U.S. patent application number 16/348209 was filed with the patent office on 2019-10-24 for lubricant composition.
The applicant listed for this patent is BASF SE. Invention is credited to Kevin J. DeSantis, Roger Kuhlman, Eugene Scanlon.
Application Number | 20190322958 16/348209 |
Document ID | / |
Family ID | 60409454 |
Filed Date | 2019-10-24 |
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United States Patent
Application |
20190322958 |
Kind Code |
A1 |
DeSantis; Kevin J. ; et
al. |
October 24, 2019 |
Lubricant Composition
Abstract
A lubricant composition includes a base oil and an additive
package. The additive package includes a seal compatibility
additive chosen from a halide seal compatibility additive, an
epoxide seal compatibility additive, a boroxine seal compatibility
additive, a sulfonate ester seal compatibility additive, and
combinations thereof. The alkoxylated amide and the ester are set
forth in general formulas A and B, respectively: In general
formulas A and B, each R.sup.13, R.sup.II, R.sup.III, and R.sup.IV,
is, independently, a linear or branched, saturated or unsaturated,
hydrocarbyl group. In addition, at least one of R.sup.II and
R.sup.III include an alkoxy group, and R.sup.IV includes an amine
group. ##STR00001##
Inventors: |
DeSantis; Kevin J.; (Upper
Nyack, NY) ; Scanlon; Eugene; (Mamaroneck, NY)
; Kuhlman; Roger; (Ringwood, NJ) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
Ludwigshafen am Rhein |
|
DE |
|
|
Family ID: |
60409454 |
Appl. No.: |
16/348209 |
Filed: |
November 8, 2017 |
PCT Filed: |
November 8, 2017 |
PCT NO: |
PCT/US2017/060527 |
371 Date: |
May 8, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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62418932 |
Nov 8, 2016 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 141/08 20130101;
C10M 141/06 20130101; C10M 133/04 20130101; C10M 2207/042 20130101;
C10M 2215/082 20130101; C10M 2215/26 20130101; C10M 2227/061
20130101; C10M 141/12 20130101; C10M 131/04 20130101; C10M 2201/087
20130101; C10M 2219/044 20130101; C10M 133/16 20130101; C10M 169/00
20130101; C10N 2030/36 20200501; C10M 2207/28 20130101; C10M
2219/042 20130101; C10M 2227/062 20130101; C10M 139/00 20130101;
C10M 2211/022 20130101; C10M 135/10 20130101; C10M 129/18 20130101;
C10M 2215/28 20130101 |
International
Class: |
C10M 141/12 20060101
C10M141/12; C10M 169/00 20060101 C10M169/00; C10M 129/18 20060101
C10M129/18; C10M 131/04 20060101 C10M131/04; C10M 135/10 20060101
C10M135/10; C10M 139/00 20060101 C10M139/00; C10M 133/16 20060101
C10M133/16; C10M 133/04 20060101 C10M133/04 |
Claims
1. A lubricant composition comprising: a base oil; and an additive
package comprising: a seal compatibility additive chosen from a
halide seal compatibility additive, an epoxide seal compatibility
additive, a boroxine seal compatibility additive, a sulfonate ester
seal compatibility additive, and combinations thereof; an
alkoxylated amide having a general formula (A): ##STR00077## and an
ester having a general formula (B): ##STR00078## wherein each
R.sup.13, R.sup.II, R.sup.III, and R.sup.IV, is, independently, a
linear or branched, saturated or unsaturated, hydrocarbyl group, at
least one of R.sup.II and R.sup.III comprises an alkoxy group, and
R.sup.IV comprises an amine group.
2. The lubricant composition of claim 1 wherein said seal
compatibility additive is an epoxide compound that has the general
formula: ##STR00079## wherein each Z and R.sup.11 is independently
a substituted or unsubstituted divalent hydrocarbon group.
3. The lubricant composition of claim 1 wherein said seal
compatibility additive is an epoxide compound that has the general
formula: ##STR00080## wherein each Z and R.sup.12 is independently
a substituted or unsubstituted divalent hydrocarbon group.
4. The lubricant composition of claim 1, wherein said seal
compatibility additive is an epoxide compound, wherein the epoxide
compound includes fewer than five oxirane rings per molecule of
said epoxide compound, and wherein said epoxide compound has a
weight average molecular weight of from 30 to 1500.
5. (canceled)
6. The lubricant composition claim 5 wherein said epoxide compound
has the following structure: ##STR00081##
7. The lubricant composition of claim 1 wherein at least one of
R.sup.II and R.sup.III of said alkoxylated amide comprises at least
one propoxy group.
8. The lubricant composition of claim 1 wherein: R.sup.II of said
alkoxylated amide has a general formula: ##STR00082## and;
R.sup.III of said alkoxylated amide has a general formula:
##STR00083## wherein; each R.sup.17 is, independently, an alkyl
group, each R.sup.18 is, independently, an alkoxy group, n is an
integer from 0 to 5, m is an integer from 0 to 5, and
1.ltoreq.(n+m).ltoreq.5.
9. The lubricant composition of claim 8 wherein
1.ltoreq.(n+m).ltoreq.3.
10. The lubricant composition of claim 1 wherein R.sup.IV has a
general formula (XIV): ##STR00084## wherein; R.sup.17 is an alkyl
group, and each R.sup.19 and R.sup.20 is, independently, a linear
or branched, saturated or unsaturated hydrocarbyl group.
11. The lubricant composition of claim 10 wherein: R.sup.19 is a
hydrocarbyl group having a general formula (XV): ##STR00085## and
R.sup.20 is a hydrocarbyl group having a general formula (XVI):
##STR00086## wherein; each R.sup.17 is, independently, an alkyl
group, each R.sup.18 is, independently, an alkoxy group, q is an
integer from 0 to 5, if q is 0, p is an integer from 0 to 5, if q
is .gtoreq.0, p is an integer from 1 to 5, and
0.ltoreq.(p+q).ltoreq.5.
12. The lubricant composition of claim 11 wherein
0.ltoreq.(p+q).ltoreq.3.
13. The lubricant composition of claim 1 wherein R.sup.13 of said
alkoxylated amide and said ester are each, independently, a linear
or branched, saturated or unsaturated, C.sub.7-C.sub.23 aliphatic
hydrocarbyl group.
14. The lubricant composition of claim 12 wherein R.sup.13 of said
alkoxylated amide or said ester comprises a hydroxyl group.
15. The lubricant composition of claim 1 wherein: said alkoxylated
amide is further defined as having a general formula:
R.sup.13--C(.dbd.O)--N[R.sup.17--O--R.sup.18.sub.n--H][R.sup.17--O--R.sup-
.18.sub.m--H]; and said ester is further defined as having a
general formula:
R.sup.13--C(.dbd.O)--O--R.sup.17--N[R.sup.17--O--R.sup.18.sub.q-
--H][R.sup.18.sub.p--H]; wherein, each R.sup.13 is, independently,
a linear or branched, saturated or unsaturated, C.sub.7-C.sub.23
aliphatic hydrocarbyl group, each R.sup.17 is, independently, an
alkyl group, each R.sup.18 is, independently, an alkoxy group, n is
an integer from 0 to 5, m is an integer from 0 to 5,
1.ltoreq.(n+m).ltoreq.5, q is an integer from 0 to 5, if q is 0, p
is an integer from 0 to 5, if q is >0, p is an integer from 1 to
5, and 0.ltoreq.(p+q).ltoreq.5.
16. The lubricant composition of claim 1 wherein said alkoxylated
amide has the following formula: ##STR00087## wherein R.sup.13 is a
linear or branched, saturated or unsaturated, C.sub.7-C.sub.23
aliphatic hydrocarbyl group.
17. The lubricant composition of claim 1 wherein said ester has the
following formula: ##STR00088## wherein R.sup.13 is a linear or
branched, saturated or unsaturated, C.sub.7-C.sub.23 aliphatic
hydrocarbyl group.
18. The lubricant composition according to claim 1 wherein said
seal compatibility additive is an epoxide compound that has the
following chemical structure: ##STR00089## wherein said alkoxylated
amide has the following formula: ##STR00090## wherein said ester
has the following formula: ##STR00091## and wherein each R.sup.13
of said alkoxylated amide and said ester is, independently, a
linear or branched, saturated or unsaturated, C.sub.7-C.sub.23
aliphatic hydrocarbyl group.
19. The lubricant composition of claim 1 wherein said seal
compatibility additive is an epoxide compound that is present in an
amount of 0.01 to 8 wt. %, based on the total weight of said
lubricant composition; and wherein said alkoxylated amide and said
ester are present in a combined total amount of 0.01 to 8 wt. %,
based on the total weight of said lubricant composition.
20. The lubricant composition of claim 1 having a fluoropolymer
seal compatibility such that a fluoropolymer seal submerged in said
lubricant composition exhibits a change in tensile strength of from
-50 to 10% when tested according to CEC L-39-T96.
21. (canceled)
22. An additive package comprising: a seal compatibility additive
chosen from a halide seal compatibility additive, an epoxide seal
compatibility additive, a boroxine seal compatibility additive, a
sulfonate ester seal compatibility additive, and combinations
thereof; an alkoxylated amide having a general formula (A):
##STR00092## and an ester having a general formula (B):
##STR00093## wherein each R.sup.13, R.sup.II, R.sup.III, and
R.sup.IV, is, independently, a linear or branched, saturated or
unsaturated, hydrocarbyl group, at least one of R.sup.II and
R.sup.III comprises an alkoxy group, and R.sup.IV comprises an
amine group.
Description
FIELD OF THE DISCLOSURE
[0001] The present disclosure generally relates to a lubricant
composition that includes a base oil and a particular seal
compatibility additive. The disclosure also relates to an additive
package for a lubricant composition and to a method of lubricating
a system including a fluoropolymer seal.
BACKGROUND
[0002] Additives are used with lubricant compositions based on
mineral or synthetic oils to improve their performance
characteristics. Some nitrogen containing compounds (e.g. amines)
are effective stabilizers for lubricant compositions. Other
nitrogen containing compounds, such as alkoxylated amides and
esters containing amines, may be used to improve the fuel
efficiency of the lubricant composition. However, these nitrogen
containing compounds are generally not employed in combustion
engines due to their detrimental effects on fluoropolymer seals. It
is an object of the present disclosure to provide new types of
lubricant compositions having improved fluoropolymer seal
compatibility while allowing the inclusion of nitrogen containing
compounds.
SUMMARY
[0003] The present disclosure provides a lubricant composition. The
lubricant composition includes a base oil and an additive package.
The additive package includes a seal compatibility additive chosen
from a halide seal compatibility additive, an epoxide seal
compatibility additive, a boroxine seal compatibility additive, a
sulfonate ester seal compatibility additive, and combinations
thereof. The alkoxylated amide and the ester are set forth in
general formulas A and B, respectively:
##STR00002##
In general formulas A and B, each R.sup.13, R.sub.II, R.sup.III,
and R.sup.IV, is, independently, a linear or branched, saturated or
unsaturated, hydrocarbyl group. In addition, at least one of
R.sup.II and R.sup.III include an alkoxy group, and R.sup.IV
includes an amine group.
DETAILED DESCRIPTION
[0004] The present disclosure provides a lubricant composition. The
lubricant composition includes a base oil and an additive package.
