U.S. patent application number 14/051689 was filed with the patent office on 2015-12-03 for lubricant compositions comprising trimethoxyboroxines and sterically hindered amines to improve fluoropolymer seal compatibilty.
This patent application is currently assigned to BASF SE. The applicant listed for this patent is BASF SE. Invention is credited to Alex Attlesey, David Chasan, Kevin J. DeSantis, Michael D. Hoey, Roger L. Kuhlman, Phil Rabbat.
Application Number | 20150344806 14/051689 |
Document ID | / |
Family ID | 50475855 |
Filed Date | 2015-12-03 |
United States Patent
Application |
20150344806 |
Kind Code |
A1 |
DeSantis; Kevin J. ; et
al. |
December 3, 2015 |
Lubricant Compositions Comprising Trimethoxyboroxines and
Sterically Hindered Amines To Improve Fluoropolymer Seal
Compatibilty
Abstract
A lubricant composition including a boroxine compound is
disclosed. A lubricant composition and additive package including a
boroxine compound and a sterically hindered amine compound are also
disclosed. The boroxine compound of the lubricant composition acts
to improve compatibility of the lubricant composition with a
fluoropolymer seal.
Inventors: |
DeSantis; Kevin J.; (Upper
Nyack, NY) ; Hoey; Michael D.; (Maplewood, NJ)
; Attlesey; Alex; (Morristown, NJ) ; Kuhlman;
Roger L.; (Ringwood, NJ) ; Chasan; David;
(Teaneck, NJ) ; Rabbat; Phil; (Springfield,
NJ) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
Ludwigshafen |
|
DE |
|
|
Assignee: |
BASF SE
Ludwigshafen
DE
|
Family ID: |
50475855 |
Appl. No.: |
14/051689 |
Filed: |
October 11, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61713088 |
Oct 12, 2012 |
|
|
|
61713103 |
Oct 12, 2012 |
|
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|
Current U.S.
Class: |
508/185 |
Current CPC
Class: |
C10N 2030/52 20200501;
C10M 2215/221 20130101; C10M 2203/1006 20130101; C10N 2030/10
20130101; C10M 2205/0285 20130101; C10N 2040/12 20130101; C10N
2040/08 20130101; C10N 2030/12 20130101; C10M 2223/045 20130101;
C10N 2040/25 20130101; C10M 161/00 20130101; C10M 141/12 20130101;
C10N 2040/135 20200501; C10M 2215/26 20130101; C10M 2215/04
20130101; C10M 2203/1025 20130101; C10M 2227/062 20130101; C10M
141/10 20130101; C10N 2030/36 20200501; C10M 2203/1025 20130101;
C10N 2020/02 20130101; C10M 2203/1025 20130101; C10N 2020/02
20130101 |
International
Class: |
C10M 161/00 20060101
C10M161/00 |
Claims
1. A lubricant composition comprising: a base oil; a boroxine
compound having a formula: ##STR00018## and a sterically hindered
amine compound included in an amount ranging from 0.5 to 5 wt. %
based on a total weight of said lubricant composition.
2. The lubricant composition of claim 1 wherein said boroxine
compound is included in an amount ranging from 0.1 to 5 wt. % based
on said total weight of said lubricant composition.
3. The lubricant composition of claim 1 wherein at least 50 wt. %
of said boroxine compound remains unreacted in said lubricant
composition based on said total weight of said boroxine compound
utilized to form said lubricant composition prior to any reaction
in said lubricant composition.
4. The lubricant composition of claim 1 wherein said sterically
hindered amine compound comprises at least one piperidine ring and
at least one ester group.
5. The lubricant composition of claim 1 wherein said sterically
hindered amine compound is (2,2,6,6-tetramethyl-4-piperidyl)
dodecanoate.
6. The lubricant composition of claim 1 wherein said sterically
hindered amine compound has a total base number of at least 70 mg
KOH/g when tested according to ASTM D4739.
7. The lubricant composition of claim 1 wherein said base oil has a
viscosity ranging from 1 to 20 cSt when tested at 100.degree. C.
according to ASTM D445 and is selected from the group of API group
I oils, API group II oils, API group III oils, API group IV oils,
API group V oils, and combinations thereof.
8. The lubricant composition of claim 1 further comprising a
dispersant.
9. The lubricant composition of claim 8 wherein said dispersant is
a polyalkene amine derived from a polyisobutene.
10. The lubricant composition of claim 9 wherein said dispersant is
included in said lubricant composition in an amount ranging from
0.01 to 15 wt. % based on said total weight of said lubricant
composition.
11. The lubricant composition of claim 1 further comprising a
dihydrocarbyldithiophosphate salt.
12. The lubricant composition of claim 11 wherein said
dihydrocarbyldithiophosphate salt comprises a zinc
dihydrocarbyldithiophosphate salt.
13. The lubricant composition of claim 11 wherein said
dihydrocarbyldithiophosphate salt is included in said lubricant
composition in an amount ranging from 0.1 to 20 wt. % based on said
total weight of said lubricant composition.
14. The lubricant composition of claim 1 wherein said lubricant
composition has a fluoropolymer seal compatibility such that a
fluoropolymer seal submerged in said lubricant composition exhibits
a change in tensile strength of less than 45% when tested according
to CEC L-39-T96 or wherein said lubricant composition has a
fluoropolymer seal compatibility such that a fluoropolymer seal
submerged in said lubricant composition exhibits a change in
elongation at rupture of less than 60% when tested according to CEC
L-39-T96.
15. A lubricant composition comprising: a base oil; a boroxine
compound having a formula: ##STR00019## and a sterically hindered
amine compound having the general formula (I) or (II): ##STR00020##
wherein each R.sup.1 is independently a hydrogen atom or a
hydrocarbyl group having from 1 to 17 carbon atoms, and wherein at
least two groups designated by R.sup.1 are an alkyl group; wherein
each R.sup.2 is independently a hydrogen atom or a hydrocarbyl
group having from 1 to 17 carbon atoms; wherein each R.sup.3 is
independently a hydrogen atom or a hydrocarbyl group having from 1
to 17 carbon atoms, and wherein at least two groups designated by
R.sup.3 are an alkyl group; wherein each R.sup.4 is independently a
hydrogen atom or a hydrocarbyl group having from 1 to 17 carbon
atoms, and wherein said hydrocarbyl groups designated by R.sup.1,
R.sup.2, R.sup.3, and R.sup.4 are each independently an alcohol
group, an alkyl group, an amide group, an ether group, or an ester
group.
16. The lubricant composition of claim 15 wherein said boroxine
compound is included in an amount ranging from 0.1 to 5 wt. % based
on a total weight of said lubricant composition.
17. The lubricant composition of claim 15 wherein said amine
compound is included in an amount ranging from 0.5 to 5 wt. % based
on a total weight of said lubricant composition.
18. The lubricant composition of claim 15 further comprising a
dispersant.
19. The lubricant composition of claim 15 further comprising a
dihydrocarbyldithiophosphate salt.
20. An additive package for a lubricant composition, said additive
package comprising: a boroxine compound having a formula:
##STR00021## and a sterically hindered amine compound having the
general formula (I) or (II): ##STR00022## wherein each R.sup.1 is
independently a hydrogen atom or a hydrocarbyl group having from 1
to 17 carbon atoms, and wherein at least two groups designated by
R.sup.1 are an alkyl group; wherein each R.sup.2 is independently a
hydrogen atom or a hydrocarbyl group having from 1 to 17 carbon
atoms; wherein each R.sup.3 is independently a hydrogen atom or a
hydrocarbyl group having from 1 to 17 carbon atoms, and wherein at
least two groups designated by R.sup.3 are an alkyl group; wherein
each R.sup.4 is independently a hydrogen atom or a hydrocarbyl
group having from 1 to 17 carbon atoms, and wherein said
hydrocarbyl groups designated by R.sup.1, R.sup.2, R.sup.3, and
R.sup.4 are each independently an alcohol group, an alkyl group, an
amide group, an ether group, or an ester group.
Description
RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Patent
Application No. 61/713,088 filed on Oct. 12, 2012 and U.S.
Provisional Patent Application No. 61/713,103 filed on Oct. 12,
2012, each of which is incorporated by reference herein in its
entirety.
FIELD OF THE INVENTION
[0002] The present invention generally relates to a lubricant
composition that includes a base oil, a boroxine compound, and a
sterically hindered amine compound. The invention also relates to
an additive package for a lubricant composition.
BACKGROUND OF THE INVENTION
[0003] It is known and customary to add stabilizers to lubricant
compositions based on mineral or synthetic oils in order to improve
their performance characteristics. Some conventional amine
compounds are effective stabilizers for lubricants. These
conventional amine compounds may help neutralize acids formed
during the combustion process. However, these conventional amine
compounds are generally not employed in combustion engines due to
their detrimental effects on fluoropolymer seals.
[0004] It is an object of the present invention to provide new
types of lubricant compositions having improved fluoropolymer seal
compatibility.
SUMMARY OF THE INVENTION
[0005] The present invention provides a lubricant composition
including a base oil, a boroxine compound, and a sterically
hindered amine compound in an amount ranging from 0.5 to 5 wt. %
based on a total weight of said lubricant composition. The boroxine
compound has the formula:
##STR00001##
[0006] The present invention is also directed to a lubricant
composition including the base oil, the boroxine compound, and the
sterically hindered amine compound having the general formula (I)
or (II):
##STR00002##
wherein each R.sup.1 is independently a hydrogen atom or a
hydrocarbyl group having from 1 to 17 carbon atoms, and wherein at
least two groups designated by R.sup.1 are an alkyl group; wherein
each R.sup.2 is independently a hydrogen atom or a hydrocarbyl
group having from 1 to 17 carbon atoms; wherein each R.sup.3 is
independently a hydrogen atom or a hydrocarbyl group having from 1
to 17 carbon atoms, and wherein at least two groups designated by
R.sup.3 are an alkyl group; wherein each R.sup.4 is independently a
hydrogen atom or a hydrocarbyl group having from 1 to 17 carbon
atoms, and wherein said hydrocarbyl groups designated by R.sup.1,
R.sup.2, R.sup.3, and R.sup.4 are each independently an alcohol
group, an alkyl group, an amide group, an ether group, or an ester
group.
