U.S. patent application number 17/336809 was filed with the patent office on 2021-10-07 for lubricating compositions.
This patent application is currently assigned to The Lubrizol Corporation. The applicant listed for this patent is The Lubrizol Corporation. Invention is credited to Betsy J. Butke, Stephen J. Cook, Samuel M. Kilsby, Edward P. Sampler, Gary M. Walker.
Application Number | 20210309932 17/336809 |
Document ID | / |
Family ID | 1000005625500 |
Filed Date | 2021-10-07 |
United States Patent
Application |
20210309932 |
Kind Code |
A1 |
Sampler; Edward P. ; et
al. |
October 7, 2021 |
Lubricating Compositions
Abstract
A lubricating composition suited to use for lubricating a
hydraulic system includes an oil of lubricating viscosity and a
compound comprising a polyolefin-substituted bridged
hydroxyaromatic compound or metal salt thereof, wherein the wherein
the polyolefin is derived from a isobutylene having a number
average molecular weight of 150 to 800.
Inventors: |
Sampler; Edward P.; (Belper,
GB) ; Walker; Gary M.; (Belper, GB) ; Cook;
Stephen J.; (Belper, GB) ; Kilsby; Samuel M.;
(Belper, GB) ; Butke; Betsy J.; (Mentor,
OH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Lubrizol Corporation |
Wickliffe |
OH |
US |
|
|
Assignee: |
The Lubrizol Corporation
Wickliffe
OH
|
Family ID: |
1000005625500 |
Appl. No.: |
17/336809 |
Filed: |
June 2, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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16305088 |
Nov 28, 2018 |
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PCT/US17/37463 |
Jun 14, 2017 |
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17336809 |
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62351483 |
Jun 17, 2016 |
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62517292 |
Jun 9, 2017 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 2219/104 20130101;
C10M 2205/026 20130101; C10M 2207/028 20130101; C10N 2040/12
20130101; C10N 2030/06 20130101; C10M 2207/024 20130101; C10N
2010/04 20130101; C10M 2201/084 20130101; C10N 2060/14 20130101;
C10N 2030/04 20130101; C10N 2020/02 20130101; C10N 2030/12
20130101; C10N 2030/10 20130101; C10M 2215/086 20130101; C10M
159/22 20130101; C10N 2040/08 20130101; C10N 2030/40 20200501; C10M
2205/028 20130101; C10M 169/048 20130101; C10M 2215/02 20130101;
C10N 2010/06 20130101; C10M 2223/04 20130101 |
International
Class: |
C10M 169/04 20060101
C10M169/04 |
Claims
1. A lubricating composition comprising: an oil of lubricating
viscosity; a corrosion inhibitor selected from
2,5-bis(tert-dodecyldithio)-1,3,4-thiadiazole, tolyltriazole, or
mixtures thereof; an antioxidant selected from aminic or phenolic
antioxidants, or mixtures thereof; a dispersant; a neutral of
slightly overbased calcium sulfonate; an anti-wear agent selected
from zinc dialkyldithiophosphate, zinc dialkylphosphate, amine salt
of a phosphorus acid ester, or mixtures thereof; and a compound
comprising a polyolefin-substituted bridged hydroxyaromatic
compound or salt thereof, wherein the polyolefin is derived from
isobutylene having a number average molecular weight of 150 to 400
and wherein the compound is bridged with a sulfide bridge.
2. (canceled)
3. (canceled)
4. (canceled)
5. The lubricating composition of claim 1, wherein the compound is
a metal salt or pnictogen salt.
6. The lubricating composition of claim 5, wherein the metal in the
salt comprises calcium.
7. The lubricating composition of claim 1, wherein the metal is
overbased.
8. (canceled)
9. (canceled)
10. The lubricating composition of claim 1, wherein the compound is
a bridged metal phenate.
11. The lubricating composition of claim 1, wherein the compound is
free of C8 and higher unbranched alkyl chains.
12. The lubricating composition of claim 1, wherein the compound
includes a bridged phenate unit represented by the formula:
##STR00010## and salts thereof, where each R1 and each R2
represents an isobutylene group; X represents a sulfide 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.
13. The lubricating composition of claim 12, wherein the compound
is not coupled with cresol.
14. The lubricating composition of claim 12, wherein n is 1.
15. (canceled)
16. (canceled)
17. The lubricating composition of claim 12, wherein each R1 is a
300-400 MW polyisobutylene.
18. The lubricating composition of claim 1, wherein the compound
has a weight-average molecular weight of 550-5600 in its unsalted
form.
19. The lubricating composition of claim 1, wherein the compound
has a weight average molecular weight of up to 2800 in its unsalted
form.
20. The lubricating composition of claim 1, wherein the dispersant
comprises a borated succinimide or a non-borated succinimide
dispersant or a substantially nitrogen free dispersant as described
herein
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 20, wherein the compound
is at least 0.01 wt % of the lubricating composition.
23. The lubricating composition of claim 1, wherein the oil of
lubricating viscosity comprises at least one of an API Group I, II,
III, IV, or V base oil.
24. The lubricating composition of claim 1, wherein the oil of
lubricating viscosity is at least 10 wt. % up to 99.5 wt % of the
lubricating composition.
25. (canceled)
26. (canceled)
27. (canceled)
28. A method of lubricating a hydraulic system, comprising
supplying to the hydraulic system a lubricant comprising: 0.0001 wt
% to 0.15 wt % of a corrosion inhibitor selected from
2,5-bis(tert-dodecyldithio)-1,3,4-thiadiazole, tolyltriazole, or
mixtures thereof, an oil of lubricating viscosity, 0.02 wt % to 3
wt % of antioxidant chosen from aminic or phenolic antioxidants, or
mixtures thereof, 0.005 wt % to 1.5 wt % of a dispersant, 0.001 wt
% to 1.5 wt % of a neutral or slightly overbased calcium
sulphonate, 0.001 wt % to 2 wt % of an antiwear agent chosen from
zinc dialkyldithiophosphate, zinc dialkylphosphate, amine salt of a
phosphorus acid ester, or mixtures thereof; and 0.001 wt % to 5 wt
% of a compound comprising a polyolefin-substituted bridged
hydroxyaromatic compound or salt thereof, wherein the polyolefin is
derived from isobutylene having a number average molecular weight
of 150 to 400 and wherein the compound is bridged with a sulfide
bridge.
