Note: Descriptions are shown in the official language in which they were submitted.
CA 02530846 2005-12-19
TITLE OF THE INVENTION
AN ANTI-SHUDDER ADDITIVE COMPOSITION AND LUBRICATING OIL
COMPOSITION CONTAINING THE SAME
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
The present invention is directed to an improved anti-shudder additive
composition that is used in automatic transmission fluids and continuously
variable transmissions; and it is also directed to the process of making the
same.
DESCRIPTION OF THE RELATED ART
Srinivasan et al., U.S. Publication No. 2002/0151441, is directed to an
automatic transmission fluid with improved anti-shudder properties. The
automatic transmission fluids described contain at least 0.2 wt% of a metal-
containing detergent, a dispersant, and a mixture of friction modifiers. This
automatic transmission fluid is used in electronically controlled converter
clutch applications.
Ohtani et at., U.S. Patent Number 5,441,656 is directed to an automatic
transmission fluid (ATF) that is used to overcome shudder. This ATF consists
essentially of (i) an N-aliphatic hydrocarbyl-substituted diethanolamine in
which the N-aliphatic hydrocarbyl substituent is at least one straight chain
aliphatic hydrocarbyl group free of acetylenic unsaturation and having in the
range of 14 to 20 carbon atoms, and (ii) an N-aliphatic hydrocarbyl-
substituted
trimethylenediamine in which the N-aliphatic hydrocarbyl-substituent is at
least one straight chain aliphatic hydrocarbyl group free of acetylenic
unsaturation and having in the range of about 14 to about 20 carbon atoms.
-1-
CA 02530846 2005-12-19
Kugimiya, Takanori, "Effects of Additives of ATF and Components of Friction
Material for AT on p-v Characteristics", Japanese Journal of Tribology, Vol.
45, Number 3, 2000. This article describes the effects of typical additives
applied to automatic transmission fluids and of each component (graphite,
cashew dust, aramid fiber and carbon filter) applied to paper-based friction
materials on friction coefficient versus sliding velocity (p-v )
characteristics.
Watts et al., U.S. Patent No. 6,660,695 discloses a power transmission fluid
comprising a mixture of a major amount of a lubricating oil and an effective
amount of a performance enhancing additive combination comprising: (a) at
least one organic phosphite; (b) a calcium detergent and (c) a friction
modifier.
Watts et al., U.S. Patent No. 5,942,472 discloses a power transmission fluid
that is formed which comprise a major amount of lubricating oil and an
additive combination comprising (a) a viscosity modifier having a molecular
weight no greater than about 175, 000 atomic mass units, and (b) a selected
friction modifier.
Watts et al., U.S. Patent No. 6,337,309 discloses a lubricating composition
for
a continuously variable transmission. This composition is zinc free and
comprises an (a) ashless polyisobutenyl succinimide dispersant; (b) at least
one organic thioether phosphite; (c) a calcium phenate overbased detergent
at a concentration such that the total amount of calcium in the fluid is less
than about 500 ppm; (d) friction modifiers comprising one or more
succinimides and one or more ethoxylated amines; and (e) a primary amide of
a long chain carboxylic acid.
Jaffe, U.S. Patent No. 4,342,709 discloses a process of producing diethyl
phosphite by reacting an excess of triethyl phosphite with phosphorous acid.
-2-
CA 02530846 2005-12-19
Watts et al., U.S. Patent No. 6,127,323 discloses a composition and method
of improving the anti-shudder durability of power transmitting fluids,
particularly those in automatic transmission fluids. This composition
comprises a mixture of (1) a major amount of a lubricating oil and (2) an anti-
shudder improving effective amount of an additive composition comprising (a)
an oil-soluble alkyl phosphonate, (b) an ashless dispersant, and (c) a
metallic
detergent.
Watts et al., U.S. Patent No. 6,225,266 discloses a continuously variable
transmission fluid that is zinc-free and comprises (a) an additive dispersant;
(b) at least one organic phosphite; (c) a calcium detergent; (d) one or more
friction modifiers selected from the group consisting of: succinimides and
ethoxylated amines; and (e) a primary amide of a long chain carboxylic acid.
BRIEF SUMMARY OF THE INVENTION
Accordingly, in its broadest embodiment, the present invention is directed to
an anti-shudder additive composition comprising:
(a) At least one neutral phosphite compound; and
(b) At least one hydrocarbyl substituted succinic dispersant
selected
from the group consisting of a hydrocarbyl bissuccinimide and a
hydrocarbyl substituted succinic ester of a polyol and mixtures
thereof, wherein the hydrocarbyl substituent has at least 50
carbon atoms,
wherein the additive composition does not comprise an ethoxylated amine,
and wherein the additive composition does not comprise a primary amide of a
long chain carboxylic acid, and provided that if the lubricating oil
composition
also contains a monosuccinimide, then the ratio of the hydrocarbyl substituted
succinic dispersant to monosuccinimide is at least 7:3.
-3-
CA 02530846 2005-12-19
The present invention is further directed to a lubricating oil composition
cornprising:
a major amount of an oil of lubricating viscosity;
(b) an effective amount of an anti-shudder additive composition
comprising:
(i) At least one neutral phosphite compound, and
(ii) At least one hydrocarbyl substituted succinic dispersant
selected from the group consisting of a hydrocarbyl
bissuccinimide and a hydrocarbyl substituted succinic ester of a
polyol and mixtures thereof, wherein the hydrocarbyl substituent
has at least 50 carbon atoms; and
wherein the additive composition does not comprise an ethoxylated
amine, and wherein the additive composition does not comprise a primary
amide of a long chain carboxylic acid, and provided that if the lubricating
oil
composition also contains a monosuccinimide, then the ratio of the
hydrocarbyl substituted succinic dispersant to monosuccinimide is at least
7:3.
The present invention is further directed to a method of making an anti-
shudder additive composition comprising:
mixing from about 0.1 wt% to about 90.9 wt% of at least one neutral phosphite
compound with from about 9.1 wt% to about 99.9 wt% of at least one
hydrocarbyl substituted succinic dispersant selected from the group consisting
of a hydrocarbyl bissuccinimide and a hydrocarbyl substituted succinic ester
of a polyol and mixtures thereof, in the absence of an ethoxylated amine and
a primary amide of a long chain carboxylic acid, and provided that if the
additive composition also contains a monosuccinimide, then the ratio of the
hydrocarbyl substituted succinic dispersant to monosuccinimide is at least
7:3.
-4-
CA 02530846 2014-07-08
The present invention is further directed to a method of making a transmission
fluid comprising:
mixing from about 0.11 wt% to about 11.0 wt% of the anti-shudder additive
composition described herein with a major amount of an oil of lubricating
viscosity.
A method of reducing shudder in a transmission comprising:
(a) mixing an oil of lubricating viscosity with a shudder reducing effective
amount of an anti-shudder additive composition comprising:
(i) at least one neutral phosphite compound;
(ii) at least one hydrocarbyl substituted succinic dispersant
selected from the group consisting of a hydrocarbyl
bissuccinimide and a hydrocarbyl substituted succinic ester of a
polyol and mixtures thereof, wherein the hydrocarbyl substituent
has at least 50 carbon atoms;
in the absence of an ethoxylated amine and a primary amide of a
long chain carboxylic acid; and
provided that if the lubricating oil composition also contains
monosuccinimide, then the ratio of the hydrocarbyl substituted
succinic dispersant to monosuccinimide is at least 7:3.
(b) adding the mixture of (a) to a transmission.
In accordance with another aspect, there is provided an anti-shudder additive
composition comprising: (a) At least one neutral phosphite compound; and (b)
At least one hydrocarbyl substituted succinic dispersant selected from the
group consisting of a hydrocarbyl substituted succinic ester of a polyol and a
mixture of a hydrocarbyl substituted succinic ester of a polyol and a
hydrocarbyl
bissuccinimide, wherein the hydrocarbyl substituent has at least 50 carbon
atoms, wherein the additive composition does not comprise an ethoxylated
-5-
CA 02530846 2014-07-08
amine, and wherein the additive composition does not comprise a primary
amide of a long chain carboxylic acid, and provided that if the anti-shudder
additive composition also contains a monosuccinimide, then the weight ratio of
the hydrocarbyl substituted succinic dispersant to the monosuccinimide is at
least 7:3.
