U.S. patent application number 16/769049 was filed with the patent office on 2021-07-29 for alkylphenol detergents.
The applicant listed for this patent is The Lubrizol Corporation. Invention is credited to James D. Burrington, Ewan E. Delbridge, Patrick E. Mosier, James S. Puckace.
Application Number | 20210230498 16/769049 |
Document ID | / |
Family ID | 1000005535608 |
Filed Date | 2021-07-29 |
United States Patent
Application |
20210230498 |
Kind Code |
A1 |
Delbridge; Ewan E. ; et
al. |
July 29, 2021 |
Alkylphenol Detergents
Abstract
The disclosed technology relates to hydrocarbyl- (e.g. alkyl-)
phenol detergents and their salts, where the hydrocarbyl group
includes moieties equivalent to 5 to 10 carbon branched polyene
compounds. Such compounds and their salts are useful as lubricant
additives.
Inventors: |
Delbridge; Ewan E.; (Concord
Township, OH) ; Burrington; James D.; (Gates Mills,
OH) ; Mosier; Patrick E.; (Bay Village, OH) ;
Puckace; James S.; (Palm Harbor, FL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Lubrizol Corporation |
Wickliffe |
OH |
US |
|
|
Family ID: |
1000005535608 |
Appl. No.: |
16/769049 |
Filed: |
November 2, 2018 |
PCT Filed: |
November 2, 2018 |
PCT NO: |
PCT/US2018/058850 |
371 Date: |
June 2, 2020 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62594251 |
Dec 4, 2017 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 2207/144 20130101;
C10N 2010/04 20130101; C10M 2207/028 20130101; C10N 2030/04
20130101; C10N 2020/071 20200501; C10M 159/22 20130101; C10M
2223/045 20130101; C10N 2040/252 20200501; C10M 2219/106
20130101 |
International
Class: |
C10M 159/22 20060101
C10M159/22 |
Claims
1. An alkylphenol detergent composition comprising at least one
phenol moiety having a hydrocarbyl group attached thereto, the
hydrocarbyl group comprising at least one oligomer comprising
monomers equivalent to 5 to 10 carbon atom branched olefins.
2. The alkylphenol detergent composition of claim 1, where the
monomers are equivalent to 5 to 10 carbon atom branched
polyenes.
3. The alkylphenol detergent composition of claim 2, where the
monomers are equivalent to isoprene.
4. The alkylphenol detergent composition of claim 1, where the
oligomer is a terpene.
5. (canceled)
6. The detergent composition of claim 1, wherein the oligomer is
equivalent to a partially or completely hydrogenated form of a
terpene.
7. (canceled)
8. The detergent composition of claim 1, where the hydrocarbyl unit
comprises 15 to 60 carbon atoms.
9. The detergent composition of claim 1, where the detergent
comprises an alkylphenol moiety of any of formula: ##STR00021##
10. The detergent composition of claim 1, wherein the detergent is
a sulfur-bridged phenate detergent, a sulfur-free alkylene-bridged
phenate detergent, a salicylate detergent, or mixtures thereof.
11. The detergent composition of claim 1, where the detergent
comprises one or more alkali metals, one or more alkaline earth
metals, or mixtures thereof.
12. The detergent composition of claim 1, where the detergent is
overbased.
13. (canceled)
14. (canceled)
15. (canceled)
16. The detergent composition of claim 1, wherein the detergent is
a neutral or overbased salt of alkylsalicylic acid.
17. (canceled)
18. A lubricating composition comprising (a) an oil of lubricating
viscosity and (b) the alkylphenol detergent composition of claim
1.
19. The lubricating composition of claim 18, wherein the
alkylphenol detergent is present from about 0.01 to about 2 wt % of
the lubricating composition.
20. The lubricating composition of claim 18, wherein the
composition is substantially free of an alkylphenol-containing
detergent wherein the alkylphenol is derived from oligomers of
propene.
21. The lubricating composition of claim 18, further comprising a
zinc dialkyldithiophosphate.
22. The lubricating composition of claim 18, further comprising a
dispersant.
23. (canceled)
24. (canceled)
25. The lubricating composition of claim 18, further comprising a
phosphorus-containing antiwear agent chosen from (i) a non-ionic
phosphorus compound, which may be a hydrocarbyl phosphite; or (ii)
an amine salt of a phosphorus compound.
26. The lubricating composition of claim 18, further comprising a
thiadiazole.
27. (canceled)
28. A method of lubricating a mechanical device comprising
supplying to the device the lubricating composition of claim
18.
29. (canceled)
30. (canceled)
31. (canceled)
32. (canceled)
33. (canceled)
34. (canceled)
Description
BACKGROUND OF THE INVENTION
[0001] The disclosed technology relates to hydrocarbyl- (e.g.
alkyl-) phenol detergents and their salts having oligomers of
branched olefins, including branched polyenes, such as terpenes.
Such compounds and their salts are useful as lubricant
additives.
[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, and, historically,
dodecylphenol (or propylene tetramer-substituted phenol) has been
widely used. An early reference to basic sulfurized polyvalent
metal phenates is U.S. Pat. No. 2,680,96, Walker et al., Jun. 1,
1954; see also U.S. Pat. No. 3,372,116, Meinhardt, Mar. 6,
1968.
[0003] Recently, however, certain alkylphenols and products
prepared from them have come under increased scrutiny due to their
association as potential endocrine disruptive materials. In
particular, alkylphenol detergents which are based on phenols
alkylated with oligomers of propylene, specifically propylene
tetramer (or tetrapropenyl), may contain residual alkyl phenol
species. There is interest, therefore, in developing
alkyl-substituted phenol detergents, for uses in lubricants, fuels,
and as industrial additives, which contain a reduced or eliminated
amount of dodecylphenol component and other substituted phenols
having propylene oligomer substituents of 10 to 15 carbon atoms.
Nevertheless, it is desirable that the products should have similar
oil-solubility parameters as phenates prepared from C10-15
propylene oligomers.
[0004] There have been several efforts to prepare phenate
detergents that do not contain C.sub.n alkyl phenols derived from
oligomers of propylene. U.S. Pat. No. 7,435,709, Stonebraker et
al., Oct. 14, 2008, discloses a linear alkylphenol derived
detergent substantially free of endocrine disruptive chemicals. It
comprises a salt of a reaction product of (1) an olefin having at
least 10 carbon atoms, where greater than 90 mole % of the olefin
is a linear C20-C30 n-alpha olefin, and wherein 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 a branched chain olefin of 18
carbons or less, and (2) a hydroxyaromatic compound
[0005] U.S. Application 2011/0190185, Sinquin et al, Aug. 4, 2011,
discloses an overbased salt of an oligomerized alkylhydroxyaromatic
compound. The alkyl group is derived form an olefin mixture
comprising propylene oligomers having an initial boiling point of
at least about 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 comprise at least about 50 weight
percent of C 14 to C20 carbon atoms.
[0006] U.S. Application 2011/0124539, Sinquin et al, May 26, 2011,
discloses an overbased, sulfurized salt of an alkylated
hydroxyaromatic compound. The alkyl substituent is a residue of at
least one isomerized .alpha.-olefin having from 15 to about 99 wt.
% branching. The hydroxyaromatic compound may be phenol, cresols,
xylenols, or mixtures thereof.
