Note: Descriptions are shown in the official language in which they were submitted.
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
COMPOSITIONS WITH FAST AND SLOW RELEASE COMPONENTS
FIELD OF THE INVENTION
[0001] The present invention relates to gel-containing systems that include:
(a) a
slow release component, comprising one or more performance additives in the
form
of a solid or semi-solid mass; and (b) a fast release component comprising (i)
a
matrix material and (ii) one or more additives that can be dissolved and/or
dispersed
into the matrix material as well as additive delivery systems and processes
using
such compositions, and which release one or more additives into a fluid.
BACKGROUND OF THE INVENTION
[0002] Functional fluids degrade over time through use. The additives in the
functional fluids deplete over the lifetime of the fluid in an engine or other
mechanical device. The ability to supply additives to a fluid over its
lifetime or use
may help preserve and even improve the performance of the functional fluid and
the
equipment in which it is used. Time release additives for engine oil are
known.
These additives are typically incorporated into thermoplastic polymers which
slowly
dissolve into the engine oil, see U.S. Patent 4,075,098. Time release
additives have
also been incorporated into polymers which are oil-permeable at elevated
engine
temperatures, see U.S. Patent 4,066,559.
[0003] Replenishment of additives in a functional fluid, by using a controlled
release gel or other means to add additional additive to the functional fluid,
improves the performance of the functional fluid and the device using the
functional
fluid. Use of controlled release gels, as described in U.S. Patent 6,843,916,
has been
shown to be an effective means to replenish a lubricant with fresh additives
over
time. Such gels are formed by incorporating additive components which are
compatible with the functional fluid to which the additive is to be delivered
into a
gel matrix. These gel matrixes often result from the interaction of a basic
component and an acidic component, forming the gel.
[0004] However, it would be beneficial to supply certain additives or groups
of
additives to a fluid at certain release rates while simultaneously supplying
certain
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
other additives or groups of additives to the same fluid, but at certain other
release
rates. It would also be beneficial to accomplish this independent, dual
delivery
while maintaining an integrated additive package and/or system.
SUMMARY OF THE INVENTION
[0005] The present invention provides compositions, processes and additive
delivery systems that address the problems described above. The present
invention
allow for the controlled release of multiple additives to a functional fluid
and also
allow for independent release rates for two or more additives and/or groups of
additives, thus allowing for more refined and beneficial fluid conditioning,
which in
turn provides lengthened fluid life and/or improved fluid performance.
[0006] The present invention provides a composition comprising: (a) a slow
release component that is made up of one or more performance additives in the
form
of a solid or semi-solid mass, wherein the additive components making up the
mass
are slowly released into a fluid; and (b) a fast release component that
contains (i) a
matrix material which is soluble in the fluid and (ii) one or more performance
additives that can be dissolved and/or dispersed into the matrix material. The
performance additives within the matrix material may be quickly released into
the
fluid; and the weight ratio of components (a):(b) may be 1:100 to 100:1.
[0007] The invention further provides that components (a) and (b) may each be
in the form of one or more distinct layers within the composition. One or more
layers each of (a) and (b) can be combined to form a controlled release
additive
composition, wherein the layers of (a) and (b) may be arranged such that
either
component (a) and/or (b) may form one or more external layers, internal
layers, or
interstitial layers of the controlled release additive composition.
[0008] The invention further provides a process of releasing, at controlled
rates,
one or more performance additives into a fluid, wherein each additive or group
of
additives is released at an independent rate; wherein at least one additive or
group of
additives is released slowly over time into the fluid; and wherein at least
one
additive or group of additives is released quickly into the fluid; wherein
process
includes the step of contacting the fluid with one or more of the compositions
described above.
2
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
[0009] The invention further provides an additive delivery system that
includes
one or more of the controlled release compositions described above and a means
of
contacting the composition with the fluid, resulting in the fast release of
one more
additives, and the slow release of one or more additives, into the fluid.
DETAILED DESCRIPTION OF THE INVENTION
[0010] Various preferred features and embodiments will be described below by
way of non-limiting illustration.
[0011] The present invention provides a performance additive controlled
release
composition that contains: (a) a slow release component and (b) a fast release
component. These two components may each be present in the composition in the
form of one or more distinct layers. One or more layers each of (a) and (b)
are
combined to form a controlled release additive composition. The layers of (a)
and (b)
may be arranged such that either component (a) and/or (b) may form one or more
external layers, internal layers, or interstitial layers of the controlled
release additive
package.
[0012] In some embodiments, component (b), the fast release component, forms
an exterior layer that completely encompasses component (a), the slow release
component, and/or forms a barrier between component (a) and the functional
fluid
with which the combination is used. In other embodiments, component (a) is
completely encompassed by component (b), in the same manner as described
above.
[0013] In some embodiments, components (a) and (b) are aligned and/or
positioned side by side or positioned such that one component partially
encompasses
the other. In such embodiments, some portions of both (a) and (b) are exposed
to
the functional fluid with which the combination is used.
[0014] The ratio of components (a):(b) can be from 1:100 to 100:1, or 1:10 to
10:1 or even 1:5 to 5:1. In some embodiments the ratio of components (a):(b)
is
from 100:1 or 90:10 or 80:20 to 40:60, or 50:50 or 60:40.