The additive package includes a seal compatibility additive, an
alkoxylated amide, and an ester.
Base Oil:
[0005] 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).
[0006] 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.
[0007] 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.
[0008] 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.
[0009] 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.
[0010] 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.
[0011] 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.
Additive Package:
[0012] The additive package includes the seal compatibility
additive, the alkoxylated amide, and the ester.
Seal Compatibility Additive:
[0013] Referring now to the seal compatibility additive (SCA), this
seal compatibility additive may be any known in the art. For
example, the seal compatibility additive may be chosen from a
halide seal compatibility additive, an epoxide seal compatibility
additive, a boroxine seal compatibility additive, a sulfonate ester
seal compatibility additive, or combinations thereof. The seal
compatibility additive can be present in the additive package in
various amounts, e.g. from 0.1 to 99, from 0.1 to 50, or from 0.1
to 10, wt. %, based on the total weight of the additive
package.
Halide Seal Compatibility Additive:
[0014] In one embodiment, the seal compatibility additive is the
halide seal compatibility additive. The halide seal compatibility
additive includes or is a halogen compound. The halogen compound
minimally includes one or more halogen atoms. However, the halogen
compound can take various forms. For example, the halogen compound
may include a hydrocarbon backbone. More specifically, the halogen
compound may include an alkyl halide compound, or may include a
quaternary amine compound having one or more halogen atoms bonded
thereto. Alternatively, the halogen compound may be an elemental
halogen, such as Cl.sub.2, Br.sub.2, I.sub.2 or F.sub.2.
[0015] In one or more embodiments, the halogen compound includes
the hydrocarbon backbone and at least one halogen atom bonded to a
carbon atom in the hydrocarbon backbone. The halogen compound may
be straight or branched. The hydrocarbon backbone may be cyclic or
acyclic. The hydrocarbon backbone may also be straight. The
hydrocarbon backbone may include from 1 to 30, 2 to 25, 2 to 20, 2
to 15, 9 to 15, or 9 to 12, carbon atoms.
[0016] The halogen compound may include one or more pendant groups
selected from the group of alcohol groups, alkoxy groups, alkenyl
groups, alkynyl groups, amine groups, aryl groups, alkylaryl,
arylalkyl, heteroaryl groups, alkyl groups, cycloalkyl groups,
cycloalkenyl, amide groups, ether groups, ester groups, and
combinations thereof, each independently having from 1 to 30, 1 to
20, 1 to 15, or 3 to 12, carbon atoms. Each of these pendant groups
may be bonded to a carbon atom positioned in hydrocarbon backbone
of the halogen compound. 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.
[0017] In one embodiment, the halogen compound is cyclic, meaning
that the halogen compound includes one or more pendant cyclic
groups, that the hydrocarbon backbone, if present, is cyclic, or
both. In another embodiment, the halogen compound is acyclic,
meaning that the hydrocarbon backbone, if present, is acyclic and
the halogen compound is free from pendant cyclic groups.
[0018] The hydrocarbon backbone, if present, may include functional
groups other than the halogen atom, such as hydroxyl, carboxyl,
carbonyl, epoxy, oxide, thio, and thiol groups. These functional
groups may be bonded to the carbon atoms which are positioned in
the hydrocarbon backbone of the halogen compound. The hydrocarbon
backbone, if present, may also include one or more heteroatoms,
such as oxygen, sulfur, and nitrogen heteroatoms; or one or more
heterogroups, such as pyridyl, furyl, thienyl, and imidazolyl.
[0019] Alternatively, if present, the hydrocarbon backbone may
include no pendant or functional groups bonded to the carbon atoms
in the hydrocarbon backbone other than the halogen atom. In
addition, or as an alternative, the hydrocarbon backbone may be
free from heteroatoms and heterogroups. The hydrocarbon backbone
may be saturated or unsaturated.
[0020] The halogen compound may include fluorine atoms, bromine
atoms, iodine atoms, and combinations thereof. Each of these
halogen atoms may be bonded to a carbon atom in the hydrocarbon
backbone, a carbon atom in one of the pendant groups of the
hydrocarbon backbone, or both. The halogen compound may include 1,
2, 3, 4, 5, 6, 7, 8, 9 or 10 or more halogen atoms per molecule. It
is also contemplated that one or more different halogen atoms may
be present in the same molecule of the halogen compound.
[0021] In certain embodiments, the halogen compound includes the
alkyl halide compound and may have a general formula (I):
C.sub.nH.sub.2n+2-mX.sub.m (I)
In general formula (I), n.gtoreq.1, 1.ltoreq.m.ltoreq.(2n+2), and X
is a halogen atom. X may be selected from the group including
fluorine, bromine, iodine, and combinations thereof. In some
embodiments, n may range from 1 to 30, 2 to 25, 2 to 20, 2 to 15, 9
to 15, or 9 to 12; and m may have a value of 1, 2, 3, 4, 5, 6, or
more. The alkyl halide compound may be primary, secondary, or
tertiary. The alkyl halide compound may be a mono-halide,
di-halide, tri-halide, or tetrahalide in some embodiments. It is
also contemplated that one or more different halogen atoms may be
present in the same alkyl halide compound.
[0022] The quaternary halogen compound may be understood as a
quaternary amine salt that includes one or more halogen atoms
bonded thereto. The halogen atoms may be bonded along the body of
the quaternary amine salt or may be bonded to the quaternary amine
salt as a halide counter-ion. The quaternary amine compound may
include 1, 2, 3, 4, 5, or more nitrogen atoms. The quaternary amine
compound may also include 1, 2, 3, 4, 5, or more halogen atoms. It
is also contemplated that one or more different halogen atoms may
be present in the same quaternary amine compound. The quaternary
amine compound may include a variety of different pendent groups,
such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl, arylalkyl, or
heteroaryl groups, each having from 1 to 30, 1 to 20, 1 to 15, or 3
to 12, carbon atoms, and may be further substituted by one or more
amine, imine, hydroxyl, halogen, and/or carboxyl groups. The
quaternary amine compound may be cyclic or acyclic.
[0023] The halogen compound may have a weight average molecular
weight from 30 to 1500, 50 to 1000, 100 to 500, 150 to 500, 200 to
500, or 250 to 500.
[0024] The halogen compound may have a boiling point from 50 to
650, 100 to 450, 135 to 450, 140 to 450, 145 to 450, 150 to 450,
155 to 450, or 200 to 400, .degree. C., at 1 atmosphere.
Alternatively, the halogen compound may have a boiling point of at
least 100, at least 110, at least 120, at least 130, at least 140,
at least 150, or at least 160, .degree. C., at 1 atmosphere, and
less than 450, less than 400, less than 350, less than less than
300, or less than 250, .degree. C., at 1 atmosphere.
[0025] The halogen compound may also have a flash point from 10 to
300, 25 to 250, 50 to 250, 75 to 250, or 85 to 200, .degree. C.
Alternatively, the halogen compound may have a flash point of at
least 10, at least 15, at least 20, at least 25, at least 30, at
least 35, at least 40, at least 45, at least 50, at least 55, at
least 60, at least 65, at least 70, at least 75, at least 80, or at
least 85, .degree. C., and a flash point less than 250, less than
225, less than 200, less than 175, less than 150, or less than 125,
.degree. C.
[0026] In certain embodiments, the halogen compound is a liquid at
a temperature of 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80,
85, 90, 95 or 100, .degree. C., and 1 atmosphere
[0027] The halogen compound may be synthesized in a variety of
ways. For example, the halogen compound can be prepared by reacting
an alkene with a halogen halide, such as hydrogen chloride or
hydrogen bromide to yield the corresponding monohalogenated alkene.
Alternatively, the halogen compound may be prepared by reacting an
alcohol with a hydrogen halide. Alternatively still, the halogen
compound may be prepared by reacting an alkyl alcohol with carbon
tetra bromide, sodium bromide, and a ruthenium catalyst, all in a
dimethylformamide solvent. The carbon tetrabromide may be replaced
with other halogen compounds if halogens other than bromide are
desired.
[0028] Exemplary halogen compounds include tetrabromoethane;
ethyliodide; ethylbromide; 1,2-dibromoethane;
trifluoro-1,2,2-dibromoethane; 1-fluorooctane; tribromopropane;
dibromo cyclohexane; dibromoethane; n-propylbromide; 1-bromo,
4-fluoro cyclohexane; butylbromide; octylbromide; 1-iodododecane;
1-bromododecane; 1,4-di iodobutane; 1,4-dibromobutane;
tetrafluoroethane; 3-iodo-1-propanol; 1-bromohexane; 1-iodohexane;
1-bromopropane; and 1-iodopropane.
[0029] Conventional uses of the halogen compound involve forming a
reaction product of the halogen compound. In such conventional
uses, more than 50 wt. % of the halogen compound is typically
reacted based on the total weight of the halogen compound before
reaction. In certain embodiments, at least 50, at least 60, at
least 70, at least 80 or, at least 90, wt. %, of the halogen
compound remains unreacted in the additive package and/or lubricant
composition based on the total weight of halogen compound utilized
to form the additive package and/or the lubricant composition prior
to any reaction in the additive package or the lubricant
composition.
[0030] Alternatively, at least 95, at least 96, at least 97, at
least 98, or at least 99, wt. %, of the halogen compound remains
unreacted in the additive package and/or the lubricant composition
based on the total weight of the halogen compound prior to any
reaction in the additive package or the lubricant composition.
[0031] The term "unreacted" refers to the fact that the unreacted
amount of the halogen compound does not react with any components
in the additive package or lubricant composition. Accordingly, the
unreacted portion of the halogen compound remains in its virgin
state when present in the additive package or the lubricant
composition before the lubricant composition has been used in an
end-use application, such as an internal combustion engine.
[0032] The phrase "prior to any reaction" refers to the basis of
the amount of the halogen compound in the additive package or
lubricant composition. This phrase does not require that the
halogen compound reacts with other components in the additive
package or the lubricant composition, i.e., 100 wt. % of the
halogen compound may remain unreacted in the additive package
and/or the lubricant composition based on the total weight of the
halogen compound prior to any reaction in the additive package
and/or the lubricant composition.
[0033] Alternatively, the percentage of the halogen compound that
remains unreacted is determined after all of the components which
are present in the additive package or lubricant composition reach
equilibrium with one another. The time period necessary to reach
equilibrium in the additive package or lubricant composition may
vary widely. For example, the amount of time necessary to reach
equilibrium may range from a single minute to many days, or even
weeks. In certain embodiments, the percentage of the halogen
compound that remains unreacted in the additive package or
lubricant composition is determined after 1 minute, 1 hour, 5
hours, 12 hours, 1 day, 2 days, 3 days, 1 week, 1 month, 6 months,
or 1 year.
[0034] In one aspect, the halide seal compatibility additive is an
iodide seal compatibility additive. The iodide seal compatibility
additive includes at least iodine atom. Beyond that, the iodide
seal compatibility additive may take many forms. For example, the
iodide seal compatibility additive may include a hydrocarbon
backbone. Furthermore, the iodide seal compatibility additive may
be an alkyl iodide compound, or may be a quaternary amine compound
having at least one iodine atom bonded thereto. Alternatively
still, the iodide seal compatibility additive may be elemental
iodine (I.sub.2).
