U.S. patent application number 12/374379 was filed with the patent office on 2009-12-10 for multi-dispersant lubricating composition.
This patent application is currently assigned to The Lubrizol Corporation. Invention is credited to William D. Abraham, James L. Sumiejski, Craig D. Tipton.
Application Number | 20090305919 12/374379 |
Document ID | / |
Family ID | 38982292 |
Filed Date | 2009-12-10 |
United States Patent
Application |
20090305919 |
Kind Code |
A1 |
Tipton; Craig D. ; et
al. |
December 10, 2009 |
Multi-Dispersant Lubricating Composition
Abstract
The present invention relates to a lubricating composition
containing a corrosion inhibitor compound and a mixture of two or
more dispersants, wherein 0 mole % to less than 50 mole % of the
second dispersant molecules contain a carbocyclic ring. The
invention further provides a method for lubricating a mechanical
device using the lubricating composition.
Inventors: |
Tipton; Craig D.; (Perry,
OH) ; Sumiejski; James L.; (Mentor, OH) ;
Abraham; William D.; (Concord, OH) |
Correspondence
Address: |
THE LUBRIZOL CORPORATION;ATTN: DOCKET CLERK, PATENT DEPT.
29400 LAKELAND BLVD.
WICKLIFFE
OH
44092
US
|
Assignee: |
The Lubrizol Corporation
Wickliffe
OH
|
Family ID: |
38982292 |
Appl. No.: |
12/374379 |
Filed: |
July 25, 2007 |
PCT Filed: |
July 25, 2007 |
PCT NO: |
PCT/US07/74316 |
371 Date: |
April 28, 2009 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
60820516 |
Jul 27, 2006 |
|
|
|
Current U.S.
Class: |
508/162 ;
508/186 |
Current CPC
Class: |
C10M 163/00 20130101;
C10N 2040/04 20130101; C10N 2060/12 20130101; C10N 2030/76
20200501; C10N 2030/06 20130101; C10M 2207/142 20130101; C10N
2030/12 20130101; C10M 2215/082 20130101; C10N 2040/045 20200501;
C10M 2209/084 20130101; C10M 2207/142 20130101; C10M 2215/28
20130101; C10M 2219/106 20130101; C10N 2060/14 20130101; C10M
2207/142 20130101; C10M 2217/043 20130101; C10M 2219/106 20130101;
C10N 2060/14 20130101; C10M 2207/142 20130101; C10M 2215/28
20130101; C10M 2219/106 20130101; C10N 2060/14 20130101; C10M
2207/142 20130101; C10M 2217/043 20130101; C10M 2219/106 20130101;
C10N 2060/14 20130101 |
Class at
Publication: |
508/162 ;
508/186 |
International
Class: |
C10M 125/24 20060101
C10M125/24; C10M 163/00 20060101 C10M163/00 |
Claims
1.-29. (canceled)
30. A lubricating composition comprising: (a) an oil of lubricating
viscosity; (b) a first dispersant comprising a product prepared by
heating together: (i) a first dispersant substrate; (ii) a
thiadiazole compound; (iii) a borating agent; and (iv) a
dicarboxylic acid of an aromatic compound selected from the group
consisting of 1,3 diacids and 1,4 diacids, and (v) optionally a
phosphorus acid compound, said heating being sufficient to provide
a product of (i), (ii), (iii) and (iv) and optionally (v), which is
soluble in an oil of lubricating viscosity; (c) a second
dispersant, wherein 0 mole % to less than 50 mole % of the second
dispersant molecules contain a carbocyclic ring; and (d) a
corrosion inhibitor.
31. The lubricating composition of claim 30, wherein the corrosion
inhibitor comprises an oil soluble
2,5-dimercapto-1,3,4-thiadiazole, other than (b).
32. The lubricating composition of claim 31, wherein the corrosion
inhibitor is present in the range of 0.005 wt % to 5 wt % of the
lubricating composition.
33. The lubricating composition of claim 30, wherein the first
dispersant is prepared by an "ene" reaction.
34. The lubricating composition of claim 30, wherein the second
dispersant is prepared from a succinic anhydride from an "ene"
reaction.
35. The lubricating composition of claim 30, wherein 0 mole % to
less than 20 mole % of the second dispersant molecules contain a
carbocyclic ring.
36. The lubricating composition of claim 30, wherein the first
dispersant and second dispersant both have a CO:N ratio of 2:1 to
1:10.
37. The lubricating composition of claim 30, wherein the first
dispersant is prepared in the presence of a dicarboxylic acid of an
aromatic compound selected from the group consisting of 1,3 diacids
and 1,4 diacids.
38. The lubricating composition of claim 37, wherein the
dicarboxylic acid of an aromatic compound comprises terephthalic
acid.
39. The lubricating composition of claim 30, wherein the oil of
lubricating viscosity has a sulphur content in range of 0 ppm to
1000 ppm.
40. The lubricating composition of claim 30, further comprising a
friction stabilising agent, wherein the friction stabilising agent
comprises H.sub.3PO.sub.4, H.sub.3PO.sub.3 or mixtures thereof, and
wherein the friction stabilising agent is present at 0.01 wt % to
0.5 wt % of the lubricating composition.
41. The lubricating composition of claim 30, further comprising an
antiwear agent selected from the group consisting of (i) a
non-ionic phosphorus compound; (ii) an amine salt of a phosphorus
compound; (iii) an ammonium salt of a phosphorus compound; (iv) a
monovalent metal salt of a phosphorus compound, such as a metal
dialkyldithiophosphate or a metal dialkylphosphate; and (v)
mixtures of (i), (ii), (iii) or (iv).
42. The lubricating composition of claim 30, further comprising an
antioxidant, wherein the antioxidant comprises at least one of
sulphurised olefins, hindered phenols, phenylalphanaphthylamines,
alkylated diphenylamines, hydroxylalkyl sulphides, or mixtures
thereof.
43. The lubricating composition of claim 42, wherein the
antioxidant is present at 0.01 wt % to 5 wt % of the lubricating
composition.
44. The lubricating composition of claim 30, further comprising a
friction modifier.
45. The lubricating composition of claim 44, wherein the friction
modifier is present at 0.1 wt % to 4 wt %.
46. The lubricating composition of claim 30, wherein the oil of
lubricating viscosity has an aromatic content of 0 wt % to 10 wt
%.
47. The lubricating composition of claim 30, wherein the oil of
lubricating viscosity has a viscosity index of 105 or more.
48. A method of lubricating a mechanical device, comprising
supplying the lubricating composition of claim 30 to the mechanical
device.
49. The method of claim 27, wherein the mechanical device comprises
an automatic transmission.
50. A lubricating composition comprising: (a) an oil of lubricating
viscosity; (b) a first dispersant comprising a product prepared by
heating together: (i) a first dispersant substrate; (ii) a
thiadiazole compound; (iii) a borating agent; and (iv) optionally a
dicarboxylic acid of an aromatic compound selected from the group
consisting of 1,3 diacids and 1,4 diacids, and (v) optionally a
phosphorus acid compound, said heating being sufficient to provide
a product of (i), (ii), (iii) and optionally (iv) and optionally
(v), which is soluble in an oil of lubricating viscosity; (c) a
second dispersant, wherein 0 mole % to less than 50 mole % of the
second dispersant molecules contain a carbocyclic ring; and (d) an
oil soluble dimercaptothiadiazole corrosion inhibitor, other than
(b).
Description
FIELD OF INVENTION
[0001] The present invention relates to a lubricating composition
comprising a corrosion inhibitor and a mixture of two or more
dispersants, where at least one of the dispersants has a
carbocyclic ring present on less than 50 mole % of the dispersant
molecules. The invention further provides a method for lubricating
a mechanical device using the lubricating composition.
BACKGROUND OF THE INVENTION
[0002] Driveline transmissions such as gears or transmissions,
especially automatic transmission fluids (ATFs), present highly
challenging technological problems for satisfying the multiple and
often conflicting lubricating and power transmitting requirements
of modern automatic transmissions (including continuously variable
transmissions of various types). Many additive components are
typically included in an ATF, providing such performance
characteristics as lubrication, dispersancy, friction control (for
clutches), antiwear performance, anti-shudder performance,
anti-corrosion and anti-oxidation performance. In some instances
additive performance may be reduced in the presence of
hydro-cracked basestocks such as API Group II or Group III oils.