[0015] The release rate of an additive from the components described herein,
into the functional fluid with which they are used, is the rate at which one
or more of
additives that make up and/or are present in the component of the performance
additive controlled release composition is released from the component to the
3
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
functional fluid. The release rate is determined primarily by the formulation
of the
component and/or overall composition. The release rate is also dependent on
the
mode of addition of the performance additive controlled release composition,
the
physical orientation and arrangement of the components that make up the
composition, the location of the composition within the system that utilizes
the
functional fluid, the flow rate of the functional fluid in the system and
particularly in
the part of the system where the composition is located, and the form of the
components of the additive composition (e.g., stiffness, consistency,
homogeneity
and the like) and the like.
The Slow Release Component
[0016] The slow release component of the present invention may comprise one
or more performance additives and be in the form of a solid or a semi-solid
mass,
such as a gel. The additive components making up the slow release component
are
slowly released into the fluid with which it is used.
[0017] By slow release, it is meant that one or more of the additives in the
slow
release component are released into the functional fluid with which it is used
at a
rate slower than the release rate of the fast release component. In one
embodiment,
slow release means that no more than 80 wt% of component (a) is released into
the
functional fluid with which it is used over the first 50% or more of the
fluid's
service life. In other embodiments no more than 70, 80, 90, or even 95 wt% of
component (a) is released into the functional fluid over the first 50, 60, or
70% of
the fluid's service life. In other embodiments the amount of the fast release
component may be measured relative to the amount of slow release component
released or instead to the total amount of release of the additives in both
components.
In some of these embodiments, at the point where up to 60 wt% of the additives
to
be released from the overall composition have been released, no more than 40
wt%
of the additives to be released from the slow release component will have been
released. In some of these embodiments, at the point where up to 50 wt% of the
additives to be released from the overall composition have been released, no
more
than 31 wt% of the additives to be released from the slow release component
will
have been released.
4
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
[0018] A fluid's service life is the period during which a fluid is utilized
in the
application and/or equipment for which it has been designed. Service life may
be a
fluid's useful life, that is the period during which a fluid can effectively
perform its
designed function. Service life may be a preset period selected by a fluid's
manufacture and/or retailer or the manufacture and/or retailer of the
equipment in
which the fluid is utilized. Service life may be determined by monitoring the
fluid
involved, and using data collected from the fluid to determine when its
service life
will end or has ended. As an example, an engine's lubricating oil's service
life starts
when the oil is added to the engine and ends when the oil is changed. Service
life
may be measured by time, such as the amount of time since the fluid has been
added
to a piece of equipment and/or the amount of time the equipment has been
operated
since the fluid was added. Service life may be measured by units of distance,
as in
the case of a vehicle engine where the engine oil may be changed after so many
miles traveled. Service life may be measure by a number of operations, such as
a
piece of manufacturing equipment, where the fluid life is measured by the
number if
cycles completed and/or number of units produced.
[0019] Component (a), the slow release component, can be a performance
additive gel. Gels are materials that comprise mixtures of two or more
substances
and which exist in a semi-solid state more like a solid than a liquid. A gel
exists in a
semi-solid state more like a solid than a liquid, see Parker, Dictionary of
Scientific
and Technical Terms, Fifth Edition, McGraw Hill, 1994. See, also, Larson,
"The
Structure and rheology of Complex Fluids", Chapter 5, Oxford University Press,
New York, New York, 1999, each which is incorporated herein by reference.
The
rheological properties of a gel can be measured by small amplitude oscillatory
shear
testing. This technique measures the structural character of the gel and
produces a
term called the storage modulus which represents the storage of elastic energy
and
the loss modulus which represents the viscous dissipation of that energy. The
ratio
of the loss modulus/storage modulus, which is called the loss tangent, or "tan
delta",
is >1 for materials that are liquid-like and <1 for materials that are solid-
like. The
gels herein can have tan delta values of about < 1 or < 0.95, or about < 0.75,
or in
other embodiments of about < 0.5 or < 0.3.
5
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
[0020] Gel compositions can also be evaluated by using a cone penetrometer,
according to ASTM D 217. The cone penetrometer (cone pen) value obtained is
one
measurement of the stiffness and/or firmness of a gel. In one embodiment, the
additive gel compositions of the present invention have a cone pen value of
300 or
less, 200 or less, or from 30 to 200, or from 40 to 165.
[0021] Gel compositions suitable for use in the present invention are
typically
made by blending of a mixture of additives selected to simultaneously provide
the
desired performance and to form a gel upon mixing or mixing with subsequent
thermal curing. In some embodiments, the gel composition is formed by
combining
at least two components selected from the group consisting of. detergents,
dispersants, acids, bases, over based detergent, and succinated polyolefins.
The
components are selected, and combined in specific ratios, so that when
combined,
they form a gel.
[0022] The gel's formulation may be composed of. (i) a basic component
comprising an overbased detergent, an ashless dispersant, or mixtures thereof;
(ii) an
acidic component comprising a maleic anhydride styrene-copolymer or an ester
thereof, an ashless dispersant, polyolefin, succinated polyolefin or mixtures
thereof;
(iii) an additive component which is substantially insoluble in, has low
solubility in,
or is otherwise incompatible with a functional fluid, as described above and
referred
to as an "incompatible additive" herein; and (d) optionally at least one
additive
comprising one or more viscosity modifiers, friction modifiers, detergents,
cloud
point depressants, pour point depressants, demulsifiers, flow improvers,
antistatic
agents, dispersants, antioxidants, antifoams, corrosion/rust inhibitors,
extreme
pressure/antiwear agents, seal swell agents, lubricity aids, antimisting
agents, or
combinations thereof.
