Field of the Disclosure
[0001] The present disclosure relates to release additive composition comprising at least
one dispersant viscosity index improver present in a form chosen from a solid and
a semi-solid.
Background of the Disclosure
[0002] Internal combustion engines, in particular diesel fueled engines, generate carbonaceous
soot particles. During combustion, the fuel is injected into the combustion chamber
in the form of small droplets. Soot particles form from incompletely combusted fuel
droplets and can be present on the cylinders and the rings. As the pistons move up
and down in the chamber, the soot particles migrate into the lubricating oil system
of the pistons, rings, through the cylinder and ultimately into the oil reservoir.
Soot may also enter the oil from the EGR system. Accordingly, the soot in the engine
oil can contribute to problems with engine lubrication.
[0003] Soot can also be a problem in modern gasoline engines with direct fuel injection
systems. The fuel injection system has been designed to produce less emissions and
increased power, but has increased the formation of soot in the lubricating oil of
the engine. It further requires more frequent oil change intervals to prevent the
concentration of soot particles in the oil from exceeding acceptable limits.
[0004] The suspended soot particles in the lubricating oil can have the effect of increasing
the viscosity and creating wear particles. Accordingly, soot acts like an abrasive
and induces wear in the engine parts. A lubricant composition that comprises a dispersant
that is slowly released over the life of the lubricant composition can effect at least
one of the following properties, such as minimizing the abrasive soot related wear
on an engine, and improving the drain interval of engine oil.
SUMMARY OF THE DISCLOSURE
[0005] In accordance with the disclosure, there is provided a release additive composition
comprising at least one dispersant viscosity index improver present in a form chosen
from a solid and a semi-solid; a lubricant composition comprising a major amount of
a base oil, and a minor amount of a release additive composition comprising at least
one dispersant viscosity index improver present in a form chosen from a solid and
a semi-solid; and a method for improving the drain interval of engine oil comprising
adding to a lubrication system a release additive composition comprising at least
one dispersant viscosity index improver present in a form chosen from a solid and
a semi-solid.
[0006] Additional objects and advantages of the disclosure will be set forth in part in
the description which follows, and can be learned by practice of the disclosure. The
objects and advantages of the disclosure will be realized and attained by means of
the elements and combinations particularly pointed out in the appended claims.
[0007] It is to be understood that both the foregoing general description and the following
detailed description are exemplary and explanatory only and are not restrictive of
the disclosure, as claimed.
DESCRIPTION OF THE EMBODIMENTS
[0008] The engines that can use the release additive composition include, but are not limited
to internal combustion engines, stationary engines, generators, diesel and/or gasoline
engines, on highway and/or off highway engines, two stroke and four stroke cycle engines,
aviation engines, piston engines, marine engines, railroad engines, biodegradable
fuel engines and the like. In one embodiment, the engine can be equipped with after-treatment
devices, such as exhaust gas recirculation systems, catalytic converters, diesel particulate
filters, NO
x traps, and the like.
[0009] In accordance with the present disclosure, the level and agglomeration of soot in
engine oil can be decreased by using the release additive composition thereby effecting
at least one of the following properties: reducing deposit formation and soot agglomeration,
increasing the maintenance time interval on a vehicle, and extending the engine life.
Moreover, the soot level can be reduced by contact of the lubricating composition
with the release additive composition. It is believed, without being limited to any
particular theory, that the use of the disclosed release additive composition can
achieve at least one of the above disclosed properties because the disclosed dispersant
viscosity index improver will be slowly released into the lubricating composition
and will be present over the life of the lubricating composition. One of ordinary
skill in the art would understand that the life of the lubricating composition is
dependent upon several factors including, but not limited to, engine operation, engine
type, engine service, mileage of the vehicle, quality of the base oil in the lubricating
composition, etc.
[0010] The term "release" as used herein is understood to mean that the components of the
additive composition are released over an extended period of time, e.g., over the
life of the lubricating composition. The release rate can be moderated by several
factors, such as, the location of the additive composition in the lubrication system,
the additive composition formulation, the form of the composition, and/or the mode
of addition of the additive composition into a lubricating composition. One of ordinary
skill in the art can modify any and/or all of the above factors in order to obtain
the desired release rate of the additive composition.
[0011] The release additive composition can be located anywhere within a lubrication system
so long as the additive composition will be in contact with a lubricating composition.
For example, the release additive composition can be located in at least one of a
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, and the like. In an embodiment, the lubrication system can comprise an oil
filter. The oil filter can comprise the release additive composition disclosed herein.
