Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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LUBRICANT COMPOSITIONS COMPRISING BOROXINES
TO IMPROVE FLUOROPOLYMER SEAL COMPATIBILITY
FIELD OF THE INVENTION
[0001] 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
[0002] 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.
[0003] It is an object of the present invention to provide new types of
lubricant
compositions having improved fluoropolymer seal compatibility.
SUMMARY OF THE INVENTION
[0004] The present invention provides a lubricant composition including a base
oil, a
boroxine compound, and a sterically hindered amine compound. The boroxine
compound has general formula (I):
Ri
0
I
0 0
1 l I
0 0 0
1 1
R (I),
wherein each R1 is independently an alkyl group having from 1 to 7 carbon
atoms.
[0005] The present invention provides a lubricant composition including a base
oil, a
boroxine compound, and a sterically hindered amine compound. The boroxine
compound has general formula (I):
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Ri
/
0
I
0 0
1 l I
R.., .....-B,,,, ......-B,....,
0 0 0
1 l
R (I),
wherein each R1 is independently an alkyl group having from 1 to 7 carbon
atoms.
[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 (II) or (III):
R3
2
R-/ \-R2
R I 3 R
R (II);
R4 R4
5
R( R
R
I 5 R
R (III),
wherein each R2 is independently a hydrogen atom or a hydrocarbyl group having
from 1 to 17 carbon atoms, and wherein at least two groups designated by R2
are an
alkyl group; wherein each R3 is independently a hydrogen atom or a hydrocarbyl
group having from 1 to 17 carbon atoms; wherein each R4 is independently a
hydrogen atom or a hydrocarbyl group having from 1 to 17 carbon atoms, and
wherein at least two groups designated by R4 are an alkyl group; wherein each
R5 is
independently a hydrogen atom or a hydrocarbyl group having from 1 to 17
carbon
atoms, and wherein said hydrocarbyl groups designated by R2, R3, R4, and R5
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.
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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
compounds.
It is believed that, when present in a lubricant composition with the
sterically hindered
amine compound, the boroxine compound 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 general formula (I):
Ri
0
I
....B.,
0 0
1 l I
R.., ......-B., ......-B.,
0 0 0
1 1
R (I).
In general formula (I), each R1 is independently an alkyl group having equal
to or
fewer than 7 carbon atoms. For example, each R1 may independently be an alkyl
group having from 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 to 2, carbon
atoms. Each R1
may independently be linear or branched. In one specific formulation, each R1
may be
a methyl group. Exemplary R1 groups may independently include methyl, ethyl, n-
propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, and n-hexyl groups.
[0011] The boroxine compound may be exemplified by trimethoxy boroxine,
tripropoxy boroxine, triisopropoxy boroxine, tributoxy boroxine, tripentoxy
boroxine,
trihexoxy boroxine, and triheptoxy boroxine. By way of example, trimethoxy
boroxine has the formula:
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/CH3
0
0 0
H3
0 0 0
CH-
[0012] In certain embodiments, each R1 may represent distinct alkyl groups.
For
example, the boroxine compound may be exemplified by the formula:
CH3
0
0 0
H3 C 0 0 0
CH3where one group designated by R1 in formula (I) is methyl, one group
designated by
R1 in formula (I) is ethyl, and one group designated by R1 in formula (I) is
propyl.
Alternatively still, groups designated by R1 may be the same, and one group
designated by R1 may be different in formula (I).
[0013] 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.
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[0014] 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.
Mixtures
of different boroxine compounds may also be used in combination in the
lubricant
composition or the additive package.
[0015] If formulated as the 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.
[0016] 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 (H3B03) with 1 mole tri-alkyl borate. The alkyl borate may have from 1 to
7
carbon atoms, depending on the number of carbon atoms desired in the groups
designated by R1 in general formula (I). The reaction can be conducted at a
temperature ranging from 50 to 150 C in order to remove 1 mol H20.
[0017] 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).
[0018] In such applications of conventional boron compounds, more than 50 wt.%
of
the conventional boron compound is typically reacted with the conventional
amine
compounds, or is hydrolyzed, based on the total weight of the conventional
boron
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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.