[0023] The basic component can be an overbased detergent, an ashless
dispersant with a total base number (TBN) greater than 13, or mixtures
thereof.
[0024] Dispersants suitable for use in the basic component include ashless
dispersants such as a polyisobutylene succinimide and the like so long as the
dispersant has a total base number (TBN) greater than 13. Polyisobutylene
succinimide ashless dispersants are commercially-available products which are
typically made by reacting together polyisobutylene having a number average
6
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
molecular weight ("Mn") of about 300 to 10,000 with maleic anhydride to form
polyisobutylene succinic anhydride ("PIBSA") and then reacting the product so
obtained with a polyamine typically ethylene polyamines containing 2 to 10
nitrogen
atoms per molecule.
[0025] Detergents suitable for use in the basic component include overbased
sulfonates, phenates, salicylates, carboxylates, overbased calcium sulfonate
detergents which are commercially-available, overbased detergents containing
metals such as Mg, Ba, Sr, Na, Ca and K and mixtures thereof and the like.
[0026] The basic component may further comprise copolymers such as ethylene-
propylene diene monomer (EPDM) copolymer. Suitable ethylene-propylene diene
monomer (EPDM) copolymers include those with a number average molecular
weight between 1x102 and 1x109. In one embodiment the basic component
comprises a copolymer, an overbased detergent, or a combination thereof. In
one
embodiment the copolymer comprises an ethylene-propylene diene monomer
(EPDM) copolymer. In another embodiment the overbased detergent comprises an
overbased calcium alkylbenzenesulfonate detergent. In yet another embodiment
the
EPDM copolymer and the overbased calcium alkylbenzenesulfonate detergent are
used in combination with one another.
[0027] The basic component may be present in ranges such that the weight ratio
of the basic component to the acidic component is, in one embodiment, 0.01 to
0.99:1, and in another embodiment 0.05 to 0.2:1. This corresponds to a range
of
about 1% by weight to about 100% by weight in one embodiment for the combined
basic and acidic components in the gel, and a range of about 1% by weight to
about
50% by weight in another embodiment. As to the basic component alone, the gel
may be, in one embodiment, about 0.1 % by weight to about 80% by weight basic
component and in another embodiment, about 0.5% by weight to about 70% by
weight basic component. In still other embodiments, the basic component is
present
in the gel from 0.5% by weight to 60% by weight, from 30 to 60 % by weight,
from
40 to 60 % by weight, from 50 to 60 % by weight, or from 55 to 58% by weight.
[0028] The acidic component of the gel may comprise a functionalized polymer
with an acidic group, an ashless dispersant, a polyolefin, a succinated
polyolefin or
mixtures thereof.
7
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
[0029] Functionalized polymers useful in the present invention include olefin
copolymers and acrylate or methacrylate copolymers. Functionalized olefin
copolymers can be, for instance, interpolymers of ethylene and propylene which
are
grafted with an active monomer such as maleic anhydride and then derivatized
with
an alcohol or an amine. Other such copolymers are copolymers of ethylene and
propylene which are reacted or grafted with nitrogen compounds. Derivatives of
polyacrylate esters are well known as dispersant viscosity index modifiers
additives.
Dispersant acrylate or polymethacrylate viscosity modifiers such as AcryloidTM
985
or ViscoplexTM 6-054, from RohMax, are particularly useful. Solid, oil-soluble
polymers such as polyisobutylene, methacrylate, polyalkylstyrene,
ethylene/propylene and ethylene/propylene/1,4-hexadiene polymers, can also be
used as viscosity index improvers.
[0030] In one embodiment, the acidic component of the present invention
comprises maleic anhydride styrene copolymer (MSC) and may further comprises
an ashless dispersant.
[0031] The maleic anhydride styrene copolymer may be partially esterified with
an alcohol where the equivalent ratio of alcohol to acid groups is in one
embodiment
from about 0.1 to about 0.99 and in another embodiment from 0.45 to 0.95.
Appropriate alcohols for use in preparing the copolymer include alcohols
containing
6 to 32 carbon atoms, and in another embodiment, alcohols containing 8 to 18
carbon atoms. Suitable maleic anhydride styrene copolymers comprise those with
a
total acid number (TAN), in one embodiment, greater than 1, and in another
embodiment greater than 3 where TAN is in the units of milligrams of KOH per
gram of material.
[0032] The ashless dispersants suitable for use in the acidic component are
the
same as the dispersants described above in regards to the basic component
except
that suitable ashless dispersants for use in the acidic component have a
measurable
total acid number (TAN). In some embodiments suitable dispersants have a TAN
greater than 15. In one embodiment, the acidic component comprises a
polyisobutylene succinimide dispersant.
[0033] The acidic component may be present in ranges such that the weight
ratio
of the basic component to the acidic component is typically 0.01 to 0.99, and
more
8
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
typically 0.05 to 0.2. This corresponds to a range of about 1% by weight to
about
100% by weight in one embodiment for the combined basic and acidic components
in the gel, and a range of about 1% by weight to about 50% by weight in
another
embodiment. As to the acidic component alone, the gel may be, in one
embodiment,
about 0.5% by weight to about 99% by weight acidic component and in another
embodiment, about 0.5% by weight to about 98% by weight acidic component. In
other embodiment the acidic component may be present in the gel from 0.1 % to
40%
by weight, from 0.1 % to 20 % by weight, from 0.1 % to 10% by weight, or from
5 to
10% by weight.
[0034] The gel compositions of the present invention may contain at least one
additional desired additive for controlled release into the functional fluid.
