U.S. patent application number 13/513661 was filed with the patent office on 2012-11-29 for method of lubricating a manual transmission.
This patent application is currently assigned to THE LUBRIZOL CORPORATION. Invention is credited to Robert W. Alger, Simon D. Evans, Malcolm G.J. Macduff, Paul A. Robinson.
Application Number | 20120302479 13/513661 |
Document ID | / |
Family ID | 43640257 |
Filed Date | 2012-11-29 |
United States Patent
Application |
20120302479 |
Kind Code |
A1 |
Robinson; Paul A. ; et
al. |
November 29, 2012 |
Method of Lubricating a Manual Transmission
Abstract
The present invention relates to a method of lubricating a
driveline device comprising supplying to the driveline device a
lubricating composition comprising an oil of lubricating viscosity
and an aromatic hydroxy-substituted compound. The invention further
provides for the use of the lubricating composition comprising the
aromatic hydroxy-substituted compound as at least one of a
filterability aid, and a wax crystal growth modifier/gelation
inhibitor in the driveline device.
Inventors: |
Robinson; Paul A.;
(Nottingham, GB) ; Alger; Robert W.; (Derby,
GB) ; Evans; Simon D.; (Derby, GB) ; Macduff;
Malcolm G.J.; (Shanghai, CN) |
Assignee: |
THE LUBRIZOL CORPORATION
Wickliffe
OH
|
Family ID: |
43640257 |
Appl. No.: |
13/513661 |
Filed: |
December 3, 2010 |
PCT Filed: |
December 3, 2010 |
PCT NO: |
PCT/US10/58820 |
371 Date: |
August 6, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61267143 |
Dec 7, 2009 |
|
|
|
Current U.S.
Class: |
508/585 |
Current CPC
Class: |
C10N 2030/00 20130101;
C10M 145/20 20130101; C10M 2209/101 20130101; C10M 2209/062
20130101; C10N 2040/044 20200501; C10N 2030/02 20130101; C10M
2205/04 20130101; C10M 2209/084 20130101; C10M 129/14 20130101;
C10M 2207/024 20130101; C10N 2070/00 20130101; C10M 2205/04
20130101; C10M 2209/086 20130101 |
Class at
Publication: |
508/585 |
International
Class: |
C10M 129/10 20060101
C10M129/10 |
Claims
1.-7. (canceled)
8. A method of lubricating a manual transmission, comprising
supplying to the manual transmission a lubricating composition
comprising an oil of lubricating viscosity and a compound
represented by formula (1): ##STR00005## wherein each R.sup.1 is
independently hydrogen or a linear hydrocarbyl group containing at
least 1 carbon atom; each R.sup.2 is independently a linear
hydrocarbyl group containing at least 10 carbon atoms; each R.sup.3
and R.sup.4 are independently hydrogen or a linear hydrocarbyl
group containing 1 to 5 carbon atoms; each R.sup.5 is independently
hydrogen or a linear hydrocarbyl group containing 1 to 10 carbon
atoms; and n is 1 to 20,
9. The method of claim 8, wherein n is 6 to 8.
10. The method of claim 8, wherein R.sup.3 and R.sup.4 are both
hydrogen.
11. The method of claim 8, wherein R.sup.5 is hydrogen.
12. The method of claim 8, wherein R.sup.3, R.sup.4 and R.sup.5 are
hydrogen.
13. The method of claim 8, wherein each R.sup.1 is independently a
linear hydrocarbyl group containing at least 6 carbon atoms; and
each R.sup.2 is independently a linear hydrocarbyl group containing
10 to 60 carbon atoms; R.sup.3 and R.sup.4 are hydrogen; R.sup.5 is
hydrogen; and n is 6 to 8.
14. The method of claim 13, wherein R.sup.2 contains 18 to 24
carbon atoms.
15. The method of claim 8, wherein each R.sup.1 is hydrogen; each
R.sup.2 is a linear hydrocarbyl group containing 16 to 40 carbon
atoms; R.sup.3 and R.sup.4 are hydrogen; R.sup.5 is hydrogen; and n
is 6 to 8.
16. The method of claim 8, wherein the oil of lubricating viscosity
comprises bright stock present from 10 wt % to 97 wt % of the
lubricating composition.
17. The method of claim 8, wherein the oil of lubricating viscosity
comprises bright stock present from 20 wt % to 95 wt % of the
lubricating composition
18. The method of claim 8, wherein the oil of lubricating viscosity
comprises bright stock present from 80 wt % to 95 wt % of the
lubricating composition.
19. The method of claim 8, wherein the lubricating composition has
a SAE viscosity grade of XW--Y, wherein X is 70, 75, 80 or 85 and Y
is 80, 85, 90, or 140.