[0019] 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.
[0020] 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.
[0021] 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.
[0022] 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,
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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.
[0023] 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.
[0024] 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.
[0025] "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.
[0026] The lubricant composition may include less than 100, less than 50, less
than
10, or less than 5, ppm B(OH)3- 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)3- ions are present in the conventional lubricant composition. In such a
hydrolyzed state, the inventors of the subject application surprisingly
realized that the
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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.
[0027] 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.
[0028] 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 25, 0.1 to 20, 0.1 to
15,
or 0.1 to 10, 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, 1 to 2, wt.%, based on
the total
weight of the lubricant composition.
[0029] 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.
[0030] 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
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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.
[0031] 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.
[0032] 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 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.
[0033] 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.
[0034] 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.
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[0035] 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,
amine
salt and/or sulfate amine salt.
[0036] In other 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 compound may have a weight average molecular weight of less
than
500.
[0037] As used herein, the term "sterically hindered amine compound" means an
organic molecule having fewer than two hydrogen atoms bonded to at least one
alpha-
carbon with reference to a secondary or tertiary nitrogen atom. In other
embodiments,
the term "sterically hindered amine compound" means an organic molecule having
no
hydrogen atoms bonded to at least one alpha-carbon with reference to a
secondary or
tertiary nitrogen atom. In still other embodiments, the term "sterically
hindered amine
compound" means an organic molecule having no hydrogen atoms bonded to each of
at least two alpha-carbons with reference to a secondary or tertiary nitrogen
atom.
[0038] The sterically hindered amine compound may have general formula (II) or
(III):
R3
R2 C A- R2
2 N- \ 2
R I 3 R
R (II);
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R4 R4
5
Rk R
4 N)(4
R
I 5 R
R (III).
In general formula (II), each R2 is independently a hydrogen atom or a
hydrocarbyl
group having from 1 to 17 carbon atoms, wherein at least two of R2 are an
alkyl group
in one molecule; and R3 is independently a hydrogen atom or a hydrocarbyl
group
having from 1 to 17 carbon atoms. In general formula (III), each R4 is
independently
a hydrogen atom or a hydrocarbyl group having from 1 to 17 carbon atoms,
wherein
at least two of R4 are an alkyl group, and each R5 is independently a hydrogen
atom or
a hydrocarbyl group having from 1 to 17 carbon atoms.
[0039] Each R2, R3, R4, and R5 may independently be an alcohol group, an alkyl
group, an amide group, an ether group, or an ester group. Each R2, R3, R4, and
R5
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 R2, R3, R4, and R5 may independently be
straight or
branched. For example, each R2, R3, R4, and R5 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.
[0040] In certain embodiments, at least one group designated by R2, R3, R4,
and R5 is
unsubstituted. Alternatively, at least two, three, four, five, or six groups
designated
by R2, R3, R4, and R5 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 R2, R3, R4, and R5 is unsubstituted.
Alternatively still, it is contemplated that one, two, three, four, five, or
six groups
designated by R2, R3, R4, and R5 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.
[0041] Exemplary R2, R3, R4, and R5 groups may be independently selected from
methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-
ethylhexyl,
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n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl,
or n-
octadecyl.
[0042] In general formula (II), at least two, at least three, or all four
groups,
designated by R2 are independently an alkyl group. Similarly, in general
formula
(III), at least two groups designated by R4 are an alkyl group. Alternatively,
at least
three, or all four groups, designated by R4 are an alkyl group.
[0043] The sterically hindered amine compound of general formula (II) may be
exemplified by the following compounds:
2,2,6,6-tetramethy1-4-octylpiperdine:
H3C\
\ CH3
\ CH3
\ ______________________________________ ( NH
(.....'CH3
CH3
2,2,6,6-tetramethy1-4-decylpiperdine:
H3C\
\
\ cH3
\ ____________________________________________ ....õ,.cii3
\ ________________________________________ ( NH
(.....CH3
CH3
2,2,6,6-tetramethy1-4-butylpiperdine:
H3C CH3
\ _____________________________________ k......CH3
\ _________________________________ ( NH
(....CH3
CH3
2,2,6,6-tetramethy1-4-hexadecylpiperdine:
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H 3C\
CH3
( NH
CH3
CH3
[0044] The sterically hindered amine compound of general formula (III) is
acyclic.