These
optional gel component additives include viscosity modifier(s), friction
modifier(s),
detergent(s), cloud point depressant(s), pour point depressant(s),
demulsifier(s), flow
improver(s), anti static agent(s), dispersant(s), antioxidant(s), antifoam(s),
corrosion/rust inhibitor(s), extreme pressure/antiwear agent(s), seal swell
agent(s),
lubricity aid(s), antimisting agent(s), and mixtures thereof with the proviso
that these
additional additives are not the same as the additives present in any of the
other
components in the gel composition, though they may be the same type of
additive,
and they may be the same as additives that are already present in the
functional fluid
with which the gel composition is used. The presence of one or more of these
optional additives results in a controlled release gel that over time releases
the
desired additive(s) into a functional fluid when the gel is contacted with the
functional fluid. The desired additive component is further determined by the
functional fluid formulation, performance characteristics, function and the
like and
what additive is desired to be added for depleted additives and/or added new
depending on the desired functions.
[0035] The optional additive component comprising one or more desired
additives for controlled release, when present, is present in ranges such that
the
weight ratio of the optional additive component to the combined total of gel
components is in one embodiment 0.001 to 0.99, and in another embodiment 0.01
to
0.5. This corresponds to a range of about 0% by weight to about 99% by weight
in
one embodiment of the optional additive component in the gel and a range of
about
9
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
1% by weight to about 50% by weight in another embodiment. In other
embodiments the optional additive component is present in the gel from 0 to
40% by
weight, from 0 to 30% by weight, from 0 to 25 % by weight, from 0 to 20% by
weight, from 0 to 20 % by weight, from 15 to 30 % by weight, and from 15 to
25%
by weight.
[0036] Suitable antioxidants include, but are not limited to aromatic amines,
alkyl-substituted phenols, sterically hindered phenols (such as 2,6-di-tert-
butylphenol), and hindered ester-substituted phenols.
[0037] Suitable extreme pressure/anti-wear agents include sulfur and/or
chlorosulphur EP agents, chlorinated hydrocarbon EP agents, phosphorus EP
agents,
or mixtures thereof.
[0038] Suitable antifoams include organic silicones such as polydimethyl
siloxane, polyethylsiloxane, polydiethylsiloxane, polyacrylates and
polymethacrylates, trimethyl-triflouro-propylmethyl siloxane and the like.
[0039] Suitable viscosity modifiers include vinyl pyridine, N-vinyl-2-
pyrrolidone and N,N'-dimethylaminoethyl methacrylate as well as polyacrylates
obtained from the polymerization of one or more alkyl acrylates.
[0040] Suitable friction modifiers include organo-molybdenum compounds,
including molybdenum dithiocarbamate, and fatty acid based materials,
including
those based on oleic acid (such as glycerol mono oleate) and stearic acid and
hydroxy acids such as tartaric acid, malic acid and citric acid. Examples of
this last
type include hydroxy acid derived esters and imides having a hydrocarbon group
containing from 8 to 20 carbon atoms.
[0041] Suitable anti-misting agents include very high (>100,000Mn) polyolefins
such as 1.5 Mn polyisobutylene (for example the material of the trades name
Vistanex ), or polymers of 2-(N-acrylamido)-2-methyl propane sulfonic acid
(also
known as AMPS), or derivatives thereof, and the like.
[0042] Suitable corrosion inhibitors include alkylated succinic acids and
anhydrides derivatives thereof, organo phosphonates and the like. The rust
inhibitors may be used alone or in combination.
[0043] Suitable metal deactivators include derivatives of benzotriazoles (such
as
tolyltriazole and the like). Suitable demulsifiers include polyethylene oxide
and
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
polypropylene oxide copolymers and the like. Suitable lubricity aids include
glycerol monooleate, sorbitan monooleate and the like. Suitable flow improvers
include ethylene vinyl acetate copolymers and the like. Suitable cloud point
depressants include alkylphenols, and specifically waxy coupled alkylphenols,
and
derivatives thereof, ethylene vinyl acetate copolymers and the like. Suitable
pour
point depressants include alkylphenols and derivatives thereof, ethylene vinyl
acetate copolymers and the like. Suitable seal swell agents include organo
sulfur
compounds such as thiophene derivatives, 3-(decyloxy)tetrahydro- 1, 1 -dioxide
(i.e.
3-decyloxysulfolane) and the like.
[0044] In some embodiments the optional additive component may comprise
dispersants and detergents such as those above. In addition, the optional
additive
component may also comprise additional types of dispersants. These additional
types of dispersants include Mannich dispersants, carboxylic dispersants,
amine
dispersants, and polymeric dispersants.
[0045] The Mannich dispersant are the reaction products of alkyl phenols in
which the alkyl group contains at least about 30 carbon atoms with aldehydes
(especially formaldehyde) and amines (especially polyalkylene polyamines).
[0046] Another class of dispersants is carboxylic dispersants. Examples of
these
"carboxylic dispersants" are described in Patent U.S. Patents 3,219,666 and
3,172,892.
[0047] Amine dispersants are reaction products of relatively high molecular
weight aliphatic halides and amines, preferably polyalkylene polyamines.
Examples
thereof are described, in U.S. Patent 3,565,804.
[0048] Polymeric dispersants are interpolymers of oil-solubilizing monomers
such as decyl methacrylate, vinyl decyl ether and high molecular weight
olefins with
monomers containing polar substituents, e.g., amino alkyl acrylates or
acylamides
and poly-(oxyethylene)-substituted acrylates. Examples of polymer dispersants
thereof are disclosed in the following U.S. Patents 3,329,658, and 3,702,300.