[0007] U.S. Application 2011/0118160, Campbell et al., May 19,
2011, discloses an alkylated hydroxyaromatic compound substantially
free of endocrine disruptive chemicals. An alkylated
hydroxyaromatic compound is prepared by reacting a hydroxyaromatic
compound with at least one branched olefinic propylene oligomer
having from about 20 to about 80 carbon atoms. Suitable
hydroxyaromatic compounds include phenol, catechol, resorcinol,
hydroquinone, pyrogallol, cresol, and the like.
[0008] U.S. Application 2010/0029529, Campbell et al., Feb. 4,
2010, discloses an overbased salt of an oligomerized
alkylhydroxyaromatic compound. The alkyl group is derived from an
olefin mixture comprising propylene oligomers having an initial
boing point of at least about 195.degree. C. and a final boiling
point of no more than about 325.degree. C. Suitable hydroxyaromatic
compounds include phenol, catechol, resorcinol, hydroquinone,
pyrogallol, cresol, and the like.
[0009] U.S. Application 2008/0269351, Campbell et al., Oct. 30,
2008, discloses an alkylated hydroxyaromatic compound substantially
free of endocrine disruptive chemicals, prepared by reacting a
hydroxyaromatic compound with a branched olefinic oligomer having
from about 20 to about 80 carbon atoms.
[0010] U.S. Application 2017/0211008, Walker et al., Jul. 27, 2017,
discloses metal salts and overbased metal salts of an oligomerized
alkylphenol compound. The alkyl group is derived from oligomers of
an olefin compound containing 3 to 8 carbon atoms, and wherein the
polyolefin-derived alkyl group comprises at least 30 mol percent of
an olefin with 4 or more carbon atoms, especially n-butene.
[0011] WO/PCT application 2013/059173, Cook et al., discloses
discloses an overbased salt of an oligomerized alkylhydroxyaromatic
compound. The alkyl group is a combination of very short
hydrocarbyl group (i.e. 1 to 8 carbon atoms) and a long hydrocarbyl
group (at least about 25 carbon atoms). Suitable compounds include
those made from a mixture of para-cresol and
polyisobutylene-substituted phenol.
[0012] Other general technology includes that of U.S. Pat. No.
6,310,009, Carrick et al., Oct. 30, 2001, which discloses salts of
the general structure
##STR00001##
where R.sup.1 may be an alkyl group of 1 to 60 carbon atoms, e.g.,
9 to 18 carbon atoms. It is understood that R.sup.1 will normally
comprise a mixture of various chain lengths, so that the foregoing
numbers will normally represent an average number of carbon atoms
in the R1 groups (number average).
SUMMARY OF THE INVENTION
[0013] The disclosed technology, may solve at least one problem of
providing a phenolic material with appropriate oil solubility,
providing anti-wear performance, frictional performance, providing
oxidation performance, viscosity performance, and detergency
(characteristic of moderate chain length alkyl groups). In one
embodiment the disclosed technology may also solve the problem of
containing C12 alkyl phenol moieties i.e., the disclosed technology
may be free from or substantially free from C12 alkyl phenol
moieties typically formed from oligomerisation or polymerisation of
propylene.
[0014] One aspect of the disclosed technology relates to an
alkylphenol detergent composition comprising at least one phenol
moiety having a hydrocarbyl group attached thereto. The hydrocarbyl
group can include at least one oligomer having monomers equivalent,
in some embodiments, to 5 to 10 carbon atom branched olefins, and
in some embodiments, more particularly to 5 to 10 carbon atom
branched polyenes. In embodiments, the monomers making up the
oligomers can be equivalent to isoprene. The oligomer itself can be
equivalent to a terpene, and more particularly can be equivalent to
any of (2E,5E,7E,10E)-3,6,10-trimethyldodeca-2,5,7,10-tetraene;
(3E,7E,10E)-2,7,10-trimethyldodeca-1,3,7,10-tetraene;
(E)-2,9-dimethyl-5-(prop-1-ene-2-yl)deca-1,3,8-triene;
(3E,6E,10E)-2,6,10-trimethyldodeca-1,3,6,10-tetraene;
(E)-7,11-dimethyl-3-methylenedodeca-1,6,10-triene;
(6E,10E)-7,11,15-trimethyl-3-methylenehexadeca-1,6,10,14-tetraene;
(3E,6E,10E)-3,7,11,15-tetramethylhexadeca-1,3,6,10,1-pentaene;
(6E,10E,14E)-7,11,14-trimethyl-3-methylenehexadeca-1,6,10,14-tetraene;
(3E,9E,13E)-2,10,13-trimethyl-6-(prop-1-en-2-yl)pentadeca-1,3,9,13-tetrae-
ne.
[0015] The oligomer can also be equivalent to a hydrogenated
(partial or complete) form of a terpene, such as, for example, any
of 3,7,11-trimethyldodec-1-ene; 2,6,10-trimethyldodec-2-ene;
(E)-3,7,11-trimethyldodec-2-ene; 2,6-dimethyl-10-methylenedodecane;
(E)-2,6,10-trimethyldodec-6-ene; (E)-3,7,11-trimethyldodec-3-ene;
(E)-2,6,10-trimethyldodec-5-ene;
3,7,11-trimethyldodeca-1,10-diene
[0016] In embodiments, the hydrocarbyl unit of the alkylphenol
detergent can contain from 15 to 60 carbon atoms.
[0017] The alkylphenol detergent can include alkylphenol moiety
equivalent to any of 4-(3,7,11-trimethyldodecan-2-yl)phenol;
4-(2,6,10-trimethyldodecan-2-yl)phenol;
4-(3,7,11-trimethyldodec-10-en-2-yl)phenol;
4-(2,6,10-trimethyldodec-11-en-2-yl)phenol.
[0018] The alkylphenol detergent can be a sulfur-bridged phenate
detergent, a sulfur-free alkylene-bridged phenate detergent, a
salicylate detergent, or mixtures thereof. The alkylphenol
detergent can include one or more alkali metals, one or more
alkaline earth metals, or mixtures thereof. The alkylphenol
detergent composition can be overbased, and in embodiments, have a
metal ratio of at least 1.5, at least 5, or at least 7.
[0019] In an embodiment, the alklylphenol detergent can be an
overbased sulfur-coupled phenate detergent with a metal ratio of at
least 1.5.
[0020] In an embodiment, the alkylphenol detergent composition can
be a sulfur-bridged phenate represented by the structure
##STR00002##
wherein each R is an aliphatic hydrocarbyl group equivalent to an
oligomer of isoprene, higher branched olefins, or mixtures thereof,
that contains 15 to 60 carbon atoms; each y can be 1 to 4; and n=0
to 8, or 1 to 6, or 1 to 4, or 2 to 4.
[0021] In an embodiment, the alkylphenol detergent can be a neutral
or overbased salt of alkylsalicylic acid.
[0022] In an embodiment, the alkylphenol detergent can be an
alkylsalicylate represented by the structure
##STR00003##
where R is an aliphatic hydrocarbyl group equivalent to an oligomer
of isoprene, higher branched olefins, or mixtures thereof, and
wherein the hydrocarbyl group contains 15 to 60 carbon atoms.