[0007] The present invention also provides an additive package for
a lubricant composition including the boroxine compound and the
sterically hindered amine compound.
[0008] Lubricant compositions including the boroxine compound
demonstrate improved compatibility with fluoropolymer seals as
demonstrated by CEC L-39-T96.
DETAILED DESCRIPTION OF THE INVENTION
[0009] As described below, a boroxine compound may be included in a
lubricant composition or an additive package for a lubricant
composition to improve the seal compatibility of the lubricant
composition. The boroxine compound may be combined in the lubricant
composition with one or more sterically hindered amine compound. It
is believed that, when present in a lubricant composition with the
sterically hindered amine compound, the boroxine compound
surprisingly interacts with these sterically hindered amine
compounds so as to interfere with the tendency of the sterically
hindered amine compound to negatively interact with a fluoropolymer
seal as that lubricant composition contacts the fluoropolymer seal,
without affecting the stabilizing effect of the sterically hindered
amine compound.
[0010] The boroxine compound has the formula:
##STR00003##
[0011] The boroxine compound may be included in the lubricant
composition and/or additive package in an amount sufficient to
provide a desired concentration of boron in the lubricant
composition and/or additive package. For example, the boroxine
compound can be included in an amount sufficient to provide from 1
to 5000 ppm boron in the lubricant composition based the total
weight of the lubricant composition. Alternatively, the boroxine
compound may be included in an amount in the lubricant composition
or additive package sufficient to provide from 100 to 5000, 300 to
3000, 500 to 1500, or 700 to 1200, ppm boron, in the lubricant
composition based the total weight of the lubricant composition.
Alternatively still, the boroxine compound may be provided in an
amount sufficient to provide from 1 to 100, 1 to 40, 1 to 20, or 10
to 20, ppm boron, in the lubricant composition based the total
weight of the lubricant composition.
[0012] Alternatively, the boroxine compound may be present in the
lubricant composition in an amount ranging from 0.1 to 10, 0.1 to
5, 0.1 to 1, 0.3 to 0.7, 0.5 to 3, or 0.5 to 1.5, wt. %, based on
the total weight of the lubricant composition. In other
embodiments, the boroxine compound is included in an amount greater
than 1 wt. %, but less than 5 wt. %, based on the total weight of
the lubricant composition.
[0013] If formulated as an additive package, the boroxine compound
may be present in an amount ranging from 0.1 to 75 wt. % based on
the total weight of the additive package. The boroxine compound may
also be present in the additive package in an amount ranging from
0.1 to 50, 0.1 to 33, or 0.1 to 25, wt. %, based on the total
weight of the additive package.
[0014] The boroxine compound may be prepared via numerous methods.
As but one example, the boroxine compound can be prepared by
reacting 2 mole of orthoboric acid (H.sub.3BO.sub.3) with 1 mole
tri-alkyl borate. The reaction can be conducted at a temperature
ranging from 50 to 150.degree. C. in order to remove 1 mol
H.sub.2O.
[0015] Conventional uses of conventional boron compounds involve
forming a reaction product between a conventional amine compound
and a conventional boron compound. The conventional boron compound
may be exemplified by reactive borate esters and boric acids. In
these applications, the conventional boron compound is consumed by
chemical reactions such that the ultimately formed lubricant
composition does not contain appreciable amounts of the
conventional boron compound. Furthermore, in these applications,
the conventional amine compound is reacted with the conventional
boron compound to form a salt. The salt formation is evidenced by
the electronic impact upon the reaction of the conventional boron
compound and the conventional amine compound, which is visible as a
chemical shift in NMR spectroscopy. There are also physical
indications that a reaction takes place, such as the evolution of
heat and the thickening of the solution (cross-linking).
[0016] In such applications of conventional boron compounds, more
than 50 wt. % of the conventional boron compound may be reacted
with the conventional amine compounds, or is hydrolyzed, based on
the total weight of the conventional boron compound before
reaction. In contrast, the inventive lubricant compositions,
additive packages, and inventive methods may contain a significant
amount of the boroxine compound in an unreacted state. Furthermore,
the inventive lubricant compositions, inventive additive packages,
and inventive methods do not involve the formation of a substantial
amount of a salt of the boroxine compound. As such, the lubricant
composition may be free from a salt formed through the reaction of
the boroxine compound, or may contain less than 10, less than 5, or
less than 1, wt. %, of the salt formed through the reaction of the
boroxine compound based on the total weight of the lubricant
composition after any reaction.
[0017] In certain embodiments, at least 50, at least 60, at least
70, at least 80, or at least 90, wt. %, of the boroxine compound
remains unreacted in the lubricant composition based on a total
weight of boroxine compound utilized to form the lubricant
composition prior to any reaction in the lubricant composition.
Alternatively, at least 95, at least 96, at least 97, at least 98,
or at least 99, wt. %, of the boroxine compound remains unreacted
in the lubricant composition based on a total weight of the
boroxine compound prior to any reaction in the lubricant
composition.
[0018] The term "unreacted" refers to the fact that the designated
amount of the boroxine compound does not react with any components
in the lubricant composition, such as the conventional amine
compound or water. Accordingly, the unreacted amount of the
boroxine compound remains in its virgin state when present in the
lubricant composition before the lubricant composition has been
used in an end-use application, such as an internal combustion
engine.
[0019] The phrase "prior to any reaction in the lubricant
composition" refers to the basis of the amount of the boroxine
compound in the lubricant composition. This description does not
require that the boroxine compound reacts with other components in
the lubricant composition, i.e., 100 wt. % of the boroxine compound
may remain unreacted in the lubricant composition based on a total
weight of the boroxine compound prior to any reaction in the
lubricant composition.
[0020] In one embodiment, the percentage of the boroxine compound
that remains unreacted is determined after all of the components
which are present in the lubricant composition reach equilibrium
with one another. The time period necessary to reach equilibrium in
the lubricant composition may vary widely. For example, the amount
of time necessary to reach equilibrium may range from a single
minute to many days, or even weeks. In certain embodiments, the
percentage of the boroxine compound that remains unreacted in the
lubricant composition is determined after 1 minute, 1 hour, 5
hours, 12 hours, 1 day, 2 days, 3 days, 1 week, 1 month, 6 months,
or 1 year. Generally, the percentage of the boroxine compound that
remains unreacted in the lubricant composition is determined before
an end use.
[0021] In certain embodiments, the lubricant composition includes
less than 0.1, less than 0.01, less than 0.001, or less than
0.0001, wt. %, of compounds which would react with the boroxine
compound based on the total weight of the lubricant composition. In
certain embodiments, the lubricant composition may include a
collective amount of acids, anhydrides, triazoles, and/or oxides
which is less than 0.1 wt. %, of the total weight of the lubricant
composition. Alternatively, the lubricant composition may include a
collective amount of acids, anhydrides, triazoles, and/or oxides
which is less than 0.01, less than 0.001, or less than 0.0001, wt.
%, based on the total weight of the lubricant compositions.
Alternatively still, the lubricant composition may be free of
acids, anhydrides, triazoles, and/or oxides.
[0022] The term "acids" includes both traditional acids and Lewis
acids. For example, acids include carboxylic acids, such as lactic
acid and hydracylic acid; alkylated succinic acids; alkylaromatic
sulfonic acids; and fatty acids. Exemplary Lewis acids include
alkyl aluminates; alkyl titanates; molybdenumates, such as
molybdenum thiocarbamates and molybdenum carbamates; and molybdenum
sulfides.
[0023] "Anhydrides" are exemplified by alkylated succinic
anhydrides and acrylates. Triazoles may be exemplified by
benzotriazoles and derivatives thereof; tolutriazole and
derivatives thereof; 2-mercaptobenzothiazole,
2,5-dimercaptothiadiazole, 4,4'-methylene-bis-benzotriazole,
4,5,6,7-tetrahydro-benzotriazole, and salts thereof. Oxides may be
exemplified by alkylene oxides, such as ethylene oxide and
propylene oxide; metal oxides; alkoxylated alcohols; or alkoxylated
esters.
[0024] The lubricant composition may include less than 100, less
than 50, less than 10, or less than 5, ppm B(OH).sub.3.sup.- ions,
based the total weight of the lubricant composition. Conventional
boroxine compounds may be hydrolyzed before they are combined with
a conventional lubricant composition such that more than 100 ppm
B(OH).sub.3.sup.- ions are present in the conventional lubricant
composition. In such a hydrolyzed state, the inventors of the
subject application surprisingly realized that the resultant
conventional boroxine compounds do not provide the desired effect
on seal compatibility. In other words, at least 50, at least 60, at
least 70, at least 80, at least 90, at least 95, or at least 99,
wt. %, of the boroxine compound is in an unhydrolyzed state in the
lubricant composition based on the total weight of the boroxine
compound. The amount of the boroxine compound which is hydrolyzed
is accounted for when determining the amount of the boroxine
compound which remains unreacted.
[0025] Furthermore, the boroxine compound does not negatively
affect the total base number (TBN) of the lubricant composition.
The TBN value of the lubricant composition can be determined
according to ASTM D2896 and ASTM D4739 as will be described
below.
[0026] As described above, the boroxine compound may be combined
with at least one sterically hindered amine compound. It should be
appreciated that mixtures of different sterically hindered amine
compounds may also be combined with the boroxine compound. If
included, the lubricant composition includes the sterically
hindered amine compound in an amount ranging from 0.1 to 10 wt. %,
based on the total weight of the lubricant composition. In other
embodiments, the lubricant composition includes the sterically
hindered amine compound in an amount ranging from 0.1 to 25, 0.1 to
20, or 1 to 15, wt. %, based on the total weight of the lubricant
composition. Alternatively, the lubricant composition may comprise
the sterically hindered amine compound in an amount ranging from
0.5 to 5, 1 to 3, or 1 to 2, wt. %, based on the total weight of
the lubricant composition.