[0012] In another embodiment, the oil filter can comprise a housing, such as a sleeve or
cup, that can be partitioned, for example with a non-diffusible barrier, thereby creating
at least one pocket. Each pocket can comprise an identical, similar and/or a different
release additive composition wherein the composition can be in an identical, similar
and/or different form, such as a semi-solid or solid form. A non-limiting example
of this concept includes one pocket comprising a release additive composition comprising
a dispersant viscosity index improver in a solid form and an antioxidant in a semi-solid
form and a second pocket comprising a release additive composition comprising a dispersant
viscosity index improver in a semi-solid form. The filter can be a desirable location
to place the release additive composition because the additive composition and/or
spent additive composition can easily be removed and then replaced with a new and/or
recycled additive composition.
[0013] In yet another embodiment, the release additive can be located anywhere within the
lubrication system. For example, the release additive can be located outside of an
oil filter on the "dirty" side or it can be located inside of the oil filter on the
"clean" side. One of ordinary skill in the art would understand that the location
of the release additive in the lubrication system is not critical so long as the release
additive composition is in contact with a lubricating composition.
[0014] Moreover, the release rate of the release additive formulation can be moderated by
the formulation and/or the form of the additive composition. For example, the release
additive composition can comprise at least one component that selectively dissolves
completely or that is poorly oil-soluble and thus remains till the end of its service
life, or combinations thereof. The release rate can also be moderated by the polymer's
molecular weight, the degree of graft ("DOG"), polymer content, and type of capping
amine. In general, as the molecular weight, DOG or polymer content increases for the
dispersant viscosity index improver, the release rate into a lubricating composition
can be expected to be slow. Selection of the capping amine can also be a factor in
the release rate. For example, some capping amines cross-link, hydrogen bond or have
some other solubilizing affect that can serve to either increase the rate or reduce
the rate at which a product can dissolve into a lubricating composition.
[0015] Further, the additive composition can be in the form of a semi-solid, solid, or combinations
thereof. Non-limiting examples include an oil filter comprising a dispersant viscosity
index improver in a semi-solid form, an oil filter comprising a dispersant viscosity
index improver in a solid form and an antioxidant in a semi-solid form, and an oil
filter comprising a dispersant viscosity index improver in a solid form and an overbased
detergent in a semi-solid form. A "semi-solid" form as used herein is understood to
mean one component having rigidity and viscosity intermediate between a solid and
a liquid, for example the one component is not a liquid or free flowing at room temperature
(23°C).
[0016] Moreover, the release rate of the additive composition can be controlled by varying
the degree of solidity of the composition. For example, a semi-solid additive composition
can have a faster release rate into a lubricating composition as compared to a solid
additive composition. One of ordinary skill in the art can select the form of the
additive composition based upon the desired release rate.
[0017] The release additive composition can be added to the lubrication system by any known
method depending on the desired form of the additive composition, the desired speed
of addition, the desired release rate, the desired mode of operation and/or any of
the combinations of the above. In an embodiment, the additive composition can be a
semi-solid and can be added to the lubrication system by means of an injector pump,
or a container in an oil filter. In another embodiment, the additive composition can
be a solid and can be introduced into the lubricating oil system by means of an auger.
It is contemplated that the release additive composition can be released into a lubricating
composition slowly over a long period of time, such as the life of the lubricating
composition, or quickly over a short period of time, but remain in the lubricating
composition over the life of the lubricating composition.
[0018] A lubricating composition can comprise a minor amount of the release additive composition.
A "minor amount" as used herein is understood to mean less than about 50%, such as
for example less than about 40%, and as a further example from less than about 30%
by weight relative to the total weight in the lubricating composition.
[0019] In embodiments, the lubricating composition can also comprise a major amount of a
base oil. The base oil can be selected from, for example, natural oils such as mineral
oils, vegetable oils, paraffinic oils, naphthenic oils, aromatic oils, synthetic oils,
derivatives thereof, and mixtures thereof. The synthetic oils can comprise at least
one of an oligomer of an alpha-olefin, an ester, an oil derived from a Fischer-Tropsch
process, and a gas-to-liquid stock. A "major amount" can be understood to mean greater
than or equal to about 50%.
[0020] In accordance with the present disclosure, a release additive composition can comprise
at least one dispersant viscosity index improver. The dispersant viscosity index improver
can be a functionalized olefin copolymer. The polymer or copolymer substrate can be
prepared from ethylene and propylene or it can be prepared from ethylene and at least
one higher olefin within the range of C
3 to C
23 alpha-olefins.
[0021] Non-limiting examples of polymers for use herein include copolymers of ethylene and
at least one C
3 to C
23 alpha-olefins. In an embodiment, copolymers of ethylene and propylene can be used.
Other alpha-olefins suitable in place of propylene to form the copolymer or to be
used in combination with ethylene and propylene to form a terpolymer include 1-butene,
2-butene, isobutene, 1-pentene, 1-hexene, 1-octene and styrene; α,ω.-diolefins such
as 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene; branched chain alpha-olefins such
as 4-methylbutene-1,5-methylpentene-1, and 6-methylheptene-1; and mixtures thereof.