[0023] Another aspect of the technology relates to a lubricating
composition having (a) an oil of lubricating viscosity and (b) the
alkylphenol detergent composition as described herein. In
embodiments, lubricating composition can be substantially free to
free of an alkylphenol-containing detergent wherein the alkylphenol
is derived from oligomers of propene. The lubricating composition
can also include other additives, such as, for example, other
detergents besides the instant alkylphenol detergent, zinc
dialkyldithiophosphate, dispersants, antiwear agents, extreme
pressure agents, corrosion inhibitors, etc.
[0024] A further aspect of the technology relates to methods of
lubricating a mechanical device, for example, by supplying to the
device the lubricating composition described herein containing the
alkylphenol detergent. The mechanical device can be, for example,
an internal combustion engine, an automotive driveline device, such
as a transmission or an axle, or an off-highway vehicle. The
technology could also be employed in industrial applications, such
as industrial hydraulics.
DETAILED DESCRIPTION OF THE INVENTION
[0025] Various preferred features and embodiments will be described
below by way of non-limiting illustration.
[0026] The disclosed technology includes an alkylphenol detergent
composition (or just alkylphenol for short), a lubricating
composition containing the alkylphenol, a method for lubricating a
mechanical device with a lubricating composition containing the
alkylphenol, and a use of the alkylphenol, all of which will be
more particularly described herein.
[0027] One aspect of the disclosed technology is an alkylphenol
detergent composition. The alkylphenol detergent will include at
least one phenol moiety with at least one hydrocarbyl group
attached thereto. Those of ordinary skill in the art can observe a
chemical composition and readily imagine the moieties to which the
composition may be derived from. As used herein, reference to the
phenol moiety means that moiety of the alkylphenol detergent
composition one of ordinary skill in the art could imagine would be
derived from a phenol, i.e., of Formula I.
##STR00004##
[0028] The alkylphenol will also include a hydrocarbyl group. As
used herein, the term "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. Examples of hydrocarbyl groups include, for
example: hydrocarbon substituents, including aliphatic, alicyclic,
and aromatic substituents; 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; and hetero substituents,
that is, substituents which similarly have a predominantly
hydrocarbon character but contain other than carbon in a ring or
chain.
[0029] While the hydrocarbyl group can include elements of
non-hydrocarbyl character (i.e., nitrogen, halogens, etc.), in many
embodiments the hydrocarbyl group can be of substantially, or even
completely, hydrocarbon character. In some embodiments, the
hydrocarbyl group can be of substantially or completely aliphatic
character.
[0030] The hydrocarbyl group can comprise, consist essentially of,
or consist of at least one oligomer, and the at least one oligomer
itself can comprise, consist essentially of, or consist of monomers
equivalent to 5 to 10 carbon atom branched olefins. By employing
the terminology "equivalent to," it is recognized that the
referenced compound, in this case the monomers of the oligomer, are
slightly altered in their final state from their original state;
for example, an oligomerized monomer versus the lone monomer. In
other words, the hydrocarbyl group, when looked at in discreet
units, contains identifiable oligomer units, and the identifiable
oligomer units can be further broken down into identifiable alkyl
units that, as a monomer would be considered a 5 to 10 carbon atom
branched olefin.
[0031] A branched olefin, as used herein, refers to an alkyl chain
having at least one double bond and at least one tertiary carbon
atom. Without limiting the branched olefin, examples of such
branched olefins can be represented by the following example
branched olefin formulas.
##STR00005##
where Ra, Rb, and Rc can be H or a lower C.sub.1 to C.sub.5 alkyl
group; n and m can be, independently, integers of 0 to 6, with the
proviso that n+m is from 1 to 6; and the olefin has from 5 to 10
carbon atoms. An oligomer of such a branched olefin could be, for
example, oligomers of the following formula.
##STR00006##
where Ra, Rb, Rc, m and n are as above, and y is an integer of 2 to
18, or 2 to 15, or 2 to 12.
[0032] The branched olefin can also be polyenes. That is, the
hydrocarbyl group can comprise, consist essentially of, or consist
of at least one oligomer, and the at least one oligomer itself can
comprise, consist essentially of, or consist of monomers equivalent
to 5 to 10 carbon atom branched polyene compounds. As used herein a
polyene is a poly-unsaturated alkylene compound having at least 2
double bonds (also known as a diene), and in some cases 3, 4, or 5
double bonds.
[0033] Branched polyene compounds can be described as alkyl chains
having at least two double bonds in the chain, and at least one
tertiary carbon atom. Although the polyene compound may include
more than 2 double bonds, an example branched polyene compound may
be a branched conjugated diene represented by the following
formula,
##STR00007##
where R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are independently H,
or lower C.sub.1 to C.sub.5 alkyl groups; with the proviso that at
least one of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 is an alkyl
group and that taken together the conjugated diene has a total of
from 5 to 10 carbon atoms.
[0034] The at least one oligomer in the hydrocarbyl group can be
oligomerized from 5 to 10 carbon atom branched olefin/polyenes, or
the oligomer may be prepared in some other manner. For example, the
oligomer may be formed by 1,2-monomer addition or 1,4-monomer
addition. In one embodiment, oligomers of 5 to 10 carbon atom
branched polyenes may formed by 1,4-addition of the monomers,
followed by partial hydrogenation of the resulting material to form
a mono-olefinic alkylating agent, which could then react with
phenol to form the oligomeric alkyl phenol. The hydrocarbyl group
may also be derived from an alkylating agent containing a
heteroatom, such as phytol or farnesol, which may be prepared from
reacting monomers of a mono or polyene containing a heteroatom. For
instance, Tetrahedron Vol 43. No. 19. pp. 4481 to 4486, 1987
describes the synthesis of phytol from two C10 units derived from
geraniol.
In another example, the oligomer may also be produced via
biological activity, such as through the fermentation of a cell
culture system that is capable of producing the desired branched
olefin/polyene or a composition having the appearance of an
oligomer containing monomers equivalent to 5 to 10 carbon atom
branched olefin/polyene compounds. For instance, WO 2011/160081
provides a biological pathway for the production of isoprene, and
the use of the so-produced isoprene to produce oligomers (also
called terpenes, i.e., having a formula of (C.sub.5H.sub.8).sub.n,
where n is 2, 3, 4, 5 or higher). The hydrocarbyl group may also be
derived from an alkylating agent produced from a biological
pathway, including, for instance, a biological pathway for the
production of natural phytol from the crude extraction of silkworm
excrement, Morus alba leaf, bamboo leaf, pine needle and Ginkgo
biloba leaf, for example as taught in CN 102807471 A Dec. 5, 2012.
Other biological pathways are known to produce the oligomers (e.g.,
terpenes) themselves.
[0035] An oligomer containing monomers equivalent to 5 to 10 carbon
atom branched olefins could be, for example, oligomers of the
following formula
##STR00008##
where R1, R2, R3, and R4 and y are the same as defined above.
[0036] The branched polyene compound containing 5 to 10 carbon
atoms may include isoprene monomers of Formula IV.
##STR00009##
In addition to isoprene, suitable branched olefins
2-methyl-1-butene, 3-methyl-1-butene, 4-methyl-1-pentene,
2-methyl-1-pentene, 3-methyl-1-pentene, 2-methyl-1-hexene,
3-methyl-1-hexene, 5-methyl-1-hexene, 4-methyl-1-hexene,
2-methyl-1-heptene, 2.3-dimethyl-1,3-butadiene,
2,4-dimethyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, and mixtures
thereof.