In accordance with a further aspect, there is provided a lubricating oil
composition comprising: (a) a major amount of an oil of lubricating viscosity;
and (b) an effective amount of an anti-shudder additive composition
comprising: (i) At least one neutral phosphite compound, and (ii) At least one
hydrocarbyl substituted succinic dispersant selected from the group consisting
of a hydrocarbyl substituted succinic ester of a polyol and a mixture of a
hydrocarbyl substituted succinic ester of a polyol and a hydrocarbyl
bissuccinimide, wherein the hydrocarbyl substituent has at least 50 carbon
atoms; and wherein the anti-shudder additive composition does not comprise
an ethoxylated amine, and wherein the anti-shudder additive composition does
not comprise a primary amide of a long chain carboxylic acid, and provided
that
if the anti-shudder additive composition also contains a monosuccinimide, then
the weight ratio of the hydrocarbyl substituted succinic dispersant to the
monosuccinimide is at least 7:3.
In accordance with another aspect, there is provided a method of making an
anti-shudder additive composition comprising: mixing from about 0.1 wt % to
about 90.9 wt % of at least one neutral phosphite compound with from about
9.1 wt `)/0 to about 99.9 wt % of at least one hydrocarbyl substituted
succinic
dispersant selected from the group consisting of a hydrocarbyl substituted
succinic ester of a polyol and a mixture of a hydrocarbyl substituted succinic
ester of a polyol and a hydrocarbyl bissuccinimide, in the absence of an
ethoxylated amine and a primary amide of a long chain carboxylic acid, and
provided that if the anti-shudder additive composition also contains a
monosuccinimide, then the weight ratio of the hydrocarbyl substituted succinic
dispersant to the monosuccinimide is at least 7:3.
-5a-
CA 02530846 2014-07-08
In accordance with a further aspect, there is provided a method of reducing
shudder in a transmission comprising: (a) mixing an oil of lubricating
viscosity
with a shudder reducing effective amount of an anti-shudder additive
composition comprising: (i) at least one neutral phosphite compound; (ii) at
least one hydrocarbyl substituted succinic dispersant selected from the group
consisting of a hydrocarbyl substituted succinic ester of a polyol and a
mixture
of a hydrocarbyl substituted succinic ester of a polyol and a hydrocarbyl
bissuccinimide, wherein the hydrocarbyl substituent has at least 50 carbon
atoms; in the absence of an ethoxylated amine and a primary amide of a long
chain carboxylic acid; and provided that if the anti-shudder additive
composition
also contains monosuccinimide, then the weight ratio of the hydrocarbyl
substituted succinic dispersant to the monosuccinimide is at least 7:3; and
(b)
adding the mixture of (a) to a transmission.
It is therefore an object of an aspect of the invention to provide an improved
shudder control additive to be used in an oil of lubricating viscosity.
DETAILED DESCRIPTION OF THE INVENTION
While the invention is susceptible to various modifications and alternative
forms, specific embodiments thereof have been shown by way of example in
the drawings and are herein described in detail. It should be understood
-5b-
CA 02530846 2013-02-14
=
however, that the description herein of specific embodiments is not intended
to limit the invention to the particular forms disclosed, but on the contrary,
the
intention is to cover all modifications, equivalents, and alternatives falling
within the scope of the invention as defined by the appended claims.
Vehicular transmissions supply the power created by the engine to the wheels
of the vehicle. Not only is the transmission's function important to the
working
of the vehicle, but also it is very complex. The transmission is comprised of
numerous components, such as clutches with plates or bands, a torque
converter, gears, and optionally, a wet clutch among others. Transmissions
are usually either manual, automatic, or continuosly variable. Because of the
variety of functions performed by the ATE, it is essential to carefully select
ATF additives. Transmission fluid may comprise numerous additives such as
dispersants, friction modifiers, anti-wear agents, oxidation inhibitors,
detergents, and others to name a few. Friction modifiers are often used to
control shudder. Without a suitable fluid, the transmission would not operate
at its peak, and the cost of operating the car would may be increased.
Until recently, the clutch mechanism used in most automatic transmissions
was a continuous slipping torque converter clutch (CSTCC). The CSTCC
require specific friction requirements that must be maintained in order to
achieve fuel efficiency and a smooth ride. However, if the friction does not
increase with the speed, as required with a CSTCC, then "stick-slip" occurs.
"Stick-slip" is oscillatory relative motion of two or more surfaces in contact
due
to fluctuations in the frictional forces as the contact time or the velocity
of the
surfaces change. In transmissions, stick-slip can result in vibrations in the
driveline that are detected in the ride of the vehicle; such vibrations are
referred to as shudder. Automatic transmission fluids often contain anti-
shudder additives to decrease the stick-slip phenomenon.
A common way to reduce shudder is by adding friction modifiers to the fluid.
Friction modifiers are components that reduce friction between surfaces when
-6-
CA 02530846 2005-12-19
mild sliding occurs. In general, these components consists of a long linear
hydrocarbon chain and a small polar functional group. Examples of friction
modifiers include: fatty acids, fatty amines, fatty amides, and esters of
fatty
acids. Often, friction modifiers are corrosive towards Pb and Cu, common
materials in bushings. Also, friction modifiers can cause an undesirable
decrease in clutch capacity.
Now, however, automobile manufacturers have begun to use an electronically
controlled converter clutch (ECCC) as the clutch mechanism. This type of
clutch mechanism is configured differently from the CSTCC and has different
energy densities and higher operating temperatures. Similarly to the CSTCC,
shudder must also be minimized in the ECCC in order to maintain optimum
operating conditions. Accordingly, transmission fluids must also be suitable
for this type of clutch mechanism.
Accordingly, a novel, non-obvious transmission fluid has been discovered that
may be used to decrease stick-slip and, thereby, control shudder without
adding a friction modifier. The transmission fluids (TF) of the present
invention are particularly effective controlling initial shudder when used in
automatic transmissions or continuously variable transmissions.
Definitions
The following terms used with the description are defined as such:
The term "shudder" describes friction-induced vibration. The vibration is
caused by a stick-slip phenomena and is related to the behavior of the
friction
coefficient relative to the velocity of metal surfaces sliding on each other.
The term "finished oil" describes a lubricating oil composition that comprises
additives.
-7-
CA 02530846 2005-12-19
The term "succinimide," which includes alkenyl or alkyl mono-, bis-
succinimides and other higher analogs, has been generally accepted as
meaning the product of a reaction of an alkenyl substituted succinic acid or
anhydride with a polyamine.
The term "bissuccinimide" describes the reaction product that is primarily a
bissuccinimide that may contain up to about 5 wt% monosuccinimide.
The Anti-Shudder Additive Composition
The anti-shudder additive composition of the present invention comprises an
oil-soluble additive composition. This anti-shudder additive composition may
be used in lubricating oils, such as but not limited to, automatic
transmission
fluids and continuously variable transmission fluids, and are particularly
effective when used in transmission fluids for electronically controlled
converter clutches. The anti-shudder additive composition of the present
invention comprises (a) at least one neutral phosphite compound and least
one phosphorous-free dispersant selected from (b) at least one hydrocarbyl
substituted succinic dispersant selected from the group consisting of a
hydrocarbyl bissuccinimide and a hydrocarbyl substituted succinic ester of a
polyol and mixtures thereof, wherein the hydrocarbyl substituent has at least
50 carbon atoms, in a proportion that drastically reduces shudder, or friction
induced vibration, that is caused by stick-slip phenomena. Because the
present invention reduces frictionally induced vibration, a friction modifier
is
optionally added to the additive composition and/ or the lubricating oil
composition. All types of friction modifiers may be added to the anti-shudder
additive composition and/or the lubrication oil composition except for
ethoxylated amines. The anti-shudder additive composition or the lubricating
oil composition does not comprise a primary amide of a long chain carboxylic
acid. Furthermore, if the lubricating oil composition also contains
monosuccinimide, then the ratio of the hydrocarbyl substituted succinic
dispersant to monosuccinimide is at least 7:3. More preferred, the ratio of
the
-8-
CA 02530846 2013-02-14
hydrocarbyl substituted succinic dispersant to monosuccinimide is at least
7.5:2.5. Even more preferred, the ratio of the hydrocarbyl substituted
succinic
dispersant to monosuccinimide is at least 8:2. Most preferred, the ratio of
the
hydrocarbyl substituted succinic dispersant to monosuccinimide is at least
9:1.
Hydrocarbyl Substituted Succinic Dispersant
In the present invention, a hydrocarbyl substituted succinic dispersant is
mixed with a neutral phosphite compound thereby producing an anti-shudder
additive composition. In one embodiment of the invention, the hydrocarbyl
substituted succinic dispersant is a hydrocarbyl bissucinimide. More preferred
the bissuccinimide is a borated bissuccinimide.
