U.S. patent application number 16/468766 was filed with the patent office on 2019-12-05 for lubricating composition including n-alkylated dianiline.
This patent application is currently assigned to THE LUBRIZOL CORPORATION. The applicant listed for this patent is THE LUBRIZOL CORPORATION. Invention is credited to Jason J. Hanthorn, Yanshi Zhang.
Application Number | 20190367833 16/468766 |
Document ID | / |
Family ID | 60937905 |
Filed Date | 2019-12-05 |
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United States Patent
Application |
20190367833 |
Kind Code |
A1 |
Hanthorn; Jason J. ; et
al. |
December 5, 2019 |
LUBRICATING COMPOSITION INCLUDING N-ALKYLATED DIANILINE
Abstract
A lubricating composition includes an oil of lubricating
viscosity, an N-alkylated dianiline compound, and at least one of
a) an ashless antioxidant, and b) an overbased calcium detergent.
The ashless antioxidant may be selected from a diarylamine
antioxidant, a phenolic antioxidant, and combinations thereof. The
lubricating composition may contain less than 0.15 weight percent
of phosphorus.
Inventors: |
Hanthorn; Jason J.;
(Wickliffe, OH) ; Zhang; Yanshi; (Wickliffe,
OH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
THE LUBRIZOL CORPORATION |
Wickliffe |
OH |
US |
|
|
Assignee: |
THE LUBRIZOL CORPORATION
Wickliffe
OH
|
Family ID: |
60937905 |
Appl. No.: |
16/468766 |
Filed: |
December 13, 2017 |
PCT Filed: |
December 13, 2017 |
PCT NO: |
PCT/US2017/066103 |
371 Date: |
June 12, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62439246 |
Dec 27, 2016 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 2219/046 20130101;
C10M 137/10 20130101; C10N 2030/52 20200501; C10M 141/10 20130101;
C10M 2219/022 20130101; C10M 2217/06 20130101; C10M 133/12
20130101; C10M 149/10 20130101; C10N 2010/04 20130101; C10N 2040/25
20130101; C10M 2215/06 20130101; C10M 2207/283 20130101; C10M
2215/064 20130101; C10M 2207/026 20130101; C10M 161/00 20130101;
C10M 2207/289 20130101; C10M 163/00 20130101; C10N 2020/04
20130101; C10N 2030/04 20130101; C10M 2207/028 20130101; C10M
2215/26 20130101; C10M 2203/003 20130101; C10M 2223/045 20130101;
C10N 2030/10 20130101; C10N 2060/14 20130101; C10M 2207/262
20130101; C10M 2215/28 20130101; C10M 129/76 20130101; C10M 135/10
20130101; C10M 169/044 20130101; C10M 2205/022 20130101; C10N
2030/42 20200501; C10M 2205/022 20130101; C10M 2205/024 20130101;
C10M 2223/045 20130101; C10N 2010/04 20130101 |
International
Class: |
C10M 133/12 20060101
C10M133/12; C10M 169/04 20060101 C10M169/04; C10M 135/10 20060101
C10M135/10; C10M 137/10 20060101 C10M137/10; C10M 129/76 20060101
C10M129/76; C10M 141/10 20060101 C10M141/10; C10M 149/10 20060101
C10M149/10; C10M 161/00 20060101 C10M161/00 |
Claims
1. A lubricating composition comprising: a) an oil of lubricating
viscosity; b) an N-alkylated dianiline compound; and c) an ashless
antioxidant selected from a diarylamine antioxidant, a phenolic
antioxidant, and combinations thereof, and d) an overbased calcium
detergent; wherein the lubricating composition comprises less than
0.15 weight percent of phosphorus; and wherein the N-alkylated
dianiline is an N,N'-alkylated dianiline compound represented by
the formula: ##STR00027## wherein R.sup.1 and R.sup.2 are
independently selected from alkyl groups of 1 to 24 carbon atoms;
R.sup.3 and R.sup.4 are independently selected from hydrocarbyl
groups of 1 to 6 carbon atoms; each n is from 0 to 3, and X
represents a C.sub.1-C.sub.3 alkylene group.
2. (canceled)
3. The lubricating composition of claim 1, wherein the lubricating
composition has a TBN of at least 4 mg KOH/g, as measured in
accordance with ASTM D-2896.
4. (canceled)
5. The lubricating composition of claim 1, wherein at least one of
R.sup.1 and R.sup.2 includes a cyclohexyl group.
6. (canceled)
7. The lubricating composition of claim 1, wherein the N-alkylated
dianiline compound is at least 0.10 weight percent of the
lubricating composition.
8. (canceled)
9. (canceled)
10. The lubricating composition of claim 1, wherein X is a
methylene group.
11. The lubricating composition of claim 1, wherein the N-alkylated
dianiline compound is represented by the formula: ##STR00028##
wherein R.sup.1 and R.sup.2 are independently selected from alkyl
groups of 1 to 24 carbon atoms.
12. The lubricating composition of claim 11, wherein the
N-alkylated dianiline compound is represented by the formula:
##STR00029##
13. The lubricating composition of claim 1, wherein the N-alkylated
dianiline compound is selected from the group consisting of:
##STR00030## and mixtures thereof.
14. The lubricating composition of claim 13, wherein the
N-alkylated dianiline compound is selected from
4,4'-2-ethylhexylmethylenedianiline,
4,4'-cyclohexylmethylenedianiline, and mixtures thereof.
15. The lubricating composition of claim 1, wherein the oil of
lubricating viscosity is at least 40 weight percent of the
lubricating composition.
16. The lubricating composition of claim 1, wherein the ashless
antioxidant is at least 0.1 weight % of the lubricating
composition.
17. The lubricating composition of claim 1, wherein a ratio of the
ashless antioxidant to the N-alkyl dianiline compound is from 20:1
to 1:20.
18. The lubricating composition of claim 1, wherein the ashless
antioxidant comprises at least one of: a phenolic ester and a
diarylamine; and a sulfurized olefin.
19. (canceled)
20. The lubricating composition of claim 1, wherein the overbased
calcium detergent is selected from sulfonates, non-sulfur
containing phenates, sulfur containing phenates, salixarates,
salicylates, mixtures thereof, and borated equivalents thereof.
21. The lubricating composition of claim 1, wherein the overbased
calcium detergent is present in an amount to deliver at least 2 mg
KOH/g of total base number (TBN), as measured in accordance with
ASTM D-2896, to the composition.
22. The lubricating composition of claim 1, wherein the overbased
calcium detergent is least 0.01 wt. % of the lubricating
composition.
23. The lubricating composition of claim 1, wherein a ratio of
calcium to magnesium in the lubricating composition, by weight, is
at least 9:10.
24. The lubricating composition of claim 1, further comprising a
polyolefin succinimide dispersant, wherein a polyolefin group of
the polyolefin succinimide dispersant has a number average
molecular weight of at least 300.
25. The lubricating composition of claim 1, further comprising a
zinc dialkyldithiophosphate.
26. The lubricating composition of claim 1, wherein the lubricating
composition comprises at least 0.02 weight percent of
phosphorus.
27. (canceled)
28. A method for reducing deposit formation in an internal
combustion engine comprising lubricating the internal combustion
engine with a lubricating composition comprising: a) an oil of
lubricating viscosity; b) an N-alkylated dianiline compound; c) an
ashless antioxidant selected from a diarylamine antioxidant, a
phenolic antioxidant, and combinations thereof, and d) an overbased
calcium detergent; wherein the lubricating composition comprises
less than 0.15 weight percent of phosphorus; and wherein the
N-alkylated dianiline is an N,N'-alkylated dianiline compound
represented by the formula: ##STR00031## wherein R.sup.1 and
R.sup.2 are independently selected from alkyl groups of 1 to 24
carbon atoms; R.sup.3 and R.sup.4 are independently selected from
hydrocarbyl groups of 1 to 6 carbon atoms; each n is from 0 to 3,
and X represents a hydrocarbylene group.
29. (canceled)
30. A method for forming a lubricating composition comprising:
forming an N,N'-alkylated dianiline compound represented by the
formula: ##STR00032## wherein R.sup.1 and R.sup.2 are independently
selected from alkyl groups of 1 to 24 carbon atoms; R.sup.3 and
R.sup.4 are independently selected from hydrocarbyl groups of 1 to
6 carbon atoms; each n is from 0 to 3, and X represents a
hydrocarbylene group; and combining the N-alkylated dianiline
compound with an oil of lubricating viscosity and at least one of:
an ashless antioxidant selected from a diarylamine antioxidant, a
phenolic antioxidant, and combinations thereof, and an overbased
calcium detergent; whereby the lubricating composition comprises
less than 0.15 weight percent of phosphorus.
31. The lubricating composition of claim 1, wherein R.sup.1 and
R.sup.2 are independently selected from alkyl groups of at least 4
carbon atoms.
Description
[0001] This application claims the priority of International
Application PCT/US2017/066103, filed Dec. 13, 2017, and U.S.
Provisional Application No. 62/439,246, filed Dec. 27, 2016, from
which the PCT application claims priority, the disclosures of which
are incorporated herein by reference, in their entireties.
BACKGROUND
[0002] The exemplary embodiment relates to additives for
lubricating compositions and finds particular application in
connection with N-alkylated dianilines for improved deposit control
in as deposit boosters in internal combustion engines.
[0003] U.S. Pat. No. 3,779,923 describes alkylated
methylenedianiline tars as antioxidants in lubricant compositions.
The compounds are formed with a phosphorus-based catalyst.
[0004] U.S. Pat. No. 8,242,066 describes aniline compounds useful
as ashless TBN sources for lubricating oil compositions that are
compatible with fluoroelastomeric engine seal materials.
[0005] U.S. Pat. Nos. 4,100,082; 4,200,545; 4,320,021, and
4,663,063; 4,708.809 generally describe amino-phenol compounds as
lubricating oil additives (e.g., dispersant/detergents).
[0006] One test for assessing deposit formation is the "Standard
Test Method for Determination of Moderately High Temperature Piston
Deposits by Thermo-Oxidation Engine Oil Simulation Test-TEOST MHT,"
ASTM D7097-09. MHT TEOST, as it will be referred to herein, is a
bench test that is designed to predict the deposit-forming
tendencies of engine oil in the piston ring belt and upper piston
crown area during service, and is one of the required test methods
in Specification D 4485 to define API Category-Identified engine
oils.
[0007] Some methylenedianiline compounds (MDAs) have been found to
improve thermal oxidation performance in engine oils and to boost
thin-film antioxidancy. However, formulating an engine oil for high
performance on MHT TEOST can compromise performance in other key
areas. For example, adding dispersants and detergents in large
amounts can negatively impact the viscometric properties of the
lubricating composition or seals performance.
[0008] It would be desirable for a lubricating composition to be
able to provide good deposit control, both in fired engine tests
and in bench tests such as MHT TEOST, while also providing other
performance properties.
BRIEF DESCRIPTION
[0009] In accordance with one aspect of the exemplary embodiment, a
lubricating composition includes an oil of lubricating viscosity,
an N-alkylated dianiline compound and an oil of lubricating
viscosity, and at least one of an ashless antioxidant and an
overbased calcium detergent. The ashless antioxidant may be
selected from a diarylamine antioxidant, a phenolic antioxidant,
and combinations thereof. The lubricating composition includes less
than 0.15 weight percent of phosphorus.
[0010] In accordance with another aspect of the exemplary
embodiment, a method for reducing deposit formation in an internal
combustion engine which includes lubricating the internal
combustion engine with the lubricating composition.
[0011] In accordance with another aspect of the exemplary
embodiment, a method for forming a lubricating composition includes
forming an N-alkylated dianiline compound and combining the
N-alkylated dianiline compound with an oil of lubricating viscosity
and at least one of an ashless antioxidant and an overbased calcium
detergent. The ashless antioxidant may be selected from a
diarylamine antioxidant, a phenolic antioxidant, and combinations
thereof. The lubricating composition includes less than 0.15 weight
percent of phosphorus.
[0012] In various aspects of the exemplary embodiment:
[0013] The N-alkylated dianiline compound is
hydrocarbylene-coupled.
[0014] The lubricating composition has a TBN of at least 4 mg
KOH/g, as measured in accordance with ASTM D-2896.
[0015] The N-alkylated dianiline includes at least one N-alkyl
group selected from cyclic alkyl groups, acyclic alkyl groups, and
combinations thereof.
