U.S. patent application number 10/884466 was filed with the patent office on 2006-01-05 for additives and lubricant formulations for improved corrosion protection.
Invention is credited to Gregory Paul Anderson, Cathy C. Devlin, Charles A. Passut.
Application Number | 20060003905 10/884466 |
Document ID | / |
Family ID | 35514752 |
Filed Date | 2006-01-05 |
United States Patent
Application |
20060003905 |
Kind Code |
A1 |
Devlin; Cathy C. ; et
al. |
January 5, 2006 |
Additives and lubricant formulations for improved corrosion
protection
Abstract
A lubricated surface and method for lubricating moving parts.
The lubricated surface includes a thin film coating of a lubricant
composition containing a base oil of lubricating viscosity and from
about 9.5 to about 25 percent by weight of an additive comprising a
nitrogen containing olefin copolymer derived from an olefin
copolymer having grafted thereon from about 0.15 to about 1.0
carboxylic groups per 1000 number average molecular weight units of
the copolymer. The copolymer has a number average molecular weight
ranging from about 10,000 to about 100,000. The amount of additive
in the lubricant composition is based on a total weight of the
lubricant composition.
Inventors: |
Devlin; Cathy C.; (Richmond,
VA) ; Anderson; Gregory Paul; (Midlothian, VA)
; Passut; Charles A.; (Midlothian, VA) |
Correspondence
Address: |
DENNIS H. RAINEAR
CHIEF PATENT COUNSEL, ETHYL CORPORATION
330 SOUTH FOURTH STREET
RICHMOND
VA
23219
US
|
Family ID: |
35514752 |
Appl. No.: |
10/884466 |
Filed: |
July 2, 2004 |
Current U.S.
Class: |
508/454 ;
508/508 |
Current CPC
Class: |
C10N 2040/252 20200501;
C10N 2030/02 20130101; C10N 2060/09 20200501; C10M 2205/022
20130101; C10M 2215/30 20130101; C10M 2215/223 20130101; C10M
2217/06 20130101; C10M 2215/064 20130101; C10M 133/52 20130101;
C10M 149/10 20130101; C10M 149/06 20130101; C10M 133/56 20130101;
C10M 159/12 20130101; C10M 2205/00 20130101; C10M 133/58 20130101;
C10M 2215/24 20130101; C10N 2030/12 20130101; C10M 2205/022
20130101; C10M 2205/024 20130101 |
Class at
Publication: |
508/454 ;
508/508 |
International
Class: |
C10M 149/00 20060101
C10M149/00; C10M 159/12 20060101 C10M159/12 |
Claims
1. A lubricated surface comprising a thin film coating of a
lubricant composition containing a base oil of lubricating
viscosity and from about 9.5 to about 25 percent by weight of an
additive comprising a nitrogen containing olefin copolymer derived
from an olefin copolymer having grafted thereon from about 0.15 to
about 1.0 carboxylic groups per 1000 number average molecular
weight units of the copolymer, wherein the copolymer has a number
average molecular weight ranging from about 10,000 to about
100,000, and wherein the amount of additive in the lubricant
composition is based on a total weight of the lubricant
composition.
2. The lubricated surface of claim 1, wherein the lubricated
surface comprises an engine drive train.
3. The lubricated surface of claim 1, wherein the lubricated
surface comprises an internal surface or component of an internal
combustion engine.
4. The lubricated surface of claim 1, wherein the lubricated
surface comprises an internal surface or component of a compression
ignition engine.
5. The lubricated surface of claim 1, wherein the copolymer has
grafted thereon from about 0.3 to about 0.75 carboxylic groups per
1000 number average molecular weight units of the copolymer,
wherein the copolymer has a number average molecular weight ranging
from about 30,000 to about 60,000.
6. A motor vehicle comprising the lubricated surface of claim
1.
7. A vehicle having moving parts and containing a lubricant for
lubricating the moving parts, the lubricant comprising an oil of
lubricating viscosity and from about 9.5 to about 25 percent by
weight of an additive comprising a nitrogen containing olefin
copolymer derived from an olefin copolymer having grafted thereon
from about 0.15 to about 1.0 carboxylic groups per 1000 number
average molecular weight units of the copolymer, wherein the
copolymer has a number average molecular weight ranging from about
10,000 to about 100,000, and wherein the amount of additive in the
lubricant composition is based on a total weight of the lubricant
composition.