Description
FIELD OF INVENTION
[0001] The present invention relates to a method of lubricating a
driveline device comprising supplying to the driveline device a
lubricating composition comprising an oil of lubricating viscosity
and an aromatic hydroxy-substituted compound. The invention further
provides for the use of the lubricating composition comprising the
aromatic hydroxy-substituted compound as at least one of a
filterability aid and a wax crystal growth modifier/gelation
inhibitor in the driveline device.
BACKGROUND OF THE INVENTION
[0002] In driveline devices (in particular, a manual transmission)
lubricants, whilst circulating in the device, frequently pass
through filters. In some instances additives, waxes, or other
contaminants may become trapped in the filter, thereby causing a
decrease in lubricant flow and/or filter blockage. Decreasing
lubricant flow or filter blockage may be more apparent at low
temperature or with lubricants containing brightstock. It is known
that waxes, in general, can be suppressed by pour-point depressants
or agents which improve flow or change the size and shape of the
deposits (such as wax crystals) and, in this way, counteract
increases in the viscosity of the oils.
[0003] U.S. Pat. No. 6,495,495 discloses a filterability improver
for mineral oil distillates and heavy base oils containing wax
material consisting essentially of a blend containing from about
30% to about 70% of an alkyl ester polymer and from about 70% to
about 30% naphthenic oil, based upon the total weight of said
blend, wherein such filterability improver prevents filter blockage
due to wax formation at ambient temperatures. The filterability
improver may be used in manual transmission oils, axle factory fill
oils, and extended drain oils.
[0004] German Patent No. DE 11 47 799 B1 discloses oil-soluble
copolymers of ethylene and vinyl acetate, having molecular masses
between 1,000 and 3,000 g/mol, that are added to petroleum
distillate propellants or fuels. The copolymers that contain 60% to
99% by weight of ethylene and 1% to 40% by weight of vinyl
acetate.
[0005] Other polymers employed as agents which improve flow
contain, for example, 1-hexene, as described in EP 184,083, or
diisobutylene, as set forth in EP 203,554, in addition to ethylene
and vinyl acetate. Copolymers of ethylene, alkenecarboxylic acid
esters, vinyl esters and/or vinyl ketones are also used as
pour-point depressants and for improving the flow properties of
crude oils and middle distillates.
[0006] EP 111,883 discloses that ethylene and vinyl acetate,
copolymers of ethylene, alkenecarboxylic acid esters, vinyl esters
and/or vinyl ketones are also used as pour-point depressants and
for improving the flow properties of crude oils and middle
distillates.
[0007] U.S. Pat. Nos. 5,039,437 and 5,082,470 disclose alkyl
phenol-formaldehyde condensates additives for improving the low
temperature flow properties of hydrocarbon oils. The polymer
composition has a number average molecular weight of at least about
3,000 and a molecular weight distribution of at least about 1.5; in
the alkylated phenol reactant the alkyl groups are essentially
linear, have between 6 and 50 carbon atoms, and have an average
number of carbon atoms between about 12 and 26; and not more than
about 10 mole % of the alkyl groups on the alkylated phenol have
less than 12 carbon atoms and not more than about 10 mole % of the
alkyl groups on the alkylated phenol have more than 26 carbon
atoms.
[0008] U.S. Pat. Nos. 4,565,460; 4,559,155; 4,575,526 and 4,613,342
all disclose additive combinations for improving the cold flow
properties of hydrocarbon fuel compositions. The composition
includes a pour point depressant which can be a
hydrocarbyl-substituted phenol of the formula
(R*).sub.a--Ar--(OH).sub.b wherein R* is a hydrocarbyl group
selected from the group consisting of hydrocarbyl groups of from
about 8 to about 39 carbon atoms and polymers of at least 30 carbon
atoms. Ar is an aromatic moiety which can include linked
polynuclear aromatic moieties represented by the general formula
ar-(-Lng-ar-)-.sub.w(Q).sub.mw wherein w is an integer of 1 to
about 20. Each Lng is a bridging linkage of the type including
alkylene linkages (e.g., --CH.sub.2-- among others).
[0009] U.S. Pat. No. 5,171,330 discloses methacyclophanes with
substituents, obtained from the condensation reaction of a resorcin
with a product containing an aldehyde group, followed by a reaction
with halides of organic acids or alkyl halides.
[0010] U.S. Pat. No. 5,707,946 discloses a pour point depressant
which is the reaction product of a hydrocarbyl-substituted phenol
having a number average of greater than 30 carbon atoms in the
hydrocarbyl-substituent, and an aldehyde of 1 to about 12 carbon
atoms, or a source therefore.