Any reduction in additive performance results in increased wear and
corrosion and influences frictional characteristics. Therefore
finding and providing the correctly balanced composition is a
significant formulating challenge to meet industry specifications
such as the Ford MERCON.RTM.-V or MERCON.RTM.-VI specifications or
the General Motors specifications DEXRON.RTM.-II, DEXRON.RTM.-III
or DEXRON.RTM.-SP.
[0003] Examples of formulations that have been employed in the past
include those represented by U.S. Pat. No. 5,164,103, Papay, Nov.
17, 1992, which discloses preconditioned ATFs made by using a
preblend formed by heating an alkenyl succinimide or succinimide
detergent with a phosphorus ester and water to partially hydrolyze
the ester, and then mixing the preblend and other additives with a
base oil. Boronating agents may also be used. Thiadiazole
derivatives may be included as another additive.
[0004] A number of other patents disclose an additive derived from
the reaction of (i) alkenyl succinimide or succinimide with a
phosphorus compound. These patents include U.S. Pat. No. 5,089,156
(Chrisope et al., Feb. 18, 1992 and related U.S. Pat. No.
5,360,562, Chrisope et al., Nov. 1, 1994), U.S. Pat. No. 5,256,324
(Papay, Oct. 26, 1993, and a division thereof: U.S. Pat. No.
53,244,606, Papay, Aug. 8, 1994), U.S. Pat. No. 5,527,478
(Romanelli et al., Jun. 18, 1996), U.S. Pat. No. 5,652,201 (Papay
et al., Jul. 29, 1997), U.S. Pat. No. 5,817,605 (Papay, Oct. 6,
1998), U.S. Pat. No. 5,972,851 (Srinivasan et al. Oct. 26, 1999),
U.S. Pat. No. 4,857,214 (Papay et al, Aug. 15, 1989), and U.S. Pat.
No. 3,502,677 (Le Suer, Mar. 24, 1970).
[0005] U.S. Pat. No. 5,344,579, Ohtani et al, Sep. 6, 1994,
discloses a friction modifier composition which may be used in a
wet clutch or wet brake system. The composition comprises a
hydroxyalkyl aliphatic imidazoline and a di(hydroxyalkyl)aliphatic
tertiary amine. The compositions may also contain a
phosphorus-containing ashless dispersant and/or a boron-containing
ashless dispersant. Among other components are copper corrosion
inhibitors such as 2,5-dimercapto-3,4-thiadiazole.
[0006] U.S. Pat. No. 6,251,840, Ward, Jr. et al., Jun. 26, 2001,
discloses an automatic transmission fluid comprising a majority of
an oil having a certain viscosity, 0.025-5 weight percent
2,5-dimercapto-1,3,4-thiadiazole (DMTD) or one or more derivatives
of DMTD, an antifoam agent, and 0.01-0.3 weight percent of 85%
phosphoric acid. Derivatives of DMTD include products from
combining an oil soluble dispersant with DMTD. These may be
obtained by mixing a thiadiazole, preferably DMTD with an
oil-soluble carboxylic dispersant in a diluent and heating the
mixture above about 100.degree. C.
[0007] U.S. Pat. No. 4,136,043, Davis, Jan. 23, 1979, discloses
compositions which form homogeneous blends with lubricating oils
and the like, produced by preparing a mixture of an oil-soluble
dispersant and a dimercaptothiadiazole and heating the mixture
above about 100.degree. C. The compositions are useful for
suppression of copper activity and "lead paint" deposition in
lubricants.
[0008] US Patent Application 2003/0224948, Van Dam et al.,
published Dec. 4, 2003, discloses an additive formulation
containing ethylene carbonate polyalkene succinimides, borated
dispersants and dispersed aromatic dicarboxylic acid corrosion
inhibitors that are succinimide salts of one or more aromatic
dicarboxylic acids.
[0009] International Application WO/US2006/04319, Sumiejski et al.,
discloses a lubricating composition containing a friction modifier,
a corrosion inhibitor, an antiwear agent and a product prepared by
heating a dispersant, a thiadiazole, a borating agent and
optionally at least one of a 1,3- or 1,4-dicarboxylic acid and a
phosphorus acid.
[0010] International Publication WO 2005/021692, Tipton et al.,
Aug. 21, 2003 discloses a composition containing the product
prepared by heating together: (a) a dispersant and (b)
2,5-dimercapto-1,3,4-thiadiazole or a hydrocarbyl-substituted
2,5-dimercapto-1,3,4-thiadiazole which is substantially insoluble
in a hydrocarbon oil of lubricating viscosity at 25.degree. C., and
further either (c) a borating agent or (d) an inorganic phosphorus
compound, or both (c) and (d), said heating being sufficient to
provide a reaction product of (a), (b), and (c) or (d) which is
soluble in said hydrocarbon oil at 25.degree. C. The composition
further contains dibutyl hydrogen phosphite antiwear agent, calcium
sulphonate detergents and friction stabilizing additive
(H.sub.3PO.sub.4).
[0011] The present invention solves the problem of providing a
lubricating composition, especially for an ATF capable of providing
at least one property from acceptable friction performance,
acceptable wear protection, acceptable corrosion resistance,
acceptable anti-shudder performance, acceptable oxidation
resistance and acceptable gear protection.
SUMMARY OF THE INVENTION
[0012] In one embodiment the invention provides a lubricating
composition comprising: [0013] (a) an oil of lubricating viscosity;
[0014] (b) a first dispersant comprising a product prepared by
heating together: [0015] (i) a first dispersant substrate; [0016]
(ii) a thiadiazole compound, such as, a dimercaptothiadiazole or
oligomers thereof; [0017] (iii) a borating agent; and [0018] (iv)
optionally a dicarboxylic acid of an aromatic compound selected
from the group consisting of 1,3 diacids and 1,4 diacids, and
[0019] (v) optionally a phosphorus acid compound, said heating
being sufficient to provide a product of (i), (ii), (iii) and
optionally (iv) and optionally (v), which is soluble in an oil of
lubricating viscosity; [0020] (c) a second dispersant, wherein 0
mole % to less than 50 mole % of the second dispersant molecules
contain a carbocyclic ring; and [0021] (d) a corrosion inhibitor
such as an oil soluble 2,5-dimercapto-1,3,4-thiadiazole or a
hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole
derivative, other than (b).
[0022] In one embodiment the invention provides a method of
lubricating a mechanical device, comprising supplying a lubricating
composition described herein to the mechanical device.
DETAILED DESCRIPTION OF THE INVENTION
[0023] The present invention provides a lubricating composition and
a method for lubricating a mechanical device as disclosed
above.
[0024] The first dispersant may be prepared/obtained/obtainable
from reaction of succinic anhydride by a Diels-Alder reaction or an
"ene" reaction. The "ene" reaction mechanism and general reaction
conditions are summarised in "Maleic Anhydride", pages, 147-149,
Edited by B. C. Trivedi and B. C. Culbertson and Published by
Plenum Press in 1982.
[0025] When the first dispersant is prepared by an "ene" reaction,
0 mole % to less than 50 mole %, or 0 to less than 30 mole % of the
first dispersant molecules contain a carbocyclic ring.
[0026] The second dispersant is typically
prepared/obtained/obtainable by an "ene" reaction and comprises a
dispersant molecule with 0 mole % to less than 50 mole %, or 0 to
less than 30 mole % of the second dispersant molecules containing a
carbocyclic ring.
[0027] In one embodiment both the first and second dispersant are
prepared by an "ene" reaction. The "ene" reaction may have a
reaction temperature of 180.degree. C. to less than 300.degree. C.,
or 200.degree. C. to 250.degree. C., or 200.degree. C. to
220.degree. C.
[0028] Typically the first and second dispersant may be succinimide
dispersants prepared by reacting a hydrocarbyl-substituted succinic
anhydride with an amine (e.g., a polyamine). The first dispersant
and second dispersant may independently have a carbonyl to nitrogen
ratio (CO:N ratio) of 5:1 to 1:10, 2:1 to 1:10, or 1:1 to 1:10, or
1:1 to 1:5, or 1:1 to 1:2. In one embodiment the first dispersant
and second dispersant both have a CO:N ratio of 1:1 to 1:10, or 1:1
to 1:5, or 1:1 to 1:2.
[0029] The weight ratio of the dispersant 2 to dispersant 1 may be
5:1 to 1:10, or 4:1 to 1:2.