[0037] In an embodiment, the oligomer contains units equivalent to
isoprene. An isoprene oligomer containing 15 to 60 carbon atoms
would contain 3 to 12 isoprene monomer units. An isoprene polymer
or oligomer containing 15 to 30 carbon atoms would contain 3 or 6
isoprene monomer units.
[0038] In an embodiment, the oligomer can be a trimer of isoprene,
which can be envisioned in the following forms
##STR00010##
[0039] Tetramers of isoprene may also be employed in the oligomer,
and can be envisioned in the following forms
##STR00011##
[0040] In one embodiment, the hydrocarbyl group of the alkylphenol
detergent can comprise, consist essentially of, or consist of
oligomer compounds comprising, consisting essentially of, or
consisting of at least 50 mol % monomers equivalent to isoprene, at
least 75 mol % monomers equivalent to isoprene, or at least 90 mol
% monomers equivalent to isoprene. In one embodiment, the
hydrocarbyl group in the alkylphenol detergent consists of
oligomers of isoprene.
[0041] In some embodiments, the oligomer can be hydrogenated forms,
either partial or complete, of what the oligomer of the alkylene
units would otherwise appear as. Hydrogenation may be performed,
for example, by any hydrogenating agent known to a skilled artisan.
For example, a saturated oligomer of polyene compounds can be
prepared by hydrogenating at least a portion of the double bonds in
the oligomer in the presence of a hydrogenation reagent, such as
hydrogen in the presence of a catalyst, or by treatment with
hydrazine in the presence of a catalyst.
[0042] In some embodiments, at least a portion of the C.dbd.C bonds
of the oligomer is reduced to the corresponding C--C bonds by
hydrogenation. In some embodiments, all of the C.dbd.C bonds of the
oligomer are reduced to the corresponding C--C bonds by
hydrogenation. In an embodiment, the oligomer can include a
hydrogenated form of oligomer in the form of any of the following
structures:
##STR00012##
[0043] Whether prepared from the oligomerization of discreet units
or otherwise, one of ordinary skill in the art will recognize the
presence of the oligomers and monomers therein equivalent to 5 to
10 carbon atom branched polyenes within the hydrocarbyl group.
[0044] The hydrocarbyl group can contain from 10 to 200 carbon
atoms, or in some examples 12 to 100 carbon atoms, or even 15 to 80
carbon atoms. In some embodiments, the hydrocarbyl group can have
15 to 60 carbon atoms, or in some cases 15 to 30 or 45 carbon
atoms, or 20 to 30 carbon atoms.
[0045] The alkylphenol detergent, including the phenol moiety and
the hydrocarbyl group, may include the structure represented by the
following formula.
##STR00013##
where R represents the hydrocarbyl group described above. For
example, the alkylphenol can include the structure shown in the
following formulas.
##STR00014##
[0046] In certain embodiments, the alkylphenol-containing detergent
may be a sulfur-bridged phenate detergent, a sulfur-free
alkylene-bridged phenate detergent, or mixtures thereof. Detergents
of this type are ionic (usually metal) salts of bridged phenolic
compounds. The bridged phenolic compound material may be
represented by the structure:
##STR00015##
or isomers thereof, wherein each R represents the hydrocarbyl group
described above having substantially or completely aliphatic
character and 15 to 60, or in some cases 15 to 30 carbon atoms;
aliphatic hydrocarbyl groups containing 30 to 200 or 35 to 80
carbon atoms; methyl groups; and mixtures thereof, each y can be 1
to 4.
[0047] The average number of carbon atoms in all the R groups,
combined, may be 15 to 100 (or 20 to 50, or 24 to 36 or 14 to 20 or
18 to 36). Where the bridging group may be listed as "X", each X
may independently a carbon-containing bridge, or an alkylene group,
or a methylene group, or a bridge of 1 or more sulfur atoms
represented by S.sub.y, where y may be 1 to 4, especially 1 or 2.
In these structures, n may, in certain embodiments, be 0 to 8, or 1
to 6, or 1 to 4, or 2 to 4. That is, the bridged material may, in
these embodiments, contain 2 to 10 bridged phenolic groups, or 3 to
7, or 3 to 5, or 4 such groups. Since n may be zero, it may be
evident that throughout this specification, the expression
"oligomeric" may be interpreted to include dimeric species.
Accordingly, sometimes the expression "dimeric or oligomeric" may
be used to express this concept, which may include, as above, as an
example, 0 to 8 interior units bracketed by [ ].sub.n or 2 to 10
units overall.
[0048] In one embodiment, the sulfur-bridged alkylphenol-containing
detergent may be an oligomer of p-(isoprene)phenol. A
sulfur-bridged oligomer of oligo(isoprene)phenol may be represented
by the structure
##STR00016##
where n=0 to 4, and m=1 to 4 and each y can be 1 to 4.
[0049] In certain embodiments, the alkylene-bridged phenate
detergent may be a saligenin detergent. A saligenin detergent
contains a bridged-alkyl phenol compound that may be an alkylene
coupled alkylphenol represented by the structure
##STR00017##
where each R represents the hydrocarbyl group described above
having 15 to 60, or in some cases 15 to 30 carbon atoms; aliphatic
hydrocarbyl groups containing 30 to 200 or 35 to 80 carbon atoms;
methyl groups; and mixtures thereof; where the each bridging group
(X) may be independently a carbon-containing bridge, or a
hydrocarbylether linkage (such as --CH.sub.2--O--CH.sub.2--), or an
alkylene group, or a methylene group; each Y may be independently
--CHO or --CH.sub.2OH; wherein the --CHO groups comprise at least
about 10 mole percent of the X and Y groups; and n may be an
integer from 1 to 10.
[0050] In certain embodiments, the alkylene-bridged phenate
detergent may be a salixarate detergent. A salixarate detergent
contains a bridged-alkyl phenol compound that may be an alkylene
coupled alkylphenol that may be further bridged or coupled to
salicylic acid. The bridged phenol of a salixarate may be
represented by the structure (V)
##STR00018##
where R represents the hydrocarbyl group described above having
substantially or completely aliphatic character and 15 to 60, or in
some cases 15 to 30 carbon atoms; aliphatic hydrocarbyl groups
containing 30 to 200 or 35 to 80 carbon atoms; methyl groups; and
mixtures thereof; where the each bridging group (X) may be
independently a carbon-containing bridge, or an alkylene group, or
a methylene group; and n may be an integer from 1 to 10.
[0051] The bridged alkylphenol detergents may be neutral or
overbased or superbased. Such overbased detergents are generally
single phase, homogeneous Newtonian systems characterized by a
metal and/or ammonium content in excess of that which would be
present for neutralization according to the stoichiometry of the
metal or ammonium and the particular acidic organic compound
reacted with the metal or ammonium compound. The overbased
materials are typically prepared by reacting an acidic material
(typically an inorganic acid or lower carboxylic acid such as
carbon dioxide) with a mixture of bridged alkylphenol compounds
(referred to as a substrate), a stoichiometric excess of a metal
base, typically in a reaction medium of an one inert, organic
solvent (e.g., mineral oil, naphtha, toluene, xylene) for the
acidic organic substrate. Typically also a small amount of promoter
such as a phenol or alcohol is present, and in some cases a small
amount of water. The acidic organic substrate will normally have a
sufficient number of carbon atoms to provide a degree of solubility
in oil.
