U.S. patent application number 11/173669 was filed with the patent office on 2007-01-04 for additive composition.
Invention is credited to Carl K. JR. Esche, Naresh C. Mathur, Charles A. Passut.
Application Number | 20070004604 11/173669 |
Document ID | / |
Family ID | 37057076 |
Filed Date | 2007-01-04 |
United States Patent
Application |
20070004604 |
Kind Code |
A1 |
Mathur; Naresh C. ; et
al. |
January 4, 2007 |
Additive composition
Abstract
A release additive composition including at least one dispersant
viscosity index improver present in a form chosen from a semi-solid
and a solid is disclosed.
Inventors: |
Mathur; Naresh C.;
(Midlothian, VA) ; Esche; Carl K. JR.; (Richmond,
VA) ; Passut; Charles A.; (Midlothian, VA) |
Correspondence
Address: |
NEW MARKET SERVICES CORPORATION;(FORMERLY ETHYL CORPORATION)
330 SOUTH 4TH STREET
RICHMOND
VA
23219
US
|
Family ID: |
37057076 |
Appl. No.: |
11/173669 |
Filed: |
July 1, 2005 |
Current U.S.
Class: |
508/545 |
Current CPC
Class: |
C10M 2207/026 20130101;
C10M 175/0091 20130101; C10M 2205/022 20130101; C10M 2215/28
20130101; C10M 2209/086 20130101; C10M 2207/129 20130101; C10M
133/56 20130101; C10M 2215/102 20130101; C10M 2215/064 20130101;
C10N 2020/04 20130101; C10M 129/93 20130101; C10M 171/00 20130101;
C10M 2205/022 20130101; C10M 2205/024 20130101; C10M 2217/024
20130101; C10M 2205/022 20130101; C10M 2205/024 20130101; C10M
2209/086 20130101; C10N 2060/09 20200501; C10M 2205/022 20130101;
C10M 2205/024 20130101; C10M 2209/086 20130101; C10N 2060/09
20200501 |
Class at
Publication: |
508/545 |
International
Class: |
C10M 133/06 20060101
C10M133/06 |
Claims
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. The composition of claim 1, wherein the at least one dispersant
viscosity index improver is a solid.
3. The composition of claim 2, wherein the at least one dispersant
viscosity index improver is a semi-solid.
4. The composition of claim 1, wherein the at least one dispersant
viscosity index improver has a number average molecular weight from
about 700 to about 500,000.
5. The composition of claim 1, wherein the at least one dispersant
viscosity index improver has a number average molecular weight from
about 700 to about 100,000.
6. The composition of claim 1, wherein the at least one dispersant
viscosity index improver has a degree of graft ranging from about
1.0 to about 3.0.
7. The composition of claim 1, wherein the at least one dispersant
viscosity index improver comprises an amine chosen from
N-phenyl-phenylene diamine and amino guanidine bicarbonate.
8. The composition of claim 1, further comprising an
antioxidant.
9. The composition of claim 8, wherein the antioxidant is a
semi-solid.
10. The composition of claim 8, 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
comprising at least one dispersant viscosity index improver present
in a form chosen from a solid and a semi-solid.
12. The lubricant composition of 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 claim 1 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.
14. The system of claim 13, wherein the at least one dispersant
viscosity index improver is a semi-solid.
15. The system of claim 13, wherein the release additive
composition is located in the filter.
16. The system of claim 13, 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.
17. The system of claim 16, wherein each of the at least one pocket
comprises a different at least one release additive
composition.
19. 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.
20. The method of claim 19, further comprising an antioxidant.
Description
DESCRIPTION OF THE DISCLOSURE
[0001] 1. Field of the Disclosure
[0002] 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.
[0003] 2. Background of the Disclosure
[0004] 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.
[0005] 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.
[0006] 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
[0007] 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.
[0008] 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.
[0009] 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
[0010] 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.sub.x traps, and the
like.
[0011] 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.
[0012] 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.
[0013] 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.
[0014] 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.
[0015] 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.
[0016] 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.
[0017] 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.degree. C.).
[0018] 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.
[0019] 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.
[0020] 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.
[0021] 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%.
[0022] 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.sub.3 to C.sub.23 alpha-olefins.
[0023] Non-limiting examples of polymers for use herein include
copolymers of ethylene and at least one C.sub.3 to C.sub.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;
.alpha.,.omega.-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.
[0024] 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.
