U.S. patent application number 15/266369 was filed with the patent office on 2017-02-02 for lubricant compositions comprising epoxide compounds.
This patent application is currently assigned to BASF SE. The applicant listed for this patent is BASF SE. Invention is credited to Kevin J. DeSantis, Michael D. Hoey, Stephen Jones, Alfred Karl Jung, Phil Rabbat.
Application Number | 20170029737 15/266369 |
Document ID | / |
Family ID | 49674409 |
Filed Date | 2017-02-02 |
United States Patent
Application |
20170029737 |
Kind Code |
A1 |
DeSantis; Kevin J. ; et
al. |
February 2, 2017 |
LUBRICANT COMPOSITIONS COMPRISING EPOXIDE COMPOUNDS
Abstract
A lubricant composition including an epoxide compound is
disclosed. An additive package including the epoxide compound is
also disclosed. The epoxide compound of the lubricant composition
acts to improve compatibility of the lubricant composition with a
fluoropolymer seal and improve the total base number of the
lubricant composition.
Inventors: |
DeSantis; Kevin J.; (Upper
Nyack, NY) ; Hoey; Michael D.; (Maplewood, NJ)
; Jung; Alfred Karl; (Carmel, NY) ; Rabbat;
Phil; (Maplewood, NJ) ; Jones; Stephen;
(Pomona, NY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
Ludwigshafen |
|
DE |
|
|
Assignee: |
BASF SE
Ludwigshafen
DE
|
Family ID: |
49674409 |
Appl. No.: |
15/266369 |
Filed: |
September 15, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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14081551 |
Nov 15, 2013 |
|
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15266369 |
|
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61727414 |
Nov 16, 2012 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 2207/24 20130101;
C10M 149/10 20130101; C10N 2020/04 20130101; C10M 137/10 20130101;
C10M 133/40 20130101; C10M 2203/1006 20130101; C10M 2215/221
20130101; C10M 141/06 20130101; C10N 2030/36 20200501; C10N 2030/42
20200501; C10M 129/56 20130101; C10N 2020/071 20200501; C10M
2207/042 20130101; C10M 2215/04 20130101; C10M 133/06 20130101;
C10M 137/105 20130101; C10M 2205/0285 20130101; C10M 129/18
20130101; C10N 2030/06 20130101; C10M 2223/045 20130101; C10M
141/10 20130101; C10N 2030/52 20200501; C10M 2223/047 20130101;
C10N 2040/25 20130101; C10N 2070/02 20200501; C10M 2203/1025
20130101; C10M 129/66 20130101; C10M 2215/28 20130101; C10M
2223/045 20130101; C10N 2010/04 20130101; C10M 2203/1025 20130101;
C10N 2020/02 20130101; C10M 2203/1025 20130101; C10N 2020/02
20130101; C10M 2223/045 20130101; C10N 2010/04 20130101 |
International
Class: |
C10M 133/40 20060101
C10M133/40; C10M 129/18 20060101 C10M129/18; C10M 141/10 20060101
C10M141/10; C10M 137/10 20060101 C10M137/10; C10M 141/06 20060101
C10M141/06; C10M 129/66 20060101 C10M129/66; C10M 133/06 20060101
C10M133/06 |
Claims
1. A lubricant composition comprising: a base oil included in an
amount of greater than 70 wt. % based on a total weight of said
lubricant composition, wherein said base oil has a viscosity of
from 1 to 20 cSt when tested at 100.degree. C. according to ASTM
D445, and wherein said base oil is selected from the group of API
Group I base oils, API Group II base oils, API Group III base oils,
and combinations thereof; an epoxide compound; and a sterically
hindered amine compound having the general formula (XIV) or (XV):
##STR00076## wherein each R.sup.16 is independently a hydrogen atom
or a hydrocarbyl group having from 1 to 17 carbon atoms, wherein at
least two groups designated by R.sup.16 are each an alkyl group,
wherein each R.sup.17 is independently a hydrogen atom or a
hydrocarbyl group having from 1 to 17 carbon atoms, wherein each
R.sup.18 is independently a hydrogen atom or a hydrocarbyl group
having from 1 to 17 carbon atoms, wherein at least two groups
designated by R.sup.18 are each an alkyl group, wherein each
R.sup.19 is independently a hydrogen atom or a hydrocarbyl group
having from 1 to 17 carbon atoms, and wherein the hydrocarbyl
groups designated by R.sup.16, R.sup.17, R.sup.18, and R.sup.19 are
each independently and optionally substituted with an alcohol
group, an amide group, an ether group, or an ester group.
2. The lubricant composition of claim 1 wherein said epoxide
compound is a polyepoxide compound including at least two oxirane
rings per molecule of the polyepoxide compound.
3. The lubricant composition of claim 2 wherein said polyepoxide
compound has the formula: ##STR00077##
4. The lubricant composition of claim 1 wherein said epoxide
compound is included in an amount of from 0.05 to 5 wt. % based on
a total weight of said lubricant composition.
5. The lubricant composition of claim 1 wherein said epoxide
compound has a weight average molecular weight of from 30 to
1500.
6. The lubricant composition of claim 1 wherein said epoxide
compound has a boiling point of from 50 to 450.degree. C. at 1
atmosphere of pressure.
7. The lubricant composition of claim 1 wherein said epoxide
compound has a flash point of from 25 to 250.degree. C. at 1
atmosphere of pressure.
8. The lubricant composition of claim 1 wherein at least 50 wt. %
of said epoxide compound remains unreacted in said lubricant
composition based on a total weight of said epoxide compound
utilized to form said lubricant composition prior to any reaction
in said lubricant composition.
9. The lubricant composition of claim 1 wherein said lubricant
composition is a crankcase lubricant composition.
10. (canceled)
11. The lubricant composition of claim 1 wherein said sterically
hindered amine compound is included in an amount of from 0.1 to 10
wt. % based on a total weight of said lubricant composition.
12. The lubricant composition of claim 11 wherein said sterically
hindered amine compound is (2,2,6,6-tetramethyl-4-piperidyl)
dodecanoate.
13. The lubricant composition of claim 1 further comprising an
antiwear additive comprising phosphorous.
14. The lubricant composition of claim 13 wherein said antiwear
additive comprising phosphorous is included in said lubricant
composition in an amount of from 0.1 to 5 wt. % based on a total
weight of said lubricant composition.
15. The lubricant composition of claim 1 further comprising a
dispersant.
16. The lubricant composition of claim 15 wherein said dispersant
is included in said lubricant composition in an amount of from 0.01
to 15 wt. % based on a total weight of said lubricant
composition.
17. (canceled)
18. 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 elongation at rupture of from -60 to 10% when tested
according to CEC L-39-T96.
19. (canceled)
20. (canceled)
21. An additive package for a lubricant composition, said additive
package comprising: an epoxide compound; and a sterically hindered
amine compound having the general formula (XIV) or (XV):
##STR00078## wherein each R.sup.16 is independently a hydrogen atom
or a hydrocarbyl group having from 1 to 17 carbon atoms, wherein at
least two groups designated by R.sup.16 are each an alkyl group,
wherein each R.sup.17 is independently a hydrogen atom or a
hydrocarbyl group having from 1 to 17 carbon atoms, wherein each
R.sup.18 is independently a hydrogen atom or a hydrocarbyl group
having from 1 to 17 carbon atoms, wherein at least two groups
designated by R.sup.18 are each an alkyl group, wherein each
R.sup.19 is independently a hydrogen atom or a hydrocarbyl group
having from 1 to 17 carbon atoms, and wherein the hydrocarbyl
groups designated by R.sup.16, R.sup.17, R.sup.18, and R.sup.19 are
each independently and optionally substituted with an alcohol
group, an amide group, an ether group, or an ester group.
22. The additive package of claim 21 wherein said additive package
further comprises an antiwear additive comprising phosphorous.
23. A lubricant composition comprising: a base oil included in an
amount of greater than 70 wt. % based on a total weight of said
lubricant composition, wherein said base oil has a viscosity of
from 1 to 20 cSt when tested at 100.degree. C. according to ASTM
D445, and wherein said base oil is selected from the group of API
Group I base oils, API Group II base oils, API Group III base oils,
and combinations thereof; an epoxide compound present in an amount
of from 0.1 to 2 wt. % based on a total weight of said lubricant
composition; an antiwear additive comprising phosphorous, wherein
said antiwear additive is included in said lubricant composition in
an amount of from 0.1 to 5 wt. % based on a total weight of said
lubricant composition; a sterically hindered amine in an amount of
from 1 to 3 wt. % based on the total weight of said lubricant
composition, wherein said sterically hindered amine is
(2,2,6,6-tetramethyl-4-piperidyl) dodecanoate; and a dispersant in
an amount of from 0.01 to 15 wt. % based on a total weight of said
lubricant composition.
24. The lubricant composition of claim 23 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 from -60 to 10% when tested
according to CEC L-39-T96.
Description
RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Patent
Application No. 61/727,414, filed on Nov. 16, 2012, 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 and an epoxide compound. The
invention also relates to an additive package for a lubricant
composition and to a method of lubricating a system including a
fluoropolymer seal.
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 lubricant compositions.
These conventional amine compounds may help neutralize acids formed
during the combustion process when the lubricant compositions are
utilized in combustion engines. 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 and improved neutralization.
SUMMARY OF THE INVENTION
[0005] The present invention provides a lubricant composition. The
lubricant composition includes a base oil included in an amount of
greater than 70 wt. % based on a total weight of the lubricant
composition. The base oil has a viscosity of from 1 to 20 cSt when
tested at 100.degree. C. according to ASTM D445. The lubricant
composition also includes an epoxide compound and a sterically
hindered amine compound. The sterically hindered amine compound has
the general formula (XIV) or (XV):
##STR00001##
wherein each R.sup.16 is independently a hydrogen atom or a
hydrocarbyl group having from 1 to 17 carbon atoms; wherein at
least two groups designated by R.sup.16 are each an alkyl group;
wherein each R.sup.17 is independently a hydrogen atom or a
hydrocarbyl group having from 1 to 17 carbon atoms; wherein each
R.sup.18 is independently a hydrogen atom or a hydrocarbyl group
having from 1 to 17 carbon atoms; wherein at least two groups
designated by R.sup.18 are each an alkyl group; wherein each
R.sup.19 is independently a hydrogen atom or a hydrocarbyl group
having from 1 to 17 carbon atoms; and wherein the hydrocarbyl
groups designated by R.sup.16, R.sup.17, R.sup.18, and R.sup.19 are
each independently and optionally substituted with an alcohol
group, an amide group, an ether group, or an ester group.
[0006] The present invention is also directed to a lubricant
composition including a base oil, an epoxide compound, and a
sterically hindered amine compound. The sterically hindered amine
compound is included in an amount of from 0.5 to 5 wt. % based on a
total weight of the lubricant composition. The sterically hindered
amine compound has the general formula (XIV) or (XV) described
above.
[0007] The present invention also provides a method of lubricating
system that includes a fluoropolymer seal. The method includes
providing a lubricant composition that includes a base oil, an
epoxide compound, and a sterically hindered amine compound. The
method also includes contacting the fluoropolymer seal with the
lubricant composition. The sterically hindered amine compound is
included in an amount of from 0.5 to 5 wt. % based on a total
weight of the lubricant composition and has the general formula
(XIV) or (XV) described above.
[0008] The present invention is also directed to an additive
package for a lubricant composition. The additive package includes
an epoxide compound and a sterically hindered amine compound having
the general formula (XIV) or (XV) described above.
[0009] Lubricant compositions including the epoxide compound
demonstrate improved compatibility with fluoropolymer seals as
demonstrated by CEC L-39-T96 and improved neutralization ability as
demonstrated by ASTM D4739 and ASTM D2896.