(i) The First Dispersant
[0030] The product prepared by heating comprises a first
dispersant. The first dispersant of the invention may be prepared
from a first dispersant substrate that is well known. The first
dispersant substrate includes a succinimide dispersant (for
example, N-substituted long chain alkenyl succinimides), a Mannich
dispersant, an ester-containing dispersant, a condensation product
of a fatty hydrocarbyl monocarboxylic acylating agent with an amine
or ammonia, an alkyl amino phenol dispersant, a hydrocarbylamine
dispersant, a polyether dispersant, a polyetheramine dispersant, a
viscosity modifier containing dispersant functionality (for example
polymeric viscosity index modifiers (VMs) containing dispersant
functionality), or mixtures thereof. Typically the first dispersant
substrate includes a succinimide dispersant or a Mannich
dispersant.
[0031] Generally the dispersant suitable for preparing component
(b) of the present invention may be prepared as described in
Examples 1-4 of International Patent Application PCT/US06/004576;
or Examples 1-4 of International Publication WO2005/021692, both
titled "Multifunctional Dispersants".
[0032] In several embodiments the N-substituted long chain alkenyl
succinimides of (b) contain an average of at least 8, or 30, or 35
up to 350, or to 200, or to 100 carbon atoms. In one embodiment,
the long chain alkenyl group is derived from a polyalkene
characterised by an M.sub.n (number average molecular weight) of at
least 500. Generally, the polyalkene is characterised by an M.sub.n
of 500, or 700, or 800, or even 900 up to 5000, or to 2500, or to
2000, or even to 1500 or 1200. In one embodiment the long chain
alkenyl group is derived form one or more polyolefins. The
polyolefins may be, in turn, derived from monomers including
monoolefins having 2 to 10 carbon atoms such as ethylene,
propylene, 1-butene, isobutylene, and 1-decene. An especially
useful monoolefin source is a C.sub.4 refinery stream having a 35
to 75 weight percent butene content and a 30 to 60 weight percent
isobutene content. Useful polyolefins include polyisobutylenes
having a number average molecular weight of 140 to 5000, in another
instance of 400 to 2500, and in a further instance of 140 or 500 to
1500. The polyisobutylene may have a vinylidene double bond content
of 5 to 69%, in a second instance of 50 to 69%, and in a third
instance of 50 to 95%.
[0033] Succinimide dispersants suitable as the first dispersant
substrate are described in more detail along with their methods of
preparation in U.S. Pat. Nos. 4,234,435 and 3,172,892.
[0034] Mannich dispersants suitable as the first dispersant
substrate include the reaction product of a hydrocarbyl-substituted
phenol, an aldehyde, and an amine or ammonia. The hydrocarbyl
substituent of the hydrocarbyl-substituted phenol may have 10 to
400 carbon atoms, in another instance 30 to 180 carbon atoms, and
in a further instance 10 or 40 to 110 carbon atoms. This
hydrocarbyl substituent may be derived from an olefin or a
polyolefin. Useful olefins include alpha-olefins, such as 1-decene,
or isobutylene, which are commercially available.
(ii) The Thiadiazole Compound
[0035] The present invention further comprises a thiadiazole which
is reacted as a part of the first dispersant. This is in addition
to any dimercaptothiadiazole which may be present within a
lubricating composition as a separate corrosion inhibitor. Examples
of a thiadiazole include 2,5-dimercapto-1,3,4-thiadiazole,
2,5-dimercapto-1,3,4-thiadiazole, or oligomers thereof, a
hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole, a
hydrocarbylthio-substituted 2,5-dimercapto-1,3-4-thiadiazole, or
oligomers thereof. The oligomers of hydrocarbyl-substituted
2,5-dimercapto-1,3,4-thiadiazole typically form by forming a
sulphur-sulphur bond between 2,5-dimercapto-1,3,4-thiadiazole units
to form oligomers of two or more of said thiadiazole units.
[0036] The number of carbon atoms on the hydrocarbyl substituents
in several embodiments range from 1 to 30, 2 to 20 or 3 to 16.
[0037] In one embodiment the thiadiazole compound, e.g.,
hydrocarbyl-substituted mercaptothiadizoles (as well as the
unsubstituted materials), is typically substantially soluble at
25.degree. C. in non-polar media such as an oil of lubricating
viscosity. Thus, the total number of carbon atoms in the
hydrocarbyl-substituents, which tend to promote solubility, will
generally be 8 or more, or 10 or more, or at least 12. If there are
multiple hydrocarbyl substituents, typically each substituent will
contain 8 or fewer carbon atoms.
[0038] In one embodiment the thiadiazole compound, e.g.,
hydrocarbyl-substituted mercaptothiadazoles (as well as the
unsubstituted materials), is typically substantially insoluble at
25.degree. C. in non-polar media such as an oil of lubricating
viscosity. Thus, the total number of carbon atoms in the
hydrocarbyl-substituents, which tend to promote solubility, will
generally be fewer than 8, or 6, or 4. If there are multiple
hydrocarbyl substituents, typically each substituent will contain 4
or fewer carbon atoms.
[0039] By the term "substantially insoluble" it is meant that the
thiadiazole compound e.g., a dimercaptothiadiazole (DMTD) compound,
may typically dissolve to an extent of less than 0.1 weight
percent, or less than 0.01 or 0.005 weight percent in oil at room
temperature (25.degree. C.). A suitable hydrocarbon oil of
lubricating viscosity in which the solubility may be evaluated is
Chevron.TM. RLOP 100 N oil. The specified amount of the DMTD or
substituted DMTD is mixed with the oil and the solubility may be
evaluated by observing clarity versus the appearance of residual
sediment after, e.g., 1 week of storage.
[0040] Examples of a suitable thiadiazole compound include those
disclosed below in the corrosion inhibitor definition. In one
embodiment the thiadiazole compound includes a
hydrocarbyl-substituted 2,5-dimercapto-1,3-4-thiadiazole comprising
at least one of 2,5-bis(tert-octyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-nonyldithio)-1,3,4-thiadiazole, or
2,5-bis(tert-decyldithio)-1,3,4-thiadiazole.
(iii) Borating Agent
[0041] The borating agent includes various forms of boric acid
(including metaboric acid, HBO.sub.2, orthoboric acid,
H.sub.3BO.sub.3, and tetraboric acid, H.sub.2B.sub.4O.sub.7), boric
oxide, boron trioxide, and alkyl borates, such as those of the
formula (RO).sub.xB(OH).sub.y wherein x is 1 to 3 and y is 0 to 2,
the sum of x and y being 3, and where R is an alkyl group
containing 1 to 6 carbon atoms. In one embodiment, the boron
compound is an alkali or mixed alkali metal and alkaline earth
metal borate. These metal borates are generally hydrated
particulate metal borates which are known in the art. In one
embodiment the metal borates include mixed alkali and alkaline
earth metal borates. These metal borates are available
commercially.
(iv) Dicarboxylic Acid of an Aromatic Compound
[0042] In one embodiment the first dispersant further comprises a
1,3-dicarboxylic acid or 1,4-dicarboxylic acid of an aromatic
compound, or reactive equivalents thereof, or mixtures thereof. The
1,3-dicarboxylic acid or 1,4-dicarboxylic acid is reacted or
complexed with the first dispersant. The term "reactive equivalents
thereof" includes acid halides, esters, amides or mixtures thereof.
The "aromatic component" of the 1,3-dicarboxylic acid or
1,4-dicarboxylic acid is typically a benzene (phenylene) ring or a
substituted benzene ring, although other aromatic materials such as
fused ring compounds or heterocyclic compounds are also
contemplated. It is believed (without intending to be bound by any
theory) that the dicarboxylic acid aromatic compound may be bound
to the first dispersant by salt formation or complexation, rather
than formation of covalently bonded structures such as amides,
which may also be formed but may play a less important role.
Typically the presence of the dicarboxylic acid aromatic compound
within the present invention is believed to impart corrosion
inhibition properties to the composition. Examples of suitable
dicarboxylic acids include 1,3-dicarboxylic acids such as
isophthalic acid and alkyl homologues such as 2-methyl isophthalic
acid, 4-methyl isophthalic acid or 5-methyl isophthalic acid; and
1,4-dicarboxylic acids such as terephthalic acid and alkyl
homologues such as 2-methyl terephthalic acid. Other ring
substituents such as hydroxy or alkoxy (e.g., methoxy) groups may
also be present in certain embodiments. In one embodiment the
aromatic compound is terephthalic acid.