The term "acyclic" is intended to mean that the sterically hindered amine
compound
of general formula (III) is free from any cyclic structures and aromatic
structures.
The sterically hindered amine compound of general formula (III) can be
exemplified
by:
N-tert-butyl-2-ethyl-N-methyl-hexan- 1 - amine:
CH3
/ ___________________________________________ CH3
CH/
H3C-N
CH3
tert-amyl-tert-butylamine:
H3C CH3
\ A CH3
H3C NH CH3
CH3
N-tert-butylheptan-2-amine:
CH
H3C..)(
NH
H3C
H3CWCH3
[0045] The sterically hindered amine compound may further alternatively be
exemplified by the general formula (IV):
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3
R
0 0
...õ,/\...
2 2
RI 3 R
R (IV).
In general formula (IV), each R2 and R3 are as described above, wherein at
least three
of R2 are independently an alkyl group. The sterically hindered amine compound
of
general formula (IV) may be exemplified by the following compounds:
(1,2,2,6,6-pentamethy1-4-piperidyl) octanoate:
H3c _________________ \
\ ID cH3
ID _____________________________________ ( N¨CH3
(...'cii3
cH3
(1,2,2,6,6-pentamethy1-4-piperidyl) decanoate:
H3C _______________ \
\
\ 0 CH3
0 ________________________________________ ( N-CH3
(....-CH3
CH3
(1,2,2,6,6-pentamethy1-4-piperidyl) dodecanoate:
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H3C _____________ \
\\
\ 0 CH3
0 ___________________________________________ ( N-CH3
(.....'CH3
CH3
(2,2,6,6-tetramethy1-4-piperidyl) dodecanoate
H3c ______________ \
\\\ti) CH3
\ _______________________________________ < c113
CH3
CH3
[0046] 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.
[0047] 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.
[0048] 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
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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.
[0049] 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' describes 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.
[0050] In some aspects, the lubricant composition includes 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).
[0051] 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.
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[0052] The base oil may have a viscosity ranging from 1 to 20 cSt when tested
according to ASTM D445 at 100 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
C.
[0053] 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.
[0054] 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 C3-
C8 fatty acid esters, and the C13 oxo acid diester of tetraethylene glycol may
also be
utilized as the base oil.
[0055] 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.
[0056] 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
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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.
[0057] 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. The term "SAPS"
refers
to sulfated ash, phosphorous, and sulfur.
[0058] 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.
[0059] 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 C2_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.
[0060] 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 (V):
18
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polymer _________________________
(V).
The bonds shown in general formulas (V) 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.
[0061] 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 one specific
embodiment,
derivatives with aliphatic polyamines such as ethylenediamine,
diethylenetriamine,
triethylenetetramine or tetraethylenepentamine may be used.
[0062] To prepare the polyalkene amine, the polyalkene component may be
aminated
in a known manner. An exemplary process proceeds via the preparation of an oxo
intermediate by hydroformylation and subsequent reductive amination in the
presence
of a suitable nitrogen compound.
[0063] The dispersant may be a poly(oxyalkyl) radical or a polyalkylene
polyamine
radical of the general formula (VI):
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R6¨NH¨(C1-C6-alkylene-NH)m¨C1-C6-alkylene (VI)
where m is an integer ranging from 1 to 5, R6 is a hydrogen atom or a
hydrocarbyl
group having from 1 to 6 carbon atoms with C1-C6 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 C1-C4 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 C1-C4 alkyl radicals and optionally bears one further ring heteroatom
such as
oxygen or nitrogen.
[0064] 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.
[0065] Examples of C4-C18 cycloalkyl radical include cyclobutyl, cyclopentyl
and
cyclohexyl, and also the analogs thereof substituted by 1 to 3 C1-C4 alkyl
radicals.
The C1-C4 alkyl radicals are, for example, selected from methyl, ethyl, iso-
or n-
propyl, n-, iso-, sec- or tert-butyl.
[0066] Examples of the arylalkyl radical include a C1-C18 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.
