U.S. patent application number 16/305083 was filed with the patent office on 2020-12-03 for lubricating compositions.
The applicant listed for this patent is The Lubrizol Corporation. Invention is credited to Stephen J. Cook, Samuel M. Kilsby, Blayne M. McKenzie, Edward P. Sampler, Gary M. Walker.
Application Number | 20200377817 16/305083 |
Document ID | / |
Family ID | 1000005060856 |
Filed Date | 2020-12-03 |
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United States Patent
Application |
20200377817 |
Kind Code |
A1 |
Sampler; Edward P. ; et
al. |
December 3, 2020 |
Lubricating Compositions
Abstract
A lubricating composition suited for use in lubricating a
driveline device includes an oil of lubricating viscosity and a
compound comprising a polyolefin-substituted bridged
hydroxyaromatic compound or metal salt thereof, wherein the
polyolefin is derived from a isobutylene having a number average
molecular weight of 150 to 800.
Inventors: |
Sampler; Edward P.; (Belper,
Derby, GB) ; Walker; Gary M.; (Belper, Derby, GB)
; Cook; Stephen J.; (Belper, Derby, GB) ; Kilsby;
Samuel M.; (Belper, Derby, GB) ; McKenzie; Blayne
M.; (Willoughby Hills, OH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Lubrizol Corporation |
Wickliffe |
OH |
US |
|
|
Family ID: |
1000005060856 |
Appl. No.: |
16/305083 |
Filed: |
June 14, 2017 |
PCT Filed: |
June 14, 2017 |
PCT NO: |
PCT/US2017/037458 |
371 Date: |
November 28, 2018 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 2203/003 20130101;
C10M 169/044 20130101; C10M 141/10 20130101; C10M 161/00 20130101;
C10M 135/04 20130101; C10N 2040/044 20200501; C10N 2030/04
20130101; C10M 2219/022 20130101; C10M 143/18 20130101; C10N
2040/042 20200501; C10M 135/10 20130101; C10M 2205/12 20130101;
C10M 2223/045 20130101; C10N 2020/04 20130101; C10M 2219/044
20130101; C10M 137/02 20130101; C10M 137/10 20130101; C10M 2223/049
20130101; C10N 2030/06 20130101 |
International
Class: |
C10M 169/04 20060101
C10M169/04; C10M 143/18 20060101 C10M143/18; C10M 135/10 20060101
C10M135/10; C10M 137/10 20060101 C10M137/10; C10M 137/02 20060101
C10M137/02; C10M 135/04 20060101 C10M135/04; C10M 141/10 20060101
C10M141/10; C10M 161/00 20060101 C10M161/00 |
Claims
1. A lubricating composition comprising: an oil of lubricating
viscosity; a dispersant; and a compound comprising a
polyolefin-substituted bridged hydroxyaromatic compound or salt
thereof, wherein the polyolefin is derived from a branched alkene
having at least 4 carbon atoms and wherein the polyolefin has a
number average molecular weight of 150 to 800.
2. The lubricating composition of claim 1, wherein the branched
alkene comprises isobutylene.
3. The lubricating composition of claim 1, wherein the polyolefin
includes a chain derived from at least 4, or at least 5, or up to
6, or up to 7, or up to 8, or up to 18 branched alkene units.
4. The lubricating composition claim 1, wherein the polyolefin has
a number average molecular weight of 150 to 400.
5. The lubricating composition of claim 1, wherein the compound is
a metal salt or pnictogen salt.
6. The lubricating composition claim 1, wherein the polyolefin is
prepared in the absence of a chain transfer agent and has a
polydispersity greater than 1.5.
7. The lubricating composition of claim 6, wherein the metal in the
salt comprises calcium.
8. The lubricating composition of claim 1, wherein the
polyolefin-substituted bridged hydroxyaromatic compound or salt
thereof is overbased.
9. The lubricating composition of claim 1, wherein the compound is
bridged with a sulfide bridge.
10. The lubricating composition of claim 1, wherein the compound is
bridged with an alkylene bridge.
11. The lubricating composition of claim 1, wherein the compound is
a bridged metal phenate.
12. The lubricating composition of claim 1, wherein the compound is
free of C.sub.8 and higher unbranched alkyl chains.
13. The lubricating composition of claim 1, wherein the compound
includes a bridged phenate unit represented by the formula:
##STR00017## and salts thereof, where each R1 and each R2
represents a polyolefin group; X represents a bridging group; Y and
Z each represent a terminal group; each n is at least 1; m is at
least 1; and p is at least 1.
14. The lubricating composition of claim 13, wherein the compound
is not coupled with cresol.
15. The lubricating composition of claim 13, wherein n is 1.
16. The lubricating composition of claim 1, wherein each R1 and R2
is independently a polyolefin of 8 to 50 carbon atoms, or at least
10 carbon atoms, or at least 10 carbon atoms, or at least 12 carbon
atoms, or at least 14 carbon atoms, or at least 16 carbon atoms, or
at least 18 carbon atoms, or at least 20 carbon atoms, or at least
24 carbon atoms, or up to 40 carbon atoms, or up to 35 carbon
atoms, or up to 30 carbon atoms.
17. The lubricating composition of claim 1, wherein each R1 and
each R2 is a polyisobutylene.
18. The lubricating composition of claim 1, wherein each R1 is a
300-400 MW polyisobutylene.
19. The lubricating composition of claim 1, wherein the compound
has a weight-average molecular weight of 550-5600 in its unsalted
form.
20. The lubricating composition of claim 1, wherein the compound
has a weight average molecular weight of up to 2800 in its unsalted
form.
21. The lubricating composition of claim 1, wherein the compound is
at least 0.01 wt. % of the lubricating composition.
22. The lubricating composition of claim 21, wherein the compound
is at least 0.1 wt. %, or at least 0.5 wt. %, or at least 1 wt. %,
or at least 2 wt. % of the lubricating composition.
23. The lubricating composition of claim 21, wherein the compound
is up to 20 wt. %, or up to 10 wt. %, or up to 5 wt. %, or up to 3
wt. %, or up to 2.5 wt. % of the lubricating composition.
24. The lubricating composition of claim 1, wherein the oil of
lubricating viscosity comprises at least one of an API Group I, II,
III, IV, and V base oil.
25. The lubricating composition of claim 1, wherein the oil of
lubricating viscosity is at least 10 wt. % of the lubricating
composition.
26. The lubricating composition of claim 25, wherein the oil of
lubricating viscosity is at least 30 wt. % of the lubricating
composition.
27. The lubricating composition of claim 1, wherein the oil of
lubricating viscosity is up to 95 wt. % of the lubricating
composition.
28. The lubricant claim 1 further comprising at least one of a
phosphorus-containing antiwear agent comprising a non-ionic
phosphorus compound; an amine salt of a phosphorus compound; a
calcium-containing detergent; another phenate detergent; a
sulphur-containing extreme pressure agent; a sulphur-containing
corrosion inhibitor; or combinations thereof.
29. The lubricating composition claim 1 further comprising from
about 0.05 to about 3 wt % of a C2-C18 di- or tri-hydrocarbyl
phosphite, based on the total weight of said lubricant.
30. The lubricating composition claims 1 further comprising less
than 2000 ppm zinc based on a total weight of said lubricant.
31. The lubricating composition of claim 1, wherein the lubricant
is substantially free of to free of a phenol alkylated with
oligomers of propylene.
32. A method of lubricating a manual transmission comprising
supplying the lubricant composition of claim 1 to said manual
transmission.
33. The method of claim 32, wherein the lubricating composition
further comprises: a thiadiazole and a phosphorous containing
antiwear agent.
34. A method of lubricating automatic transmission comprising
supplying the lubricating composition of claim 1 to said automatic
transmission.
35. The method of claim 34, wherein the lubricating composition
further comprises: a thiadiazole and a phosphorous containing
antiwear agent.
36. A method of lubricating an off-highway vehicle comprising
supplying the lubricating composition of claim 1 to said
off-highway vehicle.
37. The method of claim 36, wherein the lubricating composition
further comprises: a zinc dialkyl dithiophosphate antiwear
agent
38. The method of claim 37, wherein the vehicle is a farm-tractor
vehicle or a construction vehicle.
39. A method of lubricating a highway vehicle comprising supplying
the lubricating composition of claim 1 to said off-highway
vehicle.
40. The method of claim 39, wherein the lubricating composition
further comprises: a sulfurized olefin; a thiadiazole; and a
phosphorous containing antiwear agent.
41. A lubricating composition comprising: an oil of lubricating
viscosity; a dispersant; a sulfurized olefin; a thiadazole; a
phosphorous-containing anti-wear agent; and a bridged phenate unit
represented by the formula ##STR00018## and salts thereof, where
each R.sup.1 and each R.sup.2 represents a polyolefin group having
a number average molecular weight of 200 to 500, or 300 to 400; X
represents a bridging group; Y and Z each represent a terminal
group; each n is at least 1; m is at least 1; and p is at least 1.
Description
BACKGROUND
[0001] The invention relates generally to lubricating compositions
(lubricants) and finds particular application in connection with an
additive for a lubricating composition and to a lubricating
method.
[0002] Phenol-based detergents are known. Among these are phenates
based on phenolic monomers linked with sulfur bridges or alkylene
bridges such as methylene linkages derived from formaldehyde. The
phenolic monomers themselves are typically substituted with an
aliphatic hydrocarbyl group to provide a measure of oil solubility.
The hydrocarbyl groups may be alkyl groups, such as dodecylphenol
(or propylene tetramer-substituted phenol). Basic sulfurized
polyvalent metal phenates are described, for example, in U.S. Pat.
No. 2,680,096, to Walker et al., issued Jun. 1, 1954; and U.S. Pat.
No. 3,372,116, to Meinhardt, issued Mar. 6, 1968.
[0003] Recently, however, certain alkylphenols and products
prepared from them have come under increased scrutiny due to their
classification as potentially harmful materials. In particular,
alkylphenol detergents which are based on oligomers of C.sub.12
alkyl phenols may contain residual monomeric C.sub.12 alkyl phenol
species. These detergents include those derived from para-dodecyl
phenol. There is interest, therefore, in developing
alkyl-substituted phenate detergents, for uses in lubricants,
fuels, and as industrial additives, which reduce or eliminate the
need for dodecylphenol-based compounds.
[0004] There have been several efforts to prepare phenate
detergents that do not contain C.sub.n alkyl phenols. U.S. Pat. No.
7,435,709, to Stonebraker, et al., issued Oct. 14, 2008, discloses
a linear alkylphenol-derived detergent which is a salt of a
reaction product of an olefin having at least 10 carbon atoms and a
hydroxyaromatic compound. Greater than 90 mole % of the olefin is a
linear C.sub.20-C.sub.30 n-alpha olefin, less than 10 mole % of the
olefin is a linear olefin of less than 20 carbon atoms, and less
than 5 mole % of the olefin is a branched chain olefin of 18
carbons or less.
[0005] U.S. Pub. No. 2011/0190185, to Sinquin, et al, published
Aug. 4, 2011, discloses an overbased salt of an oligomerized
alkylhydroxyaromatic compound. The alkyl group is derived from an
olefin mixture comprising propylene oligomers having an initial
boiling point of at least 195.degree. C. and a final boiling point
of greater than 325.degree. C. The propylene oligomers may contain
a distribution of carbon atoms that include at least 50 wt. %
C.sub.14 to C.sub.20 carbon atoms.
[0006] U.S. Pub. No. 2011/0124539, to Sinquin, et al, published May
26, 2011, discloses an overbased, sulfurized salt of an alkylated
hydroxyaromatic compound. The alkyl substituent is a residue of at
least one isomerized olefin having from 15 to 99 wt. % branching.
The hydroxyaromatic compound may be a phenol, cresol, xylenol, or
mixture thereof.
[0007] U.S. Pub. No. 2011/0118160, to Campbell, et al., published
May 19, 2011, discloses an alkylated hydroxyaromatic compound
prepared by reacting a hydroxyaromatic compound with at least one
branched olefinic propylene oligomer having from 20 to 80 carbon
atoms. Suitable hydroxyaromatic compounds include phenol, catechol,
resorcinol, hydroquinone, pyrogallol, cresol, and the like.
[0008] U.S. Pub. No. 2010/0029529, to Campbell, et al., published
Feb. 4, 2010, discloses an overbased salt of an oligomerized
alkylhydroxyaromatic compound. The alkyl group is derived from an
olefin mixture comprising propylene oligomers having an initial
boing point of at least 195.degree. C. and a final boiling point of
no more than 325.degree. C.
[0009] U.S. Pub. No. 2008/0269351, to Campbell, et al., published
Oct. 30, 2008, discloses an alkylated hydroxyaromatic compound
prepared by reacting a hydroxyaromatic compound with a branched
olefinic oligomer having from 20 to 80 carbon atoms.
[0010] U.S. Pat. No. 6,310,009, to Carrick, et al., issued Oct. 30,
2001, discloses bridged phenolic compounds, each phenol group being
substituted with an alkyl group of 1 to 60 carbon atoms, e.g., 9 to
18 carbon atoms.
[0011] There remains a need for a phenolic material with
appropriate oil solubility, viscosity performance, and detergency
(characteristic of moderate chain length alkyl groups) but free
from or substantially free from C.sub.12 alkyl phenol moieties.
BRIEF DESCRIPTION
[0012] In accordance with one aspect of the exemplary embodiment, a
lubricating composition includes an oil of lubricating viscosity
and a compound containing a polyolefin-substituted bridged
hydroxyaromatic compound or metal salt thereof.
[0013] In accordance with another aspect of the exemplary
embodiment, a method of lubricating a mechanical device with the
lubricating composition is disclosed.
[0014] In accordance with another aspect of the exemplary
embodiment, a method of forming a lubricating composition including
an oil of lubricating viscosity and a compound containing a
polyolefin-substituted bridged hydroxyaromatic compound or metal
salt thereof is described.
[0015] In accordance with another aspect, a use of the composition
for lubricating a mechanical device is also disclosed.
DETAILED DESCRIPTION
[0016] Aspects of the exemplary embodiment relate to a lubricating
composition, method of use and method of manufacturing the
composition. The lubricating composition contains an oil of
lubricating viscosity and a polyolefin-substituted bridged
hydroxyaromatic compound or salt thereof.
[0017] The exemplary compounds described herein are bridged
polyolefin-substituted hydroxyaromatic (e.g., phenol) compounds and
their salts. The compounds are free from or substantially free from
unsubstituted phenol moieties. Such compounds and their salts are
useful as lubricant additives.
[0018] Suitable hydroxyaromatic compounds include phenol, catechol,
resorcinol, hydroquinone, pyrogallol, cresol, and the like. In one
embodiment, the hydroxyaromatic compounds that are bridged include
no more than one aromatic ring.
[0019] The term "substantially free" as it refers to the exemplary
compound, means that less than 0.01 mol. %, or less than 0.001 mol.
%, or less than 0.0001 mol. % of the exemplary
polyolefin-substituted bridged hydroxyaromatic compound in the
lubricating composition is substituted with one or more C.sub.12
alkyl groups. In one embodiment, the lubricating compound contains
less than 0.5 wt. %, or less than 0.1 wt. %, or less than 0.01 wt.
%, or less than 0.001 wt. %, of C.sub.12 alkyl hydroxyaromatic
compounds.
[0020] The lubricating composition may also include a bridged
phenate. In the exemplary embodiment, the compound is not coupled
with cresol. The compound can serve as a dispersant or detergent in
the lubricating composition.
[0021] A. The Polyolefin-Substituted Bridged Hydroxyaromatic
Compound
[0022] The exemplary polyolefin-substituted, bridged
hydroxyaromatic compound is a bridged phenol in which at least one
hydroxyl group is directly bonded to an aromatic ring that is
substituted with a polyolefin group.
[0023] The aromatic polyol on which the exemplary compound is based
may be a substituted or unsubstituted compound that has at least
one hydroxyl group directly bonded to an aromatic group (within the
definition of HUckel Rule 47+2 electrons) such as phenol. An
exemplary polyolefin-substituted aromatic polyol compound may be
represented by the general structure shown in Formula I:
##STR00001##
[0024] and salts thereof,
[0025] where each R.sup.1 and each R.sup.2 represents a polyolefin
group,
[0026] X represents a bridging group, such as a sulfur or an
alkylene bridging group containing 1 to 8 carbon atoms (e.g., a
bridge derived from one or more aldehyde and/or propanal monomer
units);
[0027] Y and Z each represent a terminal group, such as --H, --OH,
a C.sub.1-C.sub.6 alkyl group, or a group derived from the bridging
monomer (e.g., --SH, an aldehyde-derived group, such as
--C(H).dbd.O, or the like);
[0028] each n is at least 1, such as up to 3, on average, or up to
2, or 1;
[0029] m is at least 1, such as up to 5, or up to 4, or up to 3, on
average, such as 1 or 2; and
[0030] p is at least 1, such as up to 5, on average, or 1 or 2. For
example, when X is an alkylene bridge, p is 1, 2, or 3, for
example, 1 or 2, further for example 1. Further for example, when X
is sulfur, p is 1 or 2 or 3.
[0031] An exemplary salt may be represented by the general
structure shown in Formula II:
##STR00002##
[0032] where M represents a cation which is linked to at least one
of the O.sup.- groups; and x is at least 1, such as 2 in the case
of a calcium ion.
[0033] The exemplary compound of Formula II may also be associated
with a counter ion in the compound. For example, in an overbased
compound, the metal ion to compound ratio may be raised above the
stoichiometric amount, e.g., by bubbling CO.sub.2 through the
mixture to provide a carbonate counterion. As will be appreciated,
these aspects can also be used in combinations thereof.
[0034] Examples of branched polyolefin groups suitable for use as
R.sup.1 and R.sup.2 include polyolefin groups which are derived
from a branched alkene having at least 4 carbon atoms, or up to 12
carbon atoms, or up to 8 carbon atoms, or up to 6 carbon atoms,
such as a C.sub.4-C.sub.6 branched alkene. Suitable branched
alkenes include isobutylene (2-methylpropene), 2-methylbutene,
2-ethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene,
4-methyl-l-pentene, 2-methyl, 3-methyl-1-pentene, 2-ethyl-1
-pentene, 3-ethyl-1 -pentene, 2-methyl-1-hexene, 3-methyl-1-hexene,
2-ethyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene,
2-methyl-1-heptene, 3-methyl-1-heptene, 2-methyl-1-octene,
2-methyl-1-nonene, 2-methyl-1-decene, 2-methyl-1-undecene, and
mixtures thereof. Each polyolefin group is derived from at least
two or at least three, or at least four, or up to twenty, or up to
eighteen, or up to twelve branched alkene monomer units to form a
chain with at least two or at least three, or at least four
branches from the main chain. In one embodiment, the polyolefin
includes a chain derived from at least four, or at least five, or
up to eighteen, or up to eight, or up to seven, or up to six
branched alkene units. The branched alkene may be branched at the
alpha or beta position, or further along the longest chain. In one
embodiment, at least one or both of R.sup.1 and R.sup.2 are derived
from a branched alkene which is solely or at least partially
isobutylene and at least one or both of R.sup.1 and R.sup.2 is/are
each polyisobutylene (PIB).