[0011] International publication WO 2009/064827 discloses pour
point depressant composition comprising the reaction product of:
(a) a hydrocarbyl-substituted phenol which is the reaction product
of (i) phenol and (ii) an olefin; and (b) an aldehyde; wherein the
olefin has a vinylidene end group content of at least about 10 mole
% and less than about 85 mole %, wherein the reaction between (a)
and (b) is catalyzed, and wherein the catalyst comprises an acid
catalyst or a base catalyst.
SUMMARY OF THE INVENTION
[0012] The inventors of this invention have discovered that the
lubricating composition disclosed herein may be capable of at least
one of increased filterability, wax crystal growth reduction or
modification, and reduced or minimised gelation in a driveline
device.
[0013] As used herein the term "linear hydrocarbyl" means that the
hydrocarbyl group has a carbon chain that is substantially free of
branching, apart from the carbon atom that is the point of
attachment to the phenol ring shown in formula (1) below.
[0014] In one embodiment the invention provides a method of
lubricating a driveline device comprising supplying to the
driveline device a lubricating composition comprising an oil of
lubricating viscosity and a compound represented by formula
(1):
##STR00001##
wherein [0015] each R.sup.1 is independently hydrogen or a linear
hydrocarbyl group containing at least 1, or at least 3, or at least
4, or at least 6, or at least 8, or at least 10 carbon atoms
(typically R.sup.1 is a linear hydrocarbyl group containing at
least 1 carbon atom); [0016] each R.sup.2 is independently a linear
hydrocarbyl group containing at least 10, or at least 12, or at
least 14, or at least 16 carbon atoms (R.sup.2 may contain carbon
atoms in the range of 10 to 60, or 16 to 50, or 16 to 40, or 16 to
30, or 18 to 24, or 20 to 28, or 22 to 26); [0017] each R.sup.3 and
R.sup.4 is independently hydrogen or a linear hydrocarbyl group
containing 1 to 5, or 1 to 2 carbon atoms (typically R.sup.3 and
R.sup.4 are both hydrogen); [0018] each R.sup.5 is independently
hydrogen or a linear hydrocarbyl group containing 1 to 10, or 1 to
5, or 1 to 2 carbon atoms (typically R.sup.5 may be methyl or
hydrogen, or R.sup.5 may be hydrogen); and [0019] n is 1 to 20, or
3 to 15, or 4 to 8, or 6 to 8.
[0020] A person skilled in the art will appreciate that the
compound of formula (1) may have repeat units shown in random or
block architecture.
[0021] A person skilled in the art will appreciate that the
compound of formula (1), during preparation, may have a portion of
compounds that alkylate phenol at the ortho-position relative to a
hydroxy group of phenol. Compounds having alkylated
ortho-substitution may then couple at the para-position relative to
the hydroxyl group. Consequently, a person skilled in the art will
realize that compounds of this type are also encompassed by the
present invention. In addition, a portion of phenol groups may not
be alkyated; and, if incorporated into the structure of formula
(1), would contain a portion of unsubstituted phenol in formula
(1). The person skilled in the art will also appreciate that in
some instances the phenol may contain lower alkylated impurities
(e.g., methyl, or ethyl, or propyl groups) that may also become
incorporated into the structure of formula (1). Consequently, a
person skilled in the art will realize that compounds of this type
are also encompassed by the present invention.
[0022] Typically, the compound of formula (1) as defined above is
the dominant product (typically present at least 50 mole % or at
least 70 mole %) in the reaction to prepare compounds of the
present invention.
[0023] In one embodiment the invention provides a method of
lubricating a driveline device comprising supplying to the
driveline device a lubricating composition comprising an oil of
lubricating viscosity and a compound represented by formula
(1a):
##STR00002##
wherein [0024] each R.sup.1 is independently hydrogen or a linear
hydrocarbyl group containing at least 1, or at least 3, or at least
4, or at least 6, or at least 8, or at least 10 carbon atoms
(typically R.sup.1 is a linear hydrocarbyl group containing at
least 1 carbon atoms); and [0025] each R.sup.2 is independently a
linear hydrocarbyl group containing at least 10, or at least 12, or
at least 14, or at least 16 carbon atoms (R.sup.2 may contain
carbon atoms in the range of 16 to 50, or 16 to 40, or 16 to 30, or
18 to 24).
[0026] In one embodiment the mechanical device may be an axle gear
or a manual transmission (typically a manual transmission).
[0027] In one embodiment the lubricating composition may have a SAE
viscosity grade from XW--Y, wherein X is 70, 75, 80 or 85 and Y is
80, 85, 90, or 140. Typically, Y is greater than X.