DETAILED DESCRIPTION
[0010] The lubricant composition or additive package includes at
least one epoxide compound. In some embodiments, the epoxide
compound may be represented by general formula (I):
##STR00002##
In general formula (I), each R is independently a hydrogen atom or
a hydrocarbyl group. Multiple groups designated by R may be bonded
together to form a cyclic structure.
[0011] The term "cyclic" is intended to refer to compounds that
include any molecules having at least three atoms joined together
to form a ring. In some embodiments, the term "cyclic" does not
include aromatic compounds.
[0012] The epoxide compound may include one or more oxirane ring.
The oxirane ring may be a terminal oxirane ring or an internal
oxirane ring. The term "terminal oxirane ring" means that one of
the carbon atoms which form the oxirane ring must contain two
hydrogen atoms, or that two carbons which form the oxirane ring
also form part of a cyclic ring. The term "internal oxirane ring"
means that neither of the carbon atoms which form the oxirane ring
is bonded to more than one hydrogen atom. The epoxide compound may
be free from internal oxirane rings, or may include fewer than 4,
3, 2, or 1, internal oxirane rings. Alternatively, the epoxide
compound may include 1, 2, 3, 4, or more internal oxirane rings.
Alternatively still, the epoxide compound may include at least 1,
at least 2, at least 3, at least 4 terminal oxirane rings. In
certain embodiments, at least one, or at least two, oxirane rings
may be terminal and may be cyclic, i.e, the carbons of the oxirane
rings are part of a cyclic ring.
[0013] Each hydrocarbyl group designated by R may independently be
substituted or unsubstituted, straight or branched, alkyl, alkenyl,
cycloalkyl, cycloalkenyl, aryl, alkylaryl, arylalkyl group, or
combinations thereof. Each hydrocarbyl group designated by R may
independently include from 1 to 100, 1 to 50, 1 to 40, 1 to 30, 1
to 20, 1 to 15, 1 to 10, 1 to 6, or 1 to 4, carbon atoms.
Alternatively, each hydrocarbyl group designated by R may
independently include less than 20, less than 15, less than 12, or
less than 10, carbon atoms.
[0014] By "unsubstituted," it is intended that the designated
hydrocarbyl group or hydrocarbon group is free from substituent
functional groups, such as alkoxy, amide, amine, keto, hydroxyl,
carboxyl, oxide, thio, and/or thiol groups, and that the designated
hydrocarbyl group or hydrocarbon group is free from heteroatoms
and/or heterogroups.
[0015] Alternatively, each hydrocarbyl group designated by R may be
independently substituted, and include one or more heteroatoms,
such as oxygen, nitrogen, sulfur, chlorine, fluorine, bromine, or
iodine, and/or one or more heterogroups, such as pyridyl, furyl,
thienyl, and imidazolyl. Alternatively, or in addition to including
heteroatoms and heterogroups, each hydrocarbyl group designated by
R may independently include one or more substituent groups selected
from alkoxy, amide, amine, carboxyl, epoxy, ester, ether, hydroxyl,
keto, metal salt, sulfuryl, and thiol groups. Alternatively, each
hydrocarbyl group designated by R may be independently
unsubstituted.
[0016] Exemplary alkyl groups include methyl, ethyl, propyl,
isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl,
iso-amyl, hexyl, 2-ethylhexyl, octyl and dodecyl groups. Exemplary
cycloalkyl groups cyclopropyl, cyclopentyl and cyclohexyl groups.
Exemplary aryl groups include phenyl and naphthalenyl groups.
Exemplary arylalkyl groups include benzyl, phenylethyl, and
(2-naphthyl)-methyl.
[0017] As described above with respect to general formula (I), the
hydrocarbyl group designated by R may include one or more epoxy
groups. These hydrocarbyl epoxy groups may be represented by the
general formula (II):
##STR00003##
In general formula (II), R.sup.1 is a divalent hydrocarbon group
and each R.sup.2 may independently be a hydrogen atom or a
hydrocarbyl group. The divalent hydrocarbon group designated by
R.sup.1 may be substituted or unsubstituted, straight or branched,
alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkylaryl,
arylalkyl group, or combinations thereof. Each hydrocarbon group
designated by R.sup.1 may independently include from 1 to 100, 1 to
50, 1 to 40, 1 to 30, 1 to 20, 1 to 15, 1 to 10, 1 to 6, or 1 to 4,
carbon atoms. Alternatively still, each hydrocarbyl group
designated by R.sup.1 may independently include less than 20, less
than 15, less than 12, or less than 10, carbon atoms.
Alternatively, each hydrocarbon group designated by R.sup.1 may be
independently substituted, and include one or more heteroatoms,
such as oxygen, nitrogen, sulfur, chlorine, fluorine, bromine, or
iodine, and/or one or more heterogroups, such as pyridyl, furyl,
thienyl, and imidazolyl. Alternatively, or in addition to including
heteroatoms and heterogroups, each hydrocarbon group designated by
R.sup.1 may independently include one or more substituent groups
selected from alkoxy, amide, amine, carboxyl, epoxy, ester, ether,
hydroxyl, keto, metal salt, sulfuryl, and thiol groups. The
hydrocarbyl groups designated by R.sup.2 may have the same meaning
as R as described above with respect to general formula (I).
Multiple groups designated by R.sup.2 may be bonded together to
form a cyclic structure.
[0018] Referring again to general formula (I), if at least one R is
a hydrocarbyl group including an amide group, exemplary epoxide
compounds include N-methyl 2,3-epoxypropionamide, N-ethyl
2,3-epoxypropionamide, N-propyl 2,3-epoxypropionamide, N-isopropyl
2,3-epoxypropionamide, N-butyl 2,3-epoxypropionamide, N-isobutyl
2,3-epoxypropionamide, N-tert-butyl 2,3-epoxypropionamide, N-hexyl
2,3-epoxypropionamide, N-octyl 2,3-epoxypropionamide,
N-(2-ethylhexyl)-2,3-epoxypropionamide, and N-dodecyl
2,3-epoxypropanionamide.
[0019] In certain embodiments, the epoxide compound of general
formula (I) may be an alkyl epoxide compound. The alkyl epoxide
compound may be exemplified by 1,2-epoxybutane, 2-methyl 2,3-epoxy
butane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane,
1,2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane,
1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxytridecane,
1,2-epoxytetradecane, 1,2-epoxypentadecane, 1,2-epoxyhexadecane,
1,2-epoxyheptadecane, 1,1-,2-epoxyoctadecane, 1,2-epoxynonadecane,
and 2,3-epoxy pentane.
[0020] Alternatively, in other embodiments, the epoxide compound of
general formula (I) may be an alkyl glycidyl ether compound. The
alkyl glycidyl ether compound may be exemplified by decyl glycidyl
ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl
glycidyl ether, tetradecyl glycidyl ether, 2-ethylhexyl glycidyl
ether, neopentyl glycol diglycidyl ether, trimethylolpropane
triglycidyl ether, pentaerythritol tetraglycidyl ether, 1,6-hexane
diol diglycidyl ether, sorbitol polyglycidyl ether, polyalkylene
glycol monoglycidyl ether, and polyalkylene glycol diglycidyl
ether.
[0021] Exemplary epoxide compounds also include glycidol, glycidol
derivatives, glycidyl, glycidyl derivatives, allyl 2,3-epoxypropyl
ether, isopropyl 2,3-epoxypropyl ether, (tert-butoxymethyl)oxirane,
and [[(2-ethylhexyl)oxy]methyl]oxirane.
[0022] In some embodiments, the epoxide compound may be an epoxide
ester compound. The epoxide ester compound may be represented by
general formula (III):
##STR00004##
In general formula (III), each group designated by R.sup.3 is
independently a hydrogen atom or a hydrocarbyl group, and wherein
at least one group designated by R.sup.3 is an epoxy group or is a
hydrocarbyl group substituted with an epoxy group. Alternatively,
in certain embodiments, each group designated by R.sup.3 is an
epoxy group or a hydrocarbyl group substituted with at least one
epoxy group. Further still, at least one of the groups designated
by R.sup.3 in general formula (III) may designate a cyclic
hydrocarbyl group where two carbons of the oxirane ring are part of
the cyclic ring. The hydrocarbyl groups designated by R.sup.3 may
independently have the same meaning as R described above with
respect to general formula (I).
[0023] The epoxide ester compound of general formula (III) may be
exemplified by methyl 2,3-epoxypropionate, ethyl
2,3-epoxypropionate, propyl 2,3-epoxypropionate, isopropyl
2,3-epoxypropionate, butyl 2,3-epoxypropionate, isobutyl
2,3-epoxypropionate, hexyl 2,3-epoxypropionate, octyl
2,3-epoxypropionate, 2-ethylhexyl 2,3-epoxypropionate, and dodecyl
2,3-epoxypropionoate.
[0024] In certain embodiments, the epoxide ester compound of
general formula (III) may be more specifically represented by
general formula (IV):
##STR00005##
In general formula (IV), each group designated by R.sup.4 may be a
hydrogen atom or a hydrocarbyl group. The hydrocarbyl group
designated by R.sup.4 may have the same meaning as R described
above with respect to general formula (I). The epoxide ester
compound of general formula (IV) may be exemplified by
glycidyl-2,2-dimethyl octanoate, glycidyl benzoate,
glycidyl-tert-butyl benzoate, glycidyl acrylate, and glycidyl
methacrylate.
[0025] In certain embodiments, the epoxide compound is a cyclic
epoxide compound. The cyclic epoxide compound may be represented by
general formula (V):
##STR00006##
[0026] In general formula (V), Z represents the type and number of
atoms necessary to complete the cyclic ring of general formula (V).
The ring designated by Z may include from 2 to 20, 3 to 15, 5 to
15, carbon atoms. For example, the ring designated by Z may include
1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbons, not accounting
for the number of carbon atoms in any substituent groups. Z may be
a substituted or unsubstituted, branched or unbranched, divalent
hydrocarbon group that may include one or more heteroatoms, such as
oxygen, nitrogen, sulfur, chlorine, fluorine, bromine, or iodine,
or one or more heterogroups, such as pyridyl, furyl, thienyl, and
imidazolyl. In addition to, or alternatively to, including
heteroatoms and/or heterogroups, the ring designated by Z may
include one or more hydrocarbyl substituent groups, such as those
described for R.sup.1 in general formula (I). The divalent
hydrocarbon group designated by Z may be aliphatic or aromatic. In
some embodiments, the divalent hydrocarbon group designated by Z
may be exemplified by: cyclopropyl, cyclopentyl, cyclohexyl,
phenyl, naphthalenyl, benzyl, phenylethyl, and (2-naphthyl)-methyl
groups. It should be appreciated that the heteroatoms,
heterogroups, and/or substituent groups described above may be
bonded to various atoms in the ring designated by Z; for example,
the hydrocarbyl substituent groups may be bonded directly to one or
more carbons in the ring designated by Z that form part of the
oxirane ring. Alternatively, the substituent groups, heterogroups,
and heteroatoms may be bonded to other carbon atoms in the
hydrocarbon group, such as carbons that are not part of the oxirane
ring. In some embodiments, the cyclic epoxide compound of general
formula (V) may be a cycloaliphatic epoxide compound having at
least two terminal oxirane rings.
[0027] The cyclic epoxide compound of general formula (V) may be
exemplified by 1,2-epoxycyclohexane, 1,2-epoxycyclopentane,
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate,
bis(3,4-epoxy cyclohexylmethyl) adipate,
bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, and
4-epoxyethyl-1,2-epoxycyclohexane.