8. The vehicle of claim 7, wherein the copolymer has grafted
thereon from about 0.3 to about 0.75 carboxylic groups per 1000
number average molecular weight units of the copolymer, wherein the
copolymer has a number average molecular weight ranging from about
30,000 to about 60,000.
9. The vehicle of claim 7, wherein the moving parts comprise a
heavy duty diesel engine including exhaust gas recirculation and a
lubricating system for the engine.
10. A fully formulated lubricant composition comprising a base oil
component of lubricating viscosity and from about 9.5 to about 25
percent by weight of an additive comprising a nitrogen containing
olefin copolymer derived from an olefin copolymer having grafted
thereon from about 0.15 to about 1.0 carboxylic groups per 1000
number average molecular weight units of the copolymer, wherein the
copolymer has a number average molecular weight ranging from about
10,000 to about 100,000, and wherein the amount of additive in the
lubricant composition is based on a total weight of the lubricant
composition.
11. The lubricant composition of claim 10 wherein the lubricant
composition comprises a low ash, low sulfur lubricant compositions
suitable for compression ignition engines.
12. The lubricant composition of claim 10, wherein the copolymer
has grafted thereon from about 0.3 to about 0.75 carboxylic groups
per 1000 number average molecular weight units of the copolymer,
wherein the copolymer has a number average molecular weight ranging
from about 30,000 to about 60,000.
13. A method for reducing corrosion of metal parts in an engine
comprising contacting the engine parts with a lubricant composition
comprising a base oil component of lubricating viscosity and from
about 9.5 to about 25 percent by weight of an additive comprising a
nitrogen containing olefin copolymer derived from an olefin
copolymer having grafted thereon from about 0.15 to about 1.0
carboxylic groups per 1000 number average molecular weight units of
the copolymer, wherein the copolymer has a number average molecular
weight ranging from about 10,000 to about 100,000, and wherein the
amount of additive in the lubricant composition is based on a total
weight of the lubricant composition.
14. The method of claim 13 wherein the engine comprises a diesel
engine provided with exhaust gas recirculation.
15. The method of claim 13 wherein the engine comprises an inboard
or outboard marine engine.
16. The method of claim 13 wherein the engine comprises an engine
exposed to a salt water environment.
17. The method of claim 13, wherein the copolymer has grafted
thereon from about 0.3 to about 0.75 carboxylic groups per 1000
number average molecular weight units of the copolymer, wherein the
copolymer has a number average molecular weight ranging from about
30,000 to about 60,000.
18. A lubricant additive concentrate comprising a diluent or
carrier oil and from about 5 to about 90 percent by weight of an
additive comprising a nitrogen containing olefin copolymer derived
from an olefin copolymer having grafted thereon from about 0.15 to
about 1.0 carboxylic groups per 1000 number average molecular
weight units of the copolymer dissolved in a suitable solvent,
wherein the copolymer has a number average molecular weight ranging
from about 10,000 to about 100,000, wherein the amount of additive
in the concentrate is based on a total weight of the concentrate,
and wherein a fully formulated lubricant composition containing the
concentrate will contain from about 9.5 to about 25 percent by
weight of the additive based on a total weight of the lubricant
composition.
19. The additive concentrate of claim 18, wherein the copolymer has
grafted thereon from about 0.3 to about 0.75 carboxylic groups per
1000 number average molecular weight units of the copolymer,
wherein the copolymer has a number average molecular weight ranging
from about 30,000 to about 60,000.
20. A lubricant composition comprising a base oil and the additive
concentrate of claim 18.
21. A method of lubricating moving parts of a vehicle, the method
comprising using as a lubricating oil for one or more moving parts
of the vehicle a lubricant composition containing a base oil and a
lubricant additive, the lubricant additive comprising a diluent or
carrier oil and a nitrogen containing olefin copolymer derived from
an olefin copolymer having grafted thereon from about 0.15 to about
1.0 carboxylic groups per 1000 number average molecular weight
units of the copolymer dissolved in a suitable solvent, wherein the
copolymer has a number average molecular weight ranging from about
10,000 to about 100,000, wherein the lubricant composition contains
from about 9.5 to about 25 percent by weight of the additive based
on a total weight of the lubricant composition.