[0027] The sterically hindered amine compound does not
substantially react with the boroxine compound to form a salt. The
absence of salt formation is evidenced by the lack of a chemical
shift in the NMR spectra of the boroxine compound and the
sterically hindered amine compound when they are combined in the
lubricant composition and/or additive package. In other words, at
least 50, 60, 70, 80, 90, 95, or 99 wt. % of the sterically
hindered amine compound remains unreacted after the lubricant
composition and/or additive package reaches equilibrium.
[0028] The basicity of the sterically hindered amine compound can
be determined by acid titration. The resulting neutralization
number is expressed as the TBN, and can be measured using various
methods. ASTM D4739 is a potentiometric hydrochloric acid
titration. The ASTM D4739 method is favored in engine tests and
with used oils to measure TBN depletion/retention. When testing
used engine lubricants, it should be recognized that certain weak
bases are the result of the service rather than having been built
into the oil. This test method can be used to indicate relative
changes that occur in lubricant composition during use under
oxidizing or other service conditions regardless of the color or
other properties of the resulting lubricant composition.
[0029] The sterically hindered amine compound may have a TBN value
of at least 70 mg KOH/g when tested according to ASTM D4739.
Alternatively, the sterically hindered amine compound may have a
TBN value of at least 80, at least 90, at least 100, at least 110,
at least 120, at least 130, at least 140, at least 150, or at least
160, mg KOH/g, when tested according to ASTM D4739.
[0030] If the sterically hindered amine compound is included in the
additive package, the additive package includes the sterically
hindered amine compound in an amount ranging from 0.1 to 50 wt. %,
based on the total weight of the additive package. Alternatively,
the additive package may comprise the sterically hindered amine
compound in an amount ranging from 1 to 25, 0.1 to 15, 1 to 10, 0.1
to 8, or 1 to 5, wt. %, based on the total weight of the additive
package. Combinations of various sterically hindered amine
compounds are also contemplated.
[0031] In some embodiments, the sterically hindered amine compound
includes at least one nitrogen atom. In other embodiments, the
sterically hindered amine compound does not include triazoles,
triazines, or similar compounds where there are three or more
nitrogens in the body of a cyclic ring.
[0032] In some embodiments, the sterically hindered amine compound
may consist of, or consist essentially of, hydrogen, carbon,
nitrogen, and oxygen. Alternatively, the sterically hindered amine
compound may consist of, or consist essentially of, hydrogen,
carbon, and nitrogen. In the context of the sterically hindered
amine compound, the phrase "consist essentially of" refers to
compounds where at least 95 mole % of the sterically hindered amine
compound are the recited atoms (i.e., hydrogen, carbon, nitrogen,
and oxygen; or hydrogen, carbon, and nitrogen). For example, if the
sterically hindered amine compound consists essentially of
hydrogen, carbon, nitrogen, and oxygen, at least 95 mole % of the
sterically hindered amine compound is hydrogen, carbon, nitrogen,
and oxygen. In certain configurations, at least 96, at least 97, at
least 98, at least 99, or at least 99.9, mole %, of the sterically
hindered amine compound are hydrogen, carbon, nitrogen and oxygen,
or, in other embodiments, are carbon, nitrogen, and hydrogen.
[0033] The sterically hindered amine compound may consist of
covalent bonds. The phrase "consist of covalent bonds" is intended
to exclude those compounds which bond to the sterically hindered
amine compound through an ionic association with one or more ionic
atoms or compounds. That is, in configurations where the sterically
hindered amine compound consists of covalent bonds, the sterically
hindered amine compound excludes salts of sterically hindered amine
compounds, such as phosphate amine salts and amine salts. As such,
in certain embodiments, the lubricant composition is free of a salt
of the sterically hindered amine compound. More specifically, the
lubricant composition may be free of a phosphate amine salt, an
ammonium salt, and/or amine sulfate salt.
[0034] In one or more embodiments, the sterically hindered amine
compound may have a weight average molecular weight ranging from
100 to 1200. Alternatively, the sterically hindered amine compound
may have a weight average molecular weight ranging from 200 to 800,
or from 200 to 600. Alternatively still, the sterically hindered
amine may have a weight average molecular weight of less than
500.
[0035] As used herein, the term "sterically hindered amine
compound" means an organic molecule containing at least one
nitrogen atom, and fewer than two hydrogen atoms on any carbon atom
directly attached to a carbon atom that is bonded to a nitrogen
atom. That is, there are either no hydrogen atoms or only one
hydrogen atom on at least one beta-carbon with reference to the at
least one nitrogen atom. In other embodiments, the term "sterically
hindered amine compound" refers to molecules where there are no
hydrogen atoms on any beta-carbon with respect to at least one
nitrogen atom.
[0036] The sterically hindered amine compound may have general
formula (I) or (II):
##STR00004##
In general formula (I), each R.sup.1 is independently a hydrogen
atom or a hydrocarbyl group having from 1 to 17 carbon atoms,
wherein at least two of R.sup.1 are an alkyl group in one molecule;
and R.sup.2 is independently a hydrogen atom or a hydrocarbyl group
having from 1 to 17 carbon atoms. In general formula (II), each
R.sup.3 is independently a hydrogen atom or a hydrocarbyl group
having from 1 to 17 carbon atoms, wherein at least two of R.sup.3
are an alkyl group, and each R.sup.4 is independently a hydrogen
atom or a hydrocarbyl group having from 1 to 17 carbon atoms.
[0037] Each R.sup.1, R.sup.2, R.sup.3, and R.sup.4 may
independently be an alcohol group, an alkyl group, an amide group,
an ether group, or an ester group. Each R.sup.1, R.sup.2, R.sup.3,
and R.sup.4 may independently have from 1 to 17, 1 to 15, 1 to 12,
1 to 8, 1 to 6, or 1 to 4, carbon atoms. Each group designated by
R.sup.1, R.sup.2, R.sup.3, and R.sup.4 may independently be
straight or branched. For example, each R.sup.1, R.sup.2, R.sup.3,
and R.sup.4 may be an alcohol group, amino group, alkyl group,
amide group, ether group, or ester group having 1 to 17 carbon
atoms, with the designated functional group (alcohol, etc) bonded
at various positions on the carbon chain.
[0038] In certain embodiments, at least one group designated by
R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is unsubstituted.
Alternatively, at least two, three, four, five, or six groups
designated by R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are
unsubstituted. By "unsubstituted," it is intended that the
designated group is free from pendant functional groups, such as
hydroxyl, carboxyl, oxide, thio, and thiol groups, and that the
designated group is free from acyclic heteroatoms, such as oxygen,
sulfur, and nitrogen heteroatoms. In other embodiments, every group
designated by R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is
unsubstituted. Alternatively still, it is contemplated that one,
two, three, four, five, or six groups designated by R.sup.1,
R.sup.2, R.sup.3, and R.sup.4 are substituted. The term
"substituted" indicates that the designated group includes at least
one pendant functional group, or that the designated group includes
at least one acyclic heteroatom.
[0039] Exemplary R.sup.1, R.sup.2, R.sup.3, and R.sup.4 groups may
be independently selected from methyl, ethyl, n-propyl, n-butyl,
sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl,
n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl,
n-hexadecyl, or n-octadecyl.
[0040] In general formula (I), at least two, at least three, or all
four groups, designated by R.sup.1 are independently an alkyl
group. Similarly, in general formula (II), at least two groups
designated by R.sup.3 are an alkyl group. Alternatively, at least
three, or all four groups, designated by R.sup.3 are an alkyl
group.
[0041] The sterically hindered amine compound of general formula
(I) may be exemplified by the following compounds:
2,2,6,6-tetramethyl-4-octylpiperdine:
##STR00005##
2,2,6,6-tetramethyl-4-decylpiperdine:
##STR00006##
2,2,6,6-tetramethyl-4-butylpiperdine:
##STR00007##
2,2,6,6-tetramethyl-4-hexadecylpiperdine:
##STR00008##
[0042] The sterically hindered amine compound of general formula
(II) is acyclic. The term "acyclic" is intended to mean that the
sterically hindered amine compound of general formula (II) is free
from any cyclic structures and aromatic structures. The sterically
hindered amine compound of general formula (II) can be exemplified
by:
N-tert-butyl-2-ethyl-N-methyl-hexan-1-amine:
##STR00009##
tert-amyl-tert-butylamine:
##STR00010##
N-tert-butylheptan-2-amine:
##STR00011##
[0043] The sterically hindered amine compound may further
alternatively be exemplified by the general formula (III):
##STR00012##
In general formula (III), each R.sup.1 and R.sup.2 are as described
above, wherein at least three of R.sup.1 are independently an alkyl
group. The sterically hindered amine compound of general formula
(III) may be exemplified by the following compounds:
(1,2,2,6,6-pentamethyl-4-piperidyl) octanoate:
##STR00013##
(1,2,2,6,6-pentamethyl-4-piperidyl) decanoate:
##STR00014##
(1,2,2,6,6-pentamethyl-4-piperidyl) dodecanoate:
##STR00015##
(2,2,6,6-tetramethyl-4-piperidyl) dodecanoate
##STR00016##
[0044] The sterically hindered amine compound may include a single
ester group. However, the sterically hindered amine compound may
alternatively be free from ester groups. In certain embodiments,
the sterically hindered amine compound may include at least one, or
only one, piperidine ring.
[0045] The boroxine compound and the sterically hindered amine
compound may be provided in an amount such that 1 part of boron is
provided for every 1 to 20 parts nitrogen in the sterically
hindered amine compound within the lubricant composition.
Alternatively, the boroxine compound and the sterically hindered
amine compound may be provided in an amount such that 1 part of
boron is provided for every 1 to 15, 1 to 10, or 1 to 5, parts
nitrogen, in the sterically hindered amine compound within the
lubricant composition.