[0035] In one or more embodiments, the iodide seal compatibility
additive includes a hydrocarbon backbone and at least one iodine
atom bonded to a carbon atom in the hydrocarbon backbone. In
certain embodiments, the iodide seal compatibility additive
includes the hydrocarbon backbone and at least one iodine atom. The
iodide seal compatibility additive may be straight or branched. The
hydrocarbon backbone may be cyclic or acyclic. The hydrocarbon
backbone may include from 1 to 30, 2 to 25, 2 to 20, 2 to 15, 9 to
15, or 9 to 12, carbon atoms. As used herein, the term "acyclic" is
intended to refer to hydrocarbon backbones which are free from any
cyclic structures and to exclude aromatic structures.
[0036] In some aspects, the iodide seal compatibility additive may
include at least one pendant group. In some embodiments, the at
least one pendant group is selected from alcohol groups, alkoxy
groups, alkenyl groups, alkynyl groups, amine groups, aryl groups,
alkylary groups, arylalkyl groups, heteroaryl groups, alkyl groups,
cycloalkyl groups, cycloalkenyl, amide groups, ether groups, ester
groups, and combinations thereof, each having from 1 to 30, 1 to
20, 1 to 15, or 3 to 12, carbon atoms. Each of these pendant groups
may be bonded to a carbon atom positioned in the hydrocarbon
backbone of the iodide seal compatibility additive.
[0037] In one embodiment, the iodide seal compatibility additive is
cyclic, meaning that the iodide seal compatibility additive
includes the hydrocarbon backbone and that the hydrocarbon backbone
includes at least one pendant cyclic group, that the hydrocarbon
backbone is cyclic, or both. In another embodiment, the iodide seal
compatibility additive is acyclic, meaning that the hydrocarbon
backbone is acyclic and that the iodide seal compatibility additive
is free from pendant cyclic groups. Alternatively, the hydrocarbon
backbone of the iodide seal compatibility additive may be free of
pendant and/or functional groups bonded to the carbon atoms in the
hydrocarbon backbone other than the iodine atom.
[0038] The hydrocarbon backbone of the iodide seal compatibility
additive may include functional groups, such as hydroxyl, carboxyl,
carbonyl, epoxy, oxide, thio, and thiol groups. One or more of
these functional groups may be bonded to hydrocarbon backbone of
the iodide seal compatibility additive. The hydrocarbon backbone of
the iodide seal compatibility additive may also include at least
one heteroatom, such as oxygen, sulfur, and nitrogen heteroatoms;
or at least one heterogroup, such as pyridyl, furyl, thienyl, and
imidazolyl. In addition, or as an alternative, the hydrocarbon
backbone may be free from heteroatoms and heterogroups. For
example, the hydrocarbon backbone may be free from oxygen hetero
atoms. The hydrocarbon backbone may be saturated or
unsaturated.
[0039] The iodide seal compatibility additive may additionally
include fluorine atoms, chlorine atoms, bromine atoms, and
combinations thereof. Each of these halogen atoms may be bonded to
a carbon atom in the hydrocarbon backbone of the iodide seal
compatibility additive or a carbon atom in one of the pendant
groups of the hydrocarbon backbone of the iodide seal compatibility
additive. The iodide seal compatibility additive may include 1, 2,
3, 4, 5, 6, 7, 8, 9, 10, or more halogen atoms per molecule. It is
also contemplated that two or more different, or that two or more
of the same, halogen atoms may be present in the same iodide seal
compatibility additive. For example, the iodide seal compatibility
additive may include at least one iodine atom and at least one
bromine atom.
[0040] As described above, the iodide seal compatibility additive
may be an alkyl iodide compound. The alkyl iodide compound may have
a general formula:
C.sub.nH.sub.2n+2-mI.sub.m (II).
In formula (II), n.gtoreq.1, and 1.ltoreq.m.ltoreq.(2n+2). In some
embodiments, n may range from 1 to 30, 2 to 25, 2 to 20, 2 to 15, 9
to 15, or 9 to 12; and m may have a value of 1, 2, 3, 4, 5, 6, or
more. The alkyl iodide compound may be primary, secondary, or
tertiary. It is also contemplated that two or more different, or
two or more of the same, halogen atoms may be present in the same
alkyl iodide compound. For example, the iodide seal compatibility
additive may include 1,4 diiodobutane or 1-iodo-4-bromobutane.
[0041] The quaternary halogen compound may be understood as a
quaternary amine salt that includes at least one iodine atom bonded
thereto. The iodine atom may be bonded along the body of the
quaternary amine salt or may be bonded to the quaternary amine salt
as a iodide counter-ion. The quaternary amine compound may include
1, 2, 3, 4, 5, or more nitrogen atoms. The quaternary amine
compound may also include 1, 2, 3, 4, 5, or more iodine atoms. The
quaternary amine compound may include a variety of different
pendent groups, such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl,
arylalkyl, or heteroaryl groups, each having from 1 to 30, 1 to 20,
1 to 15, or 3 to 12, carbon atoms, and may be further substituted
by at least one amine, imine, hydroxyl, halogen, and/or carboxyl
group. The quaternary amine compound may be cyclic or acyclic.
[0042] Exemplary iodide seal compatibility additives include:
##STR00003##
[0043] The iodide seal compatibility additive may have a weight
average molecular weight from 50 to 1500, 50 to 1000, 100 to 500,
150 to 500, 200 to 500, or 250 to 500.
[0044] The iodide seal compatibility additive may have a boiling
point from 50 to 650, 100 to 450, 135 to 450, 140 to 450, 145 to
450, 150 to 450, 155 to 450, or 200 to 400, .degree. C., at 1
atmosphere. Alternatively, the iodide seal compatibility additive
may have a boiling point of at least 100, at least 110, at least
120, at least 130, at least 140, at least 150, or at least 160,
.degree. C., at 1 atmosphere, and less than 450, less than 400,
less than 350, less than less than 300, or less than 250, .degree.
C., at 1 atmosphere.
[0045] The iodide seal compatibility additive may also have a flash
point from 10 to 300, 25 to 250, 50 to 250, 75 to 250, or 85 to
200, .degree. C. Alternatively, the iodide seal compatibility
additive may have a flash point of at least 10, at least 15, at
least 20, at least 25, at least 30, at least 35, at least 40, at
least 45, at least 50, at least 55, at least 60, at least 65, at
least 70, at least 75, at least 80, or at least 85, .degree. C.,
and a flash point less than 250, less than 225, less than 200, less
than 175, less than 150, or less than 125, .degree. C.
[0046] In certain embodiments, the iodide seal compatibility
additive is a liquid at a temperature of 25, 30, 35, 40, 45, 50,
55, 60, 65, 70, 75, 80, 85, 90, 95 or 100, .degree. C., and 1
atmosphere.
[0047] The iodide seal compatibility additive may be synthesized in
a variety of ways. For example, the iodide seal compatibility
additive can be prepared by reacting an alkene with hydrogen iodide
to yield the corresponding monohalogenated alkane. Alternatively,
the iodide seal compatibility additive may be prepared by reacting
an alcohol with a hydrogen iodide.
[0048] In the context of the additive package, the halide seal
compatibility additive, such as the iodide seal compatibility
additive, can be present in an amount from 0.1 to 99, 5 to 50, or
10 to 40, wt. %, based on the total weight of the additive package.
In the context of a lubricant composition, the halide seal
compatibility additive, such as the iodide seal compatibility
additive, can be present in an amount from 0.01 to 10, 0.05 to 5,
0.01 to 3, 0.01 to 2, 0.01 to 1.5, 0.01 to 1, 0.01 to 0.75, 0.01 to
0.5, 0.01 to 0.25, or 0.01 to 0.1, wt. %, based on the total weight
of the lubricant composition.
Epoxide Seal Compatibility Additive:
[0049] Referring now to the epoxide seal compatibility additive,
this compound is or includes at least one epoxide compound. In some
embodiments, the epoxide compound may be represented by general
formula (III):
##STR00004##
In general formula (III), 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.
[0050] 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.
[0051] 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.
[0052] 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.
[0053] 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.
[0054] 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.
[0055] 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.
[0056] As described above with respect to general formula (III),
the hydrocarbyl group designated by R may include one or more epoxy
groups. These hydrocarbyl epoxy groups may be represented by the
general formula (IV):
##STR00005##
In general formula (IV), 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 (III).
Multiple groups designated by R.sup.2 may be bonded together to
form a cyclic structure.
[0057] Referring again to general formula (III), 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.
[0058] In certain embodiments, the epoxide compound of general
formula (III) 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.
[0059] 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.
[0060] 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.
[0061] In some embodiments, the epoxide compound may be an epoxide
ester compound. The epoxide ester compound may be represented by
general formula (V):
##STR00006##
In general formula (V), 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 (V) 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 (III).
[0062] The epoxide ester compound of general formula (V) 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.
[0063] In certain embodiments, the epoxide ester compound of
general formula (V) may be more specifically represented by general
formula (VI):
##STR00007##
In general formula (VI), 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 (III). The epoxide ester
compound of general formula (VI) may be exemplified by
glycidyl-2,2-dimethyl octanoate, glycidyl benzoate,
glycidyl-tert-butyl benzoate, glycidyl acrylate, and glycidyl
methacrylate.
[0064] In certain embodiments, the epoxide compound is a cyclic
epoxide compound. The cyclic epoxide compound may be represented by
general formula (VII):
##STR00008##
[0065] In general formula (VII), Z represents the type and number
of atoms necessary to complete the cyclic ring of general formula
(VII). 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 (VII) may be a cycloaliphatic epoxide compound having at
least two terminal oxirane rings.
[0066] The cyclic epoxide compound of general formula (VII) 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.
[0067] As should be appreciated from general formulas 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.
[0068] 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.
[0069] In some embodiments, the polyepoxide compound may be
represented by the general formula (VIII):
##STR00009##
In general formula (VIII), 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 may have the same meaning as described above with respect
to R in general formula (III). The divalent hydrocarbon group
designated by R.sup.10 in general formula (VIII) may have the same
meaning as described above with respect to R.sup.1 in general
formula (IV). 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 (VIII) 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 (VIII) is directly bonded to two cyclic carbons,
i.e., carbons which form part of a cyclic ring.