The bissucciminide is the completed reaction product from reaction between
one or more polyamine reactants and a hydrocarbon substituted succinic acid
or anhydride (or like succinic acylating agent), and is intended to encompass
compounds wherein the product may have amide, amidine, and/or salt
linkages in addition to the imide linkage of the type that results from the
reaction of a primary amino group and anhydride moiety. The bissuccinimide
is prepared according to methods that are well known in the art, including but
not limited to, the following:
Certain fundamental types of succinimides and related materials
encompassed by the term of art "succinimide" are taught in U.S. Pat. Nos.
2,992,708; 3,018,291; 3,024,237; 3,100,673; 3,219,666; 3,172,892; and
3,272,746. The term "succinimide" is understood in the art to include many
of the amide, imide and amidine species which are also formed by this
reaction. The predominant product however is succinimide and this term
has been generally accepted as meaning the product of a reaction of an
alkenyl substituted succinic acid or anhydride with a polyamine as shown
in reaction (1) above.
-9-
CA 02530846 2013-02-14
As used herein, included within this term are the alkenyl or alkyl mono-, bis-
succinimides and other higher analogs.
A(1) Succinic Anhydride
The preparation of the alkenyl-substituted succinic anhydride by reaction with
a polyolefin and maleic anhydride has been described, e.g., U.S. Pat. Nos.
3,018,250 and 3,024,195. Such methods include the thermal reaction of the
polyolefin with maleic anhydride and the reaction of a halogenated polyolefin,
such as a chlorinated polyolefin, with maleic anhydride. Reduction of the
alkenyl-substituted succinic anhydride yields the corresponding alkyl
derivative. Alternatively, the alkenyl substituted succinic anhydride may be
prepared as described in U.S. Pat. Nos. 4,388,471 and 4,450,281,
Polyolefin polymers for reaction with the maleic anhydride are polymers
comprising a major amount of C2 to C5 mono-olefin, e.g., ethylene, propylene,
butylene, isobutylene and pentene. The polymers can be homopolymers such
as polyisobutylene as well as copolymers of 2 or more such olefins such as
copolymers of: ethylene and propylene, butylene, and isobutylene, etc. Other
copolymers include those in which a minor amount of the copolymer
monomers, e.g., 1 to 20 mole percent is a C4 to C8 nonconjugated diolefin,
e.g., a copolymer of isobutylene and butadiene or a copolymer of ethylene,
propylene and 1,4-hexadiene, etc.
The polyolefin polymer, the alkenyl or alkyl moiety which is represented as R,
usually contains from about 10 to 300 carbon atoms, although preferably 10 to
200 carbon atoms; more preferably 12 to 100 carbon atoms and most
preferably 20-100 carbon atoms.
A particularly preferred class of olefin polymers comprises the polybutenes,
which are prepared by polymerization of one or more of 1-butene, 2-butene
-10-
CA 02530846 2013-02-14
and isobutene. Especially desirable are polybutenes containing a substantial
proportion of units derived from isobutene. The polybutene may contain minor
amounts of butadiene which may or may not be incorporated in the polymer.
Most often the isobutene units constitute 80%, preferably at least 90%, of the
units in the polymer. These polybutenes are readily available commercial
materials well known to those skilled in the art. Disclosures thereof will be
found, for example, in U.S. Pat. Nos. 3,215,707; 3,231,587; 3,515,669, and
3,579,450, as well as 3,912,764.
In addition to the reaction of a polyolefin with maleic anhydride, many other
alkylating hydrocarbons may likewise be used with maleic anhydride to
produce alkenyl succinic anhydride. Other suitable alkylating hydrocarbons
include cyclic, linear, branched and internal or alpha olefins with molecular
weights in the range 100-4,500 or more with molecular weights in the range of
200-2,000 being more preferred. For example, alpha olefins obtained from the
thermal cracking of paraffin wax. Generally, these olefins range from 5-20
carbon atoms in length. Another source of alpha olefins is the ethylene growth
process which gives even number carbon olefins. Another source of olefins is
by the dimerization of alpha olefins over an appropriate catalyst such as the
well known Ziegler catalyst. Internal olefins are easily obtained by the
isomerization of alpha olefins over a suitable catalyst such as silica.
A(2) Poly_amine
The polyamine employed to prepare the alkenyl or alkyl succinimides is
preferably a polyamine having from 2 to about 12 amine nitrogen atoms and
from 2 to about 40 carbon atoms. The polyamine is reacted with an alkenyl or
alkyl succinic anhydride to produce the polyamino alkenyl or alkyl
succinimide, employed in this invention. The polyamine is so selected so as to
provide at least one basic amine per succinimide. Since the reaction of a
nitrogen of a polyamino alkenyl or alkyl succinimide to form a hydrocarbyl
-11-
CA 02530846 2005-12-19
oxycarbonyl, a hydroxy hydrocarbyl oxycarbonyl or a hydroxy polyoxyalkylene
oxycarbonyl is believed to efficiently proceed through a secondary or primary
amine, at least one of the basic amine atoms of the polyamino alkenyl or alkyl
succinimide must either be a primary amine or a secondary amine.
Accordingly, in those instances in which the succinimide contains only one
basic amine, that amine must either be a primary amine or a secondary
amine. The polyamine preferably has a carbon-to-nitrogen ratio of from about
1:1 to about 10:1.
The polyamine portion of the polyamino alkenyl or alkyl succinimide may be
substituted with substituents selected from (A) hydrogen, (B) hydrocarbyl
groups of from Ito about 10 carbon atoms, (C) acyl groups of from 2 to about
10 carbon atoms, and (D) monoketo, monohydroxy, mononitro, monocyano,
lower alkyl and lower alkoxy derivatives of (B) and (C). "Lower", as used in
terms like lower alkyl or lower alkoxy, means a group containing from 1 to
about 6 carbon atoms. At least one of the substituents on one of the amines
of the polyamine is hydrogen, e.g., at least one of the basic nitrogen atoms
of
the polyamine is a primary or secondary amino nitrogen atom.
Hydrocarbyl, as used in describing the polyamine components of this
invention, denotes an organic radical composed of carbon and hydrogen
which may be aliphatic, alicyclic, aromatic or combinations thereof, e.g.,
aralkyl. Preferably, the hydrocarbyl group will be relatively free of
aliphatic
unsaturation, i.e., ethylenic and acetylenic, particularly acetylenic
unsaturation. The substituted polyamines of the present invention are
generally, but not necessarily, N-substituted polyamines. Exemplary
hydrocarbyl groups and substituted hydrocarbyl groups include alkyls such as
methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl, etc., alkenyls
such as
propenyl, isobutenyl, hexenyl, octenyl, etc., hydroxyalkyls, such as 2-
hydroxyethyl, 3-hydroxypropyl, hydroxyisopropyl, 4-hydroxybutyl, etc.,
ketoalkyls, such as 2-ketopropyl, 6-ketooctyl, etc., alkoxy and lower alkenoxy
alkyls, such as ethoxyethyl, ethoxypropyl, propoxyethyl, propoxypropyl, 2-(2-
-12-
CA 02530846 2005-12-19
ethoxyethoxy)ethyl, 2-(2-(2-ethoxy-ethoxy)ethoxy)ethyl, 3,6,9,12-
tetraoxatetradecyl, 2-(2-ethoxyethoxy)hexyl, etc. The acyl groups of the
aforementioned (C) substituents are such as propionyl, acetyl, etc. The more
preferred substituents are hydrogen, C1 -C6 alkyls and C1 -C6 hydroxyalkyls.
In a substituted polyamine the substituents are found at any atom capable of
receiving them. The substituted atoms, e.g., substituted nitrogen atoms, are
generally geometrically inequivalent, and consequently the substituted amines
finding use in the present invention can be mixtures of mono- and
polysubstituted polyamines with substituent groups situated at equivalent
and/or inequivalent atoms.
The more preferred polyamine finding use within the scope of the present
invention is a polyalkylene polyamine, including alkylene diamine, and
including substituted polyamines, e.g., alkyl substituted polyalkylene
polyamine. Preferably, the alkylene group contains from 2 to 6 carbon atoms,
there being preferably from 2 to 3 carbon atoms between the nitrogen atoms.
Such groups are exemplified by ethylene, 1,2-propylene, 2,2-
dimethylpropylene, trimethylene, etc. Examples of such polyamines include
ethylene diamine, diethyiene triamine, di(trimethylene)triamine, dipropylene
triamine, triethylene tetramine, tripropylene tetramine, tetraethylene
pentamine, and pentaethylene hexamine. Such amines encompass isomers
such as branched-chain polyamines and the previously mentioned substituted
polyamines, including hydrocarbyl-substituted polyamines. Among the
polyalkylene polyamines, those containing 2-12 amine nitrogen atoms and 2-
24 carbon atoms are especially preferred, and the C2 -05 alkylene polyamines
are most preferred, in particular, the lower polyalkylene polyamines, e.g.,
ethylene diamine, dipropylene triamine, etc.