[0022] More complex polymer substrates, often designated as interpolymers, can be prepared
using a third component. The third component generally used to prepare an interpolymer
substrate can be a polyene monomer selected from non-conjugated dienes and trienes.
The non-conjugated diene component can be one having from 5 to 14 carbon atoms in
the chain. For example, the diene monomer can be characterized by the presence of
a vinyl group in its structure and can include cyclic and bicyclo compounds. Representative
dienes include 1,4-hexadiene, 1,4-cyclohexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene,
5-methylene-2-norborene, 1,5-heptadiene, and 1,6-octadiene. A mixture of more than
one diene can be used in the preparation of the interpolymer. In an embodiment, a
non-conjugated diene for preparing a terpolymer or interpolymer substrate can be 1,4-hexadiene.
[0023] The triene component can have at least two non-conjugated double bonds, and up to
about 30 carbon atoms in the chain. Typical trienes useful in preparing the interpolymer
of the invention can be 1-isopropylidene-3α,4,7,7α.-tetrahydroindene, 1-isopropylidenedicyclopentadiene,
dihydro-isodicyclopentadiene, and 2-(2-methylene-4-methyl-3-pentenyl)(2.2.1) bicyclo-5-heptene.
[0024] Ethylene-propylene or higher alpha-olefin copolymers can comprise from about 15 to
80 mole percent ethylene and from about 85 to 20 mole percent C
3 to C
23 alpha-olefin with, for example, mole ratios from about 35 to 75 mole percent ethylene
and from about 65 to 25 mole percent of a C
3 to C
23 alpha-olefin, with for example proportions being from 50 to 70 mole percent ethylene
and 50 to 30 mole percent C
3 to C
23 alpha-olefin, and as a further example proportions being from 55 to 65 mole percent
ethylene and 45 to 35 mole percent C
3 to C
23 alpha-olefin.
[0025] Terpolymer variations of the foregoing polymers can comprise from about 0.1 to 10
mole percent of a non-conjugated diene or triene.
[0026] The terms polymer and copolymer can be used generically to encompass ethylene copolymers,
terpolymers or interpolymers. These materials can comprise minor amounts of other
olefinic monomers so long as the basic characteristics of the ethylene copolymers
are not materially changed.
[0027] The polymerization reaction used to form the ethylene-olefin copolymer substrate
can be generally carried out in the presence of a conventional Ziegler-Natta or metallocene
catalyst system. The polymerization medium is not specific and can include solution,
slurry, or gas phase processes, as known to those skilled in the art. When solution
polymerization is employed, the solvent can be any suitable inert hydrocarbon solvent
that is liquid under reaction conditions for polymerization of alpha-olefins. Non-limiting
examples of satisfactory hydrocarbon solvents include straight chain paraffins having
from about 5 to about 8 carbon atoms, such as hexane. Aromatic hydrocarbons, for example
an aromatic hydrocarbon having a single benzene nucleus, such as benzene, toluene
and the like; and saturated cyclic hydrocarbons having boiling point ranges approximating
those of the straight chain paraffinic hydrocarbons and aromatic hydrocarbons described
above, can be suitable. The solvent selected can be a mixture of at least one of the
foregoing hydrocarbons. When slurry polymerization is employed, the liquid phase for
polymerization can be, for example, liquid propylene. In an embodiment, the polymerization
medium can be free of substances that will interfere with the catalyst components.
[0028] The number average molecular weight as determined by gel permeation chromatography,
Mn, of the copolymer substrate can be from about 700 to about 500,000, and for example
from about 700 to about 100,000. The molecular weight distribution, Mw/Mn, of the
polymer substrate can be less than about 15, for example from about 1 to about 10.
[0029] An ethylenically unsaturated carboxylic acid material can next be grafted onto the
prescribed polymer backbone to form an acylated ethylene copolymer. These carboxylic
reactants which are suitable for grafting onto the ethylene copolymer contain at least
one ethylenic bond and at least one, for example two, carboxylic acid or its anhydride
groups or a polar group which is convertible into said carboxyl groups by oxidation
or hydrolysis. For example, the carboxylic reactants can be selected from acrylic,
methacrylic, cinnamic, crotonic, maleic, fumaric and itaconic reactants. As a further
example, the carboxylic reactants can be selected from maleic acid, fumaric acid,
maleic anhydride, and a mixture of two or more of these. Maleic anhydride or a derivative
thereof can be used, for example, due to its commercial availability and ease of reaction.
In the case of unsaturated ethylene copolymers or terpolymers, itaconic acid or its
anhydride can be used due to its reduced tendency to form a cross-linked structure
during the free-radical grafting process.
[0030] The ethylenically unsaturated carboxylic acid materials typically can provide one
or two carboxylic groups per mole of reactant to the grafted polymer. That is, methyl
methacrylate can provide one carboxylic group per molecule to the grafted polymer
while maleic anhydride can provide two carboxylic groups per molecule to the grafted
polymer.