[0028] As should be appreciated from general formulas (I), (II),
(III), (IV), and (V) described above, the epoxide compound may be a
monoepoxide, or a polyepoxide compound, such as a diepoxide. The
polyepoxide compound includes at least two oxirane rings.
Furthermore, in some embodiments, the polyepoxide compound may
include fewer than 10, fewer than 8, fewer than 5, fewer than 4, or
fewer than 3, oxirane rings per molecule.
[0029] The polyepoxide compound may include one or more substituted
or unsubstituted, branched or unbranched, hydrocarbyl or divalent
hydrocarbon groups, such alkyl, alkenyl, cycloalkyl,
alkylcycloalkyl, aryl, alkylaryl group, arylalkyl groups, and
combinations thereof. Each hydrocarbyl or divalent hydrocarbon
group included in the polyepoxide compound may independently be
substituted with one or more heteroatoms, such as oxygen, nitrogen,
sulfur, chlorine, bromine, fluorine, or iodine, and/or may
independently include one or more heterogroups, such as pyridyl,
furyl, thienyl, and imidazolyl. Each hydrocarbyl or divalent
hydrocarbon group in the polyepoxide compound may include one or
more substituent groups selected from alkoxy, amide, amine,
carboxyl, epoxy, ester, ether, hydroxyl, keto, metal salt,
sulfuryl, and thiol groups. Each of the hydrocarbyl or divalent
hydrocarbon groups in the polyepoxide compound may independently
include from 1 to 100, 1 to 50, 1 to 40, 1 to 30, 1 to 20, 1 to 10,
1 to 6, or 1 to 4, carbon atoms. The hydrocarbyl or divalent
hydrocarbon groups may be bonded to one another or to one or more
carbon atoms of the oxirane rings to form the polyepoxide
compound.
[0030] In some embodiments, the polyepoxide compound may be
represented by the general formula (VI):
##STR00007##
In general formula (VI), R.sup.5, R.sup.6, R.sup.7, R.sup.8 and
R.sup.9 are each independently a hydrogen atom or a hydrocarbyl
group. R.sup.10 is a divalent hydrocarbon group. The hydrocarbyl
groups designated by R.sup.5, R.sup.6, R.sup.7, R.sup.8, and
R.sup.9 in general formula (VI) may have the same meaning as
described above with respect to R in general formula (I). The
divalent hydrocarbon group designated by R.sup.10 in general
formula (VI) may have the same meaning as described above with
respect to R.sup.1 in general formula (II). In certain embodiments,
R.sup.5 and R.sup.6, together with the two carbons of the oxirane
ring, form a cyclic structure. In other embodiments, R.sup.7 and
R.sup.8, together with the two carbons of the oxirane ring, form a
cyclic structure. As such, the polyepoxide compound of general
formula (VI) may include one, two, or more than two, cyclic rings.
Furthermore, in certain embodiments, at least one, or at least two,
of the oxirane oxygens in general formula (VI) is directly bonded
to two cyclic carbons, i.e., carbons which form part of a cyclic
ring.
[0031] Alternatively, the polyepoxide compound may be represented
by general formula (VII) shown below:
##STR00008##
In general formula (VII), each Z may have the same meaning as
described above with respect to general formula (V). In general
formula (VII), R.sup.11 is a divalent hydrocarbon group. R.sup.11
may have the same meaning as described above with respect to
R.sup.1 in general formula (II). It should be appreciated that the
divalent hydrocarbon group designated by R.sup.11 may be bonded to
various atoms in the divalent hydrocarbon group designated by Z.
For example, the divalent hydrocarbon group designated by R.sup.11
may be bonded directly to one or more oxirane ring carbons in
certain embodiments. Alternatively, the divalent hydrocarbon group
designated by R.sup.11 may be bonded to non-oxirane ring carbon
atoms in the hydrocarbon group designated by Z. The polyepoxide
compound of general formula (VII) may be exemplified by:
3-(1-(6-oxabicyclo[3.1.0]hexan-3-yl)propyl)-7-oxabicyclo[4.1.0]heptane
##STR00009##
[0032]
3-((7-oxabicyclo[4.1.0]heptan-3-yl)methyl)-8-oxabicyclo[5.1.0]octan-
e
##STR00010##
[0033]
4-[1-(7-oxabicyclo[4.1.0]heptan-4-yl)propyl]-7-oxabicyclo[4.1.0]hep-
tane
##STR00011##
[0034]
4-[1-methyl-1-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]-7-oxabicyclo[4-
.1.0]heptane
##STR00012##
[0036] In one specific embodiment, the polyepoxide compound may be
a polyepoxide ester compound including at least two oxirane rings.
In certain embodiments, the polyepoxide ester compound may be
exemplified by the general formula (VIII):
##STR00013##
In general formula (VIII), each Z may have the same meaning as
described above with respect to general formula (V). In general
formula (VIII), R.sup.12 is a divalent hydrocarbon group. R.sup.12
may have the same meaning as described above with respect to
R.sup.1 in general formula (II). It should be appreciated that the
divalent hydrocarbon group designated by R.sup.12 may be bonded to
various atoms in the divalent hydrocarbon group designated by Z.
For example, the divalent hydrocarbon group designated by R.sup.12
may be bonded directly to one or more oxirane ring carbons in
certain embodiments. Alternatively, the divalent hydrocarbon group
designated by R.sup.12 may be bonded to non-oxirane ring carbon
atoms in the ring designated by Z. In one embodiment, the epoxide
compound of general formula (VIII) is a 3,4-epoxycycloalkyl,
3,4-epoxy-cycloalkyl carboxylate, such as
3,4-epoxycyclohexylmethyl, 3,4-epoxy-cyclohexane carboxylate. The
polyepoxide ester compound of general formula (VIII) may be
exemplified by:
3-((7-oxabicyclo[4.1.0]heptane-3-carbonyl)oxy)propyl
9-oxabicyclo[6.1.0]nonane-4-carboxylate
##STR00014##
[0037] 7-((6-oxabicyclo[3.1.0]hexan-2-yl)methoxy)heptyl
7-oxabicyclo[4.1.0]heptane-3-carboxylate
##STR00015##
[0038]
3-((7-oxabicyclo[4.1.0]heptane-3-carbonyl)oxy)-2-(methoxymethyl)-2--
methylpropyl 7-oxabicyclo[4.1.0]heptane-2-carboxylate
##STR00016##
[0039] 3-(7-oxabicyclo[4.1.0]heptane-4-carbonyloxy)propyl
7-oxabicyclo[4.1.0]heptane-4-carboxylate
##STR00017##
[0040] 7-(7-oxabicyclo[4.1.0]heptan-4-ylmethoxy)heptyl
7-oxabicyclo[4.1.0]heptane-4-carboxylate
##STR00018##
[0041]
[2-(methoxymethyl)-2-methyl-3-(7-oxabicyclo[4.1.0]heptane-4-carbony-
loxy)propyl]7-oxabicyclo[4.1.0]heptane-4-carboxylate
##STR00019##
[0043] Alternatively still, the epoxide compound may be exemplified
by general formula (IX):
[A].sub.w[B].sub.x (IX)
In general formula (IX), each A is independently a hydrocarbyl
group or a divalent hydrocarbon group and each B is an epoxy group.
The group designated by A may have the same meaning as described
above with respect to R in general formula (I) or R.sup.1 in
general formula (II). "w" is an integer having a value of from 0 to
50, and "x" is an integer having a value of from 0 to 10, where
w+x.gtoreq.1, and with the proviso that if x=0, at least one moiety
designated by A is a hydrocarbyl group including an epoxy
substituent group. "w" may be an integer having a value of from 1
to 40, 1 to 30, 1 to 20, 1 to 10, 1 to 8, 1 to 5, or 1 to 3, and
"x" may be an integer having a value of 10, 9, 8, 7, 6, 5, 4, 3, 2,
or 1. It should be appreciated that groups A and B in general
formula (IX) may be bonded to one another in any order, with
varying number of iterations.
[0044] The epoxide compound may be exemplified by the following
compounds: [0045]
2,2'-[ethane-1,2-diylbis(oxymethanediyl)]dioxirane:
[0045] ##STR00020## [0046]
2,2'-[butane-1,4-diylbis(oxymethanediyl)]dioxirane:
[0046] ##STR00021## [0047]
2,2'-[ethane-1,2-diylbis(sulfanediylmethanediyl)]dioxirane:
[0047] ##STR00022## [0048] bis(oxiran-2-ylmethyl) hexanedioate:
[0048] ##STR00023## [0049] bis(oxiran-2-ylmethyl) butanedioate:
[0049] ##STR00024## [0050] bis(oxiran-2-ylmethyl)
(2E)-but-2-enedioate:
[0050] ##STR00025## [0051] 2,2'-butane-1,4-diyldioxirane:
[0051] ##STR00026## [0052]
2,2'-[benzene-1,3-diylbis(oxymethanediyl)]dioxirane:
[0052] ##STR00027## [0053]
2-({3-(oxiran-2-ylmethoxy)-2-[(oxiran-2-ylmethoxy)methyl]propoxy}methyl)o-
xirane:
[0053] ##STR00028## [0054]
3-(oxiran-2-yl)-8-oxabicyclo[5.1.0]octane:
[0054] ##STR00029## [0055] 8-oxabicyclo[5.1.0]oct-3-ylmethyl
8-oxabicyclo[5.1.0]octane-3-carboxylate:
[0055] ##STR00030## [0056] N-methyl 2,3-epoxypropionamide:
[0056] ##STR00031## [0057] 1,2-epoxybutane:
[0057] ##STR00032## [0058] decyl glycidyl ether:
[0058] ##STR00033## [0059] trimethylolpropane triglycidyl
ether:
[0059] ##STR00034## [0060] glycidol:
[0060] ##STR00035## [0061] [[(2-ethylhexyl)oxy]methyl]oxirane:
[0061] ##STR00036## [0062] methyl 2,3-epoxypropionate:
[0062] ##STR00037## [0063] glycidyl-2,2-dimethyl octanoate:
[0063] ##STR00038## [0064] glycidyl benzoate:
[0064] ##STR00039## [0065] glycidyl acrylate:
[0065] ##STR00040## [0066] 1,2-epoxycyclohexane:
[0066] ##STR00041## [0067] bis(3,4-epoxy cyclohexylmethyl)
adipate:
[0067] ##STR00042## [0068] exo-2,3-epoxynorbornane:
[0068] ##STR00043## [0069]
4-(1'-methylepoxyethyl)-1,2-epoxy-2-methylcyclohexane:
[0069] ##STR00044## [0070] 3,4-epoxycyclohexylmethyl,
3,4-epoxy-cyclohexane carboxylate:
##STR00045##
[0070] It should be appreciated that all of these exemplary
compounds fall within the scope of one or more of the general
formulas (I), (III), (IV), (V), (VI), (VII), (VIII), and (IX)
and/or within the scope of the written description of the epoxide
compound herein.
[0071] In certain embodiments, the epoxide compound may be free
from nitrogen, sulfur, phosphorous, chlorine, bromine, and/or
iodine atoms. As described above, the epoxide compound may be
aliphatic, cyclic, acyclic, and/or aromatic.
[0072] The epoxide compound may have a weight average molecular
weight of from 44 to 1000, 50 to 750, 100 to 500, 100 to 400, or
100 to 200. Alternatively still, the epoxide compound may have a
weight average molecular weight of at least 30, at least 50, at
least 70, at least 90, at least 110, or at least 130.
Alternatively, the epoxide compound may have a weight average
molecular weight of less than 1500, less than 1300, less than 1100,
less than 900, less than 700, less than 500, less than 400, or less
than 300.