22. The method of claim 21 wherein the vehicle includes a diesel
engine provided with exhaust gas recirculation and wherein the
moving parts include moving parts of the engine.
23. The method of claim 21 wherein the vehicle includes a marine
vehicle having an engine, and wherein the moving parts include
moving parts of the engine.
24. The method of claim 21, wherein the copolymer has grafted
thereon from about 0.3 to about 0.75 carboxylic groups per 1000
number average molecular weight units of the copolymer, wherein the
copolymer has a number average molecular weight ranging from about
30,000 to about 60,000.
25. The method of claim 21 wherein the vehicle includes an internal
combustion engine having a crankcase and wherein the lubricant
composition comprises a crankcase oil present in the crankcase of
the vehicle.
26. The method of claim 21 wherein the lubricant composition
comprises a drive train lubricant present in an automotive drive
train of the vehicle.
27. A method of lubricating moving parts comprising contacting the
moving parts with a lubricant composition containing a lubricant
additive, the lubricant additive comprising a diluent or carrier
oil and a nitrogen containing olefin copolymer derived from an
olefin copolymer having grafted thereon from about 0.15 to about
1.0 carboxylic groups per 1000 number average molecular weight
units of the copolymer dissolved in a suitable solvent, wherein the
copolymer has a number average molecular weight ranging from about
10,000 to about 100,000, wherein the lubricant composition contains
from about 9.5 to about 25 percent by weight of the additive based
on a total weight of the lubricant composition.
28. The method of claim 27 wherein the moving parts comprise moving
parts of a vehicle.
29. The method of claim 28 wherein the vehicle includes a marine
vehicle having an engine, and wherein the moving parts include
moving parts of the engine.
30. The method of claim 27, wherein the copolymer has grafted
thereon from about 0.3 to about 0.75 carboxylic groups per 1000
number average molecular weight units of the copolymer, wherein the
copolymer has a number average molecular weight ranging from about
30,000 to about 60,000.
31. The method of claim 27 wherein the moving parts include an
internal combustion engine having a crankcase and wherein the
lubricant composition comprises a crankcase oil present in the
crankcase of the vehicle.
32. The method of claim 27 wherein the lubricant composition
comprises a drive train lubricant present in an automotive drive
train of the vehicle.
33. A metal surface comprising a corrosion inhibiting amount of an
oleaginous coating composition containing from about 9.5 to about
25 percent by weight of an additive comprising a nitrogen
containing olefin copolymer derived from an olefin copolymer having
grafted thereon from about 0.15 to about 1.0 carboxylic groups per
1000 number average molecular weight units of the copolymer,
wherein the copolymer has a number average molecular weight ranging
from about 10,000 to about 100,000, and wherein the amount of
additive in the composition is based on a total weight of the
oleaginous coating composition.
34. The metal surface of claim 33, wherein the copolymer has
grafted thereon from about 0.3 to about 0.75 carboxylic groups per
1000 number average molecular weight units of the copolymer,
wherein the copolymer has a number average molecular weight ranging
from about 30,000 to about 60,000.
Description
TECHNICAL FIELD
[0001] The following disclosure is directed to lubricants,
lubricant compositions and additives, lubricated parts and engines,
and methods for lubricating moving parts to provide improved
performance in harsh atmospheres.
BACKGROUND
[0002] Environmental concerns have led to continued efforts to
reduce the CO, hydrocarbon and nitrogen oxide (NO.sub.x) emissions
of engines, particularly of compression ignition engines such as
diesel engines. Several methods are currently used to reduce such
emissions. One method used to reduce the emissions of diesel
engines is known as exhaust gas recirculation or EGR. EGR reduces
NO.sub.x emissions by introducing non-combustible components
(exhaust gas) into the engine combustion chamber. The
non-combustible components reduce the peak flame temperature and
thus reduce NO.sub.x formation. Additional reduction of NO.sub.x
emissions is achieved by cooling the exhaust gas before it is
returned to the engine. A cooler combustion mixture leads to
greater power generation and better fuel economy at a fixed
NO.sub.x emission level.