[0031] The carboxylic reagent, such as maleic anhydride, can be grafted onto the polymer
backbone in an amount from about 0.5 to about 4.0 grams of carboxylic reagent per
100 grams of polymer and can be expressed as a wt%. For example, if a 10,000 mol.
wt. polymer was reacted with enough maleic anhydride to form a product that contained
1.8 grams of maleic anhydride per 100 gms of polymer backbone, then the resultant
grafted product would be a 10,000 mol. wt. E-P copolymer with a DOG of 1.8 wt%. Co-incidentally,
this additive would contain 1.8 molecules of maleic anhydride per polymer molecule.
This maleic anhydride to polymer ratio could be described as the carboxylic reagent
to olefin copolymer ratio. In a second example, if a 20,000 mol. wt E-P copolymer
was reacted with 1.8 gms of maleic anhydride per 100 gms of E-P polymer, then the
resultant product would be a 20,000 mol. wt. E-P copolymer with a DOG of 1.8 wt% and
a carboxylic reagent to olefin copolymer ratio of 3.6. In a third example, a nominal
70,000 molecular weight E-P polymer with a DOG of 1.8 wt% would have a carboxylic
reagent to olefin polymer ratio of 12.6. In an embodiment, at a minimum, one molecule
of carboxylic reagent per one polymer molecule can be used.
[0032] The grafting reaction to form the acylated olefin copolymers can be generally carried
out with the aid of a free-radical initiator either in solution or in bulk, as in
an extruder or intensive mixing device. When the polymerization is carried out in
hexane solution, it can be economically convenient to carry out the grafting reaction
in hexane as described in
U.S. Pat. Nos. 4,340,689,
4,670,515 and
4,948,842, the disclosures of which are hereby incorporated by reference. The resulting polymer
intermediate can be characterized by having carboxylic acid acylating functionality
randomly within its structure.
[0033] In the bulk process for forming the acylated olefin copolymers, the olefin copolymer
can be fed to rubber or plastic processing equipment such as an extruder, intensive
mixer or masticator, heated to a temperature of about 150°C to about 400°C and the
ethylenically unsaturated carboxylic acid reagent and free-radical initiator can be
separately co-fed to the molten polymer to effect grafting. The reaction can be carried
out optionally with mixing conditions to effect shearing and grafting of the ethylene
copolymers according to
U.S. Pat. No. 5,075,383, incorporated herein by reference. The processing equipment can be generally purged
with nitrogen to prevent oxidation of the polymer and to aid in venting unreacted
reagents and byproducts of the grafting reaction. The residence time in the processing
equipment can be sufficient to provide for the desired degree of acylation and to
allow for purification of the acylated copolymer via venting. Mineral or synthetic
lubricating oil can optionally be added to the processing equipment after the venting
stage to dissolve the acylated copolymer.
[0034] The free-radical initiators which can be used to graft the ethylenically unsaturated
carboxylic acid material to the polymer backbone include peroxides, hydroperoxides,
peresters, and also azo compounds and, for example, those which have a boiling point
greater than about 100°C and decompose thermally within the grafting temperature range
to provide free radicals. Representatives of these free-radical initiators can be
azobutyronitrile, dicumyl peroxide, 2,5-dimethylhexane-2,5-bis-tertiarybutyl peroxide
and 2,5-dimnethylhex-3-yne-2,5-bis-tertiary-butyl peroxide. The initiator can be used
in an amount from about 0.005% to about 1% by weight based on the weight of the reaction
mixture.
[0035] Other methods known in the art for effecting reaction of ethylene-olefin copolymers
with ethylenically unsaturated carboxylic reagents, such as halogenation reactions,
thermal or "ene" reactions or mixtures thereof, can be used instead of the free-radical
grafting process. Such reactions are conveniently carried out in mineral oil or bulk
by heating the reactants at temperatures from about 250°C to about 400°C under an
inert atmosphere to avoid the generation of free radicals and oxidation byproducts.
[0036] The acylated olefin copolymers can be reacted with coupling compounds and performance
enhancing compounds. The reaction sequence can be in any order or simultaneous. In
an embodiment, the performance enhancing compound can be first reacted with an oil
or solvent solution of the acylated olefin copolymer followed by addition of the coupling
compound. Because both reactants combine with the free carboxylic functionality of
the acylated copolymers, the ratio of coupling compound to the performance enhancing
compound can be adjusted as well as the ratio of coupling compound and performance
enhancing compound to acylated olefin copolymer to provide for the desired balance
of viscosity index improvement-dispersancy and additional performance criteria.
[0037] For purposes of the present disclosure, coupling compounds can be defined as those
compounds containing more than one amine, thiol and/or hydroxy functional groups capable
of reacting with the acylated olefin copolymer so as to link or couple two or more
acylated olefin copolymers.