The polyamine component also may contain heterocyclic polyamines,
heterocyclic substituted amines and substituted heterocyclic compounds,
wherein the heterocycle comprises one or more 5-6 membered rings
-13-
CA 02530846 2005-12-19
containing oxygen and/or nitrogen. Such heterocycles may be saturated or
unsaturated and substituted with groups selected from the aforementioned
(A), (B), (C) and (D). The heterocycles are exemplified by piperazines, such
as 2-methylpiperazine, N-(2-hydroxyethyl)piperazine, 1,2-bis-(N-
piperazinyl)ethane, and N,N1-bis(N-piperazinyl)piperazine, 2-
methylimidazoline, 3-aminopiperidine, 2-aminopyridine, 2-(3-aminoethyl)-3-
pyrroline, 3-aminopyrrolidine, N-(3-aminopropyI)-morpholine, etc. Among
heterocyclic compounds, the piperazines are preferred.
Typical polyamines that can be used to form the compounds of this invention
include the following: ethylene diamine, 1,2-propylene diamine, 1,3-propylene
diamine, diethylene triamine, triethylene tetramine, hexamethylene diamine,
tetraethylene pentamine, methylaminopropylene diamine, N-
(betaaminoethyl)piperazine, N,N1-di(betaaminoethyl)piperazine, N,N'-di(beta-
aminoethyl)-imidazolidone-2, N-(beta-cyanoethyl)ethane-1,2-diamine, 1,3,6,9-
tetraaminooctadecane, 1,3,6-triamino-9-oxadecane, N-(beta-
aminoethyl)diethanolamine, N-methyl-1,2-propanediamine, 2-(2-
aminoethylamino)-ethano1,242-(2-aminoethylamino)ethylamino]-ethanol.
Another group of suitable polyamines are the propyleneamines,
(bisaminopropylethylenediamines). Propyleneamines are prepared by the
reaction of acrylonitrile with an ethyleneamine, for example, an ethyleneamine
having the formula H2 N(CH2 CH NH)z H wherein Z is an integer from 1 to 5,
followed by hydrogenation of the resultant intermediate. Thus, the product
prepared from ethylene diamine and acrylonitrile would be FI2 N(CF12)3
NH(CF12)2 NH(CH2)3 NH2-
In many instances the polyamine used as a reactant in the production of
succinimides of the present invention is not a single compound but a mixture
in which one or several compounds predominate with the average
composition indicated. For example, tetraethylene pentamine prepared by the
polymerization of aziridine or the reaction of dichloroethylene and ammonia
-14-
CA 02530846 2013-02-14
will have both lower and higher amine members, e.g., triethylene tetramine,
substituted piperazines and pentaethylene hexamine, but the composition will
be largely tetraethylene pentamine and the empirical formula of the total
amine composition will closely approximate that of tetraethylene pentamine.
Finally, in preparing the succinimide for use in this invention, where the
various nitrogen atoms of the polyamine are not geometrically equivalent,
several substitutional isomers are possible and are encompassed within the
final product. Methods of preparation of polyamines and their reactions are
detailed in Sidgewick's "The Organic Chemistry of Nitrogen", Clarendon
Press, Oxford, 1966; Noller's "Chemistry of Organic Compounds", Saunders,
Philadelphia, 2nd Ed., 1957; and Kirk-Othmer's "Encyclopedia of Chemical
Technology", 2nd Ed., especially Volumes 2, pp. 99-116.
Examples of suitable polyamines include tetraethylene pentamine,
pentaethylene hexamine, and Dow HPA-X heavy polyamine (number average
molecular weight of 275, available from Dow Chemical Company, Midland,
Michigan). Such amines encompass isomers, such as branched-chain
polyamines, and the previously mentioned substituted polyamines, including
hydrocarbyl-substituted polyamines. HPA-X heavy polyamine ("H PA-X")
contains an average of approximately 6.5 amine nitrogen atoms per molecule.
Such heavy polyamines generally afford excellent results.
The reaction of a polyamine with an alkenyl or alkyl succinic anhydride to
produce the polyamino alkenyl or alkyl succinimides is well known in the art
and is disclosed in U.S. Pat. Nos. 2,992,708; 3,018,291; 3,024,237,
3,100,673; 3,219,666; 3,172,892 and 3,272,746.
As noted above, the term "polyamino alkenyl or alkyl succinimide" refers to
both polyamino alkenyl or alkyl mono- and bis-succinimides and to the higher
analogs of alkenyl or alkyl poly succinimides. Preparation of the bis- and
-15-
CA 02530846 2005-12-19
higher analogs may be accomplished by controlling the molar ratio of the
reagents. For example, a product comprising predominantly mono- or bis-
succinimide can be prepared by controlling the molar ratios of the polyamine
and succinic anhydride. Thus, if one mole of polyamine is reacted with one
mole of an alkenyl or alkyl substituted succinic anhydride, a predominantly
mono-succinimide product will be prepared. If two moles of an alkenyl or alkyl
substituted succinic anhydride are reacted per mole of polyamine, a bis-
succinimide is prepared. Higher analogs may likewise be prepared.
A particularly preferred class of polyamino alkenyl or alkyl succinimides
employed in the process of the instant invention may be represented by
Formula II:
0
R3
r
al a
wherein R is alkenyl or alkyl of from 10 to 300 carbon atoms; R2 is alkylene
of
2 to 10 carbon atoms; R3 is hydrogen, lower alkyl or lower hydroxy alkyl; a is
an integer from 0 to 10; and W is --NH2 or represents a group of Formula III:
R
0
wherein R is alkenyl or alkyl of from 10 to 300 carbon atoms; with the proviso
that when W is the group of Formula III above, then a is not zero and at least
one of R3 is hydrogen.
-16-
CA 02530846 2005-12-19
As indicated above, the polyamine employed in preparing the succinimide is
often a mixture of different compounds wherein the resulting succinimide has
an average composition indicated as the Formula II. Accordingly, in Formula II
each value of R2 and R3 may be the same as or different from other R2 and
R3.
Preferably R is alkenyl or alkyl, more preferably 10 to 200 carbon atoms, and
most preferably 20 to 100 carbon atoms.
Preferably R2 is alkylene of 2 to 6 carbon atom and most preferably is either
ethylene or propylene.
Preferably, R3 is hydrogen.
Preferably, a is an integer from 1 to 6.
In formula II, the polyamino alkenyl or alkyl succinimides may be conveniently
viewed as being composed of three moieties that is the alkenyl or alkyl moiety
R, the succinimide moiety represented by the formula:
CI
11/
J-1
-
C
0
and the polyamino moiety represented by the group
R3
a
-17-
CA 02530846 2013-02-14
The preferred alkylene polyamines employed in this reaction are generally
represented by the formula:
H2 N-(R1-NH)a ¨R'-NH2
wherein R' is an alkylene moiety of 2 to 10 carbon atoms and a is an integer
from about 0 to 10. However, the preparation of these alkylene polyamines do
not produce a single compound and cyclic heterocycles, such as piperazine,
may be included to some extent in the alkylene diamines.
Additionally, the succinimide may be prepared by other methods including, but
not limited to, those described in the following: Harrison et al., U.S. Patent
No.
5,616,668; Harrison et al., U.S. Patent No. 5,565,528; Harrison et al., U.S.
Patent No. 5,753,597; Harrison et al., U.S. Patent No. 6,617,396; Harrison et
al., U.S. Patent No. 6,451,920; and Wollenberg et al., U.S. Patent No.
4,746,446.
The post-treated succinimide is made in accordance with methods that are
well known in the art including, but not limited to the following: Harrison et
al.,
U.S. Patent No. 5,716,912; Harrison et al., U.S. Patent No. 5,821,205;
Harrison et al., U.S. Patent No. 5,849,676; Harrison et al., U.S. Patent No.
5,872,083; Harrison et al., U.S. Patent No. 6,015,776; Harrison et al., U.S,
Patent No. 6,107,450; Harrison et al., U.S. Patent No. 6,146,431; Harrison et
al., U.S. Patent No. 6,358,892. Essentially, the phosphorous-free nitrogen
containing dispersant may also be post treated, such as by reacting them
with boric acid or a similar boron compound to form borated dispersants. In
addition to boric acid (boron acid), examples of suitable boron compounds
include boron oxides, boron halides and esters of boric acid. Generally from
about 0.1 equivalents to 10 equivalents of boron compound to the
phosphorous-free nitrogen containing dispersant may be employed.