[0049] Dispersants can also be post-treated by reaction with any of a variety
of
agents. Among these are urea, thiourea, dimercaptothiadiazoles, carbon
disulfide,
aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic
anhydrides,
nitrites, epoxides, boron compounds, and phosphorus compounds.
11
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
[0050] Optionally, other components can be added to the additive gel which
includes base stock oils, inert carriers, dyes, bacteriostatic agents, solid
particulate
additives, and the like so long as the free standing additive gel is
maintained.
[0051] In some embodiments the gels of the present invention are free from
thermoplastic polymers. In such embodiments the gels of the present invention
may
be substantially free of thermoplastic polymers or completely free of
thermoplastic
polymers.
[0052] In one embodiment, the gel composition used as the slow release
component of the present invention is prepared by mixing a detergent, (which
may
be a sulfonate, phenate, salicylate carboxylate or mixtures thereof) with a
dispersant,
(which may be a N-substituted long chain alkenyl succinimide, polyisobutylene
succinimide, high molecular weight ester, Mannich base, amine dispersant,
polymeric dispersant or mixtures thereof) and/or an acid, (which may be a
polymer
containing acidic groups in the backbone, a polyacidic compound, or mixtures
thereof).
[0053] Component (a), the slow release component, can be a solid. The solid
can be a material that (i) has a melting point from 40 to 250 C, 50 to 150 C
or even
60 to 120 . The solid can be a material that (ii) is at least partially
soluble in the
fluid with which the overall composition is used. The solid can be a material
that (iii)
is formed by mixing of one or more additives, such additives may include
viscosity
modifiers, friction modifiers, ashless detergents, cloud point depressants,
pour point
depressants, demulsifiers, flow improvers, anti static agents, ashless
dispersants,
ashless antioxidants, antifoams, corrosion/rust inhibitors, extreme
pressure/antiwear
agents, wear reducing agents, seal swell agents, lubricity aids, antimisting
agents and
mixtures thereof. The solid may possess one or more of the characteristics
(i), (ii)
and (iii) described above.
[0054] When the slow release component is contacted with a functional fluid,
the additives that make up the slow release component, including the additives
described above as well as the additional additives provided for below, are
released
into the fluid at a slow rate, as defined above.
[0055] Component (a), the slow release component, may be more than 70 wt%
dispersant and detergent and/or may be more than 45 wt% detergent.
12
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
[0056] Both component (a), the slow release component described above, and
component (b), the fast release component described below, may further contain
one
or more additional performance additives. Suitable additives include viscosity
modifiers, friction modifiers, ashless detergents, cloud point depressants,
pour point
depressants, demulsifiers, flow improvers, antistatic agents, ashless
dispersants,
ashless antioxidants, antifoams, corrosion/rust inhibitors, extreme
pressure/antiwear
agents, wear reducing agents, seal swell agents, lubricity aids, antimisting
agents and
mixtures thereof. These additional additives may not participate in forming
the gel
and/or matrix materials described herein, but may instead be present in the
compositions without any such interaction.
The Fast Release Component
[0057] The fast release component of the present invention may comprise (i) a
matrix material which can be soluble in the functional fluid with which it is
to be
used and (ii) one or more additives that can be dissolved and/or dispersed
into the
matrix material. The additives present in the fast release component are
quickly
released into the fluid with which it is used.
[0058] By fast release, it is meant that one or more of the additives present
in the
fast release component are released into the functional fluid with which it is
used at
a rate faster than the release rate of the slow release component. In one
embodiment,
fast release means that at least 80 wt% of component (b) is released into the
functional fluid with which it is used over the first 25% or less of the
fluid's service
life. In other embodiments at least 80, 90, 95 or even 100 wt% of component
(a) is
released into the functional fluid over the first 25, 20, or 10% of the
fluid's service
life. The service life of a fluid is defined above.
[0059] The matrix material can be a solid, as described above, including waxy
materials with melting points just above, or just below, or about at the
operating
temperature of the functional fluid with which it is used. With regards to the
matrix
material of the fast release component, the term soluble means that the matrix
materials can fully dissolve into the functional fluid in which the overall
composition is used, however such dissolution may not occur immediately, but
rather over an extended period of time, even longer than the time during which
the
additives described above are releases into the fluid. In some embodiments the
13
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
matrix material is a solid at ambient conditions but melts to a liquid at the
conditions
present in the functional fluid during the fluids use, resulting in the matrix
material
melting. In such embodiments the melted matrix material is fully soluble in
the
functional fluid and would mix into it immediately.
[0060] The additives which may be dispersed into the matrix material include
glycerol esters, borated glycerol esters, fatty phosphites, fatty acid amines,
fatty
epoxides, borated fatty epoxides, alkoxylated fatty amines, borated
alkoxylated fatty
amines, metal salts of fatty acids, sulfurized olefins, fatty imidazolines,
condensation
products of carboxylic acids and polyalkylene-polyamines, amine salts of
alkylphosphoric acids, molybdenum-containing friction modifiers, friction
modifiers
derived from hydroxy acids such as tartaric acid, malic acid and citric acid,
or
combinations thereof, so long as the additives are different from the matrix
material.
When the fast release component is contacted with a functional fluid, these
additives
are released from the matrix material into the fluid at a fast rate, as
defined above.