[0028] In one embodiment the oil of lubricating viscosity may be
bright stock. The bright stock may be present from 10 wt % to 97 wt
%, or 20 wt % to 95 wt %, or 80 wt % to 95 wt % of the lubricating
composition.
[0029] In one embodiment the invention provides for the use of a
lubricating composition comprising an oil of lubricating viscosity
and a compound of formula (1) as at least one of a filterability
aid and a wax crystal growth/gelation inhibitor (may also be
referred to as a wax crystal growth modifier/gelation modifier) in
a driveline device (typically a manual transmission), wherein the
compound of formula (1) is represented by:
##STR00003##
wherein R.sup.1 to R.sup.5 and n are described above.
DETAILED DESCRIPTION OF THE INVENTION
[0030] The present invention provides a method and use as disclosed
herein.
[0031] In one embodiment the compound of the invention may be
represented by the formula (1) herein, wherein R.sup.1 may be
hydrogen; R.sup.2 may be a linear hydrocarbyl group containing at
least 10 carbon atoms (typically 10 to 100, or 16 to 70, or 16 to
40 carbon atoms); R.sup.3 and R.sup.4 may be hydrogen; R.sup.5 may
be hydrogen; and n may be 4 to 8, or 6 to 8.
[0032] In one embodiment the compound of the invention may be
represented by the formula (1) described herein, wherein R.sup.1
may independently be a linear hydrocarbyl group containing at least
1 (or at least 3, or at least 6) carbon atoms; R.sup.2 may be a
linear hydrocarbyl group containing at least 10 carbon atoms
(typically R.sup.2 may contain carbon atoms in the range of 10 to
60, or 16 to 50, or 16 to 40, or 16 to 30, or 18 to 24, or 20 to
28, or 22 to 26); R.sup.3 and R.sup.4 may be hydrogen; R.sup.5 may
be hydrogen; and n may be 1 to 20, or 3 to 15, or 4 to 8, or 6 to
8.
[0033] R.sup.1 and R.sup.2 may be derived from an olefin or
polyolefin (typically an olefin), where the polyolefin or olefin is
reacted with a phenol to form the hydrocarbyl-substituted phenol of
the present invention.
[0034] Examples of a suitable olefin include dodecene, tetradecene,
hexadecene, octadecene, eicosene, doeicosene, tetraeicosene,
hexaeicosene or octaeicosene, or mixtures thereof. The olefin may
be a mixture of 15 to 18, or 16 to 18, or 16 to 22, or 24 to 28, or
26 to 30 carbon atoms. In one embodiment the olefin may be a
mixture of 24 to 28 carbon atoms.
[0035] The carbon atom bonded to both R.sup.1 and R.sup.2 may be a
carbon atom of the olefin. As a consequence the structural unit
R.sup.1R.sup.2HC--, the point of attachment to the phenol ring in
the formula above may vary the number of carbon atoms present in
R.sup.1 and R.sup.2 depending on where the double bond of the
olefin is positioned at the time of alkylation. For example if the
olefin is eicosene, a carbocation intermediate formed during
alkylation of phenol may be nearly equally likely to be located
along the carbon chain on any carbon atoms due to migration of the
double bond or cation along the carbon chain. For illustrative
purposes the resultant product may have R.sup.1 having 9 carbon
atoms, R.sup.2 having 10 carbon atoms and it may be represented by
formula (2):
##STR00004##
[0036] Alternatively, the resultant product may have R.sup.1 having
8 carbon atoms, R.sup.2 having 11 carbon atoms, or R.sup.1 having 5
carbon atoms, R.sup.2 having 14 carbon atoms, or R.sup.1 having 3
carbon atoms, R.sup.2 having 16 carbon atoms, R.sup.1 having 1
carbon atoms, R.sup.2 having 18 carbon atoms and so on. However,
since it is believed that the carbocation is more stable if it is a
secondary carbocation (rather than a primary carbocation) there is
likely to be a tendency for the carbocation to react when in a more
central (or internal) position. In view of the above, the compound
of the invention may be considered as a mixture of varying lengths
of hydrocarbyl groups represented by the structural unit
R.sup.1R.sup.2HC--. Often the carbocation may favour one end of the
hydrocarbyl group such as at the second, third, fourth or fifth
carbon.