29. (canceled)
30. (canceled)
31. A method of lubricating a turbine system, comprising supplying
to the turbine system a lubricant comprising: 0.0001 wt % to 0.5 wt
% of a corrosion inhibitor chosen from
2,5-bis(tert-dodecyldithio)-1,3,4-thiadiazole, tolyltriazole, or
mixtures thereof; an oil of lubricating viscosity; 0.01 wt % to 1.5
wt % of antioxidant chosen from aminic or phenolic antioxidants, or
mixtures thereof; 0.01 wt % to 2 wt % of a dispersant, 0.001 wt %
to 1.5 wt % of a neutral or slightly overbased calcium sulphonate;
0.001 to 1 wt % of a carboxylic acid or anhydride chosen from
polyisobutylene succinic acid or anhydride thereof or dodecenyl
succinic acid; 0.05 wt % to 1.5 wt % of an antiwear agent chosen
from zinc dialkyldithiophosphate, zinc dialkylphosphate, amine salt
of a phosphorus acid ester, or mixtures thereof; 0.01 wt % to 1.5
wt % of a compound comprising a polyolefin-substituted bridged
hydroxyaromatic compound or salt thereof, wherein the polyolefin is
derived from isobutylene having a number average molecular weight
of 150 to 400 and wherein the compound is bridged with a sulfide
bridge.
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.12 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
boiling 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 4.pi.+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.
[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-1-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 M.sub.n 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.+, Ir.sup.4+, 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.+, In.sup.3+, In.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.++,
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-octylamine, 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 succinimides
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.
[0066] Reaction Scheme 1 illustrates the reaction:
##STR00004##
[0067] where b is for example, from 4-10.
[0068] 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.
[0069] ii) Coupling the Intermediate Compound with Sulfur or
Aldehyde and Formation of Salt
[0070] 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##
[0071] where x is from 1-5, on average, such as up to 3, or up to
2, on average.
[0072] 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.
[0073] 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.
[0074] 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.
[0075] 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.
[0076] The sulfurization reaction is carried out in the presence of
a base, which in one embodiment is the cation source, as described
below.
[0077] 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.
[0078] In general, sulfur coupling produces a more acidic compound
which makes over-basing easier.
[0079] 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.
[0080] 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).
[0081] 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.
[0082] 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.
[0083] 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.
[0084] In one embodiment, the pnictogen base includes a phosphorus
acid amine salt which includes an amine with C.sub.11 to C.sub.22
tertiary alkyl primary groups, or mixtures thereof.
[0085] 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.
[0086] The amine may be quaternized with a quaternizing agent, or
mixture thereof.
[0087] 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).
[0088] 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.
[0089] 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).
[0090] 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.
[0091] 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.
[0092] 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%.
[0093] 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.
[0094] 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.
[0095] 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.
[0096] 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.
[0097] 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.
[0098] 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.
[0099] 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.
[0100] 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.
[0101] In one embodiment, the salt of the polyolefin-substituted
bridged hydroxyaromatic compound does not contain any sulfonate
functional groups.
[0102] In one embodiment, the salt of the polyolefin-substituted
bridged hydroxyaromatic compound does not contain any phosphate
functional groups.
[0103] In one embodiment, the salt of the polyolefin-substituted
bridged hydroxyaromatic compound does not contain any borate
functional groups.
[0104] In another embodiment, the salt of the
polyolefin-substituted bridged hydroxyaromatic compound does
contain a borate functional group.
[0105] 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. %.
[0106] 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.
[0107] 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.
[0108] 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
[0109] 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.
[0110] 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
[0111] 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.
[0112] 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.
[0113] 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.ltoreq.0.03 wt.
%, and .gtoreq.90 wt. % saturates, viscosity index 80-120); Group
III (sulfur content.ltoreq.0.03 wt. %, and .gtoreq.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
[0114] 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.
[0115] 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.
[0116] 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).
[0117] 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.
[0118] Exemplary synthetic oils include poly-alpha olefins,
polyesters, polyacrylates, 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.
[0119] 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).
[0120] 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.
[0121] 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.
[0122] 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
[0123] 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.
[0124] 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.
[0125] 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.
[0126] 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).
[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] 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).
[0129] 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.
[0130] 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.
[0131] In one embodiment, the alkylbenzene sulfonate detergent may
be a branched alkylbenzene sulfonate, a linear alkylbenzene
sulfonate, or mixtures thereof.
[0132] 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.
[0133] 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.
[0134] 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.
[0135] 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.
[0136] The lubricating composition optionally further includes at
least one dispersant, other than the exemplary compound. Exemplary
dispersants include succinimide dispersants, Mannich dispersants,
succinamide dispersants, and polyolefin succinic acid esters,
amides, and ester-amides, and mixtures thereof. The succinimide
dispersant, where present, may be as described above for the
succinimides described as useful for cation M.
[0137] 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.
[0138] 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.
[0139] 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.
[0140] 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.
[0141] 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.
[0142] 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.
[0143] 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.
[0144] 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.
[0145] 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.
[0146] 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.
[0147] When present in the lubricating composition, the amount of
oil-soluble titanium compounds is included as part of the antiwear
agent.
[0148] 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 P.sub.2O.sub.5; and mixtures
thereof. Some useful extreme pressure agents are described in U.S.
Pat. No. 3,197,405.
[0149] 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.
[0150] 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.
[0151] 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.
[0152] 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.
[0153] The lubricating composition may include a corrosion
inhibitor. Corrosion inhibitors/metal deactivators that may be
useful in the exemplary lubricating composition include fatty
amines, octylamine octanoate, condensation products of dodecenyl
succinic acid or anhydride, and a fatty acid such as oleic acid
with a polyamine, derivatives of benzotriazoles (e.g.,
tolyltriazole), 1,2,4-triazoles, benzimidazoles,
2-alkyldithiobenzimidazoles and 2-alkyldithiobenzothiazoles.
[0154] The lubricating composition may include a pour point
depressant. Pour point depressants that may be useful in the
exemplary lubricating composition include polyalphaolefins, esters
of maleic anhydride-styrene copolymers, polymethacrylates,
polyacrylates, and polyacrylamides.
[0155] 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.
[0156] In one embodiment, the ash-free friction modifier may be
represented by the formula:
##STR00006##
[0157] 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).sub.2, and >CHOR.sup.28; where R.sup.24
and R.sup.25 are independently selected from >CH.sub.2,
>CHR.sup.26, >CR.sup.26R.sup.27, >C(OH)(CO.sub.2R.sup.22),
and >CHOR.sup.28; q is 0 to 10, with the proviso that when q=1,
E is not >CH.sub.2, and when n=2, both Es are not >CH.sub.2;
p is 0 or 1; R.sup.21 is independently hydrogen or a hydrocarbyl
group, typically containing 1 to 150 carbon atoms, with the proviso
that when R.sup.21 is hydrogen, p is 0, and q is more than or equal
to 1; R.sup.22 is a hydrocarbyl group, typically containing 1 to
150 carbon atoms; R.sup.23, R.sup.24, R.sup.25, R.sup.26 and
R.sup.27 are independently hydrocarbyl groups; and R.sup.28 is
hydrogen or a hydrocarbyl group, 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.