(v) Phosphorus Acid Compound
[0043] In one embodiment the first dispersant is optionally
prepared in the presence of a phosphorus acid compound. The
phosphorus acid compound may contain an oxygen atom and/or a sulfur
atom as its constituent elements, and is typically a phosphorus
acid or anhydride. This component includes the following examples:
phosphorous acid, phosphoric acid, hypophosphorous acid,
polyphosphoric acid, phosphorus trioxide, phosphorus tetroxide,
phosphorus pentoxide (P.sub.2O.sub.5), phosphorotetrathionic acid
(H.sub.3PS.sub.4), phosphoromonothionic acid (H.sub.3PO.sub.3S),
phosphorodithionic acid (H.sub.3PO.sub.2S.sub.2),
phosphorotrithionic acid (H.sub.3PO.sub.2S.sub.3), and
P.sub.2S.sub.5. Among these, phosphorous acid and phosphoric acid
or their anhydrides are typically used. A salt, such as an amine
salt of a phosphorus acid compound may also be used. It is also
possible to use a plurality of these phosphorus acid compounds
together. The phosphorus acid compound is often phosphoric acid or
phosphorous acid or their anhydride.
[0044] The phosphorus acid compound may also include phosphorus
compounds with a phosphorus oxidation of +3 or +5, such as
phosphates, phosphonates, phosphinates, or phosphine oxides. A more
detailed description for these suitable phosphorus acid compounds
is given in U.S. Pat. No. 6,103,673, column 9, line 64 to column
11, line 8.
[0045] The amount of the first dispersant present in the
lubricating composition may be in ranges of 0.1 wt % to 10 wt %, or
0.2 wt % to 7 wt %, or 0.3 wt % to 6 wt % of the lubricating
composition.
The Second Dispersant
[0046] The second dispersant includes a succinimide dispersant (for
example N-substituted long chain alkenyl succinimides), an
ester-containing dispersant, a condensation product of a fatty
hydrocarbyl monocarboxylic acylating agent with an amine or
ammonia, a hydrocarbyl-amine dispersant, a polyether dispersant, a
polyetheramine dispersant, a viscosity modifier containing
dispersant functionality (for example polymeric viscosity index
modifiers (VMs) containing dispersant functionality), or mixtures
thereof. Typically the second dispersant is a succinimide
dispersant.
[0047] In one embodiment the second dispersant may be a
multifunctional dispersant prepared by heating (i) a dispersant
substrate; (ii) a borating agent; and (iii) optionally a
dicarboxylic acid of an aromatic compound selected from the group
consisting of 1,3 diacids and 1,4 diacids, and (iv) optionally a
phosphorus acid compound, said heating being sufficient to provide
a product of (i), (ii), and optionally (iii), which is soluble in
an oil of lubricating viscosity. Typically a multifunctional
dispersant of this type (i.e. the second dispersant) is not
prepared in the presence of 2,5-dimercapto-1,3,4-thiadiazole, or a
2,5-dimercapto-1,3,4-thiadiazole derivative.
[0048] The second dispersant is typically described in a similar
way to the first dispersant substrate (defined above) or the
multifunctional dispersant described immediately above, except the
second dispersant has 0 mole % to less than 50 mole % of the second
dispersant molecules containing a carbocyclic ring. In one
embodiment the second dispersant has 0 mole % to less than 20 mole
% of the second dispersant molecules containing a carbocyclic ring.
In one embodiment the second dispersant has 0 mole % of the second
dispersant molecules containing a carbocyclic ring
[0049] The amount of the second dispersant present in the
lubricating composition may be in ranges of 0.1 wt % to 10 wt %, or
0.2 wt % to 7 wt %, or 0.3 wt % to 6 wt % of the lubricating
composition.
Corrosion Inhibitor
[0050] The lubricating composition further comprises a corrosion
inhibitor or mixtures thereof. In one embodiment the corrosion
inhibitor also exhibits antiwear properties.
[0051] In several embodiments the amount of corrosion inhibitor
present in the lubricating composition ranges from 0.001 wt % to 10
wt %, 0.005 wt % to 5 wt %, 0.01 wt % to 3 wt % or 0.02 wt % to 2
wt % of the lubricating composition.
[0052] The corrosion inhibitors of the invention include
benzotriazoles (typically tolyltriazole),
2-alkyldithiobenzimidazoles or 2-alkyldithio benzothiazoles,
1,2,4-triazoles, benzimidazoles, octylamine octanoate, condensation
products of dodecenyl succinic acid or anhydride,
dimercaptothiadiazoles and reactive equivalents thereof, or
mixtures thereof.
[0053] The corrosion inhibitor may comprise at least one of a
dimercaptothiadiazole, 5-dimercapto-[1,3,4]-thiadiazole,
3,5-dimercapto-[1,2,4]-thiadiazole,
3,4-dimercapto-[1,2,5]-thiadiazole, or
4-5-dimercapto-[1,2,3]-thiadaizole. Typically readily available
materials such as 2,5-dimercapto-1,3-4-thiadiazole or a
hydrocarbyl-substituted 2,5-dimercapto-1,3-4-thiadiazole are
commonly utilised, with 2,5-dimercapto-[1,3,4]-thiadiazole most
commonly utilised due to availability. In several embodiments the
number of carbon atoms on the hydrocarbyl-substituent group
includes 1 to 30, 2 to 25, 4 to 20, 6 to 16, or 8 to 10.
[0054] In one embodiment, the thiazole compound may be the reaction
product of a phenol with an aldehyde and a dimercaptothiadiazole.
The phenol may be an alkyl phenol wherein the alkyl group contains
at least about 6, e.g., 6 to 24, or 6, or 7, to 12 carbon atoms.
The aldehyde may be an aldehyde containing 1 to 7 carbon atoms or
an aldehyde synthon, such as formaldehyde. In one embodiment, the
aldehyde is formaldehyde or paraformaldehyde. The aldehyde, phenol
and dimercaptothiadiazole are typically reacted by mixing them at a
temperature up to about 150.degree. C. such as 50.degree. C. to
130.degree. C., in molar ratios of 0.5 to 2 moles of phenol and 0.5
to 2 moles of aldehyde per mole of dimercaptothiadiazole. In one
embodiment, the three reagents are reacted in equal molar amounts.
The product may be described as an
alkylhydroxyphenylmethylthio-substituted [1,3,4]-thiadiazole; the
alkyl moiety may be, among others, hexyl, heptyl, octyl, or
nonyl.
[0055] Useful thiadiazole compounds thus may include
2-alkyldithio-5-mercapto-[1,3,4]-thiadiazoles,
2,5-bis(alkyldithio)-[1,3,4]-thiadiazoles,
2-alkyl-hydroxyphenylmethylthio-5-mercapto-[1,3,4]-thiadiazoles,
and mixtures thereof.
[0056] Examples of suitable thiadiazole compounds include
2-octyldithio-5-mercapto-1,3,4-thiadiazole,
2-nonyldithio-5-mercapto-1,3,4-thiadiazole,
2-dodecydithio-5-mercapto-1,3,4-thiadiazole,
2,5-dimercapto-1,3-4-thiadiazole and
2,5-bis(alkyl-dithio)-1,3,4-thiadiazoles including
2,5-bis(tert-octyldithio)-1,3,4-thiadiazole
2,5-bis(tert-nonyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-decyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-undecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-dodecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-tridecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-tetradecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-pentadecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-hexadecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-heptadecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-octadecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-nonadecyldithio)-1,3,4-thiadiazole or
2,5-bis(tert-eicosyldithio)-1,3,4-thiadiazole, or oligomers
thereof. In one embodiment the hydrocarbyl-substituted
2,5-dimercapto-1,3-4-thiadiazole comprises at least one of
2,5-bis(tert-octyldithio)-1,3,4-thiadiazole
2,5-bis(tert-nonyldithio)-1,3,4-thiadiazole, or
2,5-bis(tert-decyldithio)-1,3,4-thiadiazole.
Oils of Lubricating Viscosity
[0057] The lubricating composition comprises an oil of lubricating
viscosity. Such oils include natural and synthetic oils, oil
derived from hydrocracking, hydrogenation, and hydrofinishing,
unrefined, refined and re-refined oils and mixtures thereof.
[0058] Unrefined oils are those obtained directly from a natural or
synthetic source generally without (or with little) further
purification treatment.