[0035] R.sup.1 and R.sup.2 may be independently a polyolefin of 8
to 50 carbon atoms, or at least 10 carbon atoms, or at least 12
carbon atoms, or at least 14 carbon atoms, or at least 16 carbon
atoms, or at least 18 carbon atoms, or at least 20 carbon atoms, or
at least 24 carbon atoms, or up to 40 carbon atoms, or up to 35
carbon atoms, or up to 30 carbon atoms.
[0036] The polyolefin group may have a number-average molecular
weight Mn of at least 150, or at least 200, or at least 300, or up
to 800, or up to 600, or up to 500, or up to 400, or up to 360. In
some embodiments R.sub.1 and R.sub.2 may have different chain
lengths. In the exemplary embodiment, R.sub.1 and R.sub.2 are of
the same chain length (or have the same number of branches off the
main chain or differ by no more than .+-.1 branch). A polyolefin
group with M.sub.n of less than 500, e.g., up to about 400 is
particularly suitable as it allows the compound to provide good
detergent properties for deposit control and cleanliness without
resulting in viscosity creep or undesirable thickening of the
oil.
[0037] In one embodiment, the compound may be a mixture of
polyolefin-substituted, bridged hydroxyaromatic compounds with high
and low molecular weight polyolefin groups, respectively. The low
molecular weight polyolefin may be up to a C.sub.30 or up to a
C.sub.25 polyolefin. The high molecular weight polyolefin may be up
to a C.sub.40 or up to a C.sub.35 polyolefin. A ratio of the
compound with low molecular weight polyolefin to the compound with
high molecular weight polyolefin may be at least 50:50 by weight,
or at least 80:20, or at least 90:10.
[0038] In one embodiment, the compound is free of C.sub.8 and
higher unbranched alkyl groups.
[0039] In one embodiment, R.sub.1 and R.sub.2 are each composed
solely of carbon and hydrogen.
[0040] In one embodiment, the compound consists solely of elements
selected from the group consisting of C, H, O, S and the
counterion(s).
[0041] The compound may have a weight average molecular weight Mw
of at least 550, or at least 700, or at least 750, or at least 800
in its unsalted form. The weight average molecular weight of the
compound may be up to 5600, or up to 2800, or up to 1200, or up to
1000, or up to 950, in its unsalted form.
[0042] In one embodiment X is an alkylene, e.g., a methylene
bridge, or a sulfur bridge. In the case of an alkylene bridge, the
bridge may be up to 4 carbons in length, or up to 3 carbons in
length.
[0043] As will be appreciated, these aspects can also be used in
combinations thereof.
[0044] The salt of the compound of Formula I may be formed by
reacting a cation or source of the cation with the compound. The
compound of Formula I thus serves as the anion (or "substrate") in
the salt. The cation or source thereof reacts with one or more of
the residual OH groups to form a neutral or overbased salt of the
above-described coupled polyolefin-substituted aromatic polyol.
[0045] In one embodiment, the cation is a metallic cation. The
metallic cation may be derived from an alkaline earth metal, such
as calcium, barium or magnesium (typically calcium), or an alkali
metal, such as sodium or potassium (typically sodium). The metal
cation may have an atomic weight of at least 6 or at least 12.
[0046] Exemplary metal cations include alkali metal cations,
alkaline earth metal cations, transition metal cations, and
combinations thereof. Examples of metal cations include Li.sup.+,
Na.sup.+, K.sup.+, Rb.sup.+, Cs.sup.+, Be.sup.2+, Mg.sup.2+,
Ca.sup.2+, Sr.sup.2+, Ba.sup.2+, Sc.sup.3+, Sc.sup.2+, Sc.sup.+,
Y.sup.3+, Y.sup.2+, Y.sup.+, Ti.sup.4+, Ti.sup.3+, Ti.sup.2+,
Zr.sup.4+, Zr.sup.3+, Zr.sup.2+, Hf.sup.4+, Hf.sup.3+, V.sup.4+,
V.sup.3+, V.sup.2+, Nb.sup.4+, Nb.sup.3+, Nb.sup.2+, Ta.sup.4+,
Ta.sup.3+, Ta.sup.2+, Cr.sup.4+, Cr.sup.3+, Cr.sup.2+, Cr.sup.+,
Mo.sup.4+, Mo.sup.3+, Mo.sup.2+, Mo.sup.+, W.sup.4+, W.sup.3+,
W.sup.2+, W.sup.+, Mn.sup.4+, Mn.sup.3+, Mn.sup.2+, Mn.sup.+,
Re.sup.4+, Re.sup.3+, Re.sup.2+, Re.sup.+, Fe.sup.6+, Fe.sup.4+,
Fe.sup.3+, Fe.sup.2+, Fe.sup.+, Ru.sup.4+, Ru.sup.3+, Ru.sup.2+,
Os.sup.4+, Os.sup.3+, Os.sup.2+, Os.sup.+, Co.sup.5+, Co.sup.4+,
Co.sup.3+, Co.sup.2+, Co.sup.+Rh.sup.4+, Ru.sup.3+, Rh.sup.2+,
Rh.sup.+, 10.sup.+, Ir.sup.3+, Ir.sup.2+, Ir.sup.+, Ni.sup.3+,
Ni.sup.2+, Ni.sup.+, Pd.sup.4+, Pd.sup.2+, Pd.sup.+, Pt.sup.4+,
Pt.sup.3+, Pt.sup.2+, Pt.sup.+, Cu.sup.4+, Cu.sup.3+, Cu.sup.2+,
Cu.sup.+, Ag.sup.3+, Ag.sup.2+, Ag.sup.+, Au.sup.4+, Au.sup.3+,
Au.sup.2+, Au.sup.+, Zn.sup.2+, Zn.sup.+, Cd.sup.2+, Cd.sup.+,
Hg.sup.4+, Hg.sup.2+, Hg.sup.+, Al.sup.3+, Al.sup.2+, Al.sup.+,
Ga.sup.3+, Ga.sup.+, ln.sup.3+, ln.sup.2+, Tl.sup.3+, Tl.sup.+,
Si.sup.4+, Si.sup.3+, Si.sup.2+, Si.sup.+, Ge.sup.4+, Ge.sup.3+,
Ge.sup.2+, Ge.sup.+, Sn.sup.4+, Sn.sup.2+, Pb.sup.4+, Pb.sup.2+,
As.sup.3+, As.sup.2+, As.sup.+, Sb.sup.3+, Bi.sup.3+, Te.sup.4+,
Te.sup.2+, La.sup.3+, La.sup.2+, Ce.sup.4+, Ce.sup.3+, Ce.sup.2+,
Pr.sup.4+, Pr.sup.3+, Pr.sup.2+, Nd.sup.3+, Nd.sup.2+, Sm.sup.3+,
Sm.sup.2+, Eu.sup.3+, Eu.sup.2+, Gd.sup.3+, Gd.sup.2+, Gd.sup.+,
Tb.sup.4+, Tb.sup.3+, Tb.sup.2+, Tb.sup.+, Db.sup.3+,
Db.sup.+.sup.+, Ho.sup.3+, Er.sup.3+, Tm.sup.4+, Tm.sup.3+,
Tm.sup.2+, Yb.sup.3+, Yb.sup.2+, and Lu.sup.3+. Particularly useful
are those which form stable salts, i.e., which do not decompose by
more than a minor amount over the expected lifetime and operating
conditions of the lubricating composition.
[0047] In one embodiment, the metallic cation is derived from a
metal base such as a metal base of a hydroxide, an oxide,
carbonate, or bicarbonate. The metal base may be a hydroxide or an
oxide. For example the metallic cation may be derived from calcium
hydroxide, calcium oxide, sodium hydroxide, sodium oxide, magnesium
hydroxide, magnesium oxide, or mixture thereof.
[0048] In one embodiment, the cation is an ash-free cation. An
ash-free (ashless) organic cation is an organic ion that does not
contain ash-forming metals. In one embodiment, the compound in the
salt form has a sulfated ash of up to 0.5 wt. %, or up to 0.4 wt.
%, according to ASTM D874.
[0049] In one embodiment, the cation is a pnictogen cation. As used
herein the term "pnictogens" includes the elements in column 15 of
the periodic table. The non-metallic pnictogens include nitrogen
and phosphorus (typically nitrogen). The pnictogen cation may be
derived from a source of the cation containing a primary amine, a
secondary amine, a tertiary amine, or mixture thereof. In one
embodiment, the amine salt may be derived from a secondary or
tertiary amine.
[0050] When the cation is pnictogen cation derived from an amine or
ammonium compound, the pnictogen cation (or the amine from which it
is derived) may have molecular weight of at least 260 g/mol, or at
least 300 g/mol or at least 350 g/mol, or at least 500 g/mol.
[0051] The pnictogen cation may be derived from a mono-, di-, or
tri-substituted amine. Specific examples include primary
alkylamines, such as methylamine, ethylamine, n-propylamine,
n-butylamine, n-hexylamine, n-octylam ine, 2-ethylhexylamine,
benzylamine, 2-phenylethylamine, cocoamine, oleylamine, and
tridecylamine (CAS #86089-17-0); secondary and tertiary alkylamines
such as isopropylamine, sec-butylamine, t-butylamine,
cyclopentylamine, cyclohexylamine, and 1-phenylethylamine;
dialkylamines, such as dimethylamine, diethylamine, dipropylamine,
diisopropylamine, dibutylamine, dicyclohexylamine,
di-(2-ethylhexyl)amine, dihexylamine, ethylbutylamine,
N-ethylcyclohexylamine, and N-methylcyclohexylamine;
cycloalkylamines, such as piperidine, N-ethylpiperidine,
N,N'-dimethylpiperazine, morpholine, N-methylmorpholine,
N-ethylmorpholine, N-methylpiperidine, pyrrolidine,
N-methylpyrrolidine, and N-ethylpyrrolidine; and trialkylamines,
such as trimethylamine, triethylamine, tripropylamine,
triisopropylamine, tri-n-butylamine, trihexylamine, N,
N-dimethylbenzylamine, dimethylethylamine, dimethylisopropylamine,
dimethylbutylamine, and N,N-dimethylcyclohexylamine.
[0052] When the pnictogen cation includes at least one hydrocarbyl
group (a quaternary ammonium ion), the pnictogen cation may be an
ashless organic cation. Example ammonium cations of this type
include N-substituted long chain alkenyl succinimides and aliphatic
polyamines. N-substituted long chain alkenyl succinimides useful
herein may be derived from an aliphatic polyamine, or mixture
thereof. The aliphatic polyamine may be aliphatic polyamine such as
an ethylenepolyamine, a propylenepolyamine, a butylenepolyamine, or
mixture thereof. Examples of N-substituted long chain alkenyl
succinimides include polyisobutylene succinimide with number
average molecular weight of the polyisobutylene substituent of 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 succinim ides
can be formed, for example, from high vinylidene polyisobutylene
and maleic anhydride.
[0053] Example N-substituted long chain alkenyl succinimides useful
herein as pnictogen cations include those derived from succinimide
dispersants, which are more fully described 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, 6,165,235, 7,238,650, and EP
Patent Application 0 355 895 A.
[0054] Example aliphatic polyamines useful as the pnictogen cation
include ethylenepolyamines, propylenepolyamines,
butylenepolyamines, and mixtures thereof. Example
ethylenepolyamines include ethylenediamine, diethylenetriamine,
triethylenetetramine, tetraethylenepentamine,
pentaethylene-hexamine, polyamine still bottoms, and mixtures
thereof.
[0055] In one embodiment, the exemplary polyolefin-substituted
bridged hydroxyaromatic compound salt may be overbased, i.e.,
contain an excess of the metal cation in relation to the number of
hydroxyl groups present in the compound. There are two common
measures of basicity that are commonly used in the field of
lubricant additives: Total Base Number (TBN), as measured by ASTM
D2896, is a titration that measures both strong and weak bases,
while ASTM D4739-11 "Standard Test Method for Base Number
Determination by Potentiometric Hydrochloric Acid Titration," (BN)
is a titration that measures strong bases but does not readily
titrate weak bases, such as certain amines. TBN and BN are
expressed as an equivalent in milligrams of potash per gram of oil
(mg of KOH/g).
[0056] Total base number (TBN), as used herein, is the quantity of
acid, expressed in terms of the equivalent number of milligrams of
potassium hydroxide (meq KOH), that is required to neutralize all
basic constituents present in 1 gram of a sample of the lubricating
oil. The TBN values reported herein are determined according to
ASTM Standard D2896-15, "Standard Test Method for Base Number of
Petroleum Products by Potentiometric Perchloric Acid Titration"
(2015), ASTM International, West Conshohocken, PA, 2003
(hereinafter, "D2896"). In various aspects, the neutral salt
compound has a TBN of at least 50 mg of KOH/g, or at least 60 mg of
KOH/g on an oil-free basis. The TBN of the neutral salt may be up
to 300 mg KOH/g, or up to 250 mg KOH/g, or up to 165 mg KOH/g, on
an oil-free basis. In various aspects, the lubricating composition
containing the compound has a TBN of at least 3 mg KOH/g, or at
least 4 mg of KOH/g, or at least 6 mg of KOH/g.
[0057] The cation may serve as a basic component of the lubricating
composition which, in combination with any other basic components
of the lubricating composition, may provide the lubricating
composition with a TBN of at least 5, or at least 8, or at least
10, or at least 15, or at least 25. The cation itself may have a
TBN of at least 10 or at least or at least 15, or at least 25, or
at least 50.
[0058] B. Method of Forming the Polyolefin-Substituted Bridged
Hydroxyaromatic Compound
[0059] A bridged (e.g., sulfur-coupled or formaldehyde-coupled)
polyolefin-substituted hydroxyaromatic compound of Formula I or II
may be formed through well-known techniques.
[0060] In one embodiment, the salt of a polyolefin-substituted
hydroxyaromatic compound may be obtained/obtainable by (i) reacting
a hydroxy aromatic compound (e.g., phenol) with an branched alkene,
such as isobutylene, optionally in the presence of a catalyst, to
form a hydroxy-substituted intermediate compound, (ii) coupling the
intermediate compound, e.g., with sulfur or formaldehyde, and (to
form the salt) iii) reacting the bridged compound formed in step
(ii) with a metal base or a pnictogen base.
[0061] (i) Formation of Polyisoalkylene-Substituted Phenol
Compound
[0062] The intermediate compound may be formed by reaction of a
phenol with a poly(branched alkene). Substitution occurs primarily
at the para position, although minor amounts of ortho- and/or
meta-substitution may occur. The ratio of poly(branched alkene) to
phenol may be from 1:1 to 1:6, such as at least 1:2. An excess of
phenol helps to ensure primarily mono-substitution of the
poly(branched alkene).
[0063] For example, a polyisobutylene-substituted phenol:
##STR00003##
[0064] where q is, for example, from 5 to 10, or up to 7, or at
least 6, on average, may be formed by reacting phenol with a
polyolefin (e.g., polyisobutylene), optionally in the presence of a
base catalyst. Typically the reaction occurs in the presence of a
base catalyst.
[0065] Example catalysts include Lewis acid catalysts, solid acid
catalysts, trifluoromethanesulfonic acid, and acidic molecular
sieve catalysts. Suitable Lewis acid catalysts include aluminum
trichloride, aluminum tribromide, aluminum triiodide, boron
trifluoride, boron tribromide, boron triiodide and the like.
Suitable solid acidic catalysts include zeolites, acid clays,
and/or silica-alumina.
##STR00004##
[0066] The process to prepare the intermediate may be carried out a
reaction temperature of 1.degree. C. to 52.degree. C., or 5.degree.
C. to 20.degree. C., or 10.degree. C. to 15.degree. C. The
formation of the intermediate may be performed in the presence or
absence of solvent. The solvent may include a hydrocarbon such as
hexane, toluene, xylene, diluent oil, cyclohexane, or mixture
thereof. In one embodiment the process to prepare the intermediate
is performed in the presence of a solvent. Optionally the solvent
is removed before sulfurizing and/or reacting of the intermediate
with the metal base. The reaction mixture may then be neutralized
with calcium hydroxide, followed by addition of diatomaceous earth
and ammonia hydroxide to remove residual catalyst. The reaction
mixture is filtered and the filtrate heated under vacuum to remove
volatiles by distillation.
[0067] In one embodiment, the polyisobutylene is prepared in the
absence of a chain transfer agent and has a polydispersity greater
than 1.5.
[0068] ii) Coupling the Intermediate Compound with Sulfur or
Aldehyde and Formation of Salt
[0069] Sulfurization may be performed by contacting the
intermediate compound with a sulfur source which introduces S.sub.x
bridging groups between the polyolefin-substituted phenol compound
in the presence of a base. Reaction Scheme 2 illustrates the
reaction.
##STR00005##
[0070] Any suitable sulfur source can be used such as, for example,
elemental sulfur or a halide thereof such as sulfur monochloride,
sulfur dichloride, hydrogen sulfide, sulfur dioxide, or a sodium
sulfide hydrate. The sulfur can be employed either as molten sulfur
or as a solid (e.g., powder or particulate) or as a solid
suspension in a compatible hydrocarbon liquid, such as ethylene
glycol.
[0071] Sulfur may be employed at from 0.5 to 4 moles per mole of
the intermediate compound in the reaction system. In one
embodiment, sulfur is employed at from 0.8 to 2 moles per mole of
the intermediate compound.
[0072] The temperature range in which the sulfurization reaction is
carried out is generally 80-250.degree. C., e.g., 100-220.degree.
C. The reaction can be conducted under atmospheric pressure (or
slightly lower) or at elevated pressures. During sulfurization a
significant amount of by-product hydrogen sulfide gas is evolved.
In one embodiment the reaction is carried out under vacuum to
facilitate the H.sub.2S elimination.