[0016] The N-alkyl group is a cyclohexyl group.
[0017] The N-alkylated dianiline is an N,N'-alkylated dianiline
compound.
[0018] The N-alkylated dianiline compound is at least 0.10 weight
percent of the lubricating composition, or at least 0.15 wt. %, or
at least 0.2 wt. %, or at least 0.4 wt. % of the lubricating
composition.
[0019] The N-alkylated dianiline compound is up to 4.0 weight
percent of the lubricating composition, or up to 3 wt. %, or up to
1.5 wt. %, or up to 1.2 wt. % of the lubricating composition.
[0020] The N-alkylated dianiline compound is represented by the
formula of any one of Structures I to IV and A1 to A8, described
below, and mixtures thereof.
[0021] The hydrocarbylene group is a C.sub.1-C.sub.3 alkylene
group.
[0022] The N-alkylated dianiline compound is selected from
4,4'-2-ethylhexylmethylenedianiline,
4,4'-cyclohexylmethylenedianiline, and mixtures thereof.
[0023] The oil of lubricating viscosity is at least 40 weight
percent of the lubricating composition.
[0024] The ashless antioxidant is at least 0.1 weight % of the
lubricating composition, or at least 0.2 wt. %, or at least 0.4 wt.
%, or at least 0.6 wt. %, or up to 4 wt. %, or up to 1.2 wt. %, or
up to 1 wt. % of the lubricating composition.
[0025] A ratio of the ashless antioxidant to the N-alkyl dianiline
compound is from 20:1 to 1:20.
[0026] The ashless antioxidant includes a phenolic ester and a
diarylamine.
[0027] The ashless antioxidant further includes a sulfurized
olefin.
[0028] The overbased calcium detergent is selected from sulfonates,
non-sulfur containing phenates, sulfur containing phenates,
salixarates, salicylates, mixtures thereof, and borated equivalents
thereof.
[0029] The overbased calcium detergent is present in an amount to
deliver at least 2 mg KOH/g of total base number (TBN), as measured
in accordance with ASTM D-2896, to the composition.
[0030] The overbased calcium detergent is least 0.01 wt. % or at
least 0.1 wt. %, or at least 0.5 wt. %, or up to 3 wt. %, or up to
2 wt. % of the lubricating composition.
[0031] A ratio of calcium to magnesium in the lubricating
composition, by weight, is at least 9:10.
[0032] The lubricating composition further includes a polyolefin
succinimide dispersant, wherein the polyolefin of the polyolefin
succinimide has a number average molecular weight of at least
300.
[0033] The lubricating composition further includes a zinc
dialkyldithiophosphate.
[0034] The lubricating composition includes at least 0.02 weight
percent of phosphorus.
[0035] The N-alkylated dianiline compound is a reaction product of
a dianiline with at least one of an aldehyde and a ketone.
DETAILED DESCRIPTION
[0036] Aspects of the exemplary embodiment relate to lubricating
compositions and to methods of lubricating an internal combustion
engine. The lubrication composition includes an N-alkylated
dianiline compound, an oil of lubricating viscosity, and at least
one of an ashless antioxidant and a calcium overbased detergent.
The ashless antioxidant may be selected from diarylamine
antioxidants phenolic antioxidants, and mixtures thereof. The
exemplary lubricating composition includes less than 0.15 wt. %
phosphorus.
The N-Alkylated Dianiline
[0037] In the lubricating composition, the exemplary N-alkylated
dianiline compound improves deposit performance, as measured by the
MHT TEOST, while providing good TBN, without negatively impacting
(and in some cases, improving) antioxidancy performance, when
formulated for heavy duty diesel engine (HD) and passenger car
engine applications. For example, in testing, N,N'-dicyclohexyl
methylenedianiline (Cy MDA) is able to provide improvements in the
MHT TEOST in both HD and passenger car formulations while also
helping antioxidant performance, particularly under the Daimler
Oxidation Test in a HD formulation.
[0038] In the exemplary N-alkylated dianiline compound, the two
aromatic rings are hydrocarbylene coupled, e.g., with a
C.sub.1-C.sub.3 hydrocarbylene group, in particular an alkylene
group such as methylene, ethylene, methylmethylene, methylethylene,
or dimethylmethylene. N-alkylated methylenedianiline compounds can
be readily prepared. However, it is to be appreciated that other
hydrocarbylene-coupled N-alkylated dianiline compounds are also
contemplated.
[0039] By "N-alkylated" it is meant that an alkyl group is attached
to the dianiline by one or both of the amine groups attached to the
aromatic rings of the dianiline. Each of these N-alkyl groups may
be a C.sub.1-C.sub.24 alkyl group, such as a C.sub.3 or higher
alkyl group, and may be selected from acyclic alkyl groups, cyclic
alkyl groups, and combinations thereof. In the exemplary
embodiment, each amine group of the dianiline has no more than one
alkyl group. The exemplary N-alkylated methylenedianiline is an N,
N-alkylated methylenedianiline, where both amine groups are
alkylated.
[0040] The exemplary N, N-alkylated methylenedianiline contains no
more than two aromatic rings linked by a hydrocarbylene group.
While methods of generating the N-alkylated dianiline compound may
result in structures having more than two aromatic rings linked by
hydrocarbylene groups, in the exemplary embodiment, a molar ratio
of these N-alkylated polyaromatic aniline compounds to the
N-alkylated dianiline compound in the lubricating composition may
be no greater than 1:10.
[0041] The N-alkylated hydrocarbylene-coupled dianiline compound
may be represented by the formula shown in Structure I:
##STR00001##
[0042] wherein R.sup.1 and R.sup.2 are independently selected from,
or at least 3, or at least 4, or at least 5, or at least 6 carbon
atoms, or up to 20, or up to 12, or up to 10, or up to 8 carbon
atoms,
[0043] R.sup.3 and R.sup.4 are independently selected from
hydrocarbyl groups of 1 to 6 carbon atoms,
[0044] each n is from 0 to 3, or 0 to 2, or 0 to 1, or 0, and
[0045] X represents a hydrocarbylene group, as described above,
such as
[0046] --CH.sub.2--.
[0047] In one embodiment, R.sup.1 and R.sup.2 are independently of
the general form
##STR00002##
where R.sup.5 and R.sup.6 are independently selected from H and
alkyl groups of 1 to 20 carbon atoms or 1 to 12 carbon atoms, or 1
to 8 carbon atoms, and wherein at least one of R.sup.5 and R.sup.6
is not H, or wherein R.sup.5 and R.sup.6 together form a ring. In
one embodiment, R.sup.5 is H or a C.sub.1-C.sub.3 alkyl group and
R.sup.6 is a C.sub.2-C.sub.8 alkyl group, or a C.sub.4-C.sub.6
alkyl group. In another embodiment R.sup.5 and R.sup.6 together
form a C.sub.4-C.sub.8 ring.
[0048] In one embodiment, the N-alkylated dianiline compound is
represented by the formula:
##STR00003##
[0049] The N-alkylated dianiline compound may be a 4,4'-N-alkylated
dianiline compound represented by the formula:
##STR00004##
[0050] Representative acyclic alkyl groups of the general formula
C.sub.nH.sub.2n+1 suitable for R.sup.1 and R.sup.2 include straight
chain and branched chain alkyl groups, such as methyl, ethyl,
n-propyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,
undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, stearyl, icosyl,
docosyl, tetracosyl, 1-methylpropyl, 2,2-dimethylpropyl, isobutyl,
isopentyl, isohexyl, 2-ethylhexyl, isoheptyl, 2-ethylheptyl,
2-propylheptyl, isooctyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl,
isodecyl, 2-butyldecyl, 2-hexydecyl, 2-octyldodecyl,
2-hexyldodecyl, isotridecyl, 2-dodecylhexadecyl, 2-decyltetradecyl,
4-methyl-2-pentyl, 2-tetradecyloctyldecyl, monomethyl
branched-isostearyl, and isomers and combinations thereof. In
particular embodiments, the acyclic alkyl group is branched at the
second or higher carbon, such as 2-ethylhexyl, 2-ethylheptyl,
2-ethyloctyl, and the like.
[0051] Representative cyclic alkyl groups of the general formula
C.sub.nH.sub.2n-1 suitable for R.sup.1 and R.sup.2 include
cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl and combinations
thereof.
[0052] Representative hydrocarbyl groups suitable for R.sup.3 and
R.sup.4 include acyclic alkyl groups, such as methyl, ethyl,
propyl, butyl, pentyl, hexyl, and mixtures and isomers thereof. In
one embodiment n is 0, i.e., there are no R.sup.3 and R.sup.4
substituents on the aromatic rings.
[0053] Example N-alkylated dianiline compounds include compounds of
formulas A-1 to A-8:
##STR00005##
[0054] In specific embodiments, the N-alkylated dianiline compound
is selected from 4,4'-2-cyclohexylmethylenedianiline (CY-MDI)
(Formula A1), and 4,4'-2-ethylhexylmethylenedianiline (EHL-MDI)
(Formula A2).
[0055] The N-alkylated dianiline compound may be present in the
lubricating composition at a concentration of at least 0.1 wt. %
and may be up to 5 wt. %. For example, the concentration of the
compound may be at least 0.15 wt. %, or at least 0.4 wt. %, or at
least 1.5 wt. %, or up to 5.0 wt. %, or up to 2.5 wt. % of the
lubricating composition. The compound may also be present in a
concentrate, alone or with other additives and with a lesser amount
of oil. In a concentrate, the amount of the compound may be at
least 2, or at least 3 times the concentration in the lubricating
composition.
[0056] As used herein, TBN is measured according to ASTM D2896-15,
Standard Test Method for Base Number of Petroleum Products by
Potentiometric Perchloric Acid Titration, ASTM International, West
Conshohocken, Pa., 2011, DOI: 10.1520/D2896-15.
[0057] In various aspects, the N-alkylated dianiline compound has a
TBN of at least 50 mg of KOH/g, or at least 100 mg of KOH/g, as
measured according to ASTM D2896.
[0058] In various aspects, the compound has a TBN of at least.
[0059] The lubricating composition of claim 1, wherein the
composition has a TBN of at least 4 mg KOH/g, as measured in
accordance with ASTM D-2896.
[0060] The N-alkylated dianiline compound is particularly effective
at improving deposit performance in lubricating compositions which
are low in phosphorus. In the exemplary lubricating composition,
the phosphorus content of the lubricating composition is up to 0.15
wt. %, such as up to 0.12 wt. %, or up to 0.11 wt. %, or up to 0.08
wt. %, or up to 0.05 wt. %, or up to 0.04 wt. %, or up to 0.02 wt.
%. The phosphorus content of the lubricating composition may be at
least 0.01 wt. %, or at least 0.02 wt. %, or at least 0.03 wt. %.
Suitable additives for providing the lubricating composition with
such low levels of phosphorus include zinc dialkyldithiophosphates
(ZDDPs), as described below.
Methods of Preparing the N-alkylated Dianiline Compound
[0061] The exemplary compounds may be prepared, for example, from
dianilines, such as 4,4'-methylenedianiline,
2,4'-methylenedianiline, 2,2'-methylenedianiline, and mixtures
thereof.
[0062] In one embodiment, N-alkylated dianiline compounds are
prepared by reacting a dianiline with one or more aldehydes or
ketones in a 1:2 or excess molar ratio in an alcohol solvent, such
as methanol or toluene.
[0063] The aldehyde or ketone can be of the general formula:
##STR00006##
where
##STR00007##
corresponds to R.sup.1 and R.sup.2 above, at least one of R.sup.5
and R.sup.6 is not H.
[0064] In one embodiment, the aldehyde or ketone may be a
C.sub.2-C.sub.12 aldehyde or ketone, such as a C.sub.2-C.sub.9
aldehyde, or a C.sub.2-C.sub.6 aldehyde or a C.sub.3-C.sub.10
ketone, or C.sub.3-C.sub.7 ketone.