[0038] Coupling compounds for use herein include organo polyamines, polyalcohols, polyhydroxy
or thiol amines, amide-amines and amino guanidines wherein the organo group can be
aliphatic, cycloaliphatic, aromatic, heterocyclic, or combinations thereof, and wherein
the organo group can have organo heteroatom containing groups such as but not limited
to --O--, --N--, --S--, --Siand --P--.
[0039] Representative organo polyamines include triethylene tetramine, tetraethylene pentamine,
pentaethylene hexamine, di-(1,3-propylene)triamine, tri-(1,3-propylene) tetramine,
1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, N,N-di-(2-aminoethyl)ethylene
diamine, N,N-di-(2-aminoethyl) propylene diamine, N-(oleayl amino propyl)1,3-propylene
diamine, 1,4-bis(2-aminoethyl) piperazine, polyethylene amine mixtures containing
5-7 N-atoms per molecule commercially available under the trade names Polyamine H,
Polyamine 400, or Dow Polyamine E-100, and aromatic diamine mixtures such as ETHACURE
® 300 (Albemarle Corporation) which is a mixture of 2,4- and 2,6-isomers of dimethylthiotoluene
diamine.
[0040] Branched or star branched polyamines also known in the art as dendrimers can be used.
Such dendrimers are described in, for example,
U.S. Pat. Nos. 4,587,329 and
4,737,550 and
PCT published applications Nos. WO93/14147 and
WO95/02008, the disclosures of which are hereby incorporated by reference. A core group and
repeating structural unit linked by a functional group defines the dendrimers. The
repeating units can be referred to as generations. Typically, polyamine dendrimers
having 1 to 4 generations linked together via amine groups and terminated by a primary
amine can be particularly useful. A typical polyamine dendrimer can be prepared, for
example, with 1,4-diaminobutane as the core, which can then be reacted via a Michael
addition with acrylonitrile followed by hydrogenation of the cyano group to a primary
amine. A second generation of alternating reactions with acrylonitrile, followed by
hydrogenation will yield a polyamine with eight branches. Examples of useful core
molecules include, but are not limited to, ammonia, polymethylenediamines, diethylenetriamines,
diethylene tetramines, tetraethylenepentamine, linear and branched polyethylene imines,
polyaminoalkylarenes, such as 1,3,5-tris-(aminomethyl) benzene, and melamine and its
derivatives such as melamine tris-(hexamethylene diamine). Particularly useful as
chemical compounds in forming the generations can be α, β-unsaturated carboxylic and
cyano compounds, aziridines and alkylene diamines.
[0041] Other suitable organo polyamines include polyoxyalkylene polyamines such as those
of the formula: NH
2 -alkylene-(--O--alkylene)
n --NH
2
where n can have a value of about 3 to about 59, for example about 10 to about 35
and the alkylene groups can be independently straight or branched chains containing
about 2 to about 7, for example about 2 to about 4, carbon atoms. As well as polyoxyalkylene
polyamines of the formula:
R
1-(-alkylene-(--O--alkylene)
m --NH
2)
a
where m can have a value of about 1 to about 28 with the provision that the sum of
all carbon atoms is from about 2 to about 60, from example about 2 to about 40, and
R
1 can be a polyvalent saturated hydrocarbon radical of up to ten carbon atoms wherein
the number of substituents on the R
1 group can be represented by the value 'a', which can be a number from 3 to 6. The
alkylene groups can be independently straight or branched chains containing about
2 to about 7, for example from about 2 to about 4, carbon atoms.
[0042] The polyoxyalkylene polyamines described above can be, for example, polyoxyalkylene
diamines and polyoxyalkylene triamines having an average molecular weight ranging
from about 200 to about 4000, for example from about 400 to about 2000. The polyoxyalkylene
polyamines include the polyoxyethylene and polyoxypropylene diamines and the polyoxyproylene
triamines having average molecular weights ranging from about 200 to 2000. The polyoxyalkylene
polyamines can be commercially available and can be obtained, for example, from Huntsman
Chemical Company under the trade name "Jeffamines D-230, D-400, D-1000, D-2000, T-403",
etc.
[0043] Another particularly suitable class of organo polyamines comprise bis(p-amino cyclohexyl)
methane (PACM) and oligomers and mixtures of PACM with isomers and analogs thereof
containing on average, from 2 to 6 or higher, for example 3 to 4, cyclohexyl rings
per PACM oligomer molecule. The total nitrogen content of the PACM oligomers can comprise
from 8 to 16 wt. %, and for example from 10 to 14 wt. %.
[0044] The PACM oligomers can be obtained, e.g., by fractionation or distillation, as a
heavies by-product or bottoms from the PACM-containing product produced by high pressure
catalytic hydrogenation of methylene dianiline. The hydrogenation of methylene dianiline
and the separation of PACM oligomers from the resulting hydrogenation product can
be accomplished by known means, including the processes disclosed in
U.S. Pat. Nos. 2,511,028;
2,606,924;
2,606,925;
2,606,928;
3,914,307;
3,959,374;
4,293,687;
4,394,523;
4,448,995 and
4,754,070, the disclosures of which are incorporated herein by reference in their entirety.