Processes and Additive Deliver y stems
[0061] The present invention provides a process by which two or more additives
or groups of additives are effectively delivered to a functional fluid at two
or more
independent release rates. The method of the present invention comprises the
use of
an additive composition which contains one or more each of the slow release
and
fast release components described above, and the contacting of the functional
fluid
and the additive composition, resulting in the delivery of the additives to
the
functional fluid at the different rates
[0062] The present invention may be utilized in any fluid conditioning device
or
system including internal combustion engines which include mobile and
stationary
applications; hydraulic systems; automatic transmissions; gear boxes which
include
manual transmissions and differentials; metalworking fluids; pumps; suspension
systems; other lubricated mechanical systems; and the like. The fluid
conditioning
devices that can use the gel include, internal combustion engines, stationary
engines,
generators, diesel and/or gasoline engines, on highway and/or off highway
engines,
two-cycle engines, aviation engines, piston engines, marine engines, railroad
engines,
biodegradable fuel engines and the like; lubricated mechanical systems such as
gear
boxes, automatic transmissions, differentials, hydraulic systems and the like.
In
14
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
some embodiments, the present invention may be used with aqueous or organic
functional fluids. In other embodiments the present invention is used to
deliver
additives to organic functional fluids only.
[0063] The functional fluids useful to being further additized through the
methods and gel compositions of the present invention include gear oil,
transmission
oil, hydraulic fluid, engine oil, two cycle oil, metalworking fluid and the
like. In one
embodiment the preferred functional fluid is an engine oil. In another
embodiment
the preferred functional fluid is gear oil. In another embodiment the
preferred
functional fluid is transmission fluid. In another embodiment the preferred
functional fluid is a hydraulic fluid.
[0064] The additive compositions dissolve into and/or supply the additives
contained within the slow and fast release components to a functional fluid
through
the contacting of the additive compositions with the functional fluid. The
additive
composition may be positioned anywhere in a system or piece of equipment where
the additive composition will be in contact with the functional fluid. In one
embodiment, the additive composition is positioned anywhere within a piece of
equipment through which a functional fluid circulates and where the functional
fluid
may contact the additive composition.
[0065] In one embodiment the functional fluid is an engine oil and the
additive
composition is positioned in the engine oil system which can include any of
the
following: the lubricating system, filter, drain pan, oil bypass loop,
canister, housing,
reservoir, pockets of a filter, canister in a filter, mesh in a filter,
canister in a bypass
system, mesh in a bypass system, oil lines and the like. In one embodiment the
functional fluid is a gear oil and the additive composition is located in the
gear
system which can include any of the following: drain pan, sump, filters, a
full flow
or bypass oil line, lines, loop and/or filter, canisters, mesh, other spaces
within the
device in which a additive composition might be contained and the like. In one
embodiment the functional fluid is transmission fluid and the additive
composition
is located in the transmission system which can include any of the following:
the
space such as a hole within a transmission magnet, the oil pan, oil lines,
lines,
canisters, mesh and the like. In one embodiment the additive composition is
located
in the engine oil line, which can include any of the following: a full flow
filter, a by-
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
pass filter, the oil pan, and the like. In one embodiment, the functional
fluid is a
hydraulic fluid and the additive composition is located in the hydraulic
cylinder,
sump, filter, oil lines, pan, full flow or by pass oil loop, line and/or
filter, canister,
mesh, other spaces in the system and the like.
[0066] One or more locations in a line, loop and/or the functional fluid
system
can contain the additive composition. Further, if more than one additive
composition is used each, each additive composition can be an identical,
similar
and/or a different additive composition than the other additive compositions
used.
[0067] In some embodiments the invention provides a container to hold the
additive composition, such as a housing, a canister or a structural mesh
anywhere in
the functional fluid system, for example, a canister within a bypass loop of a
stationary gas engine for power generation. The necessary design feature for
the
container is that at least a portion of the additive composition is in contact
with the
functional fluid. In other embodiments, the additive composition is used
without
such a container. In still other embodiments the additive composition is
tethered,
anchored, or otherwise fixed to a position within the fluid system in which
the
functional fluid is used and so in this way is not contained within a additive
composition cup or similar container.
[0068] In some embodiments, the additive composition itself is considered to
be
the delivery device that enables the delivery of the substantially insoluble
or low
solubility additive to the functional fluid. In other embodiments the
container in
which the additive composition is located is considered to be the delivery
device. In
still other embodiments, the delivery device is considered to be a device,
such as a
filter, in which the additive composition, which may or may not be located
within a
container, is located. The primary feature of the delivery device, across all
of the
embodiments described, is its ability to allow for, and in some embodiments to
facilitate and/or control, the contacting of the functional fluid and the
additive
composition.
[0069] The additive composition needs to be in contact with the functional
fluid.
In one embodiment the additive composition is in contact with the functional
fluid in
the range of about 100% to about 1% of the functional fluid in the system, in
that 1
to 100% of the functional fluid comes into physical contact with the additive
16
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
composition during the fluid's use. In other embodiments the additives is
exposed
to 1 to 100% of the flow of the functional fluid in the system. Generally
speaking,
as the flow rate of the functional fluid as it contacts the additive
composition
decreases there is less dissolution of the additive composition into the
fluid, and as
the flow rate increases there is greater dissolution of the additive
composition.
[0070] In one embodiment, the additive composition is positioned in the
functional fluid system so that the additive composition and/or spent additive
composition can easily be removed from the functional fluid system, and then
replaced with a new and/or recycled additive composition. In some embodiments
the additive composition is contained in a cartridge or similar device,
facilitating
such removal and replacement.