[0046] In yet another embodiment, the lubricant composition may
consist, or consist essentially of, a base oil, the boroxine
compound, and the sterically hindered amine compound. It is also
contemplated that the lubricant composition may consist of, or
consist essentially of, the base oil, the boroxine compound, and
the sterically hindered amine compound, in addition to one or more
of additives that do not materially affect the functionality or
performance of the boroxine compound. For example, compounds that
materially affect the overall performance of the lubricant
composition may include compounds which negatively impact the TBN
boost, the lubricity, the fluoropolymer seal compatibility, the
corrosion inhibition, or the acidity of the lubricant
composition.
[0047] In other embodiments, the additive package may consist, or
consist essentially of, the boroxine compound and the sterically
hindered amine compound. It is also contemplated that the additive
package may consist of, or consist essentially of, the boroxine
compound, and the sterically hindered amine compound in addition to
one or more of additives that do not compromise the functionality
or performance of the boroxine compound. When used in reference to
the additive package, the term "consisting essentially of" refers
to the additive package being free of compounds that materially
affect the overall performance of the lubricant composition. For
example, compounds that materially affect the overall performance
of the additive package may include compounds which negatively
impact the TBN boost, the lubricity, the fluoropolymer seal
compatibility, the corrosion inhibition, or the acidity of the
additive package.
[0048] In some aspects, the lubricant composition may include a
base oil. The base oil is classified in accordance with the
American Petroleum Institute (API) Base Oil Interchangeability
Guidelines. In other words, the base oil may be further described
as one or more of five types of base oils: Group I (sulphur content
>0.03 wt. %, and/or <90 wt. %, saturates, viscosity index
80-119); Group II (sulphur content less than or equal to 0.03 wt.
%, and greater than or equal to 90 wt. %, saturates, viscosity
index 80-119); Group III (sulphur content less than or equal to
0.03 wt. %, and greater than or equal to 90 wt. %, saturates,
viscosity index greater than or equal to 119); Group IV (all
polyalphaolefins (PAO's)); and Group V (all others not included in
Groups I, II, III, or IV).
[0049] The base oil is selected from the group of API Group I base
oils; API Group II base oils; API Group III base oils; API Group IV
base oils; API Group V base oils; and combinations thereof. In one
specific formulation, the base oil includes API Group II base
oils.
[0050] The base oil may have a viscosity ranging from 1 to 20 cSt
when tested according to ASTM D445 at 100.degree. C. Alternatively,
the viscosity of the base oil may range from 3 to 17, or 5 to 14,
cSt, when tested according to ASTM D445 at 100.degree. C.
[0051] The base oil may be further defined as a crankcase
lubrication oil for spark-ignited and compression-ignited internal
combustion engines, including automobile and truck engines,
two-cycle engines, aviation piston engines, marine engines, and
railroad diesel engines. Alternatively, the base oil can be further
defined as an oil to be used in gas engines, diesel engines,
stationary power engines, and turbines. The base oil may be further
defined as heavy or light duty engine oil.
[0052] In still other embodiments, the base oil may be further
defined as synthetic oil that includes one or more alkylene oxide
polymers and interpolymers, and derivatives thereof. The terminal
hydroxyl groups of the alkylene oxide polymers may be modified by
esterification, etherification, or similar reactions. These
synthetic oils may be prepared through polymerization of ethylene
oxide or propylene oxide to form polyoxyalkylene polymers which can
be further reacted to form the synthetic oil. For example, alkyl
and aryl ethers of these polyoxyalkylene polymers may be used. For
example, methylpolyisopropylene glycol ether having an average
molecular weight of 1000; diphenyl ether of polyethylene glycol
having a molecular weight of 500-1000; or diethyl ether of
polypropylene glycol having a molecular weight of 1000-1500 and/or
mono- and polycarboxylic esters thereof, such as acetic acid
esters, mixed C.sub.3-C.sub.8 fatty acid esters, and the C.sub.13
oxo acid diester of tetraethylene glycol may also be utilized as
the base oil.
[0053] In one embodiment, one or more of the components described
herein are blended into the additive package that is subsequently
blended into the base oil to make the lubricant composition. The
additive package may be formulated to provide the desired
concentration in the lubricant composition when the concentrate is
combined with a predetermined amount of base oil. It is to be
appreciated that most references to the lubricant composition
throughout this disclosure also apply to the description of the
additive package. For example, it is to be appreciated that the
additive package may include, or exclude the same components as the
lubricant composition, albeit in different amounts.
[0054] The base oil may be present in the lubricant composition in
an amount ranging from 50 to 99.9, 60 to 99.9, 70 to 99.9, 80 to
99.9, 90 to 99.9, 75 to 95, 80 to 90, or 85 to 95, wt. %, based on
the total weight of the lubricant composition. Alternatively, the
base oil may be present in the lubricant composition in amounts of
greater than 50, 60, 70, 75, 80, 85, 90, 95, 98, or 99, wt. %,
based on the total weight of the lubricant composition. In various
embodiments, the amount of base oil in a fully formulated lubricant
composition (including diluents or carrier oils presents) ranges
from 50 to 99, 60 to 90, 80 to 99.5, 85 to 96, or 90 to 95, wt. %,
based on the total weight of the lubricant composition. In various
embodiments, the amount of base oil in a additive package, if
included, (including diluents or carrier oils present) ranges from
0.1 to 50, 1 to 25, or 1 to 15, wt. %, based on the total weight of
the additive package.
[0055] In one or more embodiments, the lubricant composition may be
classified as a low SAPS lubricant having a sulfated ash content of
no more than 3, 2, 1, or 0.5, wt. %, based on the total weight of
the lubricant composition. "SAPS" refers to the sulfated ash,
phosphorous, and sulfur.
[0056] The lubricant composition may have a TBN value of at least 1
mg KOH/g of lubricant composition. Alternatively, the lubricant
composition has a TBN value ranging from 1 to 15, 5 to 15, or 9 to
12, mg KOH/g of lubricant composition, when tested according to
ASTM D2896.
[0057] The lubricant composition or the additive package may
further include a dispersant in addition to the boroxine compound
and/or the sterically hindered amine compound. The dispersant may
be a polyalkene amine. The polyalkene amine includes a polyalkene
moiety. The polyalkene moiety is the polymerization product of
identical or different, straight-chain or branched C.sub.2-6 olefin
monomers. Examples of suitable olefin monomers are ethylene,
propylene, 1-butene, isobutene, 1-pentene, 2-methyl butene,
1-hexene, 2-methylpentene, 3-methylpentene, and 4-methylpentene.
The polyalkene moiety has a weight average molecular weight of
ranging from 200 to 10000, 500 to 10000, or 800 to 5000.
[0058] In one embodiment, the polyalkene amine is derived from
polyisobutenes. Particularly suitable polysiobutenes are known as
`highly reactive` polyisobutenes which feature a high content of
terminal double bonds. Terminal double bonds are alpha-olefinic
double bonds of the type shown in general formula (IV):
##STR00017##
The bonds shown in general formulas (IV) are known as vinylidene
double bones. Suitable highly reactive polypolyisobutenes are, for
example, polyisobutenes which have a fraction of vinylidene double
bonds of greater than 70, 80, 85, mole %. Preference is given in
particular to polyisobutenes which have uniform polymer frameworks.
Uniform polymer frameworks have in particular those polyisobutenes
which are composed of at least 85, 90, or 95, wt. %, of isobutene
units. Such highly reactive polyisobutenes preferably have a
number-average molecular weight in the abovementioned range. In
addition, the highly reactive polyisobutenes may have a
polydispersity ranging from 1.05 to 7, or 1.1 to 2.5. The highly
reactive polyisobutenes may have a polydispersity less than 1.9, or
less than 1.5. Polydispersity refers to the quotients of
weight-average molecular weight Mw divided by the number-average
molecular weight Mn.
[0059] The amine dispersant may include moieties derived from
succinic anhydride and having hydroxyl and/or amino and/or amido
and/or imido groups. For example, the dispersant may be derived
from polyisobutenylsuccinic anhydride which is obtainable by
reacting conventional or highly reactive polyisobutene having a
weight average molecular weight ranging from 500 to 5000 with
maleic anhydride by a thermal route or via the chlorinated
polyisobutene. In specific embodiments, derivatives with aliphatic
polyamines such as ethylenediamine, diethylenetriamine,
triethylenetetramine or tetraethylenepentamine may be used.
[0060] To prepare the polyalkene amine, the polyalkene component
may be aminated in a known manner. One exemplary process proceeds
via the preparation of an oxo intermediate by hydroformylation and
subsequent reductive amination in the presence of a suitable
nitrogen compound.
[0061] The dispersant may be a poly(oxyalkyl) radical or a
polyalkylene polyamine radical of the general formula (V):
R.sup.5--NH--(C.sub.1-C.sub.6-alkylene-NH).sub.m--C.sub.1-C.sub.6-alkyle-
ne (VI)
where m is an integer ranging from 1 to 5, R.sup.5 is a hydrogen
atom or a hydrocarbyl group having from 1 to 6 carbon atoms with
C.sub.1-C.sub.6 alkylene representing the corresponding bridged
analogs of the alkyl radicals. The dispersant may also be a
polyalkylene imine radical composed of from 1 to 10 C.sub.1-C.sub.4
alkylene imine groups; or, together with the nitrogen atom to which
they are bonded, are an optionally substituted 5- to 7-membered
heterocyclic ring which is optionally substituted by one to three
C.sub.1-C.sub.4 alkyl radicals and optionally bears one further
ring heteroatom such as oxygen or nitrogen.
[0062] Examples of suitable alkenyl radicals include mono- or
polyunsaturated, preferably mono- or diunsaturated analogs of alkyl
radicals has from 2 to 18 carbon atoms, in which the double bonds
may be in any position in the hydrocarbon chain.