[0073] The epoxide compound may have an epoxide equivalent weight
of from 75 to 300, 75 to 250, 75 to 200, 85 to 190, 85 to 175, 95
to 160, or 100 to 145, g per mole of oxirane ring of the epoxide
compound. Alternatively, the epoxide compound may have an epoxide
equivalent weight of at least 50, 60, 70, 80, 90, 100, 110, 120,
130, 140, or 150, g per mole of oxirane ring of the epoxide
compound. As referred to throughout this disclosure, the term
"epoxide equivalent weight" is the numerical value which is
obtained by dividing the weight average molecular weight of the
epoxide compound by the number of oxirane rings in the
molecule.
[0074] The basicity effect of the epoxide compound can be
determined by acid titration. The resulting neutralization number
is expressed as the total base number (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.
[0075] In some embodiments, the epoxide compound does not
negatively affect the total base number of the lubricant
composition. Alternatively, the epoxide compound may improve the
TBN of the lubricant composition by, at 0.5, 1, 1.5, 2, 2.5, 3,
3.5, 4, 4.5, 5, 10, or 15, mg KOH/g of epoxide compound. The TBN
value of the lubricant composition can be determined according to
ASTM D2896 and/or ASTM D4739 as will be described below.
[0076] In certain embodiments, the epoxide compound is monomeric.
The term "monomeric" is intended to indicate that the subject
compound does not include more than three, more than two, or more
than one, repeating monomer units bonded to one another.
Alternatively, the term monomeric may refer to compounds that do
not include any repeating monomer units. In other words, the term
"monomeric" is intended to exclude compounds which are either
oligomeric or polymeric. In certain embodiments, the monomeric
epoxide compound excludes oils or alkyl fatty acid esters which
have been epoxidized to include one or more oxirane rings, such as
epoxidized vegetable oils. Alternatively, the lubricant composition
or additive package may include less than 5, 4, 3, 2, 1, 0.5, 0.1,
or 0.01, wt. %, of an epoxidized fatty acid ester or epoxidized oil
based on a total weight of said lubricant composition. As used
herein, the term "epoxidized oil" refers to a natural oil which was
epoxidized to include at least 1, at least 2, at least 3, at least
4, at least 5, at least 6, at least 7, at least 8, or at least 9,
epoxide groups per molecule and/or has an epoxide equivalent weight
of greater than 200, 250, 300, or 350. As used herein, the term
"epoxidized fatty acid ester" refers to a natural fatty acid ester
or acid that includes at least 1, at least 2, at least 3, at least
4, at least 5, at least 6, at least 7, at least 8, or at least 9,
epoxide groups per molecule and/or has a epoxide equivalent weight
of greater than 200, 250, 300, or 350. As used herein, the term
"natural" refers to compounds which are naturally-occurring.
[0077] The epoxide compound may have a boiling point of at least
50, 60, 70, 80, 90, 100, 110, 120, 130, 140, or 150.degree. C., at
1 atmosphere of pressure. Alternatively, the epoxide compound has a
boiling point of from 50 to 450, 55 to 450, 65 to 450, 75 to 450,
85 to 450, 100 to 450, 115 to 450, 125 to 450, 135 to 450, 150 to
450, or from 200 to 400.degree. C., at 1 atmosphere of pressure.
Furthermore, in certain embodiments, the epoxide compound is a
liquid at a steady state temperature of 50.degree. C. and a steady
state pressure of 1 atmosphere of pressure.
[0078] The epoxide compound may have a flash point of from 25 to
250, 50 to 250, 65 to 250, 75 to 250, 100 to 250, or from 115 to
250.degree. C. at 1 atmosphere of pressure. Alternatively, the
epoxide compound may have a flash point of at least 25, 35, 45, 55,
65, 75, 85, 95, 105, 115, 125, or 135.degree. C. at 1 atmosphere of
pressure.
[0079] The amount of the epoxide compound included in the lubricant
composition ranges from 0.01 to 8, 0.05 to 5, 0.1 to 2, 0.1 to 1.5,
0.3 to 1.2, 0.4 to 1, 0.1 to 1, 0.1 to 0.8, or 0.2 to 0.7, wt. %,
based on the total weight of the lubricant composition. The epoxide
compound may be included in the additive package in an amount of
from 0.5 to 90, 1 to 50, 1 to 30, or 5 to 25, wt. %, based on the
total weight of the additive package. The lubricant composition
and/or additive package may include mixtures of two or more
different epoxide compounds.
[0080] In certain embodiments, the epoxide compound is included in
the lubricant composition in an amount sufficient to provide from
0.01 to 5, 0.01 to 4.5, 0.01 to 4, 0.01 to 3.5, 0.01 to 3, 0.01 to
2.5, 0.01 to 2, 0.01 to 1.5, 0.01 to 1, 0.1 to 0.9, 0.2 to 0.8, or
0.3 to 0.7, wt. % of oxirane oxygen, based on total weight of the
lubricant composition.
[0081] The epoxide compound may be prepared using various methods
as will be appreciated by one of ordinary skill in the art. For
example, the epoxide compound may be prepared by the epoxidation of
an allyl ether, .alpha.,.beta.-unsaturated amide to the
corresponding glycidyl ether, glycidic ester, or glycidic amide.
Alternatively, an olefin may be epoxidized with hydrogen peroxide
and an organic peracid to produce the epoxide compound.
Alternatively, the olefin can be epoxidized in the presence of a
transition metal catalyst and a co-oxidant to form the epoxide
compound. Suitable co-oxidants include hydrogen peroxide,
tert-butyl hydroperoxide, iodosylbenzene, sodium hypocholorite, and
the like. Alternatively, glycidic esters may be prepared by Darzens
condensation of an a-halo ester and an aldehyde or ketone, in the
presence of a base.
[0082] In some embodiments, the lubricant composition and/or
additive package is free of, or contains less than 5, 3, 1, 0.5,
0.1, or 0.05, wt. % of an epoxide reaction catalyst, based on the
total weight of the lubricant composition. The epoxide reaction
catalyst may be a metal salt, such as a metallic salt of fatty
acids, naphthenates, phenolates, alcoholates, carboxylates, and the
corresponding thio analogues, sulfonates, and sulphinates. The
epoxide reaction catalyst may also refer to calcium cetyl
alcoholate, barium isoamyl thiiphenolate, calcium naphthnate, and
metal salts of alkyl substituted benzene sulphonic acid. In some
embodiments, the epoxide reaction catalyst is defined as a
component that catalyzes the reaction of the epoxide compound with
an additional component in the lubricant composition at a
temperature less than 100, 80, or, 60.degree. C. The additional
component may include, but is not limited to, any compound
described in this specification other than the epoxide reaction
catalyst and the epoxide compound. For example, the additional
component referred to above may be a dispersant, an antiwear
additive, an antioxidant, or a component that affects the total
base number of the lubricant composition.
[0083] Conventional uses of epoxide compounds in lubricant
compositions involve forming a reaction product between a
conventional dispersant and a conventional epoxide compound. In
these applications, the conventional epoxide compound is consumed
by chemical reactions such that the ultimately formed lubricant
composition does not contain appreciable amounts of the
conventional epoxide compound in an unreacted state. The
conventional epoxide compound may react via an addition reaction
such that the addition of one or more small molecules to the
lubricant composition may cause the epoxide group of the
conventional epoxide compound to ring-open without eliminating or
cleaving any part of the conventional epoxide compound.
[0084] In such conventional uses, more than 50 wt. % of the
conventional epoxide compound is typically reacted with the
conventional dispersants or other compounds based on the total
weight of the conventional epoxide compound in the lubricant
composition prior to the reaction. In contrast, the inventive
lubricant compositions may contain a significant amount of the
epoxide compound in an unreacted state. In certain embodiments, at
least 50, 60, 70, 80 or, 90, wt. % of the epoxide compound remains
unreacted in the lubricant composition based on a total weight of
the epoxide compound utilized to form the lubricant composition
prior to any reaction in the lubricant composition. Alternatively,
at least 95, 96, 97, 98, or 99, wt. %, of the epoxide compound
remains unreacted in the lubricant composition based on a total
weight of the epoxide compound prior to any reaction in the
lubricant composition.
[0085] The phrase "prior to any reaction in the lubricant
composition" refers to the basis of the amount of the epoxide
compound in the lubricant composition. This phrase does not require
that the epoxide compound reacts with other components in the
lubricant composition, i.e., 100 wt. % of the epoxide compound may
remain unreacted in the lubricant composition based on a total
weight of the epoxide compound prior to any reaction in the
lubricant composition.
[0086] The percentage of the epoxide compound that remains
unreacted is typically 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. The percentage of the epoxide compound
that remains unreacted in the lubricant composition may be
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.
[0087] In certain embodiments, the lubricant composition includes
less than 10, 5, 1, 0.5, 0.1, 0.01, 0.001, or 0.0001, wt. %, of
compounds which would react with the epoxide compound at a
temperature less than 150, less than 125, less than 100, or less
than 80.degree. C., based on a total weight of the lubricant
composition. Exemplary types of compounds which may react with the
epoxide compound at a temperature less than 100.degree. C. include
acids, amine curing agents, anyhydrides, triazoles, and/or oxides.
In certain embodiments, the lubricant composition may include a
collective amount of acids, amine curing agents, anhydrides,
triazoles, and/or oxides which is less than 5, 3, 1, 0.5, or 0.1,
wt. % based on a total weight of the lubricant composition.
Alternatively, the lubricant composition may include a collective
amount of acids, amine curing agents, anhydrides, triazoles, and/or
oxides which is less than 0.01, 0.001, or 0.0001, wt. %, based on
the total weight of the lubricant composition. Alternatively still,
the lubricant composition may be free of acids, amine curing
agents, anhydrides, triazoles, and/or oxides.
[0088] The term "acids" may include 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.
[0089] Anhydrides are exemplified by alkylated succinic anhydrides
and acrylates. Triazoles may be represented 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 represented by alkylene oxides,
such as ethylene oxide and propylene oxide; metal oxides;
alkoxylated alcohols; alkoxylated amines; or alkoxylated
esters.
[0090] In other conventional uses, conventional epoxide compounds
undergo tribopolymerization in lubricant compositions to form
protective lubricating films. In the tribopolymerization process,
polymer-formers are adsorbed on a solid surface and polymerize
under rubbing conditions to form organic polymeric films directly
on the rubbing surface. In such conventional uses, more than 50 wt.
% of the conventional epoxide compound is typically reacted via
tribopolymerization. In contrast, the inventive lubricant
compositions may contain a significant amount of the epoxide
compound that does not react via tribopolymerization. In certain
embodiments, at least 50, 60, 70, 80, or 90, wt. %, of the epoxide
compound does not react via tribopolymerization in the lubricant
composition at a temperature less than 100, 80, or 60.degree. C.,
based on the total weight of epoxide compound utilized to form the
lubricant composition. Alternatively, at least 95, 96, 97, 98, or
99, wt. %, of the epoxide compound does not react via
tribopolymerization in the lubricant composition at a temperature
less than 100, 80, or 60.degree. C., based on a total weight of the
epoxide compound in the lubricant composition.
[0091] As described above, the epoxide compound may be combined
with at least one amine compound in the lubricant composition or
additive package. It should be appreciated that mixtures of
different amine compounds may also be combined with the epoxide
compound in the lubricant composition and/or additive package. If
utilized, the lubricant composition includes the amine compound in
an amount of 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 include the amine
compound in an amount of from 0.5 to 5, 1 to 3, or 1 to 2, wt. %,
based on the total weight of the lubricant composition.
[0092] The amine compound does not substantially react with the
epoxide 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
epoxide compound and the 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 amine
compound remains unreacted after the lubricant composition and/or
additive package reaches equilibrium.
[0093] In certain embodiments, the amine compound has a TBN value
of at least 80 mg KOH/g when tested according to ASTM D4739.