[0059] Refined oils are similar to the unrefined oils except they
have been further treated in one or more purification steps to
improve one or more properties. Purification techniques are known
in the art and include solvent extraction, secondary distillation,
acid or base extraction, filtration, and percolation.
[0060] Re-refined oils are also known as reclaimed or reprocessed
oils, and are obtained by processes similar to those used to obtain
refined oils and often are additionally processed by techniques
directed to removal of spent additives and oil breakdown
products.
[0061] Natural oils useful in making the inventive lubricants
include animal oils (e.g., lard oil), vegetable oils (e.g., castor
oil), mineral lubricating oils such as liquid petroleum oils and
solvent-treated or acid-treated mineral lubricating oils of the
paraffinic, naphthenic or mixed paraffinic-naphthenic types and
oils derived from coal or shale or mixtures thereof.
[0062] Synthetic lubricating oils are useful and include
hydrocarbon oils such as polymerised and interpolymerised olefins
(e.g., polybutylenes, polypropylenes, propyleneisobutylene
copolymers); poly(1-hexenes), poly(1-octenes), poly(1-decenes), and
mixtures thereof, alkyl-benzenes (e.g. dodecylbenzenes,
tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes);
polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls);
alkylated diphenyl ethers and alkylated diphenyl sulphides and the
derivatives, analogs and homologs thereof or mixtures thereof.
[0063] Other synthetic lubricating oils include polyol esters (such
as Priolube.RTM.3970), diesters, liquid esters of
phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl
phosphate, and the diethyl ester of decane phosphonic acid), or
polymeric tetrahydrofurans. Synthetic oils may 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.
[0064] Oils of lubricating viscosity may also be defined as
specified in the American Petroleum Institute (API) Base Oil
Interchangeability Guidelines. The five base oil groups are as
follows: Group I (sulphur content >0.03 wt %, and/or <90 wt %
saturates, viscosity index 80-120); Group II (sulphur content
.ltoreq.0.03 wt %, and .gtoreq.90 wt % saturates, viscosity index
80-120); Group III (sulphur 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
comprises an API Group I, Group II, Group III, Group IV, Group V
oil or mixtures thereof. In one embodiment the oil of lubricating
viscosity may be an API Group I, Group II, Group III, Group IV oil
or mixtures thereof. In one embodiment the oil of lubricating
viscosity may be an API Group II, Group III or Group IV oil or
mixtures thereof. In one embodiment the oil of lubricating
viscosity may be an API Group II or Group III oil or mixtures
thereof.
[0065] The oil of lubricating viscosity may have a sulphur content
in ranges of 0 ppm to 1000 ppm, or 0 ppm to 500 ppm, or 0 or 1 ppm
to 300 ppm.
[0066] The oil of lubricating viscosity may have an aromatic
content of 0 wt % to 10 wt %, or 0 wt % to 5 wt %, or 0 or 0.1 wt %
to 2 wt % of the oil of lubricating viscosity.
[0067] The oil of lubricating viscosity may have a viscosity index
of 105 or more, 108 or more, or 110 or more (as determined by ASTM
method D2270).
[0068] In one embodiment the oil of lubricating viscosity may have
a sulphur content of 0 ppm to 1000 ppm, an aromatic content of 0 wt
% to 10 wt % and a viscosity index of at least 105. Examples of
such an oil of lubricating viscosity include Yubase-3, Yubase-6, or
Korean S-3 (3 mm.sup.2/s) and S-8 (8 mm.sup.2/s) base oils.
[0069] 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 first dispersant, the second dispersant,
the corrosion inhibitor and the other performance additives
(described below).
[0070] The lubricating composition may be in the form of a
concentrate and/or a fully formulated lubricant. If the first
dispersant, the second dispersant, the corrosion inhibitor and the
other performance additives are 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 (a), (b) and
(c) (i.e. the first dispersant, the second dispersant and the
corrosion inhibitor) 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 Additive
[0071] The composition of the invention optionally further includes
at least one other performance additive. The other performance
additives include detergents, viscosity index improvers (also
referred to as viscosity modifiers), antiwear agents, friction
modifiers, friction stabilising agents, antioxidants, foam
inhibitors, demulsifiers, pour point depressants, seal swelling
agents and mixtures thereof.
Antiwear Agent
[0072] The antiwear agent may be a phosphorus-containing acid, salt
or ester or mixtures thereof.
[0073] The antiwear agent may be metal-containing or metal free
(prior to being mixed with other components).
[0074] The antiwear agent may be derived from a phosphoric acid,
phosphorous acid, thiophosphoric acid, thiophosphorous acid, or
mixtures thereof.
[0075] The antiwear agent may include (i) a non-ionic phosphorus
compound; (ii) an amine salt of a phosphorus compound; (iii) an
ammonium salt of a phosphorus compound; (iv) a monovalent metal
salt of a phosphorus compound, such as a metal
dialkyldithiophosphate or a metal dialkylphosphate; or (v) mixtures
of (i), (ii), (iii) or (iv).
[0076] In one embodiment the antiwear agent comprises a metal
dialkyldithiophosphate or a metal dialkylphosphate. The alkyl
groups of the dialkyldithiophosphate and/or the dialkylphosphate
may be linear or branched containing 2 to 20 carbon atoms, provided
that the total number of carbons is sufficient to make the metal
dialkyldithiophosphate oil soluble. The metal of the metal
dialkyldithiophosphate and/or dialkylphosphate typically includes
monovalent or divalent metals. Examples of suitable metals include
sodium, potassium, copper, calcium, magnesium, barium or zinc. In
one embodiment the antiwear agent is a zinc dialkyldithiophosphate.
In one embodiment the antiwear agent is a zinc
dialkylphosphate.
[0077] Examples of a suitable zinc dialkyldithiophosphate (often
referred to as ZDDP, ZDP or ZDTP) include zinc di-(amyl)
dithiophosphate, zinc di-(1,3-dimethylbutyl)dithiophosphate, zinc
di-(heptyl)dithiophosphate, zinc di-(octyl)dithiophosphate
di-(2-ethylhexyl)dithiophosphate, zinc di-(nonyl)dithiophosphate,
zinc di-(decyl)dithiophosphate, zinc di-(dodecyl)dithiophosphate,
zinc di-(dodecylphenyl)dithiophosphate, zinc
di-(heptylphenyl)dithiophosphate, or mixtures thereof. In one
embodiment the zinc dialkyldithiophosphate comprises a mixed alkyl
ZDDP compound, wherein the alkyl groups include 2-methylpropyl and
amyl. In one embodiment the zinc dialkyldithiophosphate comprises a
mixed alkyl ZDDP compound, wherein one alkyl group comprises
isopropyl and at least one of 1,3-dimethylbutyl, 2-ethylhexyl and
iso-octyl.
[0078] In one embodiment the antiwear agent is other than metal
dialkyldithiophosphate.
[0079] In one embodiment the antiwear agent comprises an ammonium
or amine salt of a phosphorus-containing acid or ester.
[0080] The amine salt of a phosphorus acid or ester includes
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.
[0081] The amine salt of a phosphorus acid or ester may be used
alone or in combination. In one embodiment the antiwear agent is
derived from an amine salt of a phosphorus compound, or mixtures
thereof.
[0082] In one embodiment the amine salt of a phosphorus acid or
ester includes a partial amine salt-partial metal salt compounds or
mixtures thereof. In one embodiment the amine salt of a phosphorus
acid or ester further comprises a sulphur atom in the molecule.
[0083] 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.
[0084] 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.
[0085] Examples of suitable secondary amines include dimethylamine,
diethylamine, dipropylamine, dibutylamine, diamylamine,
dihexylamine, diheptylamine, methylethylamine, ethylbutylamine,
di-cocoalkyl amine (or di-cocoamine) and ethylamylamine. The
secondary amines may be cyclic amines such as piperidine,
piperazine and morpholine.
[0086] 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.
[0087] In one embodiment the amine salt of a phosphorus acid or
ester includes an amine with C11 to C14 tertiary alkyl primary
groups or mixtures thereof. In one embodiment the amine salt of a
phosphorus compound includes an amine with C14 to C18 tertiary
alkyl primary amines or mixtures thereof. In one embodiment the
amine salt of a phosphorus compound includes an amine with C18 to
C22 tertiary alkyl primary amines or mixtures thereof.