[0063] Examples of C.sub.4-C.sub.18 cycloalkyl radical include
cyclobutyl, cyclopentyl and cyclohexyl, and also the analogs
thereof substituted by 1 to 3 C.sub.1-C.sub.4 alkyl radicals. The
C.sub.1-C.sub.4 alkyl radicals are, for example, selected from
methyl, ethyl, iso- or n-propyl, n-, iso-, sec- or tert-butyl.
[0064] Examples of the arylalkyl radical include a C.sub.1-C.sub.18
alkyl group and an aryl group which are derived from a monocyclic
or bicyclic fused or nonfused 4- to 7-membered, in particular 6
membered, aromatic or heteroaromatic group, such as phenyl,
pyridyl, naphthyl and biphenyl.
[0065] If additional dispersants other than the dispersant
described above are employed, these dispersants can be of various
types. Suitable examples of dispersants include polybutenylsuccinic
amides or -imides, polybutenylphosphonic acid derivatives and basic
magnesium, calcium and barium sulfonates and phenolates, succinate
esters and alkylphenol amines (Mannich bases), and combinations
thereof.
[0066] If employed, the dispersant can be used in various amounts.
The dispersant may be present in the lubricant composition in an
amount ranging from 0.01 to 15, 0.1 to 12, 0.5 to 10, or 1 to 8,
wt. %, based on the total weight of the lubricant composition.
Alternatively, the dispersant may be present in amounts of less
than 15, less than 12, less than 10, less than 5, or less than 1,
wt. %, each based on the total weight of the lubricant
composition.
[0067] In the additive package, the total weight of the dispersant
and the boroxine compound is less than 50, less than 45, less than
40, less than 35, or less than 30, wt. %, of the additive package
based on the total weight of the additive package. Surprisingly, it
has been found that if the combined concentration of the dispersant
and boroxine compound is too high in the additive package, a
reaction will take place between the dispersant and the boroxine
compound which causes thickening and formation of a precipitate,
along with a decrease in fluropolymer seal compatibility of the
lubricant composition.
[0068] The lubricant composition or the additive package may
further comprise a dihydrocarbyldithiophosphate salt. The
dihydrocarbyldithiophosphate salt may be represented by the
following general formula: [R.sup.6O(R.sup.7O)PS(S)].sub.2M, where
R.sup.6 and R.sup.7 are each hydrocarbyl groups having from 1 to 20
carbon atoms, wherein M is a metal atom or an ammonium group. For
example, R.sup.6 and R.sup.7 may each independently be C.sub.1-20
alkyl groups, C.sub.2-20 alkenyl groups, C.sub.3-20 cycloalkyl
groups, C.sub.1-20 aralkyl groups or C.sub.3-20 aryl groups. The
groups designated by R.sup.6 and R.sup.7 may be substituted or
unsubstituted. The metal atom may be selected from the group
including aluminum, lead, tin, manganese, cobalt, nickel, or zinc.
The ammonium group may be derived from ammonia or a primary,
secondary, or tertiary amine. The ammonium group may be of the
formula R.sup.8R.sup.9R.sup.10R.sup.11N.sup.+, wherein R.sup.8,
R.sup.9, R.sup.10, and R.sup.11 each independently represents a
hydrogen atom or a hydrocarbyl group having from 1 to 150 carbon
atoms. In certain embodiments, R.sup.8, R.sup.9, R.sup.10, and
R.sup.11 may each independently be hydrocarbyl groups having from 4
to 30 carbon atoms. In one specific embodiment, the
dihydrocarbyldithiophosphate salt is zinc dialkyl
dithiophosphate.
[0069] The dihydrocarbyldithiophosphate salt can be present in the
lubricant composition in an amount ranging from 0.1 to 20, 0.5 to
15, 1 to 10, 0.1 to 5, 0.1 to 1, 0.1 to 0.5, or 0.1 to 1.5, wt. %,
each based on the total weight of the lubricant composition.
Alternatively, the dihydrocarbyldithiophosphate salt may be present
in amounts of less than 20, less than 10, less than 5, less than 1,
less than 0.5, or less than 0.1, wt. %, each based on the total
weight of the lubricant composition. The additive package may also
include the dihydrocarbyldithiophosphate salt in an amount ranging
from 0.1 to 20, 0.5 to 15, 1 to 10, 0.1 to 5, 0.1 to 1, 0.1 to 0.5,
or 0.1 to 1.5, wt. %, each based on the total weight of the
additive package.
[0070] The lubricant composition or the additive package may
additionally include one or more additives to improve various
chemical and/or physical properties of the lubricant composition.
These additives may be in addition to the boroxine compound or in
addition to the combination of the boroxine compound and the
sterically hindered amine compound. Specific examples of the one or
more additives include anti-wear additives, antioxidants, metal
deactivators (or passivators), rust inhibitors, viscosity index
improvers, pour point depressors, dispersants, detergents, and
antifriction additives. Each of the additives may be used alone or
in combination. The one or more additives can be used in various
amounts, if employed. The lubricant composition may be formulated
with the addition of several auxiliary components to achieve
certain performance objectives for use in certain applications. For
example, the lubricant composition may be a rust and oxidation
lubricant formulation, a hydraulic lubricant formulation, turbine
lubricant oil, and an internal combustion engine lubricant
formulation. Accordingly, it is contemplated that the base oil may
be formulated to achieve these objectives as discussed below.
[0071] If employed, the anti-wear additive can be of various types.
The anti-wear additive may include sulfur- and/or phosphorus-
and/or halogen-containing compounds, e.g., sulfurised olefins and
vegetable oils, alkylated triphenyl phosphates, tritolyl phosphate,
tricresyl phosphate, chlorinated paraffins, alkyl and aryl di- and
trisulfides, amine salts of mono- and dialkyl phosphates, amine
salts of methylphosphonic acid, diethanolaminomethyltolyltriazole,
bis(2-ethylhexyl)aminomethyltolyltriazole, derivatives of
2,5-dimercapto-1,3,4-thiadiazole, ethyl
3-[(diisopropoxyphosphinothioyl)thio]propionate, triphenyl
thiophosphate (triphenylphosphorothioate),
tris(alkylphenyl)phosphorothioate and mixtures thereof, diphenyl
monononylphenyl phosphorothioate, isobutylphenyl diphenyl
phosphorothioate, the dodecylamine salt of
3-hydroxy-1,3-thiaphosphetane 3-oxide, trithiophosphoric acid
5,5,5-tris[isooctyl 2-acetate], derivatives of
2-mercaptobenzothiazole such as
1-[N,N-bis(2-ethylhexyl)aminomethyl]-2-mercapto-1H-1,3-benzothiaz-
ole, ethoxycarbonyl-5-octyldithio carbamate, and/or combinations
thereof.
[0072] If employed, in addition or in exchange of the
dihydrocarbyldithiophosphate salt described above, the anti-wear
additive can be used in various amounts. The anti-wear additive may
be present in the lubricant composition in an amount ranging from
0.1 to 20, 0.5 to 15, 1 to 10, 0.1 to 1, 0.1 to 0.5, or 0.1 to 1.5,
wt. %, each based on the total weight of the lubricant composition.
Alternatively, the anti-wear additive may be present in amounts of
less than 20, less than 10, less than 5, less than 1, less than
0.5, or less than 0.1, wt. %, each based on the total weight of the
lubricant composition.
[0073] If employed, the antioxidant can be of various types.
Suitable antioxidants include alkylated monophenols, for example
2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,
2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,
2,6-di-tert-butyl-4-isobutylphenol,
2,6-dicyclopentyl-4-methylphenol,
2-(.alpha.-methylcyclohexyl)-4,6-dimethylphenol,
2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,
2,6-di-tert-butyl-4-methoxymethylphenol,
2,6-di-nonyl-4-methylphenol,
2,4-dimethyl-6(1'-methylundec-1'-yl)phenol,
2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol,
2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol, and combinations
thereof.
[0074] Further examples of suitable antioxidants includes
alkylthiomethylphenols, for example
2,4-dioctylthiomethyl-6-tert-butylphenol,
2,4-dioctylthiomethyl-6-methylphenol,
2,4-dioctylthiomethyl-6-ethylphenol,
2,6-didodecylthiomethyl-4-nonylphenol, and combinations thereof.
Hydroquinones and alkylated hydroquinones, for example
2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,
2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,
2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,
3,5-di-tert-butyl-4-hydroxyanisole,
3,5-di-tert-butyl-4-hydroxyphenyl stearate,
bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate, and combinations
thereof, may also be utilized.
[0075] Furthermore, hydroxylated thiodiphenyl ethers, for example
2,2'-thiobis(6-tert-butyl-4-methylphenol),
2,2'-thiobis(4-octylphenol),
4,4'-thiobis(6-tert-butyl-3-methylphenol),
4,4'-thiobis(6-tert-butyl-2-methylphenol),
4,4'-thiobis-(3,6-di-sec-amylphenol),
4,4'-bis-(2,6-dimethyl-4-hydroxyphenyl)disulfide, and combinations
thereof, may also be used.
[0076] It is also contemplated that alkylidenebisphenols, for
example 2,2'-methylenebis(6-tert-butyl-4-methylphenol),
2,2'-methylenebis(6-tert-butyl-4-ethylphenol),
2,2'-methylenebis[4-methyl-6-(.alpha.-methylcyclohexyl)phenol],
2,2'-methylenebis(4-methyl-6-cyclohexylphenol),
2,2'-methylenebis(6-nonyl-4-methylphenol),
2,2'-methylenebis(4,6-di-tert-butylphenol),
2,2'-ethylidenebis(4,6-di-tert-butylphenol),
2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol),
2,2'-methylenebis[6-(.alpha.-methylbenzyl)-4-nonylphenol],
2,2'-methylenebis[6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonylphenol],
4,4'-methylenebis(2,6-di-tert-butylphenol),
4,4'-methylenebis(6-tert-butyl-2-methylphenol),
1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,
2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,
1,1,3-tris(5-tert-butyl-4-hydroxy-2-methyl-phenyl) butane,
1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercapto
butane, ethylene glycol
bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate],
bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,
bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphe-
nyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,
2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,
2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane-
, 1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methyl phenyl)pentane,
and combinations thereof may be utilized as antioxidants in the
lubricant composition.