[0070] Alternatively, the polyepoxide compound may be represented
by general formula (IX) shown below:
##STR00010##
In general formula (IX), each Z may have the same meaning as
described above with respect to general formula (VIII). In general
formula (IX), 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. 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.1 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 (IX) may be exemplified by: [0071]
3-(1-(6-oxabicyclo[3.1.0]hexan-3-yl)propyl)-7-oxabicyclo[4.1.0]heptane:
[0071] ##STR00011## [0072]
3-((7-oxabicyclo[4.1.0]heptan-3-yl)methyl)-8-oxabicyclo[5.1.0]octane:
[0072] ##STR00012## [0073]
4-[1-(7-oxabicyclo[4.1.0]heptan-4-yl)propyl]-7-oxabicyclo[4.1.0]heptane:
[0073] ##STR00013## [0074]
4-[1-methyl-1-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]-7-oxabicyclo[4.1.0]h-
eptane:
##STR00014##
[0075] 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 (X):
##STR00015##
[0076] In general formula (X), each Z may have the same meaning as
described above with respect to general formula (VIII). In general
formula (X), 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 (X) 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 (X) may be
exemplified by: [0077]
3-((7-oxabicyclo[4.1.0]heptane-3-carbonyl)oxy)propyl
9-oxabicyclo[6.1.0]nonane-4-carboxylate:
[0077] ##STR00016## [0078]
7-((6-oxabicyclo[3.1.0]hexan-2-yl)methoxy)heptyl
7-oxabicyclo[4.1.0]heptane-3-carboxylate:
[0078] ##STR00017## [0079]
3-((7-oxabicyclo[4.1.0]heptane-3-carbonyl)oxy)-2-(methoxymethyl)-2-methyl-
propyl 7-oxabicyclo[4.1.0]heptane-2-carboxylate:
[0079] ##STR00018## [0080]
3-(7-oxabicyclo[4.1.0]heptane-4-carbonyloxy)propyl
7-oxabicyclo[4.1.0]heptane-4-carboxylate:
[0080] ##STR00019## [0081]
7-(7-oxabicyclo[4.1.0]heptan-4-ylmethoxy)heptyl
7-oxabicyclo[4.1.0]heptane-4-carboxylate:
[0081] ##STR00020## [0082]
[2-(methoxymethyl)-2-methyl-3-(7-oxabicyclo[4.1.0]heptane-4-carbonyloxy)p-
ropyl]7-oxabicyclo[4.1.0]heptane-4-carboxylate:
##STR00021##
[0083] Alternatively still, the epoxide compound may be exemplified
by general formula (XI):
[A]w[B].sub.x (XI)
In general formula (XI), 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 (III) or R.sup.1 in
general formula (IV). "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 (XI) may be bonded to one another in any order, with
varying number of iterations.
[0084] The epoxide compound may be exemplified by the following
compounds: [0085]
2,2'-[ethane-1,2-diylbis(oxymethanediyl)]dioxirane:
[0085] ##STR00022## [0086]
2,2'-[butane-1,4-diylbis(oxymethanediyl)]dioxirane:
[0086] ##STR00023## [0087]
2,2'-[ethane-1,2-diylbis(sulfanediylmethanediyl)]dioxirane:
[0087] ##STR00024## [0088] bis(oxiran-2-ylmethyl) hexanedioate:
[0088] ##STR00025## [0089] bis(oxiran-2-ylmethyl) butanedioate:
[0089] ##STR00026## [0090] bis(oxiran-2-ylmethyl)
(2E)-but-2-enedioate:
[0090] ##STR00027## [0091] 2,2'-butane-1,4-diyldioxirane:
[0091] ##STR00028## [0092]
2,2'-[benzene-1,3-diylbis(oxymethanediyl)]dioxirane:
[0092] ##STR00029## [0093]
2-({3-(oxiran-2-ylmethoxy)-2-[(oxiran-2-ylmethoxy)methyl]propoxy}methyl)o-
xirane:
[0093] ##STR00030## [0094]
3-(oxiran-2-yl)-8-oxabicyclo[5.1.0]octane:
[0094] ##STR00031## [0095] 8-oxabicyclo[5.1.0]oct-3-ylmethyl
8-oxabicyclo[5.1.0]octane-3-carboxylate:
[0095] ##STR00032## [0096] N-methyl 2,3-epoxypropionamide:
[0096] ##STR00033## [0097] 1,2-epoxybutane:
[0097] ##STR00034## [0098] decyl glycidyl ether:
[0098] ##STR00035## [0099] trimethylolpropane triglycidyl
ether:
[0099] ##STR00036## [0100] glycidol:
[0100] ##STR00037## [0101] [[(2-ethylhexyl)oxy]methyl]oxirane:
[0101] ##STR00038## [0102] methyl 2,3-epoxypropionate:
[0102] ##STR00039## [0103] glycidyl-2,2-dimethyl octanoate:
[0103] ##STR00040## [0104] glycidyl benzoate:
[0104] ##STR00041## [0105] glycidyl acrylate:
[0105] ##STR00042## [0106] 1,2-epoxycyclohexane:
[0106] ##STR00043## [0107] bis(3,4-epoxy cyclohexylmethyl)
adipate:
[0107] ##STR00044## [0108] exo-2,3-epoxynorbornane:
[0108] ##STR00045## [0109]
4-(1'-methylepoxyethyl)-1,2-epoxy-2-methylcyclohexane:
[0109] ##STR00046## [0110] 3,4-epoxycyclohexylmethyl,
3,4-epoxy-cyclohexane carboxylate:
##STR00047##
[0110] It should be appreciated that all of these exemplary
compounds fall within the scope of one or more of the general
formulas and/or within the scope of the written description of the
epoxide compound herein.
[0111] 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.
[0112] 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.
[0113] 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.
[0114] 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.
[0115] 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.
[0116] 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.
[0117] 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.
[0118] 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.
[0119] 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, 0.5 to 3.0, 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. Although not
required, the lubricant composition and/or additive package may
include mixtures of two or more different epoxide compounds.
[0120] 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.
[0121] 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 .alpha.-halo ester and an aldehyde or ketone, in
the presence of a base.
[0122] 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.
[0123] 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.
[0124] 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.
[0125] 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 initially added to the lubricant
composition.
[0126] 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.
[0127] 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.
[0128] 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.
[0129] 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.
[0130] 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.
Boroxine Seal Compatibility Additive:
[0131] In other embodiments, the seal compatibility additive is the
boroxine compound. As such, the boroxine compound may be included
in a lubricant composition or an additive package for a lubricant
composition to improve the seal compatibility of the lubricant
composition.
[0132] The boroxine compound may be represented by general formula
(XII):
##STR00048##
[0133] In general formula (XII), each R.sup.14 is independently an
alkyl group having equal to or fewer than 7 carbon atoms. For
example, each R.sup.14 may independently be an alkyl group having
from 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 to 2, carbon
atoms. Each R.sup.14 may independently be linear or branched. In
one formulation, each R.sup.14 may be a methyl group. Exemplary
R.sup.14 groups may independently include methyl, ethyl, n-propyl,
iso-propyl, n-butyl, sec-butyl, tert-butyl, and n-hexyl groups.
[0134] The boroxine compound may include, but is not limited to,
trimethoxy boroxine, tripropoxy boroxine, triisopropoxy boroxine,
tributoxy boroxine, tripentoxy boroxine, trihexoxy boroxine, and
triheptoxy boroxine. By way of example, trimethoxy boroxine may be
exemplified by the formula:
##STR00049##
[0135] In certain embodiments, each R.sup.14 may represent distinct
alkyl groups. For example, the boroxine compound may be exemplified
by the formula:
##STR00050##
where one group designated by R.sup.14 in general formula (XII) is
methyl, one group designated by R.sup.14 in formula (XII) is ethyl,
and one group designated by R.sup.14 in formula (XII) is propyl.
Alternatively still, groups designated by R.sup.14 may be the same,
and one group designated by R.sup.14 may be different in general
formula (XII).
[0136] The boroxine compound may be prepared via numerous methods.
As but one example, the boroxine compound can be prepared by
reacting 2 mole of orthoboric acid (H.sub.3BO.sub.3) with 1 mole
tri-alkyl borate. The alkyl borate may have from 1 to 7 carbon
atoms, depending on the number of carbon atoms desired in the
groups designated by R.sup.14 in general formula (XII). The
reaction can be conducted at a temperature from 50 to 150.degree.
C. in order to remove 1 mol H.sub.2O.
[0137] Conventional uses of conventional boron compounds involve
forming a reaction product between a conventional amine compound
and a conventional boron compound. The conventional boron compound
may be exemplified by reactive borate esters and boric acids. In
these applications, the conventional boron compound is consumed by
chemical reactions such that the ultimately formed lubricant
composition does not contain appreciable amounts of the
conventional boron compound. Furthermore, in these applications,
the conventional amine compound is reacted with the conventional
boron compound to form a salt. The salt formation is evidenced by
the electronic impact upon the reaction of the conventional boron
compound and the conventional amine compound, which is visible as a
chemical shift in NMR spectroscopy. There are also physical
indications that a reaction takes place, such as the evolution of
heat and the thickening of the solution (cross-linking).
[0138] In such applications of conventional boron compounds, more
than 50 wt. % of the conventional boron compound is typically
reacted with the conventional amine compounds, or is hydrolyzed,
based on the total weight of the conventional boron compound before
reaction. The lubricant composition may be free from a salt formed
through the reaction of the boroxine compound, or may contain less
than 10, less than 5, or less than 1, wt. %, of the salt formed
through the reaction of the boroxine compound based on the total
weight of the lubricant composition after any reaction.
[0139] In certain embodiments, at least 50, at least 60, at least
70, at least 80, or at least 90, wt. %, of the boroxine compound
remains unreacted in the lubricant composition based on a total
weight of boroxine compound utilized to form the lubricant
composition prior to any reaction in the lubricant composition.
Alternatively, at least 95, at least 96, at least 97, at least 98,
or at least 99, wt. %, of the boroxine compound remains unreacted
in the lubricant composition based on a total weight of the
boroxine compound prior to any reaction in the lubricant
composition.
[0140] In one embodiment, the percentage of the boroxine compound
that remains unreacted is determined after all of the components
which are present in the lubricant composition reach equilibrium
with one another. The time period necessary to reach equilibrium in
the lubricant composition may vary widely. For example, the amount
of time necessary to reach equilibrium may range from a single
minute to many days, or even weeks. In certain embodiments, the
percentage of the boroxine compound that remains unreacted in the
lubricant composition is determined after 1 minute, 1 hour, 5
hours, 12 hours, 1 day, 2 days, 3 days, 1 week, 1 month, 6 months,
or 1 year. Generally, the percentage of the boroxine compound that
remains unreacted in the lubricant composition is determined before
an end use.
[0141] In certain embodiments, the lubricant composition includes
less than 0.1, less than 0.01, less than 0.001, or less than
0.0001, wt. %, of compounds which would react with the boroxine
compound based on the total weight of the lubricant
composition.
[0142] The lubricant composition may include less than 100, less
than 50, less than 10, or less than 5, ppm B(OH)3- ions, based the
total weight of the lubricant composition. Conventional boroxine
compounds may be hydrolyzed before they are combined with a
conventional lubricant composition such that more than 100 ppm
B(OH)3- ions are present in the conventional lubricant composition.
In other words, at least 50, at least 60, at least 70, at least 80,
at least 90, at least 95, or at least 99, wt. %, of the boroxine
compound is in an unhydrolyzed state in the lubricant composition
based on the total weight of the boroxine compound. The amount of
the boroxine compound which is hydrolyzed is accounted for when
determining the amount of the boroxine compound which remains
unreacted.
[0143] Furthermore, the boroxine compound does not negatively
affect the total base number (TBN) of the lubricant composition.
The TBN value of the lubricant composition can be determined
according to ASTM D2896 and ASTM D4739 as will be described
below.
Sulfonate Ester Seal Compatibility Additive:
[0144] In other embodiments, the seal compatibility additive is the
sulfonate ester. As such, the sulfonate ester may be included in a
lubricant composition or an additive package for a lubricant
composition to improve the seal compatibility of the lubricant
composition.