[0045] Suitable polyalcohol coupling compounds useful herein include polyol compounds containing
at least two reactive hydroxy groups. The polyalcohols generally comprise up to about
100 carbon atoms and from 2 to about 10, for example about 3 to about 8 hydroxy groups
per molecule. These polyols can be quite diverse in structure and chemical composition.
For example, they can be substituted or unsubstituted, hindered or unhindered, branched
chain or straight chain, etc. as desired. Typical polyols include alkylene glycols
such as ethylene glycol, propylene glycol, trimethylene glycol, butylene glycol, and
polyglycol such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene
glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, and other alkylene
glycols and polyalkylene glycols in which the alkylene radical contains from about
two to about eight carbon atoms. Other useful polyalcohols include glycerol, monomethyl
ether of glycerol, trimethylopropane, pentaerythritol, dipentaerythritol, tripentaerythritol,
1,2-propanediol, 1,2-butanediol, 1,4-butanediol, 2,3-hexanediol, pinacol, erythritol,
arabitol, sorbitol, mannitol etc.
[0046] Cyclic poly(methylol) compounds, such as 2,2,6,6-tetramethylol cyclohexanol, tetrahydro-3,3,5,5-tetrakis-(hydroxymethyl)-4-pyranol,
tetrahydro-3,3,5-tris-(hydroxymethyl)-5-methyl-4-pyranol, as well as heterocyclic
polyols can also be used as coupling compounds in the present disclosure. The heterocyclic
polyols and cyclic poly(methylol) compounds can be described more fully in
U.S. Pat. No. 4,797,219, the disclosure of which is incorporated herein in its entirety.
[0047] Organo polyhydroxy or thiol amines particularly useful herein include 2-(2-aminoethyl)aminoethanol,
N-(2-hydroxypropyl) ethylene diamine, N,N-di-(2-hydroxyethyl) 1,3-propylene diamine,
hexamethylene diamine-2-propylene oxide (HMDA-2PO), hexamethylene diamine-3-propylene
oxide (HMDA-3PO), hexamethylene diamine-4-propylene oxide (HMDA-4PO), dimethyl aminopropylamine-2-propylene
oxide (DMAPA-2PO), and Mannich condensation products which can be formed from a hydroxyaromatic
compound (e.g., phenol, alkyl substituted phenol etc.), an aldehyde (e.g., formaldehyde,
formalin, clyoxal etc.), and a polyalkenyl polyamine (e.g., pentaethylene hexamine
and tetraethylene pentamine). Suitable polythiol amines include aminomercaptotriazoles.
[0048] Organo amide-amines include the linear and branched products from the reaction of
alkylene diamines and alkylacrylates such as ethylene diamine and methyl acrylate
or 1,4-butane diamine and methyl acrylate. Amido-amine dendrimers, described in
U.S. Pat. Nos. 4,587,329 and
4,737,550, are prepared by alternating reactions with alkylene diamines and alkyl acrylates
or acrylamides. Amido-amine dendrimers having up to 4 generations can be used to couple
the acylated olefin polymers.
[0049] Also useful are the amino guanidines such as amino guanidine bicarbonate (AGBC).
[0050] The performance enhancing compound includes a polyamine compound selected from:
(a) an N-arylphenylenediamine represented by the formula:

wherein R1 can be hydrogen, --NH-aryl, --NH-arylalkyl, --NH-alkyl, or a branched or straight
chain radical having from about 4 to about 24 carbon atoms that can be alkyl, alkenyl,
alkoxyl, aralkyl, alkaryl, hydroxyalkyl or aminoalkyl; R2 can be --NH2, CH2 --(CH2)n --NH2, CH2 -aryl-NH2, in which n has a value from 1 to 10; and R3 can be hydrogen, alkyl, alkenyl, alkoxyl, aralkyl, alkaryl having from about 4 to
about 24 carbon atoms;
(b) an aminothiazole selected from the group consisting of aminothiazole, aminobenzothiazole,
aminobenzothiadiazole and aminoalkylthiazole;
(c) an aminocarbazole represented by the formula:

wherein R and R1 can be the same or different, and can be hydrogen, an alkyl, alkenyl, or alkoxy radical
having from about 1 to about 14 carbon atoms; (d) an aminoindole represented by the
formula:

wherein R can be hydrogen or an alkyl radical having from about 1 to about 14 carbon
atoms;
(e) an aminopyrrole represented by the formula:

wherein R can be a divalent alkylene radical having from about 2 to about 6 carbon
atoms and R1 can be hydrogen or an alkyl radical having from about 1 to about 14 carbon atoms;
(f) an amino-indazolinone represented by the formula:

wherein R can be hydrogen or an alkyl radical having from about 1 to about 14 carbon
atoms;
(g) an aminomercaptotriazole represented by the formula:

wherein R can be absent or can be a C1-C10 linear or branched hydrocarbon selected from the group consisting of alkyl, alkenyl,
arylalkyl, and aryl;
(h) an aminoperimidine represented by the formula:

wherein R can be hydrogen, an alkyl, or alkoxyl radical having from about 1 to about
14 carbon atoms;
(i) aminoalkyl imidazoles, such as 1-(2-aminoethyl) imidazole, 1-(3-aminopropyl) imidazole;
and
(j) aminoalkyl morpholines, such as 4-(3-aminopropyl) morpholine.