[0037] Since the compound of formula (1) may be considered a
mixture, the mole percent of compounds defined by formula (1) that
is, in which R.sup.1 is H or C.sub.1 or higher, may be at least 30
mole percent, or at least 40 mole percent, or at least 45 mole
percent, or at least 50 mole percent of molecules formed during
preparation of compounds of the invention. For example, the mole
percent of compounds of formula (1) may be 30 to 99.9 mole percent,
or 40 to 90 mole percent, or 55 to 75 mole percent of molecules
formed during preparation of compounds of the invention.
[0038] The attachment of a hydrocarbyl group to the phenol group of
the compound of the invention may be accomplished by a number of
techniques well known to those skilled in the art, for example, a
Friedel-Crafts reaction. The Friedel-Crafts reaction may react an
olefin (e.g., a polymer containing an olefinic bond), or
halogenated or hydrohalogenated derivative thereof, with a phenol
in the presence of a Lewis acid catalyst. Methods and conditions
for carrying out such reactions are well known to those skilled in
the art. See, for example, the discussion in the article entitled,
"Alkylation of Phenols" in "Kirk-Othmer Encyclopedia of Chemical
Technology", Third Edition, Vol. 2, pages 65-66, Interscience
Publishers.
[0039] The compound of the invention may be prepared by known
processes to prepare novolak chemistry. For example the compound
may be prepared by reacting an aromatic hydroxy-substituted
compound and an aldehyde. International publication WO 2009/064827,
and U.S. Pat. Nos. 5,707,946; 5,171,330; 4,565,460; 4,559,155;
4,575,526; 4,613,342; 5,039,437 and 5,082,470 all disclose methods
of preparing aromatic hydroxy-substituted compounds.
[0040] The aldehyde may have 1 to 5 or 1 to 2 carbon atoms.
Examples of a suitable aldehyde include formaldehyde, acetaldehyde,
propionaldehyde, butyraldehyde, isobutyraldehyde, and pentanal.
Formaldehyde may be supplied as a solution, but is more commonly
used in the polymeric form, as paraformaldehyde. Polymeric
aldehydes, such as paraformaldehyde, may be considered a reactive
equivalent of, or a source for, an aldehyde. Aqueous solutions of
aldehydes such as formalin may also be considered a reactive
equivalent of, or a source for, an aldehyde.
[0041] The compound may be present in the lubricating composition
in a range including 100 ppm to 2000 ppm, or 200 ppm to 1000 ppm,
or 300 ppm to 750 ppm or 400 ppm to 600 ppm.
Oils of Lubricating Viscosity
[0042] The lubricating composition comprises an oil of lubricating
viscosity. The oil of lubricating viscosity in one embodiment
includes bright stock. In other embodiments, the oil of lubricating
viscosity may include oils such as 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 more detailed description of natural and
synthetic lubricating oils is described in paragraphs [0058] to
[0059] respectively of WO2008/147704. Synthetic oils may also be
produced by Fischer-Tropsch reactions and typically may be
hydroisomerised 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.
[0043] 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". In one embodiment the oil of lubricating viscosity may
be an API Group II or Group III oil. In one embodiment the oil of
lubricating viscosity may be an API Group III base oil (typically
including hydrocracked/hydroisomerized base oil).
[0044] 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 compound of the invention and the other
performance additives.
[0045] The lubricating composition may be in the form of a
concentrate and/or a fully formulated lubricant. If the lubricating
composition of the invention (comprising the additives disclosed
herein) 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 these additives 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.
Other Performance Additives
[0046] The lubricating composition described herein optionally
further includes at least one other performance additives. The
other performance additives include at least one of metal
deactivators, detergents, dispersants, viscosity modifiers,
friction modifiers, corrosion inhibitors, dispersant viscosity
modifiers, antiwear agents, extreme pressure agents, antiscuffing
agents, antioxidants, foam inhibitors, demulsifiers, pour point
depressants (other than the compound of formula (1)), seal swelling
agents and mixtures thereof. Typically, fully-formulated
lubricating oil will contain one or more of these performance
additives.
Dispersants
[0047] Dispersants are known and include for example an
N-substituted long chain alkenyl succinimide, a Mannich base, or
mixtures thereof. Examples of N-substituted long chain alkenyl
succinimides include polyisobutylene succinimides, wherein the
polyisobutylene from which it is derived has a number average
molecular weight in the range 350 to 5000, or 500 to 3000, or 750
to 1150.
[0048] 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 disulphide, 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.
Detergents
[0049] Detergents are known and include neutral or overbased
detergents, i.e., ones prepared by conventional processes known in
the art. Suitable detergent substrates include, phenates, sulphur
containing phenates, sulphonates, salixarates, salicylates,
carboxylic acids, phosphorus acids, alkyl phenols, sulphur coupled
alkyl phenol compounds, or saligenins. In one embodiment the
detergent includes a magnesium or calcium sulphonate, or mixtures
thereof.