[0067] 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.
[0068] If employed, the dispersant can be used in various amounts. The
dispersant is
typically 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.
[0069] In the additive package, the total weight of the dispersant and the
boroxine
compound may be less than 50, less than 45, less than 40, less than 35, or
less than 30,
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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.
[0070] The lubricant composition or the additive package may further comprise
a
dihydrocarbyldithiophosphate salt. The dihydrocarbyldithiophosphate salt may
be
represented by the following general formula: 11R70(R80)PS(S)12M, where R7 and
R8
are each hydrocarbyl groups having from 1 to 20 carbon atoms, wherein M is a
metal
atom or an ammonium group. For example, R7 and R8 may each independently be
C1_
zo alkyl groups, C2_20 alkenyl groups, C3_20 cycloalkyl groups, C1_20 aralkyl
groups or
C3_20 aryl groups. The groups designated by R7 and R8 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 R9RioRtiRiz.,IN+,
wherein R9, R10, R11,
and R12 each independently
represents a hydrogen atom or a hydrocarbyl group having from 1 to 150 carbon
atoms. In certain embodiments, R9, R10, R11,
and R12 may each independently be
hydrocarbyl groups having from 4 to 30 carbon atoms. In one specific
embodiment,
the dihydrocarbyldithiophosphate salt is zinc dialkyl dithiophosphate.
[0071] 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.
[0072] 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
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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.
[0073] 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 -dimerc apto- 1,3 ,4-
thiadiazole,
ethyl 3- Rdiisopropoxyphosphinothioyl)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-trisksooctyl 2-acetate], derivatives of 2-
mercaptobenzothiazole such as 14N,N-bis (2-ethylhexyl)aminomethy11-2-mercapto-
1H-1 ,3-benzothiazole, ethoxycarbony1-5-octyldithio carbamate, and/or
combinations
thereof.
[0074] 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
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0.5, or less than 0.1, wt.%, each based on the total weight of the lubricant
composition.
[0075] 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-
buty1-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-buty1-4-
n-
butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopenty1-4-
methylphenol, 2-
(a-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecy1-4-methylphenol, 2,4,6-
tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nony1-4-
methylphenol, 2,4-dimethyl- 6( 1 '-methylundec- l'-yl)phenol, 2,4-
dimethyl- 6-( l -
methylheptadec- l'-yl)phenol, 2,4-dimethyl- 6-
( 1 '-methyltridec- l'-yl)phenol, and
combinations thereof.
[0076] Further examples of suitable antioxidants includes
alkylthiomethylphenols, for
example 2,4-dioctylthiomethy1-6-tert-
butylphenol, 2,4-dioctylthiomethy1-6-
methylphenol, 2,4-dioctylthiomethy1-6-ethylphenol, 2,6-didodecylthiomethy1-4-
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-
dipheny1-4-
octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5 -di-
tert-buty1-4-
hydroxyanisole, 3,5-di-tert-buty1-4-hydroxyanisole, 3,5-di-tert-buty1-4-
hydroxyphenyl
stearate, bis-(3,5-di-tert-buty1-4-hydroxyphenyl) adipate, and combinations
thereof,
may also be utilized.
[0077] Furthermore, hydroxylated thiodiphenyl ethers, for example 2,2'-
thiobis(6-tert-
buty1-4-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-dimethy1-4-hydroxyphenyl) disulfide, and
combinations
thereof, may also be used.