[0065] Example ketones useful in forming the compound include
methyl alkyl ketones and ethyl alkyl ketones of from 3-12 carbon
atoms where the alkyl group may be alicyclic or cyclic. Examples of
such ketones include those in which the alkyl portions are methyl,
ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,
cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl and as well as the
various isomeric forms thereof. Examples of ketones include
acetone, 2-butanone, 2-pentanone, 3-pentanone, 4-methyl-2-butanone,
2-hexanone, 4-methyl-2-hexanone, 4-heptanone, 5-methyl-2-hexanone,
5,6-dimethyl-2-hexanone, 5,5-dimethyl-2-hexanone,
4,5-dimethyl-2-hexanone, 4-ethyl-2-hexanone, 5-ethyl-2-hexanone,
4,5,5-trimethyl-2-hexanone, 2-heptanone, 3-heptanone,
5,5-dimethyl-2-heptanone, 4,5-dimethyl-2-heptanone,
5-ethyl-2-heptanone, 4-ethyl-2-heptanone, 2-octanone, 3-octanone,
4-octanone, 6-methyl-2-octanone, 7,7-dimethyl-2-octanone,
6-methyl-3-octanone, 6-ethyloctanone, 2-nonanone, 3-nonanone,
4-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone,
5-decanone, cyclobutanone, cyclopentanone, cyclohexanone,
methyl-cyclohexanones, ethyl-cyclohexanones, cycloheptanone,
cyclooctanone, and the like.
[0066] As an example, 4,4'-methylenedianiline is reacted with an
aldehyde/ketone in a 1:2 or excess molar ratio in a suitable
solvent, such as toluene, at a temperature of over 100.degree. C.
Water formed in the reaction is removed. Once the reaction is
complete, the solvent is removed. The product may be purified by
redissolving it in a suitable solvent, such as methanol, and adding
sodium borohydride. The mixture is poured into water and the
product extracted using ethyl acetate. The solvent is removed
yielding the purified product. An illustrative reaction scheme
shown in Scheme 1:
##STR00008##
[0067] where R.sup.5 and R.sup.6 are as described above.
[0068] N-alkylated dianiline compounds can also be prepared by
reacting a methylenedianiline and one or more aldehydes or ketones
in a 1:2 or excess molar ratio in the presence of hydrogen and a
hydrogenation catalyst, such as platinum, palladium, cobalt or
nickel, either as such or carried on a suitable support, such as
carbon, in methanol solvent, as described, for example, in U.S.
Pat. Nos. 2,045,574 and 3,779,923.
[0069] In general, the reaction results in mono-substitution of
each --NH.sub.2 group, although there may be a small amount of
di-substituted compounds present.
[0070] A lubricating composition may be prepared by adding the
N-alkylated dianiline compound and ashless antioxidant to an oil of
lubricating viscosity, optionally in the presence of other
performance additives (as described herein below), or by adding
reagents for forming the N-alkylated dianiline compound to an oil
of lubricating viscosity. The lubricating composition may further
include additional performance additives, such as antioxidants,
additional dispersants, antiwear agents, and friction modifiers. A
method for forming a lubricating composition includes forming an
N-alkylated dianiline compound and combining the N-alkylated
dianiline compound with an oil of lubricating viscosity and at
least one ashless antioxidant and/or overbased calcium detergent,
to provide a lubricating composition comprising less than 0.15
weight percent of phosphorus.
The Ashless Antioxidant
[0071] The lubricating composition may include one or more ashless
antioxidant(s) (AAO) selected from a diarylamine antioxidant, a
phenolic antioxidant, and a mixture thereof. The AAO may be present
in the lubricating composition at a concentration of at least 0.2
wt. %, such as at least 0.3 wt. %, or up to 5 wt. %, or up to 2.5
wt. %, or up to 2 wt. %, or up to 1 wt. %. A weight ratio of the
AAO to the N-alkylated dianiline compound may be at least 1:20 or
up to 20:1
[0072] Exemplary phenolic antioxidants useful herein include
alkylated diphenylamine antioxidants, such as C.sub.1-C.sub.24
monoalkylated, dialkylated and polyalkylated diphenylamines, as
described, for example, in U.S. Pat. Nos. 2,943,112; 4,824,601;
5,672,752; 6,204,412; 6,315,925; 6,355,839, and U.S. Pub. Nos.
2015/0307803 and 2016/0017252. Particularly useful are
monoalkylated and dialkylated diphenylamines in which the alkyl
group(s) include(s) at least 6 carbon atoms, such as at least 8, or
at least 9 carbon atoms.
[0073] Exemplary phenolic antioxidants that may be used include
C.sub.7-C.sub.9 branched alkyl esters of
3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-benzenepropanoic acid,
2-tert-butylphenol, 2-tert-butyl-4-methylphenol,
2-tert-butyl-5-methylphenol, 2,4-di-Cert-butylphenol,
2,4-dimethyl-6-tert-butylphenol, 2-tert-butyl-4-methoxyphenol,
3-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,
2,6-di-tert-butyl-4-alkylphenols such as 2,6-di-tert-butylphenol,
2,6-di-tert-butyl-4-methylphenol and
2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-alkoxyphenols
such as 2,6-di-tert-butyl-4-methoxyphenol and
2,6-di-tert-butyl-4-ethoxyphenol,
3,5-di-tert-butyl-4-hydroxybenzylmercaptooctylacetate,
alkyl-3-(3,5-di-tert-butyl-4-hyd roxyphenyl)propionates such as
n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,
n-butyl-3-(3,5-di-cert-butyl-4-hydroxyphenyl)propionate and
2'-ethylhexyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,
2,6-di-tert-butyl-.alpha.-dimethylamino-p-cresol,
2,2'-methylene-bis(4-alkyl-6-tert-butylphenol) such as
2,2'-methylenebis(4-methyl-6-cert-butylphenol, and
2,2-methylenebis(4-ethyl-6-tert-butylphenol), bisphenols such as
4,4'-butylidenebis(3-methyl-6-tert-butylphenol,
4,4'-methylenebis(2,6-di-tert-butylphenol),
4,4'-bis(2,6-di-tert-butylphenol), 2,2-(di-p-hydroxyphenyl)propane,
2,2-bis(3,5-di-cert-butyl-4-hydroxyphenyl)propane,
4,4'-cyclohexylidenebis(2,6-tert-butylphenol),
hexamethyleneglycol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],
triethyleneglycolbis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]-
,
2,2'-thio-[diethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],
3,9-bis{1,1-dimethyl-2-[3-(3-tert-butyl-4-hydroxy-5-methyl-phenyl)propion-
yloxy]ethyl}2,4,8,10-tetraoxaspiro[5,5]undecane,
4,4'-thiobis(3-methyl-6-tert-butylphenol) and
2,2'-thiobis(4,6-di-tert-butylresorcinol), polyphenols such as
tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methan-
e, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,
bis-[3,3'-bis(4'-hydroxy-3'-tert-butylphenyl)butyric acid]glycol
ester,
2-(3',5'-di-tert-butyl-4-hydroxyphenyl)methyl-4-(2'',4''-di-tert-butyl-3'-
'-hydroxyphenyl)methyl-6-tert-butylphenol and
2,6-bis(2'-hydroxy-3'-tert-butyl-5'-methylbenzyl)-4-methylphenol,
p-t-butylphenol-formaldehyde condensates and
p-t-butylphenol-acetaldehyde condensates.
[0074] Phenol-based antioxidants often contain a secondary butyl
and/or a tertiary butyl group as a steric hindering group. The
phenol group may be further substituted with a hydrocarbyl group
(e.g., a linear or branched alkyl) and/or a bridging group linking
to a second aromatic group.
[0075] Examples of particularly suitable hindered phenol
antioxidants include 2,6-di-tert-butylphenol,
4,4'-methylenebis-(2,6-di-tert-butylphenol),
4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol,
4-propyl-2,6-di-tert-butylphenol, 4-butyl-2,6-di-tert-butylphenol,
4-dodecyl-2,6-di-tert-butylphenol,
2,2'-methylenebis(4-methyl-6-tert-butylphenol),
2,2'-methylenebis(4-ethyl-6-tert-butylphenol), as described, for
example, in U.S. Pub. Nos. 2009/0111720, 2010/0269774, and
2012/0103290. In one embodiment, the hindered phenol antioxidant
may be an ester, such as those described in U.S. Pat. No.
6,559,105, such as an alkyl alcohol esters of
3-(4-hydroxy-3,5-di-tert-butyl-phenyl)propionic acid. One such
hindered phenol ester is sold as Irganox.TM. L-135, obtainable from
Ciba.
[0076] The phenolic antioxidant, where present in the lubricating
composition, may be at least 0.1 weight % of the lubricating
composition, or at least 0.5 wt. %, or at least 1.5 wt. %, or at
least 2.5 wt. %, and may be up to 5 wt. %, such as up to 4 wt. %,
or up to 3 wt. % of the lubricating composition.
[0077] Examples of alkylated diphenylamines useful herein include
those of the general formula:
##STR00009##
[0078] where each of R.sup.7, R.sup.8, R.sup.9 and R.sup.10, is
selected from H and C.sub.8-C.sub.24 or C.sub.8-C.sub.12 alkyl
groups, and wherein at least one of R.sup.7, R.sup.8, R.sup.9, and
R.sup.10 is not H. In one embodiment, R.sup.8 and R.sup.10 (and
optionally also R.sup.9) are not H. Para-substitution by the alkyl
group is common.
[0079] Example alkylated diphenylamines include dinonyl
diphenylamine, nonyl diphenylamine, octyl diphenylamine, dioctyl
diphenylamine, dodecyl diphenylamine, decyl diphenylamine, and
mixtures thereof.
[0080] Methods for producing monoalkylated diphenylamines are
described in U.S. Pat. No. 5,672,752. Methods for selectively
producing p,p'-di-alkylated diphenylamines are described in U.S.
Pub. No. 2016/0017252.
[0081] Other exemplary diarylamine antioxidants include alkylated
phenylnaphthylamines of the general form:
##STR00010##
[0082] where each of R.sup.7, R.sup.8 are as defined above and at
least one of R.sup.7 and R.sup.8 is not H.
[0083] Example alkylated phenylnaphthylamines include octyl,
dioctyl, nonyl, dinonyl, decyl and dodecyl phenylnaphthylamines,
such as N-(Dodecylphenyl)naphthalen-1-amine:
##STR00011##
[0084] In one embodiment, a ratio of the diarylamine to the N-alkyl
dianiline compound is from 20:1 to 1:20.
[0085] The alkylated diarylamine, where present in the lubricating
composition, may be at least 0.1 weight % of the lubricating
composition, or at least 0.2 wt. %, or at least 0.4 wt. %, or at
least 0.5 wt. %, or at least 1.0 wt. %, or at least 2.5 wt. %, and
may be up to 5 wt. %, such as up to 2.5 wt. %, or up to 1.5 wt. %
of the lubricating composition.
[0086] Mixtures of phenolic and/or alkylated diarylamine
antioxidants may be employed. When both an alkylated diarylamine
and phenolic antioxidant are used, the combined amount of ashless
antioxidant may be at least 0.1 weight % of the lubricating
composition, or at least 0.8 wt. %, or at least 1.5 wt. %, or at
least 3 wt. %, and may be up to 5 wt. %, such as up to 4 wt. %, or
up to 3.5 wt. % of the lubricating composition.
Overbased Calcium Detergent
[0087] In one embodiment, the lubricating composition includes one
or more overbased calcium detergents. In one embodiment, the
lubricating composition includes an alkaline earth metal overbased
detergent in an amount sufficient to deliver at least 2 mg KOH/g of
total base number (TBN), as measured in accordance with ASTM
D-2896-15, to the lubricating composition.
[0088] The overbased calcium detergent may be chosen from
sulfonates, non-sulfur containing phenates, sulfur containing
phenates, salixarates, salicylates, and mixtures thereof, or
borated equivalents thereof. The overbased detergent may be borated
with a borating agent such as boric acid.
[0089] The overbased calcium-containing detergent may also include
"hybrid" detergents formed with mixed surfactant systems including
phenate and/or sulfonate components, e.g., phenate/salicylates,
sulfonate/phenates, sulfonate/salicylates,
sulfonates/phenates/salicylates, as described, for example, in U.S.
Pat. Nos. 6,429,178; 6,429,179; 6,153,565; and 6,281,179. Where a
hybrid sulfonate/phenate detergent is employed, the hybrid
detergent can be considered equivalent to amounts of distinct
phenate and sulfonate detergents introducing like amounts of
phenate and sulfonate soaps, respectively.