[0051] In one aspect of the disclosure, the polyamines for use herein can be the N-arylphenylenediamines,
for example the N-phenylphenylenediamines, and as a further example, N-phenyl-1,4-phenylenediamine,
N-phenyl-1,3-phenylendiamine, and N-phenyl-1,2-phenylenediamine.
[0052] The polyamines can contain only one primary amine group so as to avoid coupling and/or
gelling of the olefin copolymers.
[0053] The reaction between the acylated olefin polymer and the coupling compound and/or
performance enhancing compound, such as the polyamine, can be conveniently carried
out in natural or synthetic lubricating oil under inert conditions. In an embodiment,
a surfactant is not used. The ingredients can be agitated at a temperature from about
120° to 200°C, for example 140° to 180°C with a purge of inert gas to remove water
and/or other low molecular weight byproducts. The reaction time can vary from about
30 minutes to about 16 hours.
[0054] The composition can also include other additives such as dispersants, non-dispersant
viscosity index improver, overbased detergents, antioxidants, detergents, graphite,
molybdenum disulfide, magnesium carbonate, silica, alumina, titania, magnesium oxide,
calcium carbonate, lime, clay, zeolites, extreme pressure (EP) agents, wear reduction
agents, anti-foaming agents, friction reducing agents, anti-misting agents, cloud-point
depressants, pour-point depressants, mineral and/or synthetic oils mixtures thereof
and combination thereof. These additives can be used alone or in combination. These
additives can be used alone or in combination, such as in an optional additional additive
package.
[0055] Lubricant compositions, such as modern motor oils, can be made by combining a pre-formed
additive package with a refined or synthetic base oil stock. A lubricant composition
can comprise various different lubricant additive packages. Because lubricant additives
can be easier to handle and measure in liquid form those additives which are normally
solid can be dissolved in small amounts of base oil stock.
[0056] In one embodiment, there is disclosed a method for improving the drain interval of
an engine oil comprising adding to a lubrication system the disclosed release additive
composition.
EXAMPLES
Example 1 - Nominal 66,000 Mol. Wt. Ethylene-Propylene Polymer
[0057] Into a round bottom flask equipped with a mechanical stirrer, air inlet tube, thermocouple
and condenser was added 300 gms of a ethylene-propylene copolymer with a degree of
graft of 1.99 wt% maleic anhydride, PA-1275 manufactured by DSM for Afton Chemical.
The reactant was blanketed with nitrogen gas and heated to 160°C. With vigorous stirring,
the capping amine, n-phenyl-phenylene diamine (1.4 gms) was added to the reaction.
The reaction was stirred for one hour at 160°C. Analytical data: %N = 0.088 wt%. The
product solidified upon cooling.
Example 2 - Nominal 20,000 Mol. Wt. Ethylene-Propylene Polymer
[0058] Into a round bottom flask equipped with a mechanical stirrer, air inlet tube, thermocouple
and condenser was added 600 gms of a 20,000 mol. wt. ethylene-propylene copolymer
with a degree of graft of 2.1 wt% maleic anhydride. The reactant was blanketed with
nitrogen gas and heated to 160°C. With vigorous stirring, the capping amine, n-phenyl-phenylene
diamine (4.7 gms) was added to the reaction. The reaction was stirred for two hours
at 160°C. Analytical data: %N = 0.14 wt%. The product solidified upon cooling.
Example 3 - Nominal 10,000 Mol. Wt. Ethylene-Propylene Polymer
[0059] Into a round bottom flask equipped with a mechanical stirrer, air inlet tube, thermocouple
and condenser was added 600 gms of a 10,000 mol. wt. ethylene-propylene copolymer
with a degree of graft of 1.76 wt.% maleic anhydride. The reactant was blanketed with
nitrogen gas and heated to 160°C. With vigorous stirring, the capping amine, n-phenyl-phenylene
diamine (6.5 gms) was added to the reaction. The reaction was stirred for two hours
at 160°C. Analytical data: %N = 0.19 wt%. The product solidified upon cooling.