[0078] It is also contemplated that alkylidenebisphenols, for example 2,2'-
methylenebis(6-tert-buty1-4-methylphenol), 2,2'-
methylenebis(6-tert-buty1-4-
ethylphenol), 2,2' -
methylenebis [4-methyl-6-(a-methylcyclohexyl)phenoll , 2,2'-
methylenebi s (4-methyl- 6-cyc lohexylphenol) , 2,2'-
methylenebis(6-nony1-4-
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- (a-methylbenzy0-4-nonylphenoll , 2,2'-
methylenebis 1L6- (a,a-dimethylbenzy1)-4-
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nonylphenoll, 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-
tert-
buty1-2-methylphenol), 1 , 1 -bi s (5 -tert-butyl-4-hydroxy-2-
methylphenyl)butane, 2,6-
bis (3 -tert-butyl- 5 -methy1-2-hydroxybenzy1)-4-methylphenol, 1, 1,3 -tris (5
-tert-buty1-4-
hydroxy-2-methylphenyl) butane, 1,1-bis(5-tert-buty1-4-hydroxy-2-methyl-
pheny1)-3-
n-dodecylmercapto butane, ethylene glycol
bis [3,3 -bis (3' -tert-buty1-4' -
hydroxyphenyl)butyratel, bis (3 -
tert-buty1-4-hydroxy- 5 -methyl-
phenyl)dicyclopentadiene, bis 1L243
'-tert-butyl-2'-hydroxy-5 ' -methylbenzy1)- 6-tert-
buty1-4-methylphenyll terephthalate, 1, 1 -bis-(3 ,5 -dimethy1-2-
hydroxyphenyl)butane,
2,2-bis-(3 ,5 -di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis-(5 -tert-buty1-4-
hydroxy-
2-methylpheny1)-4-n-dodecylmercaptobutane, 1, 1,5 ,5 -tetra- (5 -tert-buty1-4-
hydroxy-2-
methyl phenyl)pentane, and combinations thereof may be utilized as
antioxidants in
the lubricant composition.
[0079] 0-, N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-buty1-
4,4'-
dihydroxydibenzyl ether, octadecy1-4-hydroxy-3,5-
dimethylbenzylmercaptoacetate,
tris -(3 ,5 -di-tert-butyl-4-hydroxybenzyl) amine , bis(4-tert-
buty1-3-hydroxy-2,6-
dimethylbenzyl)dithiol terephthalate, bis(3,5-di-tert-buty1-4-
hydroxybenzyl)sulfide,
isoocty1-3,5di-tert-buty1-4-hydroxy benzylmercaptoacetate, and combinations
thereof,
may also be utilized.
[0080] Hydroxybenzylated malonates, for example dioctadecy1-2,2-bis-(3,5-di-
tert-
buty1-2-hydroxybenzy1)-malonate, di-
octadecy1-2- (3 -tert-butyl-4-hydroxy-5 -
methylbenzy1)-malonate, di-dodec
ylmerc aptoethy1-2,2-bis- (3 ,5-di-tert-buty1-4-
hydroxybenzyl)malonate, bis 1144 1, 1,3 ,3-tetramethylbutyl)phenyll -2,2-bis
(3 ,5 -di-tert-
buty1-4-hydroxybenzyl)malonate, and combinations thereof are also suitable for
use
as antioxidants.
[0081] Triazine compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-
buty1-
4-hydroxyanilino)- 1,3 ,5 -triazine, 2-
octylmerc apto-4,6-bis (3 ,5 -di-tert-buty1-4-
hydroxyanilino)- 1 ,3 ,5 -triazine, 2-
octylmerc apto-4,6-bis (3 ,5 -di-tert-buty1-4-
hydroxyphenoxy)- 1 ,3 ,5 -triazine, 2,4,6-tris (3 ,5 -di-tert-buty1-4-
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-buty1-4-
hydroxyphenylethyl)- 1,3 , 5 -triazine , 1 ,3 ,5 -
tris (3 ,5-di-tert-butyl-4-hydroxyphenyl
propiony1)-hexahydro- 1,3,5 -triazine, 1,3,5 -tris- (3 ,5-dicyclohexy1-4-
hydroxybenzy1)-
isocyanurate, and combinations thereof, may also be used.
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[0082] Additional examples of antioxidants include aromatic hydroxybenzyl
compounds, for example, 1 ,3 ,5 -
tris- (3 ,5-di-tert-buty1-4-hydroxybenzy1)-2,4,6-
trimethylbenzene, 1,4-bi s
(3 ,5 -di-tert-buty1-4-hydro xybenzy1)-2,3 ,5 ,6-
tetramethylbenzene , 2,4,6-tris (3 ,5 -di-tert-butyl-4-
hydroxybenzyl)phenol, and
combinations thereof. Benzylphosphonates, for example dimethy1-2,5-di-tert-
buty1-4-
hydroxybenzylphosphonate, diethyl-3,5-di-tert-buty1-4-
hydroxybenzylphosphonate,
dioctadecy13,5-di-tert-buty1-4-hydroxybenzylphosphonate, dioctadecy1-5 -tert-
buty1-4-
hydroxy3 -methylbenzylphosphonate, the calcium salt of the monoethyl ester of
3,5-
di-tert-buty1-4-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-buty1-4-hydroxyphenyl)carbamate.