[0052] In certain embodiments, the overbased bridged-phenol
detergent may be a metal-containing detergent, an amine or ammonium
containing detergent, or mixtures thereof. In one embodiment, the
overbased metal-containing detergent may be zinc, sodium, calcium
or magnesium salts of a phenate, sulfur containing phenate,
salixarate or saligenin. In one embodiment, the overbased detergent
comprises a salt of an alkylamine or quaternary ammonium compound.
Overbased salixarates, phenates and saligenins typically have a
total base number (TBN) (by ASTM D3896) of 120 to 600 mg KOH/g.
[0053] In certain embodiments, the alkylphenol detergent
composition may be an alkylsalicylate or salicylate detergent. A
salicylate detergent may be a neutral or overbased metal salt of
alkylsalicylic acid. Alkylsalicylic acid may be represented by the
formula (VI)
##STR00019##
where R represents the hydrocarbyl group described above having
substantially or completely aliphatic character and 15 to 60, or in
some cases 15 to 30 carbon atoms; aliphatic hydrocarbyl groups
containing 30 to 200 or 35 to 80 carbon atoms; methyl groups; and
mixtures thereof.
[0054] The alkylsalicylate may be a neutral or nearly neutral salt
of alkylsalicylic acid; by nearly neutral, it is meant that there
is an excess of base of no more than 15 mol percent, i.e. if the
salt is metal-containing, the metal ratio is 1.15 or less. In one
embodiment, the neutral salt of the alkylsalicylic acid may be an
amine or ammonium salt, a metal salt, or mixtures thereof.
[0055] Amines suitable for use in the preparation of the neutral
amine salted alkylsalicylate are not overly limited and may include
any alkyl amine, di- or tri-alkyl amine, though generally are fatty
acid amines derived from fatty carboxylic acids. The alkyl group
present in the amine may contain from 10 to 30 carbon atoms, or
from 12 to 18 carbon atoms, and may be linear or branched. In some
embodiments, the alkyl group may be linear and unsaturated. Typical
amines include 2-ethylexhylamine, pentadecylamine, octadecylamine,
cetylamine, oleylamine, decylamine, dodecylamine,
dimethyldodecylamine, tridecylamine, heptadecylamine,
octadecylamine, stearylamine, and any combination thereof. In some
embodiments, the fatty acid derived amine salt of an alkylsalicylic
acid may be a salt of oleylamine. In certain embodiments, the amine
may be a gamma-aminoester compound; aminoesters of this type may be
derived from Michael addition of a primary amine to an alkyl
diester of itaconic acid represented by the formula
##STR00020##
where R.sub.10 and R.sub.11 are hydrocarbyl groups containing 2 to
30 carbon atoms, and Rig is a hydrocarbyl group containing 4 to 50
carbon atoms. In some embodiments, R12 of the aminoester compound
is an alkyl group that has at least one hydrocarbyl group
substituted at the 1-, or 2-position of the alkyl group. In one
embodiment, the aminoester is dibutyl
2-(((2-ethylhexyl)-amino)methyl)succinate.
[0056] In certain embodiments, the neutral salt of the
alkylsalicylic acid may be a quaternary ammonium salt, also
referred to as a quaternary nitrogen compound. Quaternary nitrogen
compounds are characterized in that the nitrogen atom is
four-coordinate; this results in a cationic species that is not
protic, i.e. an acidic proton is not released under basic
conditions. Quaternary nitrogen compounds may be characterized as
falling into two large groups, four coordinate
tetrahydrocarbylammonium compounds, for example tetrabutylammonium,
and three coordinate aromatic compounds, for example
N-hydrocarbylpyridinium.
[0057] The alkylphenol-containing detergents, be they phenates,
saligenins, salixrates, or salicylates, may be metal-containing
detergents. Metal-containing detergents may be neutral, or very
nearly neutral, or overbased. An overbased detergent contains a
stoichiometric excess of a metal base for the acidic organic
substrate. This is also referred to as metal ratio. The term "metal
ratio" is the ratio of the total equivalents of the metal to the
equivalents of the acidic organic compound. A neutral metal salt
has a metal ratio of one. A salt having 4.5 times as much metal as
present in a normal salt will have metal excess of 3.5 equivalents,
or a ratio of 4.5. The term "metal ratio is also explained in
standard textbook entitled "Chemistry and Technology of
Lubricants", Third Edition, Edited by R. M. Mortier and S. T.
Orszulik, Copyright 2010, page 219, sub-heading 7.25.
[0058] In one embodiment the overbased metal-containing alkylphenol
detergent may be calcium or magnesium overbased detergent. In one
embodiment, the overbased detergent may comprise a calcium
alkylphenol detergent with a metal ratio of at least 1.5, at least
3, at least 5, or at least 7. In certain embodiments, the overbased
calcium alkylphenol detergent may have a metal ratio of 1.5 to 25,
2.5 to 20 or 5 to 16.
[0059] Alternatively, the alkylphenol detergent may be described as
having TBN. Overbased phenates and salicylates typically have a
total base number of 120 to 600 mg KOH/g, or 150 to 550 mg KOH/g,
or 180 to 350 mg KOH/g. The amount of the alkylphenol-containing
detergent present in a lubricant composition may be defined as the
amount necessary to deliver an amount, or range of amounts, of TBN
to the lubricant composition. In certain embodiments, the
alkylphenol-containing detergent may be present in a lubricant
composition in amount to deliver 0.5 to 10 TBN to the composition,
or 1 to 7 TBN, or 1.5 to 5 TBN to the composition.
[0060] Overbased detergents may also be defined as the ratio of the
neutral detergent salt, also referred to as detergent soap, and the
detergent ash. The overbased detergent may have a weight ratio of
ash to soap of 3:1 to 1:8, or 1.5:1 to 1 to 4.1, or 1.3:1 to
1:3.4.
[0061] The product of the disclosed technology may beneficially be
used as an additive in a lubricant. The amount of the alkylphenol
detergent in a lubricant may be 0.1 to 8 percent by weight, on an
oil-free basis, but including the calcium carbonate and other salts
present in an overbased composition. When present as an overbased
detergent, the amount may typically be in the range of 0.1 to 25
weight percent, or 0.2 to 28, or 0.3 to 20, or 0.5 to 15 percent.
The higher amounts are typical of marine diesel cylinder
lubricants, e.g., 1 or 3 or 5 percent up to 25, 20, or 15 percent.
Amounts used in gasoline or heavy-duty diesel engines (not marine)
will typically be in lower ranges, such as 0.1 to 10 percent or 0.5
to 5 or 1 to 3 percent by weight. When used as a substantially
neutral or non-overbased salt, its amount may typically be
correspondingly less for each of the engine types, e.g., 0.1 to 10
percent or 0.2 to 8 or 0.3 to 6 percent.
[0062] In certain embodiments, the amount of the alkylphenol
detergent in a lubricant may be measured as the amount of
alkylphenol-containing soap that is provided to the lubricant
composition, irrespective of any overbasing. In one embodiment, the
lubricant composition may contain 0.05 weight percent to 1.5 weight
percent alkylphenol-containing soap, or 0.1 weight percent to 0.9
weight percent alkylphenol-containing soap. In one embodiment, the
alkylphenol-containing soap provides 20 percent by weight to 100
percent by weight of the total detergent soap in the lubricating
composition. In one embodiment the alkylphenol-containing soap
provides 30 percent by weight to 80 percent by weight of the total
detergent soap, or 40 percent by weight to 75 percent by weight of
the total detergent soap of the lubricating composition.