Alternatively, the amine compound has a TBN value of 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. Alternatively still, the amine compound may have a
TBN value of from 80 to 200, 90 to 190, 100 to 180, or 100 to 150,
mg KOH g, when tested according to ASTM D4739.
[0094] In some embodiments, the amine compound does not negatively
affect the total base number of the lubricant composition.
Alternatively, the amine compound may improve the TBN of the
lubricant composition by, at least 0.5, at least 1, at least 1.5,
at least 2, at least 2.5, at least 3, at least 3.5, at least 4, at
least 4.5, at least 5, at least 10, or at least 15, mg KOH/g of the
amine compound. The TBN value of the lubricant composition can be
determined according to ASTM D2896.
[0095] If the amine compound is included in the additive package,
the additive package includes the amine compound in an amount of
from 0.1 to 50 wt. %, based on the total weight of the additive
package. Alternatively, the additive package may include the amine
compound in an amount of 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 amine compounds are also
contemplated.
[0096] The amine compound includes at least one nitrogen atom.
Furthermore, in some configurations, the amine compound does not
include triazoles, triazines, or similar compounds where there are
three or more nitrogen atoms in the body of a cyclic ring. The
amine compound may be aliphatic.
[0097] In some embodiments, the amine compound consists of, or
consists essentially of, hydrogen, carbon, nitrogen, and oxygen.
Alternatively, the amine compound may consist of, or consist
essentially of, hydrogen, carbon, and nitrogen. In the context of
the amine compound, the phrase "consist essentially of" refers to
compounds where at least 95 mole % of the amine compound are the
recited atoms (i.e., hydrogen, carbon, nitrogen, and oxygen; or
hydrogen, carbon, and nitrogen). For example, if the amine compound
consists essentially of hydrogen, carbon, nitrogen, and oxygen, at
least 95 mole % of the 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 amine compound are hydrogen, carbon, nitrogen and oxygen, or,
in other embodiments, are carbon, nitrogen, and hydrogen.
[0098] The amine compound may consist of covalent bonds. The phrase
"consist of covalent bonds" is intended to exclude those compounds
which bond to the amine compound through an ionic association with
one or more ionic atoms or compounds. That is, in configurations
where the amine compound consists of covalent bonds, the amine
compound excludes salts of amine compounds, for example, phosphate
amine salts and ammonium salts. As such, in certain embodiments,
the lubricant composition is free of a salt of the amine compound.
More specifically, the lubricant composition may be free of a
phosphate amine salt, ammonium salt, and/or amine sulfate salt.
[0099] The amine compound may be a monomeric acyclic amine compound
having a weight average molecular weight of less than 500.
Alternatively, the monomeric acyclic amine compound may have a
weight average molecular weight of less than 450, less than 400,
less than 350, less than 300, less than 250, less than 200, or less
than 150. Alternatively still, the amine compound may have a weight
average molecular weight of at least 30, at least 50, at least 75,
at least 100, at least 150, at least 200, or at least 250.
[0100] The term "acyclic" is intended to refer to compounds which
are free from any cyclic structures and to exclude aromatic
structures. For example, the monomeric acyclic amine compound does
not include compounds having a ring having at least three atoms
bonded together in a cyclic structure and those compounds including
benzyl, phenyl, or triazole groups.
[0101] The monomeric acyclic amine compound may be exemplified by
general formula (X):
##STR00046##
where each R.sup.13 is independently a hydrogen atom or a
hydrocarbyl group. The hydrocarbyl group designated by R.sup.13 may
have the same meaning as R described above with respect to general
formula (I). For example, each R.sup.13 may independently be a
hydrocarbyl group including an alcohol group, an amino group, an
amide group, an ether group, or an ester group. The monomeric
acyclic amine includes monoamines and polyamines (including two or
more amine groups).
[0102] In certain embodiments, at least one group designated by
R.sup.13 is unsubstituted. Alternatively, two or three groups
designated by R.sup.13 are unsubstituted. Alternatively still, it
is contemplated that one, two, or three groups designated by
R.sup.13 are substituted. As outlined above with respect to R in
general formula (I), the term "substituted" indicates that the
designated group includes at least one substituent group, and/or
that the designated group includes at least one heteroatom or
heterogroup.
[0103] Exemplary alkyl R.sup.13 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.
[0104] Exemplary monomeric acyclic amine compounds include, but are
not limited to, primary, secondary, and tertiary amines, such as:
[0105] methylamine:
[0105] H.sub.2N--CH.sub.3 [0106] ethanolamine:
[0106] ##STR00047## [0107] dimethylamine:
[0107] ##STR00048## [0108] methylethanolamine:
[0108] ##STR00049## [0109] trimethylamine:
[0109] ##STR00050## [0110] bis (2-ethylhexyl) amine:
[0110] ##STR00051## [0111] ditridecylamine:
##STR00052##
[0112] The monomeric acyclic amine compound may alternatively be
one or more other primary amines such as ethylamine, n-propylamine,
isopropylamine, n-butylamine, isobutylamine, sec-butylamine,
tert-butylamine, pentylamine, and hexylamine; primary amines of the
formulas: CH.sub.3--O--C.sub.2H.sub.4--NH.sub.2,
C.sub.2H.sub.5--O--C.sub.2H.sub.4--NH.sub.2,
CH.sub.3--O--C.sub.3H.sub.6--NH.sub.2,
C.sub.2H.sub.5--O--C.sub.3H.sub.6--NH.sub.2,
C.sub.4H.sub.9--O--C.sub.4H.sub.8--NH.sub.2,
HO--C.sub.2H.sub.4--NH.sub.2, HO--C.sub.3H.sub.6--NH.sub.2 and
HO--C.sub.4H.sub.8--NH.sub.2; secondary amines, for example
diethylamine, methylethylamine, di-n-propylamine, diisopropylamine,
diisobutylamine, di-sec-butylamine, di-tert-butylamine,
dipentylamine, dihexylamine; and also secondary amines of the
formulas: (CH.sub.3--O--C.sub.2H.sub.4).sub.2NH,
(C.sub.2H.sub.5--O--C.sub.2H.sub.4).sub.2NH,
(CH.sub.3--O--C.sub.3H.sub.6).sub.2NH,
(C.sub.2H.sub.5--O--C.sub.3H.sub.6).sub.2NH,
(n-C.sub.4H.sub.9--O--C.sub.4H.sub.8).sub.2NH,
(HO--C.sub.2H.sub.4).sub.2NH, (HO--C.sub.3H.sub.6).sub.2NH and
(HO--C.sub.4H.sub.8).sub.2NH; and polyamines, such as
n-propylenediamine, 1,4-butanediamine, 1,6-hexanediamine,
diethylenetriamine, triethylenetetramine and
tetraethylenepentamines, and also their alkylation products, for
example 3-(dimethylamino)-n-propylamine,
N,N-dimethylethylenediamine, N,N-diethylethylenediamine, and
N,N,N',N'-tetramethyldiethylenetriamine.
[0113] Alternatively, the amine compound may be a monomeric cyclic
amine compound. The monomeric cyclic amine compound may have a
weight average molecular weight of from 100 to 1200, 200 to 800, or
200 to 600. Alternatively, the monomeric cyclic amine compound may
have a weight average molecular weight of less than 500, or at
least 50. In some embodiments, the monomeric cyclic amine compound
is free from aromatic groups, such as phenyl and benzyl rings. In
other embodiments, the monomeric cyclic amine compound is
aliphatic.
[0114] The monomeric cyclic amine compound may include two or fewer
nitrogen atoms per molecule. Alternatively, the monomeric cyclic
amine compound may include only one nitrogen per molecule. The
phrase "nitrogen per molecule" refers to the total number of
nitrogen atoms in the entire molecule, including the body of the
molecule and any substituent groups. In certain embodiments, the
monomeric cyclic amine compound includes one or two nitrogen atoms
in the cyclic ring of the monomeric cyclic amine compound.
[0115] The monomeric cyclic amine compound may be exemplified by
the general formula (XI):
##STR00053##
or general formula (XII):
##STR00054##
In general formulas (XI) and (XII), Y represents the type and
number of atoms necessary to complete the cyclic ring of general
formulas (XI) or (XII). The ring designated by Y may include from 2
to 20, 3 to 15, 5 to 15, or 5 to 10, carbon atoms. The ring
designated by Y may be a substituted or unsubstituted, branched or
unbranched, divalent hydrocarbon group that includes one or more
hetero atoms, such as oxygen, or sulfur, and may include one or
more heterogroups. In addition to including heteroatoms and/or
heterogroups, the ring designated by Y may include one or more
hydrocarbyl substituent groups, as described above with respect to
R in general formula (I). In certain embodiments, the ring
designated by Y is free from nitrogen heteroatoms, or free from any
heteroatoms. The heteroatoms, heterogroups, and/or substituent
groups may be bonded to different atoms in the divalent hydrocarbon
group designated by Y. The substituent nitrogen atom in general
formula (XII) may be bonded to one or more hydrogen atoms, or may
be bonded to one or two hydrocarbyl groups.
[0116] In formula (XI), R.sup.14 is a hydrogen atom or a
hydrocarbyl group. The hydrocarbyl group designated by R.sup.14 may
have the same meaning as R described above with respect to formula
(I). For example, R.sup.14 may be an alcohol group, an amino group,
an alkyl group, an amide group, an ether group, or an ester group.
R.sup.14 may have 1 to 50, 1 to 25, 1 to 17, 1 to 15, 1 to 12, 1 to
8, 1 to 6, or 1 to 4, carbon atoms. R.sup.14 may be straight or
branched. For example, each R.sup.12 may be an alcohol group, amino
group, alkyl group, amide group, ether group, or ester group having
1 to 50 carbon atoms, with the designated functional group
(alcohol, etc.), heteroatom, or heterogroup bonded at various
positions on the carbon chain. The substituent nitrogen atom in
general formula (XII) may be bonded to one or more hydrogen atoms,
or may be bonded to one or two hydrocarbyl groups, such as those
described above with respect to R.sup.14.
[0117] In one more specific embodiment, the monomeric cyclic amine
compound may be exemplified by general formula (XIII):
##STR00055##
In general formula (XIII), each R.sup.15 is independently a
hydrogen atom or a hydrocarbyl group having from 1 to 17 carbon
atoms. The hydrocarbyl group designated by R.sup.15 may have the
same meaning as R in general formula (I). For example, each
R.sup.15 may independently be substituted with an alcohol group, an
amino group, an amide group, an ether group, or an ester group.
Each R.sup.15 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. In certain
embodiments, at least one group designated by R.sup.15 is
unsubstituted. Alternatively, at least two, three, four, five, or
six groups designated by R.sup.15 are unsubstituted. Alternatively
still, it is contemplated that one, two, three, four, five, or six
groups designated by R.sup.15 are substituted. For example, each
R.sup.15 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.
[0118] Exemplary monomeric cyclic amine compounds include: [0119]
cyclopentylamine:
[0119] ##STR00056## [0120] cyclohexylamine:
[0120] ##STR00057## [0121] aziridine:
[0121] ##STR00058## [0122] piperidine:
[0122] ##STR00059## [0123] n-methylpiperidine:
##STR00060##
[0124] In some embodiments, the monomeric acyclic amine compound or
the monomeric cyclic amine compound may be a sterically hindered
amine compound. In one or more embodiments, the sterically hindered
amine compound may have a weight average molecular weight of from
100 to 1200. Alternatively, the sterically hindered amine compound
may have a weight average molecular weight of 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.
[0125] 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.