[0083] Esters of 1L3-(3,5-di-tert-buty1-4-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 -thi aundec anol, 3 -
thiapentadec anol,
trimethylhexanediol, trimethylolpropane, 4-
hydroxymethyl- 1 -phospha-2,6,7 -
trioxabicyclo [2.2.21 octane, and combinations thereof, may also be used. It
is further
contemplated that esters of 13-(5-tert-buty1-4-hydroxy-3-methylpheny1)-
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-
thiapentadec anol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl- 1
-
phospha-2,6,7-trioxabicyclol2.2.2loctane, and combinations thereof, may be
used.
[0084] Additional examples of suitable antioxidants include those that include
nitrogen, such as amides of 13-(3,5-di-tert-buty1-4-hydroxypheny1)propionic
acid, e.g.,
N,N'-bis (3 ,5 -di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenedi amine ,
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-
dimethylpenty1)-p-phenylenediamine, N,N' -bis
( 1 -ethyl-3 -methylpenty1)-p-
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phenylenediamine, N,N'-bi s (1 -methylhepty1)-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-buty1)-N' -phenyl-p-phenylenedi amine, N- (1 -
methylhepty1)-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-l-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'-tetramethy1-4,4'-diaminodiphenylmethane, 1,2-
bis R2-methyl-phenyllaminol ethane, 1 ,2-bis (phenylamino)propane, (o-
tolyl)biguanide, bis [4-(1',3'-dimethylbutyl)phenyll amine, tert-octylated N-
pheny1-1-
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-
butyldiphenylamine s , 2,3- dihydro-3 ,3 -dimethy1-4H- 1,4-benzothi azine,
phenothiazine,
N-allylphenothiazine, N,N,N',N'-tetrapheny1-1,4-diaminobut-2-ene, and
combinations
thereof.
[0085] 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-tetramethy1-5,9-dihydroxy-
3,7,1trithiatridecane and 2,2,15,15-
tetramethy1-5,12-dihydroxy-3,7,10,14-
tetrathiahexadecane, and combinations thereof. Furthermore, sulfurized fatty
esters,
sulfurized fats and sulfurized olefins, and combinations thereof, may be used.
[0086] 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.
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[0087] 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- lbis(2-
ethylhexyl)aminomethylltolutriazole and 1-
lbis(2-ethylhexyl)aminomethyllbenzotriazole; and alkoxyalkylbenzotriazoles
such as
1 -(nonyloxymethyl)benzotriazole, 1- (1 -
butoxyethyl)benzotriazole and 1 -(1 -
cyclohexyloxybutyl) tolutriazole, and combinations thereof.
[0088] 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- lbis(2-
ethylhexyl)aminomethy1-1,2,4-triazole; alkoxyalky1-1,2,4-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-undecy1-5-methylimidazole) and
bis RN-
methyllimidazol-2-yllcarbinol octyl ether, and combinations thereof.
Further
examples of suitable metal deactivators include sulfur-containing heterocyclic
compounds, for example 2-mercaptobenzothiazole, 2,5 -dimerc apto- 1,3 ,4-
thiadiazole
and derivatives thereof; and 3 ,5-bis ldi (2-ethylhexyl) aminomethyll - 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.
[0089] 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.
[0090] 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 dodecyloxy acetic acid,
dodecyloxy(ethoxy)acetic acid, and also N-oleoylsarcosine, sorbitan
monooleate, lead
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naphthenate, alkenylsuccinic anhydrides, for example, dodecenylsuccinic
anhydride,
2-carboxymethy1-1-dodecy1-3-methylglycerol, and combinations thereof. Further
examples include heterocyclic compounds, for example: substituted imidazolines
and
oxazolines , and 2-heptadeceny1-1-(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-
carboxyalky1-1,3-dialkylglycerols, and combinations thereof.