[0073] Other sulfurization techniques which may be adapted to use
herein are described, for example, in U.S. Pat. No. 2,680,096, to
Walker et al., issued Jun. 1, 1954; U.S. Pat. No. 3,372,116, to
Meinhardt, issued Mar. 6, 1968; U.S. Pat. No. 3,036,971, to Otto,
issued May 29, 1962, U.S. Pat. No. 7,435,709, to Stonebraker, et
al., issued Oct. 14, 2008, U.S. Pat. No. 8,772,209 to Mahieux, et
al., issued Jul. 8, 2014, U.S. Pat. No. 9,062,271 to Jukes, et al.,
issued Jun. 23, 2015, and U.S. Pub. No. U.S. Pub. No. 20150045269,
published Feb. 12, 2015, to Walker, et al. The 20150045269
publication, for example, describes preparation of a sulfurized
alkaline earth metal (e.g., calcium) dodecylphenate by reacting
dodecylphenol with calcium hydroxide or calcium oxide and an
alkylene glycol. The reaction product is reacted with sulfur.
[0074] The sulfurization reaction is carried out in the presence of
a base, which in one embodiment is the cation source, as described
below.
[0075] In other embodiments the intermediate compound is contacted
with formaldehyde or other aldehyde, which introduces alkylene
bridging groups between polyolefin-substituted phenols in the
presence of a base.
[0076] In general, sulfur coupling produces a more acidic compound
which makes over-basing easier.
[0077] Formation of the salt may be performed by reaction of the
sulfurized polyolefin-substituted compound or other sulfurized
intermediate compound or alkylene bridged polyolefin-substituted
compound with a basic metal compound which serves as a cation
source, such as lime (calcium hydroxide/oxide) or magnesium oxide,
or with a pnictogen base, in approximately equimolar amounts, with
respect to the OH groups in the intermediate compound, optionally
in the presence of a solvent.
[0078] Suitable basic metal compounds include hydroxides, oxides
and alkoxides of the metal such as (1) an alkali metal salt derived
from a metal base selected from an alkali hydroxide, alkali oxide
or an alkali alkoxide, or (2) an alkaline earth metal salt derived
from a metal base selected from an alkaline earth hydroxide,
alkaline earth oxide or alkaline earth alkoxide. Representative
examples of metal basic compounds with hydroxide functionality
include lithium hydroxide, potassium hydroxide, sodium hydroxide,
magnesium hydroxide, calcium hydroxide, barium hydroxide, aluminum
hydroxide and the like. Representative examples of metal basic
compounds with oxide functionality include lithium oxide, magnesium
oxide, calcium oxide, barium oxide and the like. In one embodiment,
the alkaline earth metal base is slaked lime (calcium
hydroxide).
[0079] The pnictogen cation may be derived/derivable from a
compound with a primary amine, a secondary amine, a tertiary amine,
or mixtures thereof. Typically the amine salt may be derived from a
secondary or a tertiary amine.
[0080] The amine that can be used to prepare a pnictogen may be any
amine capable of salting with a protic acid. The amine may be an
alkyl amine, typically a di- or tri-alkyl amine. The alkyl amine
may have alkyl groups having 1 to 30, or 2 to 20, or 3 to 10 carbon
atoms. Examples of a dialkyl amines include diethylamine,
dipropylamine, dibutylamine, dipentylamine, dihexylamine,
di-(2-ethylhexyl)amine, di-decylamine, di-dodecylamine,
di-stearylamine, di-oleylamine, di-eicosylamine, or mixtures
thereof. Examples of a trialkyl amine include triethylamine,
tripropylamine, tributylamine, tripentylamine, trihexylamine,
tri-(2-ethylhexyl)amine, tri-decylamine, tri-dodecylamine,
tri-stearylamine, tri-oleylamine, tri-eicosylamine, and mixtures
thereof.
[0081] The amine may also be a tertiary-aliphatic primary amine.
The aliphatic group in this case may be an alkyl group containing 2
to 30, or 6 to 26, or 8 to 24 carbon atoms. Tertiary alkyl amines
include monoamines such as tert-butylamine, tert-hexylamine,
1-methyl-1-amino-cyclohexane, tert-octylamine, tert-decylamine,
tert-dodecylamine, tert-tetradecylamine, tert-hexadecylamine,
tert-octadecylamine, tert-tetracosanylamine, and
tert-octacosanylamine.
[0082] In one embodiment, the pnictogen base includes a phosphorus
acid amine salt which includes an amine with Cii to C.sub.22
tertiary alkyl primary groups, or mixtures thereof.
[0083] In one embodiment the amine salt may be in the form of a
quaternary ammonium salt. Examples of quaternary ammonium salts
containing a hydroxyalkyl group, and methods for their synthesis,
are disclosed in U.S. Pat No. 3,962,104. In certain embodiments,
the quaternary ammonium compound is derived from a monoamine by
means of alkylation, i.e., from a tertiary amine having only a
single amino group, that is, having no additional amine nitrogen
atoms in any of the three hydrocarbyl groups or substituted
hydrocarbyl groups attached to the tertiary amine nitrogen. In
certain embodiments there are no additional amine nitrogen atoms in
any of the hydrocarbyl groups or substituted hydrocarbyl groups
attached to the central nitrogen in the quaternary ammonium ion.
The tetraalkylammonium hydroxide may contain alkyl groups having 1
to 30, or 2 to 20, or 3 to 10 carbon atoms. The tetraalkylammonium
hydroxide may include tetrapropylammonium hydroxide,
tetrabutylammonium hydroxide, tetra-pentylammonium hydroxide,
tetrahexylammonium hydroxide, tetra-2-ethylhexyl-ammonium
hydroxide, tetradecylammonium hydroxide, or a mixture thereof.
[0084] The amine may be quaternized with a quaternizing agent, or
mixture thereof.
[0085] The pnictogen base may include an aminoalkyl substituted
heterocyclic compound, such as 1-(3-aminopropyl)imidazole,
4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine,
3,3-diamino-N-methyldipropylamine, and
3,3-aminobis(N,N-dimethylpropylamine).
[0086] Other examples of quaternary ammonium salts and methods for
preparing the same are described in U.S. Pat. Nos. 3,778,371,
4,171,959, 4,253,980, 4,326,973, 4,338,206, and 5,254,138.
[0087] When the amine salt is derived from an aromatic amine, the
aromatic amine may form an ion such as a pyridinium ion, or an
imidazolium ion. Certain quaternary phosphonium salts may be
prepared by the reaction of phosphine with aldehydes and a halide
e.g., tetrakis(hydroxymethyl)phosphonium halide (typically
chloride).
[0088] A quaternary pnictogen halide compound may be a commercially
available material, or it may be prepared by reaction of a tertiary
amine with a hydrocarbyl halide, by known techniques. This reaction
may be performed in a separate vessel or in the same vessel in
which it is subsequently (or simultaneously) reacted with the
oil-soluble acidic compound, which may be converted previously (or
simultaneously) into its metal neutralized form.
[0089] Neutralization of the sulfurized intermediate compound may
be carried out in a continuous or batch process by any method known
to a person skilled in the art. In general, neutralization can be
carried out by contacting the sulfurized or intermediate compound
with a metal or pnictogen base under reactive conditions, e.g., in
an inert-compatible liquid hydrocarbon diluent. If desired, the
reaction can be conducted under an inert gas, such as nitrogen. The
metal or pnictogen base may be added either in a single addition or
in a plurality of additions at intermediate points during the
reaction.
[0090] Neutralization may be conducted in a suitable solvent or
diluent oil, such as toluene, xylene and commonly with a promoter
such as an alcohol, e.g., a C.sub.1 to C.sub.16 alcohol, such as
methanol, decyl alcohol, or 2-ethylhexanol; a diol, e.g., C.sub.2
to C.sub.4 alkylene glycols, such as ethylene glycol; and/or
carboxylic acids. Suitable diluent oils include naphthenic oils and
mixed oils, e.g., paraffinic. The quantity of solvent or diluent
oil used may be such that the amount of solvent or oil in the final
product constitutes from 15% to 65% by weight of the final product,
such as from 25% to 50%.
[0091] The neutralization reaction may be conducted at temperatures
above room temperature (20.degree. C.). In general, neutralization
can be carried out at a temperature of between 150-200.degree. C.
The neutralization reaction itself may take place for over 5 to 60
minutes up to 9 hours, for example, 7 hours.
[0092] In another embodiment, the salt of the
polyolefin-substituted bridged hydroxyaromatic compound can be
prepared in a one-pot method. In this method, the intermediate
compound is combined with diluent oil and ethylene glycol and
heated while stirring. A metal or pnictogen base, such as hydrated
lime, is added to the heated reaction mixture, e.g., in several
portions. Sulfur is added to the reaction mixture, and optionally
additional metal or pnictogen base is added and the mixture
stirred. The reaction mixture may be vacuum stripped to remove
excess solvent.
[0093] In one embodiment, the exemplary polyolefin-substituted
bridged hydroxyaromatic compound may be overbased. Overbasing can
be carried out either during or after one of the sulfurization
and/or neutralization steps. Alternatively, sulfurization,
neutralization and overbasing can be carried out simultaneously. In
general, the overbasing is carried out by reaction of the salt of
the sulfur-coupled polyolefin-substituted aromatic polyol with an
acidic overbasing compound, such as carbon dioxide or boric acid.
In one embodiment, an overbasing process is by way of carbonation,
i.e., a reaction with carbon dioxide. Such carbonation can be
conveniently effected by addition of solvents such as aromatic
solvents, alcohols or a polyols, typically an alkylene diol, e.g.,
ethylene glycol. Conveniently, the reaction is conducted by
bubbling of gaseous carbon dioxide through the reaction mixture,
optionally in the presence of sulfonic acid. Excess solvents and
any water formed during the overbasing reaction can be conveniently
removed by distillation either during or after the reaction.
[0094] In one embodiment, the overbasing reaction is carried out in
a reactor by reacting the salt of the polyolefin-substituted
bridged hydroxyaromatic compound with a source of an alkaline earth
metal such as lime (i.e., an alkaline earth metal hydroxide) in the
presence of carbon dioxide, and optionally in the presence of an
aromatic solvent (e.g., xylene), and/or a hydrocarbyl alcohol, such
as methanol. The reaction may be conducted by bubbling gaseous
carbon dioxide through the reaction mixture. The carbon dioxide is
introduced over a period of 1 hour to 3 hours, at a temperature
ranging from 150-200.degree. C. The degree of overbasing may be
controlled by the quantity of the source of an alkaline earth
metal, carbon dioxide and the reactants added to the reaction
mixture and the reaction conditions used during the carbonation
process.
[0095] In another embodiment, the overbasing reaction can be
carried out at from 140-180.degree. C. in the presence of a polyol,
typically an alkylene diol, e.g., ethylene glycol, and/or alkanols,
e.g., C.sub.6 to C.sub.16 alkanol(s), such as decyl alcohols or
2-ethyl hexanol. Excess solvent and any water formed during the
overbasing reaction can be conveniently removed by distillation
either during or after the reaction.
[0096] Methods for forming overbased detergents useful herein are
described, for example, in U.S. Pat. Nos. 5,259,966, 6,015,778,
5,534,168, and 6,268,318, and U.S. Pub. No. 2013/0203639.
[0097] The resulting overbased salt of the polyolefin-substituted
bridged hydroxyaromatic compound may contain some amount of
unsulfurized hydroxy-substituted intermediate compound and/or its
unsulfurized metal salt.
[0098] The composition containing the overbased salt of the
polyolefin-substituted bridged hydroxyaromatic compound may be
sparged, e.g., by bubbling gas, such as air or nitrogen, at a
temperature ranging from 190-250.degree. C. through the
composition. The sparging results in removing substantially all of
the unsulfurized hydroxy-substituted intermediate compound and
salts thereof to provide a composition substantially free of the
unsulfurized hydroxy-substituted intermediate compound and
unsulfurized salts thereof. The term "substantially free" as used
herein means less than 1.5 wt. %, or less than 1 wt. %, or less
than 0.3 wt. % of these unsulfurized compounds, such as 0.1-0.3 wt.
%, or less.
[0099] In one embodiment, the salt of the polyolefin-substituted
bridged hydroxyaromatic compound does not contain any sulfonate
functional groups.
[0100] In one embodiment, the salt of the polyolefin-substituted
bridged hydroxyaromatic compound does not contain any phosphate
functional groups.
[0101] In one embodiment, the salt of the polyolefin-substituted
bridged hydroxyaromatic compound does not contain any borate
functional groups.
[0102] In another embodiment, the salt of the
polyolefin-substituted bridged hydroxyaromatic compound does
contain a borate functional group.
[0103] The salts described above can be boronated by processes
known to those skilled in the art. Boration can be accomplished
either prior to, or after, the overbasing step. The boration can be
accomplished by a number of boronating agents, such as boric acid,
metaboric acid, orthoboric acid, alkyl borates, boron halides,
polymers of boron, esters of boron and similar materials. When
present, the boron content of the salt may be 0.1 wt. % to 5 wt. %,
or 1 wt. % to 5 wt. %, or 2 wt. % to 4 wt. %.
[0104] The salt of the polyolefin-substituted bridged
hydroxyaromatic compound, in one embodiment, may be formed from an
anion composed of carbon, hydrogen, oxygen, boron and nitrogen; and
a metallic cation.
[0105] In one embodiment, the salt of the polyolefin-substituted
bridged hydroxyaromatic compound may comprise or consist of an
anion composed of carbon, hydrogen, oxygen and optionally nitrogen;
and a metallic cation, such as a calcium, magnesium or sodium
cation.
[0106] Examples of suitable ethylenically unsaturated esters of
boron include(meth)acrylates, fumarates and maleates which are
derived from saturated alcohols, such as 2-ethylhexyl
(meth)acrylate, heptyl (meth)acrylate, 2-tert-butylheptyl
(meth)acrylate, octyl (meth)acrylate, 3-isopropylheptyl
(meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl
(meth)acrylate; and the corresponding fumarates and maleates. The
expression "(meth)acrylates" encompasses methacrylates and
acrylates and also mixtures of the two.
Lubricating Compositions
[0107] The exemplary polyolefin-substituted bridged hydroxyaromatic
compound or salt thereof may be present in a lubricating
composition at a concentration of at least 0.1 wt. % and may be up
to 20 wt. %. For example, the concentration of the compound may be
at least 0.25 wt. %, or at least 0.5 wt. %, or at least 1 wt. %, or
at least 5 wt. %, or at least 10 wt. %, or at least 15 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.
[0108] In addition to the polyolefin-substituted bridged
hydroxyaromatic compound or metal salt thereof, the exemplary
lubricating composition includes an oil of lubricating viscosity
and optionally one or more additional performance additives suited
to providing the performance properties of a fully formulated
lubricating composition, e.g., a marine diesel cylinder lubricant.
Examples of these additional performance additives include
(overbased) detergents, viscosity modifiers, friction modifiers,
antioxidants, dispersants, antiwear/antiscuffing agents, metal
deactivators, extreme pressure agents, foam inhibitors,
demulsifiers, pour point depressants, corrosion inhibitors, seal
swelling agents, and the like, which may be used singly or in
combination.
Oil of Lubricating Viscosity
[0109] 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. % of the lubricating composition.
[0110] 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 WO2008/147704 and US 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.
[0111] 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 .gtoreq.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).
Engine Lubricating Compositions
[0112] For lubricating compositions useful in engines, the oil of
lubricating viscosity may have a kinematic viscosity of up to 30
mm.sup.2/s or up to 25 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 15 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.
[0113] The viscosity grade of cylinder oils suited to use in
2-stroke marine diesel engines 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.
[0114] 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).
[0115] 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.
[0116] 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.
[0117] 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).
[0118] Synthetic ester base oils may be present in the lubricating
composition of the invention 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 of the
invention 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.
[0119] 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.
[0120] 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 amino-carboxylate compound
and the other performance additives.
Engine Lubricating Compositions--Other Additives
[0121] Engine lubricating compositions in accordance with the
present invention may also contain other additives that provide
particular performance benefits to the engine lubricant. These
additional additives may include detergents, antioxidants,
dispersants, anti-wear agents, oil soluble titanium compounds,
extreme pressure agents, foam inhibitors, viscosity modifiers,
corrosion inhibitors, metal deactivators, pour point depressants,
friction modifiers, demulsifiers, and seal swell agents. These
additional components are described in more detail below.
[0122] The lubricating composition optionally further includes at
least one detergent, other than the exemplary compound. Exemplary
detergents useful herein include overbased metal-containing
detergents. The metal of the metal-containing detergent may be
zinc, sodium, calcium, barium, or magnesium. 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.
[0123] 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.
[0124] Example overbased metal-containing detergents include zinc,
sodium, calcium 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).
[0125] 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.
[0126] Typically, an overbased metal-containing detergent may be a
zinc, sodium, calcium 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).
[0127] 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.
[0128] 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.
[0129] In one embodiment, the alkylbenzene sulfonate detergent may
be a branched alkylbenzene sulfonate, a linear alkylbenzene
sulfonate, or mixtures thereof.
[0130] 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.
[0131] The lubricating composition may include at least 0.01 wt. %
or at least 0.1 wt. % of the detergent other than the exemplary
compound, and in some embodiments, up to 2 wt. %, or up to 1 wt. %
detergent.
[0132] The lubricating composition optionally further includes at
least one antioxidant. Exemplary antioxidants useful herein include
phenolic and aminic antioxidants, such as diarylamines, alkylated
diarylamines, hindered phenols, and mixtures thereof. The
diarylamine or alkylated diarylamine may be a
phenyl-.alpha.-naphthylamine (PANA), an alkylated diphenylamine, an
alkylated phenylnapthylamine, or mixture thereof. Example alkylated
diphenylamines include dinonyl diphenylamine, nonyl diphenylamine,
octyl diphenylamine, dioctyl diphenylamine, didecyl diphenylamine,
decyl diphenylamine, and mixtures thereof. Example alkylated
diarylamines include octyl, dioctyl, nonyl, dinonyl, decyl and
didecyl phenylnapthylamines. Hindered phenol 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. Examples of
suitable hindered phenol antioxidants include
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, and
4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered
phenol antioxidant may be an ester, such as those described in U.S.
Pat. No. 6,559,105. One such hindered phenol ester is sold as
Irganox.TM. L-135, obtainable from Ciba.
[0133] 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. % antioxidant.
[0134] The lubricating composition optionally further includes at
least one dispersant, other than the exemplary compound. Exemplary
dispersants include succinimide dispersants, Mannich dispersants,
succinimide dispersants, and polyolefin succinic acid esters,
amides, and ester-amides, and mixtures thereof. The succinimide
dispersant, where present, may be as described above for the
succinim ides described as useful for cation M.
[0135] 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.
[0136] 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.
[0137] 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 350 to 5000, or
550 to 3000 or 750 to 2500. 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.
[0138] The succinimide dispersant may comprise a polyisobutylene
succinimide, wherein the polyisobutylene from which polyisobutylene
succinimide is derived has a number average molecular weight of 350
to 5000, or 750 to 2500.
[0139] 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.
[0140] 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. % of other dispersant(s), 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.