[0063] A lubricant composition may contain alkylphenol-containing
detergents different from that of the disclosed technology. In one
embodiment, the lubricant composition of the disclosed technology
comprises the alkylphenol detergent of the disclosed technology in
an amount 0.1 to 25 weight percent, or 0.2 to 23, or 0.3 to 20, or
0.5 to 15 weight percent, and is free of or substantially free of
an alkylphenol-containing detergent derived from alkylphenol which
is derived from oligomers of propylene, especially tetrapropenyl.
"Substantially free of" in this case means no more than 0.01 weight
percent or an amount considered to arise through contamination or
other unintentional means. In some embodiments, the lubricant
composition can include the alkylphenol detergent at from about
0.01 to about 2 wt %, or from about 0.1 to about 1.75 wt %, or
about 0.2 to about 1.5 wt % of the lubricating composition.
Oil of Lubricating Viscosity
[0064] Another aspect of the technology is a lubricant containing
the alkylphenol detergent composition. The lubricating composition
includes an oil of lubricating viscosity. Such oils include natural
and synthetic oils, oil derived from hydrocracking, hydrogenation,
and hydrofinishing, unrefined, refined, re-refined oils or mixtures
thereof. A more detailed description of unrefined, refined and
re-refined oils is provided in International Publication
WO2008/147704, paragraphs [0054] to [0056] (a similar disclosure is
provided in US Patent Application 2010/197536, see [0072] to
[0073]). A more detailed description of natural and synthetic
lubricating oils is described in paragraphs [0058] to [0059]
respectively of WO2008/147704 (a similar disclosure is provided in
US Patent Application 2010/197536, see [0075] to [0076]). Synthetic
oils may also be produced by Fischer-Tropsch reactions and
typically may be hydroisomerized Fischer-Tropsch hydrocarbons or
waxes. In one embodiment oils may be prepared by a Fischer-Tropsch
gas-to-liquid synthetic procedure as well as other gas-to-liquid
oils.
[0065] Oils of lubricating viscosity may also be defined as
specified in the American Petroleum Institute (API) Base Oil
Interchangeability Guidelines (2011). The five base oil groups are
as follows: Group I (sulfur content >0.03 wt %, and/or <90 wt
% saturates, viscosity index 80 to less than 120); Group II (sulfur
content .ltoreq.0.03 wt %, and .gtoreq.90 wt % saturates, viscosity
index 80 to less than 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 oil of lubricating
viscosity may also be a Group II+ base oil, which is an unofficial
API category that refers to a Group II base oil having a viscosity
index greater than or equal to 110 and less than 120, as described
in SAE publication "Design Practice: Passenger Car Automatic
Transmissions," fourth Edition, AE-29, 2012, page 12-9, as well as
in U.S. Pat. No. 8,216,448, column 1 line 57. The oil of
lubricating viscosity may also be a Group III+ base oil, which,
again, is an unofficial API category that refers to a Group III
base oil having a viscosity index of greater than 130, for example
130 to 133 or even greater than 135, such as 135-145. Gas to liquid
("GTL") oils are sometimes considered Group III+ base oils.
[0066] The oil of lubricating viscosity may be an API Group IV oil,
or mixtures thereof, i.e., a polyalphaolefin. The polyalphaolefin
may be prepared by metallocene catalyzed processes or from a
non-metallocene process. The oil of lubricating viscosity may also
comprise an API Group I, Group II, Group III, Group IV, Group V oil
or mixtures thereof. Often the oil of lubricating viscosity is an
API Group I, Group II, Group II+, Group III, Group IV oil or
mixtures thereof. Alternatively the oil of lubricating viscosity is
often an API Group II, Group II+, Group III or Group IV oil or
mixtures thereof. Alternatively the oil of lubricating viscosity is
often an API Group II, Group II+, Group III oil or mixtures
thereof.
[0067] The oil of lubricating viscosity, or base oil, will overall
have a kinematic viscosity at 100.degree. C. of 2 to 10 cSt or, in
some embodiments 2.25 to 9 or 2.5 to 6 or 7 or 8 cSt, as measured
by ASTM D445. Kinematic viscosities for the base oil at 100.degree.
C. of from about 3.5 to 6 or from 6 to 8 cSt are also suitable.
[0068] The amount of the oil of lubricating viscosity present is
typically the balance remaining after subtracting from 100 wt % the
sum of the amount of the performance additives in the composition.
Illustrative amounts may include 50 to 99 percent by weight, or 60
to 98, or 70 to 95, or 80 to 94, or 85 to 93 percent.
[0069] The lubricating composition may be in the form of a
concentrate and/or a fully formulated lubricant. If the lubricating
composition of the invention is in the form of a concentrate (which
may be combined with additional oil to form, in whole or in part, a
finished lubricant), the ratio of the of components of the
invention to the oil of lubricating viscosity and/or to diluent oil
include the ranges of 1:99 to 99:1 by weight, or 80:20 to 10:90 by
weight.
[0070] A lubricating composition may be prepared by adding the
product of the process described herein to an oil of lubricating
viscosity, optionally in the presence of other performance
additives (as described herein below).
[0071] The other performance additives can include at least one of
metal deactivators, viscosity modifiers (other than the soot
dispersing additive of the present invention), detergents, friction
modifiers, antiwear agents, corrosion inhibitors, dispersants
(other than those of the present invention), extreme pressure
agents, antioxidants, foam inhibitors, demulsifiers, pour point
depressants, seal swelling agents and mixtures thereof. Typically,
fully-formulated lubricating oil will contain one or more of these
performance additives.
[0072] In one embodiment the invention provides a lubricating
composition further comprising an overbased metal-containing
detergent in addition to the alkylphenol-containing detergent of
the present invention. The metal of the metal-containing detergent
may be zinc, sodium, calcium, barium, or magnesium. Typically the
metal of the metal-containing detergent may be sodium, calcium, or
magnesium.
[0073] 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.
[0074] 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,
for example, a "hybrid" sulfonate/phenate detergent is employed,
the "hybrid" detergent would be considered equivalent to amounts of
distinct phenate and sulfonate detergents introducing like amounts
of phenate and sulfonate soaps, respectively.
[0075] 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.
[0076] Typically, the overbased metal-containing detergent may be a
calcium or magnesium overbased detergent.
[0077] In another embodiment the lubricating composition further
comprises a calcium sulfonate overbased detergent having a TBN of
120 to 700. 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.
[0078] 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).
Overbased detergents are known in the art. In one embodiment the
sulfonate detergent may be a predominantly linear alkylbenzene
sulfonate detergent having a metal ratio of at least 8 as is
described in paragraphs [0026] to [0037] of US Patent Application
2005065045 (and granted as U.S. Pat. No. 7,407,919). Linear alkyl
benzenes may have the benzene ring attached anywhere on the linear
chain, usually at the 2, 3, or 4 position, or mixtures thereof. The
predominantly linear alkylbenzene sulfonate detergent may be
particularly useful for assisting in improving fuel economy. In one
embodiment the sulfonate detergent may be a metal salt of one or
more oil-soluble alkyl toluene sulfonate compounds as disclosed in
paragraphs [0046] to [0053] of US Patent Application
2008/0119378.
