated cylinder. The
resulting mixture is then left to stand for about 30 minutes to
allow a degree of separation of water and the composition of the
invention to occur. The amount of separation is measured after
every 5 minutes of the test. The results reported are based on
X--Y--Z, where X indicates the amount of oil separated out, Y
indicates the amount of water separated out and Z indicates the
amount of oil and water still in an emulsion. The less time it
takes for a sample to reach a reported result of 40-40-0, or a
result roughly equivalent thereto, the better its performance.
[0117] The thermal stability test used for this testing involves
placing standard sized copper and steel rods, after polishing and
weighing, in a sample of the example formulation with the rods
arranged so that they are in contact with one another at their
midpoint (forming an X). The submerged rods are then held at
135.degree. C..+-.1.degree. C. for 168 hours. The rods are then
rated for corrosion and weighed. The reported results for this test
include the copper rod corrosion rating, the steel rod corrosion
rating, and the amount of sludge generated which is determined by
filtering a 100 mL portion of the oil, rinsing and drying the
filter pad with any accumulated deposit; then weighing the dried
filter paper and reported in mg per 100 ml. The corrosion ratings
are on a scale of 1 to 10 with 1 being a freshly polished rod and
10 being a severely corroded rod. The lower the corrosion ratings
and the lower the reported sludge, the better the performance of
the sample.
[0118] The results of this testing are presented in the tables
below. If no results are listed for a specific sample it indicates
the sample was not tested by that method.
TABLE-US-00003 TABLE 1-3 Results for Comparative Examples and
Examples 1-A to 1-E Comp Comp Comp Ex Ex Ex Ex Ex Test Method Ex 1
Ex 2 Ex 3 1-A 1-B.sup.17 1-C 1-D 1-E D1401 0 min 0-0-80 0-0-80
0-0-80 0-0-80 0-0-80 5 min 12-6-62 26-22-32 10-0-70 5-5-70 1-25-54
10 min 36-36-8 29-40-1 35-26-20 35-30-15 40-40-0 15 min 40-40-0
40-40-0 40-40-0 40-40-0 20 min 25 min 30 min Therm Stability Copper
Rating 3 5 4 3 3 4 4 Steel Rating 3 8 2 7 1 1 2 Sludge (mg/100 ml)
39.8 15.9 26.8 17.75 1.9 3.6 37.6 .sup.17Example 1-B was tested
three times using the D1401 method. In one instance the sample did
not reach a 40-40-0 rating in 30 minutes. In one instance the
sample reached a 40-40-0 rating in 15 minutes. In one instance the
sample reached a 40-40-0 rating in 10 minutes. The middle result is
reported in the table above and is expected to be a fair
representation of the sample's performance.
TABLE-US-00004 TABLE 1-4 Results for Examples 1-F to 1-M Ex Ex Ex
Ex Ex Ex Ex Ex Test Method 1-F 1-G 1-H 1-I 1-J 1-K 1-L 1-M D1401 0
min 0-0-80 0-0-80 0-0-80 0-0-80 0-0-80 0-0-80 0-0-80 0-0-80 5 min
37-39-4 38-40-2 10-2-68 2-25-53 7-0-73 1-0-79 2-0-78 35-35-10 10
min 38-40-2 40-40-0 29-20-31 2-27-51 30-27-23 1-0-79 4-0-76 39-40-1
15 min 39-40-1 40-40-0 3-28-49 40-40-0 1-0-79 7-11-62 39-40-1 20
min 39-40-1 5-30-45 1-0-79 7-20-53 39-40-1 25 min 39-40-1 9-30-41
1-0-79 30-38-12 39-40-1 30 min 39-40-1 19-32-29 1-0-79 38-38-4
39-40-1 Therm Stability Copper Rating 3 3 4 3 4 5 Steel Rating 1 1
1 1 2 1 Sludge (mg/100 ml) 3.7 19.5 2.8 3.4 1.7 2.8
[0119] The results show that the compositions of the invention give
improved thermal stability protection while also maintaining
acceptable water separability. In some embodiments the invention
provides both improved thermal stability and water
separability.
Example Set 2
[0120] A set of examples is prepared where the formulations contain
a borated succinimide dispersant. The tables below summarize these
formulations, including the comparative formulations described
above. Except for the differences noted in the tables and their
footnotes, the formulations of the listed examples are
substantially equivalent. The values in the tables are pbw.