-18-
CA 02530846 2013-02-14
Hydrocarbyl Substituted Succinic Ester of a Polypi
In another embodiment of the present invention, a hydrocarbyl substituted
succinic ester of a polyol may be mixed with the neutral phosphite compound.
Such succinic esters are usually the reaction product of hydrocarbyl
substituted succinic acids or anhydrides (e.g. polyisobutenylsuccinic
anhydride) with polyols (e.g. pentaerythritol). The hydrocarbyl substituted
ester of a polyol may be prepared as described in U.S. Patent No. 3,381,022
and U.S. Patent No. 4,173,540.
Suitable polyols include ethylene glycol, diethylene glycol, triethylene
glycol,
tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene
glycol,
tributylene glycol, and other alkylene glycols in which the alkylene group
contains from two to eight carbon atoms. Other useful polyhydric alcohols
include glycerol, pentaerythritol, 1,2-butanediol, 2,3-hexanediol, 2,4-
hexanediol, pinacol, erythritol, arabitol, sorbitol, mannitol, 1,2 ¨
cyclohexanediol, and xylene glycol. An especially preferred class of
polyhydric alcohols are those having at least three hydroxyl groups, such as
pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol and mannitol.
Most
preferred is pentaerythritol.
Additionally, the ester of pentaerythritol, used in this invention may be
purchased from Chevron Oronite Company, LLC San Ramon, California and
may also be purchased from The Lubrizol Corporation, Wycliffe, Ohio.
Neutral Phosphite
In the present invention, preferred neutral phosphite compounds include
trihydrocarbyl phosphites. More preferred trihydrocarbyl phosphites include
trialkyl phosphites. Most preferred trialkyl phosphites include trilauryl
phosphite. In addition to processes that are well known in the art, trilauryl
-19-
CA 02530846 2013-02-14
phosphite is manufactured and sold by Rhodia, Inc., Cranbury, New Jersey
and is marketed under the trade name Duraphos TM TLP. According to the
MSDS for Duraphos TM TLP, this compound contains about 90 wt% trilauryl
phosphite, 7.5 wt% of dilauryl hydrogen phosphite and less than 0.5 wt% of
phenol.
A neutral phosphite compound, such as trialkyl phosphite, is represented by
the following formula:
R-0
P-
wherein R, R', and R" are independently hydrocarbyl groups having from
about 1 to 24 carbon atoms, preferably from about 4 to about 18 carbon
atoms, and more preferably from about 6 to 16 carbon atoms. The R, R', and
R" groups may be saturated or unsaturated, and straight or branched chain
aliphatic hydrocarbyl radical, Representative examples of suitable R, R', and
R" groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-
butyl, n-
propenyl, n-butenyl, n-hexyl, nonylphenyl, n-dodecyl, n-dodecenyl, hexadecyl,
octadecenyl, stearyl, i-stearyl, hydroxystearyl, and the like. Preferably, R,
R'
and R" are each alkyl or aryl.
Preferred neutral phosphite compounds include trihydrocarbyl phosphites.
More preferred trihydrocarbyl phosphites include trialkyl phosphites. Most
preferred trialkyl phosphites include trilauryl phosphite, which is
manufactured
and sold by Rhodia, Inc. and is marketed under the trade name DuraphosTM
TLP.
In addition to being purchased from Rhodia, Inc., trialkyl phosphite may be
synthesized from well known processes such as that described in U.S. Patent
No. 2,848,474.
-20-
CA 02530846 2005-12-19
The Lubricating Oil Composition
The lubricating oil composition of the present invention contains a major
amount of oil of lubricating viscosity and a minor amount of the anti-shudder
additive composition, which comprises (a) at least one neutral phosphite
compound and at least one dispersant selected from and (b) at least one
hydrocarbyl substituted succinic dispersant selected from the group consisting
of a hydrocarbyl bissuccinimide and a hydrocarbyl substituted succinic ester
of a polyol and mixtures thereof, wherein the hydrocarbyl substituent has at
least 50 carbon atoms, wherein the additive composition does not comprise
an ethoxylated amine; and wherein the additive composition does not
comprise a primary amide of a long chain carboxylic acid, provided that if the
lubricating oil composition also contains monosuccinimide, then the ratio of
the hydrocarbyl substituted succinic dispersant to monosuccinimide is at least
7:3. More preferred the ratio of the hydrocarbyl substituted succinic
dispersant to monosuccinimide is at least 7.5:2.5. Even more preferred, the
ratio of the hydrocarbyl substituted succinic dispersant to monosuccinimide is
at least 8:2. Most preferred, the ratio of the hydrocarbyl substituted
succinic
dispersant to monosuccinimide is 9:1.
An effective amount of the anti-shudder additive composition is added to a
base oil that is sufficient to lubricate gears and other components which are
present in automatic and continuously variable transmissions, as well as
reduce the shudder that is caused by friction induced vibration. Typically,
the
lubricating oil composition of the present invention comprises a major amount
of oil of lubricating viscosity and a minor amount of the anti-shudder
additive
package.
Specifically, the lubricating oil composition comprises (a) at least one
neutral
phosphite compound comprising preferably from about 0.01 wt% to about
1.00 wt% trihydrocarbyl phosphite, such as trialkyl phosphite, such as
trilauryl
-21-
CA 02530846 2005-12-19
phosphite. More preferably, from about 0.10 wt% to about 0.85 wt%
trihydrocarbyl phosphite, such as trialkyl phosphite, such as trilauryl
phosphite, is present in the lubricating oil composition. Even more
preferably,
from about 0.20 wt% to about 0.70 wt% trihydrocarbyl phosphite, such as
trialkyl phosphite, such as trilauryl phosphite, is present in the lubricating
oil
composition. Most preferably, from about 0.30 wt% to about 0.65 wt%
trihydrocarbyl phosphite, such as trialkyl phosphite, such as trilauryl
phosphite, is present in the lubricating oil composition.
In one embodiment, component (b) of the lubricating oil composition is a
hydrocarbyl bissuccinimide, wherein the hydrocarbyl substituent has at least
50 carbon atoms, comprising preferably from about 0.10 wt% to about
10.0 wt% of bissuccinimide, such as post-treated bissuccinimide, such as
borated bissucinimide. More preferably, from about 0.20 wt% to about
8.0 wt% of bissuccinimide, such as post-treated bisuccinimde, such as
borated bissuccinimide is in the lubricating oil composition. More preferably,
from about 0.3 wt% to about 6.0 wt% of bissuccinimde, such as post-treated
bissuccinimide, such as borated bissuccinimide is in the lubricating oil
composition. Most preferably, from about 0.4 wt% to about 5.0 wt% of
bissucnimide, such as post-treated bissuccinimide, such as borated
bissuccinimide is in the lubricating oil composition.
In another embodiment, component (b) of the lubricating oil composition is a
hydrocarbyl substituted succinic ester of a polyol and mixtures thereof,
wherein the hydrocarbyl substituent has at least 50 carbon atoms, comprising
from about 0.10 wt% to about 10.0 wt% of an ester of polyalcohol, such as an
ester of pentaerythritol. More preferably, from about 0.20 wt% to about 8.0
wt% of an ester of polyalcohol, such as an ester of pentaerythritol is in the
lubricating oil composition. More preferably, from about 0.3 wt% to about 5.0
wt% of an ester of polyalcohol, such as an ester of pentaerythritol is in the
lubricating oil composition. Most preferably, from about 0.4 wt% to about 5.0
-22-
CA 02530846 2005-12-19
wt% of an ester of polyalcohol, such as an ester of pentaerythritol is in the
lubricating oil composition.
In a further embodiment of the present invention, component (b) of the
lubricating oil composition may be a mixture of the hydrocarbyl bissuccinimide
and the hydrocarbyl substituted succinic ester of a polyol.
The base oil employed may be any of a wide variety of oils of lubricating
viscosity. The base oil of lubricating viscosity used in such compositions may
be mineral oils or synthetic oils. A base oil having a viscosity of at least
2.5 cSt at 40 C and a pour point below 20 C, preferably at or below 0 C, is
desirable. The base oils may be derived from synthetic or natural sources.
Mineral oils for use as the base oil in this invention include, for example,
paraffinic, naphthenic and other oils that are ordinarily used in lubricating
oil
compositions. Synthetic oils include, for example, both hydrocarbon synthetic
oils and synthetic esters and mixtures thereof having the desired viscosity.