[0003] While reducing NO.sub.x emissions, EGR systems in engines
increase the levels of NO.sub.x and sulfur oxide (SO.sub.x)-based
acids and particulate matter in the lubricants circulated through
such engines. The API CI-4 oil specification was established for
lubricating oil compositions for use in cooled EGR equipped diesel
engines.
[0004] Other methods for reducing emissions involve adjusting
engine timing to provide an early close of the engine exhaust
valve; use of a pilot fuel injector(s) upstream of the main fuel
injectors to reduce NO.sub.x generation; rate shaping of combustion
to reduce the peak combustion temperature and reduce NO.sub.x
generation; forcing excess air into the combustion chamber using a
turbocharger to boost power output, and the use of catalytic
after-treatment devices, such as devices containing oxidation
catalysts to reduce levels of unburned hydrocarbons, carbon
monoxide, nitrogen oxide and the soluble organic fraction of
particulate matter in the engine exhaust gas.
[0005] However, diesel fuels contain sulfur. When a sulfur
containing fuel is burned in an engine, the sulfur is converted to
SO.sub.x. Water vapor formed by the combustion of the fuel mixes
with the NO.sub.x and SO.sub.x to form corrosive acidic compounds
such as nitric acid and sulfuric acid in the recirculated and
cooled exhaust gases. Such acids attack metal components in the
engines causing an increase in corrosion of such metal components.
Improved protection of metal engine components is thus required for
such applications.
[0006] Other harsh environments for lubricated parts and engines
include, for example, marine applications where lubricated parts
and engines are constantly exposed to a salt water atmosphere.
Lubricants having improved corrosion protection characteristics are
needed for such applications.
[0007] In view of the foregoing, lubricants are undergoing constant
improvement to meet demanding needs and ever changing requirements.
However, there continues to be a need for lubricant compositions
and additives that can meet the demands of harsh environments as
described above.
SUMMARY OF THE EMBODIMENTS
[0008] In one embodiment herein is presented a lubricated surface.
The lubricated surface includes a thin film coating of a lubricant
composition containing a base oil of lubricating viscosity and from
about 9.5 to about 25 percent by weight of an additive comprising a
nitrogen containing olefin copolymer derived from an olefin
copolymer having grafted thereon from about 0.15 to about 1.0
carboxylic groups per 1000 number average molecular weight units of
the copolymer. The copolymer has a number average molecular weight
ranging from about 10,000 to about 100,000. The amount of additive
in the lubricant composition is based on a total weight of the
lubricant composition.
[0009] In another embodiment, there is provided a vehicle having
moving parts and containing a lubricant for lubricating the moving
parts. The lubricant includes an oil of lubricating viscosity and
from about 9.5 to about 25 percent by weight of an additive
comprising a nitrogen containing olefin copolymer derived from an
olefin copolymer having grafted thereon from about 0.15 to about
1.0 carboxylic groups per 1000 number average molecular weight
units of the copolymer. The copolymer has a number average
molecular weight ranging from about 10,000 to about 100,000. The
amount of additive in the lubricant composition is based on a total
weight of the lubricant composition.
[0010] In yet another embodiment there is provided a method of
lubricating moving parts. The method includes contacting the moving
parts with a lubricant composition containing from about 9.5 to
about 25 percent by weight of a lubricant additive. The lubricant
additive comprises a nitrogen containing olefin copolymer derived
from an olefin copolymer having grafted thereon from about 0.15 to
about 1.0 carboxylic groups per 1000 number average molecular
weight units of the copolymer. The copolymer has a number average
molecular weight ranging from about 10,000 to about 100,000. The
amount of additive in the lubricant composition is based on a total
weight of the lubricant composition.