TABLE-US-00005 TABLE 2-1 Details of Comparative Examples and
Examples 2-A to 2-E Comp Comp Comp Ex Ex Ex Ex Ex Component Ex
1.sup.1 Ex 2.sup.2 Ex 3.sup.3 2-A.sup.4 2-B.sup.5 2-C.sup.6
2-D.sup.7 2-E.sup.8 Base Oil Grp III Grp III Grp III Grp III Grp
III Grp III Grp III Grp III Alkylated 0.375 0.510 0.775 0.375 0.375
0.375 0.375 0.375 Diphenylamine Subst Mono- 0.09 0.09 0.09 0.09
0.09 0.09 0.09 0.09 Sulfide Polyetheramine 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 Dispersant Borated 0.0 0.0 0.0 0.1 0.5 0.1 0.1 0.1
Succinimide Non-Borated 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Succinimide
Mannich 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Dispersant .sup.1See
details for Comparative Example 1 above. .sup.2See details for
Comparative Example 2 above. .sup.3See details for Comparative
Example 3 above. .sup.4Example 2-A also contains Additive Package
I, as defined above. .sup.5Example 2-B also contains Additive
Package I. .sup.6Example 2-C also contains Additive Package I and a
fatty carboxylic acid. .sup.7Example 2-D also contains Additive
Package I and a fatty carboxylic ester. .sup.8Example 2-E also
contains Additive Package I and a sarcosine corrosion
inhibitor.
TABLE-US-00006 TABLE 2-2 Details of Examples 2-F to 2-H Ex Ex Ex
Component 2-F.sup.9 2-G.sup.10 2-H.sup.11 Base Oil Grp III Grp II
Grp II Alkylated 0.375 0.375 0.375 Diphenylamine Subst Mono- 0.09
0.09 0.09 Sulfide Polyetheramine 0.0 0.0 0.0 Dispersant Borated
0.25 0.25 0.25 Succinimide Non-Borated 0.0 0.0 0.0 Succinimide
Mannich 0.0 0.0 0.0 Dispersant .sup.9Example 2-F also contains
Additive Package I. .sup.10Example 2-G also contains Additive
Package I except that the level of metal deactivator in the package
is reduced. .sup.11Example 2-H has the same additive package as
Example 2-G.
[0121] These examples are evaluated using ASTM D1401 to evaluate
each sample's water separability performance and an internal
thermal stability test, as described in the sections above. The
results of this testing are presented in the tables below. If no
results are listed for a specific sample it indicates the sample
was not tested by that method.
TABLE-US-00007 TABLE 2-3 Results for Comparative Examples and
Examples 2-A to 2-E Comp Comp Comp Ex Ex Ex Ex Ex Test Method Ex 1
Ex 2 Ex 3 2-A 2-B 2-C 2-D 2-E D1401 0 min 0-0-80 0-0-80 0-0-80
0-0-80 0-0-80 5 min 2-0-78 1-0-79 5-5-70 30-22-28 0-27-53 10 min
4-9-67 1-0-79 40-40-0 40-40-0 0-37-43 15 min 4-36-40 1-0-79 41-39-0
20 min 40-40-0 1-0-79 41-39-0 25 min 1-0-79 41-39-0 30 min 1-0-79
41-39-0 Therm Stability Copper Rating 3 5 4 3 4 5 5 6 Steel Rating
3 8 2 1 1 1 1 1 Sludge (mg/100 ml) 39.8 15.9 26.8 0.1 0.5 0.1 5.2
1.1
TABLE-US-00008 TABLE 2-4 Results for Examples 2-F to 2-H Ex Ex Ex
Test Method 2-F 2-G 2-H D1401 0 min 0-0-80 0-0-80 0-0-80 5 min
5-5-70 5-0-75 3-5-72 10 min 20-22-38 16-10-54 3-5-72 15 min
34-35-11 27-17-36 15-15-50 20 min 40-40-0 37-32-11 30-26-24 25 min
40-40-0 37-40-3 30 min 37-10-3 Therm Stability Copper Rating 5
Steel Rating 1 Sludge (mg/100 ml) 12.3
[0122] The results show that the compositions of the invention give
improved thermal stability protection while also maintaining
acceptable water separability. In some embodiments the invention
provides both improved thermal stability and water
separability.