Hydrocarbon synthetic oils may include, for example, oils prepared from the
polymerization of ethylene, polyalphaolefin or PAO oils, or oils prepared from
hydrocarbon synthesis procedures using carbon monoxide and hydrogen
gases such as in a Fisher-Tropsch process. Useful synthetic hydrocarbon oils
include liquid polymers of alpha olefins having the proper viscosity.
Especially
useful are the hydrogenated liquid oligomers of C6 to C12 olefins such as
1-decene trimer. Likewise, alkyl benzenes of proper viscosity, such as
didodecyl benzene, can be used. Useful synthetic esters include the esters of
monocarboxylic acids and polycarboxylic acids, as well as mono-hydroxy
alkanols and polyols. Typical examples are didodecyl adipate, pentaerythritol
tetracaproate, di-2-ethylhexyl adipate, dilaurylsebacate, and the like.
Complex esters prepared from mixtures of mono and dicarboxylic acids and
mono and dihydroxy alkanols can also be used. Blends of mineral oils with
synthetic oils are also useful.
-23-
CA 02530846 2005-12-19
Thus, the base oil can be a refined paraffin type base oil, a refined
naphthenic
base oil, or a synthetic hydrocarbon or non-hydrocarbon oil of lubricating
viscosity. The base oil can also be a mixture of mineral and synthetic oils,
Groups I-IV and mixtures thereof. Most preferred base oils are Group II, Ill
and mixtures thereof. Preferred base oils include a blend of Chevron Phillips
PAO 4 cSt, which may be purchased from Chevron Phillips, Woodlands,
Texas, and RLOP 100 N, which may be purchased from ChevronTexaco
Corporation, San Ramon, California. Another preferred base oil is
PetroCanad 4 which may be purchased from Petro-Canada, Calgary-Alberta,
Canada.
Additionally, other additives well known in lubricating oil compositions may
be
added to the additive composition of the present invention to complete a
finished oil.
Other Additives
The following additive components are examples of some of the components
that can be favorably employed in the present invention. These examples of
additives are provided to illustrate the present invention, but they are not
intended to limit it:
2. Metal Detergents
Sulfurized or unsulfurized alkyl or alkenyl phenates, alkyl or alkenyl
aromatic sulfonates, borated sulfonates, sulfurized or unsulfurized
metal salts of multi-hydroxy alkyl or alkenyl aromatic compounds, alkyl
or alkenyl hydroxy aromatic sulfonates, sulfurized or unsulfurized alkyl
or alkenyl naphthenates, metal salts of alkanoic acids, metal salts of an
alkyl or alkenyl multiacid, and chemical and physical mixtures thereof.
3. Anti-Oxidants
Anti-oxidants reduce the tendency of mineral oils to deteriorate in
service which deterioration is evidenced by the products of oxidation
-24-
CA 02530846 2005-12-19
,
such as sludge and varnish-like deposits on the metal surfaces and by
an increase in viscosity. Examples of anti-oxidants useful in the
present invention include, but are not limited to, phenol type (phenolic)
oxidation inhibitors, such as 4,4'-methylene-bis(2,6-di-tert-butylphenol),
4,4'-bis(2,6-di-tert-butylphenol), 4,4'-bis(2-methyl-6-tert-butylphenol),
2,2'-methylene-bis(4-methy1-6-tert-butylphenol),
4,4'-butylidene-bis(3-methyl-6-tert-butylphenol),
4,4'-isopropylidene-bis(2,6-di-tert-butylphenol), 2,2'-methylene-bis(4-
methy1-6-nonylphenol), 2,2'-isobutylidene-bis(4,6-dimethylphenol),
2,2*-5-methylene-bis(4-methy1-6-cyclohexylphenol), 2,6-di-tert-buty1-4-
methylphenol, 2,6-di-tert-buty1-4-ethylphenol, 2,4-dimethy1-6-tert-butyl-
phenol, 2,6-di-tert-l-dimethylamino-p-cresol, 2,6-di-tert-4-(N,Ni-
dimethylaminomethylphenol), 4,4'-thiobis(2-methy1-6-tert-butylphenol),
2,2'-thiobis(4-methy1-6-tert-butylphenol), bis(3-methy1-4-hydroxy-5-tert-
10-butylbenzyl)-sulfide, and bis(3,5-di-tert-buty1-4-hydroxybenzyl).
Diphenylamine-type oxidation inhibitors include, but are not limited to,
alkylated diphenylamine, phenyl-alpha-naphthylamine, and
alkylated-alpha-naphthylamine. Other types of oxidation inhibitors
include metal dithiocarbamate (e.g., zinc dithiocarbamate), and
15-methylenebis(dibutyldithiocarbamate).
4. Anti-Wear Agents
As their name implies, these agents reduce wear of moving metallic
parts. Examples of such agents include, but are not limited to,
phosphates which comprise no more than 0.08 wt% of the lubricating
oil composition , carbarmates, esters, and molybdenum complexes.
5. Rust Inhibitors (Anti-Rust Agents)
a) Nonionic polyoxyethylene surface active agents: polyoxyethylene
lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene
nonyl phenyl ether, polyoxyethylene octyl phenyl ether,
polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether,
-25-
CA 02530846 2005-12-19
polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol
mono-oleate, and polyethylene glycol mono-oleate.
b) Other compounds: stearic acid and other fatty acids, dicarboxylic
acids, metal soaps, fatty acid amine salts, metal salts of heavy
sulfonic acid, partial carboxylic acid ester of polyhydric alcohol, and
phosphoric ester.
6. Demulsifiers
Addition product of alkylphenol and ethylene oxide, polyoxyethylene
alkyl ether, and polyoxyethylene sorbitan ester.
7. Extreme Pressure Anti-Wear Agents (EP/AW Agents)
Zinc dialky-1-dithiophosphate (primary alkyl, secondary alkyl, and aryl
type), diphenyl sulfide, methyl trichlorostearate, chlorinated
naphthalene, fluoroalkylpolysiloxane, lead naphthenate, neutralized
phosphates, dithiophosphates, and sulfur-free phosphates.
8. Friction Modifiers
Fatty alcohol, fatty acid, amine, borated ester, other esters,
phosphates, phosphites and phosphonates, excluding ethoxylated
amines.
9. Multifunctional Additives
Sulfurized oxymolybdenum dithiocarbamate, sulfurized
oxymolybdenum organo phosphorodithioate, oxymolybdenum
monoglyceride, oxymolybdenum diethylate amide, amine-molybdenum
complex compound, and sulfur-containing molybdenum complex
compound.
-26-
CA 02530846 2005-12-19
10. Viscosity Index Improvers
Polymethacrylate type polymers, ethylene-propylene copolymers,
styrene-isoprene copolymers, hydrated styrene-isoprene copolymers,
polyisobutylene, and dispersant type viscosity index improvers.
11. Pour Point Depressants
Polymethyl methacrylate.
12. Foam Inhibitors
Alkyl methacrylate polymers and dimethyl silicone polymers.
13. Metal Deactivators
Disalicylidene propylenediamine, triazole derivatives, thiadiazole
derivatives, and mercaptobenzimidazoles.
13. Dispersants
Alkenyl succinimides, alkenyl succinimides modified with other organic
compounds, alkenyl succinimides modified by post-treatment with
ethylene carbonate or boric acid, pentaerythritols, phenate-salicylates
and their post-treated analogs, alkali metal or mixed alkali metal,
alkaline earth metal borates, dispersions of hydrated alkali metal
borates, dispersions of alkaline-earth metal borates, polyamide ashless
dispersants and the like or mixtures of such dispersants.