[0088] Mixtures of amines may also be used in the invention. In one
embodiment a useful mixture of amines is "Primene.RTM. 81R" and
"Primene.RTM. JMT." Primene.RTM. 81R and Primene.RTM. JMT (both
produced and sold by Rohm & Haas) are mixtures of C11 to C14
tertiary alkyl primary amines and C18 to C22 tertiary alkyl primary
amines respectively.
[0089] In one embodiment the amine salt of a phosphorus acid or
ester is the reaction product of a C14 to C.sub.18 alkylated
phosphoric acid with Primene 81R.TM. (produced and sold by Rohm
& Haas) which is a mixture of C11 to C14 tertiary alkyl primary
amines.
[0090] Examples of the amine salt of a phosphorus acid or ester
include the reaction product(s) of isopropyl, methyl-amyl
(1,3-dimethylbutyl or mixtures thereof), 2-ethylhexyl, heptyl,
octyl or nonyl dithiophosphoric acids with ethylene diamine,
morpholine, or Primene 81R.TM., and mixtures thereof.
[0091] In one embodiment a 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 (where
"lower" signifies 1 to 8, or 1 to 6, or 1 to 4, or 1 to 2 carbon
atoms in the alcohol-derived portion of the ester). The epoxide
includes an aliphatic epoxide or a styrene oxide. Examples of
useful epoxides include ethylene oxide, propylene oxide, butene
oxide, octene oxide, dodecene oxide, styrene oxide and the like. In
one embodiment the epoxide is propylene oxide. The glycols may be
aliphatic glycols having 1 to 12, or 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(1,3-dimethylbutyl)phosphorodithioate (prepared
by reacting di(1,3-dimethylbutyl)-phosphorodithioic acid with 1.3
moles of propylene oxide at 25.degree. C.). The mixture is 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).
[0092] In one embodiment the antiwear agent comprises a non-ionic
phosphorus compound. Typically the non-ionic phosphorus compound
may have an oxidation of +3 or +5. The different embodiments
comprise phosphite ester, phosphate esters, or mixtures
thereof.
[0093] In one embodiment the antiwear agent comprises a non-ionic
phosphorus compound that is a hydrocarbyl phosphite. The
hydrocarbyl phosphite of the invention includes those represented
by the formula:
##STR00001##
wherein each R''' may be independently hydrogen or a hydrocarbyl
group, with the proviso that at least one of the R''' groups is
hydrocarbyl.
[0094] Each hydrocarbyl group of R''' may contain at least 2 or 4
carbon atoms. Typically, the combined total sum of carbon atoms
present on both R''' groups may be less than 45, less than 35 or
less than 25. Examples of suitable ranges for the number of carbon
atoms present on both R''' groups includes 2 to 40, 3 to 24 or 4 to
20. Examples of suitable hydrocarbyl groups include propyl, butyl,
pentyl, hexyl dodecyl, butadecyl, hexadecyl, or octadecyl groups.
Generally the hydrocarbyl phosphite is soluble or at least
dispersible in oil. In one embodiment the hydrocarbyl phosphite may
be di-butyl hydrogen phosphite or a C.sub.16-18 alkyl hydrogen
phosphite. A more detailed description of the non-ionic phosphorus
compound is found in column 9, line 48 to column 11, line 8 of U.S.
Pat. No. 6,103,673.
[0095] The antiwear agent may be present in an amount sufficient to
provide 0.01 wt % to 0.5 wt %, or 0.02 wt % to 0.2 wt % phosphorus
to the lubricating composition.
[0096] The antiwear agent may be present at 0.01 wt % to 20 wt %,
or 0.05 wt % to 10 wt %, or 0.1 wt % to 5 wt % of the lubricating
composition.
Antioxidants
[0097] In one embodiment the lubricating composition further
comprises an antioxidant. The antioxidant may be present in ranges
of 0 wt % to 10 wt %, 0.01 wt % to 5 wt %, or 0.05 wt % to 3 wt %
of the lubricating composition.
[0098] Suitable antioxidants include molybdenum compounds such as
molybdenum dithiocarbamates, sulphurised olefins, sulphides
(including hydroxylalkyl sulphides such as
1-(tert-dodecylthio)-2-propanol or tert-nonyl mercaptan reacted
with propylene oxide (mole ratio 1:1)), hindered phenols including
ester-substituted hindered phenols, aminic compounds such as
phenylalphanaphthylamines or alkylated diphenylamines (typically
nonyl diphenylamine, di-nonyl diphenylamine, octyl diphenylamine,
di-octyl diphenylamine), or mixtures thereof.
Friction Modifiers
[0099] In one embodiment the lubricating composition further
comprises a friction modifier. The friction modifiers may be
present in ranges of 0 wt % to wt %, or 0.1 wt % to 4 wt %, or 0.25
wt % to 3.5 wt %, or 0.5 wt % to 2.5 wt %, or 1 wt % to 2.5 wt % of
the lubricating composition.
[0100] The friction modifiers may include fatty amines, borated
glycerol esters, fatty acid amides, non-borated fatty epoxides,
borated fatty epoxides, alkoxylated fatty amines, borated
alkoxylated fatty amines, metal salts of fatty acids, fatty
imidazolines, metal salts of alkyl salicylates, condensation
products of carboxylic acids or polyalkylene-polyamines, or amides
of hydroxyalkyl compounds.
[0101] In one embodiment the friction modifier may be a fatty acid
ester of glycerol, e.g., partial esters. The final product may be
in the form of a metal salt, an amide, an imidazoline, or mixtures
thereof. The fatty acids may contain 6 to 24 or 8 to 18 carbon
atoms. The fatty acids may branched or straight-chain, saturated or
unsaturated. Suitable acids include 2-ethylhexanoic, decanoic,
oleic, stearic, isostearic, palmitic, myristic, palmitoleic,
linoleic, lauric, and linolenic acids, and the acids from the
natural products tallow, palm oil, olive oil, peanut oil, corn oil,
and Neat's foot oil. In one embodiment the fatty acid is oleic
acid. When in the form of a metal salt, typically the metal may be
zinc or calcium and the products may be overbased. The zinc salts
may be acidic, neutral or basic (overbased). These zinc
carboxylates (in particular zinc oleate) are known in the art and
are described in U.S. Pat. No. 3,367,869.
[0102] When in the form of an amide, the condensation product may
be prepared with ammonia, or with primary or secondary amines such
as diethylamine and diethanolamine. When in the form of an
imidazoline, the condensation product of an acid with a diamine or
polyamine such as a polyethylenepolyamine. In one embodiment the
friction modifier is the condensation product of a C8 to C24 fatty
acid with a polyalkylene polyamine, and in particular, the product
of isostearic acid with tetraethylenepentamine.
[0103] In one embodiment the friction modifier may be formed by the
condensation of the hydroxyalkyl compound with an acylating agent
or an amine. A more detailed description of the hydroxyalkyl
compound is described in U.S. Patent Application 60/725,360 (filed
on Oct. 11, 2005, inventors Bartley, Lahiri, Baker and Tipton) in
paragraphs 8, and 19-21. The friction modifier disclosed in U.S.
Patent Application 60/725,360 may be an amide represented by the
formula R.sup.1R.sup.2N--C(O)R.sup.3, wherein R.sup.1 and R.sup.2
are each independently hydrocarbyl groups of at least 6 carbon
atoms and R.sup.3 is a hydroxyalkyl group of 1 to 6 carbon atoms or
a group formed by the condensation of said hydroxyalkyl group,
through a hydroxyl group thereof, with an acylating agent.
Preparative Examples are disclosed in Examples 1 and 2 (paragraphs
68 and 69 of U.S. Patent Application 60/725,360). In one embodiment
the amide of a hydroxylalkyl compound is prepared by reacting
glycolic acid, that is, hydroxyacetic acid, HO--CH.sub.2--COOH with
an amine.
[0104] In one embodiment the friction modifier may be a secondary
or tertiary amine being represented by the formula
R.sup.4R.sup.5NR.sup.6, wherein R.sup.4 and R.sup.5 are each
independently an alkyl group of at least 6 carbon atoms and R.sup.6
is hydrogen, a hydrocarbyl group, a hydroxyl-containing alkyl
group, or an amine-containing alkyl group. A more detailed
description of the friction modifier is described in US Patent
Application 2005/037897 in paragraphs 8 and 19 to 22.
[0105] In one embodiment the friction modifier may be a reaction
product of a di-cocoalkyl amine (or di-cocoamine) with glycolic
acid. The friction modifier may be prepared by the Preparative
Examples 1 and 2.