[0011] A further embodiment of the disclosure provides a metal
surface including a corrosion inhibiting amount of lubricant. The
lubricant is provided by a fully formulated lubricant composition
containing from about 9.5 to about 25 percent by weight of an
additive comprising a nitrogen containing olefin copolymer derived
from an olefin copolymer having grafted thereon from about 0.15 to
about 1.0 carboxylic groups per 1000 number average molecular
weight units of the copolymer. The copolymer has a number average
molecular weight ranging from about 10,000 to about 100,000, and
the amount of additive in the lubricant composition is based on a
total weight of the lubricant composition.
[0012] Without desiring to be bound by theoretical considerations,
it is believed that an additive including the nitrogen containing
olefin component, when present in a lubricant composition in an
amount of about 9.5 weight percent or more, forms an effective
corrosion barrier film on a metal surface. The corrosion barrier
film is effective to reduce or prevent contact between the surface
and corrosive agents such as acids. The additive may be mixed with
an oleaginous fluid and applied to a surface as a protective
coating material. In other applications, the additive is provided
in a fully formulated lubricant composition. Despite the presence
of detergents and dispersants in the fully formulated lubricant
composition, the nitrogen containing olefin component remains
tightly adhered to a metal surface thereby prolonging its
protective effects on the surface of the metal.
[0013] The compositions and methods described herein are
particularly suitable for harsh environments such as present in
marine applications and heavy duty diesel engines equipped with
exhaust gas recirculation (EGR). Other features and advantages of
the of the compositions and methods described herein will be
evident by reference to the following detailed description which is
intended to exemplify aspects of the preferred embodiments without
intending to limit the embodiments described herein.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0014] 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 a predominantly hydrocarbon character.
Examples of hydrocarbyl groups include:
[0015] (1) 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 an alicyclic radical);
[0016] (2) substituted hydrocarbon substituents, that is,
substituents containing non-hydrocarbon groups which, in the
context of the description herein, do not alter the predominantly
hydrocarbon substituent (e.g., halo (especially chloro and fluoro),
hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and
sulfoxy);
[0017] (3) hetero-substituents, that is, substituents which, while
having a predominantly hydrocarbon character, in the context of
this description, contain other than carbon in a ring or chain
otherwise composed of carbon atoms. Hetero-atoms include sulfur,
oxygen, nitrogen, and encompass substituents such 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.
[0018] In all of the embodiments of the disclosure, a particular
lubricant component or additive is provided. The additive is
referred to generally as a multi-functional viscosity index
modifier. However, when used in fully formulated lubricant
compositions in amounts of 9.5 percent by weight or more, the
lubricant additive provides an effective corrosion inhibiting film
that is compatible with detergents and dispersants in the lubricant
composition. Specifically, the lubricant additive includes a
nitrogen containing olefin copolymer derived from a highly grafted,
multi-functional olefin copolymer and a polyamine compound,
generally as described in U.S. Pat. No. 6,107,257 to Valcho et al.
The nitrogen containing olefin copolymer is dissolved in a suitable
solvent such as Solvent Neutral 100 to provide the additive
component.
[0019] One particularly useful nitrogen containing olefin copolymer
is derived from an olefin copolymer having grafted thereon from
about 0.15 to about 1.0 carboxylic groups per 1000 number average
molecular weight units of the copolymer. The carboxylic groups are
subsequently reacted with amines to provide the nitrogen containing
olefin copolymers. The olefin copolymer may have a number average
molecular weight ranging from about 10,000 to about 100,000.
[0020] Another nitrogen containing olefin copolymer for use in
lubricant compositions according to the disclosure is an olefin
copolymer derived from a copolymer having grafted thereon from
about 0.3 to about 0.75 carboxylic groups per 1000 number average
molecular weight units of the copolymer. In this case, the
copolymer may have a number average molecular weight ranging from
about 30,000 to about 60,000.
[0021] Other nitrogen containing olefin copolymers which may be
used according to the disclosure are described, for example, in
U.S. Pat. No. 4,089,794 to Engel et al., U.S. Pat. No. 4,137,185 to
Gardiner et al., U.S. Pat. No. 4,146,489 to Stambaugh et al., U.S.
Pat. No. 4,320,019 to Hayashi, U.S. Pat. No. 4,357,250 to Hayashi,
U.S. Pat. No. 4,382,007 to Chafetz et al., U.S. Pat. No. 4,144,181
to Elliott et al., U.S. Pat. No. 4,863,623 to Nalesnik, U.S. Pat.