[0141] 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), 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 is disclosed in US Pub. No.
20050198894.
[0142] The lubricating composition may in one embodiment further
include a phosphorus-containing antiwear agent. Example
phosphorus-containing antiwear agents include zinc
dialkyldithiophosphates, phosphites, phosphates, phosphonates, and
ammonium phosphate salts, and mixtures thereof.
[0143] 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.
[0144] 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.
[0145] When present in the lubricating composition, the amount of
oil-soluble titanium compounds is included as part of the antiwear
agent.
[0146] 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 dibenzyldisulfide,
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 dihydrocarbon and trihydrocarbon 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 P205; and mixtures thereof.
Some useful extreme pressure agents are described in U.S. Pat. No.
3,197,405.
[0147] 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.
[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] 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. PMA's 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 PMA's 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.
[0150] 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.
[0151] 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.
[0152] 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 polyacrylam ides.
[0153] 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. 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.
[0154] In one embodiment, the ash-free friction modifier may be
represented by the formula:
##STR00006##
[0155] 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
--R.sup.24--O--R.sup.25--, >CH.sub.2, >CHR.sup.26,
>CR.sup.26R.sup.27, >C(OH)(CO.sub.2R.sup.22),
>C(CO.sub.2R.sup.22).sup.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, typically 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.
[0156] 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-oleyltartrate, oleyltartrimide, and oleyl maleim ide.
[0157] 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.
[0158] 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.
[0159] 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.
[0160] The amount of the ash-free friction modifier in a lubricant
may be 0.1 to 3 percent by weight (or 0.12 to 1.2 or 0.15 to 0.8
percent by weight). 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.
[0161] Molybdenum compounds are also known as friction modifiers.
The exemplary molybdenum compound does not contain dithiocarbamate
moieties or ligands.
[0162] 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:
##STR00007##
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.
[0163] 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-dococylmethylamine, N-beef tallow alkyl methylamine, N-hardened
beef tallow alkyl methylamine, N-soybean oil alkyl methylamine,
ditetradecylamine, dipentadecylamine, dihexadecylamine,
distearylamine, dioleylamine, didococylamine,
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.
[0164] 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 and 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.
[0165] Other organomolybdenum compounds of the invention 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.
[0166] 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.
[0167] Examples of some mono-alkylated alkylene diamines that may
be used include methylam inopropylamine, methylam inoethylamine,
butylam inopropylamine, butylam ino-ethylamine, octylam
inopropylamine, octylam inoethylamine, dodecylaam inopropylaamine,
dodecylam inoethylamine, hexadecylam inopropylamine, hexadecylam
inoethylamine, 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.
[0168] 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).
[0169] 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.
[0170] 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.
[0171] Demulsifiers useful herein include trialkyl phosphates, and
various polymers and copolymers of ethylene glycol, ethylene oxide,
propylene oxide, and mixtures thereof.
[0172] Seal swell agents useful herein include sulfolene
derivatives such as Exxon Necton-37.TM. (FN 1380) and Exxon Mineral
Seal Oil.TM. (FN 3200).
Example Engine Lubricating Compositions
[0173] An engine lubricant in different embodiments may have a
composition as illustrated in Table 1. All additives are expressed
on an oil-free basis.
TABLE-US-00001 TABLE 1 Example Lubricating Compositions Embodiments
(wt. %) Additive A B C polyolefin-substituted bridged 0.1 to
20.sup. 0.5 to 10 1 to 5 hydroxyaromatic compound or salt thereof
Overbased Sulfonate Detergent 0 to 9 0.3 to 8 1 to 5 Phenol-based
detergent 0 to 10 0.5 to 7 0.75 to 5 (Borated) Dispersant 0 to 12
0.5 to 8 1 to 5 Antioxidant 0 to 13 0.1 to 10 0.5 to 5.sup.
Antiwear Agent 0 to 15 0.1 to 10 0.3 to 5.sup. Corrosion Inhibitor
0 to 2 0.1 to 1 0.2 to 0.5 Friction Modifier 0 to 6 0.05 to 4 0.1
to 2.sup. Viscosity Modifier 0 to 10 0.5 to 8 1 to 6 Other
Performance Additives 0 to 10 .sup. 0 to 8 0 to 6 Oil of
Lubricating Viscosity Balance to 100% .sup.
Use of the Lubricating Composition
[0174] The end use of the engine lubricating composition described
herein includes use as a cylinder lubricant for an internal
combustion engine, such as a 2-stroke marine diesel engine, but may
also find use as an engine oil for a two or 4-stroke engine in a
passenger car, heavy, medium and light duty diesel vehicles, 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.
[0175] An exemplary method of lubricating a mechanical device, such
as a cylinder of an internal combustion engine, includes supplying
the exemplary lubricating composition to the device.
[0176] 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, where it may be combusted with the fuel.
[0177] The internal combustion engine may be a diesel-fueled
engine, such as a 2-stroke marine diesel engine, or a gasoline
fueled engine, a natural gas fueled engine, a mixed
gasoline/alcohol fueled engine, or a biodiesel fueled engine. The
internal combustion engine may be a 2-stroke or 4-stroke
engine.
[0178] 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. %.
Driveline Lubricating Compositions
[0179] In one embodiment, the lubricating composition in accordance
with the present invention is for use in a driveline device.
Lubricating compositions for driveline devices may include the
polyolefin-substituted bridged hydroxyaromatic compound or salt
thereof as described herein in an oil of lubricating viscosisty,
optionally in the presence of other performance additives as
described below.
[0180] The lubricant composition may further include other
additives. In one embodiment the invention provides a lubricant
composition further comprising at least one of a dispersant, an
antiwear agent, a dispersant viscosity modifier, a friction
modifier, a viscosity modifier, an antioxidant, an overbased
detergent (other than the polyolefin-substituted bridged
hydroxyaromatic compound or salt thereof as described above), a
foam inhibitor, a demulsifier, a pour point depressant or mixtures
thereof. In one embodiment the invention provides a lubricant
composition further comprising at least one of a polyisobutylene
succinimide dispersant, an antiwear agent, a corrosion inhibitor, a
dispersant viscosity modifier, a friction modifier, a viscosity
modifier (typically a polymethacrylate having linear, comb or star
architecture), an antioxidant (including phenolic and aminic
antioxidants), an overbased detergent (including overbased
sulphonates, phenates, and salicylates other than the
polyolefin-substituted bridged hydroxyaromatic compound or salt
thereof described above), or mixtures thereof.
[0181] The amount of each other performance additive and chemistry
of the other performance additive will depend on type of driveline
device being lubricated. When present common additives across each
driveline lubricant includes viscosity modifiers, dispersants, foam
inhibitors, corrosion inhibitors, pour point depressants,
demulsifiers, and seal swell agents.
[0182] Viscosity modifiers may be included in the lubricant
composition. Viscosity modifiers are usually polymers, including
polyisobutenes, polymethacrylic acid esters, diene polymers,
polyalkylstyrenes, esterified styrene-maleic anhydride copolymers,
alkenylarene-conjugated diene copolymers, and polyolefins.
Multifunctional viscosity improvers, which also have dispersant
and/or antioxidancy properties are known and may optionally be
used. The amount of viscosity modifier may range from 0.1 to 70 wt
%, or 1 to 50 wt %, or 2 to 40 wt %. Typically the viscosity
modifier may be a polymethacrylate, or mixtures thereof.
[0183] The lubricant may comprise a dispersant, which may be a
nitrogen-containing dispersants, for example a hydrocarbyl
substituted nitrogen containing additive. Suitable hydrocarbyl
substituted nitrogen containing additives include ashless
dispersants and polymeric dispersants. Ashless dispersants are
so-named because, as supplied, they do not contain metal and thus
do not normally contribute to sulfated ash when added to a
lubricant. However they may, of course, interact with ambient
metals once they are added to a lubricant which includes
metal-containing species. Ashless dispersants are characterized by
a polar group attached to a relatively high molecular weight
hydrocarbon chain. Examples of such materials include succinimide
dispersants, Mannich dispersants.
[0184] The dispersant may be post-treated with other reagents, or
not post-treated. The dispersant may be post-treated with urea,
thiourea, dimercaptothiadiazoles, carbon disulphide, aldehydes,
ketones, carboxylic acids, hydrocarbon-substituted succinic
anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus
compounds. Typically a succinimide dispersant may optionally be
post-treated by conventional methods by a reaction with any of a
variety of other agents.
[0185] The polyamine may be an alkylenepolyamine. The
alkylenepolyamine may include an ethylenepolyamine, a
propylenepolyamine, a butylenepolyamine, or mixtures thereof.
Examples of propylenepolyamine include propylenediamine,
dipropylenetriamine and mixtures thereof.
[0186] In one embodiment the polyamine is chosen from
ethylenediamine, diethylenetriamine, triethylenetetramine,
tetraethylenepentamine, pentaethylenehexamine, polyamine still
bottoms and mixtures thereof.
[0187] In another embodiment, the lubricating composition may have
an antiwear additive comprising a phosphate amine salt. The
C.sub.2-C.sub.18 (or C.sub.2 to C.sub.8 or C.sub.16-C.sub.18) di-
or tri-hydrocarbyl phosphite, or mixtures thereof may be
represented by the formula:
##STR00008##
wherein at least one of R.sup.6, R.sup.7 and R.sup.8 may be a
hydrocarbyl group containing at least 4 carbon atoms and the other
may be hydrogen or a hydrocarbyl group. In one embodiment R.sup.6,
R.sup.7 and R.sup.8 are all hydrocarbyl groups. The hydrocarbyl
groups may be alkyl, cycloalkyl, aryl, acyclic or mixtures thereof.
In the formula with all three groups R.sup.6, R.sup.7 and R.sup.8,
the compound may be a tri-hydrocarbyl substituted phosphite i.e.,
R.sup.6, R.sup.7 and R.sup.8 are all hydrocarbyl groups and in some
embodiments may be alkyl groups. Typically the di- or
tri-hydrocarbyl phosphite comprises dibutyl phosphite or oleyl
phosphite.
[0188] Foam inhibitors that may be useful in the compositions
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.
[0189] Pour point depressants that may be useful in the
compositions include polyalphaolefins, esters of maleic
anhydride-styrene copolymers, poly(meth)acrylates, polyacrylates or
polyacrylam ides.
[0190] Demulsifiers include trialkyl phosphates, and various
polymers and copolymers of ethylene glycol, ethylene oxide,
propylene oxide, or mixtures thereof.
[0191] Seal swell agents include sulpholene derivatives Exxon
Necton-37.TM. (FN 1380) and Exxon Mineral Seal Oil.TM. (FN
3200).
Manual Transmission Lubricant
[0192] In one embodiment the invention provides a lubricant
composition comprising:
[0193] an oil of lubricating viscosity,
[0194] a thiadiazole (typically present at 0.05 to 1 wt %, or 0.07
to 0.7 wt %, or 0.1 to 0.3 wt %, or 0.15 to 0.25 wt %),
[0195] a dispersant (typically present at 0.1 to 5 wt %, or 0.3 to
4 wt %, or 1 to 3 wt %, or 0.1 to 3 wt %),
[0196] a phosphorus-containing antiwear agent chosen from (i) a
non-ionic phosphorus compound, which may be a hydrocarbyl
phosphite; or (ii) an amine salt of a phosphorus compound,
[0197] from about 0.1 to about 2 wt % of a detergent, typically
present in an amount to deliver 110 to 700 ppm, 130 to 600 ppm, 150
to 500 ppm or 160 to 400 ppm calcium; and wherein from about 0.01
to about 2 wt %, or from about 0.1 to about 1.75 wt %, or about 0.2
to about 1.5 wt % of the detergent comprises the
polyolefin-substituted bridged hydroxyaromatic compound or salt
thereof described herein.
[0198] The manual transmission may have synchromesh, or in another
embodiment the manual transmission does not have a synchromesh. The
synchromesh may be composed of aluminum, steel, bronze, molybdenum,
brass (sintered or non-sintered), carbon in the form of fibers,
graphitic material (optionally in combination with a cellulosic
material), or a cellulosic material, or a phenolic resin.
[0199] In one embodiment the lubricant may comprise 0.03 to 1.0 wt
%, or 0.1 to 0.6 wt %, or 0.2 to 0.5 wt % of calcium.
[0200] The detergent may be calcium or magnesium based, and the
detergent may have at least 200 TBN, or 250 to 1000, or 450 to 900
or 650 to 800 mg KOH/g on an oil free basis. Typically the
detergent is a calcium based detergent.
[0201] The lubricant may have 100 to 2000ppm, 150 to 1500ppm, 200
to 1000, or 250 to 800ppm, or 500 to 875 ppm of phosphorus
delivered by an antiwear agent i.e., delivered by zinc dialkyl
dithiophosphate or another phosphorus-containing antiwear
agent.
[0202] In one embodiment the invention provides a method of
lubricating a manual transmission comprising supplying to the
manual transmission a lubricant composition comprising:
[0203] an oil of lubricating viscosity,
[0204] a thiadiazole (typically present at 0.05 to 1 wt %, or 0.07
to 0.7 wt %, or 0.1 to 0.3 wt %, or 0.15 to 0.25 wt %),
[0205] a dispersant (typically present at 0.1 to 5 wt %, or 0.3 to
4 wt %, or 1 to 3 wt %, or 0.1 to 3 wt %),
[0206] a phosphorus-containing antiwear agent chosen from (i) a
non-ionic phosphorus compound, which may be a hydrocarbyl
phosphite; or (ii) an amine salt of a phosphorus compound,
[0207] from about 0.1 to about 5 wt % of a detergent, typically
present in an amount to deliver 110 to 700ppm, 130 to 600ppm, 150
to 500ppm or 160 to 400ppm calcium; and wherein from about 0.01 to
about 2 wt %, or from about 0.1 to about 1.75 wt %, or about 0.2 to
about 1.5 wt % of the detergent comprises the
polyolefin-substituted bridged hydroxyaromatic compound or salt
thereof described herein.
[0208] The thiadiazole compound may include mono- or di-hydrocarbyl
substituted 2,5-dimercapto-1,3,4-thiadiazole compounds. Examples of
a thiadiazole include 2,5-dimercapto-1,3,4-thiadiazole, or
oligomers thereof, a hydrocarbyl-substituted
2,5-dimercapto-1,3,4-thiadiazole, a hydrocarbylthio-substituted
2,5-dimercapto-1,3,4-thiadiazole, or oligomers thereof. The
oligomers of hydrocarbyl-substituted
2,5-dimercapto-1,3,4-thiadiazole typically form by forming a
sulphur-sulphur bond between 2,5-dimercapto-1,3,4-thiadiazole units
to form oligomers of two or more of said thiadiazole units. These
thiadiazole compounds may also be used in the post treatment of
dispersants as mentioned below in the formation of a
dimercaptothiadiazole derivative of a polyisobutylene
succinimide.
[0209] Examples of a suitable thiadiazole compound include at least
one of a dimercaptothiadiazole, 2,5-dimercapto-[1,3,4]-thiadiazole,
3,5-dimercapto-[1,2,4]-thiadiazole,
3,4-dimercapto-[1,2,5]-thiadiazole, or
4-5-dimercapto-[1,2,3]-thiadiazole. Typically readily available
materials such as 2,5-dimercapto-1,3,4-thiadiazole or a
hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole or a
hydrocarbylthio-substituted 2,5-dimercapto-1,3,4-thiadiazole are
commonly utilised.
[0210] The lubricant may contain a detergent aside from the
aklylphenol detergent described above. The detergent may be neutral
or overbased, typically overbased. The detergent may be calcium or
magnesium containing, typically calcium containing.
[0211] Another component of the disclosed lubricant can be an
overbased, carbonated calcium or magnesium arylsulphonate detergent
having a total base number (TBN) of at least 640 as calculated on
an oil-free basis, or a mixture of such detergents. Detergents in
general are typically overbased materials, otherwise referred to as
overbased or superbased salts, which are generally homogeneous
Newtonian systems having by a metal content in excess of that which
would be present for neutralization according to the stoichiometry
of the metal and the detergent anion. The amount of excess metal is
commonly expressed in terms of metal ratio, that is, the ratio of
the total equivalents of the metal to the equivalents of the acidic
organic compound. Overbased materials are prepared by reacting an
acidic material (such as carbon dioxide) with an acidic organic
compound, an inert reaction medium (e.g., mineral oil), a
stoichiometric excess of a metal base, and a promoter such as a
phenol or alcohol. The acidic organic material will normally have a
sufficient number of carbon atoms, to provide oil-solubility.
[0212] Overbased detergents may be characterized by Total Base
Number (TBN), the amount of strong acid needed to neutralize all of
the material's basicity, expressed as mg KOH per gram of sample.
TBN is a very well-known parameter that is described in ASTM D
4739. Since overbased detergents are commonly provided in a form
which contains diluent oil, for the purpose of this document, TBN
is to be recalculated to an oil-free basis. Various detergents may
have a TBN of 100 to 1000, or 150 to 800, or, 400 to 700. The
detergents may have a TBN of at least 640, for instance, 650 to
1000, or even 680 to 800. In each case, the units are mg KOH/g.
[0213] Typically the detergent is an overbased calcium sulphonate
detergent, but other metals may also be present, whether in a
sulphonate detergent (for example, an overbased magnesium
arylsulphonate detergent) or a different detergent substrate (for
example, an overbased calcium phenate detergent). The metal
compounds generally useful in making the basic metal salts are
generally any Group 1 or Group 2 metal compounds (CAS version of
the Periodic Table of the Elements). Examples include alkali metals
such as sodium, potassium, lithium, copper, magnesium, calcium,
barium, zinc, and cadmium. In one embodiment the metals are sodium,
magnesium, or calcium. The anionic portion of the salt may be
hydroxide, oxide, carbonate, borate, or nitrate. The detergents may
be calcium or magnesium detergents, typically prepared using
calcium or magnesium oxide or calcium or magnesium hydroxide. Since
the detergents of particular interest are carbonated detergents,
they will be materials that have been treated with carbon dioxide.
Such treatment leads to more efficient incorporation of basic metal
into the composition. Formation of high TBN detergents involving
reaction with carbon dioxide is disclosed, for instance, in U.S.
Pat. No. 7,238,651, Kocsis et al., Jul. 3, 2007, see, for instance,
examples 10-13 and the claims. Other detergents, however, may also
optionally be present, which need not be carbonated or need not be
so highly overbased (i.e., of lower TBN). However, if multiple
detergents are present, it is desirable that the overbased calcium
or magnesium arylsulphonate detergent is present as the predominant
amount by weight of the metal detergents, that is, at least 50
weight percent or at least 60 or 70 or 80 or 90 weight percent of
the metal-containing detergents, on an oil free basis.