[0106] In one embodiment the friction modifier may be derived from
the reaction product of a carboxylic acid or a reactive equivalent
thereof with an aminoalcohol, wherein the friction modifier
contains at least two hydrocarbyl groups, each containing at least
6 carbon atoms. An example of such a friction modifier includes the
reaction product of isostearic acid or an alkyl succinic anhydride
with tris-hydroxymethylaminomethane. A more detailed description of
such a friction modifier is disclosed in US Patent Application
2003/22000 (or International Publication WO04/007652) in paragraphs
8 and 9 to 14.
[0107] In one embodiment the friction modifier may be an
alkoxylated alcohol. A detailed description of suitable
alkyoxylated alcohols is described in paragraphs 19 and 20 of US
Patent Application 2005/0101497. The alkoxylated amines are also
described in U.S. Pat. No. 5,641,732 in column 7, line 15 to column
9, line 25.
[0108] In one embodiment the friction modifier may be a
hydroxylamine compound as defined in column 37, line 19, to column
39, line 38 of U.S. Pat. No. 5,534,170. Optionally the
hydroxylamine may be borated as such products are described in
column 39, line 39 to column 40 line 8 of U.S. Pat. No.
5,534,170.
[0109] In one embodiment the friction modifier may be an
alkoxylated amine e.g., an ethoxylated amine derived from 1.79%
Ethomeen T-12 and 0.90% Tomah PA-1 as described in Example E of
U.S. Pat. No. 5,703,023, column 28, lines 30 to 46. Other suitable
alkoxylated amine compounds include commercial alkoxylated fatty
amines known by the trademark "ETHOMEEN" and available from Akzo
Nobel. Representative examples of these ETHOMEEN.TM. materials is
ETHOMEEN.TM. C/12 (bis[2-hydroxyethyl]-coco-amine); ETHOMEEN.TM.
C/20 (polyoxyethylene[10]cocoamine); ETHOMEEN.TM. S/12
(bis[2-hydroxyethyl]soyamine); ETHOMEEN.TM. T/12
(bis[2-hydroxyethyl]-tallow-amine); ETHOMEEN.TM. T/15
(polyoxyethylene-[5]tallowamine); ETHOMEEN.TM. 0/12
(bis[2-hydroxyethyl]oleyl-amine); ETHOMEEN.TM. 18/12
(bis[2-hydroxyethyl]octadecylamine); and ETHOMEEN.TM. 18/25
(polyoxyethylene[1,5]octadecylamine). Fatty amines and ethoxylated
fatty amines are also described in U.S. Pat. No. 4,741,848.
[0110] In one embodiment the friction modifier may be a polyol
ester as described in U.S. Pat. No. 5,750,476 column 8, line 40 to
column 9, line 28.
[0111] In one embodiment the friction modifier may be a low potency
friction modifier as described in U.S. Pat. No. 5,840,662 in column
2, line 28 to column 3, line 26. U.S. Pat. No. 5,840,662 further
discloses in column 3, line 48 to column 6, line 25 specific
materials and methods of preparing the low potency friction
modifier.
[0112] In one embodiment the friction modifier may be a reaction
product of an isomerised alkenyl substituted succinic anhydride and
a polyamine as described in U.S. Pat. No. 5,840,663 in column 2,
lines 18 to 43. Specific embodiments of the friction modifier
described in U.S. Pat. No. 5,840,663 are further disclosed in
column 3, line 23 to column 4, line 35. Preparative examples are
further disclosed in column 4, line 45 to column 5, line 37 of U.S.
Pat. No. 5,840,663. Typically the isomerised alkenyl group is
derived from a reaction product of an isomerised alpha-olefin with
an acid catalyst followed by reaction with maleic anhydride. The
alkenyl group may contain 8 to 20 carbon atoms.
[0113] In one embodiment the friction modifier may be an
alkylphosphonate mono- or di-ester sold commercially by Rhodia
under the trademark Duraphos.RTM. DMODP.
[0114] In one embodiment the friction modifier may be a borated
fatty epoxide, known from Canadian Patent No. 1,188,704. These
oil-soluble boron-containing compositions are prepared by reacting,
at a temperature from 80.degree. C. to 250.degree. C., boric acid
or boron trioxide with at least one fatty epoxide. The fatty
epoxide typically contains at least 8 carbon atoms in the fatty
groups of the epoxide.
[0115] The borated fatty epoxides may be characterised by the
method for their preparation which involves the reaction of two
materials. Reagent A may be boron trioxide or any of the various
forms of boric acid including metaboric acid (HBO.sub.2),
orthoboric acid (H.sub.3BO.sub.3) and tetraboric acid
(H.sub.2B.sub.4O.sub.7). Boric acid, and especially orthoboric
acid. Reagent B may be at least one fatty epoxide. The molar ratio
of reagent A to reagent B is generally 1:0.25 to 1:4, or 1:1 to
1:3, or about 1:2. The borated fatty epoxides may be prepared by
merely blending the two reagents and heating them at temperature of
800 to 250.degree. C., or 100.degree. to 200.degree. C., for a
period of time sufficient for reaction to take place. If desired,
the reaction may be effected in the presence of a substantially
inert, normally liquid organic diluent. During the reaction, water
is evolved and may be removed by distillation.
Friction Stabilising Agents
[0116] In one embodiment the lubricating composition further
comprises a friction stabilising agent. Friction stabilising agents
include H.sub.3PO.sub.4, H.sub.3PO.sub.3 or mixtures thereof.
Typically H.sub.3PO.sub.4 is commercially available in 85% solution
in water. The friction stabilising agents may be present in ranges
of 0 wt % to 2 wt %, 0.01 wt % to 1 wt %, 0.01 wt % to 0.5 wt %,
0.02 wt % to 0.25 wt %, or 0.03 wt % to 0.2 wt %.
Viscosity Modifiers
[0117] In one embodiment the lubricating composition further
comprises a viscosity modifier or dispersant viscosity modifier
(also referred to as DVMs). The viscosity modifier may be present
at 0 wt % to 12 wt %, 0.1 wt % to 10 wt % or 1 wt % to 8 wt % of
the lubricating composition.
[0118] Viscosity modifiers include hydrogenated copolymers of
styrene-butadiene, ethylene-propylene copolymers, polyisobutenes,
hydrogenated styrene-isoprene polymers, hydrogenated isoprene
polymers, polymethacrylates, polyacrylates, polyalkyl styrenes,
hydrogenated alkenyl aryl conjugated diene copolymers, polyolefins,
and esters of maleic anhydride-styrene copolymers.
[0119] Dispersant viscosity modifiers include functionalised
polyolefins, for example, ethylene-propylene copolymers that have
been functionalized with the reaction product of maleic anhydride
and an amine, a polymethacrylate functionalised with an amine, or
styrene-maleic anhydride copolymers reacted with an amine; may also
be used in the composition of the invention.
Detergents
[0120] In one embodiment the lubricating composition further
comprises a detergent. The detergents may be present in ranges of 0
wt % to 8 wt %, 0.01 wt % to 6 wt % or 0.05 wt % to 4 wt % of the
lubricating composition.
[0121] Detergents include neutral or overbased detergents,
Newtonian or non-Newtonian, basic salts of alkali, alkaline earth
or transition metals with one or more of a phenate, a sulphurised
phenate, a sulphonate, a carboxylic acid, a phosphorus acid, a
saligenin, an alkylsalicylate, and a salixarate. The alkaline earth
metal may be calcium, magnesium or barium. In different embodiments
the detergent may be a magnesium sulphonate or a calcium
sulphonate.
[0122] Foam inhibitors including polydimethyl siloxane,
fluorosilicone, 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; pour point depressants including esters of maleic
anhydride-styrene copolymers, polymethacrylates, polyacrylates or
polyacrylamides; and seal swell agents including phthalate esters,
3-(decyloxy)tetrahydro-1,1-dioxide thiophene, decyloxysulpholane,
Exxon Necton-37.TM. (FN 1380) and Exxon Mineral Seal Oil (FN 3200)
may also be present in the lubricating composition. Typically the
amount of foam inhibitors, demulsifiers, pour point depressants,
and seal swell agents are independently in ranges of 0 wt % to 0.5
wt %, or 0.0001 wt % to 0.3 wt %.