No. 5,075,383 to Migdal et al., U.S. Pat. No. 5,556,923 to Caines
et al., U.S. Pat. No. 5,932,525 to Ney et al., U.S. Pat. No.
5,162,086 to Migdal et al., and U.S. Pat. No. 5,744,429 to Chung et
al. A particularly useful nitrogen containing olefin copolymer is
described in U.S. Pat. No. 6,107,257 to Valcho et al.
[0022] The terms polymer and copolymer are used generically to
encompass ethylene copolymers, terpolymers or interpolymers. Such
materials may contain minor amounts of other olefinic monomers so
long as the basic characteristics of the ethylene copolymers are
not materially changed.
[0023] The polymer or copolymer backbone of the lubricant component
is a highly grafted, multi-functional olefin copolymer prepared
from ethylene and propylene or it may be prepared from ethylene and
at least one higher olefin within the range of C.sub.3 to C.sub.23
alpha-olefins. Copolymers of ethylene and propylene are most
preferred. 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, 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 backbones, often designated as
interpolymers, may be prepared using a third component. The third
component generally used to prepare an interpolymer backbone is a
polyene monomer selected from non-conjugated dienes and trienes.
The-non-conjugated diene component is one having from 5 to 14
carbon atoms in the chain. Preferably, the diene monomer is
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. A preferred non-conjugated
diene for preparing a terpolymer or interpolymer substrate is
1,4-hexadiene.
[0025] The triene component will 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 backbone are
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 may
consist of 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 the
preferred mole ratios being 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 the more preferred 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 the most preferred
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 may contain
from about 0.1 to 10 mole percent of a non-conjugated diene or
triene.
[0028] The polymer backbone, that is the ethylene copolymer or
terpolymer, is an oil-soluble, linear or branched polymer having a
number average molecular weight from about 20,000 to 100,000 as
determined by gel permeation chromatography and universal
calibration standardization, with a preferred number average
molecular weight range of 30,000 to 60,000.
[0029] An ethylenically unsaturated carboxylic acid material is
grafted onto the prescribed polymer backbone to form an acylated
ethylene copolymer. These carboxylic reactants which are suitable
for grafting onto the copolymer backbone contain at least one
ethylenic bond and at least one, preferably two, carboxylic acid or
its anhydride groups or a polar group which is convertible into
said carboxyl groups by oxidation or hydrolysis. Preferably, the
carboxylic reactants are selected from the group consisting of
acrylic, methacrylic, cinnamic, crotonic, maleic, fumaric and
itaconic reactants. More preferably, the carboxylic reactants are
selected from the group consisting of maleic acid, fumaric acid,
maleic anhydride, or a mixture of two or more of these. Maleic
anhydride or a derivative thereof is generally most preferred due
to its commercial availability and ease of reaction. In the case of
unsaturated ethylene copolymers or terpolymers, itaconic acid or
its anhydride is preferred 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 reactant is grafted onto the prescribed
polymer backbone in an amount to provide 0.15 to 1.0 carboxylic
groups per 1000 number average molecular weight units of the
polymer backbone, preferably 0.3 to 0.75 carboxylic groups per 1000
number average molecular weight. For example, a copolymer substrate
with a number average molecular weight of 20,000 may be grafted
with 3 to 20 carboxylic groups per polymer. A copolymer with a
number average molecular weight of 100,000 may be grafted with 15
to 100 carboxylic groups per polymer chain.