Antioxidant
[0050] Antioxidant compounds are known and include sulphurised
olefins, diphenylamines (such as dinonyl diphenylamine), hindered
phenols, molybdenum dithiocarbamates, and mixtures thereof.
Antioxidant compounds may be used alone or in combination.
[0051] The hindered phenol antioxidant often contains a secondary
butyl and/or a tertiary butyl group as a sterically hindering
group. The phenol group is often further substituted with a
hydrocarbyl group and/or a bridging group linking to a second
aromatic group. Examples of suitable hindered phenol antioxidants
include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol,
4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol
or 4-butyl-2,6-di-tert-butylphenol, or
4-dodecyl-2,6-di-tert-butylphenol. In one embodiment the hindered
phenol antioxidant may be an ester and may include, e.g.,
Irganox.TM. L-135 from Ciba. Suitable examples of molybdenum
dithiocarbamates which may be used as an antioxidant include
commercial materials sold under the trade names such as Vanlube
822.TM. and Molyvan.TM. A from R. T. Vanderbilt Co., Ltd., and
Adeka Sakura-Lube.TM. S-100, S-165 and S-600 from Asahi Denka Kogyo
K. K and mixtures thereof.
Viscosity Modifiers
[0052] In addition to the polymers described herein as part of the
invention, the lubricating composition may optionally further
contain other known viscosity modifiers. The viscosity modifiers
may be hydrogenated styrene-butadiene rubbers, ethylene-propylene
copolymers, hydrogenated styrene-isoprene polymers, hydrogenated
diene polymers, polyalkyl styrenes, polyolefins, esters of maleic
anhydride-styrene copolymers, or mixtures thereof.
Antiwear Agent
[0053] The lubricating composition optionally further includes at
least one antiwear agent. Examples of suitable antiwear agents
include oil soluble amine salts of phosphorus compounds,
sulphurised olefins, metal dihydrocarbyldithiophosphates (such as
zinc dialkyldithiophosphates), thiocarbamate-containing compounds
such as thiocarbamate esters, thiocarbamate amides, thiocarbamic
ethers, alkylene-coupled thiocarbamates, and
bis(S-alkyldithiocarbamyl) disulphides.
[0054] In one embodiment the oil soluble phosphorus amine salt
antiwear agent includes an amine salt of a phosphorus acid ester or
mixtures thereof. The amine salt of a phosphorus acid ester may
include phosphoric acid esters and amine salts thereof;
dialkyldithiophosphoric acid esters and amine salts thereof; amine
salts of phosphites; and amine salts of phosphorus-containing
carboxylic esters, ethers, and amides; and mixtures thereof. The
amine salt of a phosphorus acid ester may be used alone or in
combination.
[0055] 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 sulphur atom in the molecule. In one embodiment the
amine salt of the phosphorus compound may be ashless, i.e.,
metal-free (prior to being mixed with other components).
[0056] 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.
[0057] 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.
[0058] 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.
[0059] 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.
[0060] In one embodiment the phosphorus acid amine salt includes an
amine with C11 to C14 tertiary alkyl primary amino 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.
[0061] Mixtures of amines may also be used in the invention. In one
embodiment a useful mixture of amines is "Primene.RTM. 81R" or
"Primene.RTM. JMT." Primene.RTM. 81R and Primene.RTM. JMT (both
produced and sold by Rohm & Haas) are mixtures of C11 to C14
tertiary alkyl primary amines and C18 to C22 tertiary alkyl primary
amines respectively.
[0062] In one embodiment oil soluble amine salts of phosphorus
compounds include a sulphur-free amine salt of a
phosphorus-containing compound which 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
provided in International Application PCT/US08/051126 (or
equivalent to U.S. application Ser. No. 11/627,405 and
US-2008-0182770).
[0063] 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 81R.TM..
[0064] 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.
[0065] 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
O,O-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 sulphur, and an acid number of 87
(bromophenol blue).
[0066] The dithiocarbamate-containing compounds may be prepared by
reacting a dithiocarbamate acid or salt with an unsaturated
compound. The dithiocarbamate containing compounds may also be
prepared by simultaneously reacting an amine, carbon disulphide and
an unsaturated compound. Generally, the reaction occurs at a
temperature from 25.degree. C. to 125.degree. C.
[0067] Examples of suitable olefins that may be sulphurised to form
an the sulphurised olefin include propylene, butylene, isobutylene,
pentene, hexane, heptene, octane, nonene, decene, undecene,
dodecene, undecyl, tridecene, tetradecene, pentadecene, hexadecene,
heptadecene, octadecene, nonadecene, eicosene or mixtures thereof.