Example Set 3
[0123] A set of examples is prepared where the formulations contain
a non-borated succinimide dispersant. The tables below summarize
these formulations, including the comparative formulations
described above. Except for the differences noted in the tables and
their footnotes, the formulations of the listed examples are
substantially equivalent. The values in the tables are pbw.
TABLE-US-00009 TABLE 3-1 Details of Comparative Examples and
Examples 3-A to 3-E Comp Comp Comp Ex Ex Ex Ex Ex Component Ex
1.sup.1 Ex 2.sup.2 Ex 3.sup.3 3-A.sup.4 3-B.sup.5 3-C.sup.6
3-D.sup.7 3-E.sup.8 Base Oil Grp III Grp III Grp III Grp III Grp
III Grp III Grp III Grp III Alkylated 0.375 0.510 0.775 0.375 0.375
0.775 0.775 0.375 Diphenylamine Subst Mono- 0.09 0.09 0.09 0.09
0.09 0.09 0.09 0.09 Sulfide Polyetheramine 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 Dispersant Borated 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Succinimide Non-Borated 0.0 0.0 0.0 0.1 0.5 0.5 0.5 0.5 Succinimide
Mannich 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Dispersant .sup.1See
details for Comparative Example 1 above. .sup.2See details for
Comparative Example 2 above. .sup.3See details for Comparative
Example 3 above. .sup.4Example 3-A also contains Additive Package
I, as defined above. .sup.5Example 3-B also contains Additive
Package I. .sup.6Example 3-C also contains Additive Package II, as
defined above. .sup.7Example 3-D also contains Additive Package II
and a fatty carboxylic acid. .sup.8Example 3-E also contains
Additive Package I and a sarcosine corrosion inhibitor.
TABLE-US-00010 TABLE 3-2 Details of Examples 3-F to 3-J Ex Ex Ex Ex
Ex Component 3-F.sup.9 3-G.sup.10 3-H.sup.11 3-I.sup.12 3-J.sup.13
Base Oil Grp III Grp III Grp III Grp III Grp III Alkylated 0.775
0.775 0.375 0.375 0.375 Diphenylamine Subst Mono- 0.09 0.09 0.09
0.09 0.09 Sulfide Polyetheramine 0.0 0.0 0.0 0.0 0.0 Dispersant
Borated 0.0 0.0 0.0 0.0 0.0 Succinimide Non-Borated 0.5 0.25 0.25
0.1 0.5 Succinimide Mannich 0.0 0.0 0.0 0.0 0.0 Dispersant
.sup.9Example 3-F also contains the antifoam, polyether
demulsifier, and metal deactivator of Additive Package II, as
defined above, but does not contain the antiwear agent. This set of
additives is referred to as Additive Package IV below. The example
also contains a fatty carboxylic acid but at a lower level than
Example 3-D. .sup.10Example 3-G contains Additive Package IV and
also contains a fatty carboxylic acid at the same level as Example
3-D. .sup.11Example 3-H also Additive Package I and a sarcosine
corrosion inhibitor. .sup.12Example 3-I also contains Additive
Package I and the non-borated succinimide dispersant has a higher
molecular weight than that used on the other examples.
.sup.13Example 3-J also contains Additive Package I and uses the
higher molecular weight non-borated succinimide dispersant of
Example 3-I.
[0124] These examples are evaluated using ASTM D1401 to evaluate
each sample's water separability performance and an internal
thermal stability test, as described in the sections above. The
results of this testing are presented in the tables below. If no
results are listed for a specific sample it indicates the sample
was not tested by that method.