[0158] 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 maleimide.
[0159] 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.
[0160] 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.
[0161] 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 monoester and in another embodiment the long
chain fatty acid ester may be a triglyceride.
[0162] 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.
[0163] Molybdenum compounds are also known as friction modifiers.
The exemplary molybdenum compound does not contain dithiocarbamate
moieties or ligands.
[0164] 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##
[0165] 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.
[0166] 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.
[0167] 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.
[0168] 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.
[0169] 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.
[0170] Examples of some mono-alkylated alkylene diamines that may
be used include methylaminopropylamine, methylaminoethylamine,
butylaminopropylamine, butylamino-ethylamine,
octylaminopropylamine, octylaminoethylamine,
dodecylaaminopropylaamine, dodecylaminoethylamine,
hexadecylaminopropylamine, hexadecylaminoethylamine,
octadecyl-aminopropylamine, octadecylaminoethylamine,
isopropyloxypropyl-1,3-diaminopropane, and
octyloxypropyl-1,3-diaminopropane. Mono-alkylated alkylene diamines
derived from fatty acids may also be used. Examples include N-coco
alkyl-1,3-propanediamine (Duomeen.RTM.C), N-tall oil
alkyl-1,3-propanediamine (Duomeen.RTM.T) and
N-oleyl-1,3-propanediamine (Duomeen.RTM.O), all commercially
available from Akzo Nobel.
[0171] 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).
[0172] 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.
[0173] 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.
[0174] Demulsifiers useful herein include trialkyl phosphates, and
various polymers and copolymers of ethylene glycol, ethylene oxide,
propylene oxide, and mixtures thereof.
[0175] 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
[0176] 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 Engine Lubricating Compositions
Embodiments (wt. %) Additive A B C polyolefin-substituted bridged
0.1 to 20 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 Antiwear
Agent 0 to 15 0.1 to 10 0.3 to 5 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 Viscosity
Modifier 0 to 10 0.5 to 8 1 to 6 Other Performance Additives 0 to
10 0 to 8 0 to 6 Oil of Lubricating Viscosity Balance to 100%
Use of the Lubricating Composition
[0177] 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.
[0178] 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.
[0179] 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.
[0180] 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.
[0181] 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. %.
Hydraulics Oil, Turbine Oil or Circulating Oil
[0182] In one embodiment, the lubricating composition in accordance
with the present invention is for use in a hydraulic system,
turbine system or a circulating oil system. A hydraulic system is
generally a device or apparatus in which a fluid, typically an
oil-based fluid, transmits energy to different parts of the system
by hydraulic force. A turbine lubricant is typically used to
lubricate the gears or other moving parts of a turbine (or turbine
system), such as a steam turbine or a gas turbine. A circulating
oil is typically used to distribute heat to or through a device or
apparatus through which it is circulated.
[0183] In one embodiment the lubricant composition contains the
polyolefin-substituted bridged hydroxyaromatic compound or salt
thereof as described herein in an amount from 0.001 wt % or 0.005
wt % to 5 wt %, or 0.01 wt % or 0.05 wt % to 1.5 wt %, 0.05 wt % to
1 wt %, 0.01 wt % to 1 wt %, 0.01 wt % to 0.5 wt % of the overall
composition.
[0184] The hydraulic, turbine, or circulating lubricant
compositions may also contain one or more additional additives. In
some embodiments the additional additives may include an
antioxidant, an anti-wear agent, a corrosion inhibitor, a rust
inhibitor, a foam inhibitor, a dispersant, a demulsifier, a metal
deactivator, a friction modifier, a detergent, other than the
polyolefin-substituted bridged hydroxyaromatic compound or metal
salt thereof of the present invention, an emulsifier, an extreme
pressure agent, a pour point depressant, a viscosity modifier, or
any combination thereof.
[0185] The lubricant may thus comprise an antioxidant, or mixtures
thereof. The anti-oxidant may be present at 0 wt % to 4.0 wt %, or
0.02 wt % to 3.0 wt %, or 0.03 wt % to 1.5 wt % of the
lubricant.
[0186] Anti-oxidants include diarylamine, alkylated diarylamines,
hindered phenols, molybdenum compounds (such as molybdenum
dithiocarbamates), ashless dithiocarbamates, hydroxyl thioethers,
trimethyl polyquinoline (e.g.,
1,2-dihydro-2,2,4-trimethylquinoline), or mixtures thereof.
[0187] The diarylamine or alkylated diarylamine may be a
phenyl-.alpha.-naphthylamine (PANA), an alkylated diphenylamine, or
an alkylated phenylnaphthylamine, or mixtures thereof. The
alkylated diphenylamine may include di-nonylated diphenylamine,
nonyl diphenylamine, octyl diphenylamine, di-octylated
diphenylamine, di-decylated diphenylamine, decyl diphenylamine,
benzyl diphenylamine and mixtures thereof. In one embodiment the
diphenylamine may include nonyl diphenylamine, dinonyl
diphenylamine, octyl diphenylamine, dioctyl diphenylamine, or
mixtures thereof. In one embodiment the alkylated diphenylamine may
include nonyl diphenylamine, or dinonyl diphenylamine. The
alkylated diarylamine may include octyl, di-octyl, nonyl, di-nonyl,
decyl or di-decyl phenylnapthylamines. In one embodiment, the
diphenylamine is alkylated with a benzene and t-butyl
substituent.
[0188] The hindered phenol antioxidant often contains a secondary
butyl and/or a tertiary butyl group as a sterically hindering
group. The phenol group may be further substituted with a
hydrocarbyl group (typically 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-butyl-phenol
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 BASF GmbH. A more detailed description of
suitable ester-containing hindered phenol anti-oxidant chemistry is
found in U.S. Pat. No. 6,559,105.
[0189] Examples of molybdenum dithiocarbamates, which may be used
as an antioxidants, include commercial materials sold under the
trade names such as Molyvan 822.RTM., Molyvan.RTM. A, Molyvan.RTM.
855 and from R. T. Vanderbilt Co., Ltd., and Adeka Sakura-Lube.TM.
S100, S165, S600 and S525, or mixtures thereof. An example of an
ashless dithiocarbamate which may be used as an anti-oxidant or
anti-wear agent is Vanlube.RTM. 7723 from R. T. Vanderbilt Co.,
Ltd.