INDUSTRIAL APPLICATION
[0123] The method of the invention is useful for lubricating a
variety of mechanical devices. The mechanical device comprises at
least one of a gear, a gearbox, a traction drive transmission, an
automatic transmission or a manual transmission. In one embodiment
the mechanical device is an automatic transmission.
[0124] The automatic transmission includes continuously variable
transmissions (CVT), infinitely variable transmissions (IVT),
Toridal transmissions, continuously slipping torque converter
clutches (CSTCC), stepped automatic transmissions or dual clutch
transmissions (DCT).
[0125] The following examples provide illustrations of the
invention. These examples are non-exhaustive and are not intended
to limit the scope of the invention.
EXAMPLES
Preparative Example 1
[0126] Armeen.TM.2C, dicocoamine, from Akzo, 468.2 g (1.2
equivalents) is added to a vessel equipped with a mechanical
stirrer, nitrogen inlet, thermocouple, and Dean-Stark trap with a
condenser. The vessel and its contents are heated to 80.degree. C.
with stirring. To the vessel is added 130.4 g glycolic acid, 70% in
water, from TCI (1.2 equivalents), via an addition funnel over 20
minutes. The reaction mixture is heated to 180.degree. C. over a 2
hour period while collecting distillate. The mixture is held at
180.degree. C. for an additional 51/2 hours, then cooled overnight.
Thereafter, the mixture is heated to 70.degree. C. and 20 g filter
aid is added. The mixture is stirred for 15 minutes and filtered
through a cloth pad. The reaction product is a clear light-amber
liquid filtrate, 503.6 g, having an analysis of 3.15% N, TBN 9.57,
and TAN 1.75.
Preparative Example 2
[0127] The procedure of Preparative Example 1 is substantially
repeated, except that the amine used is the corresponding amount of
Armeen.TM. HTL8 (a (2-ethylhexyl)(hydrogenated tallow) amine).
Preparative Example 3
[0128] 1950 g of Armeen.TM.2C, dicocoamine, from Akzo, 586 g of
chloroglycerine and 562 g of sodium carbonate are added to a 5 L
4-neck flask equipped with a mechanical stirrer, nitrogen inlet,
thermocouple, and Dean-Stark trap with a condenser. The vessel is
heated to 80.degree. C. and held for 4 hours, followed by heating
to 90.degree. C. and holding for a further 4 hours. The vessel is
then cooled overnight. The vessel is then reheated to 90.degree. C.
and held for a further 4 hours. The vessel is then held under
vacuum at 120.degree. C. for 30 minutes. The contents of the vessel
are cooled to ambient before filtering over FAX-5 cloth pad. The
final product yield is 82%.
[0129] Preparative Examples 4-7 are the same as Examples 1-4 of
PCT/US06/004576 respectively.
Preparative Example 4
[0130] A reaction vessel with a 4-neck round bottom flask fitted
with a mechanical stirrer, subsurface nitrogen sparge, thermowell,
and Dean-Stark trap fitted with a condenser vented to caustic and
bleach traps is charged with 2137 g succinimide dispersant
(reaction product of polyisobutylene substituted succinic anhydride
with polyethylene amine bottoms, containing diluent oil) and 1422 g
additional diluent oil and is heated, with stirring, to 83.degree.
C. and 114 g of boric acid is added before heating to 152.degree.
C. over 2.5 hours and water is removed. To the mixture is added
1.16 g of terephthalic acid and the mixture is heated to
160.degree. C. At 160.degree. C. 25.2 g of
2,5-dimercapto-1,3,4-thiadiazole (DMTD) in portions such that each
subsequent addition is effected after the previous portion has
dissolved. The mixture is stirred until evolution of H.sub.2S
ceases before filtration to produce a final product.
Preparative Example 5
[0131] Preparative Example 4 is substantially repeated except that
77.8 g phosphorous acid is added along with the boric acid.
Preparative Example 6
[0132] Preparative Example 4 is substantially repeated except that
the dispersant is a Mannich dispersant.
[0133] Preparative Example 7 is substantially the same as
Preparative Example 5, except 85% H.sub.3PO.sub.4 is used instead
of phosphorous acid.
[0134] Preparative Example 8 is similar to Preparative Example 4,
except the DMTD material is not present in the reaction.
[0135] Lubricating compositions are prepared as is shown in the
table below. The lubricating compositions of the invention are LC1
and LC2. Comparative lubricating compositions are REF1 and REF2.
All the lubricating compositions contain the additives shown below
and the balance of base oil. The base oil is predominately mixture
of Yubase.TM.-3 and Yubase.TM.-6 oils (other than residual diluent
oil factored out of the examples below). Approximately 42 wt % of
the base oil mixture is Yubase.TM.-3, 58 wt % of Yubase.TM.-6.
TABLE-US-00001 Lubricating Composition Additives (wt % on oil-free
basis) Additive LC1 LC2 REF1 REF2 Preparative Example 4 1.61 0.76
3.22 0 Preparative Example 8 1.61 3.10 0 3.22 Corrosion Inhibitor
0.02 0.02 0.02 0.02 Phosphorus Antiwear Agents 0.32 0.32 0.31 0.32
& Friction Stabiliser Friction Modifier* 1.11 1.01 0.63 1.11
Antioxidant 1.1 1.1 0.95 1.1 Polymethacrylate Pour Point 0.1 0.1
0.1 0.1 Depressant Polymethacrylate Viscosity 1.26 1.23 1.26 1.26
Modifier Seal Swell Agent 1.0 1.0 1.0 1.0 Foam Inhibitor 0.01 0.01
0.01 0.01 Footnote: *the friction modifier comprises at least one
additve prepared from Preparative Examples 1 to 3.
[0136] The lubricating compositions are evaluated using ASTM Method
D130 (copper corrosion, at 150.degree. C. for 3 hours); and
Mercon.RTM.V Falex extreme pressure test (procedure 528.042.01,
also referred to as ASTM D3233-93 (2003), employing method B); and
Mercon.RTM.V 4-ball wear test (procedure 528.003.01, also referred
to as ASTM D4172-94 (2002)). The data obtained is shown below in
the table.
TABLE-US-00002 Test Test Conditions LC1 LC2 RF1 RF2 Copper ASTM 1B
1B 1B 3A Corrosion D130, 50.degree. C., 3 hours Mercon .RTM.
Average 795.5 795.5 681.8 738.6 V Falex Load in kg, (1750 lb) (1750
lb) (1500 lb) (1625 lb) EP test over two experiments at 100.degree.
C. Average 511.4 568.2 340.9 511.4 Load in kg, (1125 lb) (1250 lb)
(750 lb) (1125 lb) over two experiments at 150.degree. C. Mercon
.RTM. Wear Scar 0.42 0.39 0.38 0.4 V 4-ball (.mu.m) at wear test
100.degree. C. Wear Scar 0.50 0.45 0.59 0.46 (.mu.m) at 150.degree.
C. Footnote: * ( ) values in pounds as measured during the Mercon
.RTM. V Falex EP test.
[0137] Overall the data indicates that the lubricating composition
of the invention is capable of providing at least one property from
acceptable friction performance and acceptable wear protection,
acceptable corrosion resistance, acceptable anti-shudder
performance, acceptable oxidation resistance and acceptable gear
protection.
[0138] 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:
[0139] (i) hydrocarbon substituents, that is, aliphatic (e.g.,
alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl)
substituents, and aromatic-, aliphatic-, and alicyclic-substituted
aromatic substituents, as well as cyclic substituents wherein the
ring is completed through another portion of the molecule (e.g.,
two substituents together form a ring);
[0140] (ii) substituted hydrocarbon substituents, that is,
substituents containing non-hydrocarbon groups which, in the
context of this invention, do not alter the predominantly
hydrocarbon nature of the substituent (e.g., halo (especially
chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto,
nitro, nitroso, and sulphoxy);
[0141] (iii) hetero substituents, that is, substituents which,
while having a predominantly hydrocarbon character, in the context
of this invention, contain other than carbon in a ring or chain
otherwise composed of carbon atoms; and
[0142] (iv) heteroatoms include sulphur, oxygen, nitrogen, and
encompass substituents as pyridyl, furyl, thienyl and imidazolyl.
In general, no more than two, preferably no more than one,
non-hydrocarbon substituent will be present for every ten carbon
atoms in the hydrocarbyl group; typically, there will be no
non-hydrocarbon substituents in the hydrocarbyl group.
[0143] 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.
[0144] 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.
[0145] 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.
* * * * *