[0090] Example overbased calcium-containing detergents include
calcium salts of sulfonates, phenates (including sulfur-containing
and non-sulfur containing phenates), salixarates and salicylates.
Such overbased sulfonates, salixarates, phenates and salicylates
may have a total base number of 120 to 700, or 250 to 600, or 300
to 500 (on an oil free basis).
[0091] Overbased calcium sulfonates, salixarates, phenates and
salicylates typically have a total base number of 120 to 700 TBN.
Overbased sulfonates typically have a total base number of 120 to
700, or 250 to 600, or 300 to 500 (on an oil free basis).
[0092] By "overbased," it is meant that the calcium is in excess of
stoichiometric amounts with respect to the soap counterion (e.g.,
sulfonate). The overbased calcium detergent may have a metal:
counterion ratio of at least 3:1, or at least 4:1, or at least
6:1.
[0093] Example sulfonate detergents include linear and branched
alkylbenzene sulfonate detergents, and mixtures thereof, which may
have a metal ratio of at least 8, as described, for example, in
U.S. Pub. No. 2005065045. Linear alkyl benzenes may have the
benzene ring attached anywhere on the linear chain, usually at the
2, 3, or 4 position, or be mixtures thereof. Linear alkylbenzene
sulfonate detergents may be particularly useful for assisting in
improving fuel economy.
[0094] In one embodiment, the alkylbenzene sulfonate detergent may
be a branched alkylbenzene sulfonate, a linear alkylbenzene
sulfonate, or mixtures thereof.
[0095] In one embodiment, the lubricating composition may be free
of linear alkylbenzene sulfonate detergent. The sulfonate detergent
may be a calcium salt of one or more oil-soluble alkyl toluene
sulfonate compounds as disclosed in U.S. Pub. No. 20080119378.
[0096] The lubricating composition may include at least 0.01 wt. %
or at least 0.1 wt. %, or at least 0.5 wt. %, of overbased calcium
detergent, and in some embodiments, up to 3 wt. %, or up to 2 wt. %
overbased calcium detergent(s).
Oil of Lubricating Viscosity
[0097] The lubricating composition may include the oil of
lubricating viscosity as a minor or major component thereof, such
as at least 5 wt. %, or at least 10 wt. %, or at least 20 wt. %, or
at least 30 wt. %, or at least 40 wt. %, or at least 60 wt. %, or
at least 80 wt. %, or up to 98 wt. %, or up to 95 wt. %, of the
lubricating composition.
[0098] The amount of the oil of lubricating viscosity present may
be typically the balance remaining after subtracting from 100 wt.
%, the sum of the amount of the compound and antioxidant, as
described above and any other performance additives.
[0099] Suitable oils include natural and synthetic oils, oil
derived from hydrocracking, hydrogenation, and hydrofinishing,
unrefined, refined, re-refined oils or mixtures thereof. Unrefined,
refined and re-refined oils, and natural and synthetic oils are
described, for example, in WO 2008/147704 and U.S. Pub. No.
2010/197536. Synthetic oils may also be produced by Fischer-Tropsch
reactions and typically may be hydroisomerized Fischer-Tropsch
hydrocarbons or waxes. Oils may be prepared by a Fischer-Tropsch
gas-to-liquid synthetic procedure as well as other gas-to-liquid
procedures.
[0100] Oils of lubricating viscosity may also be defined as
specified in April 2008 version of "Appendix E--API Base Oil
Interchangeability Guidelines for Passenger Car Motor Oils and
Diesel Engine Oils", section 1.3 Sub-heading 1.3. "Base Stock
Categories". The API Guidelines are also summarized in U.S. Pat.
No. 7,285,516. The five base oil groups are as follows: Group I
(sulfur content >0.03 wt. %, and/or <90 wt. % saturates,
viscosity index 80-120); Group II (sulfur content <0.03 wt. %,
and >90 wt. % saturates, viscosity index 80-120); Group III
(sulfur content <0.03 wt. %, and >90 wt. % saturates,
viscosity index >120); Group IV (all polyalphaolefins (PAOs));
and Group V (all others not included in Groups I, II, III, or IV).
The exemplary oil of lubricating viscosity includes an API Group I,
Group II, Group III, Group IV, Group V oil, or mixtures thereof. In
some embodiments, the oil of lubricating viscosity is an API Group
I, Group II, Group III, or Group IV oil, or mixtures thereof. In
some embodiments, the oil of lubricating viscosity is an API Group
I, Group II, or Group III oil, or mixture thereof. In one
embodiment the oil of lubricating viscosity may be an API Group II,
Group III mineral oil, a Group IV synthetic oil, or mixture
thereof. In some embodiments, at least 5 wt. %, or at least 10 wt.
%, or at least 20 wt. %, or at least 40 wt. % of the lubricating
composition is a polyalphaolefin (Group IV).
[0101] The lubricating composition disclosed herein may have a SAE
viscosity grade of XW-Y, wherein X may be 0, 5, 10 or 15; and Y may
be 16, 20, 30 or 40.
[0102] The oil of lubricating viscosity may have a kinematic
viscosity of up to 12 mm.sup.2/s or up to 8 mm.sup.2/s (cSt) at
100.degree. C. and can be at least 12 mm.sup.2/s at 100.degree. C.,
and in other embodiments at least 3.5 mm.sup.2/s. As used herein,
kinematic viscosity is determined at 100.degree. C. by ASTM
D445-14, "Standard Test Method for Kinematic Viscosity of
Transparent and Opaque Liquids (and Calculation of Dynamic
Viscosity)," ASTM International, West Conshohocken, Pa., 2003, DOI:
10.1520/D0445-14 and may be referred to as KV_100.
[0103] The viscosity grade of the oil depends on the end use. For
passenger car and diesel engines, the viscosity grade may be
SAE-5W-30, SAE 10W-30 or SAE 15W-40. The base oil may be a blend of
two or more fractions having different oligomer distributions. A
fraction rich in lower oligomers is typically blended with a
fraction rich in higher oligomers to achieve the desired oligomer
distribution. However, any combination of fractions which will
yield a composite having the required distribution of oligomers is
acceptable. The fractions employed for such blending may be
different distillation cuts from the same process or may be
obtained from entirely different oligomerization processes. A
single fraction may be used to produce different multigrade oils,
e.g. SAE 10W-30 and SAE 15W-40 oils. The composite obtained after
blending can be hydrogenated or the individual fractions can be
hydrogenated before they are blended.
[0104] For 2-stroke marine diesel engines the viscosity grade may
be from SAE-40 to SAE-60, which corresponds to a KV_100 of 12.5 to
26 mm.sup.2/s. SAE-50 grade oils, for example, have a KV_100 of
16.3-21.9 mm.sup.2/s. Cylinder oils for 2-stroke marine diesel
engines may be formulated to achieve a KV_100 of 19 to 21.5
mm.sup.2/s. This viscosity can be obtained by a mixture of
additives and base oils, for example containing mineral bases of
Group I such as Neutral Solvent (for example 500 NS or 600 NS) and
Bright Stock bases. Any other combination of mineral or synthetic
bases or bases of vegetable origin having, in mixture with the
additives, a viscosity compatible with the grade SAE 50 can be
used.
[0105] As an example, an oil formulation suited to use as a
cylinder lubricant for low-speed 2-stroke marine diesel engines
contains 18 to 25 wt. % of a Group I base oil of a BSS type
(distillation residue, with a KV_100 of 28-32 mm.sup.2/s, with a
density at 15.degree. C. of 895-915 kg/m.sup.3), and 50 to 60 wt. %
of a Group I base oil of a SN 600 type (distillate, with a density
at 15.degree. C. of 880-900 kg/m.sup.3, with a KV_100 of about 12
mm.sup.2/s).
[0106] In certain embodiments, the lubricating composition may
contain synthetic ester base fluids. Synthetic esters may have a
kinematic viscosity measured at 100.degree. C. of 2.5 mm.sup.2/s to
30 mm.sup.2/s. In one embodiment, the lubricating composition
comprises less than 50 wt. % of a synthetic ester base fluid with a
KV_100 of at least 5.5 mm.sup.2/s, or at least 6 mm.sup.2/s, or at
least 8 mm.sup.2/s.
[0107] Exemplary synthetic oils include poly-alpha olefins,
polyesters, poly-acrylates, and poly-methacrylates, and co-polymers
thereof. Example synthetic esters include esters of a dicarboxylic
acid (e.g., selected from phthalic acid, succinic acid, alkyl
succinic acids, alkenyl succinic acids, maleic acid, azelaic acid,
suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic
acid dimer, malonic acid, alkyl malonic acids, and alkenyl malonic
acids) with an alcohol (e.g., selected from butyl alcohol, hexyl
alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol,
diethylene glycol monoether, and propylene glycol). Specific
examples of these esters include dibutyl adipate, di(2-ethylhexyl)
sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl
azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate,
dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid
dimer, and the complex ester formed by reacting one mole of sebacic
acid with two moles of tetraethylene glycol and two moles of
2-ethylhexanoic acid.
[0108] Esters useful as synthetic oils also include those made from
C.sub.5 to C.sub.12 monocarboxylic acids and polyols and from
polyol ethers such as neopentyl glycol, trimethylolpropane,
pentaerythritol, dipentaerythritol, and tripentaerythritol. Esters
can also be monoesters, such as are available under the trade name
Priolube 1976.TM. (C.sub.18-alkyl-COO--C.sub.20 alkyl).
[0109] Synthetic ester base oils may be present in the lubricating
composition in an amount less than 50 wt. % of the composition, or
less than 40 weight %, or less than 35 weight %, or less than 28
weight %, or less than 21 weight %, or less than 17 weight %, or
less than 10 weight %, or less than 5 weight % of the composition.
In one embodiment, the lubricating composition is free of, or
substantially free of, a synthetic ester base fluid having a KV_100
of at least 5.5 mm.sup.2/s.
[0110] Example natural oils include animal and vegetable oils, such
as long chain fatty acid esters. Examples include linseed oil,
sunflower oil, sesame seed oil, beef tallow oil, lard oil, palm
oil, castor oil, cottonseed oil, corn oil, peanut oil, soybean oil,
olive oil, whale oil, menhaden oil, sardine oil, coconut oil, palm
kernel oil, babassu oil, rape oil, and soya oil.
[0111] The amount of the oil of lubricating viscosity present is
typically the balance remaining after subtracting from 100 weight %
the sum of the amount of the exemplary N-alkylated
methylenedianiline compound and the other performance
additives.
Other Performance Additives
[0112] In addition to the exemplary N-alkylated dianiline
compound(s) disclosed herein, the lubricating composition may
further include one or more of the following additional performance
additives: antioxidants (different from above), dispersants,
viscosity modifiers, antiwear/antiscuffing agents, metal
deactivators, friction modifiers, extreme pressure agents, foam
inhibitors, demulsifiers, pour point depressants, corrosion
inhibitors, seal swelling agents, TBN boosters, and the like. The
additional performance additive(s) may be suited to providing the
performance properties of a fully formulated lubricating
composition, e.g., a passenger car or HD engine lubricant.
[0113] A. Detergents
[0114] The lubricating composition optionally further includes at
least one detergent, in addition to the overbased calcium detergent
discussed above. Exemplary detergents useful herein include
overbased metal-containing detergents, where the metal is other
than calcium.
[0115] The metal of the metal-containing detergent may be zinc,
sodium, barium, or magnesium. In one embodiment, the lubricating
composition includes an alkaline earth metal overbased detergent in
an amount sufficient to deliver at least 2 mg KOH/g of total base
number (TBN), as measured in accordance with ASTM D-2896-15, to the
lubricating composition.
[0116] The overbased metal-containing detergent may be chosen from
sulfonates, non-sulfur containing phenates, sulfur containing
phenates, salixarates, salicylates, and mixtures thereof, or
borated equivalents thereof. The overbased detergent may be borated
with a borating agent such as boric acid.
[0117] The overbased metal-containing detergent may also include
"hybrid" detergents formed with mixed surfactant systems including
phenate and/or sulfonate components, e.g., phenate/salicylates,
sulfonate/phenates, sulfonate/salicylates,
sulfonates/phenates/salicylates, as described, for example, in U.S.
Pat. Nos. 6,429,178; 6,429,179; 6,153,565; and 6,281,179. Where a
hybrid sulfonate/phenate detergent is employed, the hybrid
detergent can be considered equivalent to amounts of distinct
phenate and sulfonate detergents introducing like amounts of
phenate and sulfonate soaps, respectively.