[0145] It should be understood that, in certain aspects, the
sulfonate ester may take many forms, so long as the sulfonate ester
includes a sulfonate group. For example, the sulfonate ester may
refer to mono-sulfonate esters, di-sulfonate esters, tri-sulfonate
esters, and sulfonate esters including four or more sulfonate
groups. It is also contemplated that two or more different, or two
or more of the same, sulfonate groups may be present in the same
sulfonate ester. For example, the sulfonate ester may include at
least one mesylate group and at least one tosylate group in the
same molecule.
[0146] In one aspect, the sulfonate ester has the following general
formula (0):
##STR00051##
wherein R.sup.15 and R.sup.16 are each independently selected
hydrocarbyl groups. Each hydrocarbyl group designated by R.sup.15
and R.sup.16 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.sup.15 and R.sup.16 may
independently include from 1 to 100, 1 to 50, 1 to 40, 1 to 30, 1
to 20, 1 to 17, 1 to 15, 1 to 10, 1 to 6, or 1 to 4, carbon atoms.
Alternatively, each hydrocarbyl group designated by R.sup.15 and
R.sup.16 may independently include less than 20, less than 15, less
than 12, or less than 10, carbon atoms. Exemplary alkyl groups
include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl,
sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, 2-ethylhexyl,
octyl, cetyl, 3,5,5-trimethylhexyl, 2,5,9-trimethyldecyl, 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.
[0147] In some embodiments, the sulfonate ester is free from, or
includes a limited number of certain substituent groups. For
example, the sulfonate ester may include fewer than three, fewer
than two, one, or be completely free from, carbonyl groups. In
other aspects, the sulfonate ester is free from an estolide groups
(and is not an estolide). In still other aspects, the sulfonate
ester is free from metal ions and/or other ions.
[0148] In certain aspects, each hydrocarbyl group designated by
R.sup.15 and R.sup.16 may be independently substituted, and include
at least one heteroatom, such as oxygen, nitrogen, sulfur,
chlorine, fluorine, bromine, or iodine, and/or at least one
heterogroup, such as pyridyl, furyl, thienyl, and imidazolyl.
Alternatively, or in addition to including heteroatoms and
heterogroups, each hydrocarbyl group designated by R.sup.15 and
R.sup.16 may independently include at least one substituent group
selected from alkoxy, amide, amine, carboxyl, epoxy, ester, ether,
hydroxyl, keto, sulfonate, sulfuryl, and thiol groups. For example,
each hydrocarbyl group designated by R.sup.15 and R.sup.16 may
include a hydrocarbyl group that includes a sulfonate group.
Alternatively still at least one hydrocarbyl group designated by
R.sup.15 and R.sup.16 may include a hydrocarbyl group that includes
at least two sulfonate groups.
[0149] In one embodiment, the sulfonate ester of general formula
(XIII) is cyclic, meaning that at least one group designated by
R.sup.15 and R.sup.16 is cyclic, or that R.sup.15 or R.sup.16
include a pendant cyclic group. In other aspects, the sulfonate
ester of general formula (XIII) is acyclic hydrocarbyl groups,
meaning that both R.sup.15 and R.sup.16 are acyclic and that
R.sup.15 and R.sup.16 are free from pendant cyclic groups.
Alternatively still, with respect to general formula (XIII),
R.sup.15 is a methyl group and R.sup.16 is a hydrocarbyl group
having from 1 to 17 carbon atoms; R.sup.15 is a methyl group and
R.sup.16 may be an alkyl group having from 1 to 17 carbon atoms;
R.sup.15 is a methylbenzyl group and R.sup.16 is a hydrocarbyl
group having from 1 to 17 carbon atoms; or R.sup.15 is a
methylbenzyl group and R.sup.16 may be an alkyl group having from 1
to 17 carbon atoms.
[0150] Alternatively, as contemplated by general formula (XIII), in
other aspects, R.sup.15 is selected from a p-nitrobenzenesulfonate
and a p-bromobenzenesulfonate, and R.sup.16 is a hydrocarbyl group
having from 1 to 17 carbon atoms.
[0151] In some aspects, the sulfonate ester is free from ionic
bonds. In other words, the bonds present between the atoms of the
sulfonate ester in this aspect consist solely of covalent bonds. As
such, the sulfonate ester is not a salt.
[0152] The sulfonate ester may have a weight average molecular
weight from 96 to 1500, 100 to 1000, 100 to 500, 150 to 500, or 250
to 400.
[0153] In some aspects, the sulfonate ester may include 1 to 50, 1
to 40, 5 to 30, 5 to 25, or 10 to 25, mole % sulfur, based on the
total number of moles in the sulfonate ester.
[0154] By way of example, the sulfonate esters encompassed by
general formula (XIII) and the above description may be exemplified
by one or more of the following compounds: Cetyl mesylate:
##STR00052## [0155] 3,5,5-Trimethylhexyl methanesulfonate:
[0155] ##STR00053## [0156] 2,5,9-Trimethyldecyl
methanesulfonate:
[0156] ##STR00054## [0157]
(2,4-Dimethyl-5-octylsulfonyloxy-pentyl)octane-1-sulfonate:
[0157] ##STR00055## [0158] Hexyl 4-methylbenezene sulfonate:
##STR00056##
[0159] The sulfonate ester may be synthesized in a variety of ways.
For example, the sulfonate may be formed by alcoholysis of sulfonyl
chlorides by the following reaction mechanism:
R.sup.15SO.sub.2Cl+R.sup.16OH.fwdarw.R.sup.15SO.sub.2OR.sup.16+HCl,
where R.sup.15 and R.sup.16 are each independently hydrocarbyl
groups as described above in general formula (XIII). However, it
should be appreciated that other methods of synthesizing the
sulfonate ester are also contemplated.
[0160] In certain embodiments, at least 50, at least 60, at least
70, at least 80 or, at least 90, wt. %, of the sulfonate ester
remains unreacted in the additive package and/or lubricant
composition based on the total weight of sulfonate ester utilized
to form the additive package and/or the lubricant composition prior
to any reaction in the additive package or the lubricant
composition. Alternatively, at least 95, at least 96, at least 97,
at least 98, or at least 99, wt. %, of the sulfonate ester remains
unreacted in the additive package and/or the lubricant composition
based on the total weight of the sulfonate ester prior to any
reaction in the additive package or the lubricant composition.
Alkoxylated Amide and Ester:
[0161] As described above, the lubricant composition or additive
package further includes an alkoxylated amide of general formula
(A) and an ester of general formula (B). Although not required, the
alkoxylated amide and ester typically increase the fuel efficiency
of the lubricant composition.
[0162] In particular general formula (A) and general formula (B)
are described immediately below.
##STR00057##
In general formula (A), each R.sup.13, R.sup.II, and R.sup.III, is,
independently, a linear or branched, saturated or unsaturated,
hydrocarbyl group.
[0163] In general formula (B), each R.sup.13 and R.sup.IV, is,
independently, a linear or branched, saturated or unsaturated,
hydrocarbyl group. It is to be appreciated that the hydrocarbyl
group R.sup.13 of the alkoxylated amide may be the same or
different than the hydrocarbyl group R.sup.13 of the ester. In
addition, R.sup.IV, independently includes an amine group, such
that the ester of general formula (B) may also be referred to as an
ester containing an amine. It is to be appreciated that the ester
containing the amine of general formula (B), may adversely impact a
fluoropolymer seal if the epoxide compound was not present in the
lubricant composition. In other words, despite the fact that the
lubricant composition includes a compound containing an amine
(i.e., the ester of general formula (B), the adverse impact of the
ester of general formula (B) on the fluoropolymer seal is minimized
or eliminated, because the lubricant composition also includes the
epoxide compound.
[0164] As referred to herein, the hydrocarbyl groups of R.sup.13,
R.sup.II, R.sup.III, and R.sup.IV are each, independently, a
monovalent organic radical which includes, but is not limited to,
hydrogen and carbon atoms. Each hydrocarbyl group designated by
R.sup.13, R.sup.II, R.sup.III, and R.sup.IV may be, independently,
linear or branched. Each hydrocarbyl group may be, independently,
aromatic, aliphatic, or alicyclic. Each hydrocarbyl group may be,
independently, saturated or ethylenically unsaturated. Each
hydrocarbyl group may, independently, include an alkyl, alkenyl,
cycloalkyl, cycloalkenyl, aryl, alkylaryl, arylalkyl group, or
combinations thereof. Each hydrocarbyl group designated by
R.sup.13, R.sup.II, R.sup.III, and R.sup.IV may, independently,
include from 1 to 100, 1 to 50, 1 to 40, 1 to 30, 1 to 20, 1 to 17,
1 to 15, 1 to 10, 1 to 6, or 1 to 4, carbon atoms. Alternatively,
each hydrocarbyl groups designated by R.sup.13, R.sup.II,
R.sup.III, and R.sup.IV may, independently, include less than 20,
less than 15, less than 12, or less than 10, carbon atoms.
[0165] Exemplary alkyl groups include methyl, ethyl, propyl,
isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl,
iso-amyl, hexyl, 2-ethylhexyl, octyl, cetyl, 3,5,5-trimethylhexyl,
2,5,9-trimethyldecyl, hexyl, and dodecyl groups. Additional
exemplary alkyl groups are carbon chains derived from coconut oil,
such as carbon chains from about 6 to about 18 carbons in length.
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.
[0166] The hydrocarbyl groups designated by R.sup.13, R.sup.II,
R.sup.III, and R.sup.IV may be, independently, unsubstituted or
substituted. By "unsubstituted," it is intended that the designated
hydrocarbyl group, R.sup.I for example, 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.
[0167] In some embodiments, the hydrocarbyl groups of R.sup.13,
R.sup.II, R.sup.III, and R.sup.IV are, independently, free from, or
includes a limited number of certain substituent groups. For
example, R.sup.13, R.sup.II, R.sup.III, and R.sup.IV may,
independently, include fewer than three, fewer than two, one, or be
completely free from, carbonyl groups. In other aspects, the
hydrocarbyl groups of R.sup.13, R.sup.II, R.sup.III, and R.sup.IV
are, independently, free from an estolide groups (and is not an
estolide). In still other aspects, the hydrocarbyl groups of
R.sup.13, R.sup.II, R.sup.III, and R.sup.IV may be, independently,
free from metal ions and/or other ions.
[0168] In certain aspects, each hydrocarbyl group designated by
R.sup.13, R.sup.II, R.sup.III, and R.sup.IV may be, independently,
substituted, and include at least one heteroatom, such as oxygen,
nitrogen, sulfur, chlorine, fluorine, bromine, or iodine, and/or at
least one heterogroup, such as pyridyl, furyl, thienyl, and
imidazolyl. Alternatively, or in addition to including heteroatoms
and heterogroups, each hydrocarbyl group designated by R.sup.13,
R.sup.II, R.sup.III, and R.sup.IV may, independently, include at
least one substituent group selected from alkoxy, amide, amine,
carboxyl, cyano, epoxy, ester, ether, hydroxyl, keto, sulfonate,
sulfuryl, and thiol groups.
[0169] In certain embodiments, the alkoxylated amide having general
formula (A), R.sup.13 may include from 1 to 40, 3 to 35, 5 to 30, 6
to 25, 7 to 23, 8 to 16, 9 to 13, or 6 to 18 carbon atom(s). In
some embodiments, R.sup.I is a linear or branched, saturated or
unsaturated, C.sub.7-C.sub.23 aliphatic hydrocarbyl group which
optionally includes a hydroxyl group.