[0190] The antioxidant may include a substituted hydrocarbyl
mono-sulfide represented by the formula:
##STR00008##
wherein R.sup.6 may be a saturated or unsaturated branched or
linear alkyl group with 8 to 20 carbon atoms; R.sup.1, R.sup.8,
R.sup.9 and R.sup.10 are independently hydrogen or alkyl containing
1 to 3 carbon atoms. In some embodiments the substituted
hydrocarbyl monosulfides include n-dodecyl-2-hydroxyethyl sulfide,
1-(tert-dodecylthio)-2-propanol, or combinations thereof. In some
embodiments the substituted hydrocarbyl monosulfide is
1-(tert-dodecylthio)-2-propanol.
[0191] The lubricant compositions may also include a dispersant or
mixtures thereof. Suitable dispersants include: (i)
polyetheramines; (ii) borated succinimide dispersants; (iii)
non-borated succinimide dispersants; (iv) Mannich reaction products
of a dialkylamine, an aldehyde and a hydrocarbyl substituted
phenol; or any combination thereof. In some embodiments the
dispersant may be present at 0 wt % or 0.01 wt % to 2.0 wt %, 0.05
wt % to 1.5 wt %, or 0.005 wt % to 1 wt %, or 0.05 wt % to 0.5 wt %
of the overall composition.
[0192] Dispersants which may be included in the composition include
those with an oil soluble polymeric hydrocarbon backbone and having
functional groups that are capable of associating with particles to
be dispersed. The polymeric hydrocarbon backbone may have a weight
average molecular weight ranging from 750 to 1500 Daltons.
Exemplary functional groups include amines, alcohols, amides, and
ester polar moieties which are attached to the polymer backbone,
often via a bridging group. Example dispersants include Mannich
dispersants, described in U.S. Pat. Nos. 3,697,574 and 3,736,357;
ashless succinimide dispersants described in U.S. Pat. Nos.
4,234,435 and 4,636,322; amine dispersants described in U.S. Pat.
Nos. 3,219,666, 3,565,804, and 5,633,326; Koch dispersants,
described in U.S. Pat. Nos. 5,936,041, 5,643,859, and 5,627,259,
and polyalkylene succinimide dispersants, described in U.S. Pat.
Nos. 5,851,965, 5,853,434, and 5,792,729.
[0193] In an embodiment, the dispersant can be a "substantially
nitrogen free" dispersant. As used herein the term "substantially
nitrogen free" means the dispersant contributes about 35 ppm or
less, in one embodiment about 25 ppm or less, in another embodiment
about 15 ppm or less and in another embodiment about 5 ppm or less
nitrogen to the composition. In one embodiment of the invention
substantially nitrogen free dispersant is free of nitrogen. The
substantially nitrogen free dispersants are prepared by a process
described in U.S. Pat. Nos. 3,804,763, 4,031,118 and British Patent
Application GB 2,111,256.
[0194] In one embodiment, the dispersant can be a polyether
represented by the formula R7O[CH2CH(R8)O]qH, where R7 is a
hydrocarbyl group, R8 is selected from the group consisting of
hydrogen, hydrocarbyl groups of 1 to 16 carbon atoms, and mixtures
thereof, and q is a number from 2 to about 50. A commercial example
of a polyether is Lyondell ND.TM. series. Other suitable polyethers
are also available from Dow Chemicals, Huntsman, and Akzo.
[0195] Anti-foam agents, also known as foam inhibitors, are known
in the art and include organic silicones and non-silicon foam
inhibitors. Examples of organic silicones include dimethyl silicone
and polysiloxanes. Examples of non-silicon foam inhibitors include
copolymers of ethyl acrylate and 2-ethylhexylacrylate, terpolymers
of ethyl acrylate, 2-ethylhexylacrylate and vinyl acetate,
polyethers, polyacrylates and mixtures thereof. In some embodiments
the anti-foam is a polyacrylate. Antifoams may be present in the
composition from 0.001 wt % to 0.012 wt % or 0.004 wt % or even
0.001 wt % to 0.003 wt %.
[0196] Demulsifiers are known in the art and include derivatives of
propylene oxide, ethylene oxide, polyoxyalkylene alcohols, alkyl
amines, amino alcohols, diamines or polyamines reacted sequentially
with ethylene oxide or substituted ethylene oxides or mixtures
thereof. Examples of demulsifiers include polyethylene glycols,
polyethylene oxides, polypropylene oxides, (ethylene
oxide-propylene oxide) polymers and mixtures thereof. In some
embodiments the demulsifiers is a polyether. Demulsifiers may be
present in the composition from 0.002 wt % to 0.012 wt %.
[0197] Pour point depressants are known in the art and include
esters of maleic anhydride-styrene copolymers, polymethacrylates;
polyacrylates; polyacrylamides; condensation products of
haloparaffin waxes and aromatic compounds; vinyl carboxylate
polymers; and terpolymers of dialkyl fumarates, vinyl esters of
fatty acids, ethylene-vinyl acetate copolymers, alkyl phenol
formaldehyde condensation resins, alkyl vinyl ethers and mixtures
thereof.
[0198] The lubricant composition may also include a rust inhibitor.
Suitable rust inhibitors include hydrocarbyl amine salts of
alkylphosphoric acid, hydrocarbyl amine salts of
dialkyldithiophosphoric acid, hydrocarbyl amine salts of
hydrocarbyl aryl sulfonic acid fatty carboxylic acids or esters
thereof, an ester of a nitrogen-containing carboxylic acid, an
ammonium sulfonate, an imidazoline, alkylated succinic acid
derivatives reacted with alcohols or ethers, or any combination
thereof; or mixtures thereof.
[0199] Suitable hydrocarbyl amine salts of alkylphosphoric acid may
be represented by the following formula:
##STR00009##
wherein R.sup.26 and R.sup.27 are independently hydrogen, alkyl
chains or hydrocarbyl, typically at least one of R.sup.26 and
R.sup.27 are hydrocarbyl. R.sup.26 and R.sup.27 contain 4 to 30, or
8 to 25, or 10 to 20, or 13 to 19 carbon atoms. R.sup.28, R.sup.29
and R.sup.30 are independently hydrogen, alkyl branched or linear
alkyl chains with 1 to 30, or 4 to 24, or 6 to 20, or 10 to 16
carbon atoms. R.sup.28, R.sup.29 and R.sup.30 are independently
hydrogen, alkyl branched or linear alkyl chains, or at least one,
or two of R.sup.28, R.sup.29 and R.sup.30 are hydrogen.
[0200] Examples of alkyl groups suitable for R.sup.28, R.sup.29 and
R.sup.30 include butyl, sec butyl, isobutyl, tert-butyl, pentyl,
n-hexyl, sec hexyl, n-octyl, 2-ethyl, hexyl, decyl, undecyl,
dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,
octadecyl, octadecenyl, nonadecyl, eicosyl or mixtures thereof.