[0118] Example overbased metal-containing detergents include zinc,
sodium, and magnesium salts of sulfonates, phenates (including
sulfur-containing and non-sulfur containing phenates), salixarates
and salicylates. Such overbased sulfonates, salixarates, phenates
and salicylates may have a total base number of 120 to 700, or 250
to 600, or 300 to 500 (on an oil free basis).
[0119] Typically, an overbased metal-containing detergent may be a
zinc, sodium, or magnesium salt of a sulfonate, a phenate,
sulfur-containing phenate, salixarate or salicylate. Overbased
sulfonates, salixarates, phenates and salicylates typically have a
total base number of 120 to 700 TBN. Overbased sulfonates typically
have a total base number of 120 to 700, or 250 to 600, or 300 to
500 (on an oil free basis).
[0120] The overbased metal-containing detergent may be alkali metal
or alkaline earth metal salts. In one embodiment, the overbased
detergent may be sodium salts, calcium salts, magnesium salts, or
mixtures thereof of the phenates, sulfur-containing phenates,
sulfonates, salixarates and salicylates. In one embodiment, the
overbased detergent is a calcium detergent, a magnesium detergent
or mixtures thereof. In one embodiment, the overbased calcium
detergent may be present in an amount to deliver at least 500 ppm
calcium by weight and no more than 3000 ppm calcium by weight, or
at least 1000 ppm calcium by weight, or at least 2000 ppm calcium
by weight, or no more than 2500 ppm calcium by weight to the
lubricating composition. In one embodiment, the overbased detergent
may be present in an amount to deliver no more than 500 ppm by
weight of magnesium to the lubricating composition, or no more than
330 ppm by weight, or no more than 125 ppm by weight, or no more
than 45 ppm by weight. In one embodiment, the lubricating
composition is essentially free of (i.e., contains less than 10
ppm) magnesium resulting from the overbased detergent. In one
embodiment, the overbased detergent may be present in an amount to
deliver at least 200 ppm by weight of magnesium, or at least 450
ppm by weight magnesium, or at least 700 ppm by weight magnesium to
the lubricating composition. In one embodiment, both calcium and
magnesium containing detergents may be present in the lubricating
composition. Calcium and magnesium detergents may be present such
that the weight ratio of calcium to magnesium is 10:1 to 1:10, or
8:3 to 4:5, or 1:1 to 1:3. In one embodiment, the overbased
detergent is free of or substantially free of sodium.
[0121] The overbased sulfonate detergent may have a metal ratio of
12 to less than 20, or 12 to 18, or 20 to 30, or 22 to 25.
[0122] Example sulfonate detergents include linear and branched
alkylbenzene sulfonate detergents, and mixtures thereof, which may
have a metal ratio of at least 8, as described, for example, in
U.S. Pub. No. 2005065045. Linear alkyl benzenes may have the
benzene ring attached anywhere on the linear chain, usually at the
2, 3, or 4 position, or be mixtures thereof. Linear alkylbenzene
sulfonate detergents may be particularly useful for assisting in
improving fuel economy.
[0123] In one embodiment, the alkylbenzene sulfonate detergent may
be a branched alkylbenzene sulfonate, a linear alkylbenzene
sulfonate, or mixtures thereof.
[0124] In one embodiment, the lubricating composition may be free
of linear alkylbenzene sulfonate detergent. The sulfonate detergent
may be a metal salt of one or more oil-soluble alkyl toluene
sulfonate compounds as disclosed in U.S. Pub. No. 20080119378.
[0125] The lubricating composition may include at least 0.01 wt. %
or at least 0.1 wt. %, detergent, and in some embodiments, up to 2
wt. %, or up to 1 wt. % detergent.
[0126] B. Antioxidants
[0127] The lubricating composition optionally further includes at
least one antioxidant, in addition to the AAOs listed above.
Exemplary antioxidants useful herein include sulfurized olefins.
Examples of suitable olefins that may be sulfurized to form the
sulfurized olefin include propylene, butylene, isobutylene,
pentene, hexene, heptene, octene, nonene, decene, undecene,
dodecene, undecene, tridecene, tetradecene, pentadecene,
hexadecene, heptadecene, octadecene, nonadecene, eicosene, and
mixtures thereof. In one embodiment, hexadecene, heptadecene,
octadecene, nonadecene, eicosene, or mixtures thereof and their
dimers, trimers and tetramers are especially useful olefins.
[0128] Alternatively, the olefin may be a Diels-Alder adduct of a
diene such as 1,3-butadiene and an unsaturated ester, such as,
butyl acrylate. Another class of sulfurized olefin includes fatty
acids and their esters. The fatty acids are often obtained from
vegetable oil or animal oil; and typically contain 4 to 22 carbon
atoms. Examples of suitable fatty acids and their esters include
triglycerides, oleic acid, linoleic acid, palmitoleic acid, and
mixtures thereof. The fatty acids may be obtained from lard oil,
tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed
oil or mixtures thereof. In one embodiment fatty acids and/or ester
are mixed with olefins. When present, the lubricating composition
may include at least 0.1 wt. % or at least 0.5 wt. %, or at least 1
wt. % antioxidant, and in some embodiments, up to 3 wt. %, or up to
2.75 wt. %, or up to 2.5 wt. %, or up to 1.2 wt. % of such
additional antioxidants.
[0129] C. Dispersants
[0130] The lubricating composition optionally further includes at
least one dispersant other than the exemplary compound. Exemplary
dispersants include succinimide dispersants, Mannich dispersants,
succinamide dispersants, and polyolefin succinic acid esters,
amides, and ester-amides, and mixtures thereof.
[0131] The succinimide dispersant may be derived from an aliphatic
polyamine, or mixtures thereof. The aliphatic polyamine may be an
ethylenepolyamine, a propylenepolyamine, a butylenepolyamine, or a
mixture thereof. In one embodiment the aliphatic polyamine may be
an ethylenepolyamine. In one embodiment the aliphatic polyamine may
be chosen from ethylenediamine, diethylenetriamine,
triethylenetetramine, tetraethylenepentamine,
pentaethylenehexamine, polyamine still bottoms, and mixtures
thereof.
[0132] In one embodiment, the dispersant may be a polyolefin
succinic acid ester, amide, or ester-amide. A polyolefin succinic
acid ester-amide may be a polyisobutylene succinic acid reacted
with an alcohol (such as pentaerythritol) and a polyamine as
described above. Example polyolefin succinic acid esters include
polyisobutylene succinic acid esters of pentaerythritol and mixture
thereof.
[0133] The dispersant may be an N-substituted long chain alkenyl
succinimide. An example of an N-substituted long chain alkenyl
succinimide is polyisobutylene succinimide. Typically the
polyisobutylene from which polyisobutylene succinic anhydride is
derived has a number average molecular weight of at least 300, or
at least 350, or at least 500, or at least 550, or at least 750,
and can be up to 5000, or up to 3000, or up to 2500. Such
succinimides can be formed, for example, from high vinylidene
polyisobutylene and maleic anhydride. Succinimide dispersants and
their preparation are disclosed, for example, in U.S. Pat. Nos.
3,172,892, 3,219,666, 3,316,177, 3,340,281, 3,351,552, 3,381,022,
3,433,744, 3,444,170, 3,467,668, 3,501,405, 3,542,680, 3,576,743,
3,632,511, 4,234,435, Re 26,433, and 6,165,235, and 7,238,650 and
EP Patent Application 0 355 895 A.
[0134] The exemplary dispersants may also be post-treated by
conventional methods by a reaction with any of a variety of agents.
Among these are boron compounds (such as boric acid), urea,
thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes,
ketones, carboxylic acids, such as terephthalic acid,
hydrocarbon-substituted succinic anhydrides, maleic anhydride,
nitriles, epoxides, and phosphorus compounds. In one embodiment the
post-treated dispersant is borated. In one embodiment the
post-treated dispersant is reacted with dimercaptothiadiazoles. In
one embodiment the post-treated dispersant is reacted with
phosphoric or phosphorous acid. In one embodiment the post-treated
dispersant is reacted with terephthalic acid and boric acid (as
described in U.S. Pub. No. 2009/0054278.
[0135] Dispersant viscosity modifiers (DVMs) are dispersants which
provide both dispersancy and viscosity modification. Example DVMs
are made from polymers such as an olefin polymer (e.g., ethylene
propylene copolymer) and/or vinyl aromatic polymers (e.g.,
polystyrene) that have been radically grafted with an ethylenically
unsaturated carboxylic acid material, such as maleic anhydride
which is functionalized with one or more amines and/or a pendent
functional group which has sulfonate functionality. DVMs of this
type are disclosed, for example, in U.S. Pat. Nos. 4,863,623;
5,264,140; 5,409,623; 6,107,257; 6,107,258; 6,117,825; U.S. Pub.
Nos. 2012/0178656; 2012/0178659; 2009/0305923, and WO
2016044262.
[0136] When present, the lubricating composition may include at
least 0.01 wt. %, or at least 0.1 wt. %, or at least 0.5 wt. %, or
at least 1 wt. % dispersant, and in some embodiments, up to 20 wt.
%, or up to 15 wt. %, or up to 10 wt. %, or up to 6 wt. % or up to
3 wt. % dispersant.
[0137] D. Anti-Wear Agents
[0138] The lubricating composition optionally further includes at
least one antiwear agent. Examples of suitable antiwear agents
suitable for use herein include titanium compounds, tartrates,
tartrimides, oil soluble amine salts of phosphorus compounds,
sulfurized olefins, metal dihydrocarbyldithiophosphates (such as
zinc dialkyldithiophosphates (ZDDPs)), phosphites (such as dibutyl
phosphite), phosphonates, thiocarbamate-containing compounds, such
as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers,
alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl)
disulfides. The antiwear agent may in one embodiment include a
tartrate or tartrimide, as described in U.S. Pub. Nos.
2006/0079413; 2006/0183647; and 2010/0081592. The tartrate or
tartrimide may contain alkyl-ester groups, where the sum of carbon
atoms on the alkyl groups is at least 8. The antiwear agent may, in
one embodiment, include a citrate as disclosed in U.S. Pub. No.
20050198894.
[0139] When present, the lubricating composition may include at
least 0.01 wt. %, or at least 0.1 wt. %, or at least 0.5 wt. %
antiwear agent, and in some embodiments, up to 3 wt. %, or up to
1.5 wt. %, or up to 0.9 wt. antiwear agent.
[0140] In one embodiment, the lubricating composition is free or
substantially free of phosphorus-containing antiwear agents. For
example phosphorus-containing antiwear agents are present, if at
all, in an amount which enables the lubricating composition to have
no more than 0.15 wt. % phosphorus, or up to 1.1 wt. % phosphorus,
or up to 0.8 wt. % phosphorus. For example, C3/6 mixed secondary
ZDDP's may be present at up to 1.2 wt. %, or up to 1 wt. %, or up
to 0.5 wt. %.
[0141] E. Oil Soluble Titanium Compounds
[0142] The lubricating composition may include one or more
oil-soluble titanium compounds, which may function as antiwear
agents, friction modifiers, antioxidants, deposit control
additives, or more than one of these functions. Example oil-soluble
titanium compounds are disclosed in U.S. Pat. No. 7,727,943 and
U.S. Pub. No. 2006/0014651. Example oil soluble titanium compounds
include titanium (IV) alkoxides, such as titanium (IV) isopropoxide
and titanium (IV) 2-ethylhexoxide. Such alkoxides may be formed
from a monohydric alcohol, a vicinal 1,2-diol, a polyol, or mixture
thereof. The monohydric alkoxides may have 2 to 16, or 3 to 10
carbon atoms. In one embodiment, the titanium compound comprises
the alkoxide of a vicinal 1,2-diol or polyol. 1,2-vicinal diols
include fatty acid mono-esters of glycerol, where the fatty acid
may be, for example, oleic acid. Other example oil soluble titanium
compounds include titanium carboxylates, such as titanium
neodecanoate.
[0143] When present in the lubricating composition, the amount of
oil-soluble titanium compounds is included as part of the antiwear
agent.