Method of Making Anti-Shudder Additive Composition
The anti-shudder additive composition is prepared by mixing the following two
components at elevated temperatures of about 70 F to 195 F, for example, at
about 140 F: (a) at least one neutral phosphite compound, such as
trihydrocarbyl phosphite, such as trialkyl phosphite, such as trilauryl
phosphite; and (b) at least one phosphorous-free hydrocarbyl substituted
succinic dispersant selected from the group consisting of a hydrocarbyl
-27-
CA 02530846 2005-12-19
bissuccinimide and a hydrocarbyl substituted succinic ester of a polyol and
mixtures thereof, wherein the hydrocarbyl substituent has at least 50 carbon
atoms. Preferably, from about 0.10 wt% to about 90.9 wt% of at least one
neutral phosphite compound is used in the additive composition. More
preferably, from about 1.2 wt% to about 81.0 wt% of at least one neutral
phosphite compound is used in the additive composition. Even more
preferably, from about 3.9 wt% to about 70.0 wt%, and most preferably from
about 5.7 wt% to about 61.9 wt%, of at least one neutral phosphite compound
is used in the additive composition. Preferably, from about 9.1 wt% to about
99.9 wt% of at least one hydrocarbyl substituted succinic dispersant selected
from the group consisting of a hydrocarbyl bissuccinimde and a hydrocarbyl
substituted succinic ester of a polyol and mixtures thereof, wherein the
hydrocarbyl substituent has at least 50 atoms is used in the additive
composition. More preferably, from about 19.0 wt% to about 98.8 wt% of at
least one hydrocarbyl substituted succinic dispersant is used in the additive
composition. Even more preferably, from about 30.0 wt% to about 96.1 wt%,
and most preferably from about 38.1 wt% to about 94.3 wt%, of at least one
hydrocarbyl substituted succinic dispersant is used in the additive
composition. =
The Finished Oil of the Present Invention
A first process for making the finished lubricating oil composition comprises
the addition of the anti-shudder additive composition described above to a
major amount of an oil of lubricating viscosity, with or without other
additives
present, wherein the major amount is greater than 50 wt%, provided that if the
lubricating oil composition also contains monosuccinimide, then the ratio of
the hydrocarbyl substituted succinic dispersant to monosuccinimide is at least
7:3. More preferred, the ratio of the hydrocarbyl substituted succinic
dispersant to monosuccinimide is at least 7.5:2.5. Even more preferred, the
ratio of the hydrocarbyl substituted succinic dispersant to monosuccinimide is
at least 8:2. Most preferred the ratio of the hydrocarbyl substituted succinic
-28-
CA 02530846 2005-12-19
dispersant to monosuccinimide is at least 9:1. Preferably, the anti-shudder
additive composition is present in the lubricating oil composition in the
range
of about 0.11 wt% to about 11.00 wt%, more preferably from about 0.30 wt%
to about 8.85 wt%, even more preferably from about 0.50 wt% to about 6.70
wt%, and most preferably from about 0.70 wt% to about 5.65 wt%, based on
the total weight of the lubricating oil composition.
A second process for making the finished lubricating oil composition
comprises the separate addition of either component (a) and component (b) of
the anti-shudder additive composition to the oil of lubricating viscosity.
A third process for making the finished oil comprises mixing the anti-shudder
additive composition, or the individual components of the anti-shudder
additive composition, with a second additive package thereby producing a
combined additive package. The combined additive package is then added to
a majority amount of an oil of lubricating viscosity, wherein the majority
amount is greater than 50 wt%.
Method of Use of the Present Invention
The present invention is used to decrease shudder in transmissions, including
but not limited to automatic and continuously variable transmissions.
Specifically, the lubricating oil of the present invention contacts metal
components in transmissions to reduce shudder. Preferably, the anti-shudder
additive composition is present in the lubricating oil composition in the
range
of about 0.11 wt% to about 11.00 wt%, more preferably from about 0.30 wt%
to about 8.85 wt%, even more preferably from about 0.50 wt% to about 6.70
wt%, and most preferably from about 0.70 wt% to about 5.65 wt%, based on
the total weight of the lubricating oil composition. The anti-shudder additive
composition will optionally comprise sufficient inorganic liquid diluent to
make
it easy to handle during shipping and storage. Typically, the anti-shudder
additive composition will comprise from about 0.5 wt% to 45 wt% of the
-29-
CA 02530846 2013-02-14
organic liquid diluent and preferably about 2 wt% to 20 wt%. Suitable organic
diluents which can be used include, for example, solvent refined 100N (i.e.,
Cit-con 100N), and hydrotreated 100N (i.e., Chevron 100N), and the like. The
organic diluent preferably has a viscosity of about 10 to 20 cSt at 100 C.
Performance Testing
The anti-shudder lubricating oil composition of the present invention
typically
meets the General Motors Corporation (GM) added anti-shudder test
requirements to the DEXRON(D-111 specification (DEXRON -III, H Revision,
Automatic Transmission Fluid Specification, GMN10055), using the
Electronically Controlled Converter Clutch (ECCC or EC3) Test, which may be
purchased from NS Engineering, Inc. at http://www.global.ihs.com. The
ECCC Vehicle Performance Test evaluates torque converter shudder and slip
speed hunting characteristics by running the vehicle to be tested on a
dynamometer through a series of pre-determined speed and load conditions.
Actual road tests may also be used to detect whether there is shudder in the
transmission.
The following examples are presented to illustrate specific embodiments of
this invention and are not to be construed in any way as limiting the scope of
the invention.
EXAMPLES
Example 1
An anti-shudder additive package was prepared by adding 5.25 wt% berated
bissuccinimide (from polyisobutenyl [1300 WA] succinic anhydride and a
heavy polyamine, HPA-X, available from Dow Chemical Company) dispersant
(which comprises about 99 wt% bissuccinimide), 0.033 wt% high overbased
(HOB) calcium sulfonate, 0.04 wt% DuradTM 310 M (which comprises a mixture
of organophosphate esters), 0.565 wt% Duraphos TM TLP (which comprises
-30-
CA 02530846 2005-12-19
about 90 wt% trilauryl phosphite and 7.5 w% dilauryl hydrogen phosphite),
0.50 wt% phenolic oxidation inhibitor, 0.40 wt% aminic oxidation inhibitor,
0.1
wt% thiadiazole derivative, 0.75 wt% benzoate ester, 0.002 wt% silicon based
foam inhibitor, 0.020 wt% Unisol Red BHF, and 2.6 wt% Polyalkyl
Methacrylate viscosity index improver (PMA-VII - 350,000 MW average) to a
base oil composition comprised of a base oil blend comprised of about 88.77
wt% RLOP 100 N which may be purchased from ChevronTexaco Corporation,
San Ramon, California and about 11.23 wt% Chevron Phillips PAO 4 cSt
which may be purchased from Chevron Phillips Company, Woodlands, Texas.
The components were blended for approximately two hrs at a temperature of
from about 120 F to about 140 F. The lubricating oil comprising this anti-
shudder additive package passed the GM DEXRONC)-111ECCC Test.
Example 2
An anti-shudder additive package was prepared by adding 4.5 wt% succinate
ester of pentaerythritol and polyisobutenyl (1000 MW) succinic anhydride
(PIBSA) dispersant, 0.0022 wt% calcium sulfonate, 0.1 wt% polyamide of
tetraethylenepentamine (TEPA) and isostearic acid, 0.565 wt% Duraphos TLP
(which comprises about 90 wt% trilauryl phosphite and 7.5 wt% dilauryl
hydrogen phosphite), 0.02 wt% Duraphos AP 230 (dilauryl hydrogen
phosphite), 0.9 wt% phenolic oxidation inhibitor, 0.05 wt% thiadiazole
derivative, 0.05 wt% primary aliphatic amine with highly branched alkyl chains
(C12-C14), 0.5 wt% benzoate ester, 0.002 wt% silicon based foam inhibitor,
0.020 wt% Unisol Red BHF, and 2.6 wt% PMA-VII (350,000 MW average) to
a base oil blend comprised of about 88.77 wt% RLOP 100 N which may be
purchased from ChevronTexaco Corporation, San Ramon, California and
about 11.23 wt% Chevron Phillips PAO 4 cSt which may be purchased from
Chevron Phillips Company, Woodlands, Texas. The components were
blended for approximately two hrs at a temperature of from about 120 F to
about 140 F. The lubricating oil comprising this anti-shudder additive
package passed the GM DEXRON,0-111 ECCC Test.
-31-
CA 02530846 2013-02-14
Example 3
An anti-shudder additive package was prepared by adding 1.25 wt% borated
bissuccinimide dispersant from polyisobutenyl (1300 MW) succinic anhydride
and heavy polyamine, HPA-X (which dispersant comprises about 99 wt%
bissuccinimide), 3.0 wt% succininate ester of pentaerythritol and
polyisobutenyl (1000 MW) succinic anhydride (PIBSA) dispersant dispersant,
0.0022 wt% HOB calcium sulfonate, 0.1 wt% polyamide of TEPA and
isostearic acid, 0.565 wt% Duraphos TM TLP (90 wt% trilauryl phosphite and 7.5
wt% dilauryl hydrogen phosphite), 0.02 wt% Duraphos TM AP 230 (dilauryl
hydrogen phosphite), 0.5 wt% phenolic oxidation inhibitor, 0.4 wt% aminic
oxidation inhibitor, 0.1 wt% thiadiazole derivative, 0.1 wt% primary aliphatic
amine with highly branched alkyl chains (C12-C14), 0.5 wt% benzoate ester,
0.002 wt% silicon based foam inhibitor, 0.020 wt% Unisol Red TM BHF, and 2.6
wt% PMA - VII (350,000 MW average) to a base oil composition comprised of
a base oil blend comprised of about 88.77 wt% RLOP 100 N which may be
purchased from ChevronTexaco Corporation, San Ramon, California and
about 11.23 wt% Chevron Phillips PAO 4 cSt which may be purchased from
Chevron Phillips Company, Woodlands, Texas. The components were
blended for approximately two hrs at a temperature of from about 120 F to
about 140 F. The lubricating oil comprising this anti-shudder additive
package passed the GM DEXRON -111 ECCC Test.