[0170] In general formula (A), at least one of R.sup.II and
R.sup.III includes an alkoxy group. As referred to herein, an
alkoxy group is defined as an alkyl group singularly bonded to an
oxygen atom. The alkoxy group may be linear or branched.
Non-limiting examples of suitable alkoxy groups include ethoxy,
propoxy, and butoxy groups. At least one of R.sup.II and R.sup.III
may include, independently, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or more
alkoxy group(s). As one example, R.sup.II may include 2 alkoxy
groups and R.sup.III may include 3 alkoxy groups. As another
example, R.sup.II may be free from alkoxy groups and R.sup.III may
include 3 alkoxy groups. As a further example, R.sup.II may include
2 alkoxy groups and R.sup.III may include 2 alkoxy groups.
[0171] In certain embodiments, R.sup.II includes an ethoxy, a
propoxy group, a butoxy group, or a combination thereof. In other
embodiments, R.sup.III includes an ethoxy, a propoxy group, a
butoxy group, or a combination thereof. In some embodiments, both
R.sup.II and R.sup.III include an ethoxy, a propoxy group, a butoxy
group, or a combination thereof.
[0172] R.sup.II of the alkoxylated amide may have a general formula
(C):
##STR00058##
In general formula (C), R.sup.17 is an alkyl group, each R.sup.8 is
an alkoxy group, and n is an integer from 0 to 5.
[0173] In general formula (C), the alkyl group of R.sup.17 may
include from 1 to 25, 1 to 15, 1 to 10, 1 to 8, 1 to 6, 1 to 4, or
2 to 3, carbon atom(s). The alkyl group may be linear or
branched.
[0174] In certain embodiments, the alkyl group of R.sup.17 is an
ethyl group or a propyl group. In general formula (C), each alkoxy
group of R.sup.18.sub.n may independently be an ethoxy group, a
propoxy group, or a butoxy group such that R.sup.II of the
alkoxylated amide may include an ethoxy group, propoxy group,
butoxy group, or combinations thereof. In certain embodiments, each
alkoxy group of R.sup.18.sub.n is, independently, a propoxy group
or a butoxy group. For example, in embodiments wherein n of
R.sup.18.sub.n is 2, R.sup.18.sub.n may include two propoxy groups,
two butoxy groups, or one propoxy group and one butoxy group.
[0175] In various embodiments, R.sup.III of the alkoxylated amide
is a hydrocarbyl group having a general formula (D):
##STR00059##
In general formula (D), R.sup.17 is an alkyl group, each R.sup.18
is an alkoxy group, and m is an integer from 0 to 5.
[0176] In general formula (D), the alkyl group of R.sup.17 may
include from 1 to 25, 1 to 15, 1 to 10, 1 to 8, 1 to 6, 1 to 4, or
2 to 3, carbon atom(s). The alkyl group may be linear or branched.
In certain embodiments, the alkyl group of R.sup.17 is an ethyl
group or a propyl group.
[0177] In general formula (D), each alkoxy group of R.sup.18.sub.m
may independently be an ethoxy group, a propoxy group, or a butoxy
groups such that R.sup.18 of the alkoxylated amide may include one
or more ethoxy groups, propoxy groups, butoxy groups, or
combinations thereof. In certain embodiments, each alkoxy group of
R.sup.18.sub.m is, independently, a propoxy group or a butoxy
group. For example, in these certain embodiments wherein m of
R.sup.18.sub.m is 2, R.sup.18.sub.m may include two propoxy groups,
two butoxy groups, or one propoxy group and one butoxy group.
[0178] With regard to general formulas (C) and (D), in some
embodiments, 1.ltoreq.(n+m).ltoreq.5. In other words, n+m has a sum
of from 1 to 5. Alternatively, 1.ltoreq.(n+m).ltoreq.3,
1.ltoreq.(n+m).ltoreq.2, or n+m=1.
[0179] In certain embodiments, the alkoxylated amide having general
formula (A) is further defined as having a general formula (E):
R.sup.13--C(.dbd.O)--N[R.sup.7--O--R.sup.18.sub.n--H][R.sup.17--O--R.sup-
.18.sub.mH] (E).
In general formula (E), in certain embodiments, R.sup.I is a linear
or branched, saturated or unsaturated, C.sub.7-C.sub.23 aliphatic
hydrocarbyl group, R.sup.17 is an alkyl group, R.sup.18 is an
alkoxy group, n is an integer from 0 to 5, and m is an integer from
0 to 5. In general formula (E), in certain embodiments,
1.ltoreq.(n+m).ltoreq.5. In one embodiment, each alkyl group of
R.sup.17 is, independently, an ethyl group or a propyl group, and
each alkoxy group of R.sup.18.sub.n and R.sup.18.sub.m is,
independently, a propoxy group or a butoxy group. Non-limiting
examples of suitable alkoxy groups designated by R.sup.18
include:
##STR00060##
[0180] Referring specifically to the ester having general formula
(B), R.sup.13, of general formula (B), may include from 1 to 40, 3
to 35, 5 to 30, 6 to 25, 7 to 23, 8 to 16, 9 to 13, or 6 to 18,
carbon atoms. In some embodiments, R.sup.13 is a linear or
branched, saturated or unsaturated, C.sub.7-C.sub.23 aliphatic
hydrocarbyl group. R.sup.13 may include a hydroxyl group.
[0181] R.sup.IV, of general formula (B), includes an amine group.
The amine group may be a primary, secondary, or tertiary amine. In
some embodiments, the amine group is alkoxylated.
[0182] In certain embodiments, R.sup.IV of the ester of general
formula (B) has a general formula (F):
##STR00061##
(F).
[0183] In general formula (F), R.sup.17 is an alkyl group, and each
R.sup.19 and R.sup.20 is, independently, a linear or branched,
saturated or unsaturated, hydrocarbyl group. In general formula
(F), the alkyl group of R.sup.17 may include from 1 to 25, 1 to 15,
1 to 10, 1 to 8, 1 to 6, 1 to 4, or 2 to 3, carbon atom(s). The
alkyl group may be linear or branched. In certain embodiments, the
alkyl group of R.sup.17 is an ethyl group or a propyl group. In
certain embodiments, the alkyl group of R.sup.17 is an ethyl
group.
[0184] In general formula (F), at least one of R.sup.19 and
R.sup.20 includes an alkoxy group. In certain embodiments, R.sup.19
includes a propoxy group, a butoxy group, or a combination thereof.
In other embodiments, R.sup.20 includes a propoxy group, a butoxy
group, or a combination thereof. In some embodiments, both R.sup.19
and R.sup.20 include a propoxy group, a butoxy group, or a
combination thereof. In certain embodiments, both R.sup.19 and
R.sup.20 include a propoxy group.
[0185] In various embodiments, R.sup.19 is a hydrocarbyl group
having a general formula (G):
##STR00062##
In general formula (G), R.sup.18 is an alkoxy group, and p is an
integer from 0 to 5. In general formula (G), each alkoxy group of
R.sup.18.sub.p may independently be an ethoxy group, a propoxy
group, or a butoxy group. In certain embodiments, the alkoxy group
of R.sup.18.sub.p is, independently, a propoxy group or a butoxy
group. For example, in embodiments wherein p of R.sup.18.sub.p is
2, R.sup.18.sub.p may include two ethoxy groups, two propoxy
groups, two butoxy groups, or two groups selected from one ethoxy
group, one propoxy group and one butoxy group.
[0186] In various embodiments, R.sup.20 is a hydrocarbyl group
having a general formula (H):
##STR00063##
In general formula (XVI), R.sup.17 is an alkyl group, R.sup.18 is
an alkoxy group, and q is an integer from 0 to 5.
[0187] In general formula (H), the alkyl group of R.sup.17 may
include from 1 to 25, 1 to 15, 1 to 10, 1 to 8, 1 to 6, 1 to 4, or
2 to 3, carbon atom(s). The alkyl group may be linear or branched.
In certain embodiments, the alkyl group of R.sup.17 is an ethyl
group or a propyl group.
[0188] In general formula (H), each alkoxy group of R.sup.18.sub.q
may independently be an ethoxy group, a propoxy group, or a butoxy
group. In certain embodiments, each alkoxy group of R.sup.18.sub.q
is, independently, a propoxy group or a butoxy group. For example,
in embodiments wherein q of R.sup.18.sub.q is 2, R.sup.18.sub.q may
include two propoxy groups, two butoxy groups, or one propoxy group
and one butoxy group.
[0189] With regard to general formulas (G) and (H), in certain
embodiments, if q is 0, p is an integer from 0 to 5. If q is
.gtoreq.0, p is an integer from 1 to 5. In some embodiments,
0.ltoreq.(p+q).ltoreq.5. In other words, p+q has a sum of from 0 to
5. Alternatively, 0.ltoreq.(p+q).ltoreq.3, 1.ltoreq.(p+q).ltoreq.2,
or p+q=1. In some embodiments, p is 0 to 3 and q is 0, or p is 1 to
3 and q is 0. For example, in one exemplary embodiment, q is 0 and
p is 3 and in another exemplary embodiment, q=0 and p=0.
[0190] In certain embodiments, the ester having general formula
(XI) is further defined as having a general formula (J):
R.sup.13--C(.dbd.O)--O--R.sup.17--N[R.sup.17--O--R.sup.18.sub.q--H][R.su-
p.18.sub.p--H] (J).
In general formula (J), in certain embodiments, R.sup.13 is a
linear or branched, saturated or unsaturated, C.sub.7-C.sub.23
aliphatic hydrocarbyl group, R.sup.17 is an alkyl group, R.sup.18
is an alkoxy group, q is an integer from 0 to 5, and p is an
integer from 0 to 5. In general formula (J), in certain
embodiments, if q is 0, p is an integer from 0 to 5, if q is >0,
p is an integer from 1 to 5, and 0.ltoreq.(p+q).ltoreq.5. In one
embodiment, each alkyl group of R.sup.17 is, independently, an
ethyl group or a propyl group, and each alkoxy group of
R.sup.18.sub.q and R.sup.18.sub.p is, independently, a propoxy
group or a butoxy group. Non-limiting examples of suitable alkoxy
groups designated by R.sup.8 include:
##STR00064##
[0191] Exemplary alkoxylated amides include, but are not limited
to:
##STR00065## ##STR00066##
[0192] In these exemplary alkoxylated amides, R.sup.13 is a linear
or branched, saturated or unsaturated, hydrocarbyl group, n is an
integer from 0 to 5, m is an integer from 0 to 5, and
1.ltoreq.(n+m).ltoreq.5.
[0193] Exemplary esters include, but are not limited to:
##STR00067## ##STR00068##
[0194] In these exemplary esters, R.sup.13 is a linear or branched,
saturated or unsaturated, hydrocarbyl group, q is an integer from 0
to 5, if q is 0, p is an integer from 0 to 5; if q is >0, p is
an integer from 1 to 5, and 0.ltoreq.(p+q).ltoreq.5.
[0195] The amount of the alkoxylated amide and the ester included
in the lubricant composition ranges from a combined total of 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, 0.5 to
3.0, 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 alkoxylated amide and the
ester 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. Although not required, the
lubricant composition and/or additive package may include mixtures
of two or more different alkoxylated amides and/or esters.