TABLE-US-00011 TABLE 3-3 Results for Comparative Examples and
Examples 3-A to 3-E Comp Comp Comp Ex Ex Ex Ex Ex Test Method Ex 1
Ex 2 Ex 3 3-A 3-B 3-C 3-D 3-E D1401 0 min 0-0-80 0-0-80 0-0-80
0-0-80 5 min 0-5-75 0-0-80 0-0-80 2-0-78 10 min 40-40-0 0-3-77
0-0-80 30-23-27 15 min 23-30-27 10-15-55 39-40-1 20 min 40-40-0
36-32-12 40-40-1 25 min 39-40-1 30 min 40-40-0 Therm Stability
Copper Rating 3 5 4 3 3 3 7 4 Steel Rating 3 8 2 1 1 1 1 1 Sludge
(mg/100 ml) 39.8 15.9 26.8 0.6 1.1 7.5 2.4 3.3
TABLE-US-00012 TABLE 3-4 Results for Examples 3-F to 3-J Ex Ex Ex
Ex Ex Test Method 3-F 3-G 3-H 3-I 3-J D1401 0 Min 0-0-80 0-0-80 5
min 2-12-66 0-0-80 10 min 5-32-43 1-0-79 15 min 40-40-0 1-0-79 20
min 1-0-79 25 min 1-0-79 30 min 1-0-79 Therm Stability Copper
Rating 4 4 4 Steel Rating 1 1 1 Sludge (mg/100 ml) 0.4 8.0 0.1
[0125] The results show that the compositions of the invention give
improved thermal stability protection while also maintaining
acceptable water separability. In some embodiments the invention
provides both improved thermal stability and water
separability.
Example Set 4
[0126] A set of examples is prepared where the formulations contain
a Mannich reaction product of a dialkylamine, an aldehyde and a
hydrocarbyl substituted phenol. The tables below summarize these
formulations, including the comparative formulations described
above. Except for the differences noted in the tables and their
footnotes, the formulations of the listed examples are
substantially equivalent. The values in the tables are pbw.
TABLE-US-00013 TABLE 4-1 Details of Comparative Examples and
Examples 4-A to 4-B Comp Comp Comp Ex Ex Component Ex 1.sup.1 Ex
2.sup.2 Ex 3.sup.3 3-A.sup.4 3-B.sup.5 Base Oil Grp III Grp III
XGrp III Grp III Grp III Alkylated 0.375 0.510 0.775 0.375 0.375
Diphenylamine Subst Mono- 0.09 0.09 0.09 0.09 0.09 Sulfide
Polyetheramine 0.0 0.0 0.0 0.0 0.0 Dispersant Borated 0.0 0.0 0.0
0.0 0.0 Succinimide Non-Borated 0.0 0.0 0.0 0.0 0.0 Succinimide
Mannich 0.0 0.0 0.0 0.1 0.5 Dispersant .sup.1See details for
Comparative Example 1 above. .sup.2See details for Comparative
Example 2 above. .sup.3See details for Comparative Example 3 above.
.sup.4Example 4-A also contains Additive Package I, as defined
above. .sup.5Example 4-B also contains Additive Package I.
[0127] These examples are evaluated using ASTM D1401 to evaluate
each sample's water separability performance and an internal
thermal stability test, as described in the sections above. The
results of this testing are presented in the tables below. If no
results are listed for a specific sample it indicates the sample
was not tested by that method.
TABLE-US-00014 TABLE 4-2 Results for Comparative Examples and
Examples 4-A to 4-B Comp Comp Comp Ex Ex Test Method Ex 1 Ex 2 Ex 3
4-A 4-B D1401 0 min 0-0-80 5 min 34-34-12 10 min 39-40-1 15 min
40-40-0 20 min 25 min 30 min Therm Stability Copper Rating 3 5 4 4
Steel Rating 3 8 2 4 Sludge (mg/100 ml) 39.8 15.9 26.8 14.0
[0128] The results show that the compositions of the invention give
improved thermal stability protection while also maintaining
acceptable water separability. In some embodiments the invention
provides both improved thermal stability and water
separability.
[0129] While the invention has been explained, it is to be
understood that various modifications thereof will become apparent
to those skilled in the art upon reading the specification.
Therefore, it is to be understood that the invention disclosed
herein is intended to cover such modifications as fall within the
scope of the appended claims.
[0130] In this specification the terms "hydrocarbyl substituent" or
"hydrocarbyl group," as used herein are used in their ordinary
sense, which is well-known to those skilled in the art.
Specifically, they refer to a group primarily composed of carbon
and hydrogen atoms that 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.
[0131] Each of the documents referred to above is incorporated
herein by reference. Except in the Examples, or where otherwise
explicitly indicated, all numerical quantities in this description
specifying amounts of materials, reaction conditions, molecular
weights, number of carbon atoms, and the like, are to be understood
as modified by the word "about." Unless otherwise indicated, all
percent and formulation values listed herein are on a 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 invention can be used together with
ranges or amounts for any of the other elements. As used herein,
the expression "consisting essentially of" permits the inclusion of
substances that do not materially affect the basic and novel
characteristics of the composition under consideration.
* * * * *