[0201] In one embodiment the hydrocarbyl amine salt of an
alkylphosphoric acid is the reaction product of a C.sub.14 to
C.sub.18 alkylated phosphoric acid with Primene.RTM. 81 R (produced
and sold by Rohm & Haas) which is a mixture of C.sub.11 to
C.sub.14 tertiary alkyl primary amines.
[0202] Hydrocarbyl amine salts of dialkyldithiophosphoric acid may
include a rust inhibitor such as a hydrocarbyl amine salt of
dialkyldithiophosphoric acid. These may be a reaction product of
heptyl or octyl or nonyl dithiophosphoric acids with ethylene
diamine, morpholine or Primene.RTM. 81 R or mixtures thereof.
[0203] The hydrocarbyl amine salts of hydrocarbyl aryl sulfonic
acid may include ethylene diamine salt of dinonyl naphthalene
sulfonic acid.
[0204] Examples of suitable fatty carboxylic acids or esters
thereof include glycerol monooleate and oleic acid. An example of a
suitable ester of a nitrogen-containing carboxylic acid includes
oleyl sarcosine.
[0205] The rust inhibitors may be present in the range from 0 or
0.02 wt % to 0.2 wt %, from 0.03 wt % to 0.15 wt %, from 0.04 wt %
to 0.12 wt %, or from 0.05 wt % to 0.1 wt % of the lubricating oil
composition. The rust inhibitors may be used alone or in mixtures
thereof.
[0206] The lubricant may contain a metal deactivator, or mixtures
thereof. Metal deactivators may be chosen from a derivative of
benzotriazole (typically tolyltriazole), 1,2,4-triazole,
benzimidazole, 2-alkyldithiobenzimidazole or
2-alkyldithiobenzothiazole, 1-amino-2-propanol, a derivative of
dimercaptothiadiazole, octylamine octanoate, condensation products
of dodecenyl succinic acid or anhydride and/or a fatty acid such as
oleic acid with a polyamine. The metal deactivators may also be
described as corrosion inhibitors.
[0207] The metal deactivators may be present in the range from 0 or
0.001 wt % to 0.1 wt %, from 0.01 wt % to 0.04 wt % or from 0.015
wt % to 0.03 wt % of the lubricating oil composition. Metal
deactivators may also be present in the composition from 0.002 wt %
or 0.004 wt % to 0.02 wt %. The metal deactivator may be used alone
or mixtures thereof.
[0208] In one embodiment the invention provides a lubricant
composition further comprises a metal-containing detergent, other
than the polyolefin-substituted bridged hydroxyaromatic compounds
or salts as described herein. The additional metal-containing
detergent may include an neutral or overbased, Newtonian or
non-Newtonian, basic salts of alkali, alkaline earth and transition
metals with one or more a phenate, a sulfurized phenate, a
sulfonate, a carboxylic acid, a phosphorus acid, a mono- and/or a
di-thiophosphoric acid, saligenin, an alkyl salicylate, a
salixarate or mixtures thereof. A neutral detergent has a
metal:detergent (soap) equivalence ratio of approximately one. An
overbased detergent has a metal:detergent equivalence ratio
exceeding one, i.e. the metal content is more than that necessary
to provide for a neutral salt of the detergent. The
metal-containing detergent may also be an overbased detergent with
total base number ranges from 30 to 500 mg KOH/g Equivalents. In
one embodiment, the additional metal-containing detergent comprises
at least one overbased metal-containing with a metal:detergent
ratio of at least 3. The additional metal-containing detergent may
have a metal:detergent ratio of at least 5, or at least 8, or at
least 12. The additional metal-containing detergent may be borated
with a borating agent such as boric acid, e.g., a borated overbased
calcium or magnesium sulfonate detergent, or mixtures thereof.
[0209] Examples of suitable metal-containing calcium sulfonate
detergents include for example calcium dinonyl naphthalene
sulfonate, calcium didecyl naphthalene sulfonate, didodecyl
naphthalene sulfonate, calcium dipentadecyl naphthalene sulfonate,
calcium dinonyl benzene sulfonate, calcium didecyl benzene
sulfonate, didodecyl benzene sulfonate, calcium dipentadecyl
benzene sulfonate, calcium dihexadecyl benzene sulfonate, calcium
diheptadecyl benzene sulfonate, calcium dioctadecyl benzene
sulfonate or mixtures thereof. In one embodiment the
metal-containing detergent comprises neutral or slightly overbased
calcium dinonyl naphthalene sulfonate, or mixtures thereof. The
sulfonate detergent may also have corrosion inhibitor
properties.
[0210] The additional metal-containing detergent may be present at
0 wt % to 5 wt %, or 0.001 wt % to 1.5 wt %, or 0.005 wt % to 1 wt
%, or 0.01 wt % to 0.5 wt % of the hydraulic composition.
[0211] The lubricant may comprise an extreme pressure agent. The
extreme pressure agent may be a compound containing sulfur and/or
phosphorus. Examples of extreme pressure agents include
polysulfides, sulfurized olefins, thiadiazoles, or mixtures
thereof.
[0212] 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
sulfur-sulfur bond between 2,5-dimercapto-1,3,4-thiadiazole units
to form oligomers of two or more of said thiadiazole units.
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 utilized. In different embodiments the number of carbon
atoms on the hydrocarbyl-substituent group includes 1 to 30, 2 to
25, 4 to 20, 6 to 16, or 8 to 10. The
2,5-dimercapto-1,3,4-thiadiazole may be 2,5-dioctyl
dithio-1,3,4-thiadiazole, or 2,5-dinonyl
dithio-1,3,4-thiadiazole.
[0213] The polysulfide may include a sulfurized organic polysulfide
from oils, fatty acids or esters, olefins, or polyolefins.
[0214] 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.
[0215] 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. Sulfurized 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.
[0216] The polysulfide 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 sulfurized olefin includes an olefin derived
from propylene, isobutylene, pentene or mixtures thereof. In one
embodiment the polysulfide comprises a polyolefin derived from
polymerizing by known techniques an olefin as described above. In
one embodiment the polysulfide includes dibutyl tetrasulfide,
sulfurized methyl ester of oleic acid, sulfurized alkylphenol,
sulfurized dipentene, sulfurized dicyclopentadiene, sulfurized
terpene, and sulfurized Diels-Alder adducts.
[0217] The extreme pressure agent may be present at 0 wt % to 3 wt
%, 0.005 wt % to 2 wt %, 0.01 wt % to 1.0 wt % of the hydraulics
composition.