[0144] F. Extreme Pressure (EP) Agents
[0145] The lubricating composition may include an extreme pressure
agent. Example extreme pressure agents that are soluble in the oil
include sulfur- and chlorosulfur-containing EP agents,
dimercaptothiadiazole or CS.sub.2 derivatives of dispersants
(typically succinimide dispersants), derivative of chlorinated
hydrocarbon EP agents and phosphorus EP agents. Examples of such EP
agents include chlorinated wax; sulfurized olefins (such as
sulfurized isobutylene), hydrocarbyl-substituted
2,5-dimercapto-1,3,4-thiadiazoles and oligomers thereof, organic
sulfides and polysulfides, such as dibenzyl disulfide,
bis-(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized
methyl ester of oleic acid, sulfurized alkylphenol, sulfurized
dipentene, sulfurized terpene, and sulfurized Diels-Alder adducts;
phosphosulfurized hydrocarbons such as the reaction product of
phosphorus sulfide with turpentine or methyl oleate; phosphorus
esters, such as di-hydrocarbon and tri-hydrocarbon phosphites,
e.g., dibutyl phosphite, diheptyl phosphite, dicyclohexyl
phosphite, pentylphenyl phosphite; dipentylphenyl phosphite,
tridecyl phosphite, distearyl phosphite and polypropylene
substituted phenol phosphite; metal thiocarbamates, such as zinc
dioctyldithiocarbamate and barium heptylphenol diacid; amine salts
of alkyl and dialkylphosphoric acids or derivatives including, for
example, the amine salt of a reaction product of a
dialkyldithiophosphoric acid with propylene oxide and subsequently
followed by a further reaction with P.sub.2O.sub.5; and mixtures
thereof. Some useful extreme pressure agents are described in U.S.
Pat. No. 3,197,405.
[0146] When present, the lubricating composition may include at
least 0.01 wt. %, or at least 0.1 wt. %, or at least 0.5 wt. %
extreme pressure agent, and in some embodiments, up to 3 wt. %, or
up to 1.5 wt. %, or up to 0.9 wt. % of the extreme pressure
agent.
[0147] G. Foam Inhibitors
[0148] The lubricating composition may include a foam inhibitor.
Foam inhibitors that may be useful in the lubricant composition
include polysiloxanes; copolymers of ethyl acrylate and
2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers
including fluorinated polysiloxanes, trialkyl phosphates,
polyethylene glycols, polyethylene oxides, polypropylene oxides and
(ethylene oxide-propylene oxide) polymers.
[0149] H. Viscosity Modifiers
[0150] The lubricating composition may include a viscosity
modifier. Viscosity modifiers (also sometimes referred to as
viscosity index improvers or viscosity improvers) useful in the
lubricant composition are usually polymers, including
polyisobutenes, polymethacrylates (PMA) and polymethacrylic acid
esters, diene polymers, polyalkylstyrenes, esterified
styrene-maleic anhydride copolymers, hydrogenated
alkenylarene-conjugated diene copolymers and polyolefins also
referred to as olefin copolymer or OCP. PMAs are prepared from
mixtures of methacrylate monomers having different alkyl groups.
The alkyl groups may be either straight chain or branched chain
groups containing from 1 to 18 carbon atoms. Most PMAs are
viscosity modifiers as well as pour point depressants. In one
embodiment, the viscosity modifier is a polyolefin comprising
ethylene and one or more higher olefin, such as propylene.
[0151] When present, the lubricating composition may include at
least 0.01 wt. %, or at least 0.1 wt. %, or at least 0.3 wt. %, or
at least 0.5 wt. % polymeric viscosity modifiers, and in some
embodiments, up to 10 wt. %, or up to 5 wt. %, or up to 2.5 wt. %
polymeric viscosity modifiers.
[0152] I. Corrosion Inhibitors and Metal Deactivators
[0153] The lubricating composition may include a corrosion
inhibitor. Corrosion inhibitors/metal deactivators that may be
useful in the exemplary lubricating composition include fatty
amines, octylamine octanoate, condensation products of dodecenyl
succinic acid or anhydride, and a fatty acid such as oleic acid
with a polyamine, derivatives of benzotriazoles (e.g.,
tolyltriazole), 1,2,4-triazoles, benzimidazoles,
2-alkyldithiobenzimidazoles and 2-alkyldithiobenzothiazoles.
[0154] J. Pour Point Depressants
[0155] The lubricating composition may include a pour point
depressant. Pour point depressants that may be useful in the
exemplary lubricating composition include polyalphaolefins, esters
of maleic anhydride-styrene copolymers, polymethacrylates,
polyacrylates, and polyacrylamides.
[0156] K. Friction Modifiers
[0157] The lubricating composition may include a friction modifier.
Friction modifiers that may be useful in the exemplary lubricating
composition include fatty acid derivatives such as amines, esters,
epoxides, fatty imidazolines, condensation products of carboxylic
acids and polyalkylene-polyamines and amine salts of
alkylphosphoric acids. The friction modifier may be an ash-free
friction modifier. Such friction modifiers are those which
typically not produce any sulfated ash when subjected to the
conditions of ASTM D 874 (see ASTM D874-13a, "Standard Test Method
for Sulfated Ash from Lubricating Oils and Additives," ASTM
International, West Conshohocken, Pa., 2013). An additive is
referred to as "non-metal containing" if it does not contribute
metal content to the lubricant composition. As used herein the term
"fatty alkyl" or "fatty" in relation to friction modifiers means a
carbon chain having 8 to 30 carbon atoms, typically a straight
carbon chain.
[0158] The amount of the ash-free friction modifier in a lubricant
may be 0.1 to 3 wt. % (or 0.12 to 1.2 or 0.15 to 0.8 wt. %). The
material may also be present in a concentrate, alone or with other
additives and with a lesser amount of oil. In a concentrate, the
amount of material may be two to ten times the above concentration
amounts.
[0159] In one embodiment, the ash-free friction modifier may be
represented by the formula:
##STR00012##
where D and D' are independently selected from --O--, >NH,
>NR.sup.23, an imide group formed by taking together both D and
D'' groups and forming a R.sup.21--N< group between two
>C.dbd.O groups; E is selected from >CH.sub.2,
>CHR.sup.26, >CR.sup.26R.sup.27, >C(OH)(CO.sub.2R.sup.22),
>C(CO.sub.2R.sup.22).sub.2, and >CHOR.sup.28; where R.sup.24
and R.sup.25 are independently selected from >CH.sub.2,
>CHR.sup.26, >CR.sup.26R.sup.27, >C(OH)(CO.sub.2R.sup.22),
and >CHOR.sup.28; q is 0 to 10, with the proviso that when q=1,
E is not >CH.sub.2, and when n=2, both Es are not >CH.sub.2;
p is 0 or 1; R.sup.21 is independently hydrogen or a hydrocarbyl
group, typically containing 1 to 150 carbon atoms, with the proviso
that when R.sup.21 is hydrogen, p is 0, and q is more than or equal
to 1; R.sup.22 is a hydrocarbyl group, typically containing 1 to
150 carbon atoms; R.sup.23, R.sup.24, R.sup.25, R.sup.26 and
R.sup.27 are independently hydrocarbyl groups; and R.sup.28 is
hydrogen or a hydrocarbyl group, containing 1 to 150 carbon atoms,
or 4 to 32 carbon atoms, or 8 to 24 carbon atoms. In certain
embodiments, the hydrocarbyl groups R.sup.23, R.sup.24, and
R.sup.25, may be linear or predominantly linear alkyl groups.
[0160] In certain embodiments, the ash-free friction modifier is a
fatty ester, amide, or imide of various hydroxy-carboxylic acids,
such as tartaric acid, malic acid lactic acid, glycolic acid, and
mandelic acid. Examples of suitable materials include tartaric acid
di(2-ethylhexyl) ester (i.e., di(2-ethylhexyl)tartrate),
di(C.sub.8-C.sub.10) tartrate, di(C.sub.12-15) tartrate, di-oleyl
tartrate, oleyl tartrimide, and oleyl maleimide.
[0161] In certain embodiments, the ash-free friction modifier may
be chosen from long chain fatty acid derivatives of amines, fatty
esters, or fatty epoxides; fatty imidazolines such as condensation
products of carboxylic acids and polyalkylene-polyamines; amine
salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl
tartrimides; fatty alkyl tartramides; fatty phosphonates; fatty
phosphites; borated phospholipids, borated fatty epoxides; glycerol
esters; borated glycerol esters; fatty amines; alkoxylated fatty
amines; borated alkoxylated fatty amines; hydroxyl and polyhydroxy
fatty amines including tertiary hydroxy fatty amines; hydroxy alkyl
amides; metal salts of fatty acids; metal salts of alkyl
salicylates; fatty oxazolines; fatty ethoxylated alcohols;
condensation products of carboxylic acids and polyalkylene
polyamines; or reaction products from fatty carboxylic acids with
guanidine, aminoguanidine, urea, or thiourea and salts thereof.
[0162] Friction modifiers may also encompass materials such as
sulfurized fatty compounds and olefins, sunflower oil or soybean
oil monoester of a polyol and an aliphatic carboxylic acid.
[0163] In another embodiment the friction modifier may be a long
chain fatty acid ester. In another embodiment the long chain fatty
acid ester may be a mono-ester and in another embodiment the long
chain fatty acid ester may be a triglyceride.
[0164] Molybdenum compounds are also known as friction modifiers.
The exemplary molybdenum compound does not contain dithiocarbamate
moieties or ligands.
[0165] Nitrogen-containing molybdenum materials include
molybdenum-amine compounds, as described in U.S. Pat. No.
6,329,327, and organomolybdenum compounds made from the reaction of
a molybdenum source, fatty oil, and a diamine as described in U.S.
Pat. No. 6,914,037. Other molybdenum compounds are disclosed in
U.S. Pub. No. 20080280795. Molybdenum amine compounds may be
obtained by reacting a compound containing a hexavalent molybdenum
atom with a primary, secondary or tertiary amine represented by the
formula NR.sup.29R.sup.30R.sup.31, where each of R.sup.29, R.sup.30
and R.sup.31 is independently hydrogen or a hydrocarbyl group of 1
to 32 carbon atoms and wherein at least one of R.sup.29, R.sup.30
and R.sup.31 is a hydrocarbyl group of 4 or more carbon atoms or
represented by the formula:
##STR00013##
[0166] where R.sup.32 represents a chain hydrocarbyl group having
10 or more carbon atoms, s is 0 or 1, R.sup.33 and/or R.sup.34
represents a hydrogen atom, a hydrocarbyl group, an alkanol group
or an alkyl amino group having 2 to 4 carbon atoms, and when s=0,
both R.sup.33 and R.sup.34 are not hydrogen atoms or hydrocarbon
groups.
[0167] Specific examples of suitable amines include monoalkyl (or
alkenyl) amines such as tetradecylamine, stearylamine, oleylamine,
beef tallow alkylamine, hardened beef tallow alkylamine, and
soybean oil alkylamine; dialkyl(or alkenyl)amines such as
N-tetradecylmethylamine, N-pentadecylmethylamine,
N-hexadecylmethylamine, N-stearylmethylamine, N-oleylmethylamine,
N-cocoyl methylamine, N-beef tallow alkyl methylamine, N-hardened
beef tallow alkyl methylamine, N-soybean oil alkyl methylamine,
ditetradecylamine, dipentadecylamine, dihexadecylamine,
distearylamine, dioleylamine, bis(2-hexyldecyl)amine,
bis(2-octyldodecyl)amine, bis(2-decyltetradecyl)amine, beef tallow
dialkylamine, hardened beef tallow dialkylamine, and soybean oil
dialkylamine; and trialk(en)ylamines such as
tetradecyldimethylamine, hexadecyldimethylamine,
octadecyldimethylamine, beef tallow alkyldimethylamine, hardened
beef tallow alkyldimethylamine, soybean oil alkyldimethylamine,
dioleylmethylamine, tritetradecylamine, tristearylamine, and
trioleylamine. Suitable secondary amines have two alkyl (or
alkenyl) groups with 14 to 18 carbon atoms.