In one embodiment, hexadecene, heptadecene, octadecene, eicosene or
mixtures thereof and their dimers, trimers and tetramers are
especially useful olefins. Alternatively, the olefin may be a
Diels-Alder adduct of a diene such as 1,3-butadiene and an
unsaturated ester, such as butyl acrylate.
[0068] Another class of sulphurised olefin includes fatty acids and
their esters. The fatty acids are often obtained from vegetable oil
or animal oil; and typically contain 4 to 22 carbon atoms. Examples
of suitable fatty acids and their esters include triglycerides,
oleic acid, linoleic acid, palmitoleic acid or mixtures thereof.
Often, the fatty acids are obtained from lard oil, tall oil, peanut
oil, soybean oil, cottonseed oil, sunflower seed oil or mixtures
thereof. In one embodiment fatty acids and/or ester are mixed with
olefins.
[0069] In an alternative embodiment, the ashless antiwear agent may
be a monoester of a polyol and an aliphatic carboxylic acid, often
an acid containing 12 to 24 carbon atoms. Often the monoester of a
polyol and an aliphatic carboxylic acid is in the form of a mixture
with a sunflower oil or the like, which may be present in the
friction modifier mixture from 5 to 95, in several embodiments from
10 to 90, or from 20 to 85, or 20 to 80 weight percent of said
mixture. The aliphatic carboxylic acids (especially a
monocarboxylic acid) which form the esters are those acids
typically containing 12 to 24, or from 14 to 20 carbon atoms.
Examples of carboxylic acids include dodecanoic acid, stearic acid,
lauric acid, behenic acid, and oleic acid.
[0070] Polyols include diols, triols, and alcohols with higher
numbers of alcoholic OH groups. Polyhydric alcohols include
ethylene glycols, including di-, tri- and tetraethylene glycols;
propylene glycols, including di-, tri- and tetrapropylene glycols;
glycerol; butane diol; hexane diol; sorbitol; arabitol; mannitol;
sucrose; fructose; glucose; cyclohexane diol; erythritol; and
pentaerythritols, including di- and tripentaerythritol. Often the
polyol is diethylene glycol, triethylene glycol, glycerol,
sorbitol, pentaerythritol or dipentaerythritol.
[0071] The commercially available monoester known as "glycerol
monooleate" is believed to include 60.+-.5 percent by weight of the
chemical species glycerol monooleate, along with 35.+-.5 percent
glycerol dioleate, and less than 5 percent trioleate and oleic
acid. The amounts of the monoesters, described above, are
calculated based on the actual, corrected, amount of polyol
monoester present in any such mixture.
Extreme Pressure Agents
[0072] Extreme Pressure (EP) agents that are soluble in the oil
include sulphur- and chlorosulphur-containing EP agents,
chlorinated hydrocarbon EP agents and phosphorus EP agents.
Examples of such EP agents include chlorinated wax; sulphurised
olefins (such as sulphurised isobutylene), organic sulphides and
polysulphides such as dibenzyldisulphide, bis-(chlorobenzyl)
disulphide, dibutyl tetrasulphide, sulphurised methyl ester of
oleic acid, sulphurised alkylphenol, sulphurised dipentene,
sulphurised terpene, and sulphurised Diels-Alder adducts;
phosphosulphurised hydrocarbons such as the reaction product of
phosphorus sulphide 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).
[0073] Corrosion inhibitors that may be useful in the compositions
of the invention include fatty amines, octyl octanamide,
condensation products of dodecenyl succinic acid or anhydride
and/or a fatty acid such as oleic acid with a polyamine.
[0074] Foam inhibitors that may be useful in the compositions of
the invention include copolymers of ethyl acrylate and
2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers
including trialkyl phosphates, polyethylene glycols, polyethylene
oxides, polypropylene oxides and (ethylene oxide-propylene oxide)
polymers.
[0075] Pour point depressants (other than the compound of the
invention) may include polyalphaolefins, esters of maleic
anhydride-styrene copolymers, poly(meth)acrylates, polyacrylates or
polyacrylamides. In one embodiment the pour point depressant may be
(i) esters of maleic anhydride-styrene copolymers, or (ii)
polymethacrylates. The pour point depressant may be present at 0 wt
% to 0.5 wt %, or 0.1 wt % to 0.4 wt % of the lubricating
composition.
[0076] Friction modifiers that may be useful in the compositions of
the invention include fatty acid or fatty alkyl derivatives such as
amines, esters, epoxides, fatty imidazolines, condensation products
of carboxylic acids and polyalkylene-polyamines and amine salts of
alkylphosphoric acids.