[0218] The lubricant may further comprise a viscosity modifier, or
mixtures thereof. Viscosity modifiers (often referred to as
viscosity index improvers) suitable for use in the invention
include polymeric materials including a styrene-butadiene rubber,
an olefin copolymer, a hydrogenated styrene-isoprene polymer, a
hydrogenated radical isoprene polymer, a poly(meth)acrylic acid
ester, a polyalkylstyrene, an hydrogenated alkenylaryl
conjugated-diene copolymer, an ester of maleic anhydride-styrene
copolymer or mixtures thereof. In some embodiments the viscosity
modifier is a poly(meth)acrylic acid ester, an olefin copolymer or
mixtures thereof. The viscosity modifiers may be present at 0 wt %
to 10 wt %, 0.5 wt % to 8 wt %, 1 wt % to 6 wt % of the
lubricant.
[0219] In one embodiment the lubricant disclosed herein may contain
at least one friction modifier. The friction modifier may be
present at 0 wt % to 3 wt %, or 0.02 wt % to 2 wt %, or 0.05 wt %
to 1 wt %, of the lubricant composition.
[0220] As used herein the term "fatty alkyl" or "fatty" in relation
to friction modifiers means a carbon chain having 10 to 22 carbon
atoms, typically a straight carbon chain. Alternatively, the fatty
alkyl may be a mono branched alkyl group, with branching typically
at the .beta.-position. Examples of mono branched alkyl groups
include 2-ethylhexyl, 2-propylheptyl or 2-octyldodecyl.
[0221] Examples of suitable friction modifiers include 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 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.
[0222] In one embodiment the lubricant composition further includes
an anti-wear agent. Typically the anti-wear agent may be a
phosphorus anti-wear agent or mixtures thereof. The anti-wear agent
may be present at 0 wt % to 5 wt %, 0.001 wt % to 2 wt %, 0.01 wt %
to 1.0 wt % of the lubricant.
[0223] The phosphorus anti-wear agent may include a phosphorus
amine salt, or mixtures thereof. The phosphorus amine salt includes
an amine salt of a phosphorus acid ester or mixtures thereof. The
amine salt of a phosphorus acid ester includes phosphoric acid
esters and amine salts thereof; dialkyldithiophosphoric acid esters
and amine salts thereof; phosphites; and amine salts of
phosphorus-containing carboxylic esters, ethers, and amides;
hydroxy substituted di or tri esters of phosphoric or
thiophosphoric acid and amine salts thereof; phosphorylated hydroxy
substituted di or tri esters of phosphoric or thiophosphoric acid
and amine salts thereof; and mixtures thereof. The amine salt of a
phosphorus acid ester may be used alone or in combination.
[0224] In one embodiment the oil soluble phosphorus amine salt
includes partial amine salt-partial metal salt compounds or
mixtures thereof. In one embodiment the phosphorus compound further
includes a sulfur atom in the molecule.
[0225] Examples of the anti-wear agent may include a non-ionic
phosphorus compound (typically compounds having phosphorus atoms
with an oxidation state of +3 or +5). In one embodiment the amine
salt of the phosphorus compound may be ashless, i.e., metal-free
(prior to being mixed with other components).
[0226] The amines which may be suitable for use as the amine salt
include primary amines, secondary amines, tertiary amines, and
mixtures thereof. The amines include those with at least one
hydrocarbyl group, or, in certain embodiments, two or three
hydrocarbyl groups. The hydrocarbyl groups may contain 2 to 30
carbon atoms, or in other embodiments 8 to 26, or 10 to 20, or 13
to 19 carbon atoms.
[0227] Primary amines include ethylamine, propylamine, butylamine,
2-ethylhexylamine, octylamine, and dodecylamine, 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, Ill.), 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.
[0228] Examples of suitable secondary amines include dimethylamine,
diethylamine, dipropylamine, dibutylamine, diamylamine,
dihexylamine, diheptylamine, methylethylamine, ethylbutylamine and
ethylamylamine. The secondary amines may be cyclic amines such as
piperidine, piperazine and morpholine.
[0229] 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,
tertdodecylamine, tert-tetradecylamine, tert-hexadecylamine,
tert-octadecylamine, tert-tetracosanylamine, and
tert-octacosanylamine.
[0230] In one embodiment the phosphorus acid amine salt includes an
amine with C11 to C14 tertiary alkyl primary groups or mixtures
thereof. In one embodiment the phosphorus acid amine salt includes
an amine with C14 to C18 tertiary alkyl primary amines or mixtures
thereof. In one embodiment the phosphorus acid amine salt includes
an amine with C18 to C22 tertiary alkyl primary amines or mixtures
thereof. Mixtures of amines may also be used. In one embodiment a
useful mixture of amines is "Primene.RTM. 81 R" and "Primene.RTM.
JMT." Primene.RTM. 81 R and Primene.RTM. JMT (both produced and
sold by Rohm & Haas) are mixtures of C11 to C14 tertiary alkyl
primary amines and C18 to C22 tertiary alkyl primary amines
respectively.
[0231] In one embodiment oil soluble amine salts of phosphorus
compounds include a sulfur-free amine salt of a
phosphorus-containing compound may be obtained/obtainable by a
process comprising: reacting an amine with either (i) a
hydroxy-substituted di-ester of phosphoric acid, or (ii) a
phosphorylated hydroxy-substituted di- or tri-ester of phosphoric
acid. A more detailed description of compounds of this type is
disclosed in U.S. Pat. No. 8,361,941.
[0232] In one embodiment the hydrocarbyl amine salt of an
alkylphosphoric acid ester is the reaction product of a C14 to C18
alkylated phosphoric acid with Primene 81 R.RTM. (produced and sold
by Rohm & Haas) which is a mixture of C11 to C14 tertiary alkyl
primary amines.
[0233] 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 81 R.TM., and mixtures
thereof.
[0234] 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, and styrene oxide. In one
embodiment the epoxide may be propylene oxide. The glycols may be
aliphatic glycols having from 1 to 12, or from 2 to 6, or 2 to 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 58.degree. C. over a period of 45 minutes to
514 grams of hydroxypropyl
0,0'-di(4-methyl-2-pentyl)phosphorodithioate (prepared by reacting
di(4-methyl-2-pentyl)-phosphorodithioic acid with 1.3 moles of
propylene oxide at 25.degree. C.). The mixture may be heated at
75.degree. C. for 2.5 hours, mixed with a diatomaceous earth and
filtered at 70.degree. C. The filtrate contains 11.8% by weight
phosphorus, 15.2% by weight sulfur, and an acid number of 87
(bromophenol blue).
[0235] In one embodiment the anti-wear additives may include a zinc
dialkyldithiophosphate. In other embodiments the compositions of
the present invention are substantially free of, or even completely
free of zinc dialkyldithiophosphate.
[0236] In one embodiment the invention provides for a composition
that includes a dithiocarbamate antiwear agent defined in U.S. Pat.