[0168] Examples of the compound containing the hexavalent
molybdenum atom include molybdenum trioxides or hydrates thereof
(MoO.sub.3.nH.sub.2O), molybdenum acid (H.sub.2MoO.sub.4), alkali
metal molybdates (Q.sub.2MoO.sub.4) wherein Q represents an alkali
metal, such as sodium or potassium, ammonium molybdates
((NH.sub.4).sub.2MoO.sub.4 or heptamolybdate
(NH.sub.4).sub.6[Mo.sub.7O.sub.24].4H.sub.2O), MoOCl.sub.4,
MoO.sub.2Cl.sub.2, MoO.sub.2Br.sub.2, Mo.sub.2O.sub.3Cl.sub.6, and
the like. Molybdenum trioxides or hydrates thereof, molybdenum
acid, alkali metal molybdates and ammonium molybdates are often
suitable because of their availability. In one embodiment, the
lubricating composition comprises molybdenum amine compound.
[0169] Other suitable organomolybdenum compounds may be the
reaction products of fatty oils, mono-alkylated alkylene diamines
and a molybdenum source. Materials of this sort are generally made
in two steps, a first step involving the preparation of an
aminoamide/glyceride mixture at high temperature, and a second step
involving incorporation of the molybdenum.
[0170] Examples of fatty oils that may be used include cottonseed
oil, groundnut oil, coconut oil, linseed oil, palm kernel oil,
olive oil, corn oil, palm oil, castor oil, rapeseed oil (low or
high erucic acids), soyabean oil, sunflower oil, herring oil,
sardine oil, and tallow. These fatty oils are generally known as
glyceryl esters of fatty acids, triacylglycerols or
triglycerides.
[0171] Examples of some mono-alkylated alkylene diamines that may
be used include methylaminopropylamine, methylaminoethylamine,
butylaminopropylamine, butylaminoethylamine, octylaminopropylamine,
octylaminoethylamine, dodecylaminopropylamine,
dodecylaminoethylamine, hexadecylaminopropylamine,
hexadecylaminoethylamine, octadecyl-aminopropylamine,
octadecylaminoethylamine, isopropyloxypropyl-1,3-diaminopropane,
and octyloxypropyl-1,3-diaminopropane. Mono-alkylated alkylene
diamines derived from fatty acids may also be used. Examples
include N-coco alkyl-1,3-propanediamine (Duomeen.RTM.C), N-tall oil
alkyl-1,3-propanediamine (Duomeen.RTM.T) and
N-oleyl-1,3-propanediamine (Duomeen.RTM.O), all commercially
available from Akzo Nobel.
[0172] Sources of molybdenum for incorporation into the fatty
oil/diamine complex are generally oxygen-containing molybdenum
compounds include, similar to those above, ammonium molybdates,
sodium molybdate, molybdenum oxides and mixtures thereof. One
suitable molybdenum source comprises molybdenum trioxide
(MoO.sub.3).
[0173] Nitrogen-containing molybdenum compounds which are
commercially available include, for example, Sakuralube.RTM. 710
available from Adeka which is a molybdenum amine compound, and
Molyvan.RTM. 855, available from R.T. Vanderbilt.
[0174] The nitrogen-containing molybdenum compound may be present
in the lubricant composition at 0.005 to 2 wt. % of the
composition, or 0.01 to 1.3 wt. %, or 0.02 to 1.0 wt. % of the
composition. The molybdenum compound may provide the lubricant
composition with 0 to 1000 ppm, or 5 to 1000 ppm, or 10 to 750 ppm
5 ppm to 300 ppm, or 20 ppm to 250 ppm of molybdenum.
[0175] L. Demulsifiers
[0176] Demulsifiers useful herein include trialkyl phosphates, and
various polymers and copolymers of ethylene glycol, ethylene oxide,
propylene oxide, and mixtures thereof.
[0177] M. Seal Swell Agents
[0178] Seal swell agents useful herein include sulfolene
derivatives such as Exxon Necton-37.TM. (FN 1380) and Exxon Mineral
Seal Oil.TM. (FN 3200).
[0179] N. TBN Boosters
[0180] Useful TBN boosters are anthranilate ester (esters of
anthranilic acid) as described, for example, in U.S. Pub. No.
20140187458, such as decyl anthranilate.
Example Lubricating Compositions
[0181] An engine lubricant in different embodiments may have a
composition as illustrated in Table 1. All additives are expressed
on an oil-free basis.
[0182] The exemplary N-alkylated dianiline compound tends to be
more effective in low magnesium lubricating compositions. In the
lubricating composition, a ratio of calcium to magnesium by weight,
may be at least 90:10 and in one embodiment, up to 10:90. Calcium
can be provided by overbased detergents, such as calcium
sulfonates, as discussed above. In one embodiment, the lubricating
composition includes less than 500 ppm magnesium, or less than 200
ppm magnesium, or less than 100 ppm magnesium.
TABLE-US-00001 TABLE 1 Example Lubricating Composition Embodiments
(wt. %) Additive A B C Example compound 0.1 to 5 0.2 to 2.5 0.3 to
1 Ashless antioxidant selected from a 0.0 to 5 0.1 to 2.5 0.3 to 1
diarylamine antioxidant, a phenolic antioxidant, and mixtures
thereof Overbased Calcium Detergent(s) 0.1 to 8 0.3 to 6 1 to 5
Dispersant Viscosity Modifier(s) 0 to 5 0.05 to 4 0.1 to 2
Dispersants 0 to 12 1.5 to 8 0.5 to 6 Other Antioxidants 0.0 to 13
0.1 to 10 2.0 to 5 Other Detergents 0.1 to 8 0.3 to 6 1 to 5
Antiwear Agent(s) 0.1 to 10 0.1 to 5 0.3 to 2 Friction Modifier(s)
0.01 to 4 0.05 to 2 0.1 to 1 Viscosity Modifier(s), other than DVMs
0 to 10 0.5 to 8 1 to 6 Any Other Performance Additive 0 to 10 0 to
8 0 to 6 Oil of Lubricating Viscosity Balance Balance Balance to
100% to 100% to 100%
Use of the Lubricating Composition
[0183] The lubricating composition described herein may be used in
a method for reducing deposit formation in an internal combustion
engine. The internal combustion engine is lubricated with the
lubricating composition.
[0184] The end use of the lubricating composition described herein
includes use as a cylinder lubricant for an internal combustion
engine, such as in a passenger car or a heavy, medium, or light
duty diesel vehicle, but may also find use as an engine oil for
2-stroke marine diesel engines, small engines such as motorcycle
and 2-stroke oil engines, as a driveline lubricant, including gear
and automatic transmission oils, and for other industrial oils,
such as hydraulic lubricants.
[0185] An exemplary method of lubricating a mechanical device, such
as a passenger car engine cylinder, includes supplying the
exemplary lubricating composition to the device.
[0186] Generally, the lubricating composition is added to the
lubricating system of an internal combustion engine, which then
delivers the lubricating composition to the cylinder of the engine,
during its operation.
[0187] The internal combustion engine may be a gasoline fuelled
engine, a diesel-fuelled engine, such as a 2-stroke marine diesel
engine, or a natural gas fuelled engine, a mixed gasoline/alcohol
fuelled engine, or a biodiesel fuelled engine. The internal
combustion engine may be a 2-stroke or 4-stroke engine.
[0188] In one embodiment the disclosed technology provides a method
of lubricating a 2-stroke or 4-stroke internal combustion engine
comprising supplying to the internal combustion engine a
lubricating composition as disclosed herein.
[0189] The internal combustion engine may be a passenger car
internal combustion engine. The passenger car internal combustion
engine may have a reference mass not exceeding 2610 kg. The
passenger car engine may be operated on unleaded gasoline. Unleaded
gasoline is well known in the art and is defined by British
Standard BS EN 228:2008 (entitled "Automotive Fuels--Unleaded
Petrol--Requirements and Test Methods"). The internal combustion
engine may also be a heavy duty diesel internal combustion engine.
The heavy duty diesel internal combustion engine may have a
"technically permissible maximum laden mass" over 3,500 kg. The
engine may be a compression ignition engine or a positive ignition
natural gas (NG) or LPG (liquefied petroleum gas) engine.
[0190] The lubricating composition may be suitable for use as a
cylinder lubricant irrespective of the sulfur, phosphorus or
sulfated ash (ASTM D-874) content of the fuel. The sulfur content
of the lubricating composition, which is particularly suited to use
as an engine oil lubricant, may be 1 wt. % or less, or 0.8 wt. % or
less, or 0.5 wt. % or less, or 0.3 wt. % or less. In one
embodiment, the sulfur content may be in the range of 0.001 wt. %
to 0.5 wt. %, or 0.01 wt. % to 0.3 wt. %. The phosphorus content
may be 0.2 wt. % or less, or 0.12 wt. % or less, or 0.1 wt. % or
less, or 0.085 wt. % or less, or 0.08 wt. % or less, or even 0.06
wt. % or less, 0.055 wt. % or less, or 0.05 wt. % or less. In one
embodiment, the phosphorus content may be 100 ppm to 1000 ppm, or
200 ppm to 600 ppm. The total sulfated ash content may be 2 wt. %
or less, or 1.5 wt. % or less, or 1.1 wt. % or less, or 1 wt. % or
less, or 0.8 wt. % or less, or 0.5 wt. % or less, or 0.4 wt. % or
less. In one embodiment, the sulfated ash content may be 0.05 wt. %
to 0.9 wt. %, or 0.1 wt. % to 0.2 wt. % or to 0.45 wt. %.
[0191] Without intending to limit the scope of the exemplary
embodiment, the following examples illustrate preparation and
evaluation of example compounds.
EXAMPLES
[0192] All reactants and additives are expressed on an oil-free
basis.
Example 1: Synthesis of 4,4'-cyclohexylmethylenedianiline
(CY-MDI)
[0193] 4,4'-methylenedianiline (MDA) (1 eq.), cyclohexanone (2.1
eq.) and acetic acid (0.05 eq.) are charged to a flask with toluene
and heated to reflux with removal of water. Once imine formation is
complete, the toluene and residual acetic acid are removed by
vacuum. The resulting imine is dissolved in methanol and cooled to
less than 10.degree. C. using an ice bath. Sodium borohydride (2.2
eq.) is added portion-wise, keeping the reaction temperature below
15.degree. C. The solution is then allowed to warm to room
temperature and stirred for an additional 2 hours. Once reduction
is complete, the mixture is quenched with water and the product is
extracted with ethyl acetate. No further purification is needed.
The reaction results in the formation of compound A-1 shown in
TABLE 2.
Example 2: Synthesis of 4,4'-2-ethylhexylmethylenedianiline
(EHL-MDI)
[0194] The process of Example 1 is repeated, using 2-ethylhexanal
(2.1 eq.) in place of cyclohexanone as the ketone. The reaction
results in the formation of compound A-2 shown in TABLE 2:
[0195] Using the method of Examples 1 and 2, with the product being
either collected by filtration or by extraction with ethyl acetate,
the products shown in TABLE 2 are formed using the following amines
and ketones/aldehydes:
TABLE-US-00002 TABLE 2 Diamine Compounds Ketone/ Example Aldehyde
Amine A-1 ##STR00014## cyclohexanone MDA A-2 ##STR00015##
2-ethylhexanal MDA A-3 ##STR00016## 3-pentanone MDA A-4
##STR00017## 4-methyl cyclohexanone MDA A-5 ##STR00018## methyl
isobutyl ketone MDA A-6 ##STR00019## 4-tert-butyl cyclohexanone MDA
A-7 ##STR00020## isophorone MDA A-8 ##STR00021## 3,3,5-trimethyl
cyclohexanone MDA A-9 ##STR00022## acetophenone MDA A-10
##STR00023## benzophenone MDA A-11 ##STR00024## benzaldehyde MDA
A-12 ##STR00025## cyclohexanone 2,4,6- trimethyl- aniline A-13
##STR00026## 4-methyl cyclohexanone 2,4,6- trimethyl- aniline
Example 3: Lubricating Compositions
[0196] The N,N'-dialkylmethylenedianilene compounds prepared
according to Examples 1 and 2 are evaluated in various
formulations.
[0197] A. Higher Internal Combustion Engine Lubricants
[0198] Lubricating compositions suitable as 5W-30 engine lubricants
are prepared using a baseline formulation as shown in TABLE 3. All
concentrations are on an oil free (i.e., active basis).