[0214] The lubricants may contain an overbased sulphonate
detergent. Suitable sulphonic acids include sulphonic and
thiosulphonic acids, including mono- or polynuclear aromatic or
cycloaliphatic compounds. Certain oil-soluble sulphonates may be
represented by R.sup.2-T-(SO.sup.-).sub.a or
R.sup.3--(SO.sub.3.sup.-).sub.b, where a and b are each at least
one; T is a cyclic nucleus such as benzene or toluene; R.sup.2 is
an aliphatic group such as alkyl, alkenyl, alkoxy, or alkoxyalkyl;
(R.sup.2)-T typically contains a total of at least 15 carbon atoms;
and R.sup.3 is an aliphatic hydrocarbyl group typically containing
at least 15 carbon atoms. The groups T, R.sup.2, and R.sup.3 may
also contain other inorganic or organic substituents; they may also
be described as hydrocarbyl groups. In one embodiment the
sulphonate detergent may be a predominantly linear
alkylbenzenesulphonate detergent as described in paragraphs [0026]
to [0037] of US Patent Application 2005-065045. In some embodiments
the linear alkyl (or hydrocarbyl) group may be attached to the
benzene ring anywhere along the linear chain of the alkyl group,
but often in the 2, 3, or 4 position of the linear chain, and in
some instances predominantly in the 2 position. In other
embodiments, the alkyl (or hydrocarbyl) group may be branched, that
is, formed from a branched olefin such as propylene or 1-butene or
isobutene. Sulphonate detergents having a mixture of linear and
branched alkyl groups may also be used.
[0215] In certain embodiments the carbonated calcium or magnesium
arylsulphonate detergent may be based on an alkylated and
sulphonated benzene; in another embodiment, it may be based on an
alkylated and sulphonated toluene. In either case there may be one
or two or three, and in certain embodiments one, alkyl (or
hydrocarbyl) group attached to the aromatic ring, in addition to
the methyl group if toluene is used as the starting aromatic
compound. In one embodiment, the detergent is a
monoalkylbenzenemonosulphonate, and in another embodiment it is a
monoalkyltoluenemonosulphonate. If there is one alkyl group, it may
contain a sufficient number of carbon atoms to impart
oil-solubility to the detergent, such as at least 8 carbon atoms,
or 10 to 100 carbon atoms, or 10 to 50 carbon atoms, or 12 to 36
carbon atoms, or 14 to 24 or 16 to 20 or alternatively about 18
carbon atoms. If more than one alkyl group (other than methyl) is
present, each alkyl group may have the afore-described number of
carbon atoms, or all the alkyl groups together may have in total
the afore-described number of carbon atoms, (e.g., two C.sub.12
alkyl groups for a total of 24 carbon atoms in the alkyl groups).
Another type of overbased material that may additionally be present
(that is, in addition to the polyolefin-substituted bridged
hydroxyaromatic compound or salt thereof described above) in
certain embodiments of the present invention is an overbased
phenate detergent. Certain commercial grades of calcium or
magnesium sulphonate detergents contain minor amounts of calcium or
magnesium phenate detergents to aid in their processing or for
other reasons and may contain, for instance, 4% phenate substrate
content and 96% sulphonate substrate content. The phenols useful in
making phenate detergents may be represented by
(R.sup.1).sub.a--Ar--(OH).sub.b, where R.sup.1 is an aliphatic
hydrocarbyl group of 4 to 400 or 6 to 80 or 6 to 30 or 8 to 25 or 8
to 15 carbon atoms; Ar is an aromatic group such as benzene,
toluene or naphthalene; a and b are each at least one, the sum of a
and b being up to the number of displaceable hydrogens on the
aromatic nucleus of Ar, such as 1 to 4 or 1 to 2. There is
typically an average of at least 7 or 8 aliphatic carbon atoms
provided by the R.sup.1 groups for each phenol compound, and in
some instances about 12 carbon atoms. Phenate detergents are also
sometimes provided as sulphur-bridged species or as
methylene-bridged species. Sulphur-bridged species may be prepared
by reacting a hydrocarbyl phenol with sulphur. Methylene-bridged
species may be prepared by reacting a hydrocarbyl phenol with
formaldehyde (or a reactive equivalent such as paraformaldehyde).
Examples include sulphur-bridged dodecylphenol (overbased Ca salt)
and methylene-coupled heptylphenol.
[0216] In another embodiment, an optional, additional overbased
material is an overbased saligenin detergent. Overbased saligenin
detergents are commonly overbased magnesium salts which are based
on saligenin derivatives. A general example of such a saligenin
derivative may be represented by the formula:
##STR00009##
where X is --CHO or --CH.sub.2OH, Y is --CH.sub.2-- or
--CH.sub.2OCH.sub.2--, and the --CHO groups typically comprise at
least 10 mole percent of the X and Y groups; M is hydrogen,
ammonium, or a valence of a metal ion (that is, if M is
multivalent, one of the valences is satisfied by the illustrated
structure and other valences are satisfied by other species such as
anions or by another instance of the same structure), Ri is a
hydrocarbyl group of 1 to 60 carbon atoms, m is 0 to typically 10,
and each p is independently 0, 1, 2, or 3, provided that at least
one aromatic ring contains an R.sup.1 substituent and that the
total number of carbon atoms in all R.sup.1 groups is at least 7.
When m is 1 or greater, one of the X groups may be hydrogen. In one
embodiment, M is a valence (or equivalent) of a Mg ion or a mixture
of Mg and hydrogen. Saligenin detergents are disclosed in greater
detail in U.S. Pat. No. 6,310,009, with special reference to their
methods of synthesis (Column 8 and Example 1) and preferred amounts
of the various species of X and Y (Column 6).
[0217] Other optional detergents include salixarate detergents.
Salixarate detergents are overbased materials that may be
represented by a compound comprising at least one unit of formula
(I) or formula (II):
##STR00010##
each end of the compound having a terminal group of formula (III)
or (IV):
##STR00011##
such groups being linked by divalent bridging groups A, which may
be the same or different. In formulas (I)-(IV) R.sup.3 is hydrogen,
a hydrocarbyl group, or a valence of a metal ion; R.sup.2 is
hydroxyl or a hydrocarbyl group, and j is 0, 1, or 2; R.sup.6 is
hydrogen, a hydrocarbyl group, or a hetero-substituted hydrocarbyl
group; either R.sup.4 is hydroxyl and R.sup.5 and R.sup.7 are
independently either hydrogen, a hydrocarbyl group, or
hetero-substituted hydrocarbyl group, or else R.sup.5 and R.sup.7
are both hydroxyl and R.sup.4 is hydrogen, a hydrocarbyl group, or
a hetero-substituted hydrocarbyl group; provided that at least one
of R.sup.4, R.sup.5, R.sup.6 and R.sup.7 is hydrocarbyl containing
at least 8 carbon atoms; and wherein the molecules on average
contain at least one of unit (I) or (III) and at least one of unit
(II) or (IV) and the ratio of the total number of units (I) and
(III) to the total number of units of (II) and (IV) in the
composition is 0.1:1 to 2:1. The divalent bridging group "A," which
may be the same or different in each occurrence, includes
--CH.sub.2-- and --CH.sub.2OCH.sub.2--, either of which may be
derived from formaldehyde or a formaldehyde equivalent (e.g.,
paraform, formalin).
[0218] Salixarate derivatives and methods of their preparation are
described in greater detail in U.S. Pat. No. 6,200,936 and PCT
Publication WO 01/56968. It is believed that the salixarate
derivatives have a predominantly linear, rather than macrocyclic,
structure, although both structures are intended to be encompassed
by the term "salixarate." In one embodiment, a salixarate detergent
may contain a portion of molecules represented (prior to
neutralization) by the structure:
##STR00012##
where the R.sup.8 groups are independently hydrocarbyl groups
containing at least 8 carbon atoms.
[0219] Glyoxylate detergents are also optional overbased materials.
They are based on an anionic group which, in one embodiment, may
have the structure:
##STR00013##
wherein each R is independently an alkyl group containing at least
4 or 8 carbon atoms, provided that the total number of carbon atoms
in all such R groups is at least 12 or 16 or 24. Alternatively,
each R may be an olefin polymer substituent. The acidic material
upon from which the overbased glyoxylate detergent is prepared is
the condensation product of a hydroxyaromatic material such as a
hydrocarbyl-substituted phenol with a carboxylic reactant such as
glyoxylic acid or another omega-oxoalkanoic acid. Overbased
glyoxylic detergents and their methods of preparation are disclosed
in greater detail in U.S. Pat. No. 6,310,011 and references cited
therein.
[0220] Another optional overbased detergent is an overbased
salicylate, e,g., an alkali metal or alkaline earth metal salt of a
substituted salicylic acid. The salicylic acids may be
hydrocarbyl-substituted wherein each substituent contains an
average of at least 8 carbon atoms per substituent and 1 to 3
substituents per molecule. The substituents may be polyalkene
substituents. In one embodiment, the hydrocarbyl substituent group
contains 7 to 300 carbon atoms and may be an alkyl group having a
molecular weight of 150 to 2000. Overbased salicylate detergents
and their methods of preparation are disclosed in U.S. Pat. Nos.
4,719,023 and 3,372,116.
[0221] Other optional overbased detergents may include overbased
detergents having a Mannich base structure, as disclosed in U.S.
Pat. No. 6,569,818.
[0222] In certain embodiments, the hydrocarbyl substituents on
hydroxy-substituted aromatic rings in the above detergents (e.g.,
phenate, saligenin, salixarate, glyoxylate, or salicylate) are free
of or substantially free of C.sub.12 aliphatic hydrocarbyl groups
(e.g., less than 1%, 0.1%, or 0.01% by weight of the substituents
are C.sub.12 aliphatic hydrocarbyl groups). In some embodiments
such hydrocarbyl substituents contain at least 14 or at least 18
carbon atoms.
[0223] Optionally the lubricant may further include an additional
phosphorus containing material and may include a metal salt of a
phosphorus acid. Metal salts may have the formula:
[(R.sup.8O)(R.sup.9O)P(.dbd.S)--S].sub.n-M
where R.sup.8 and R.sup.9 are independently hydrocarbyl groups
containing 3 to 30 carbon atoms, are readily obtainable by heating
phosphorus pentasulfide (P.sub.2S.sub.5) and an alcohol or phenol
to form an O,O-dihydrocarbyl phosphorodithioic acid. The alcohol
which reacts to provide the R.sup.8 and R.sup.9 groups may be a
mixture of alcohols, for instance, a mixture of isopropanol and
4-methyl-2-pentanol, and in some embodiments a mixture of a
secondary alcohol and a primary alcohol, such as isopropanol and
2-ethylhexanol. The resulting acid may be reacted with a basic
metal compound to form the salt. The metal M, having a valence n,
generally is aluminum, tin, manganese, cobalt, nickel, zinc, or
copper, and in many cases, zinc, to form zinc
dialkyldithiophosphates. Such materials are well known and readily
available to those skilled in the art of lubricant formulation.
Suitable variations to provide low phosphorus volatility are
disclosed, for instance, in US published application 2008-0015129,
see, e.g., claims.
[0224] Mixtures of amines may also be used in the invention. In one
embodiment a useful mixture of amines is "Primene.RTM. 81R" and
"Primene.RTM. JMT." Primene.RTM. 81R and Primene.RTM. JMT (both
produced and sold by Rohm & Haas) are mixtures of C.sub.11 to
C.sub.14 tertiary alkyl primary amines and C.sub.18 to C.sub.22
tertiary alkyl primary amines respectively.
[0225] In one embodiment the hydrocarbyl amine salt of an
alkylphosphoric acid ester is the reaction product of a C.sub.14 to
C.sub.18 alkylated phosphoric acid with Primene 81R.TM. (produced
and sold by Rohm & Haas) which is a mixture of C.sub.11 to
C.sub.14 tertiary alkyl primary amines.
[0226] Examples of hydrocarbyl amine salts of
dialkyldithiophosphoric acid esters include the reaction product(s)
of isopropyl, methyl-amyl (4-methyl-2-pentyl or mixtures thereof),
2-ethylhexyl, heptyl, octyl or nonyl dithiophosphoric acids with
ethylene diamine, morpholine, or Primene 81R.TM., and mixtures
thereof.
[0227] In one embodiment the dithiophosphoric acid may be reacted
with an epoxide or a glycol. This reaction product is further
reacted with a phosphorus acid, anhydride, or lower ester. The
epoxide includes an aliphatic epoxide or a styrene oxide. Examples
of useful epoxides include ethylene oxide, propylene oxide, butene
oxide, octene oxide, dodecene oxide, styrene oxide and the like. In
one embodiment the epoxide is Propylene oxide. The glycols may be
aliphatic glycols having from 1 to about 12, or from about 2 to
about 6, or about 2 to about 3 carbon atoms. The dithiophosphoric
acids, glycols, epoxides, inorganic phosphorus reagents and methods
of reacting the same are described in U.S. Pat. Nos. 3,197,405 and
3,544,465. The resulting acids may then be salted with amines. An
example of suitable dithiophosphoric acid is prepared by adding
phosphorus pentoxide (about 64 grams) at about 58.degree. C. over a
period of about 45 minutes to about 514 grams of hydroxypropyl
O,O-di(4-methyl-2-pentyl)phosphorodithioate (prepared by reacting
di(4-methyl-2-pentyl)-phosphorodithioic acid with about 1.3 moles
of propylene oxide at about 25.degree. C). . The mixture is heated
at about 75.degree. C. for about 2.5 hours, mixed with a
diatomaceous earth and filtered at about 70.degree. C. The filtrate
contains about 11.8% by weight phosphorus, about 15.2% by weight
sulfur, and an acid number of 87 (bromophenol blue).
[0228] If the additional phosphorus containing material is present
it may provide 1% to 90%, or 10 to 80%, or 20 to 70% of the total
amount of phosphorus to the lubricant. In one embodiment the
additional phosphorus containing material is present, and in one
embodiment the additional phosphorus containing material is present
is absent.
[0229] The lubricant may further include an antioxidant, or
mixtures thereof. The Antioxidant may include molybdenum compounds
such as molybdenum dithiocarbamates, sulphurised olefins, hindered
phenols, aminic compounds such as alkylated diphenylamines
(typically di-nonyl diphenylamine, octyl diphenylamine, or di-octyl
diphenylamine). When present, the antioxidant may be present at 0
to 3 wt %, or 0.1 to 2.5 wt %, or 0.2 to 1.5 wt %.
Automatic Transmission Lubricants
[0230] In one embodiment the invention provides a lubricant
composition comprising:
[0231] an oil of lubricating viscosity,
[0232] a dispersant typically present at 0.01 to 5 wt %, or 0.05 to
3 wt %, or 0.1 to 3 wt %, or or 0.1 to 2 wt
[0233] from about 0.1 to about 1, typically present in an amount to
deliver 40 to 1000ppm, 50 to 700ppm, 60 to 600ppm or 70 to 250ppm
calcium; and wherein from about 0.01 to about 0.8 wt %, or from
about 0.1 to about 0.5 wt %, or about 0.2 to about 0.15 wt % of the
detergent comprises the polyolefin-substituted bridged
hydroxyaromatic compound or salt thereof described herein, and
[0234] a friction modifier typically present at 0 to 4 wt %, or 0.1
to 4 wt %, 0.2 to 3 wt %, 0.3 to 3 wt %, 0.25 to 2.5 wt %. In one
embodiment the friction modifier is present, and in an alternative
embodiment the friction modifier is not present.
[0235] In one embodiment the invention provides a method of
lubricating an automatic transmission comprising supplying to the
automatic transmission a lubricant composition comprising:
[0236] an oil of lubricating viscosity,
[0237] a dispersant typically present at 0.5 to 3 wt %, or 1 to 2.5
wt %, or 1.5 to 4 wt %, or 1.5 to 3 wt
[0238] a phosphorus-containing antiwear agent chosen from (i) a
non-ionic phosphorus compound, which may be a hydrocarbyl
phosphite; or (ii) an amine salt of a phosphorus compound,
[0239] a thiadiazole, typically present at 0.1 to 0.5 wt %,or 0.2
to 0.4 wt %, or 0.25 to 0.35 wt %.
[0240] from about 0.1 to about 5 wt % of a detergent, typically
present in an amount to deliver 40 to 700ppm, 50 to 600ppm, 60 to
500ppm or 70 to 250ppm calcium; and wherein from about 0.01 to
about 2 wt %, or from about 0.1 to about 1.75 wt %, or about 0.2 to
about 1.5 wt % of the detergent comprises the
polyolefin-substituted bridged hydroxyaromatic compound or salt
thereof described herein, and
[0241] a friction modifier typically present at 0 to 4 wt %, or 0.1
to 4 wt %, 0.2 to 3 wt %, 0.3 to 3 wt %, 0.25 to 2.5 wt %. In one
embodiment the friction modifier is present, and in an alternative
embodiment the friction modifier is not present.
[0242] The automatic transmission includes continuously variable
transmissions (CVT), infinitely variable transmissions (IVT),
Toroidal transmissions, continuously slipping torque converted
clutches (CSTCC), stepped automatic transmissions or dual clutch
transmissions (DCT).
[0243] The calcium-containing detergent may be an overbased
detergent, a non-overbased detergent, or mixtures thereof.
Typically the detergent may be overbased.
[0244] The preparation of the calcium-containing detergent is known
in the art. Patents describing the preparation of overbased
calcium-containing detergents include U.S. Pat. Nos. 2,501,731;
2,616,905; 2,616,911; 2,616,925; 2,777,874; 3,256,186; 3,384,585;
3,365,396; 3,320,162; 3,318,809; 3,488,284; and 3,629,109.
[0245] As used herein the TBN values quoted and associated range of
TBN is on "an as is basis," i.e., containing conventional amounts
of diluent oil. Conventional amounts of diluent oil typically range
from 30 wt % to 60 wt % (often 40 wt % to 55 wt %) of the detergent
component.
[0246] A more detailed description of the expressions "metal
ratio", TBN and "soap content" are known to a person skilled in the
art and explained in standard textbook entitled "Chemistry and
Technology of Lubricants", Third Edition, Edited by R. M. Mortier
and S. T. Orszulik, Copyright 2010, pages 219 to 220 under the
sub-heading 7.2.5. Detergent Classification.
[0247] The calcium-containing detergent may be a non-overbased
detergent (may also be referred to as a neutral detergent). The TBN
of a non-overbased may be 20 to less than 200, or 30 to 100, or 35
to 50 mg KOH/g. The TBN of a non-overbased calcium-containing
detergent may also be 20 to 175, or 30 to 100 mg KOH/g. When a
non-overbased calcium-containing detergent is prepared from a
strong acid such as a hydrocarbyl-substituted sulphonic acid, the
TBN may be lower (for example 0 to 50 mg KOH/g, or 10 to 20 mg
KOH/g).