No. 4,758,362 column 2, line 35 to column 6, line 11. When present
the dithiocarbamate antiwear agent may be present from 0.25 wt %,
0.3 wt %, 0.4 wt % or even 0.5 wt % up to 0.75 wt %, 0.7 wt %, 0.6
wt % or even 0.55 wt % in the overall composition.
[0237] A hydraulic lubricant may thus comprise:
[0238] 0.01 wt % to 2 wt % of the polyolefin-substituted bridged
hydroxyaromatic compound or salt thereof as described herein,
[0239] 0.0001 wt % to 0.15 wt % of a corrosion inhibitor chosen
from 2,5-bis(tert-dodecyldithio)-1,3,4-thiadiazole, tolyltriazole,
or mixtures thereof, an oil of lubricating viscosity,
[0240] 0.02 wt % to 3 wt % of antioxidant chosen from aminic or
phenolic antioxidants, or mixtures thereof,
[0241] 0 wt % to 1.5 wt % of a dispersant such as a borated
succinimide or a non-borated succinimide dispersant or a
substantially nitrogen free dispersants as described herein,
[0242] 0.001 wt % to 1.5 wt % of a neutral or slightly overbased
calcium sulfonate and
[0243] 0.001 wt % to 2 wt %, or 0.01 wt % to 1 wt % of an anti-wear
agent chosen from zinc dialkyldithiophosphate, zinc
dialkylphosphate, amine salt of a phosphorus acid ester, or
mixtures thereof.
[0244] A hydraulic lubricant may thus comprise:
[0245] 0.01 wt % to 1.5 wt % of the polyolefin-substituted bridged
hydroxyaromatic compound or salt thereof as described herein,
[0246] 0.0001 wt % to 0.15 wt % of a corrosion inhibitor chosen
from 2,5-bis(tert-dodecyldithio)-1,3,4-thiadiazole, tolyltriazole,
or mixtures thereof,
[0247] an oil of lubricating viscosity,
[0248] 0.02 wt % to 3 wt % of antioxidant chosen from aminic or
phenolic antioxidants, or mixtures thereof,
[0249] 0.005 wt % to 1.5 wt % of a dispersant, such as a borated
succinimide or a non-borated succinimide dispersant or a
substantially nitrogen free dispersant as described herein,
[0250] 0.001 wt % to 1.5 wt % of a neutral of slightly overbased
calcium sulfonate
[0251] 0.001 wt % to 2 wt %, or 0.01 wt % to 1 wt % of an anti-wear
agent chosen from zinc dialkyldithiophosphate, zinc
dialkylphosphate, amine salt of a phosphorus acid ester, or
mixtures thereof.
[0252] A hydraulic lubricant may also comprise a formulation
defined in the following table:
TABLE-US-00002 TABLE 3 Hydraulic Lubricant compositions Embodiments
(wt %) Additive A B C Polyolefin-substituted bridged 0.01 to 2.0
0.01 to 1.5 0.01 to 1.0 hydroxyaromatic compound or salt thereof as
described herein Antioxidant 0 to 4.0 0.02 to 3.0 0.03 to 1.5
Dispersant 0 to 2.0 0.005 to 1.5 0.01 to 1.0 Detergent 0 to 5.0
0.001 to 1.5 0.005 to 1.0 Anti-wear Agent 0 to 5.0 0.001 to 2 0.1
to 1.0 Friction Modifier 0 to 3.0 0.02 to 2 0.05 to 1.0 Viscosity
Modifier 0 to 10.0 0.5 to 8.0 1.0 to 6.0 Any Other Performance 0 to
1.3 0.00075 to 0.5 0.001 to 0.4 Additive (antifoam/demulsifier/
pour point depressant) Metal Deactivator 0 to 0.1 0.01 to 0.04
0.015 to 0.03 Rust Inhibitor 0 to 0.2 0.03 to 0.15 0.04 to 0.12
Extreme Pressure Agent 0 to 3.0 0.005 to 2 0.01 to 1.0 Oil of
Lubricating Viscosity Balance to Balance to Balance to 100% 100%
100%
[0253] Specific examples of a hydraulic lubricant include those
summarized in the following table:
TABLE-US-00003 TABLE 4 Hydraulic Lubricant compositions Embodiments
(wt %) Additive A B C Polyolefin-substituted bridged 0.02 0.06 0.30
hydroxyaromatic compound or salt thereof as described herein
Antioxidant-aminic/phenolic 0.4 0.4 0.4 Calcium Sulfonate Detergent
0.02 0.1 0.2 Zinc dialkyl dithiophosphate 0.2 0.5 1.0 Any Other
Performance 0.2 0.6 1.0 Additive (antifoam/ demulsifier/pour point
depressant) Triazole Metal Deactivator 0.005 0.0075 0.01 Oil of
Lubricating Viscosity Balance to Balance to Balance to 100% 100%
100%
[0254] The performance of each lubricant may be evaluated in
accordance with ASTM D4310-10 (Standard Test Method for
Determination of Sludging and Corrosion Tendencies of Inhibited
Mineral Oils). Performance is judged by measuring the total amount
of sludge formed during the oxidation of lubricants and mineral oil
based fluids in the presence of oxygen, water and copper and iron
metals at elevated temperatures as well as the ability of these
oils to corrode copper catalyst metals.
[0255] 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
[0256] Phenol is alkylated with a 350 Mw high vinylidene
polyisobutylene (obtained from Texas Petroleum Products) under
standard conditions using boron trifluoride as a catalyst, as shown
in reaction scheme 1 above.
[0257] 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 (43.7 g) over 20 mins. To this mixture, a
solution of 350 Mw 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.
[0258] 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.
[0259] 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
[0260] The material of Example 1 is used to synthesize a neutral
calcium phenate using the method shown in scheme 2, above.
[0261] The 350 Mw 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.
[0262] 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.
Analysis
[0263] Inductively Coupled Plasma (ICP) analysis of the Example
2phenate 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.
[0264] TBN is measured according to ASTM D2896 on an oil free
basis.
TABLE-US-00004 TABLE 2 Analytical Results Wt. % S Wt. % Ca by ICP
by ICP TBN Theoretical composition 4.9 5.1 190 Example 2 compound
4.2 5.0 135 Comparative overbased 4.7 5.2 199 calcium phenate
[0265] 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).
Example 3: Preparation of Lubricating Composition
[0266] The sulfur bridged calcium phenate of Example 2 is blended
into a typical marine diesel cylinder lubricant (MDCL) to provide
Example 3.
[0267] A comparative MDCL (Example 4) is blended using the
commercially available overbased calcium phenate. The compositions
of the two lubricant compositions are shown in TABLE 3.