TABLE-US-00003 TABLE 3 Baseline Lubricating Composition B1
Component Baseline B1 Base Oil Balance to 100% Calcium
alkylsulfonates (overbased detergent) 0.9 Secondary Zinc
dialkyldithiophosphate (ZDDP) 0.86 Diarylamine antioxidant.sup.1
0.9 Phenol antioxidant.sup.2 0.35 Polyisobutylene succinimide
dispersant.sup.3 2.12 Ethylene-propylene copolymer (viscosity
modifier) 0.7 Additional performance additives (friction modifiers,
0.51 corrosion inhibitors, foam inhibitors, pour point depressants,
etc.) % Phosphorus 0.075 .sup.1Dinonylated diphenylamine
.sup.2Alkyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate
.sup.3Combination of Polyisobutylene succinimide dispersants with
Mn ranging from 1600-2300
[0199] The alkylated dianilines of Examples 1 and 2 are added to
the baseline composition, as shown in TABLE 4, to form lubricating
compositions L1 and L2, respectively.
TABLE-US-00004 TABLE 4 Lubricating Oil Composition Formulations
Composition B1 L1 L2 B1 100 99.5 99.5 A-1 0.5 A-2 0.5 % Phosphorus
0.075 0.075 0.075 D2896 TBN (mg KOH/kg) 7.5 9.1 8.7
[0200] Lubricating compositions B1, L1, and L2 are evaluated in the
following oxidation bench tests:
[0201] 1. Impact on thin-film antioxidancy: The Pressure
Differently Scanning calorimeter (PDSC) test measures the
compositions' oxidative induction time (OIT). This is a standard
test procedure in the lubricating oil industry, based on CEC L-85
T-99. In this testing the lubricating composition is heated to an
elevated temperature, typically about 25.degree. C. below the
average decomposition temperature for the sample being tested (in
this case 215.degree. C. at 690 kPa), and the time to when the
composition begins to decompose is measured. The longer the test
time, reported in minutes, the better the oxidative stability of
the composition and the additives present within it.
[0202] 2. Deposits (MHT TEOST): determined according to ASTM
D7097-09. The MHT TEOST method evaluates deposit formation at
temperatures closely related to those of the piston ring zone in
reciprocating engines. An organo-metallic catalyst mixture of a
predetermined concentration equaling approximately 8.5 g is
circulated for 24 hrs over a wire-wound depositor rod at
285.degree. C. along with 10 ml/min of air. The depositor rod is
weighed before test and after testing. Any post-test deposits
collected after washing the rod along with rod deposits equals
total deposits. In the MHT TEOST, a lower amount of deposit
indicates better deposit control performance.
[0203] The results obtained are shown in TABLE 5.
TABLE-US-00005 TABLE 5 Oxidation Results for Lubricating Oil
Composition Formulations Example PDSC OIT min L-85-99 OIT min MHT
TEOST mg B1 67 80 42 L1 109 97 13 L2 84 82 18
[0204] The results shown in TABLE 5 suggest that the lubricating
compositions (L1 and L2) (for example, an internal combustion
engine lubricant) containing the alkylated dianilines of Examples 1
and 2 provide exceptional antioxidancy performance as well as
unexpected deposit control performance when compared with the
baseline formulation (B1).
[0205] B. Low-Phosphorus Internal Combustion Engine Lubricants
[0206] Lubricating compositions suitable as 5W-30 engine lubricants
are prepared using a baseline formulation (B2) as shown in TABLE 6.
All concentrations are on an oil-free (i.e., active) basis.
TABLE-US-00006 TABLE 6 Baseline lubricating composition B2
Component Baseline B2 Base Oil Balance to 100% Calcium
alkylsulfonates (overbased detergent) 0.9 Zinc
dialkyldithiophosphate (ZDDP) 0.43 Antioxidants .sup.1 1.73
Polyisobutylene succinimide dispersant.sup.2 2.65 Polymeric
Viscosity Modifier 0.7 Additional performance additives (friction
modifiers, 0.61 corrosion inhibitors, foam inhibitors, pour point
depressants, etc.) % Phosphorus 0.038 .sup.1 Combination of
diarylamine and hindered phenol .sup.2Combination of
Polyisobutylene succinimide dispersants with Mn ranging from
1600-2300
[0207] The diamines A-1, A-3, and A-4 are added to the baseline
composition B1 in the amounts shown in TABLE 7, to form lubricating
compositions L3, L4, and L5. A further lubricating composition (C1)
is prepared with an aminic antioxidant.
TABLE-US-00007 TABLE 7 Lubricating Oil Composition Formulations
Composition B2 L3 L4 L5 C1 B2 100 99.5 99.5 99.5 99.5 A-1 0.5 A-4
0.5 A-3 0.5 Aminic AO 0.5 % Phosphorus 0.038 0.038 0.038 0.038
0.038 TBN, mg of KOH/g 8.7 9.6 9.5 9 (D2896)
[0208] Lubricating compositions B2, L3, L4, L5, and C1 are
evaluated in the oxidation bench tests, as described above. The
results obtained are shown in TABLE 8.
TABLE-US-00008 TABLE 8 Oxidation Results for Lubricating Oil
Composition Formulations Example PDSC OIT min L-85-99 OIT min MHT
TEOST mg B2 65 104 39 L3 94 125 16 L4 102 160 15 L5 87 108 16 C1 70
105 40
[0209] The results shown in TABLE 8 suggest that the exemplary
lubricating compositions (L3, L4, and L5) (for example, an internal
combustion engine lubricant) containing the alkylated dianilines
A-1, A-3, and A-4 provide exceptional antioxidancy performance as
well as unexpected deposit control performance when compared with
the baseline formulation (B2), indicating that the exemplary
alkylated dianilines are very efficient in low phosphorus
formulations. Additionally, 0.5% of these alkylated dianilines
provides a much more significant performance enhancement to the
baseline formulation in both the PDSC and the MHT TEOST tests than
the addition of a further 0.5% of aminic antioxidant (C1).
[0210] C. Internal Combustion Engine Lubricants
[0211] Lubricating compositions suitable as 15W-40 engine
lubricants are prepared using a baseline formulation (B3) as shown
in TABLE 9. All concentrations are on an oil-free (i.e., active
basis).
TABLE-US-00009 TABLE 9 Baseline lubricating composition B3
Component Baseline B3 Base Oil Balance to 100% Calcium
alkylsulfonate and calcium sulfur-coupled 2.7 alkylphenol
(overbased detergent) Zinc dialkyldithiophosphate (ZDDP) 1.15
Antioxidants (combination of diarylamine and 1.25 hindered phenol)
2200 Mn polyisobutylene succinimide, TBN ~55 3.6 (ashless
dispersant) Polymeric Viscosity Modifier 0.9 Additional performance
additives (corrosion inhibitor, 0.86 foam inhibitors, pour point
depressant, and surfactant etc.) % Phosphorus 0.11
[0212] The diamines A-1 and A-2 are added to the baseline
composition B3 in the amounts shown in TABLE 10, to form
lubricating compositions L6 and L7.
TABLE-US-00010 TABLE 10 Lubricating Oil Composition Formulations
Composition B3 L6 L7 B3 100 99.5 99.5 A-2 0.5 A-1 0.5 % Phosphorus
0.11 0.11 0.11 TBN mg of KOH/g (D2896) 11.8 12.7 13.2
[0213] Lubricating compositions B3, L6, and L7 are evaluated in the
oxidation bench tests, as described above. The results obtained are
shown in TABLE 11.
TABLE-US-00011 TABLE 11 Oxidation Results for Lubricating Oil
Composition Formulations Example PDSC OIT min MHT TEOST mg B3 84 20
L6 87 5.5 L7 89 4.6
[0214] The results shown in TABLE 11 suggest that the exemplary
lubricating compositions (L6 and L7) (for example, an internal
combustion engine lubricant) containing the alkylated dianilines
A-1 and A-2 provide exceptional antioxidancy performance as well as
unexpected deposit control performance when compared with the
baseline formulation (B3), indicating that the exemplary alkylated
dianilines are very efficient in these formulations.
[0215] As used herein, the term "hydrocarbyl substituent" or
"hydrocarbyl group" is used in its ordinary sense, which is
well-known to those skilled in the art. Specifically, it refers to
a group having a carbon atom directly attached to the remainder of
the molecule and having predominantly hydrocarbon character. By
predominantly hydrocarbon character, it is meant that at least 70%
or at least 80% of the atoms in the substituent are hydrogen or
carbon.
[0216] Examples of hydrocarbyl groups include:
[0217] (i) hydrocarbon substituents, that is, aliphatic (e.g.,
alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl)
substituents, and aromatic-, aliphatic-, and alicyclic-substituted
aromatic substituents, as well as cyclic substituents wherein the
ring is completed through another portion of the molecule (e.g.,
two substituents together form a ring);
[0218] (ii) substituted hydrocarbon substituents, that is,
substituents containing non-hydrocarbon groups which, in the
context of this invention, do not alter the predominantly
hydrocarbon nature of the substituent (e.g., halo (especially
chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto,
nitro, nitroso, and sulfoxy);
[0219] (iii) hetero substituents, that is, substituents which,
while having a predominantly hydrocarbon character, may contain
other than carbon in a ring or chain otherwise composed of carbon
atoms.
[0220] Representative alkyl groups include n-butyl, iso-butyl,
sec-butyl, n-pentyl, amyl, neopentyl, n-hexyl, n-heptyl, secondary
heptyl, n-octyl, secondary octyl, 2-ethyl hexyl, n-nonyl, secondary
nonyl, undecyl, secondary undecyl, dodecyl, secondary dodecyl,
tridecyl, secondary tridecyl, tetradecyl, secondary tetradecyl,
hexadecyl, secondary hexadecyl, stearyl, icosyl, docosyl,
tetracosyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexydecyl,
2-octyldecyl, 2-hexyldodecyl, 2-octyldodecyl, 2-decyltetradecyl,
2-dodecylhexadecyl, 2-hexyldecyloctyldecyl, 2-tetradecyloctyldecyl,
monomethyl branched-isostearyl, and the like.
[0221] Representative aryl groups include phenyl, toluyl, xylyl,
cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl,
trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl,
hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl,
undecylphenyl, dodecylphenyl, benzylphenyl, styrenated phenyl,
p-cumylphenyl, .alpha.-naphthyl, .beta.-naphthyl groups, and
mixtures thereof.
[0222] Heteroatoms include sulfur, oxygen, nitrogen, and encompass
substituents, such as pyridyl, furyl, thienyl and imidazolyl. In
general, no more than two, and in one embodiment, no more than one,
non-hydrocarbon substituent will be present for every ten carbon
atoms in the hydrocarbyl group. In some embodiments, there are no
non-hydrocarbon substituents in the hydrocarbyl group.
[0223] Representative aliphatic groups may contain 4 to 14 carbon
atoms, 6 to 12 carbon atoms, or 8 to 10 carbon atoms. Examples of
suitable alkyl groups include butyl, isobutyl, pentyl, isopentyl,
neopentyl, hexyl, amyl, heptyl, octyl, iso-octyl, 2-ethylhexyl,
nonyl, decyl, iso-decyl, undecyl, dodecyl, 2-propylheptyl,
tridecyl, isotridecyl, tetradecyl, 4-methyl-2-pentyl, propyl
heptyl, and combinations thereof.
[0224] Hydrocarbylene groups are the divalent equivalents of
hydrocarbyl groups, such as alkylene groups.
[0225] Each of the documents referred to above is incorporated
herein by reference. Except in the Examples, or where otherwise
explicitly indicated, all numerical quantities in this description
specifying amounts of materials, reaction conditions, molecular
weights, number of carbon atoms, and the like, are to be understood
as modified by the word "about." Unless otherwise indicated, each
chemical or composition referred to herein should be interpreted as
being a commercial grade material which may contain the isomers,
by-products, derivatives, and other such materials which are
normally understood to be present in the commercial grade. However,
the amount of each chemical component is presented exclusive of any
solvent or diluent oil, which may be customarily present in the
commercial material, unless otherwise indicated. It is to be
understood that the upper and lower amount, range, and ratio limits
set forth herein may be independently combined. Similarly, the
ranges and amounts for each element of the invention may be used
together with ranges or amounts for any of the other elements.
[0226] It will be appreciated that variants of the above-disclosed
and other features and functions, or alternatives thereof, may be
combined into many other different systems or applications. Various
presently unforeseen or unanticipated alternatives, modifications,
variations or improvements therein may be subsequently made by
those skilled in the art which are also intended to be encompassed
by the following claims.
* * * * *