[0248] The calcium-containing detergent may be an overbased
detergent, which may have a TBN of greater than 200 mg KOH/g
(typically 250 to 600, or 300 to 500 mg KOH/g).
[0249] The calcium-containing detergent may be formed by the
reaction of a basic calcium compound and an acidic detergent
substrate. The acidic detergent substrate may include an alkyl
phenol, an aldehyde-coupled alkyl phenol, a sulphurised alkyl
phenol, an alkyl aromatic sulphonic acid (such as, alkyl
naphthalene sulphonic acid, alkyl toluene sulphonic acid or alkyl
benzene sulphonic acid), an aliphatic carboxylic acid, a
calixarene, a salixarene, an alkyl salicylic acid, or mixtures
thereof.
[0250] The metal basic compound is used to supply basicity to the
detergent. The basic calcium compound is a compound of a hydroxide
or oxide of the metal.
[0251] The oxides and/or hydroxides may be used alone or in
combination. The oxides or hydroxides may be hydrated or
dehydrated, although hydrated is typical. In one embodiment the
basic calcium compound may be calcium hydroxide, which may be used
alone or mixtures thereof with other metal basic compounds. Calcium
hydroxide is often referred to as lime. In one embodiment the metal
basic compound may be calcium oxide which may be used alone or
mixtures thereof with other metal basic compounds.
[0252] Collectively, when the alkyl phenol, the aldehyde-coupled
alkyl phenol, and the sulphurised alkyl phenol are used to prepare
a calcium-containing detergent, the detergent may be referred to as
a calcium phenate. The calcium phenate may be an alkyl phenate, an
aldehyde-coupled alkyl phenate, a sulphurised alkyl phenate, or
mixtures thereof.
[0253] The TBN of a calcium phenate may vary from less 200, or 30
to 175 typically 150 to 175) mg KOH/g for a neutral phenate to 200
or more to 500, or 210 to 400 (typically 230 to 270) mg KOH/g for
an overbased phenate.
[0254] The alkyl group of a phenate (i.e., an alkyl phenate) may
contain 4 to 80, or 6 to 45, or 8 to 20, or 9 to 15 carbon
atoms.
[0255] In one embodiment the calcium-containing detergent may be a
sulphonate, or mixtures thereof. The sulphonate may be prepared
from a mono- or di-hydrocarbyl-substituted benzene (or naphthalene,
indenyl, indanyl, or bicyclopentadienyl) sulphonic acid, wherein
the hydrocarbyl group may contain 6 to 40, or 8 to 35 or 9 to 30
carbon atoms.
[0256] The hydrocarbyl group may be derived from polypropylene or a
linear or branched alkyl group containing at least 10 carbon atoms.
Examples of a suitable alkyl group include branched and/or linear
decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,
hexadecyl, heptadecyl, octadecyl, octadecenyl, nonodecyl, eicosyl,
un-eicosyl, do-eicosyl, tri-eicosyl, tetra-eicosyl, penta-eicosyl,
hexa-eicosyl or mixtures thereof.
[0257] In one embodiment the hydrocarbyl-substituted sulphonic acid
may include polypropene benzenesulphonic acid and/or
C.sub.16-C.sub.24 alkyl benzenesulphonic acid, or mixtures
thereof.
[0258] In one embodiment a calcium sulphonate detergent may be a
predominantly linear alkylbenzene sulphonate detergent having a
metal ratio of at least 8 as is described in paragraphs [0026] to
[0037] of US Patent Application 2005065045 (and granted as U.S.
Pat. No. 7,407,919). In some embodiments the linear alkyl group may
be attached to the benzene ring anywhere along the linear chain of
the alkyl group, but often in the 2, 3 or 4 position of the linear
chain, and in some instances predominantly in the 2 position.
[0259] When neutral or slightly basic, a calcium sulphonate
detergent may have TBN of less than 100, or less than 75, typically
20 to 50 mg KOH/g, or 0 to 20 mg KOH/g.
[0260] When overbased, a calcium sulphonate detergent may have a
TBN greater than 200, or 300 to 550, or 350 to 450 mg KOH/g.
[0261] The detergent may be borated or non-borated.
[0262] Chemical structures for sulphonates, and phenates detergents
are known to a person skilled in the art. The standard textbook
entitled "Chemistry and Technology of Lubricants", Third Edition,
Edited by R. M. Mortier and S. T. Orszulik, Copyright 2010, pages
220 to 223 under the sub-heading 7.2.6 provide general disclosures
of said detergents and their structures.
[0263] In one embodiment the calcium-containing detergent may be an
overbased calcium sulphonate, an overbased calcium phenate, or
mixtures thereof. Typically the detergent may be an overbased
calcium sulphonate.
[0264] In one embodiment the calcium-containing detergent may be in
a mixture with a having zinc-, barium-, sodium-, or
magnesium-containing detergent. The zinc-, barium-, sodium-, or
magnesium-containing detergent is also well known in the art and
described in the same references describing a calcium-containing
detergent. The TBN and metal ratios may however, differ slightly.
The zinc-, barium-, sodium-, or magnesium-containing detergent may
be a phenate, a sulphur-containing phenate, sulphonate, salixarate
or salicylate. Typically a zinc-, barium-, sodium-, or
magnesium-containing detergent may be a magnesium phenate, a
magnesium sulphur-containing phenate, or a magnesium
sulphonate.
[0265] The dispersant is described above.
[0266] The lubricant composition may include a friction modifier,
typically at least two friction modifiers. Useful friction
modifiers are described below.
[0267] In one embodiment the friction modifier may be formed by the
condensation of the hydroxyalkyl compound with an acylating agent
or an amine. A more detailed description of the hydroxyalkyl
compound is described in U.S. Patent Application 60/725360 (filed
on Oct. 11, 2005, inventors Bartley, Lahiri, Baker and Tipton) in
paragraphs 8, 19-21. The friction modifier disclosed in U.S. Patent
Application 60/725360 may be an amide represented by the formula
R.sup.1R.sup.2N--C(O)R.sup.3, wherein R.sup.1 and R.sup.2 are each
independently hydrocarbyl groups of at least 6 carbon atoms and
R.sup.3 is a hydroxyalkyl group of 1 to 6 carbon atoms or a group
formed by the condensation of said hydroxyalkyl group, through a
hydroxyl group thereof, with an acylating agent. Preparative
Examples are disclosed in Examples 1 and 2 (paragraphs 68 and 69).
In one embodiment the amide of a hydroxylalkyl compound is prepared
by reacting glycolic acid, that is, hydroxyacetic acid,
HO--CH.sub.2--COOH with an amine.
[0268] In one embodiment the friction modifier may be a secondary
or tertiary amine being represented by the formula
R.sup.4R.sup.5NR.sup.6, wherein R.sup.4 and R.sup.5 are each
independently an alkyl group of at least 6 carbon atoms and R.sup.6
is hydrogen, a hydrocarbyl group, a hydroxyl-containing alkyl
group, or an amine-containing alkyl group. A more detailed
description of the friction modifier is described in U.S. patent
application Ser. No. 05/037897 in paragraphs 8 and 19 to 22.
[0269] In one embodiment the friction modifier may be derived from
the reaction of a carboxylic acid or a reactive equivalent thereof
with an aminoalcohol, wherein the friction modifier contains at
least two hydrocarbyl groups, each containing at least 6 carbon
atoms. An example of such a friction modifier includes the reaction
product of isostearic acid or an alkyl succinic anhydride with
tris-hydroxymethylaminomethane. A more detailed description of such
a friction modifier is disclosed in International Publication
WO04/007652) in paragraphs 8 and 9 to 14.
[0270] The friction modifier includes fatty amines, borated
glycerol esters, fatty acid amides, non-borated fatty epoxides,
borated fatty epoxides, alkoxylated fatty amines, borated
alkoxylated fatty amines, metal salts of fatty acids, fatty
imidazolines, metal salts of alkyl salicylates (may also be
referred to as a detergent), metal salts of sulphonates (may also
be referred to as a detergent), condensation products of carboxylic
acids or polyalkylene-polyamines, or amides of hydroxyalkyl
compounds.
[0271] In one embodiment the friction modifier includes a fatty
acid ester of glycerol. The final product may be in the form of a
metal salt, an amide, an imidazoline, or mixtures thereof. The
fatty acids may contain 6 to 24, or 8 to 18 carbon atoms. The fatty
acids may branched or straight-chain, saturated or unsaturated.
Suitable acids include 2-ethylhexanoic, decanoic, oleic, stearic,
isostearic, palmitic, myristic, palmitoleic, linoleic, lauric, and
linolenic acids, and the acids from the natural products tallow,
palm oil, olive oil, peanut oil, corn oil, and Neat's foot oil. In
one embodiment the fatty acid is oleic acid. When in the form of a
metal salt, typically the metal includes zinc or calcium; and the
products include overbased and non-overbased products. Examples are
overbased calcium salts and basic oleic acid-zinc salt complexes
which may be represented by the general formula
Zn.sub.4Oleate.sub.6O. When in the form of an amide, the
condensation product includes those prepared with ammonia, or with
primary or secondary amines such as diethylamine and
diethanolamine. When in the form of an imidazoline, the
condensation product of an acid with a diamine or polyamine such as
a polyethylenepolyamine. In one embodiment the friction modifier is
the condensation product of a fatty acid with C.sub.8 to C.sub.24
atoms, and a polyalkylene polyamine, and in particular, the product
of isostearic acid with tetraethylenepentamine.
[0272] In one embodiment the friction modifier includes those
formed by the condensation of the hydroxyalkyl compound with an
acylating agent or an amine. A more detailed description of the
hydroxyalkyl compound is described in WO 2007/0044820 paragraphs 9,
and 20-22. The friction modifier disclosed in WO2007/044820
includes an amide represented by the formula
R.sup.12R.sup.13N--C(O)R.sup.14, wherein R.sup.12 and R.sup.13 are
each independently hydrocarbyl groups of at least 6 carbon atoms
and R.sup.14 is a hydroxyalkyl group of 1 to 6 carbon atoms or a
group formed by the condensation of said hydroxyalkyl group,
through a hydroxyl group thereof, with an acylating agent.
Preparative Examples are disclosed in Examples 1 and 2 (paragraphs
72 and 73 of WO2007/044820). In one embodiment the amide of a
hydroxylalkyl compound is prepared by reacting glycolic acid, that
is, hydroxyacetic acid, HO--CH.sub.2--COOH with an amine.
[0273] In one embodiment the friction modifier includes a reaction
product of a di-cocoalkyl amine (or di-cocoamine) with glycolic
acid. The friction modifier includes compounds prepared in
Preparative Examples 1 and 2 of WO 2008/014319.
[0274] In one embodiment the friction modifier includes an
alkoxylated alcohol. A detailed description of suitable alkoxylated
alcohols is described in paragraphs 19 and 20 of US Patent
Application 2005/0101497. The alkoxylated amines are also described
in U.S. Pat. No. 5,641,732 in column 7, line 15 to column 9, line
25.
[0275] In one embodiment the friction modifier includes a hydroxyl
amine compound as defined in column 37, line 19, to column 39, line
38 of U.S. Pat. No. 5,534,170. Optionally the hydroxyl amine
includes borated as such products are described in column 39, line
39 to column 40 line 8 of U.S. Pat. No. 5,534,170.
[0276] In one embodiment the friction modifier includes an
alkoxylated amine e.g., an ethoxylated amine derived from 1.8%
Ethomeen.TM. T-12 and 0.90% Tomah.TM. PA-1 as described in Example
E of U.S. Pat. No. 5,703,023, column 28, lines 30 to 46. Other
suitable alkoxylated amine compounds include commercial alkoxylated
fatty amines known by the trademark "ETHOMEEN" and available from
Akzo Nobel. Representative examples of these ETHOMEEN.TM. materials
is ETHOMEEN.TM. C/12 (bis[2-hydroxyethyl]-coco-amine); ETHOMEEN.TM.
C/20 (polyoxyethylene-[10]cocoamine); ETHOMEEN.TM. S/12
(bis[2-hydroxyethyl]soyamine); ETHOMEEN.TM. T/12
(bis[2-hydroxyethyl]allow-amine); ETHOMEEN.TM. T/15
(polyoxyethylene-[5]tallowamine); ETHOMEEN.TM. 0/12
(bis[2-hydroxyethyl]oleyl-amine); ETHOMEEN.TM. 18/12
(bis[2-hydroxyethyl]octadecylamine); and ETHOMEEN.TM. 18/25
(polyoxyethylene[15]octadecylamine). Fatty amines and ethoxylated
fatty amines are also described in U.S. Pat. No. 4,741,848.
[0277] In one embodiment the friction modifier includes a polyol
ester as described in U.S. Pat. No. 5,750,476 column 8, line 40 to
column 9, line 28.
[0278] In one embodiment the friction modifier includes a low
potency friction modifier as described in U.S. Pat. No. 5,840,662
in column 2, line 28 to column 3, line 26. U.S. Pat. No. 5,840,662
further discloses in column 3, line 48 to column 6, line 25
specific materials and methods of preparing the low potency
friction modifier.
[0279] In one embodiment the friction modifier includes a reaction
product of an isomerised alkenyl substituted succinic anhydride and
a polyamine as described in U.S. Pat. No. 5,840,663 in column 2,
lines 18 to 43. Specific embodiments of the friction modifier
described in U.S. Pat. No. 5,840,663 are further disclosed in
column 3, line 23 to column 4, line 35. Preparative examples are
further disclosed in column 4, line 45 to column 5, line 37 of U.S.
Pat. No. 5,840,663.
[0280] In one embodiment the friction modifier includes an
alkylphosphonate mono- or di-ester sold commercially by Rhodia
under the trademark Duraphos.RTM. DMODP.
[0281] The condensation of a fatty acid and a polyamine typically
result in the formation of at least one compound chosen from
hydrocarbyl amides, hydrocarbyl imidazolines and mixtures thereof.
In one embodiment the condensation products are hydrocarbyl
imidazolines. In one embodiment the condensation products are
hydrocarbyl amides. In one embodiment the condensation products are
mixtures of hydrocarbyl imidazolines and hydrocarbyl amides.
Typically the condensation product is a mixture of hydrocarbyl
imidazolines and hydrocarbyl amides.
[0282] The fatty acid may be derived from a hydrocarbyl carboxylic
acid. The hydrocarbyl group may be alkyl, cycloalkyl, or aryl,
although alkyl is typical, and the hydrocarbyl groups may be linear
or branched. Typically the fatty acid contains 8 or more, 10 or
more, more 13 or 14 or more carbon atoms (including the carbon of
the carboxy group). Typically the fatty acid contains 8 to 30, 12
to 24, or 16 to 18 carbon atoms. Other suitable carboxylic acids
may include the polycarboxylic acids or carboxylic acids or
anhydrides having from 2 to 4 carbonyl groups, typically 2. The
polycarboxylic acids may include succinic acids and anhydrides and
Diels-Alder reaction products of unsaturated monocarboxylic acids
with unsaturated carboxylic acids (such as acrylic, methacrylic,
maleic, fumaric, crotonic and itaconic acids). The fatty carboxylic
acids include fatty monocarboxylic acids containing 8 to 30, 10 to
26, or 12 to 24 carbon atoms.
[0283] Examples of suitable fatty acids may include caprylic acid,
capric acid, lauric acid, myristic acid, palmitic acid, stearic
acid, eicosic acid and, tall oil acids. In one embodiment the fatty
acid is stearic acid, which may be used alone or in combination
with other fatty acids.
[0284] One or both friction modifiers may in one embodiment be
nitrogen-containing compounds, typically both friction modifiers
are nitrogen-containing.
[0285] In one embodiment one of friction modifiers is the
condensation product of a fatty acid with C.sub.8 to C.sub.24
atoms, and a polyalkylene polyamine, and in particular, the product
of isostearic acid with tetraethylenepentamine.
[0286] The phosphorus-containing compound may be a non-ionic
phosphorus compound.
[0287] In one embodiment the phosphorus-containing compounds
comprise two or more (possibly up to four) non-ionic phosphorus
compounds. Typically the non-ionic phosphorus compound may have an
oxidation of +3 or +5. The different embodiments comprise phosphite
ester, phosphate esters, or mixtures thereof.
[0288] In one embodiment the phosphorus-containing compound
comprises a non-ionic phosphorus compound (a C.sub.4-6 hydrocarbyl
phosphite) and an amine salt of a phosphorus acid or ester.
[0289] The phosphorus-containing compound comprises a non-ionic
phosphorus compound that is a C.sub.4-6 hydrocarbyl phosphite, or
mixtures thereof. The C.sub.4-6 hydrocarbyl phosphite includes
those represented by the formula:
##STR00014##
[0290] wherein each R''' may be independently hydrogen or a
hydrocarbyl group having 4 to 6 carbon atoms, typically 4 carbon
atoms, with the proviso that at least one of the R''' groups is
hydrocarbyl. Typically the C.sub.4-6 hydrocarbyl phosphite
comprises dibutyl phosphite.
[0291] The C.sub.4-6 hydrocarbyl phosphite may deliver at least 175
ppm, or at least 200 ppm of the total amount of phosphorus
delivered by the phosphorus-containing compounds.
[0292] The C.sub.4-6 hydrocarbyl phosphite may deliver at least 45
wt %, or 50 wt % to 100 wt %, or 50 wt % to 90 wt % or 60 wt % to
80 wt % of the total amount of phosphorus from the
phosphorus-containing compound.
[0293] The phosphorus-containing compounds may comprise a second
phosphite whose formula is similar to that disclosed above, except
R''' may contain 2 to 40, 8 to 24 or 11 to 20 carbon atoms, with
the proviso that the second phosphite is not a C.sub.4-6
hydrocarbyl phosphite. Examples of suitable hydrocarbyl groups
include propyl, dodecyl, butadecyl, hexadecyl, octadecyl, propenyl,
dodecenyl, butadecenyl, hexadeencyl, or octadecenylgroups.
[0294] As used herein the term "alk(en)yl" is intended to include
moieties that have an alkyl and/or alkenyl group.
[0295] In one embodiment the phosphorus-containing compounds
include a mixture of a C.sub.4-6 hydrocarbyl phosphite (typically
dibutyl phosphite) and a C.sub.12-18 alk(en)yl hydrogen phosphite
and optionally phosphoric acid. In different embodiments the
phosphoric acid is present or absent.
[0296] In one embodiment the phosphorus-containing compounds
include a mixture of a C.sub.4-6 hydrocarbyl phosphite (typically
dibutyl phosphite) and a C.sub.16-18 alk(en)yl hydrogen phosphite.