[0032] The polymer intermediate possessing carboxylic acid
acylating functions is reacted with a polyamine compound to provide
the nitrogen containing olefin copolymer. The polyamine compound
may be selected from the group consisting of:
[0033] (a) an N-arylphenylenediamine represented by the formula:
##STR1## in which R.sup.1 is hydrogen, --NH-aryl, --NH-arylalkyl,
--NH-alkyl, or a branched or straight chain radical having from 4
to 24 carbon atoms that can be alkyl, alkenyl, alkoxyl, aralkyl,
alkaryl, hydroxyalkyl or aminoalkyl; R.sup.2 is --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 is hydrogen, alkyl,
alkenyl, alkoxyl, aralkyl, alkaryl having from 4 to 24 carbon
atoms;
[0034] (b) an aminothiazole from the group consisting of
aminothiazole, aminobenzothiazole, aminobenzothiadiazole and
aminoalkylthiazole;
[0035] (c) an aminocarbazole represented by the formula: ##STR2##
in which R and R.sup.1 represent hydrogen or an alkyl, alkenyl, or
alkoxy radical having from 1 to 14 carbon atoms;
[0036] (d) an aminoindole represented by the formula: ##STR3## in
which R represents hydrogen or an alkyl radical having from 1 to 14
carbon atoms;
[0037] (e) an aminopyrrole represented by the formula: ##STR4## in
which R is a divalent alkylene radical having from 2 to 6 carbon
atoms and R.sup.1 is hydrogen or an alkyl radical having from 1 to
14 carbon atoms;
[0038] (f) an amino-indazolinone represented by the formula:
##STR5## in which R is hydrogen or an alkyl radical having from 1
to 14 carbon atoms;
[0039] (g) an aminomercaptotriazole represented by the formula:
##STR6## in which R can be absent or is a C.sub.1-C.sub.10 linear
or branched hydrocarbon selected from the group consisting of
alkyl, alkenyl, arylalkyl, or aryl;
[0040] (h) an aminoperimidine represented by the formula: ##STR7##
in which R represents hydrogen or an alkyl or alkoxyl radical
having from 1 to 14 carbon atoms;
[0041] (i) aminoalkyl imidazoles, such as
1-(2-aminoethyl)imidazole, 1-(3-aminopropyl)imidazole; and
[0042] (j) anminoalkyl morpholines, such as
4-(3-aminopropyl)morpholine.
[0043] Particularly preferred polyamines for reaction with the
olefin copolymer are the N-arylphenylenediamines, more specifically
the N-phenylphenylenediamines, for example,
N-phenyl-1,4-phenylenediamine, N-phenyl-1,3-phenylendiamine, and
N-phenyl-1,2-phenylenediamine.
[0044] It is preferred that the polyamines contain only one primary
amine group so as to avoid coupling and/or gelling of the olefin
copolymers.
[0045] The highly grafted, multi-functional olefin copolymers may
be post-treated so as to impart additional properties necessary or
desired for a specific lubricant application. Post-treatment
techniques are well known in the art and include boronation,
phosphorylation, maleination, and reaction with an aldehyde,
ketone, acid or acid anhydride.
[0046] Methods for stabilizing the color of nitrogen containing
olefin copolymers using an aldehyde, ketone, acid or acid anhydride
are known and are set forth, for example, in U.S. Pat. No.
5,207,938.
[0047] The highly grafted, multi-functional olefin copolymers may
be incorporated into a base oil in any convenient way. Thus, the
highly grafted, multi-functional olefin copolymers may be added
directly to the base oil by dispersing or dissolving the same in
the lubricating oil at the desired level of concentration. Such
blending into the base oil can occur at room temperature or
elevated temperatures. Alternatively, the highly grafted,
multi-functional olefin copolymers may be dissolved in a suitable
solvent in an amount ranging from about 10 to about 20% by weight
to form a solution. The solution may be blended with a suitable
oil-soluble solvent/diluent (such as benzene, xylene, toluene,
lubricating base oils and petroleum distillates) to form a
concentrate, and the concentrated then blended with a lubricating
oil to obtain the final formulation. Such additive concentrates
will typically contain (on an active ingredient (A.I.) basis, i.e.,
excluding the weight of impurities, diluents and solvents typically
associated therewith) from about 5 to about 90 wt. %, and
preferably from about 40 to about 60 wt. %, highly grafted,
multi-functional olefin copolymer solution, and typically from
about 10 to 90 wt %, preferably from about 40 to 60 wt %, base oil
based on the concentrate weight.