[0077] O-, N- and S-benzyl compounds, for example
3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether,
octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,
tris-(3,5-di-tert-butyl-4-hydroxybenzyl)amine,
bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol
terephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,
isooctyl-3,5di-tert-butyl-4-hydroxy benzylmercaptoacetate, and
combinations thereof, may also be utilized.
[0078] Hydroxybenzylated malonates, for example
dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,
di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,
di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malona-
te,
bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hy-
droxybenzyl)malonate, and combinations thereof are also suitable
for use as antioxidants.
[0079] Triazine compounds, for example
2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triaz-
ine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-tri-
azine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-t-
riazine,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl
2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenyl
propionyl)-hexahydro-1,3,5-triazine,
1,3,5-tris-(3,5-dicyclohexyl-4-hydroxybenzyl)-isocyanurate, and
combinations thereof, may also be used.
[0080] Additional examples of antioxidants include aromatic
hydroxybenzyl compounds, for example,
1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,
1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol, and
combinations thereof. Benzylphosphonates, for example
dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,
diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
dioctadecyl-5-tert-butyl-4-hydroxy3-methylbenzylphosphonate, the
calcium salt of the monoethyl ester of
3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, and combinations
thereof, may also be utilized. In addition, acylaminophenols, for
example 4-hydroxylauranilide, 4-hydroxystearanilide, and octyl
N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
[0081] Esters of [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic
acid with mono- or polyhydric alcohols, e.g. with methanol,
ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene
glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, and
combinations thereof, may also be used. It is further contemplated
that esters of
.beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with
mono- or polyhydric alcohols, e.g. with methanol, ethanol,
octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,
1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, and
combinations thereof, may be used.
[0082] Additional examples of suitable antioxidants include those
that include nitrogen, such as amides of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, e.g.,
N,N-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenyl-propionyl)trimethylenediamine,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.
Other suitable examples of antioxidants include aminic antioxidants
such as N,N'-diisopropyl-p-phenylenediamine,
N,N'-di-sec-butyl-p-phenylenediamine,
N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine,
N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,
N,N'-bis(1-methylheptyl)-p-phenylenediamine,
N,N'-dicyclohexyl-p-phenylenediamine,
N,N'-diphenyl-p-phenylenediamine,
N,N'-bis(2-naphthyl)-p-phenylenediamine,
N-isopropyl-N'-phenyl-p-phenylenediamine,
N-(1,3-dimethyl-butyl)-N'-phenyl-p-phenylenediamine,
N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine,
N-cyclohexyl-N'-phenyl-p-phenylenediamine,
4-(p-toluenesulfamoyl)diphenylamine,
N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,
N-allyldiphenylamine, 4-isopropoxydiphenylamine,
N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, octylated
diphenylamine, for example p,p'-di-tert-octyldiphenylamine,
4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol,
4-dodecanoylaminophenol, 4-octadecanoylaminophenol,
bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylamino
methylphenol, 2,4'-diaminodiphenylmethane,
4,4'-diaminodiphenylmethane,
N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane,
1,2-bis[(2-methyl-phenyl)amino]ethane, 1,2-bis(phenylamino)propane,
(o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine,
tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and
dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono-
and dialkylated isopropyl/isohexyldiphenylamines, mixtures of mono-
and dialkylated tert-butyldiphenylamines,
2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine,
N-allylphenothiazine, N,N,N',N-tetraphenyl-1,4-diaminobut-2-ene,
and combinations thereof.
[0083] Even further examples of suitable antioxidants include
aliphatic or aromatic phosphites, esters of thiodipropionic acid or
of thiodiacetic acid, or salts of dithiocarbamic or
dithiophosphoric acid,
2,2,12,12-tetramethyl-5,9-dihydroxy-3,7,1trithiatridecane and
2,2,15,15-tetramethyl-5,12-dihydroxy-3,7,10,14-tetrathiahexadecane,
and combinations thereof. Furthermore, sulfurized fatty esters,
sulfurized fats and sulfurized olefins, and combinations thereof,
may be used.
[0084] If employed, the antioxidant can be used in various amounts.
The antioxidant may be present in the lubricant composition in an
amount ranging from 0.01 to 5, 0.1 to 3, or 0.5 to 2, wt. %, based
on the total weight of the lubricant composition. Alternatively,
the antioxidant may be present in amounts of less than 5, less than
3, or less than 2, wt. %, based on the total weight of the
lubricant composition.
[0085] If employed, the metal deactivator can be of various types.
Suitable metal deactivators include benzotriazoles and derivatives
thereof, for example 4- or 5 alkylbenzotriazoles (e.g.
tolutriazole) and derivatives thereof,
4,5,6,7-tetrahydrobenzotriazole and 5,5'-methylenebisbenzotriazole;
Mannich bases of benzotriazole or tolutriazole, e.g.
1-[bis(2-ethylhexyl)aminomethyl)tolutriazole and
1-[bis(2-ethylhexyl)aminomethyl)benzotriazole; and
alkoxyalkylbenzotriazoles such as 1-(nonyloxymethyl)benzotriazole,
1-(1-butoxyethyl)benzotriazole and
1-(1-cyclohexyloxybutyl)tolutriazole, and combinations thereof.
[0086] Additional examples of suitable metal deactivators include
1,2,4-triazoles and derivatives thereof, and Mannich bases of
1,2,4-triazoles, such as
1-[bis(2-ethylhexyl)aminomethyl-1,2,4-triazole;
alkoxyalkyl-1,2,4-triazoles such as
1-(1-butoxyethyl)-1,2,4-triazole; and acylated
3-amino-1,2,4-triazoles, imidazole derivatives, for example
4,4'-methylenebis(2-undecyl-5-methylimidazole) and
bis[(N-methyl)imidazol-2-yl]carbinol octyl ether, and combinations
thereof. Further examples of suitable metal deactivators include
sulfur-containing heterocyclic compounds, for example
2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole and
derivatives thereof; and
3,5-bis[di(2-ethylhexyl)aminomethyl]-1,3,4-thiadiazolin-2-one, and
combinations thereof. Even further examples of metal deactivators
include amino compounds, for example salicylidenepropylenediamine,
salicylaminoguanidine and salts thereof, and combinations
thereof.
[0087] If employed, the metal deactivator can be used in various
amounts. The metal deactivator may be present in the lubricant
composition in an amount ranging from 0.01 to 0.1, 0.05 to 0.01, or
0.07 to 0.1, wt. %, based on the total weight of the lubricant
composition. Alternatively, the metal deactivator may be present in
amounts of less than 1.0, less than 0.7, or less than 0.5, wt. %,
based on the total weight of the lubricant composition.
[0088] If employed, the rust inhibitor and/or friction modifier can
be of various types. Suitable examples of rust inhibitors and/or
friction modifiers include organic acids, their esters, metal
salts, for example alkyl- and alkenylsuccinic acids and their
partial esters with alcohols, diols or hydroxycarboxylic acids,
partial amides of alkyl- and alkenylsuccinic acids,
4-nonylphenoxyacetic acid, alkoxy- and alkoxyethoxycarboxylic acids
such as dodecyloxyacetic acid, dodecyloxy(ethoxy)acetic acid, and
also N-oleoylsarcosine, sorbitan monooleate, lead naphthenate,
alkenylsuccinic anhydrides, for example, dodecenylsuccinic
anhydride, 2-carboxymethyl-1-dodecyl-3-methylglycerol, and
combinations thereof. Further examples include heterocyclic
compounds, for example: substituted imidazolines and oxazolines,
and 2-heptadecenyl-1-(2-hydroxyethyl)imidazoline,
phosphorus-containing compounds, for example: amine salts of
phosphoric acid partial esters or phosphonic acid partial esters,
molybdenum-containing compounds, such as molydbenum dithiocarbamate
and other sulphur and phosphorus containing derivatives,
sulfur-containing compounds, for example: barium
dinonylnaphthalenesulfonates, calcium petroleum sulfonates,
alkylthio-substituted aliphatic carboxylic acids, esters of
aliphatic 2-sulfocarboxylic acids and salts thereof, glycerol
derivatives, for example: glycerol monooleate,
1-(alkylphenoxy)-3-(2-hydroxyethyl)glycerols,
1-(alkylphenoxy)-3-(2,3-dihydroxypropyl)glycerols and
2-carboxyalkyl-1,3-dialkylglycerols, and combinations thereof.
[0089] If employed, the rust inhibitor and/or friction modifier can
be used in various amounts. The rust inhibitor and/or friction
modifier may be present in the lubricant composition in an amount
ranging from 0.01 to 0.1, 0.05 to 0.01, or 0.07 to 0.1, wt. %,
based on the total weight of the lubricant composition.
Alternatively, the rust inhibitor and/or friction modifier may be
present in amounts of less than 1, less than 0.7, or less than 0.5,
wt. %, based on the total weight of the lubricant composition.
[0090] If employed, the viscosity index improver can be of various
types. Suitable examples of viscosity index improvers include
polyacrylates, polymethacrylates, vinylpyrrolidone/methacrylate
copolymers, polyvinylpyrrolidones, polybutenes, olefin copolymers,
styrene/acrylate copolymers and polyethers, and combinations
thereof.
[0091] If employed, the viscosity index improver can be used in
various amounts. The viscosity index improver may be present in the
lubricant composition in an amount ranging from 0.01 to 20, 1 to
15, or 1 to 10, wt. %, based on the total weight of the lubricant
composition. Alternatively, the viscosity index improver may be
present in amounts of less than 10, less than 8, or less than 5,
wt. %, based on the total weight of the lubricant composition.
[0092] If employed, the pour point depressant can be of various
types. Suitable examples of pour point depressants include
polymethacrylate and alkylated naphthalene derivatives, and
combinations thereof.