[0025] 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-3.alpha.,4,7,7.alpha..-tetrahydroindene,
1-isopropylidenedicyclopentadiene, dihydro-isodicyclopentadiene,
and 2-(2-methylene-4-methyl-3-pentenyl)(2.2.1)
bicyclo-5-heptene.
[0026] 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.sub.3 to C.sub.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.sub.3 to C.sub.23
alpha-olefin, with for example proportions being from 50 to 70 mole
percent ethylene and 50 to 30 mole percent C.sub.3 to C.sub.23
alpha-olefin, and as a further example proportions being from 55 to
65 mole percent ethylene and 45 to 35 mole percent C.sub.3 to
C.sub.23 alpha-olefin.
[0027] Terpolymer variations of the foregoing polymers can comprise
from about 0.1 to 10 mole percent of a non-conjugated diene or
triene.
[0028] 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.
[0029] 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.
[0030] 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.
[0031] 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.
[0032] 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.
[0033] 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.
[0034] 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.
[0035] 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.degree. C. to
about 400.degree. 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.
[0036] 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.degree. 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.
[0037] 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.degree. C. to about 400.degree. C.
under an inert atmosphere to avoid the generation of free radicals
and oxidation byproducts.
[0038] 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.
[0039] 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.
[0040] 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--, --Si-- and
--P--.
[0041] 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.RTM. 300 (Albemarle Corporation) which is a mixture of
2,4- and 2,6-isomers of dimethylthiotoluene diamine.
[0042] 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. W093/14147 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 .alpha., .beta.-unsaturated carboxylic and cyano
compounds, aziridines and alkylene diamines.
[0043] Other suitable organo polyamines include polyoxyalkylene
polyamines such as those of the formula: NH.sub.2
-alkylene-(--O-alkylene).sub.n--NH.sub.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.sub.1--(-alkylene-(--O-alkylene).sub.m--NH.sub.2).sub.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.sup.1 can be a polyvalent saturated
hydrocarbon radical of up to ten carbon atoms wherein the number of
substituents on the R.sup.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.
[0044] 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-1 000, D-2000, T-403", etc.
[0045] 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. %.
[0046] 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.
[0047] 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.
[0048] 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.
[0049] 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.
[0050] 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.
[0051] Also useful are the amino guanidines such as amino guanidine
bicarbonate (AGBC).
[0052] The performance enhancing compound includes a polyamine
compound selected from: (a) an N-arylphenylenediamine represented
by the formula: ##STR1## wherein R.sup.1 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; R.sup.2 can be --NH.sub.2,
CH.sub.2--(CH.sub.2).sub.n--NH.sub.2, CH.sub.2 -aryl-NH.sub.2, in
which n has a value from 1 to 10; and R.sup.3 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: ##STR2## wherein R and R.sup.1 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: ##STR3## 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: ##STR4##
wherein R can be a divalent alkylene radical having from about 2 to
about 6 carbon atoms and R.sup.1 can be hydrogen or an alkyl
radical having from about 1 to about 14 carbon atoms; (f) an
amino-indazolinone represented by the formula: ##STR5## 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: ##STR6## wherein R can be absent or can be a
C.sub.1-C.sub.10 linear or branched hydrocarbon selected from the
group consisting of alkyl, alkenyl, arylalkyl, and aryl; (h) an
aminoperimidine represented by the formula: ##STR7## 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.
[0053] 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.
[0054] The polyamines can contain only one primary amine group so
as to avoid coupling and/or gelling of the olefin copolymers.
[0055] 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.degree. to 200.degree. C., for example
140.degree. to 180.degree. C. with a purge of inert gas to remove
water and/or other low molecular weight by-products. The reaction
time can vary from about 30 minutes to about 16 hours.
[0056] 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.
[0057] 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.
[0058] 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
[0059] 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.degree. 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.degree. C. Analytical
data: % N=0.088 wt %. The product solidified upon cooling.
Example 2
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.degree. 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.degree. C. Analytical data: % N=0.14 wt %. The product
solidified upon cooling.
Example 3
Nominal 10.000 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 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.degree. 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.degree. C. Analytical data: % N=0.19 wt %. The product
solidified upon cooling.
Example 4
Nominal 20.000 Mol. Wt. Ethylene-Propylene Polymer
[0062] 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.degree. 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.degree. 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
[0063] 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.degree. 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.degree. C. Amino guanidine bicarbonate, 0.87 gms, was
slowly added to the reaction. The reaction was stirred for 1 hour
at 160.degree. C. Analytical data: % N=0.216 wt %. The product
solidified upon cooling.
[0064] 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.
[0065] 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.
[0066] 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.
* * * * *