[0071] The additive composition of the present invention may comprise a free
standing gel or a non-free standing gel. A free standing gel can be used
without
being contained inside a form that holds the gel's shape and dimensions. A non-
free
standing gel is prepared in a container from which the gel cannot be removed
intact.
The gel and its forming device both become part of any functional fluid
conditioning
device the gel is used in. A free standing gel, once formed, can be removed
intact
from its forming device and can be placed or built into a functional fluid
conditioning device without the need of integrating the forming device into
the
functional fluid conditioning device. In some embodiments the free standing
gel can
be placed into a conditioning device, or otherwise used, without any container
at all.
This provides the opportunity to design the gel forming or curing container
separately from the fluid conditioning device, reducing manufacturing costs of
the
gel and the conditioning devices. In some embodiments, considered alone or in
combination with one or more of the embodiments provided both above and below,
the free standing gels of the present invention are brought into contact with
a
functional fluid without the presence of a container or holding device
surrounding or
otherwise containing the gel, or if any type of container or holder is used
with the
gel, no side wall or similar structure is present.
[0072] The additive delivery systems of the present invention utilize the
processes and compositions described above and may be integrated into the
functional fluid utilizing equipment described above. The additive delivery
systems
17
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
of the present invention may be integrated into a device's functional fluid
system,
for example, the additive delivery system may be an insert and/or form that is
placed
in the lubricant system or fuel system of an internal combustion engine. In
some
embodiments, the additive composition is contained within a fluid filter and
one or
more of the additives that make up the composition are releases into the fluid
as it
passes through the fluid filter and with a device that utilizes said fluid,
with additives
contained in the slow release component being released slowly and additives in
the
fast release component being released more quickly.
[0073] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl
group" is used in its ordinary sense, which is well-known to those skilled in
the art.
Specifically, it refers to a group having a carbon atom directly attached to
the
remainder of the molecule and having predominantly hydrocarbon character.
Examples of hydrocarbyl groups include: hydrocarbon substituents, 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); substituted
hydrocarbon
substituents, that is, substituents containing non-hydrocarbon groups which,
in the
context of this invention, do not alter the predominantly hydrocarbon nature
of the
substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy,
mercapto,
alkylmercapto, nitro, nitroso, and sulfoxy); 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. Heteroatoms include sulfur, 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.
[0074] It is known that some of the materials described above may interact in
the
final formulation, so that the components of the final formulation may be
different
from those that are initially added. For instance, metal ions (of, e.g., a
detergent)
can migrate to other acidic or anionic sites of other molecules. The products
formed
18
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
thereby, including the products formed upon employing the composition of the
present invention in its intended use, may not be susceptible of easy
description.
Nevertheless, all such modifications and reaction products are included within
the
scope of the present invention; the present invention encompasses the
composition
prepared by admixing the components described above.
SPECIFIC EMBODIMENTS
[0075] The invention will be further illustrated by the following examples,
which sets forth particularly advantageous embodiments. While the examples are
provided to illustrate the present invention, they are not intended to limit
it.
Example 1- The Additive Composition
[0076] A composition designed to release multiple friction modifiers, a
corrosion inhibitor, and an antioxidant at a fast release rate while
simultaneously
releasing friction modifiers, dispersants, and a detergent at a slow release
rate, to an
engine oil during the operation of an internal combustion engine is described
below.
[0077] A fast release component is prepared by mixing a boron-containing
corrosion inhibitor (2.9 grams), an ashless amide-containing friction modifier
(12.9
grams), a molybdenum-containing friction modifier (2.3 grams), an ashless
fatty
acid derived friction modifier (5.7 grams), and a hindered phenol antioxidant
(4.6
grams). The additives are mixed at 100 C for 12 hours.
[0078] A slow release component is prepared by mixing an ashless fatty acid
derived friction modifier (4.8 grams), an overbased calcium sulfonate
detergent
(25.4 grams, which is 42%wt oil), a polyisobutylene succinimide dispersant
derived
from 2000 number average molecular weight polyisobutylene (8.3 grams, which is
47%wt oil), a molybdenum-containing friction modifier (1.9 grams), and a
polyisobutylene succinic anhydride dispersant derived from 2000 number average
molecular weight polyisobutylene (6.6 grams). All of the components, except
for
the detergent, are mixed at 55 C. The mixture and the detergent are then
combined,
with stirring, into a cylindrical cup having a diameter of 6.35 cm (2.5 inch)
and a
height of 3.8 cm (1.5 inches). The cup, containing the resulting mixture, is
placed in
an oven at 100 C fir 12 hours. During this hold, the mixture forms a gel.
19
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
[0079] Once the slow release component has formed a gel, the fast release
component, still at 100 C, is added to the cylinder, pouring it on top of the
slow
release component already present in the cylinder. The material is allowed to
cool,
forming a solid layer in the cylinder, completely covering the slow release
component below it. A lid is placed on the cylinder, where the lid has
multiple 2
mm holes. The steps are repeated and the resulting containers are used in
Examples
2 and 3.
Example 2
[0080] A filled container of Example 1 is placed at the crown end (opposite of
the engine interfacing end) of an oil filter, the filter being of the same
size and
fittings as a FramTM PH4967 oil filter, as described in United States Patent
6,843,916. The filter is installed on a 2.2 L, 4-cynlinder 1997 Toyota CamryTM
The case is then driven under normal stop-and-go and highway conditions for
7163
km (4451 miles), with oil samples taken at regular intervals. The elemental
composition (amount of Mo and Ca present in the oil) is measured by
inductively
couple plasma and then used to calculate the amount of Ca and Mo released from
the
composition in the container to the oil. The coefficient of friction (COF) of
the oil is
also measured. The results are shown in the table below.