[0093] If employed, the pour point depressant can be used in
various amounts. The pour point depressant may be present in the
lubricant composition in an amount ranging from 0.01 to 0.1, 0.05
to 0.01, or 0.07 to 0.1, wt. %, each based on the total weight of
the lubricant composition. Alternatively, the pour point depressant
may be present in amounts of less than 1.0, less than 0.7, or less
than 0.5, wt. %, based on the total weight of the lubricant
composition.
[0094] If employed, the detergent can be of various types. Suitable
examples of detergents include overbased or neutral metal
sulphonates, phenates and salicylates, and combinations
thereof.
[0095] If employed, the detergent can be used in various amounts.
The detergent may be present in the lubricant composition in an
amount ranging from 0.01 to 5, 0.1 to 4, 0.5 to 3, or 1 to 3, wt.
%, based on the total weight of the lubricant composition.
Alternatively, the detergent may be present in amounts of less than
5, less than 4, less than 3, less than 2, or less than 1, wt. %,
based on the total weight of the lubricant composition.
[0096] In various embodiments, the lubricant composition is
substantially free of water, e.g., the lubricant composition
includes less than 5, less than 4, less than 3, less than 2, less
than 1, less than 0.5, or less than 0.1, wt. %, of water, based on
the total weight of the lubricant composition. Alternatively, the
lubricant composition may be completely free of water.
[0097] Preferred lubricant compositions provided for use and used
pursuant to this invention include those which pass the CEC
L-39-T96 seal compatibility test. The CEC L-39-T96 test involves
keeping a test specimen of a fluoropolymer in a lubricant
composition at 150.degree. C. The seal specimens are then removed
and dried and the properties of the seal specimens are assessed and
compared to the seal specimens which were not heated in the
lubricant composition. The percent change in these properties is
assessed to quantify the compatibility of the fluoropolymer seal
with the lubricant composition. The incorporation of the boroxine
compound into the lubricant composition decreases the tendency of
the lubricant composition to degrade the seals versus lubricant
compositions which are free from the boroxine compound.
[0098] The pass/fail criteria include maximum variation of certain
characteristics after immersion for 7 days in fresh oil without
pre-aging. The maximum variation for each characteristic depends on
the type of elastomer used, the type of engine used, and whether an
aftertreatment device is utilized.
[0099] The characteristics measured before and after immersion
included Hardness DIDC (points); Tensile Strength (%); Elongation
at Rupture (%); Volume Variation (%). For heavy-duty diesel
engines, the pass/fail criteria are presented below in Table 1:
TABLE-US-00001 TABLE 1 Fluoropolymer Seal Compatibility for CEC
L-39-T96 Heavy-Duty Diesel Engines Elastomer Type Property RE1
Hardness DIDC, points -1/+5 Tensile Strength, % -50/+10 Elongation
at Rupture, % -60/+10 Volume Variation, % -1/+5
[0100] In these tests, a conventional lubricant composition passes
the test if the exposed test specimen exhibits a change in hardness
from -1% to +5%; a tensile strength (as compared to an untested
specimen) from -50% to +10%; a change in elongation at rupture (as
compared to an untested specimen) from -60% to +10%; and a volume
variation (as compared to an untested specimen) from -1% to
+5%.
[0101] When the lubricant composition is tested according to CEC
L-39-T96 for Heavy-Duty Diesel Engines, the change in hardness can
range from -1 to 5%, -0.5 to 5%, -0.1 to 5%, 0.5 to 5%, or 1 to 5%;
the change in tensile strength can range from -50 to 10%, -45 to
10%, -40 to 10%, or -35 to 10%; the change in elongation at rupture
can range from -60 to 10%, -55 to 10% , -50 to 10%, or -45 to 10%;
and the change in volume variation can range from -1 to 5%, -0.75
to 5%, -0.5 to 5%, -0.1 to 5%, or 0 to 5%.
[0102] When the boroxine composition is used in the lubricant
compositions described, the resulting lubricant composition has a
fluoropolymer compatibility such that a fluoropolymer seal
submerged in said lubricant composition exhibits a change in
tensile strength of less than 10, less than 15, less than 20, less
than 25, less than 30, less than 35, less than 40, less than 45,
less than 50, less than 55, or less than 60, %, when tested
according to CEC L-39-T96 for Heavy-Duty Diesel Engines. Similarly,
when the boroxine compound is used in the lubricant compositions
described, the resulting lubricant composition has a fluoropolymer
compatibility such that a fluoropolymer exhibits a change in
tensile strength elongation at rupture of less than 20, less than
25, less than 30, less than 35, less than 40, less than 45, less
than 50, less than 55, or less than 60, %, when tested according to
CEC L-39-T96 for Heavy-Duty Diesel Engines.
[0103] Some of the compounds described above may interact in the
lubricant composition, so that the components of the lubricant
composition in final form may be different from those components
that are initially added or combined together. Some products formed
thereby, including products formed upon employing the lubricant
composition of this invention in its intended use, are not easily
described or describable. Nevertheless, all such modifications,
reaction products, and products formed upon employing the lubricant
composition of this invention in its intended use, are expressly
contemplated and hereby included herein. Various embodiments of
this invention include one or more of the modification, reaction
products, and products formed from employing the lubricant
composition, as described above.
[0104] A method of lubricating a system is provided. The method
includes contacting the system with the lubricant composition
described above. The system may further comprise an internal
combustion engine. Alternatively, the system may further comprise
any combustion engine or application that utilizes a lubricant
composition. The system includes at least one fluoropolymer
seal.
[0105] The fluoropolymer seal may comprise a fluoroelastomer. The
fluoroelastomer may be categorized under ASTM D1418 and ISO 1629
designation of FKM for example. The fluoroelastomer may comprise
copolymers of hexafluoropropylene (HFP) and vinylidene fluoride
(VDF of VF2), terpolymers of tetrafluoroethylene (TFE), vinylidene
fluoride and hexafluoropropylene, perfluoromethylvinylether (PMVE),
copolymers of TFE and propylene and copolymers of TFE, PMVE and
ethylene. The fluorine content varies for example between 66 to 70
wt. %, based on the total weight of the fluoropolymer seal. FKM is
fluoro-rubber of the polymethylene type having substituent fluoro
and perfluoroalkyl or perfluoroalkoxy groups on the polymer
chain.
[0106] In addition, a method of forming the lubricant composition
is provided. The method includes combining the base oil and the
boroxine compound, and, optionally, the sterically hindered amine
compound. The boroxine compound may be incorporated into the base
oil in any convenient way. Thus, the boroxine compound can be added
directly to the base oil by dispersing or dissolving it in the base
oil at the desired level of concentration. Alternatively, the base
oil may be added directly to the boroxine compound in conjunction
with agitation until the boroxine compound is provided at the
desired level of concentration. Such blending may occur at ambient
or lower temperatures, such as 30, 25, 20, 15, 10, or 5.degree.
C.
Examples
[0107] Without being limited, in the below examples, exemplary
lubricant compositions were formulated by blending each of the
components together until homogeneity was achieved. A fully
formulated lubricating oil composition containing dispersant,
detergent, aminic antioxidant, phenolic antioxidant, anti-foam,
base oil, antiwear additive, pour point depressant and viscosity
modifier was prepared. This lubricant composition, which is
representative of a commercial crankcase lubricant, is designated
as the "reference lubricant" and used as a baseline to compare the
effects of different components on seal compatibility.
[0108] The reference lubricant was combined with various different
boron-containing compounds and various different
nitrogen-containing compounds to demonstrate the effect of the
boron-containing compounds and the effect of nitrogen-containing
compounds on seal compatibility. Practical Examples #1 and #2 each
include one of the practical boroxine compounds and one of the
practical amine compounds. Comparative Examples #1-7 do not include
any of the practical boroxine compounds. Comparative Examples #8-14
do not include any of the practical amine compounds. Comparative
Examples #10-#14 do not include either the practical amine
compounds or the practical boroxine compounds.
[0109] The boron-containing compound added to the reference
lubricant in Practical Examples #1 and #2 is
trimethoxyboroxine.
[0110] As described above, Comparative Examples #1-7 do not include
the practical boroxine compounds. Instead, the compositions of both
Comparative Example #1 and Comparative Example #2 are free of any
boron-containing compound. Comparative Example #1 includes the
practical amine compound, whereas Comparative Example #2 does not
include the practical amine compound. The boron-containing compound
added to the reference lubricant in Comparative Example #3 is
triethoxyboroxine. The boron-containing compound added to the
reference lubricant in Comparative Example #4 is
tri-n-butoxyboroxine. The boron-containing compound added to the
reference lubricant in Comparative Example #5 was
tris-(2-ethylhexyl)boroxine. The boron-containing compound added to
the reference lubricant in Comparative Example #6 is tributyl
borate. The boron-containing compound added to the reference
lubricant in Comparative Example #7 is tri-isopropyl borate.
[0111] Comparative Examples #8 and 9 include the practical boroxine
compounds but do not include the practical amine compounds. The
boroxine compound added to the reference lubricant in Comparative
Examples #8 and 9 is trimethoxyboroxine.
[0112] Comparative Examples #10-14 do not include either the
practical boroxine compound or the practical amine compound. The
boroxine compound added to the reference lubricant in Comparative
Example #10 is triethoxyboroxine. The boroxine compound added to
the reference lubricant in Comparative Example #11 is
tri-n-butoxyboroxine. The boron-containing compound in Comparative
Example #12 is tris-(2-ethylhexyl)boroxine. The boron-containing
compound in Comparative Example #13 is tributyl borate. The
boron-containing compound in Comparative Example #14 is
tri-isopropyl borate.
[0113] The amine compound included in Practical Examples #1 and 2
and Comparative Examples #1 and 3-7 is
(2,2,6,6-tetramethyl-4-piperidyl) dodecanoate.