Example 4 - Nominal 20,000 Mol. Wt. Ethylene-Propylene Polymer
[0060] Into a round bottom flask equipped with a mechanical stirrer, air inlet tube, thermocouple
and condenser was added 600 gms of a 20,000 mol. wt. ethylene-propylene copolymer
with a degree of graft of 2.1 wt% maleic anhydride. The reactant was blanketed with
nitrogen gas and heated to 160°C. With vigorous stirring, the capping amine, amino
guanidine bicarbonate, (3.5 gms) was added to the reaction. The reaction was stirred
for two hours at 160°C or until the product was too thick to stir. Analytical data:
%N = 0.267 wt%. The product solidified upon cooling.
Example 5 - Nominal 20,000 Mol. Wt. Ethylene-Propylene Polymer
[0061] Into a round bottom flask equipped with a mechanical stirrer, air inlet tube, thermocouple
and condenser was added 600 gms of a 20,000 mol. wt. ethylene-propylene copolymer
with a degree of graft of 2.1 wt% maleic anhydride. The reactant was blanketed with
nitrogen gas and heated to 160°C. With vigorous stirring, the capping amine, n-phenyl-phenylenediamine,
3.5 gms, was slowly added to the reaction. The reaction was stirred for 1 hour at
160°C. Amino guanidine bicarbonate, 0.87 gms, was slowly added to the reaction. The
reaction was stirred for 1 hour at 160°C. Analytical data: %N = 0.216 wt%. The product
solidified upon cooling.
[0062] For the purposes of this specification and appended claims, unless otherwise indicated,
all numbers expressing quantities, percentages or proportions, and other numerical
values used in the specification and claims, are to be understood as being modified
in all instances by the term "about." Accordingly, unless indicated to the contrary,
the numerical parameters set forth in the following specification and attached claims
are approximations that can vary depending upon the desired properties sought to be
obtained by the present disclosure. At the very least, and not as an attempt to limit
the application of the doctrine of equivalents to the scope of the claims, each numerical
parameter should at least be construed in light of the number of reported significant
digits and by applying ordinary rounding techniques.
[0063] It is noted that, as used in this specification and the appended claims, the singular
forms "a," "an," and "the," include plural referents unless expressly and unequivocally
limited to one referent. Thus, for example, reference to "an antioxidant" includes
two or more different antioxidants. As used herein, the term "include" and its grammatical
variants are intended to be non-limiting, such that recitation of items in a list
is not to the exclusion of other like items that can be substituted or added to the
listed items.
[0064] While particular embodiments have been described, alternatives, modifications, variations,
improvements, and substantial equivalents that are or can be presently unforeseen
can arise to applicants or others skilled in the art. Accordingly, the appended claims
as filed and as they can be amended are intended to embrace all such alternatives,
modifications variations, improvements, and substantial equivalents.
1. A release additive composition comprising at least one dispersant viscosity index
improver present in a form chosen from a solid and a semi-solid.
2. A composition according to claim 1, wherein the at least one dispersant viscosity
index improver is a solid.
3. A composition according to claim 1, wherein the at least one dispersant viscosity
index improver is a semi-solid.
4. A composition according to any one of claims 1 to 3, wherein the at least one dispersant
viscosity index improver has a number average molecular weight from about 700 to about
500,000.
5. A composition according to claim 4, wherein the at least one dispersant viscosity
index improver has a number average molecular weight from about 700 to about 100,000.
6. A composition according to any one of claims 1 to 5, wherein the at least one dispersant
viscosity index improver has a degree of graft ranging from about 1.0 to about 3.0.
7. A composition according to any one of claims 1 to 6, wherein the at least one dispersant
viscosity index improver comprises an amine chosen from N-phenyl-phenylene diamine
and amino guanidine bicarbonate.
8. A composition according to any one of claims 1 to 7, further comprising an antioxidant.
9. A composition according to claim 8, wherein the antioxidant is a semi-solid.
10. A composition according to either claim 8 or claim 9, wherein the antioxidant is an
alkyl-substituted phenol.
11. A lubricant composition comprising:
a major amount of a base oil; and
a minor amount of a release additive composition according to any one of claims 1
to 10.
12. A lubricant composition according to claim 11, wherein the base oil is selected from
the group consisting of mineral oils, vegetable oils, paraffinic oils, naphthenic
oils, aromatic oils, synthetic oils, derivatives thereof, and mixtures thereof.
13. A lubrication system comprising at least one release additive composition according
to any one of claims 1 to 10 located in at least one of a 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 and mesh in a bypass system.
14. A system according to claim 13, wherein the release additive composition is located
in the filter.
15. A system according to either claim 13 or claim 14, wherein the filter comprises at
least one pocket, and wherein each of the at least one pocket comprises the at least
one release additive composition.
16. A system according to claim 15, wherein each of the at least one pocket comprises
a different at least one release additive composition.
17. Use of a release additive composition according to any one of claims 1 to 10 for improving
the drain interval of engine oil.