[0079] In one embodiment the lubricating composition further
comprises 0.01 wt % to 2 wt %, or 0.1 to 1 wt % of a detergent
different from the alkylphenol detergent of the disclosed
technology, wherein the further detergent is chosen from
sulfonates, non-sulfur containing phenates, sulfur containing
phenates, sulfonates, salixarates, salicylates, and mixtures
thereof, or borated equivalents thereof.
[0080] In one embodiment the lubricating composition further
comprises a "hybrid" detergent formed with mixed surfactant systems
including phenate and/or sulfonate components, e.g.
phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, or
sulfonates/phenates/salicylates.
[0081] The lubricating composition in a further embodiment
comprises an antioxidant, wherein the antioxidant comprises a
phenolic or an aminic antioxidant or mixtures thereof. The
antioxidants include diarylamines, alkylated diarylamines, hindered
phenols, or mixtures thereof. When present the antioxidant is
present at 0.1 wt % to 3 wt %, or 0.5 wt % to 2.75 wt %, or 1 wt %
to 2.5 wt % of the lubricating composition.
[0082] The diarylamine or alkylated diarylamine may be a
phenyl-.alpha.-naphthylamine (PANA), an alkylated diphenylamine, or
an alkylated phenylnapthylamine, or mixtures thereof. The alkylated
diphenylamine may include di-nonylated diphenylamine, nonyl
diphenyl amine, octyl diphenylamine, di-octylated diphenylamine,
di-decylated diphenylamine, decyl diphenylamine and mixtures
thereof. In one embodiment the diphenylamine may include nonyl
diphenylamine, dinonyl diphenylamine, octyl diphenylamine, dioctyl
diphenylamine, or mixtures thereof. In another 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.
[0083] 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-butyl
phenol. In one embodiment the hindered phenol antioxidant may be an
ester and may include, e.g., Irganox.TM. L-135 from Ciba. A more
detailed description of suitable ester-containing hindered phenol
antioxidant chemistry is found in U.S. Pat. No. 6,559,105.
[0084] The lubricating composition may in a further embodiment
include a dispersant, or mixtures thereof. The dispersant may be a
succinimide dispersant, a Mannich dispersant, a succinamide
dispersant, a polyolefin succinic acid ester, amide, or
ester-amide, or mixtures thereof. In one embodiment the dispersant
may be present as a single dispersant. In one embodiment the
dispersant may be present as a mixture of two or three different
dispersants, wherein at least one may be a succinimide
dispersant.
[0085] The succinimide dispersant may be derived from an aliphatic
polyamine, or mixtures thereof. The aliphatic polyamine may be
aliphatic polyamine such as an ethylenepolyamine, a
propylenepolyamine, a butylenepolyamine, or mixtures thereof. In
one embodiment the aliphatic polyamine may be ethylenepolyamine. In
one embodiment the aliphatic polyamine may be chosen from
ethylenediamine, diethylenetriamine, triethylenetetramine, tetra
ethylene pentamine, pentaethylenehexamine, polyamine still bottoms,
and mixtures thereof.
[0086] In one embodiment the dispersant may be a polyolefin
succinic acid ester, amide, or ester-amide. For instance, a
polyolefin succinic acid ester may be a polyisobutylene succinic
acid ester of pentaerythritol, or mixtures thereof. 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.
[0087] 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 instance 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, 7,238,650 and EP
Patent Application 0 355 895 A.
[0088] The 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 US Patent
Application US2009/0054278.
[0089] When present, the dispersant may be present at 0.01 wt % to
20 wt %, or 0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 1 wt %
to 6 wt %, or 1 to 3 wt % of the lubricating composition.
[0090] 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.
[0091] In one embodiment the friction modifier may be chosen from
long chain fatty acid derivatives of amines, long chain fatty
esters, or derivatives of long chain fatty epoxides; fatty
imidazolines; amine salts of alkylphosphoric acids; fatty alkyl
tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; fatty
glycolates; and fatty glycolamides. The friction modifier may be
present at 0 wt % to 6 wt %, or 0.01 wt % to 4 wt %, or 0.05 wt %
to 2 wt %, or 0.1 wt % to 2 wt % of the lubricating
composition.
[0092] 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.
[0093] 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 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.
[0094] Friction modifiers may also encompass materials such as
sulfurised fatty compounds and olefins, molybdenum
dialkyldithiophosphates, molybdenum dithiocarbamates, sunflower oil
or soybean oil monoester of a polyol and an aliphatic carboxylic
acid.
[0095] In another embodiment the friction modifier may be a long
chain fatty acid ester. In another embodiment the long chain fatty
acid ester may be a mono-ester and in another embodiment the long
chain fatty acid ester may be a triglyceride.
[0096] The lubricating composition optionally further includes at
least one antiwear agent. Examples of suitable antiwear agents
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.
[0097] The antiwear agent may in one embodiment include a tartrate,
or tartrimide as disclosed in International Publication
WO2006/044411 or Canadian Patent CA 1183125. 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 Patent
Application 2005/0198894.
[0098] Another class of additives includes oil-soluble titanium
compounds as disclosed in U.S. Pat. No. 7,727,943 and
US2006/0014651. The oil-soluble titanium compounds may function as
antiwear agents, friction modifiers, antioxidants, deposit control
additives, or more than one of these functions. In one embodiment
the oil soluble titanium compound is a titanium (IV) alkoxide. The
titanium alkoxide is formed from a monohydric alcohol, a polyol or
mixtures thereof. The monohydric alkoxides may have 2 to 16, or 3
to 10 carbon atoms. In one embodiment, the titanium alkoxide is
titanium (IV) isopropoxide. In one embodiment, the titanium
alkoxide is titanium (IV) 2 ethylhexoxide. In one embodiment, the
titanium compound comprises the alkoxide of a vicinal 1,2-diol or
polyol. In one embodiment, the 1,2-vicinal diol comprises a fatty
acid mono-ester of glycerol, often the fatty acid is oleic
acid.
[0099] In one embodiment, the oil soluble titanium compound is a
titanium carboxylate. In a further embodiment the titanium (IV)
carboxylate is titanium neodecanoate.
[0100] The lubricating composition may in one embodiment further
include a phosphorus-containing antiwear agent. Typically the
phosphorus-containing antiwear agent may be a zinc
dialkyldithiophosphate, phosphite, phosphate, phosphonate, and
ammonium phosphate salts, or mixtures thereof. Zinc
dialkyldithiophosphates are known in the art. The antiwear agent
may be present at 0 wt % to 3 wt %, or 0.1 wt % to 1.5 wt %, or 0.5
wt % to 0.9 wt % of the lubricating composition. In some
embodiments, the antiwear agent may be present in an amount
sufficient to provide from 0 to 0.12 wt % phosphorus to the
lubricating composition, or from 0.01 to 0.08 wt %, or 0.03 to 0.08
wt %, or even 0.025 to 0.06 wt % phosphorus.
[0101] Extreme Pressure (EP) agents that are soluble in the oil
include sulfur- and chlorosulfur-containing EP agents,
dimercaptothiadiazole or CS2 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), a hydrocarbyl-substituted
2,5-dimercapto-1,3,4-thiadiazole, or 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 the 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 (as described in U.S. Pat. No. 3,197,405).
[0102] Foam inhibitors that may be useful in the lubricant
compositions of the disclosed technology 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.