[0114] The respective amount of the reference lubricant and any
additional components for each of the Practical and Comparative
Examples are shown in Tables 2, 3, and 4 below:
TABLE-US-00002 TABLE 2 Formulations of Practical Examples #1-#2
Practical Practical #1 #2 Reference Lubricant (g) 80 80 Additional
Base Oil (g) 18 16.5 Boron-containing Compound (g) 0.5 2 Practical
Amine Compound (g) 1.5 1.5 Total Weight (g) 100 100
TABLE-US-00003 TABLE 3 Formulations of Comparative Examples #1-7
(C1-C7) C1 C2 C3 C4 C5 C6 C7 Reference 80 80 80 80 80 80 80
Lubricant (g) Additional Base Oil 18.5 20 18 18 18 18 18 (g)
Boron-containing 0 0 0.5 0.5 0.5 0.5 0.5 Compound (g) Practical
Amine 1.5 0 1.5 1.5 1.5 1.5 1.5 Compound (g) Total Weight (g) 100
100 100 100 100 100 100
TABLE-US-00004 TABLE 4 Formulations of Comparative Examples #8-14
(C8-C14) C8 C9 C10 C11 C12 C13 C14 Reference 80 80 80 80 80 80 80
Lubricant (g) Additional Base Oil 19.5 18 19.5 19.5 19.5 19.5 19.5
(g) Boron-containing 0.5 2 0.5 0.5 0.5 0.5 0.5 Compound (g)
Practical Amine 0 0 0 0 0 0 0 Compound (g) Total Weight (g) 100 100
100 100 100 100 100
[0115] The seal compatibility of the practical and comparative
examples was evaluated using an industry-standard CEC L-39-T96 seal
compatibility test. The CEC-L-39-T96 seal compatibility test is
performed by submitting the seal or gaskets in the lubricant
composition, heating the lubricant composition with the seal
contained therein to an elevated temperature, and maintaining the
elevated temperature for a period of time. The seals are then
removed and dried, and the mechanical properties of the seal are
assessed and compared to the seal specimens which were not heated
in the lubricant composition. The percent change in these
properties is analyzed to assess the compatibility of the seal with
the lubricant composition. Each formulation was tested twice (Run
#1 and Run #2) under the same conditions. The results of the seal
compatibility test are shown below in Tables 5-10.
TABLE-US-00005 TABLE 5 Seal Compatibility Test Results (Run 1) -
Practical Examples #1-#2 Practical Practical #1 #2 Volume Change
(%) 0.5 0.8 Points Hardness DIDC 4 0 Tensile Strength (%) -39 -2
Elongation at Rupture (%) -54 8
TABLE-US-00006 TABLE 6 Seal Compatibility Test Results (Run 2) -
Practical Examples #1-#2 Practical Practical #1 #2 Volume Change
(%) 0.5 0.7 Points Hardness DIDC 4 -1 Tensile Strength (%) -32 -5
Elongation at Rupture (%) -51 -5
TABLE-US-00007 TABLE 7 Seal Compatibility Test Results (Run 1) -
Comparative Examples #1-#7 (C1-C7) C1 C2 C3 C4 C5 C6 C7 Volume
Change (%) 0.3 0.2 0.5 0.5 0.8 0.4 0.7 Points Hardness DIDC 7 5 5 6
7 6 8 Tensile Strength (%) -44 -32 -41 -39 -47 -39 -44 Elongation
at Rupture -69 -40 -61 -66 -72 -64 -66 (%)
TABLE-US-00008 TABLE 8 Seal Compatibility Test Results (Run 2) -
Comparative Examples #1-#7 (C1-C7) C1 C2 C3 C4 C5 C6 C7 Volume
Change (%) 0.4 0.2 0.7 0.4 0.8 0.6 0.7 Points Hardness DIDC 8 4 5 6
8 6 7 Tensile Strength (%) -49 -31 -41 -40 -44 -41 -42 Elongation
at Rupture -71 -40 -59 -66 -68 -61 -67 (%)
TABLE-US-00009 TABLE 9 Seal Compatibility Test Results (Run 1) -
Comparative Examples #8-#14 (C8-C14) C8 C9 C10 C11 C12 C13 C14
Volume Change (%) 0.5 0.7 0.3 0.2 0.5 0.4 0.6 Points Hardness DIDC
2 1 1 2 3 4 4 Tensile Strength (%) -29 5 -26 -21 -29 -31 -29
Elongation at Rupture -38 -25 -40 -40 -43 -42 -49 (%)
TABLE-US-00010 TABLE 10 Seal Compatibility Test Results (Run 2) -
Comparative Examples #8-#14 (C8-C14) C8 C9 C10 C11 C12 C13 C14
Volume Change (%) 0.4 0.7 0.6 0.4 0.6 0.3 0.5 Points Hardness DIDC
2 1 2 2 4 4 3 Tensile Strength (%) -23 0 -23 -25 -27 -28 -26
Elongation at Rupture -34 -20 -33 -42 -45 -43 -51 (%)
[0116] Comparative Example #1 is illustrative of the effect of an
amine compound on the seal compatibility of a lubricant
composition. By comparing the tensile strength and elongation at
rupture of Comparative Example #1, which includes the practical
amine compound, and Comparative Example #2, which does not include
the practical amine compound, the inventors realized that the
addition of a practical amine compound to the reference lubricant
negatively impacts the seal compatibility of the reference
lubricant. The negative impact is quantified by the fact that the
tensile strength and elongation at rupture is much worse for
Comparative Example #1 when compared to Comparative Example #2.
[0117] Practical Examples #1 and #2 each include the same practical
amine compound as Comparative Example #1, in conjunction with one
species of the practical boroxine compound. As can be seen in the
results shown in Tables 4-7, the seal compatibility of Practical
Examples #1 and 2 is significantly improved over the seal
compatibility of Comparative Example #1 in terms of both tensile
strength and elongation at rupture. This significant improvement in
seal compatibility is evidenced by the fact that the tensile
strength and elongation at rupture is much worse for Comparative
Example #1 when compared to Practical Examples #1 and 2.
[0118] Tables 5-8 also demonstrate that the seal compatibility of
Practical Examples #1 and 2 was improved in terms of tensile
strength and elongation at rupture as compared to the seal
compatibility of Comparative Examples #3-7. The tensile strength of
Practical Example #1 was -39 and -32%; and the tensile strength of
Practical Example #2 was -2 and -5%, whereas the tensile strength
of Comparative Examples #3, 4, 5, 6, and 7 was -41 and -41%; -39
and -40%, -47 and -44%; -39 and -41; and -44 and -42%,
respectively. Similarly, the elongation at rupture for Practical
Example #1 was -54 and -51%; and the elongation at rupture for
Practical Example #2 was 8 and -5%, whereas the elongation at
rupture of Comparative Examples #3, 4, 5, 6, and 7 was -61 and
-59%; -66 and -66%: -72 and -68%; -64 and -61%; and -66% and -67%,
respectively. This testing shows that the lubricant compositions of
Practical Examples #1 and 2 were much more compatible with seals in
terms of tensile strength and elongation at rupture. This
comparison provides evidence that the combination of the practical
boroxine compounds and the practical amine compounds in a lubricant
composition yields much improved seal compatibility over a
lubricant composition that includes other boron-containing
compounds, such as those utilized in Comparative Examples #3-7.
[0119] Finally, the comparison of Comparative Example #2 and
Comparative Examples #8-14 demonstrates that lubricant compositions
which include boron-containing compounds but do not include the
practical amine compound do not negatively affect the seal
compatibility of the lubricant composition in a significant way.
Accordingly, the inventors of the subject application have
surprisingly realized that the combination of the practical amine
compound and the practical boroxine compounds have a synergistic
impact on seal compatibility when present in the reference
lubricant.
[0120] It is to be understood that the appended claims are not
limited to express and particular compounds, compositions, or
methods described in the detailed description, which may vary
between particular embodiments that fall within the scope of the
appended claims. With respect to any Markush groups relied upon
herein for describing particular features or aspects of various
embodiments, it is to be appreciated that different, special,
and/or unexpected results may be obtained from each member of the
respective Markush group independent from all other Markush
members. Each member of a Markush group may be relied upon
individually and/or in combination and provides adequate support
for specific embodiments within the scope of the appended
claims.
[0121] It is also to be understood that any ranges and subranges
relied upon in describing various embodiments of the present
invention independently and collectively fall within the scope of
the appended claims and are understood to describe and contemplate
all ranges, including whole and/or fractional values therein, even
if such values are not expressly written herein. One of skill in
the art readily recognizes that the enumerated ranges and subranges
sufficiently describe and enable various embodiments of the present
invention and such ranges and subranges may be further delineated
into relevant halves, thirds, quarters, fifths, and so on. As just
one example, a range "ranging from 0.1 to 0.9" may be further
delineated into a lower third, i.e., from 0.1 to 0.3, a middle
third, i.e., from 0.4 to 0.6, and an upper third, i.e., from 0.7 to
0.9, which individually and collectively are within the scope of
the appended claims and may be relied upon individually and/or
collectively and provide adequate support for specific embodiments
within the scope of the appended claims.
[0122] In addition, with respect to the language which defines or
modifies a range, such as "at least," "greater than," "less than,"
"no more than," and the like, it is to be understood that such
language includes subranges and/or an upper or lower limit. As
another example, a range of "at least 10" inherently includes a
subrange ranging from at least 10 to 35, a subrange ranging from at
least 10 to 25, a subrange from 25 to 35, and so on, and each
subrange may be relied upon individually and/or collectively and
provides adequate support for specific embodiments within the scope
of the appended claims. Finally, an individual number within a
disclosed range may be relied upon and provides adequate support
for specific embodiments within the scope of the appended claims.
For example, a range "ranging from 1 to 9" includes various
individual integers, such as 3, as well as individual numbers
including a decimal point (or fraction), such as 4.1, which may be
relied upon and provide adequate support for specific embodiments
within the scope of the appended claims.
[0123] The invention has been described in an illustrative manner
and it is to be understood that the terminology which has been used
is intended to be in the nature of words of description rather than
of limitation. Many modifications and variations of the present
invention are possible in light of the above teachings and the
invention may be practiced otherwise than as specifically
described.
* * * * *