[0196] It should be appreciated that various mechanisms may be used
to prepare the alkoxylated amide and the ester of the additive
package or the lubricant composition. For example, in one
embodiment, the alkoxylated amide and the ester may be prepared by
reacting (a) at least one fatty acid, at least one fatty acid
ester, or a mixture thereof, with (b) a dialkanolamine. In this
embodiment, 1 mole of the amide and the ester resulting from steps
(a) and (b) may then be reacted with from 1 to 5 moles of propylene
oxide and/or butylene oxide to form the alkoxylated amide having
general formula (A) and ester having general formula (B). In
certain embodiments, the alkoxylated amide having general formula
(A) and ester having general formula (B) are free of ethoxy groups
which can result from alkoxylation with ethylene oxide.
[0197] Particularly, the alkoxylated amide having general formula
(H) which further defines the alkoxylated amide having general
formula (A) and the ester having general formula (J) which further
defines the ester having general formula (B) may be prepared by
first reacting at least one fatty acid and/or at least one fatty
acid ester with a dialkanolamine to form a dialkanolamide having
general formula (K) and ester having general formula (L), as shown
below. Next, 1 mole of the dialkanolamide having general formula
(K) and ester having general formula (L) may be reacted with 1 to 5
moles of propylene oxide and/or butylene oxide to form the
alkoxylated amide having general formula (H) and ester having
general formula (J). In certain embodiments, the alkoxylated amide
having general formula (H) and ester having general formula (J) are
free of ethoxy groups which can result from alkoxylation with
ethylene oxide. The major product is the alkoxylated amide having
general formula (H), with the ester of general formula (J) being
present in an amount of up to 50, 40, 30, 20, 15, 10, 5, 3, 2, 1,
or 0.1, wt. %, by total weight of the alkoxylated amide having
general formula (H) and ester having general formula (J).
[0198] The alkoxylated amide having general formula (H) and ester
having general formula (J) may be formed as follows:
##STR00069##
R.sup.13 is a linear or branched, saturated or unsaturated,
hydrocarbyl group. R.sup.c is hydrogen or C.sub.1-3 alkyl, and
R.sup.d is an alkylene group containing 2 or 3 carbon atoms. If
R.sub.c is C.sub.1-3 alkyl, the R.sup.cOH by-product can remain in
the reaction mixture (not shown). Optionally, the R.sup.cOH
by-product can be removed from the reaction mixture. The amide
having general formula (K) and ester having general formula (L) may
then be reacted with propylene oxide and/or butylene oxide to
provide the alkoxylated amide having general formula (H) and ester
having general formula (J).
[0199] Alternatively, the alkoxylated amide having general formula
(H) can be prepared from a vegetable oil, animal oil, or
triglyceride as follows:
##STR00070##
R.sup.13 is a linear or branched, saturated or unsaturated,
hydrocarbyl group. R.sup.d is an alkylene group containing 2 or 3
carbon atoms. The amide having general formula (K) may be reacted
with propylene oxide and/or butylene oxide. In certain embodiments,
the propoxylation/butoxylation is the presence of the glycerin
by-product. In other embodiments, the propoxylation/butoxylation is
after separation of the amide having general formula (K) from the
glycerin by-product. It is to be appreciated that the ester having
general formula (L) is formed and, after
propoxylation/butoxylation, the ester having general formula (J) is
also formed.
[0200] The fatty acid and/or fatty acid ester used in the reaction
to form the amide contains from 2 to 24 carbon atoms, from 2 to 20
carbon atoms, or from 8 to 18 carbon atoms. The fatty acid and/or
fatty acid ester therefore can be, but not limited to, lauric acid,
myristic acid, palmitic acid, stearic acid, octanoic acid,
pelargonic acid, behenic acid, cerotic acid, monotanic acid,
lignoceric acid, doeglic acid, erucic acid, linoleic acid, isanic
acid, stearodonic acid, arachidonic acid, chypanodoic acid,
ricinoleic acid, capric acid, decanoic acid, isostearic acid,
gadoleic acid, myristoleic acid, palmitoleic acid, linderic acid,
oleic acid, petroselenic acid, esters thereof, or combinations
thereof. In certain embodiments, the fatty acid/fatty acid ester
includes lauric acid, or a compound having a lauric acid residue,
e.g. coconut oil.
[0201] The fatty acid/fatty acid ester also can be derived from a
vegetable oil or an animal oil, for example, but not limited to,
coconut oil, babassu oil, palm kernel oil, palm oil, olive oil,
castor oil, peanut oil, jojoba oil, soy oil, sunflower seed oil,
walnut oil, sesame seed oil, rapeseed oil, rape oil, beef tallow,
lard, whale blubber, seal oil, dolphin oil, cod liver oil, corn
oil, tall oil, cottonseed oil, or combinations thereof. In one
embodiment, the fatty acid/fatty acid ester is derived from coconut
oil. The vegetable oils contain a mixture of fatty acids. For
example, coconut oil may contain the following fatty acids:
caprylic (8%), capric (7%), lauric (48%), myristic (17.5%),
palmitic (8.2%), stearic (2%), oleic (6%), and linoleic (2.5%).
[0202] The fatty acid/fatty acid ester can also be derived from
fatty acid esters, such as, for example, glyceryl trilaurate,
glyceryl tristearate, glyceryl tripalmitate, glyceryl dilaurate,
glyceryl monostearate, ethylene glycol dilaurate, pentaerythritol
tetrastearate, pentaerythritol trilaurate, sorbitol monopalmitate,
sorbitol pentastearate, propylene glycol monostearate, or
combinations thereof.
[0203] The fatty acid/fatty acid ester may include one or more
fatty acids, one or more fatty acid methyl ester, one or more fatty
acid ethyl ester, one or more vegetable oil, one or more animal
oil, or combinations thereof. The amide resulting from the reaction
typically contain by-products, such as glycerin, ethylene glycol,
sorbitol, and other polyhydroxy compounds. In certain embodiments,
the water, methanol, and/or ethanol by-products may be removed from
the reaction to substantially reduce the amount of unwanted
by-products. In some embodiments, the by-product polyhydroxy
compounds are allowed to remain in the reaction mixture because
these compounds may not adversely affect the alkoxylated amide
having general formula (H). In certain embodiments, the by-products
resulting from the reaction which remain in the reaction mixture
may be included in the additive package or the lubricant
composition.
[0204] The fatty acid/fatty acid ester is reacted with a
dialkanolamine to provide an amide having general formula (K), such
as dialkanolamide. Dialkanolamines contain a hydrogen atom for
reaction with the carboxyl or ester group of the fatty acid/fatty
acid ester. Dialkanolamines also contain two hydroxy groups for
subsequent reaction with alkylene oxides, such as propylene oxide
and/or butylene oxide. A portion of the dialkanolamine reacts with
the fatty acid/fatty acid ester to provide the ester having general
formula (L) by reaction of a hydroxy group of the dialkanolamine
with the fatty acid/fatty acid ester. The amino group of the
dialkanolamine is available for a subsequent reaction with alkylene
oxides, such as propylene oxide and/or butylene oxide to form the
ester having general formula (L). In some embodiments,
dialkanolamines contain two or three carbons in each of the two
alkanol groups, such as diethanolamine, di-isopropylamine, and
di-n-propylamine. In one embodiment, the dialkanolamine is
diethanolamine.
[0205] In a preparation of the alkoxylated amide having general
formula (K) and ester having general formula (L), the
dialkanolamine can be present in an equivalent molar amount to the
fatty acid residues in the fatty acid/fatty acid ester. In another
embodiment, the dialkanolamine is present in a molar amount
different from the moles of fatty acid residues, i.e., a molar
excess or deficiency. In one embodiment, the number of moles of
dialkanolamine is substantially equivalent to the number of moles
of fatty acid residue. As used herein, the term "fatty acid
residue" is defined as R.sup.13--C(.dbd.O). Therefore, a methyl
ester of a fatty acid, i.e., R.sup.I--C(.dbd.O)OCH.sub.3, contains
one fatty acid residue, and the method may utilize a substantially
equivalent number of moles of dialkanolamine to methyl ester. A
triglyceride contains three fatty acid residues, and the method may
utilize about three moles of dialkanolamine per mole of
triglyceride. The mole ratio of dialkanolamine to fatty acid
residue may be from 0.3 to 1.5, from 0.6 to 1.3, from 0.8 to 1.2,
or from 0.9 to 1.1 moles per mole of fatty acid residue.
[0206] The reaction to prepare the amide having formula general (K)
and the ester having general formula (L) can be performed in the
presence or absence of a catalyst. In certain embodiments, a basic
catalyst is employed. In one embodiment, a catalyst can be an
alkali metal alcoholate, such as sodium methylate, sodium ethylate,
potassium methylate, or potassium ethylate. Alkali metal
hydroxides, such as sodium or potassium hydroxide acid, and alkali
metal carbonates, such as sodium carbonate or potassium carbonate,
also can be used as the catalyst.
[0207] If employed, the catalyst may be present in an amount of
from 0.01 to 5, 0.05 to 4, 0.1 to 3, or 0.5 to 2, wt. %, based on
the total weight of the amide having formula (K) and the ester
having formula (L) to be produced. The reaction temperature to form
the amide having formula (K) and the ester having formula (L) may
be from 50.degree. C. to about 200.degree. C. The reaction
temperature may be higher than the boiling point of an alcohol,
e.g., methanol, and/or water produced during the reaction to
eliminate water and/or the alcohol as it is generated in the
reaction. The reaction may be performed for from 2 to 24 hours.
[0208] Depending on the starting materials, the final reaction
mixture in the preparation of the amide having general formula (K)
and the ester having general formula (L) may contain by-product
compounds. These compounds can include, for example: (i) a
by-product hydroxy compound, e.g., glycerin or other alcohol; (ii)
a by-product mono-ester of a triglyceride, e.g., glyceryl
mono-cocoate; (iii) a by-product di-ester of a triglyceride, e.g.,
glyceryl di-cocoate; and (iv) a dialkanolamine, if an excess molar
amount of dialkanolamine is employed. The reaction mixture contains
the ester having general formula (L) wherein one or more of the
hydroxy groups of the dialkanolamine reacts with the acid, and also
can contain ester-amides wherein both ester and amide groups are
formed. In certain embodiments, such by-product compounds are
allowed to remain in the final reaction mixture containing the
alkoxylated amide having general formula (H) and the ester having
general formula (J).
[0209] As a result of which the alkoxylated amide and ester are
formed, in certain embodiments, the by-product compounds that
remain in the final reaction mixture may be included in the
additive package or the lubricant composition. It is to be
appreciated that certain by-products, such as amine byproducts or
unreacted dialkanolamine, may adversely impact a fluoropolymer seal
if the epoxide compound was not present in the lubricant
composition. In other words, despite the fact that the lubricant
composition typically includes byproducts from the process to
produce the alkoxylated amide and the ester, the byproducts do not
negatively impact the fluoropolymer seal, because the lubricant
composition also includes the epoxide compound.
[0210] After formation of the amide having general formula (K) and
the ester having general formula (L), 1 mole of the amide and ester
(in total) is reacted with from 1 to 5 or from 1 to 3, total moles
of alkylene oxide, such as propylene oxide and/or butylene oxide.