[0091] 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.
[0092] 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.
[0093] 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.
[0094] 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.
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[0095] 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.
[0096] 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.
[0097] 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.
[0098] 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.
[0099] 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 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
[00100] 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
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each characteristic depends on the type of elastomer used, the type of engine
used,
and whether an aftertreatment device is utilized.
[00101] 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 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
[00102] 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%.
[00103] 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
%, -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 %.
[00104] 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, %,
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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.
[00105] 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.
[00106] 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.
[00107] 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.
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[00108] 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 C.
EXAMPLES
[00109] 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.
[00110] 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, #2, #3, and
#4
each include one of the practical boroxine compounds and one of the practical
amine
compounds. Comparative Examples #1-5 do not include any of the practical
boroxine
compounds. Comparative Examples #6-8 do not include any of the practical amine
compounds. Comparative Examples #9-#12 do not include either the practical
amine
compounds or the practical boroxine compounds.
[00111] The boron-containing compound added to the reference lubricant in
Practical
Examples #1 and #2 is trimethoxyboroxine. The boron-containing compound added
to
the reference lubricant in Practical Example #3 is triethoxyboroxine. The
boron-
containing compound added to the reference lubricant in Practical Example #4
is tri-
n-butoxyboroxine.
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[00112] As described above, Comparative Examples #1-5 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 was tris-(2-ethylhexyl)boroxine. The boron-containing compound
added
to the reference lubricant in Comparative Example #4 is tributyl borate. The
boron-
containing compound added to the reference lubricant in Comparative Example #5
is
tri-isopropyl borate.
[00113] Comparative Examples #6-9 include the practical boroxine compounds but
do not include the practical amine compounds. The boroxine compound added to
the
reference lubricant in Comparative Examples #6 and 7 is trimethoxyboroxine.
The
boroxine compound added to the reference lubricant in Comparative Example #8
is
triethoxyboroxine. The boroxine compound added to the reference lubricant in
Comparative Example #9 is tri-n-butoxyboroxine.
[00114] Comparative Examples #10-12 do not include either the practical
boroxine
compound or the practical amine compound. The boron-containing compound in
Comparative Example #10 is tris-(2-ethylhexyl)boroxine. The boron-containing
compound in Comparative Example #11 is tributyl borate. The boron-containing
compound in Comparative Example #12 is tri-isopropyl borate.
[00115] The amine compound included in Practical Examples #1-4 and Comparative
Examples #1 and 3-5 is (2,2,6,6-tetramethy1-4-piperidyl) dodecanoate.
[00116] 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:
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TABLE 2: Formulations of Practical Examples #1-#4
Practical Practical Practical Practical
#1 #2 #3 #4
Reference Lubricant (g) 80 80 80 80
Additional Base Oil (g) 18 16.5 18 18
Boron-containing Compound (g) 0.5 2 0.5 0.5
Practical Amine Compound (g) 1.5 1.5 1.5 1.5
Total Weight (g) 100 100 100 100
TABLE 3: Formulations of Comparative Examples #1-5 (C1-05)
C1 C2 C3 C4 C5
Reference Lubricant (g) 80 80 80 80 80
Additional Base Oil (g) 18.5 20 18 18 18
Boron-containing Compound (g) 0 0 0.5 0.5 0.5
Practical Amine Compound (g) 1.5 0 1.5 1.5 1.5
Total Weight (g) 100 100 100 100 100
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TABLE 4: Formulations of Comparative Examples #6-11 (C6-C12)
C6 C7 C8 C9 C10 C11 C12
Reference Lubricant (g) 80 80 80 80 80 80 80
Additional Base Oil (g) 19.5 18 19.5 19.5 19.5 19.5 19.5
Boron-containing Compound
0.5 2 0.5 0.5 0.5 0.5 0.5
(g)
Practical Amine Compound (g) 0 0 0 0 0 0 0
Total Weight (g) 100 100 100 100 100 100 100
[00117] 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.