The alk(en)yl hydrogen phosphite be may an alkyl hydrogen
phosphite, and alkenyl hydrogen phosphite, or a mixture of alkenyl
hydrogen phosphite and alkyl hydrogen phosphite. In one embodiment
the alk(en)yl hydrogen phosphite be may a mixture of alkenyl
hydrogen phosphite and alkyl hydrogen phosphite and optionally
phosphoric acid. The phosphoric acid may be present or absent.
[0297] In one embodiment the phosphorus-containing compounds
include a mixture of a C.sub.4-6 hydrocarbyl phosphite (typically
dibutyl phosphite) and a C.sub.11-14 alk(en)yl hydrogen phosphite.
The alk(en)yl hydrogen phosphite be may an alkyl hydrogen
phosphite, and alkenyl hydrogen phosphite, ora mixture of alkenyl
hydrogen phosphite and alkyl hydrogen phosphite. In one embodiment
the alk(en)yl hydrogen phosphite may be a mixture of alkenyl
hydrogen phosphite and alkyl hydrogen phosphite and optionally
phosphoric acid.
[0298] In one embodiment the phosphorus-containing compounds
include a mixture of a C.sub.4-6 hydrocarbyl phosphite (typically
dibutyl phosphite) and phosphoric acid.
[0299] The lubricant composition in one embodiment includes a
package that comprises a phosphorus-containing compound and a
non-ionic phosphorus compound that is a hydrocarbyl phosphite.
[0300] In one embodiment the lubricant composition further
comprises a C.sub.8-20 hydrocarbyl phosphite, or a C.sub.12-18
hydrocarbyl phosphite, or C.sub.6-18 hydrocarbyl phosphite.
[0301] In one embodiment the lubricant composition includes an
amine antioxidant. The amine antioxidant may be a
phenyl-a-naphthylamine (PANA) or a hydrocarbyl substituted
diphenylamine, or mixtures thereof. The hydrocarbyl substituted
diphenylamine may include mono- or di-C.sub.4 to C.sub.16-, or
C.sub.6 to C.sub.12-, or C.sub.9-alkyl diphenylamine. For example
the hydrocarbyl substituted diphenylamine may be octyl
diphenylamine, or di-octyl diphenylamine, dinonyl diphenylamine,
typically dinonyl diphenylamine.
[0302] When present the amine antioxidant may be present at 0.2 wt
% to 1.2 wt %, or 0.3 wt % to 1.0 wt %, or 0.4 wt % to 0.9 wt % or
0.5 wt % to 0.8 wt %, of the lubricant composition.
[0303] The lubricant composition be optionally include at least one
other antixodiant that is known and includes sulphurised olefins,
hindered phenols, molybdenum dithiocarbamates, and mixtures
thereof.
[0304] The hindered phenol antioxidant often contains a secondary
butyl and/or a tertiary butyl group as a sterically hindering
group. The phenol group is often further substituted with a
hydrocarbyl group and/or a bridging group linking to a second
aromatic group. Examples of suitable hindered phenol antioxidants
include 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
or 4-butyl-2,6-di-tert-butylphenol, or
4-dodecyl-2,6-di-tert-butylphenol. In one embodiment the hindered
phenol antioxidant may be an ester and may include, e.g.,
Irganox.TM. L-135 from Ciba, or butyl
3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate.
[0305] If present, the secondary antioxidant may be present at 0.1
wt % to 1 wt %, or 0.2 wt % to 0.9 wt % or 0.1 wt % to 0.4 wt %, or
0.4 wt % to 1.0 wt %, of the lubricant composition.
Off-Highway Vehicle
[0306] The polyolefin-substituted bridged hydroxyaromatic compound
or salt thereof described herein can be employed in off-highway
vehicles, such as, for example, farm tractors and construction
vehicles. Such vehicles often have a common sump that lubricates
not only the transmission but also the gears, axles, and hydraulics
in the vehicle. In one embodiment the invention includes a
lubricant composition comprising:
[0307] an oil of lubricating viscosity,
[0308] a dispersant typically present at 0.1 to 3 wt %, or 0.1 to
2.5 wt %, or 0.2 to 2 wt %,
[0309] from about 0.1 to about 5 wt % of a detergent, typically
present in an amount to deliver 100 to 5000 ppm, 500 to 4500 ppm,
500 to 4250 ppm, 650 to 4200 ppm calcium; and wherein from about
0.01 to about 2 wt %, or from about 0.1 to about 1.75 wt %, or
about 0.2 to about 1.5 wt % of the detergent comprises the
polyolefin-substituted bridged hydroxyaromatic compound or salt
thereof described herein.
[0310] In one embodiment the invention includes a method of
lubricating an off-highway vehicle comprising supplying to the
vehicle a lubricant composition comprising:
[0311] an oil of lubricating viscosity,
[0312] a dispersant typically present at 0.1 to 3 wt %, or 0.1 to
2.5 wt %, or 0.2 to 2 wt %,
[0313] a phosphorus-containing antiwear agent chosen from (i) a
non-ionic phosphorus compound, which may be a hydrocarbyl
phosphite, such as a zinc dialkyldithiophosphate; or (ii) an amine
salt of a phosphorus compound,
[0314] from about 0.1 to about 5 wt % of a detergent, typically
present in an amount to deliver 10 to 5000ppm, 500 to 4500ppm, 500
to 4250ppm, 650 to 4200ppm calcium; and wherein from about 0.01 to
about 2 wt %, or from about 0.1 to about 1.75 wt %, or about 0.2 to
about 1.5 wt % of the detergent comprises the
polyolefin-substituted bridged hydroxyaromatic compound or salt
thereof described herein.
[0315] The off-highway vehicle lubricated typically has a
wet-brake, a transmission, a hydraulic, a final drive, a power
take-off system. These parts are typically lubricated by a single
lubricant supplied from a common sump. The transmission may be a
manual transmission or an automatic transmission.
[0316] The calcium-containing detergent may be an overbased
detergent, a non-overbased detergent, or mixtures thereof.
Typically the detergent may be overbased.
[0317] The preparation of the calcium-containing detergent is known
in the art. Patents describing the preparation of overbased
calcium-containing detergents include U.S. Pat. Nos. 2,501,731;
2,616,905; 2,616,911; 2,616,925; 2,777,874; 3,256,186; 3,384,585;
3,365,396; 3,320,162; 3,318,809; 3,488,284; and 3,629,109.
[0318] The other detergent (other than the alkylphenol) and
dispersant is described above.
[0319] The phosphorus-containing antiwear agent may include zinc
dialkyldithiophosphate, a non-ionic phosphorus compound, which may
be a hydrocarbyl phosphite; (i) a non-ionic phosphorus compound,
which may be a hydrocarbyl phosphite; or (ii) an amine salt of a
phosphorus compound, or mixtures thereof.
[0320] In one embodiment the lubricant composition disclosed herein
contains no zinc dialkyldithiophosphate.
[0321] In one embodiment the lubricant composition disclosed herein
contains zinc dialkyldithiophosphate.
[0322] The phosphorus-containing compound may be a non-ionic
phosphorus compound.
[0323] In one embodiment the phosphorus-containing compounds
comprise two or more (possibly up to four) non-ionic phosphorus
compounds. Typically the non-ionic phosphorus compound may have an
oxidation of +3 or +5. The different embodiments comprise phosphite
ester, phosphate esters, or mixtures thereof.
[0324] In one embodiment the phosphorus-containing compound
comprises a non-ionic phosphorus compound (a C.sub.4-6 hydrocarbyl
phosphite) and an amine salt of a phosphorus acid or ester.
[0325] The phosphorus-containing compound comprises a non-ionic
phosphorus compound that is a C.sub.4-6 hydrocarbyl phosphite, or
mixtures thereof. The C.sub.4-6 hydrocarbyl phosphite includes
those represented by the formula:
##STR00015##
wherein each R''' may be independently hydrogen or a hydrocarbyl
group having 4 to 6 carbon atoms, typically 4 carbon atoms, with
the proviso that at least one of the R''' groups is hydrocarbyl.
Typically the C.sub.4-6 hydrocarbyl phosphite comprises dibutyl
phosphite.
[0326] The C.sub.4-6 hydrocarbyl phosphite may deliver at least 175
ppm, or at least 200 ppm of the total amount of phosphorus
delivered by the phosphorus-containing compounds.
[0327] The C.sub.4-6 hydrocarbyl phosphite may deliver at least 45
wt %, or 50 wt % to 100 wt %, or 50 wt % to 90 wt % or 60 wt % to
80 wt % of the total amount of phosphorus from the
phosphorus-containing compound.
[0328] The phosphorus-containing compounds may comprise a second
phosphite whose formula is similar to that disclosed above, except
R''' may contain 2 to 40, 8 to 24 or 11 to 20 carbon atoms, with
the proviso that the second phosphite is not a C.sub.4-6
hydrocarbyl phosphite. Examples of suitable hydrocarbyl groups
include propyl, dodecyl, butadecyl, hexadecyl, octadecyl, propenyl,
dodecenyl, butadecenyl, hexadeencyl, or octadecenylgroups.
[0329] As used herein the term "alk(en)yl" is intended to include
moieties that have an alkyl and/or alkenyl group.
[0330] In one embodiment the phosphorus-containing compounds
include a mixture of a C.sub.4-6 hydrocarbyl phosphite (typically
dibutyl phosphite) and a C.sub.12-18 alk(en)yl hydrogen phosphite
and optionally phosphoric acid.In different embodiments the
phosphoric acid is present or absent.
[0331] In one embodiment the phosphorus-containing compounds
include a mixture of a C.sub.4-6 hydrocarbyl phosphite (typically
dibutyl phosphite) and a C.sub.16-18 alk(en)yl hydrogen phosphite.
The alk(en)yl hydrogen phosphite be may an alkyl hydrogen
phosphite, and alkenyl hydrogen phosphite, ora mixture of alkenyl
hydrogen phosphite and alkyl hydrogen phosphite. In one embodiment
the alk(en)yl hydrogen phosphite be may a mixture of alkenyl
hydrogen phosphite and alkyl hydrogen phosphite and optionally
phosphoric acid. The phosphoric acid may be present or absent.
[0332] In one embodiment the phosphorus-containing compounds
include a mixture of a C.sub.4-6 hydrocarbyl phosphite (typically
dibutyl phosphite) and a C.sub.11-14 alk(en)yl hydrogen phosphite.
The alk(en)yl hydrogen phosphite be may an alkyl hydrogen
phosphite, and alkenyl hydrogen phosphite, ora mixture of alkenyl
hydrogen phosphite and alkyl hydrogen phosphite. In one embodiment
the alk(en)yl hydrogen phosphite may be a mixture of alkenyl
hydrogen phosphite and alkyl hydrogen phosphite and optionally
phosphoric acid.
[0333] In one embodiment the phosphorus-containing compounds
include a mixture of a C.sub.4-6 hydrocarbyl phosphite (typically
dibutyl phosphite) and phosphoric acid.
[0334] The lubricant composition in one embodiment includes a
package that comprises a phosphorus-containing compound and a
non-ionic phosphorus compound that is a hydrocarbyl phosphite.
[0335] In one embodiment the lubricant composition further
comprises a C.sub.8-20 hydrocarbyl phosphite, or a C.sub.12-18
hydrocarbyl phosphite, or C.sub.16-18 hydrocarbyl phosphite, as
described above.
[0336] In on embodiment the amine salt of a phosphorus acid may be
derived from an amine salt of a phosphate. The amine salt of the
phosphorus acidmay be represented by the formula:
##STR00016##
wherein [0337] R.sup.3 and R.sup.4 may be independently hydrogen or
hydrocarbon typically containing 4 to 40, or 6 to 30, or 6 to 18,
or 8 to 18 carbon atoms, with the proviso that at least one is a
hydrocarbon group; and [0338] R.sup.5, R.sup.6, R.sup.7 and R.sup.8
may be independently hydrogen or a hydrocarbyl group, with the
proviso that at least one is a hydrocarbyl group.
[0339] The hydrocarbon groups of R.sup.3 and/or R.sup.4 may be
linear, branched, or cyclic.
[0340] Examples of a hydrocarbon group for R.sup.3 and/or R.sup.4
include straight-chain or branched alkyl groups include methyl,
ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,
undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,
heptadecyl and octadecyl.
[0341] Examples of a cyclic hydrocarbon group for R.sup.3 and/or
R.sup.4 include cyclopentyl, cyclohexyl, cycloheptyl,
methylcyclopentyl, dimethylcyclopentyl, methyl-cyclopentyl,
dimethylcyclopentyl, methylethylcyclopentyl, diethylcyclopentyl,
methylcyclohexyl, dimethylcyclohexyl, methylethylcyclohexyl,
diethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl,
methylethylcycloheptyl, and diethylcycloheptyl.
[0342] In one embodiment the phosphate may be an amine salt of a
mixture of monoalkyl and dialkyl phosphoric acid esters. The
monoalkyl and dialkyl groups may be linear or branched.
[0343] The amine salt of a phosphorus acid may be derived from an
amine such as a primary amine, a secondary amine, a tertiary amine,
or mixtures thereof. The amine may be aliphatic, or cyclic,
aromatic or non-aromatic, typically aliphatic. In one embodiment
the amine includes an aliphatic amine such as a tertiary-aliphatic
primary amine.
[0344] Examples of suitable primary amines include ethylamine,
propylamine, butylamine, 2-ethylhexylamine,
bis-(2-ethylhexyl)amine, octylamine, and dodecyl-amine, as well as
such fatty amines as n-octylamine, n-decylamine, n-dodecylamine,
n-tetradecylamine, n-hexadecylamine, n-octadecylamine and
oleyamine. Other useful fatty amines include commercially available
fatty amines such as "Armeen.RTM." amines (products available from
Akzo Chemicals, Chicago, Illinois), such as Armeen C, Armeen O,
Armeen OL, Armeen T, Armeen HT, Armeen S and Armeen SD, wherein the
letter designation relates to the fatty group, such as coco, oleyl,
tallow, or stearyl groups.
[0345] Examples of suitable secondary amines include dimethylamine,
diethylamine, dipropylamine, dibutylamine, diamylamine,
dihexylamine, diheptylamine, methylethylamine, ethylbutylamine,
N-methyl-1-amino-cyclohexane, Armeen.RTM. 2C and ethylamylamine.
The secondary amines may be cyclic amines such as piperidine,
piperazine and morpholine.
[0346] Examples of tertiary amines include tri-n-butylamine,
tri-n-octylamine, tri-decylamine, tri-laurylamine,
tri-hexadecylamine, and dimethyloleylamine (Armeen.RTM. DMOD).
[0347] In one embodiment the amines are in the form of a mixture.
Examples of suitable mixtures of amines include (i) a tertiary
alkyl primary amine with 11 to 14 carbon atoms, (ii) a tertiary
alkyl primary amine with 14 to 18 carbon atoms, or (iii) a tertiary
alkyl primary amine with 18 to 22 carbon atoms. Other examples of
tertiary alkyl primary amines include tert-butylamine,
tert-hexylamine, tert-octylamine (such as 1,1-dimethylhexylamine),
tert-decylamine (such as 1,1-dimethyloctylamine), tertdodecylamine,
tert-tetradecylamine, tert-hexadecylamine, tert-octadecylamine,
tert-tetracosanylamine, and tert-octacosanylamine.
[0348] In one embodiment a useful mixture of amines is
"Primene.RTM. 81R" or "Primene.RTM. JMT." Primene.RTM. 81R and
Primene.RTM. JMT (both produced and sold by Rohm & Haas) are
mixtures of C.sub.11 to C.sub.14 tertiary alkyl primary amines and
C.sub.18 to C.sub.22 tertiary alkyl primary amines
respectively.
[0349] The amine salt of a phosphorus acid may be prepared as is
described in US Patent 6,468,946. Column 10, lines 15 to 63
describes phosphoric acid esters formed by reaction of phosphorus
compounds, followed by reaction with an amine to form an amine salt
of a phosphate hydrocarbon ester. Column 10, line 64, to column 12,
line 23, describes preparative examples of reactions between
phosphorus pentoxide with an alcohol (having 4 to 13 carbon atoms),
followed by a reaction with an amine (typically Primene.RTM.81-R)
to form an amine salt of a phosphate hydrocarbon ester.
[0350] The sulphur-containing extreme pressure agent may be an
olefin sulphide, or mixtures thereof. The olefin sulphide may
include a polysulphide or a sulphurised olefin such as sulphurised
isobutylene, or mixtures thereof.
[0351] In one embodiment the olefin sulphide includes a
polysulphide.
[0352] In one embodiment the olefin sulphide includes sulphurized
isobutylene.
[0353] In one embodiment the olefin sulphide includes a mixture of
a sulphurised isobutylene and a polysulphide.
[0354] In one embodiment at least 50 wt % of the polysulphide
molecules are a mixture of tri- or tetra-sulphides. In other
embodiments at least 55 wt %, or at least 60 wt % of the
polysulphide molecules are a mixture of tri- or
tetra-sulphides.
[0355] The polysulphide includes a sulphurised organic polysulphide
from oils, fatty acids or ester, olefins or polyolefins.
[0356] Oils which may be sulfurized include natural or synthetic
oils such as mineral oils, lard oil, carboxylate esters derived
from aliphatic alcohols and fatty acids or aliphatic carboxylic
acids (e.g., myristyl oleate and oleyl oleate), and synthetic
unsaturated esters or glycerides.
[0357] Fatty acids include those that contain 8 to 30, or 12 to 24
carbon atoms. Examples of fatty acids include oleic, linoleic,
linolenic, and tall oil. Sulphurised fatty acid esters prepared
from mixed unsaturated fatty acid esters such as are obtained from
animal fats and vegetable oils, including tall oil, linseed oil,
soybean oil, rapeseed oil, and fish oil.
[0358] The polysulphide includes olefins derived from a wide range
of alkenes. The alkenes typically have one or more double bonds.
The olefins in one embodiment contain 3 to 30 carbon atoms. In
other embodiments, olefins contain 3 to 16, or 3 to 9 carbon atoms.
In one embodiment the sulphurised olefin includes an olefin derived
from propylene, isobutylene, pentene or mixtures thereof.
[0359] In one embodiment the polysulphide comprises a polyolefin
derived from polymerising by known techniques, an olefin as
described above.
[0360] In one embodiment the polysulphide includes dibutyl
tetrasulphide, sulphurised methyl ester of oleic acid, sulphurised
alkylphenol, sulphurised dipentene, sulphurised dicyclopentadiene,
sulphurised terpene, and sulphurised Diels-Alder adducts.