In this step, the amide and ester can be reacted with propylene
oxide first, then with butylenes oxide; or with butylenes oxide
first, then with propylene oxide; or with propylene oxide and
butylene oxide simultaneously. The amide having general formula (K)
and the ester having general formula (L) also can be solely reacted
with propylene oxide or solely be reacted with butylene oxide. In
certain embodiments, 1 mole of the amide having general formula (K)
and the ester having general formula (L), in total, is solely
reacted with about 1 to about 3 moles of propylene oxide.
[0211] The propoxylation/butoxylation reaction often is performed
under basic conditions, for example by employing a basic catalyst
of the type used in the preparation of the amide having general
formula (K) and the ester having general formula (L). Additional
basic catalysts are nitrogen-containing catalysts, for example, an
imidazole, N--N-dimethylethanolamine, and N,N-dimethylbenzylamine.
It also is possible to perform the alkoxylation reaction in the
presence of a Lewis acid, such as titanium trichloride or boron
trifluoride. If employed, the amount of catalyst utilized is from
0.5% to 0.7%, by weight, based on the amount of the amide having
general formula (K) and the ester having general formula (L), in
total, used in the alkoxylation reaction. In some embodiments, a
catalyst is omitted from the reaction.
[0212] The temperature of the alkoxylation reaction may be from
80.degree. C. to 1800.degree. C. The alkoxylation reaction may be
performed in an atmosphere that is inert under the reaction
conditions, e.g., nitrogen.
[0213] The alkoxylation reaction also can be performed in the
presence of a solvent. The solvent may be inert under the reaction
conditions. Suitable solvents are aromatic or aliphatic hydrocarbon
solvents, such as hexane, toluene, and xylene. Halogenated
solvents, such as chloroform, or ether solvents, such as dibutyl
ether and tetrahydrofuran, also can be used.
[0214] In various embodiments, the reaction mixture that yields the
amide having general formula (X) and the ester having general
formula (L) is used without purification in the alkoxylation
reaction to provide the alkoxylated amide having general formula
(H) and the ester having general formula (J). In other embodiments,
the reaction mixture that provides the alkoxylated amide having
general formula (H) and the ester having general formula (J) also
is used without purification. As a result, the reaction product may
include a variety of products and by-product compounds including,
for example, alkoxylated amide having general formula (H), the
ester having general formula (J), the amide having general formula
(K), the ester having general formula (L), unreacted
dialkanolamine, by-product hydroxy compounds (e.g., glycerin or
other alcohol), mono- and/or di-esters of a starting triglyceride,
polyalkylene oxide oligomers, aminoesters, and ester-amides. As a
result, in certain embodiments, the by-product compounds that
remain in the reaction mixture with the products may be included in
the additive package or the lubricant composition. In other
embodiments, the by-product compounds that remain in the reaction
mixture may be excluded from the additive package or the lubricant
composition.
[0215] It also should be understood that the
propoxylation/butoxylation reaction may yield a mixture of the
alkoxylated amide having general formula (H) and the ester having
general formula (J). In particular, both CH.sub.2CH.sub.2OH groups
of the amide having general formula (K) can be alkoxylated, either
to a different degree (i.e., n>0, m>0, and n.noteq.m) or to
the same degree (i.e., n>0, m>0, and n=m). In certain
embodiments, only one CH.sub.2CH.sub.2OH of the amide having
general formula (K) is alkoxylated (i.e., one of n or m is 0). In
other embodiments, the amide having general formula (K), such as
dialkanolamide, is alkoxylated with one mole of alkylene oxide and
one mole of propylene oxide. It is to be appreciated that a portion
of the amide having general formula (K) will not be alkoxylated,
thus n+m can be less than 1, i.e., a lower limit of 0.5.
[0216] In one embodiment, the lubricant composition and/or additive
package includes the epoxy compound having the following chemical
structure:
##STR00071##
the alkoxylated amide having the following formula:
##STR00072##
and the ester having the following formula:
##STR00073##
with each R.sup.13 of the alkoxylated amide and the ester being,
independently, a linear or branched, saturated or unsaturated,
C.sub.7-C.sub.23 aliphatic hydrocarbyl group. In this embodiment,
the lubricant composition may include the epoxy compound in an
amount of 0.01 to 8 wt. %, based on the total weight of the
lubricant composition. Similarly, the lubricant composition may
include the alkoxylated amide the ester in a combined total amount
of 0.01 to 8 wt. %, based on the total weight of the lubricant
composition.
[0217] 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.
[0218] 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.
[0219] 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.
[0220] 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.
[0221] 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.
[0222] 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.
[0223] 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.
[0224] 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.
[0225] 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 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, the
alkoxylated amide, the ester, 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.
[0226] The additive package may include, but is not limited to,
epoxide compounds, the alkoxylated amide, the ester, 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.
[0227] The additive package refers to the collective amount of the
epoxide compounds, the alkoxylated amide, the ester, 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, the
alkoxylated amide, the ester, 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.
[0228] 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.
[0229] 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).
[0230] 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.
[0231] 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.
[0232] 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.
[0233] 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.
[0234] 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.
[0235] 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.
[0236] 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.
[0237] 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.
[0238] 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.
[0239] 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.
[0240] 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.
[0241] 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.
[0242] 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.
[0243] The lubricant composition or the additive package may
further include a dispersant in addition to the epoxide compound
the alkoxylated amide and the ester. 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.
[0244] 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 (M):
##STR00074##
The bonds shown in general formulas (M) 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.
[0245] 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.
[0246] 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.
[0247] The dispersant may be a poly(oxyalkyl) radical or a
polyalkylene polyamine radical of the general formula (N):
R.sup.21--NH--(C.sub.1-C.sub.6-alkylene-NH).sub.m--C.sub.1-C.sub.6-alkyl-
ene (N)
where m is an integer of from 1 to 5, R.sup.21 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.
[0248] 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.
[0249] 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.
[0250] 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.
[0251] 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.
[0252] 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.
[0253] In the additive package, the total weight of the dispersant
and the seal compatibility additive 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.
[0254] 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.
[0255] 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 (P):
[R.sup.22O(R.sup.23O)PS(S)].sub.2M (P)
where R.sup.22 and R.sup.23 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.22 and R.sup.23 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.22 and R.sup.23 may be
substituted or unsubstituted. The hydrocarbyl groups designated by
R.sup.22 and R.sup.23 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.24R.sup.25R.sup.26R.sup.27N.sup.+, wherein R.sup.24,
R.sup.25, R.sup.26, and R.sup.27 each independently represents a
hydrogen atom or a hydrocarbyl group having from 1 to 150 carbon
atoms. In certain embodiments, R.sup.24, R.sup.25, R.sup.26, and
R.sup.27 may each independently be hydrocarbyl groups having from 4
to 30 carbon atoms. The hydrocarbyl groups designated by R.sup.24,
R.sup.25, R.sup.26, and R.sup.27 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.
[0256] In certain embodiments, the dihydrocarbyl dithiophosphate
salt includes a mixture of primary and secondary alkyl groups for,
R.sup.22 and R.sup.23, 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.
[0257] 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## ##STR00076##
[0258] 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.
[0259] 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 seal compatibility
additive, the ester, and the alkoxylated amide. 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.
[0260] 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.
[0261] 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.
[0262] 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.
[0263] 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)di cyclopentadiene,
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.
[0264] 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.
[0265] 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.
[0266] 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-hydroxyphenyl ethyl)-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.
[0267] 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.
[0268] 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.
[0269] Additional examples of suitable antioxidants include those
that include nitrogen, such as amides of
0-(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.
[0270] 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.
[0271] 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.
[0272] 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.
[0273] 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.
[0274] 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.
[0275] 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.
[0276] 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.
[0277] 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.
[0278] 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.
[0279] 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.
[0280] 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.
[0281] 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.
[0282] 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.
[0283] Preferred lubricant compositions provided for use and used
pursuant to this disclosure 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 seal
compatibility additive into the lubricant composition decreases the
tendency of the lubricant composition to degrade the seals versus
lubricant compositions which are free from the seal compatibility
additive.
[0284] 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.
[0285] 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
[0286] 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%.
[0287] 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%.
[0288] When the seal compatibility additive 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 seal compatibility additive 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.
[0289] 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 disclosure 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 disclosure in its intended use, are expressly
contemplated and hereby included herein. Various embodiments of
this disclosure include one or more of the modification, reaction
products, and products formed from employing the lubricant
composition, as described above.
[0290] 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.
[0291] 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.
[0292] 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.
[0293] In addition, a method of forming the lubricant composition
is provided. The method includes combining the base oil, the seal
compatibility additive, the alkoxylated amide and the ester, and,
optionally, the antiwear additive. The seal compatibility additive
may be incorporated into the base oil in any convenient way. Thus,
the seal compatibility additive 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 seal compatibility additive in conjunction with
agitation until the seal compatibility additive 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.
[0294] Lubricant compositions including the seal compatibility
additive 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.
Examples
[0295] A series of lubricant compositions are formed, as set forth
below, and evaluated to determine seal compatibility via tensile
strength and elongation at rupture, each determined using the CEC
L-39-T96 test.
[0296] The Reference Lubricant includes a base oil, a dispersant,
an over based detergent, an aminic antioxidant, a phenolic
antioxidant, an antifoam agent, a pour point depressant, and a
viscosity modifier.
TABLE-US-00002 TABLE 1 Comp. 1 Comp. 2 Comp. 3 Seal Compatibility
-- -- Epoxide SCA Additive Reference Lubricant 80 80 80 Additional
Base Oil 20 18.5 18 Combination of 0 1.5 1.5 Alkoxylated Amide (A)
and Ester (B) Epoxide -- -- 0.5 Alkyl Halide -- -- -- Alkyl -- --
-- Tosylate/Mesylate Methyl Borate -- -- -- Total 100 100 100 Seal
Computability Results CEC L-39-T96 test Tensile Strength (%) -25
-67 -38 CEC L-39-T96 test Elongation at Rupture -42 -76 -49 (%) CEC
L-39-T96 test Comp. 4 Comp. 5 Comp. 6 Seal Alkyl Halide
Tosylate/Mesylate Methylborate Compatibility SCA SCA SCA Additive
Reference 80 80 80 Lubricant Additional Base 18 18 18 Oil
Combination of 1.5 1.5 1.5 Alkoxylated Amide (A) and Ester (B)
Epoxide -- -- -- Alkyl Halide 0.5 -- -- Alkyl -- 0.5 --
Tosylate/Mesylate Methyl Borate -- -- 0.5 Total 100 100 100 Seal
Compatability Results - CEC L- 39-T96 test Tensile Strength -38 -42
-53 (%) CEC L-39-T96 test Elongation at -48 -45 -55 Rupture (%) CEC
L-39-T96 test
[0297] These results suggest that the use of the SCA significantly
improves seal compatibility as compared to when the combination of
Alkoxylated Amide (A) and Ester (B) is used alone. The values
associated with tensile strength and elongation at rupture approach
those values produced when the combination of Alkoxylated Amide (A)
and Ester (B) is not used at all, such as in Composition 1. These
results are unexpected.
[0298] 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.
[0299] It is also to be understood that any ranges and subranges
relied upon in describing various embodiments of the present
disclosure 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
disclosure 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.
[0300] 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.
[0301] The disclosure 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
disclosure are possible in light of the above teachings and the
disclosure may be practiced otherwise than as specifically
described.
* * * * *