Table 1
%Ca %Mo %Mo
KMs COF
Released in Oil Released
0 0% 0.0001% 1 % 0.140
2 1% 0.0042% 36%
243 6% 0.0048% 42%
396 7% 0.0048% 42% 0.127
644 15% 0.0050% 46% 0.120
1127 31% 0.0058% 53% 0.122
1487 40% 0.0068% 60% 0.129
1984 52% 0.0099% 64% 0.129
2723 59% 0.0095% 67% 0.129
3520 63% 0.0079% 70% 0.129
4477 71% 0.0080% 72% 0.134
5398 78% 0.0079% 73% 0.131
7163 0.0080% 77% 0.136
END' 82% 92%
1- The End of Test Sample was taken from the oil after it was drained from the
engine
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
[0081] The results show that the Mo-containing additive, the majority of which
was present in the fast release component, is released into the oil more
quickly than
the Ca-containing additive, which is only present in the slow release
component.
The data shows that more than 50% of the Mo-containing additive had been
released
into the oil by the 1127 km mark (after roughly 16% of the test period), while
less
than a third of the Ca-containing additive had been released. The results show
that
the Mo content in the engine oil increases sharply at the beginning of the
test,
indicating a fast release of the additive from the fast release component and
then a
slow increase over time, as the Mo-containing additive is released from the
slow
release component. The results also show that the COF decreased significantly
at
the start of the test and then stabilized during before beginning to increase
at the end,
indicating the friction modifiers in the fast release component were being
released
into the oil.
Example 3
[0082] The test procedure of Example 2 is repeated except that the vehicle was
driven under similar conditions for 2863 km (1779 miles). The results are
shown in
the table below.
Table 2
%Ca %Mo %Mo
KMs Released in Oil Released COF
0 0% 0.0001% 0% 0.132
161 12% 0.0065% 55% 0.122
435 26% 0.0067% 58% 0.129
901 34% 0.0077% 66% 0.133
1690 41% 0.0087% 74% 0.132
2504 57% 0.0094% 81% 0.132
2863 63% 0.0096% 84% 0.135
[0083] The results here again show that the Mo-containing additive, the
majority
of which was present in the fast release component, is released into the oil
more
quickly than the Ca-containing additive, which is only present in the slow
release
component. The data shows that about 75% of the Mo-containing additive had
been
released into the oil by the 1690 km mark (after roughly 60% of the test
period),
while about 40% of the Ca-containing additive had been released. The results
show
that the Mo content in the engine oil increases sharply at the beginning of
the test,
21
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
indicating a fast release of the additive from the fast release component and
then a
slow increase over time, as the Mo-containing additive is released from the
slow
release component. The results also show that the COF decreased significantly
at
the start of the test and then stabilized during before beginning to increase
at the end,
indicating the friction modifiers in the fast release component were being
released
into the oil.
Comparative Example 4
[0084] The test procedure of Example 2 is repeated except that the oil filter
used
does not have a container from Example 1 present. Instead 35 grams of the same
Mo-containing friction modifier as that used in the composition of Example 1
is
added as a top-treat to the engine oil in the crankcase. The vehicle was then
driven
under similar conditions for 5757 km (3577 miles). The results are shown in
the
table below.
Table 3
Mo
Ids in Oil COF
0 0.0106% 0.121
109 0.0103% 0.120
402 0.0100% 0.124
1164 0.0106% 0.126
1687 0.0103% 0.126
3158 0.0102% 0.133
4960 0.0100% 0.134
5757 0.0108%
[0085] The results of the comparative example show that when the Mo-
containing friction modifier is added as a top treat material, the Mo content
in the oil
stays constant over the duration of the test. This show that the increase in
Mo
content seen in Examples 2 and 3 is from the controlled release of the Mo-
containing friction modifier from the additive composition to the engine oil.
In
addition, the results show that the COF of the oil starts at a low value and
then
slowly climbs over the course of the test. This is in contrast to Examples 2
and 3,
where the controlled release of the additive results in a reduction in the COF
in the
early part of the test, and then maintains the COF at a low level until the
very end of
the test. It is also important to note that 35 grams of the Mo-containing
friction
22
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
modifier was added to engine in order to see this impact on COF, while only
4.2
grams is present in the additive composition used to achieve comparable and/or
improved results.
[0086] Although only a few embodiments of the present invention have been
described above, it should be appreciated that many modifications can be made
without departing from the spirit and scope of the invention. All such
modifications
are intended to be included within the scope of the present invention, which
is to be
limited only by the following claims.
[0087] 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 indicates all
percent
values and ppm values herein are weight percent values and/or calculated on a
weight basis. 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,
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 can be used together with ranges or amounts for
any
of the other elements. As used herein, the expression "consisting essentially
of'
permits the inclusion of substances that do not materially affect the basic
and novel
characteristics of the composition under consideration.
[0088] In addition, all the embodiments described above have been
contemplated as to their use, both alone and in combination, with all of the
other
embodiments described above, and these combinations are considered to be part
of
the present invention. The specific embodiments of amines and alcohols
described
23
CA 02769723 2012-01-31
WO 2011/017186 PCT/US2010/043664
above have been contemplated in combination with the specific embodiments of
the
carboxylic acids useful in the present invention.
24