[0361] The lubricant may also include a sulphur-containing
corrosion inhibitor. The sulphur-containing corrosion inhibitor may
be a thiadiazole compound, or mixtures thereof. The thiadiazole
compound may include mono- or di-hydrocarbyl substituted
2,5-dimercapto-1,3,4-thiadiazole compounds. Examples of a
thiadiazole include 2,5-dimercapto-1,3,4-thiadiazole, or oligomers
thereof, a hydrocarbyl-substituted
2,5-dimercapto-1,3,4-thiadiazole, a hydrocarbylthio-substituted
2,5-dimercapto-1,3,4-thiadiazole, or oligomers thereof. The
oligomers of hydrocarbyl-substituted
2,5-dimercapto-1,3,4-thiadiazole typically form by forming a
sulphur-sulphur bond between 2,5-dimercapto-1,3,4-thiadiazole units
to form oligomers of two or more of said thiadiazole units. These
thiadiazole compounds may also be used in the post treatment of
dispersants as mentioned below in the formation of a
dimercaptothiadiazole derivative of a polyisobutylene
succinimide.
[0362] Examples of a suitable thiadiazole compound include at least
one of a dimercaptothiadiazole, 2,5-dimercapto-[1,3,4]-thiadiazole,
3,5-dimercapto-[1,2,4]-thiadiazole,
3,4-dimercapto-[1,2,5]-thiadiazole, or
4-5-dimercapto-[1,2,3]-thiadiazole. Typically readily available
materials such as 2,5-dimercapto-1,3,4-thiadiazole or a
hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole or a
hydrocarbylthio-substituted 2,5-dimercapto-1,3,4-thiadiazole are
commonly utilised.
[0363] Without intending to limit the scope of the exemplary
embodiment, the following examples illustrate preparation and
evaluation of example compounds.
EXAMPLES
Example 1
Preparation of Isobutylene-Substituted Phenol:
[0364] Phenol is alkylated with a 350 Mn high vinylidene
polyisobutylene (obtained from Texas Petroleum Products) under
standard conditions using boron trifluoride as a catalyst, as shown
in reaction scheme 1 above.
[0365] Phenol (271.5 g) and toluene (131.2 g) are first mixed in a
nitrogen blanketed vessel followed by the dropwise addition of
BF.sub.3 phenol complex (43.7g) over 20 mins. To this mixture, a
solution of 350Mn polyisobutylene (404.3 g, Texas Petroleum
Products) diluted in toluene (132.3 g) is added dropwise over 4
hrs. The addition rate is controlled to maintain a temperature
between 13-21.degree. C. and never exceeded 28.degree. C.
[0366] The reaction mixture is then neutralized slowly with calcium
hydroxide (84.0 g) with the temperature being held below 28.degree.
C. The neutralized reaction mixture is held for 3 hrs following
which diatomaceous earth (100 g) is charged to the reaction and the
neutralization completed with ammonia hydroxide (10 g). The
reaction mixture is filtered and the filtrate heated under vacuum
to a temperature of 185.degree. C. to remove volatiles by
distillation. The resulting material is a 350 Mn
polyisobutylene-alkylated phenol.
[0367] NMR analysis shows the product to be predominately the
para-substituted isomer with <3.0% free polyisobutylene
present.
Example 2
Bridging of Polyisobutylene-Alkylated Phenol
[0368] The material of Example 1 is used to synthesize a neutral
calcium phenate using the method shown in scheme 2, above.
[0369] The 350 Mn polyisobutylene-alkylated phenol (250.2 g) is
heated to 100.degree. C. while stirring in a vessel under a
nitrogen blanket. Calcium hydroxide (22.2 g) and ethylene glycol
(17.4 g) are added and the mixture is heated to 124.degree. C.
Sulfur (45.4 g) is added and the mixture is heated to 185.degree.
C. The reaction is held at this temperature for 7 hours. Diluent
oil (52.7 g) is added and the mixture is then cooled to room
temperature.
[0370] Ethylene glycol (13.7 g) and n-decanol (31.9 g) are added to
the reaction mixture with stirring, and the mixture is then heated
to 168.degree. C. under a nitrogen blanket. Calcium hydroxide (17.3
g) is then added and the mixture is heated to 168.degree. C. while
removing volatiles by distillation. Additional diluent oil (39.3 g)
is added to the reaction mixture which is heated to 220.degree. C.
with vacuum (13 kPa pressure, 27'' Hg vacuum) for 3 hours. The
mixture is cooled to 100.degree. C. and then filtered to yield the
final product, in diluent oil.
Example 3
Polyisobutylene-Substituted Bridged Calcium Phenate Having an Oil
Free TBN of about 400
[0371] A polyisobutylene-substituted bridged calcium phenate having
an oil free TBN of about 400 was prepared using the following
procedure: The material of Example 1 (400 g) is heated to
100.degree. C. while stirring in a vessel under a nitrogen blanket.
Calcium hydroxide (23.6 g) and ethylene glycol (8.9 g) are added
and the mixture is heated to 124.degree. C. Sulfur (68.5 g) is
added and the mixture is heated to 185.degree. C. The reaction is
held at this temperature for 5 hours. Diluent oil (98.2 g) is added
and the mixture is then cooled to room temperature.
[0372] Ethylene glycol (110.2 g) and n-decanol (140 g) are added to
the reaction mixture with stirring, followed by the addition of
alkylbenzene sulfonic acid (34 g) and calcium hydroxide (186.1 g)
and the mixture is then heated to 168.degree. C. under a nitrogen
blanket. Carbon dioxide (65.3 g) is then introduced via subline
over 2 hours. Volatile components are then removed by heating the
reaction mixture to 220.degree. C., applying vacuum to the system
(27'' Hg) and holding for 1 hour. The mixture is cooled to
100.degree. C., with the addition of diluent oil (349.2 g) and
polyisobutylene-substituted succinic anhydride (59.4 g), and then
filtered to yield the final product, in diluent oil.
Example 4
Polyisobutylene-Substituted Bridged Calcium Phenate Having an Oil
Free TBN of about 200
[0373] A polyisobutylene-substituted bridged calcium phenate having
an oil free TBN of about 200 was prepared using the following
procedure: The material of Example 1 (500 g) is heated to
100.degree. C. while stirring in a vessel under a nitrogen blanket.
Calcium hydroxide (44.4 g) and ethylene glycol (34.8 g) are added
and the mixture is heated to 124.degree. C. Sulfur (90.7 g) is
added and the mixture is heated to 185.degree. C. The reaction is
held at this temperature for 7 hours. Diluent oil (103 g) is added
and the mixture is then cooled to room temperature.
[0374] Ethylene glycol (27.4 g) and n-decanol (64.2 g) are added to
the reaction mixture with stirring, followed by the addition of
calcium hydroxide (34.9 g) and the mixture is then heated to
168.degree. C. under a nitrogen blanket and held for 3 hours.
Volatile components are then removed by heating the reaction
mixture to 220.degree. C., applying vacuum to the system (27'' Hg)
and holding for 1 hour. The mixture is cooled to 100.degree. C.,
with the addition of diluent oil (112.8 g) and then filtered to
yield the final product, in diluent oil.
Example 5
Polyisobutylene-Substituted Bridged Calcium Phenate Having an Oil
Free TBN of about 550
[0375] A polyisobutylene-substituted bridged calcium phenate having
an oil free TBN of about 550 could be prepared using the following
procedure: The material of Example 1 (1000 g) is heated to
107.degree. C. while stirring in a vessel under a nitrogen blanket.
Calcium hydroxide (306.9 g) is added and stirred for 5 minutes,
followed by the addition of acetic acid (11.5 g) while maintaining
the temperature below 110.degree. C. The reaction mixture is the
heated to 141.degree. C. and stearic acid (276.1 g) and n-decanol
(535 g), followed by increasing the temperature to 154.degree. C.
and addition of ethylene glycol (168 g). Carbon dioxide (131.1 g)
is then added as fast as possible maintaining the temperature below
168.degree. C. The temperature is reduced to 154.degree. C. and
volatiles removed under vacuum (150 mm Hg) and held for 4 hours.
The reaction temperature is increased to 220.degree. C. and the
vacuum increased to 40 mm Hg. Diluent oil (156.4 g) and
diatomaceous earth (104.2 g) is added, and then filtered to yield
the final product, in diluent oil.
Example 6
Polyisobutylene-Substituted Bridged Calcium Phenate Having an Oil
Free TBN of about 300
[0376] A polyisobutylene-substituted bridged calcium phenate having
an oil free TBN of about 300 could be prepared using the following
procedure: The material of Example 1 (555 g) is heated to
100.degree. C. while stirring in a vessel under a nitrogen blanket.
Calcium hydroxide (23.6 g) and ethylene glycol (8.9 g) are added
and the mixture is heated to 124.degree. C. Sulfur (92 g) is added
and the mixture is heated to 185.degree. C. The reaction is held at
this temperature for 5 hours. Diluent oil (98.2 g) is added and the
mixture is then cooled to room temperature.
[0377] Ethylene glycol (110.2 g) and n-decanol (140 g) are added to
the reaction mixture with stirring, followed by the addition
calcium hydroxide (130 g) and the mixture is then heated to
168.degree. C. under a nitrogen blanket. Carbon dioxide (63.2 g) is
then introduced via subline over 2 hours. Volatile components are
then removed by heating the reaction mixture to 220.degree. C.,
applying vacuum to the system (27'' Hg) and holding for 1 hour. The
mixture is cooled to 100.degree. C., with the addition of diluent
oil (280 g), and then filtered to yield the final product, in
diluent oil.
Analysis
[0378] Inductively Coupled Plasma (ICP) analysis of the
polyisobutylene-substituted bridged calcium phenate of Example 2
confirms that the elemental sulfur and calcium contents (measured
as wt. % of the product, which includes some diluent in addition to
the compound) agree with the theoretical values, as shown in TABLE
2.
[0379] TBN is measured according to ASTM D2896 on an oil free
basis.
TABLE-US-00002 TABLE 2 Analytical Results Wt. % S by ICP Wt. % Ca
by ICP TBN Theoretical composition 4.9 5.1 190 Example 2 compound
4.2 5.0 135 Example 3 compound 4.6 14.7 391 Comparative overbased
4.7 5.2 199 calcium phenate
[0380] A GPC of the experimental polyisobutylene-substituted
calcium phenate shows a number of peaks of increasing molecular
weight indicating a number of oligomers including monomers, dimers,
trimers, and tetramers, primarily dimers and trimers (i.e., m is
1-2 in Formula 2 above).
Preparation of Lubricating Composition
[0381] The sulfur bridged calcium phenate of Example 3 was blended
into a driveline lubricating composition to provide Example 7
below.
Example 7
TABLE-US-00003 [0382] Component wt % .sup.1 11.6 cSt Gp I base oil
77.7 4.2 cSt Gp I base oil 13.7 PiB Succinic ester type dispersant
0.3 520TBN Ca Sulfonate detergent 0.8 Neutral Ca Sulfonate
detergent 0.5 ZDDP Antiwear 2.6 Phenate of Example 3 0.7 Additive
components (seal swell, 0.9 antifoams, PPD, solubilzers etc)
Additional diluent oil Balance to 100 .sup.1 Oil free basis
[0383] A polyolefin-substituted bridged hydroxyaromatic compound of
the present invention may be blended into driveline lubricating
compositions as shown in the examples below. All wt % for
components are on an oil free basis. Example 8
TABLE-US-00004 Component Wt % PiB succinic ester type dispersant
3.99 480TBN Calcium sulfonate 9.06 Neutral Calcium sulfonate 4.59
ZDDP Antiwear 29.77 Friction Modifier 1.37 Additional additives
(seal swell agent, 8.17 antifoams and rust inhibitor) Compound of
the invention 6.08 Base oil Balance to 100
Example 9
TABLE-US-00005 [0384] Component Wt % PiB succinimide dispersant
16.41 520TBN Calcium sulfonate 5.93 Neutral Ca Sulfonate detergent
3.13 ZDDP Antiwear 12.97 Alkylphosphite antiwear 1.56 Friction
modifier package 4.68 (Alkenyl amide & Borate ester) Antifoams
0.03 Compound of the invention 10.94 Base Oil Balance to 100
Example 10
TABLE-US-00006 [0385] Component Wt % Mixed PiB succinic ester/amide
3.06 dispersant ZDDP antiwear 20.59 Alkyl phosphite antiwear 6.86
520 TBN Mg sulfonate detergent 3.31 Addititional additives
(solubulizer, 47.74 friction modifier, antifoam) Compound of the
invention 9.05 Base oil Balance to 100
Example 11
TABLE-US-00007 [0386] Component Wt % 520TBN detergent 7.60 170TBN
Ca sulfonate detergent 10.35 PiB succinimide dispersant 1.73 ZDDP
antiwear 6.29 Additional additives (antioxidant, rust 7.61
inhibitor, friction modifier) Compound of the invention 25.56 Base
Oil Balance to 100
[0387] The lubricating oil of Example 7 (100.+-.2 ml) was heated
(160.degree. C., 192hours) in accordance with the oxidation
procedure outlined in CEC test L-48-00 (test method available from
Coordinating European Council, Kellen Europe, Avenue Jules Bordet
142-1140 Brussels, Belgium (August 2015) by following the sections
outlining the glassware and heating apparatus (Section 4), test
preparation (Section 6), test operation (Section 7) and sludge
rating (Section 8).
[0388] The dispersancy assessment was made using the following
`Spot Rating` method. (1) 25 .mu.l of the oxidised oil sample is
placed onto #1 chromatography paper (Whatman 3001-917 Grade 1
Cellulose Chromatography Paper Sheet) using a 25 .mu.L pipette with
disposable tip; (2) The chromatography paper is dried in an oven
(60.degree. C., 24 hours); (3) The vertical and horizontal
diameters of the innermost spot is measured in millimetres. In the
case of a non-circular spot, the largest measurement of the
vertical and horizontal diameters are used; (4) The vertical and
horizontal diameters of the outermost spot is measured in
millimetres. In the case of a non-circular spot, the largest
measurement of the vertical and horizontal diameters are used; (5)
Spot rating =(The average of the innermost diameter spot/the
average of the outermost diameter spot, this is usually the corona
oil).times.100; (6) The spot rating can range from 100% (a clean,
fully dispersed spot) to 1% (a very heavily sludged-out spot or a
spot that is not fully dried).
[0389] The viscosity, viscosity index, total acid number, corrected
peak area increase, dispersancy assessment, and tube assessment
were measured. The results of the evaluation are summarized in
Table 3:
TABLE-US-00008 TABLE 3 Pre- Post % Test Oxidation Oxidation Change
Viscosity at 40.degree. C. D445 97.61 144.1 47.63 (cSt) Viscosity
at 100.degree. C. D445 11.15 14.53 30.31 (cSt) Viscosity Index
D2270 99 99 Total Acid Number, Buffer D664* 2.89 7.19 point (mg
KOH/g) Corrected Peak Area D7214 Not 464.29 Increase (A
cm.sup.-1/mm) Applicable Dispersancy See above Not 94 Assessment
(%) Applicable Tube assessment CEC Not 2 L-48-00 Applicable *A
volume of 60 ml rather than 125 ml of titrant was used (Section
12.1 of test method).
[0390] Other test methods which may be used to evaluate the
efficacy of a lubricating composition made in accordance with the
present invention include: FZG Scuffing: ASTM D5182, FZG Tractor:
ASTM D4998, Copper Strip: ASTM D130, Foam testing: ASTM D892, and
Compatibility with Caterpillar Elastomers (as outlined in the TO-4
specification). In addition, certain lubricating compositions may
be evaluated to determine if they meet the requirements of various
application requirements, such as the Caterpillar Transmission and
Drive Train Fluid Requirements (CAT STM SEQ 1222). In addition, the
toxicity of the components, in particular the
polyolefin-substituted bridged hydroxyaromatic compound or salt
thereof, or the alkyl-phenol used to form the compound, may be
evaluated using tests such as the PolarScreen.TM. Estrogen Receptor
Competitor Assay, as well as transactivation assays, or any other
tests designed to assess the potential ability of compounds to bind
to the estrogen receptor. Other tests may be used to evaluate the
toxicity of the compounds of this invention to show the lower
toxicity effect.
[0391] The singular forms "a," "an," and "the" include plural
referents unless the context clearly dictates otherwise.
[0392] Unless otherwise stated, molecular weight herein is reported
as number average molecular weight, in Daltons, and is measured by
Gel Permeation Chromatography (GPC) using a polyisobutylene
standard.
[0393] 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. Hydrocarbylene groups are the bivalent equivalents of
hydrocarbyl groups, i.e., are attached at each end to two parts of
the remainder of the molecule.
[0394] Examples of hydrocarbyl groups include:
[0395] (i) hydrocarbon substituents, that is, aliphatic (e.g.,
alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl)
substituents, aryl, 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);
[0396] (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);
[0397] (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.
[0398] Representative alkyl groups useful as hydrocarbyl groups may
include at least 1, or at least 2, or at least 3, or at least 4
carbon atoms, and in some embodiments, up to 8, or up to 10, or up
to 12, or up to 14, or up to 16, or up to 18 carbon atoms.
Illustrative examples include methyl, ethyl, propyl, butyl, pentyl,
hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl,
tridecyl, tetradecyl, 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,
4-methyl-2-pentyl, 2-propylheptyl, monomethyl branched-isostearyl,
isomers thereof, mixtures thereof, and the like.
[0399] Representative alkenyl groups useful as hydrocarbyl groups
include C.sub.2-C.sub.18 alkenyl groups, such as ethynyl,
2-propenyl, 1-methylene ethyl, 2-butenyl, 3-butenyl, pentenyl,
hexenyl, heptenyl, octenyl, 2-ethylhexenyl, nonenyl, decenyl,
undecenyl, dodecenyl, tridecenyl, tetradecenyl, hexadecenyl,
isomers thereof, mixtures thereof, and the like.
[0400] Representative alicyclic groups useful as hydrocarbyl groups
include cyclobutyl, cyclopentyl, and cyclohexyl groups.
[0401] 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.
[0402] Representative 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.
[0403] Numerical values in the specification and claims of this
application should be understood to include numerical values which
are the same when reduced to the same number of significant figures
and numerical values which differ from the stated value by less
than the experimental error of conventional measurement technique
of the type described in the present application to determine the
value.
[0404] As used herein, the term "comprising" is inclusive and does
not exclude additional, un-recited elements or method steps.
However, in each recitation of "comprising" herein, it is intended
that the term also encompasses, as alternative embodiments, the
phrases "consisting essentially of" and "consisting of," where
"consisting of" excludes any element or steps not specified and
"consisting essentially of" permits the inclusion of additional
un-recited elements or steps that do not materially affect the
basic and novel, and essential characteristics of the composition
or method under consideration.
[0405] 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.
* * * * *