Example 4
An anti-shudder additive package was prepared by adding 1.5 wt% borated
bissuccinimide dispersant from polyisobutenyl (1300 MW) succinic anhydride
and heavy polyamine, HPA-X (which dispersant comprises about 99 wt%
bissuccinimide), 1.5 wt% succininate ester of pentaerythritol and
polyisobutenyl (1000 MW) succinic anhydride (PIBSA) dispersant, 0.0022
wt% HOB calcium sulfonate, 0.1 wt% polyamide of TEPA and isostearic acid,
0.565 wt% Duraphos TM TLP (90 wt% trilauryl phosphite and 7.5 wt% dilauryl
-32-
CA 02530846 2005-12-19
hydrogen phosphite), 0.02 wt% Duraphos AP 230 (dilauryl hydrogen
phosphite), 0.5 wt% phenolic oxidation inhibitor, 0.4 wt% aminic oxidation
inhibitor, 0.1 wt% thiadiazole derivative, 0.1 wt% primary aliphatic amine
with
highly branched alkyl chains (C12-C14), 0.5 wt% benzoate ester, 0.002 wt%
silicon based foam inhibitor, 0.020 wt% Unisol Red BHF, and 2.6 wt% PMA -
VII (350,000 MW average) to a base oil blend comprised of about 88.77 wt%
RLOP 100 N which may be purchased from ChevronTexaco Corporation, San
Ramon, California and about 11.23 wt% Chevron Phillips PAO 4 cSt which
may be purchased from Chevron Phillips Chemical Company, LLC,
Woodlands, Texas. The components were blended for approximately two hrs
at a temperature of from about 120 F to about 140 F. The lubricating oil
comprising this anti-shudder additive package passed the GM DEXRONO-Ill
ECCC Test.
COMPARATIVE EXAMPLES
Comparative Example A
An anti-shudder additive package was prepared by adding 5.25 wt%
monosuccinimide dispersant from polyisobutenyl (1000 MW) succinic
anhydride and a mixture of diethylene triamine and HPA-X (which dispersant
comprises about 50 wt% monosuccinimide and about 50 wt% bissuccinimide),
0.033 wt% HOB calcium sulfonate, 0.04 wt% Durad 310M (mixture of
organophosphate esters), 0.565 wt% Duraphos TLP (which comprises about
90 wt% trilauryl phosphite and about 7.5 wt% dilauryl hydrogen phosphite),
0.50 wt% phenolic oxidation inhibitor, 0.40 wt% aminic oxidation inhibitor,
0.1
wt% thiadiazole derivative, 0.75 wt% benzoate ester, 0.002 wt% silicon based
foam inhibitor, 0.020 wt% Unisol Red BHF, and 2.6 wt% PMA-VII to a base oil
blend comprised of about 88.77 wt% RLOP 100 N which may be purchased
from ChevronTexaco Corporation, San Ramon, California and about 11.23
wt% Chevron Phillips FAQ 4 cSt which may be purchased from Chevron
Phillips Company, Woodlands, Texas. The components were blended for
approximately two hrs at a temperature of from about 120 F to about 140 F.
-33-
CA 02530846 2005-12-19
The lubricating oil comprising this anti-shudder additive package failed the
GM DEXRONC)-III ECCC Test.
Comparative Example B
An anti-shudder additive package was prepared by adding 5.25 wt% borated
bissuccinimide (from polyisobutenyl [1300 MW] succinic anhydride and a
heavy polyamine, HPA-X, available from Dow Chemical Company) dispersant
(which comprises about 99 wt% bissuccinimide), 0.033 wt% HOB calcium
sulfonate, 0.45 wt% Durad 310M (which comprises a mixture of
organophosphate esters), 0.50 wt% phenolic oxidation inhibitor, 0.40 wt%
aminic oxidation inhibitor, 0.1 wt% thiadiazole derivative, 0.75 wt% benzoate
ester, 0.002 wt% silicon based foam inhibitor, 0.020 wt% Unisol Red BHF,
and 2.6 wt% PMA-VII (350,000 MW average) to a base oil composition
comprised of a base oil blend comprised of about 88.77 wt% RLOP 100 N
which may be purchased from ChevronTexaco Corporation, San Ramon,
California and about 11.23 wt% Chevron Phillips PAO 4 cSt which may be
purchased from Chevron Phillips Company, Woodlands, Texas. The
components were blended for approximately two hrs at a temperature of from
about 120 F to about 140 F. The lubricating oil comprising this anti-shudder
additive package failed the GM DEXRONC1-111 ECCC Test.
Comparative Example C
An anti-shudder additive package was prepared by adding 4.23 wt%
monosuccinimide dispersant from polyisobutenyl (1000 MW) succinic
anhydride and a mixture of diethylene triamine and HPA-X (which dispersant
comprises about 50 wt% monosuccinimide and about 50 wt% bissuccinimide),
1.00 wt% borated bissuccinimide (from polyisobutenyl [1300 MW] succinic
anhydride and a heavy polyamine, HPA-X, available from Dow Chemical
Company) dispersant (which comprises about 99 wt% bissuccinimide), 0.033
wt% HOB calcium sulfonate, 0.565 wt% Duraphos TLP (which comprises
-34-
CA 02530846 2005-12-19
about 90 wt% trilauryl phosphite and about 7.5 wt% dilauryl hydrogen
phosphite), 0.02 Duraphos AP-230 (which comprises dilauryl hydrogen
phosphite), 0.30 wt% phenolic oxidation inhibitor, 0.5 wt% aminic oxidation
inihibitor, 0.08 wt% thiadiazole derivative, 0.50 wt% benzoate ester, 0.002
wt% silicon based foam inhibitor and 2.6 wt% PMA- VII (350,000 MW
average) to approximately a base oil composition comprised of a base oil
blend comprised of about 88.77 wt% RLOP 100 N which may be purchased
from ChevronTexaco Corporation, San Ramon, California and about 11.23
wt% Chevron Phillips PAO 4 cSt which may be purchased from Chevron
Phillips Company, Woodlands, Texas. The components were blended for
approximately two his at a temperature of from about 120 F to about 140 F.
In this example, the ratio of bissuccinimide to monosuccinimide is 6:4. The
lubricating oil comprising this anti-shudder additive package failed the GM
DEXRON -Ill ECCC Test.
Comparative Example D
An anti-shudder additive package was prepared by adding 4.23 wt%
monosuccinimide dispersant from polyisobutenyl (1000 MW) succinic
anhydride and a mixture of diethylene triamine and HPA-X (which dispersant
comprises about 50 wt% monosuccinimide and about 50 wt% bissuccinimide),
1.00 wt% borated bissuccinimide (from polyisobutenyl [1300 MW] succinic
anhydride and a heavy polyamine, HPA-X, available from Dow Chemical
Company) dispersant (which comprises about 99 wt% bissuccinimide),
0.0022 wt% HOB calcium sulfonate, 0.41 wt% Durad 310 M (which comprises
a mixture of organophosphate esters), 0.2 wt% polyamide of TEPA and
isostearic acid, 0.30 wt% phenolic oxidation inhibitor, 0.5 wt% aminic
oxidation inhibitor, 0.1 wt% thiadiazole derivative, 0.50 wt% benzoate ester,
0.002 wt% silicon based foam inhibitor, 0.0125 wt% Unisol Red BHF, and
2.15 wt% PMA-VII (350,000 MW average) to a base oil composition
comprised of 100 wt% PetroCanada 4 which may be purchased from Petro-
Canada, Calgary, Alberta, Canada. The components were blended for
-35-
CA 02530846 2013-02-14
approximately two hrs at a temperature of from about 120 F to about 140 F.
In this example, the ratio of bissuccinimide to monosuccinimide is 6:4. The
lubricating oil comprising this anti-shudder additive package failed the GM
DEXRONC-III ECCC Test.
It is understood that although modifications and variations of the invention
can
be made without departing from the scope thereof, only such limitations should
be imposed as are indicated in the appended claims.
-36-