TABLE-US-00005 TABLE 3 Exemplary and Baseline Formulations (treat
rates are oil free) Example 4 Example 3 Comparative Lubricating
Lubricating composition composition Ingredient (% by wt.) (% by
wt.) 500N Oil (8-10Cst) Balance to 100% 150BS Oil 29.30 29.0 400TBN
Overbased Calcium 8.90 8.9 Sulfonate Borated Succinimide 0.67 0.67
Dispersant Anti-foam agent 0.03 0.03 150TBN Commercial -- 3.65
Overbased Calcium Phenate 150TBN Calcium Phenate-350 2.97 -- Mw
polyisobutylene Phenol
[0268] The MDCLs are tested for high temperature deposit forming
tendency in both a panel coker apparatus (Similar to GFC
Lu-29-T-97).
[0269] Panel coker testing is performed as follows: the sample, at
105.degree. C., is splashed for 4 hours on an aluminum panel
maintained at 325.degree. C. The aluminum panels are analyzed using
image analysis techniques to obtain a universal rating. The rating
score is based on 100% being a clean panel and 0% being a panel
wholly covered in deposit. Higher values are better, e.g., above
80% is good. The weight of deposit was also determined.
[0270] Viscosity at 40.degree. C. and 100.degree. C. are measured
according to ASTM D2270-10 (2016), Standard Practice for
Calculating Viscosity Index from Kinematic Viscosity at 40.degree.
C. and 100.degree. C., and the Viscosity Index (VI) calculated from
the results.
[0271] The results are shown in TABLE 4, and compared with the
baseline marine diesel formulation without the exemplary
compound.
TABLE-US-00006 TABLE 4 Results Example 4 Example 3 Comparative
Lubricating Lubricating Sample composition composition Panel Coker
results 55 46 Unit Rating (%) VISCOSITY 232.1 218.9 @40 cSt
VISCOSITY 21.05 20 @100 cSt VI 107 105
[0272] On the panel coker test, the exemplary 350 Mn
polyisobutylene-substituted sulfur bridged phenol calcium salt
showed a significant performance boost over the baseline
formulation, giving a Unit rating of 55% compared to the baseline
of 46%.
[0273] The viscosity of the Example 3 lubricating composition was
retained well over the temperature range.
[0274] Additional bridged polyisobutylene-substituted phenols were
prepared in accordance with Examples 4 and 5:
Example 4
[0275] The material of Example 1 (400 g) was heated to 100.degree.
C. while stirring in a vessel under a nitrogen blanket. Calcium
hydroxide (24 g) and ethylene glycol (9 g) were added and the
mixture was heated to 124.degree. C. Sulfur (69 g) was added and
the mixture was heated to 185.degree. C. The reaction was held at
this temperature for 5 hours. Diluent oil (98 g) was added and the
mixture was then cooled to room temperature. Ethylene glycol (110
g) and n-decanol (140 g) were added to the reaction mixture with
stirring, followed by the addition of alkylbenzene sulfonic acid
(34 g) and calcium hydroxide (186 g) and the mixture was then
heated to 168.degree. C. under a nitrogen blanket. Carbon dioxide
(65 g) was then introduced via subline over 2 hours. Volatile
components were 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 was cooled to 100.degree. C., with the
addition of diluent oil (349 g) and polyisobutylene-substituted
succinic anhydride (59.44 g), and then filtered to yield the final
product, in diluent oil, which has a oil-free TBN of 396.
Example 5
[0276] The material of Example 1 (500 g) was heated to 100.degree.
C. while stirring in a vessel under a nitrogen blanket. Calcium
hydroxide (44 g) and ethylene glycol (35 g) were added and the
mixture was heated to 124.degree. C. Sulfur (91 g) was added and
the mixture is heated to 185.degree. C. The reaction was held at
this temperature for 7 hours. Diluent oil (103 g) was added and the
mixture was then cooled to room temperature. Ethylene glycol (27 g)
and n-decanol (64 g) were added to the reaction mixture with
stirring, followed by the addition of calcium hydroxide (35 g) and
the mixture was then heated to 168.degree. C. under a nitrogen
blanket and held for 3 hours. Volatile components were 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 was
cooled to 100.degree. C., with the addition of diluent oil (113 g)
and then filtered to yield the final product, in diluent oil, which
has an oil-free TBN of 187.
[0277] Additional bridged polyisobutylene-substituted phenols could
be made according to Examples 6 and 7:
Example 6
[0278] The material of Example 4 (1000 g) is heated to 107.degree.
C. while stirring in a vessel under a nitrogen blanket. Calcium
hydroxide (306.897 g) is added and stirred for 5 minutes, followed
by the addition of acetic acid (11.493 g) while maintaining the
temperature below 110.degree. C. The reaction mixture is the heated
to 141.degree. C. and stearic acid (276 g) and n-decanol (535 g),
followed by increasing the temperature to 154.degree. C. and
addition of ethylene glycol (168.00 g). Carbon dioxide (131 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 g) and diatomaceous
earth (104 g) is added, and then filtered to yield the final
product, in diluent oil.
Example 7
[0279] The material of Example 1 (555 g) is heated to 100.degree.
C. while stirring in a vessel under a nitrogen blanket. Calcium
hydroxide (24 g) and ethylene glycol (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 g) is added and the
mixture is then cooled to room temperature. Ethylene glycol (110 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 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.
[0280] Each of the documents referred to above is incorporated
herein by reference. Except in the Examples, or where otherwise
explicitly indicated, all numerical quantities in this description
specifying amounts of materials, reaction conditions, molecular
weights, number of carbon atoms, and the like, are to be understood
as modified by the word "about." Unless otherwise indicated, each
chemical or composition referred to herein should be interpreted as
being a commercial grade material which may contain the isomers,
by-products, derivatives, and other such materials which are
normally understood to be present in the commercial grade. However,
the amount of each chemical component is presented exclusive of any
solvent or diluent oil, which may be customarily present in the
commercial material, unless otherwise indicated. It is to be
understood that the upper and lower amount, range, and ratio limits
set forth herein may be independently combined. Similarly, the
ranges and amounts for each element of the invention may be used
together with ranges or amounts for any of the other elements.
[0281] The singular forms "a," "an," and "the" include plural
referents unless the context clearly dictates otherwise.
[0282] 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.
[0283] Examples of hydrocarbyl groups include:
[0284] (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);
[0285] (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);
[0286] (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.
[0287] 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.
[0288] 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.
[0289] Representative alicyclic groups useful as hydrocarbyl groups
include cyclobutyl, cyclopentyl, and cyclohexyl groups.
[0290] 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.
[0291] 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.
[0292] 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.
[0293] 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.
[0294] 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.
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