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Table 5: Seal Compatibility Test Results (Run 1) - Practical Examples #1-#4
Practical #1 Practical #2 Practical #3 Practical #4
Volume Change (%) 0.5 0.8 0.5 0.5
Points Hardness DIDC 4 0 5 6
Tensile Strength (%) -39 -2 -41 -39
Elongation at Rupture (%) -54 8 -61 -66
Table 6: Seal Compatibility Test Results (Run 2) - Practical Examples #1-#4
Practical #1 Practical #2 Practical #3 Practical #4
Volume Change (%) 0.5 0.7 0.7 0.4
Points Hardness DIDC 4 -1 5 6
Tensile Strength (%) -32 -5 -41 -40
Elongation at Rupture (%) -51 -5 -59 -66
Table 7: Seal Compatibility Test Results (Run 1) - Comparative Examples #1-#6
(C1-
C6)
C1 C2 C3 C4 C5 C6
Volume Change (%) 0.3 0.2 0.8 0.4 0.7 0.5
Points Hardness DIDC 7 5 7 6 8 2
Tensile Strength (%) -44 -32 -47 -39 -44 -29
Elongation at Rupture (%) -69 -40 -72 -64 -66 -38
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Table 8: Seal Compatibility Test Results (Run 2) - Comparative Examples #1-#6
(C1-
C6)
C1 C2 C3 C4 C5 C6
Volume Change (%) 0.4 0.2 0.8 0.6 0.7 0.4
Points Hardness DIDC 8 4 8 6 7 2
Tensile Strength (%) -49 -31 -44 -41 -42 -23
Elongation at Rupture
-71 -40 -68 -64 -67 -34
(%)
Table 9: Seal Compatibility Test Results (Run 1) - Comparative Examples #7-#12
(C7-C12)
C7 C8 C9 C10 C11 C12
Volume Change (%) 0.7 0.3 0.2 0.5 0.4 0.6
Points Hardness DIDC 1 1 2 3 4 4
Tensile Strength (%) 5 -26 -21 -29 -31 -29
Elongation at Rupture (%) -25 -40 -40 -43 -42 -49
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Table 10: Seal Compatibility Test Results (Run 2) - Comparative Examples #7-
#12
(C7-C12)
C7 C8 C9 C10 C11 C12
Volume Change (%) 0.7 0.6 0.4 0.6 0.3 0.5
Points Hardness DIDC 1 2 2 4 4 3
Tensile Strength (%) 0 -23 -25 -27 -28 -26
Elongation at Rupture
-20 -33 -42 -45 -43 -51
(%)
[00118] 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.
[00119] Practical Examples #1, #2, #3, and #4 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 #1-4 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 #1-4.
[00120] 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 #3-5.
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
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Examples #3, 4, and 5, was -47 and -44%; -39 and -41; and -44 and -42%,
respectively. Similarly, the elongation at rupture for Practical Example #1
was -54
and -51%; the elongation at rupture for Practical Example #2 was 8 and -5%;
whereas
the elongation at rupture of Comparative Examples #3, 4, and 5, was -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 than the lubricant
compositions
of Comparative Examples #3-5. This comparison also provides evidence that the
combination of trimethoxyboroxine 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 boron-containing
compounds utilized in Comparative Examples #3-5.
[00121] Finally, the comparison of Comparative Example #2 and Comparative
Examples #6-12 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.
[00122] 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.
[00123] 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
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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.
[00124] 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.
[00125] 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.
[00126] The subject matter of all combinations of independent and dependent
claims,
both single and multiple dependent, is herein expressly contemplated. Examples
include, but are not limited to, the following:
= Claim 3 can depend from any one of claims 1 through 2;
= Claim 4 can depend from any one of claims 1 through 3;
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= Claim 5 can depend from any one of claims 1 through 4;
= Claim 6 can depend from any one of claims 1 through 5;
= Claim 7 can depend from any one of claims 1 through 6;
= Claim 9 can depend from any one of claims 1 through 8;
= Claim 10 can depend from any one of claims 1 through 9;
= Claim 11 can depend from any one of claims 1 through 10; and
= Claim 12 can depend from any one of claims 1 through 11.
41