[0126] The sterically hindered amine compound may have general
formula (XIV) or (XV):
##STR00061##
In general formula (XIV), each R.sup.16 is independently a hydrogen
atom or a hydrocarbyl group having from 1 to 17 carbon atoms,
wherein at least two of R.sup.16 are an alkyl group in one
molecule; and R.sup.17 is independently a hydrogen atom or a
hydrocarbyl group having from 1 to 17 carbon atoms. In general
formula (XV), each R.sup.18 is independently a hydrogen atom or a
hydrocarbyl group having from 1 to 17 carbon atoms, wherein at
least two of R.sup.18 are an alkyl group, and each R.sup.19 is
independently a hydrogen atom or a hydrocarbyl group having from 1
to 17 carbon atoms.
[0127] The groups designated by R.sup.16, R.sup.17, R.sup.18, and
R.sup.19 may have the same meaning as R described above with
respect to general formula (I). For example, each R.sup.16,
R.sup.17, R.sup.18, and R.sup.19 may independently substituted with
an alcohol group, an amide group, an ether group, or an ester
group, and each R.sup.16, R.sup.17, R.sup.18, and R.sup.19 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.
[0128] In certain embodiments, at least one group designated by
R.sup.16, R.sup.17, R.sup.18, and R.sup.19 is unsubstituted.
Alternatively, at least two, three, four, five, or six groups
designated by R.sup.16, R.sup.17, R.sup.18, and R.sup.19 are
unsubstituted. In other embodiments, every group designated by
R.sup.16, R.sup.17, R.sup.18, and R.sup.19 is unsubstituted.
Alternatively still, it is contemplated that one, two, three, four,
five, or six groups designated by R.sup.16, R.sup.17, R.sup.18, and
R.sup.19 are substituted.
[0129] Exemplary R.sup.16, R.sup.17, R.sup.18, and R.sup.19 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.
[0130] In general formula (XIV), at least two, at least three, or
all four groups, designated by R.sup.16 are each independently an
alkyl group. Similarly, in general formula (XV), at least two
groups designated by R.sup.18 are an alkyl group. Alternatively, at
least three, or all four groups, designated by R.sup.18 are an
alkyl group.
[0131] The sterically hindered amine compound of general formula
(XIV) may be exemplified by the following compounds: [0132]
2,2,6,6-tetramethyl-4-octylpiperdine:
[0132] ##STR00062## [0133]
2,2,6,6-tetramethyl-4-decylpiperdine:
[0133] ##STR00063## [0134]
2,2,6,6-tetramethyl-4-butylpiperdine:
[0134] ##STR00064## [0135]
2,2,6,6-tetramethyl-4-hexadecylpiperdine:
##STR00065##
[0136] The sterically hindered amine compound of general formula
(XV) is acyclic. The term "acyclic" is intended to mean that the
sterically hindered amine compound of general formula (XV) is free
from any cyclic structures and aromatic structures. The sterically
hindered amine compound of general formula (XV) can be exemplified
by:
N-tert-butyl-2-ethyl-N-methyl-hexan-1-amine
##STR00066##
[0137] tert-amyl-tert-butylamine
##STR00067##
[0138] N-tert-butylheptan-2-amine
##STR00068##
[0140] The sterically hindered amine compound may alternatively be
exemplified by the general formula (XVI):
##STR00069##
In general formula (XVI), each R.sup.16 and R.sup.17 are as
described above, wherein at least three of R.sup.16 are each
independently an alkyl group. The sterically hindered amine
compound of general formula (XVI) may be exemplified by the
following compounds: [0141] (1,2,2,6,6-pentamethyl-4-piperidyl)
octanoate:
[0141] ##STR00070## [0142] (1,2,2,6,6-pentamethyl-4-piperidyl)
decanoate:
[0142] ##STR00071## [0143] (1,2,2,6,6-pentamethyl-4-piperidyl)
dodecanoate:
[0143] ##STR00072## [0144] (2,2,6,6-tetramethyl-4-piperidyl)
dodecanoate:
##STR00073##
[0145] 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.
[0146] The epoxide compound and the amine compound may be provided
in the lubricant composition or additive package in an amount such
that 1 part of oxirane oxygen is provided for every 1 to 20 parts
nitrogen in the amine compound. Alternatively, the epoxide compound
and the amine compound may be provided in an amount such that 1
part of oxirane oxygen is provided for every 1 to 15, 1 to 10, or 1
to 5, parts nitrogen, in the amine compound within the lubricant
composition or additive package.
[0147] In one specific embodiment, the lubricant composition may
consist, or consist essentially of, a base oil, the epoxide
compound, and the amine compound. It is also contemplated that the
lubricant composition may consist of, or consist essentially of,
the base oil, the epoxide compound, and the amine compound, in
addition to one or more of additives that do not materially affect
the functionality or performance of the epoxide 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.
[0148] In other embodiments, the additive package may consist, or
consist essentially of, the epoxide compound and the amine
compound. It is also contemplated that the additive package may
consist of, or consist essentially of, the epoxide compound, and
the amine compound in addition to one or more of additives that do
not compromise the functionality or performance of the epoxide
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 additive package. 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.
[0149] 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).
[0150] In some embodiments, 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 embodiment, the base oil
includes API Group II base oils.
[0151] The base oil may have a viscosity of from 1 to 50, 1 to 40,
1 to 30, 1 to 25, or 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.
[0152] The base oil may be further defined as a crankcase lubricant
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.
[0153] 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. Typically,
these synthetic oils are 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 a weight 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 weight average
molecular weight of 1,000-1500 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.
Alternatively, the base oil may include a substantially inert,
normally liquid, organic diluent, such as mineral oil, naptha,
benzene, toluene, or xylene.
[0154] The base oil may include less than 90, less than 80, less
than 70, less than 60, less than 50, less than 40, less than 30,
less than 20, less than 10, less than 5, less than 3, less than 1,
or be free from, an estolide compound (i.e., a compound including
one or more estolide groups), based on the total weight of the
lubricant composition.
[0155] The base oil may be present in the lubricant composition in
an amount of from 1 to 99.9, 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 1, 10, 20, 30, 40, 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 present) 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. Alternatively, the base oil may be present
in the lubricant composition in an amount of from 0.1 to 50, 1 to
25, or 1 to 15, wt. %, based on the total weight of the lubricant
composition. In various embodiments, the amount of base oil in an
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.
[0156] 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 sulfated ash,
phosphorous and sulfur.
[0157] The lubricant composition may have a TBN value of at least
1, at least 3, at least 5, at least 7, at least 9, mg KOH/g of
lubricant composition, when tested according to ASTM D2896.
Alternatively, the lubricant composition has a TBN value of from 3
to 100, 3 to 75, 50 to 90, 3 to 45, 3 to 35, 3 to 25, 3 to 15, or 9
to 12, mg KOH/g of lubricant composition, when tested according to
ASTM D2896.
[0158] In certain embodiments, the lubricant composition is a
multigrade lubricant composition identified by the viscometric
descriptor SAE15WX, SAE 10WX, SAE 5WX or SAE 0WX, where X is 8, 12,
16, 20, 30, 40, or 50. The characteristics of one or more of the
different viscometric grades can be found in the SAE J300
classification.
[0159] The lubricant composition may have a phosphorus content of
less than 1500, less than 1200, less than 1000, less than 800, less
than 600, less than 400, less than 300, less than 200, or less than
100, or 0, ppm, as measured according to the ASTM D5185 standard,
or as measured according to the ASTM D4951 standard. The lubricant
composition may have a sulfur content of less than 3000, less than
2500, less than 2000, less than 1500, less than 1200, less than
1000, less than 700, less than 500, less than 300, or less than
100, ppm, as measured according to the ASTM D5185 standard, or as
measured according to the ASTM D4951 standard.
[0160] Alternatively, the lubricant composition may have a
phosphorous content of from 1 to 1000, 1 to 800, 100 to 700, or 100
to 600, ppm, as measured according to the ASTM D5185 standard.
[0161] The lubricant composition may be free from, or substantially
free from, a carboxylic acid ester and/or phosphate ester. For
example, the lubricant composition may include less than 20, less
than 15, less than 10, less than 5, less than 3, less than 1, less
than 0.5, or less than 0.1, wt. %, carboxylic acid ester and/or
phosphate ester. The carboxylic acid ester and/or phosphate ester
may be included as conventional base oil in water-reactive
functional fluids. The lubricant composition may be free from a
carboxylic acid ester base oil and/or phosphate ester base oil,
which are liquid at a steady state temperature of 25.degree. C. and
a steady state pressure of 1 atmosphere.
[0162] The lubricant composition may be unreactive with water. By
unreactive with water, it is meant that less than 5, 4, 3, 2, 1,
0.5, or 0.1, wt., %, of the lubricant composition reacts with water
at 1 atmosphere of pressure and 25.degree. C.
[0163] 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.
[0164] The lubricant composition may be a lubricant composition,
such as a crankcase lubricant composition, having a total additive
treat rate of at least 3, at least 4, at least 5, at least 6, at
least 7, or at least 8, wt. %, based on a total weight of the
lubricant composition. Alternatively, the lubricant composition may
have a total additive treat rate ranging from 3 to 20, 4 to 18, 5
to 16, or 6 to 14, wt. %, based on a total weight of the lubricant
composition. The term "total additive treat rate" refers to the
total weight percentage of additives included in the lubricant
composition. The additives accounted for in the total additive
treat rate include, but are not limited to, epoxide compounds,
amine compounds, dispersants, detergents, aminic antioxidants,
phenolic antioxidants, anti-foam additives, antiwear additives,
pour point depressants, viscosity modifiers, and combinations
thereof. In certain embodiments, an additive is any compound in the
lubricant composition other than the base oil. In other words, the
total additive treat rate calculation does not account for the base
oil as an additive.
[0165] The additive package may include, but is not limited to,
epoxide compounds, amine compounds, dispersants, detergents, aminic
antioxidants, phenolic antioxidants, anti-foam additives, antiwear
additives, pour point depressants, viscosity modifiers, and
combinations thereof. The lubricant composition may include the
additive package in amount of at least 3, at least 4, at least 5,
at least 6, at least 7, or at least 8, wt. %, based on a total
weight of the lubricant composition. Alternatively, the lubricant
composition may include the additive package in an amount of from 3
to 20, 4 to 18, 5 to 16, or 6 to 14, wt. %, based on a total weight
of the lubricant composition. In some embodiments, the additive
package does not account for the weight of the base oil as an
additive. Although not required, the additive package includes all
compounds in the lubricant composition other than the base oil.
However, it is to be appreciated that certain individual components
can be independently and individually added to the lubricant
composition separate from the addition of the additive package to
the lubricant composition, yet still be considered part of the
additive package once the additive which was individually added
into the lubricant composition is present in the lubricant
composition along with the other additives.
[0166] The additive package refers to the collective amount of the
epoxide compounds, amine compounds, dispersants, detergents, aminic
antioxidants, phenolic antioxidants, anti-foam additives, antiwear
additives, pour point depressants, viscosity modifiers, or
combinations thereof in a solution, mixture, concentrate, or blend,
such as the lubricant composition. In some embodiments, the term
"additive package" does not require that these additives are
physically packaged together or blended together before addition to
the base oil. Thus, a base oil which includes the epoxide compound
and the dispersant, each added to the base oil separately, could be
interpreted to be a lubricant composition that includes an additive
package comprising the epoxide compound and the dispersant. In
other embodiments, the additive package refers to a blend of the
epoxide compounds, amine compounds, dispersants, detergents, aminic
antioxidants, phenolic antioxidants, anti-foam additives, antiwear
additives, pour point depressants, viscosity modifiers, or
combinations thereof. The additive package may be blended into the
base oil to make the lubricant composition.
[0167] The additive package may be formulated to provide the
desired concentration in the lubricant composition when the
additive package 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.