[0103] Other viscosity modifiers may include a block copolymer
comprising (i) a vinyl aromatic monomer block and (ii) a conjugated
diene olefin monomer block (such as a hydrogenated
styrene-butadiene copolymer or a hydrogenated styrene-isoprene
copolymer), a polymethacrylate, or mixtures thereof.
[0104] Pour point depressants that may be useful in the lubricant
compositions of the disclosed technology include polyalphaolefins,
esters of maleic anhydride-styrene copolymers, poly(meth)acrylates,
polyacrylates or polyacrylamides.
[0105] Demulsifiers include trialkyl phosphates, and various
polymers and copolymers of ethylene glycol, ethylene oxide,
propylene oxide, or mixtures thereof.
[0106] Metal deactivators include derivatives of benzotriazoles
(typically tolyltriazole), 1,2,4-triazoles, benzimidazoles,
2-alkyldithiobenzimidazoles or 2-alkyldithiobenzothiazoles. The
metal deactivators may also be described as corrosion
inhibitors.
[0107] Seal swell agents include sulfolene derivatives Exxon
Necton-37.TM. (FN 1380) and Exxon Mineral Seal Oil.TM. (FN
3200).
[0108] In an embodiment, the lubricating composition can be
employed to lubricate a mechanical device. The mechanical device
can be associated with an automotive vehicle. For example, the
mechanical device may be a driveline device.
[0109] Driveline devices include automatic transmissions, manual
transmission, dual clutch transmissions, or an axle or
differential. A driveline device lubricating composition in
different embodiments may have a composition as disclosed in the
following table:
TABLE-US-00001 Embodiments (wt %) Additive A B C D Alkylphenol
Detergent 0.01 to 2 0.01 to 2 0.01 to 2 0.01 to 2 Dispersant 1 to 4
0.1 to 10, 0 to 5 1 to 6 2 to 7 Extreme Pressure Agent 3 to 6 0 to
6 0 to 3 0 to 6 Overbased Detergent 0 to 1 0.01 to 3, 0.5 to 6 0.01
to 2 0.025 to 2 Antioxidant 0 to 5 0.01 to 10 0 to 3 0 to 2 or 2
Friction Modifier 0 to 5 0.01 to 5 0.1 to 1.5 0 to 5 Viscosity
Modifier 0.1 to 70 0.1 to 15 1 to 60 0.1 to 70 Any Other
Performance 0 to 10 0 to 8 0 to 6 0 to 10 Additive or 10 Oil of
Lubricating Balance to 100% Viscosity Footnote: The viscosity
modifier in the table above may also be considered as an
alternative to an oil of lubricating viscosity. Column A may be
representative of an automotive or axle gear lubricant. Column B
may be representative of an automatic transmission lubricant.
Column C may be representative of an off-highway lubricant. Column
D may be representative of a manual transmission lubricant.
[0110] The mechanical device can be an internal combustion engine,
such as, for example, a spark ignited internal combustion engine or
a compression ignition internal combustion engine. An engine
lubricant composition in different embodiments may have a
composition as disclosed in the following table:
TABLE-US-00002 Embodiments (wt %) Additive A B C Alkylphenol
Detergent 0.05 to 10 0.2 to 5 0.5 to 2 Corrosion Inhibitor 0.05 to
2 0.1 to 1 0.2 to 0.5 Other Overbased Detergent 0 to 9 0.5 to 8 1
to 5 Dispersant Viscosity 0 to 5 0 to 4 0.05 to 2 Modifier
Dispersant 0 to 12 0 to 8 0.5 to 6 Antioxidant 0.1 to 13 0.1 to 10
0.5 to 5 Anti wear Agent 0.1 to 15 0.1 to 10 0.3 to 5 Friction
Modifier 0.01 to 6 0.05 to 4 0.1 to 2 Viscosity Modifier 0 to 10
0.5 to 8 1 to 6 Any Other Performance 0 to 10 0 to 8 0 to 6
Additive Oil of Lubricating Balance to 100% Viscosity
[0111] The mechanical device may also be in a hydraulic system. A
hydraulic lubricant may also comprise a formulation defined in the
following table:
TABLE-US-00003 Hydraulic Lubricant compositions Embodiments (wt %)
Additive A B C Alkylphenol detergent as 0.01 to 2.0 0.01 to 1.5
0.01 to 1.0 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 Other Detergent
- beside 0 to 5.0 0.001 to 1.5 0.005 to 1.0 alkylphenol detergent
as described herein 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
Balance to Balance to Balance to Viscosity 100% 100% 100%
[0112] The disclosed technology further provides a method of
lubricating a circulating oil system.
[0113] The disclosed technology further provides a method of
lubricating a turbine system.
[0114] The alkylphenol can be employed to lubricate any of the
foregoing mechanical devices by supplying to the mechanical device
the aforementioned lubricating compositions.
[0115] The amount of each chemical component described is presented
exclusive of any solvent or diluent oil, which may be customarily
present in the commercial material, that is, on an active chemical
basis, unless otherwise indicated. However, unless otherwise
indicated, each chemical or composition referred to herein should
be interpreted as being a commercial grade material which may
contain the isomers, byproducts, derivatives, and other such
materials which are normally understood to be present in the
commercial grade.
[0116] It is known that some of the materials described above may
interact in the final formulation, so that the components of the
final formulation may be different from those that are initially
added. For instance, metal ions (of, e.g., a detergent) can migrate
to other acidic or anionic sites of other molecules. The products
formed thereby, including the products formed upon employing the
composition of the present invention in its intended use, may not
be susceptible of easy description. Nevertheless, all such
modifications and reaction products are included within the scope
of the present invention; the present invention encompasses the
composition prepared by admixing the components described
above.
[0117] As used herein, the term "about" means that a value of a
given quantity is within .+-.20% of the stated value. In other
embodiments, the value is within .+-.15% of the stated value. In
other embodiments, the value is within .+-.10% of the stated value.
In other embodiments, the value is within .+-.5% of the stated
value. In other embodiments, the value is within .+-.2.5% of the
stated value. In other embodiments, the value is within .+-.1% of
the stated value.
[0118] Additionally, as used herein, the term "substantially" means
that a value of a given quantity is within .+-.10% of the stated
value. In other embodiments, the value is within .+-.5% of the
stated value. In other embodiments, the value is within .+-.2.5% of
the stated value. In other embodiments, the value is within .+-.1%
of the stated value.
[0119] Each of the documents referred to above is incorporated
herein by reference, including any prior applications, whether or
not specifically listed above, from which priority is claimed. The
mention of any document is not an admission that such document
qualifies as prior art or constitutes the general knowledge of the
skilled person in any jurisdiction. 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." 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 can be
used together with ranges or amounts for any of the other
elements.
[0120] As used herein, the transitional term "comprising," which is
synonymous with "including," "containing," or "characterized by,"
is inclusive or open-ended 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 encompass,
as alternative embodiments, the phrases "consisting essentially of"
and "consisting of," where "consisting of" excludes any element or
step not specified and "consisting essentially of" permits the
inclusion of additional un-recited elements or steps that do not
materially affect the essential or basic and novel characteristics
of the composition or method under consideration.
[0121] While certain representative embodiments and details have
been shown for the purpose of illustrating the subject invention,
it will be apparent to those skilled in this art that various
changes and modifications can be made therein without departing
from the scope of the subject invention. In this regard, the scope
of the invention is to be limited only by the following claims.
* * * * *