[0077] In several embodiments a suitable lubricating composition
includes the compound of the formula disclosed herein that may be
present (on an actives basis) in ranges as shown in the following
table.
TABLE-US-00001 TABLE Embodiments (of lubricant composition) A B C D
Compound of Invention (ppm) 100-2000 200-1000 300-750 400-600 Other
Performance Additives 0-15 0.01-15 0.5-10 0.5-10 (wt %) Oil of
Lubricating Viscosity Balance to 100% (wt %)
[0078] The following examples provide an illustration of the
invention. These examples are non exhaustive and are not intended
to limit the scope of the invention.
EXAMPLES
Preparative Example 1
[0079] A 3 L flask under nitrogen is charged with a C.sub.24-28
alkylphenol (1000 g, 2.222 mol) and heated to 85.degree. C.
Sulphuric acid (3.46 g) is added dropwise over approximately 10
minutes. The flask is then heated to 105.degree. C. and
paraformaldehyde (81.6 g, 2.717 mol) is charged over four hours.
The flask is then heated to 135.degree. C. over two hours and then
held at this temperature for a further two hours to collect any
aqueous distillate. The reaction is then cooled to 121.degree. C.
and solid calcium hydroxide (3.16 g) charged to the flask, followed
by a 50% aqueous solution of sodium hydroxide 30 minutes later. The
flask is then held at 121.degree. C. for two hours, then heated to
152.degree. C. and held there for a further two hours with a high
nitrogen sparge to quench the reaction and collect any
additional/remaining aqueous distillate. The flask is then cooled
to about 70.degree. C. and an aromatic solvent (Solvesso.TM. 150,
1022 g) charged to the flask. After 30 minutes the mixture is
discharged and filtered to give a dark oil.
[0080] Comparative lubricant 1 (COMPL1) is a manual transmission
lubricant comprising 7 wt % of a commercially available additive
package, 400 ppm of a vinyl acetate copolymer (commercially
available from The Lubrizol Corporation under the trade name
LZ.RTM.8056F, 0.3 wt % of a pour point depressant (derived from a
polymethacrylate) and the balance to 100 wt % with bright stock
lubricant.
[0081] Comparative lubricant 2 (COMPL2) is a manual transmission
lubricant comprising 7 wt % of a commercially available additive
package, 400 ppm of the material of Example 1 of International
publication WO 2009/064827, and the balance to 100 wt % with bright
stock lubricant.
[0082] Inventive lubricant 1 (INVL1) is a manual transmission
lubricant comprising 7 wt % of a commercially available additive
package, 400 ppm of the product of preparative example 1, 0.3 wt %
of a pour point depressant (derived from an esterified maleic
anhydride styrene), and the balance to 100 wt % with bright stock
lubricant.
[0083] Lubricants COMPL1, COMPL2 and INVL1 are evaluated to
determine filterability by the methodology described in ISO
Standard ISO13357-2:1998(E), except the filter pressure is 2 bar
(or 200 kPa) and a 5 .mu.m membrane is used. Stage 2 filterability
(as noted in section 4.3 of the procedure) is a ratio expressed as
a percentage between the flow rate at the start of the filtration
and the flow rate between 200 ml and 300 ml of filtered volume. The
ratio is calculated by the formula given in section 10.2 of the
procedure. The results obtained are:
TABLE-US-00002 Example COMPL1 COMPL2 INVL1 Filterability Percent
Ratio unfilterable unfilterable 91 Footnote: Unfilterable indicates
that the filtration time exceeds 7200 seconds.
[0084] The results indicate that the example of the invention has
improved filterability compared with comparative examples COMPL1
and COMPL2 in a manual transmission containing bright stock. In
particular both COMPL1 and COMPL2 fail the filterability test
because both lubricants cause the filter to block. In contrast, the
inventive lubricant allows the lubricant to pass stage 2 with a 91%
flow rate.
[0085] 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. The products formed thereby, including the products formed
upon employing lubricant 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 lubricant composition prepared by admixing
the components described above.
[0086] 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.
[0087] 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.
Examples of hydrocarbyl groups include: 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. A more detailed definition of
the term "hydrocarbyl substituent" or "hydrocarbyl group" is
described in paragraphs [0118] to [0119] of International
Publication WO2008147704 (corresponding to US-2010-0197536).
[0088] While the invention has been explained in relation to its
preferred embodiments, it is to be understood that various
modifications thereof will become apparent to those skilled in the
art upon reading the specification. Therefore, it is to be
understood that the invention disclosed herein is intended to cover
such modifications as fall within the scope of the appended
claims.
* * * * *