[0168] In one embodiment, the lubricant composition passes ASTM
D4951 for phosphorus content. ASTM D4951 is a standard test method
for determination of additive elements in lubricant compositions by
inductively coupled plasma atomic emission spectrometry
(ICP-OES).
[0169] In another embodiment, the lubricant composition passes ASTM
D6795, which is a standard test method for measuring the effect on
filterability of lubricant compositions after treatment with water
and dry ice and a short (30 min) heating time. ASTM D6795 simulates
a problem that may be encountered in a new engine run for a short
period of time, followed by a long period of storage with some
water in the oil. ASTM D6795 is designed to determine the tendency
of a lubricant composition to form a precipitate that can plug an
oil filter.
[0170] In another embodiment, the lubricant composition passes ASTM
D6794, which is a standard test method for measuring the effect on
filterability of lubricant composition after treatment with various
amounts of water and a long (6 h) heating time. ASTM D6794
simulates a problem that may be encountered in a new engine run for
a short period of time, followed by a long period of storage with
some water in the oil. ASTM D6794 is also designed to determine the
tendency of the lubricant composition to form a precipitate that
can plug an oil filter.
[0171] In another embodiment, the lubricant composition passes ASTM
D6922, which is a standard test method for determining homogeneity
and miscibility in lubricant compositions. ASTM D6922 is designed
to determine if a lubricant composition is homogeneous and will
remain so, and if the lubricant composition is miscible with
certain standard reference oils after being submitted to a
prescribed cycle of temperature changes.
[0172] In another embodiment, the lubricant composition passes ASTM
D5133, which is a standard test method for low temperature, low
shear rate, viscosity/temperature dependence of lubricating oils
using a temperature-scanning technique. The low-temperature,
low-shear viscometric behavior of a lubricant composition
determines whether the lubricant composition will flow to a sump
inlet screen, then to an oil pump, then to sites in an engine
requiring lubrication in sufficient quantity to prevent engine
damage immediately or ultimately after cold temperature
starting.
[0173] In another embodiment, the lubricant composition passes ASTM
D5800 and/or ASTM D6417, both of which are test methods for
determining an evaporation loss of a lubricant composition. The
evaporation loss is of particular importance in engine lubrication,
because where high temperatures occur, portions of a lubricant
composition can evaporate and thus alter the properties of the
lubricant composition.
[0174] In another embodiment, the lubricant composition passes ASTM
D6557, which is a standard test method for evaluation of rust
preventive characteristics of lubricant compositions. ASTM D6577
includes a Ball Rust Test (BRT) procedure for evaluating the
anti-rust ability of lubricant compositions. This BRT procedure is
particularly suitable for the evaluation of lubricant compositions
under low-temperature and acidic service conditions.
[0175] In another embodiment, the lubricant composition passes ASTM
D4951 for sulfur content. ASTM D4951 is a standard test method for
determination of additive elements in lubricant compositions by
ICP-OES. In addition, the lubricant composition also passes ASTM
D2622, which is a standard test method for sulfur in petroleum
products by wavelength dispersive x-ray fluorescence
spectrometry.
[0176] In another embodiment, the lubricant composition passes ASTM
D6891, which is a standard test method for evaluating a lubricant
composition in a sequence IVA spark-ignition engine. ASTM D6891 is
designed to simulate extended engine idling vehicle operation.
Specifically, ASTM D6891 measures the ability of a lubricant
composition to control camshaft lobe wear for spark-ignition
engines equipped with an overhead valve-train and sliding cam
followers.
[0177] In another embodiment, the lubricant composition passes ASTM
D6593, which is a standard test method for evaluating lubricant
compositions for inhibition of deposit formation in a
spark-ignition internal combustion engine fueled with gasoline and
operated under low-temperature, light-duty conditions. ASTM D6593
is designed to evaluate a lubricant composition's control of engine
deposits under operating conditions deliberately selected to
accelerate deposit formation.
[0178] In another embodiment, the lubricant composition passes ASTM
D6709, which is a standard test method for evaluating lubricant
compositions in a sequence VIII spark-ignition engine. ASTM D6709
is designed to evaluate lubricant compositions for protection of
engines against bearing weight loss.
[0179] In yet another embodiment, the lubricant composition passes
ASTM D6984--the standard test method for evaluation of automotive
engine oils in the Sequence IIIF, Spark-Ignition. In other words,
the viscosity increase of the lubricant composition at the end of
the test is less than 275% relative to the viscosity of the
lubricant composition at the beginning of the test.
[0180] In another embodiment, the lubricant composition passes two,
three, four, or more of the following standard test methods: ASTM
D4951, ASTM D6795, ASTM D6794, ASTM D6922, ASTM D5133, ASTM D6557,
ASTM D6891, ASTM D2622, ASTM D6593, and ASTM D6709.
[0181] In another embodiment, the lubricant composition passes all
of the following standard test methods: ASTM D4951, ASTM D6795,
ASTM D6794, ASTM D6922, ASTM D5133, ASTM D6557, ASTM D6891, ASTM
D2622, ASTM D6593, and ASTM D6709.
[0182] The lubricant composition or the additive package may
further include a dispersant in addition to the epoxide compound
and/or the 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 from 200
to 10000, 500 to 10000, or 800 to 5000.
[0183] 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 (XVII):
##STR00074##
The bonds shown in general formulas (XVII) 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, or 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 of 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.
[0184] 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 of from 500 to 5000 with maleic
anhydride by a thermal route or via the chlorinated polyisobutene.
For examples, derivatives with aliphatic polyamines such as
ethylenediamine, diethylenetriamine, triethylenetetramine or
tetraethylenepentamine may be used.
[0185] 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.
[0186] The dispersant may be a poly(oxyalkyl) radical or a
polyalkylene polyamine radical of the general formula (XVIII):
R.sup.20--NH--(C.sub.1-C.sub.6-alkylene-NH).sub.m--C.sub.1-C.sub.6-alkyl-
ene (XVIII)
where m is an integer of from 1 to 5, R.sup.20 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.
[0187] 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.
[0188] 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.
[0189] 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.
[0190] 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.
[0191] If employed, the dispersant can be used in various amounts.
The dispersant may be present in the lubricant composition in an
amount of 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.
[0192] In the additive package, the total weight of the dispersant
and the epoxide 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.
[0193] The lubricant composition or the additive package may
further include an antiwear additive, optionally comprising
phosphorous. The antiwear 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-benzothiazole,
ethoxycarbonyl-5-octyldithio carbamate, and/or combinations
thereof.
[0194] In some embodiments, the antiwear additive may be
exemplified by a dihydrocarbyl dithiophosphate salt. The
dihydrocarbyl dithiophosphate salt may be represented by the
following general formula (XIX):
[R.sup.21O(R.sup.22O)PS(S)].sub.2M (XIX)
where R.sup.21 and R.sup.22 are each hydrocarbyl groups
independently having from 1 to 30, 1 to 20, 1 to 15, 1 to 10, or 1
to 5, carbon atoms, wherein M is a metal atom or an ammonium group.
For example, R.sup.21 and R.sup.22 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.21 and R.sup.22 may be
substituted or unsubstituted. The hydrocarbyl groups designated by
R.sup.21 and R.sup.22 groups may have the same meaning as described
above with respect to R in general formula (I). 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.23R.sup.24R.sup.25R.sup.26N.sup.+, wherein R.sup.23,
R.sup.24, R.sup.25, and R.sup.26 each independently represents a
hydrogen atom or a hydrocarbyl group having from 1 to 150 carbon
atoms. In certain embodiments, R.sup.23, R.sup.24, R.sup.25, and
R.sup.26 may each independently be hydrocarbyl groups having from 4
to 30 carbon atoms. The hydrocarbyl groups designated by R.sup.23,
R.sup.24, R.sup.25, and R.sup.26 may have the same meaning and R in
general formula (I). In one specific embodiment, the dihydrocarbyl
dithiophosphate salt is zinc dialkyl dithiophosphate. The lubricant
composition may include mixtures of different dihydrocarbyl
dithiophosphate salts.
[0195] In certain embodiments, the dihydrocarbyl dithiophosphate
salt includes a mixture of primary and secondary alkyl groups for,
R.sup.21 and R.sup.22, wherein the secondary alkyl groups are in a
major molar proportion, such as at least 60, at least 75, or at
least 85, mole %, based on the number of moles of alkyl groups in
the dihydrocarbyl dithiophosphate salt.
[0196] In some embodiments, the antiwear additive may be ashless.
The antiwear additive may be further defined as a phosphate. In
another embodiment, the antiwear additive is further defined as a
phosphite. In still another embodiment, the antiwear additive is
further defined as a phosphorothionate. The antiwear additive may
alternatively be further defined as a phosphorodithioate. In one
embodiment, the antiwear additive is further defined as a
dithiophosphate. The antiwear additive may also include an amine
such as a secondary or tertiary amine. In one embodiment, the
antiwear additive includes an alkyl and/or dialkyl amine.
Structures of suitable non-limiting examples of antiwear additives
are set forth immediately below:
##STR00075##
[0197] The antiwear additive can be present in the lubricant
composition in an amount of 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
antiwear 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.
The additive package may also include the antiwear additive
comprising phosphorous in an amount of 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.
[0198] The additive package may consist of, or consist essentially
of, the antiwear additive and the epoxide compound. It is also
contemplated that the lubricant composition may consist of, or
consist essentially of, the epoxide compound and the antiwear
additive in addition to one or more of additives that do not
compromise the functionality or performance of the epoxide
compound. Additionally, it is also contemplated that the additive
package may consist of, or consist essentially of, the epoxide
compound, an amine compound, and the antiwear additive, in addition
to one or more additives that do not compromise the functionality
or performance of the epoxide compound.
[0199] In various embodiments where the lubricant composition
consists essentially or consists of the base oil and the epoxide
compound; the base oil, the epoxide compound, and the amine
compound; or the base oil, the epoxide compound, and the antiwear
additive, or the base oil, the amine compound, the epoxide
compound, and the antiwear additive, the lubricant composition is
free of, or includes less than 0.01, 0.001, or 0.0001 wt. % of
acids, amine curing agents, anhydrides, triazoles, and oxides.
[0200] 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 epoxide compound, in
addition to the combination of the epoxide compound and the amine
compound, or in combination with the amine compound, the epoxide
compound, and the antiwear additive. Specific examples of the one
or more additives include 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.
[0201] 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.
[0202] 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.
[0203] 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.
[0204] 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-methylphenyl) 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.
[0205] 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.
[0206] 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-h-
ydroxybenzyl)malonate, and combinations thereof are also suitable
for use as antioxidants.
[0207] 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.
[0208] 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.
[0209] 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.
[0210] 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.
[0211] 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.
[0212] If employed, the antioxidant can be used in various amounts.
The antioxidant may be present in the lubricant composition in an
amount of 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.
[0213] 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.
[0214] 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.
[0215] If employed, the metal deactivator can be used in various
amounts. The metal deactivator may be present in the lubricant
composition in an amount of 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.
[0216] 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.
[0217] 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
of 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.
[0218] 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.
[0219] 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 of 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.
[0220] 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.
[0221] 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 of 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.
[0222] 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.
[0223] If employed, the detergent can be used in various amounts.
The detergent may be present in the lubricant composition in an
amount of 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.
[0224] 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 epoxide
compound into the lubricant composition decreases the tendency of
the lubricant composition to degrade the seals versus lubricant
compositions which are free from the epoxide compound.
[0225] 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.
[0226] 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
[0227] 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%.
[0228] 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%.
[0229] When the epoxide 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 epoxide compound is used in the lubricant compositions
described, the resulting lubricant composition has a fluoropolymer
compatibility such that a fluoropolymer exhibits a change in
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.
[0230] 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.
[0231] A method of lubricating a system is provided. The method
includes contacting the system with the lubricant composition
described above. The system may further include an internal
combustion engine. Alternatively, the system may further include
any combustion engine or application that utilizes a lubricant
composition. The system includes at least one fluoropolymer
seal.
[0232] The method may include providing the lubricant composition
to the crankcase of the internal combustion engine, providing a
fuel in a combustion chamber of the internal combustion engine, and
combusting the fuel in an internal combustion engine.
[0233] The fluoropolymer seal may include a fluoroelastomer. The
fluoroelastomer may be categorized under ASTM D1418 and ISO 1629
designation of FKM for example. The fluoroelastomer may include
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.
[0234] In addition, a method of forming the lubricant composition
is provided. The method includes combining the base oil and the
epoxide compound, and, optionally, the amine compound and/or the
antiwear additive. The epoxide compound may be incorporated into
the base oil in any convenient way. Thus, the epoxide 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 epoxide compound in
conjunction with agitation until the epoxide 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
[0235] Without being limited, in the below examples, exemplary
lubricant compositions were formulated by blending each of the
components together until homogeneity was achieved. A partially
formulated lubricant composition containing dispersant, detergent,
aminic antioxidant, phenolic antioxidant, anti-foam, base oil, 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 demonstrate the effects of the epoxide
compound on TBN and seal compatibility.
[0236] The reference lubricant was combined with various different
epoxide compounds to demonstrate the effect of the epoxide compound
on TBN and seal compatibility. Other components were combined with
the reference lubricant in combination with the epoxide compound to
demonstrate synergies between the epoxide compound and these other
components with respect to TBN and seal compatibility.
[0237] The epoxide compound used in examples 5-10, 15, and 31-34 is
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate. The
epoxide compound used in example 16 is 1,4-butanediol diglycidyl
ether. The epoxide compound used in example 17 is
1,2,7,8-diepoxyoctane. The epoxide compound used in examples 18 and
22 is glycidol. The epoxide compound used in examples 19 and 23 is
N-tert-butyl-2,3-epoxypropionamide. The epoxide compound used in
examples 20 and 24 is N-isopropyl-2,3-epoxypropionamide. The
epoxide compound used in examples 21 and 25 is n-butyl-2,3-epoxy
propionate.
[0238] The amine compound used in examples 8, 9, 11, 22-25, 27, and
31 is (2,2,6,6-tetramethyl-4-piperidyl) dodecanoate. The amine
compound used in examples 12, 28, and 32 is
(1,2,2,6,6-pentamethyl-4-piperidyl) dodecanoate. The amine compound
used in examples 13, 29, and 33 is 1-dodecylamine. The amine
compound used in examples 14, 30, and 34 is Infineum C9232 (a 950
MW PIPSA-PAM dispersant).
[0239] The antiwear additive used in examples 2, 5, and 8 is
Infineum C9417 (a mixed primary/secondary
dihydrocarbyldithiophosphate salt. The antiwear additive used in
examples 3, 6, and 15-34 is HiTEC 7169 (a secondary
dithiodihydrocarbylphosphate salt). The antiwear additive used in
examples 4, 7, and 9 is ELCO 108 (a primary
dithiodihydrocarbyldiphosphate salt).
[0240] The respective amount of the reference lubricant and any
additional components for each of the examples are shown in Tables
2-7 below:
TABLE-US-00002 TABLE 2 Formulations of Examples #1-#7 Example # 1 2
3 4 5 6 7 Reference Lubricant (g) 80 80 80 80 80 80 80 Additional
Base Oil (g) 20 18.87 18.87 18.87 18.37 18.37 18.37 Epoxide
Compound (g) 0 0 0 0 0.50 0.50 0.50 Practical Amine Compound (g) 0
0 0 0 0 0 0 Antiwear Additive (g) 0 1.13 1.13 1.13 1.13 1.13 1.13
Total Weight (g) 100 100 100 100 100 100 100
TABLE-US-00003 TABLE 3 Formulations of Examples #8-#14 Example # 8
9 10 11 12 13 14 Reference Lubricant (g) 80 80 80 80 80 80 80
Additional Base Oil (g) 17.17 17.17 19.5 18.8 18.72 19.32 14.29
Epoxide Compound (g) 0.50 0.50 0.50 0 0 0 0 Amine Compound (g) 1.20
1.20 0 1.20 1.29 0.68 5.71 Antiwear Additive (g) 1.13 1.13 0 0 0 0
0 Total Weight (g) 100 100 100 100 100 100 100
TABLE-US-00004 TABLE 4 Formulations of Examples #15-#21 Example #
15 16 17 18 19 20 21 Reference Lubricant (g) 80 80 80 80 80 80 80
Additional Base Oil (g) 18.37 18.47 18.59 18.58 18.30 18.36 18.30
Epoxide Compound (g) 0.50 0.40 0.28 0.29 0.57 0.51 0.57 Amine
Compound (g) 0 0 0 0 0 0 0 Antiwear Additive (g) 1.13 1.13 1.13
1.13 1.13 1.13 1.13 Total Weight (g) 100 100 100 100 100 100
100
TABLE-US-00005 TABLE 5 Formulations of Examples #22-25 Example # 22
23 24 25 Reference Lubricant (g) 80 80 80 80 Additional Base Oil
(g) 17.38 17.10 17.16 17.10 Epoxide Compound (g) 0.29 0.57 0.51
0.57 Amine Compound (g) 1.20 1.20 1.2 1.20 Antiwear Additive (g)
1.13 1.13 1.13 1.13 Total Weight (g) 100 100 100 100
TABLE-US-00006 TABLE 6 Formulations of Examples #26-#30 Example #
26 27 28 29 30 Reference Lubricant (g) 80 80 80 80 80 Additional
Base Oil (g) 18.87 17.67 17.59 18.19 13.16 Epoxide Compound (g) 0 0
0 0 0 Amine Compound (g) 0 1.2 1.29 0.68 5.71 Antiwear Additive (g)
1.13 1.13 1.13 1.13 1.13 Total Weight (g) 100 100 100 100 100
TABLE-US-00007 TABLE 7 Formulations of Examples #31-#34 Example #
31 32 33 34 Reference Lubricant (g) 80 80 80 80 Additional Base Oil
(g) 17.17 17.09 17.69 12.66 Epoxide Compound (g) 0.50 0.50 0.50
0.50 Amine Compound (g) 1.20 1.29 0.68 5.71 Antiwear Additive (g)
1.13 1.13 1.13 1.13 Total Weight (g) 100 100 100 100
[0241] The TBN of the exemplary lubricant compositions were tested
according to ASTM D2896 and ASTM D4739. These test methods can be
used to indicate relative changes that occur in the lubricant
composition during use under oxidizing or other service conditions
regardless of the color or other properties of the resulting
lubricant composition.
[0242] The seal compatibility of the exemplary lubricant
compositions were tested according to the 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.
[0243] The results of the TBN and seal compatibility tests are
shown below in Tables 8-13:
TABLE-US-00008 TABLE 8 TBN and Seal Compatibility Test Results -
Examples #1-#7 Example # 1 2 3 4 5 6 7 Volume Change (%) 0.4 0.6
0.4 0.4 0.5 0.5 0.5 Points Hardness DIDC 3 0 1 1 1 1 1 Tensile
Strength (%) -23 -9 -6 -6 -7 -12 -8 Elongation at Rupture (%) -47
-40 -27 -24 -22 -27 -23 TBN by ASTM D4739 9.16 9.05 9.01 9.42 9.80
9.37 9.43 (mg KOH/g) TBN by ASTM D 2896 12.18 12.12 12.04 12.23
13.80 13.56 14.38 (mg KOH/g)
TABLE-US-00009 TABLE 9 TBN and Seal Compatibility Test Results -
Examples #8-#14 Example # 8 9 10 11 12 13 14 Volume Change (%) 0.9
1 1.5 0.7 0.7 21 0.3 Points Hardness DIDC 3 2 2 4 4 12 4 Tensile
Strength (%) -23 -17 -7 -24 -23 -66 -28 Elongation at Rupture (%)
-42 -33 -45 -50 -49 -72 -49 TBN by ASTM D4739 11.28 11.53 9.02
10.94 10.99 11.21 10.94 (mg KOH/g) TBN by ASTM D 2896 15.34 16.42
14.00 13.14 13.12 13.91 14.76 (mg KOH/g)
TABLE-US-00010 TABLE 10 TBN and Seal Compatibility Test Results -
Examples #15-#21 Example # 15 16 17 18 19 20 21 Volume Change (%)
0.5 0.6 0.6 0.4 0.6 0.8 0.5 Points Hardness DIDC 0 -1 -1 0 1 2 0
Tensile Strength (%) 5 2 3 2 -4 -12 8 Elongation at Rupture (%) -19
-20 -4 -9 -23 -30 -4 TBN by ASTM D4739 9.37 9.18 9.12 9.49 9.22
9.45 9.12 (mg KOH/g) TBN by ASTM D 2896 12.97 12.14 12.51 12.96
12.51 12.48 12.59 (mg KOH/g)
TABLE-US-00011 TABLE 11 TBN and Seal Compatibility Test Results -
Examples #22-#25 Example # 22 23 24 25 Volume Change (%) 0.7 0.9
0.9 0.8 Points Hardness DIDC 0 2 3 1 Tensile Strength (%) -9 -24
-32 -13 Elongation at Rupture (%) -18 -46 -54 -32 TBN by ASTM D4739
(mg KOH/g) 11.66 11.21 10.99 11.42 TBN by ASTM D 2896 (mg KOH/g)
14.67 14.66 14.75 14.55
TABLE-US-00012 TABLE 12 TBN and Seal Compatibility Test Results -
Examples #26-#30 Example # 26 27 28 29 30 Volume Change (%) 0.4 0.9
1 5.7 0.6 Points Hardness DIDC 0 3 3 14 4 Tensile Strength (%) -3
-13 -14 -67 -27 Elongation at Rupture (%) -21 -52 -55 -78 -53 TBN
by ASTM D4739 (mg KOH/g) 8.63 9.81 10.36 10.24 10.40 TBN by ASTM D
2896 (mg KOH/g) 11.64 13.15 13.38 13.04 14.55
TABLE-US-00013 TABLE 13 TBN and Seal Compatibility Test Results -
Examples #31-#34 Example # 31 32 33 34 Volume Change (%) 0.8 0.7
8.1 0.6 Points Hardness DIDC 0 0 12 3 Tensile Strength (%) -6 -3
-66 -26 Elongation at Rupture (%) -23 -19 -75 -53 TBN by ASTM D4739
(mg KOH/g) 10.84 10.93 10.85 11.08 TBN by ASTM D 2896 (mg KOH/g)
14.98 15.15 15.02 16.45
These examples demonstrate that the epoxide compound improves the
TBN and seal compatibility of a lubricant composition. For example,
the examples demonstrate that lubricant compositions that include
the epoxide compound demonstrate improved TBN, according to ASTM
D4739 and/or ASTM D2896, even when combined with components that
would not ordinarily be expected to affect, or significantly
affect, the TBN of the lubricant composition. Furthermore, the
examples demonstrate that lubricant compositions which include the
epoxide compound demonstrate improved seal compatibility in terms
of in terms of volume change, points hardness, tensile strength
and/or elongation at rupture, even when combined with components
that would ordinary be expected to negatively affect the seal
compatibility of the lubricant composition in a significant way. In
summary, lubricant compositions that include the epoxide compound
demonstrate superior results when compared to lubricant
compositions that do not include the epoxide compound
[0244] 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.
[0245] 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 "of 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.
[0246] 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 of from at least 10 to 35, a subrange of 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 "of 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.
[0247] 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.
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