[0048] In the preparation of lubricating oil formulations it is
common practice to introduce the additives in the form of 5 to 30
wt. % active ingredient concentrates in hydrocarbon oil, e.g.
mineral lubricating oil, or other suitable solvent. Usually these
concentrates may be diluted with 3 to 100, e.g., 5 to 40, parts by
weight of lubricating oil per part by weight of the additive
package in forming finished lubricants, e.g. crankcase motor oils.
The purpose of concentrates, of course, is to make the handling of
the various materials less difficult and awkward as well as to
facilitate solution or dispersion in the final blend. Thus, the
highly grafted, multi-functional olefin copolymer solution would
usually be employed in the form of a 40 to about 60 wt. %
concentrate, for example, in a lubricating oil fraction.
[0049] Lubricant compositions made with the additive containing the
nitrogen containing olefin copolymer described above are used in a
wide variety of applications. For compression ignition engines and
spark ignition engines, it is preferred that the lubricant
compositions meet or exceed published GF-4 or API-CI-4 standards.
Lubricant compositions according to the foregoing GF-4 or API-CI-4
standards include a base oil and an oil additive package to provide
a fully formulated lubricant. The base oil for lubricants according
to the disclosure is an oil of lubricating viscosity selected from
natural lubricating oils, synthetic lubricating oils and mixtures
thereof. Such base oils include those conventionally employed as
crankcase lubricating oils for spark-ignited and
compression-ignited internal combustion engines, such as automobile
and truck engines, marine and railroad diesel engines, and the
like.
[0050] Natural oils include animal oils and vegetable oils (e.g.,
castor oil, lard oil), liquid petroleum oils and hydrorefined,
solvent-treated or acid-treated mineral lubricating oils of the
paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils
of lubricating viscosity derived from coal or shale are also useful
base oils. The synthetic lubricating oils used in this invention
include one of any number of commonly used synthetic hydrocarbon
oils, which include, but are not limited to, poly-alpha-olefins,
alkylated aromatics, alkylene oxide polymers, interpolymers,
copolymers and derivatives thereof here the terminal hydroxyl
groups have been modified by esterification, etherification etc,
esters of dicarboxylic acids and silicon-based oils.
[0051] Fully formulated lubricants conventionally contain an
additive package that will supply the characteristics that are
required in the formulations. Among the types of additives included
in the additive package are detergents/dispersants, friction
modifiers, seal swell agents, antiwear agents, extreme pressure
agents, antioxidants, foam inhibitors, lubricity agents, rust
inhibitors, corrosion inhibitors, demulsifiers, viscosity index
improvers, dyes, and the like. Various of these components are well
known to those skilled in the art and are preferably used in
conventional amounts with the additives and compositions described
herein.
[0052] For example, suitable detergents/dispersants are selected
from the group consisting of, but not limited to, oil-soluble
ashless dispersants having a basic nitrogen and/or at least one
hydroxyl group in the molecule. Suitable detergents/dispersants
include alkenyl succinimides, alkenyl succinic acid esters, alkenyl
succinic ester-amides, Mannich bases, hydrocarbyl polyamines,
polymeric polyamines, or olefin copolymers.
[0053] The alkenyl succinimides in which the succinic group
contains a hydrocarbyl substituent containing at least 30 carbon
atoms are described, for example, in U.S. Pat. Nos. 3,172,892;
3,202,678; 3,216,936; 3,219,666; 3,254,025; 3,272,746; and
4,234,435.
[0054] Alkenyl succinic acid esters and diesters of polyhydric
alcohols containing 2-20 carbon atoms and 2-6 hydroxyl groups can
be used in forming phosphorus-containing ashless dispersants.
Representative examples are described in U.S. Pat. Nos. 3,331,776;
3,381,022; and 3,522,179.
[0055] Suitable alkenyl succinic ester-amides for forming
phosphorylated ashless dispersant are described, for example, in
U.S. Pat. Nos. 3,184,474; 3,576,743; 3,632,511; 3,804,763;
3,836,471; 3,862,981; 3,936,480; 3,948,800; 3,950,341; 3,957,854;
3,957,855; 3,991,098; 4,071,548; and 4,173,540.
[0056] Hydrocarbyl polyamines are described in U.S. Pat. Nos.
3,275,554; 3,394,576; 3,438,757; 3,454,555; 3,565,804; 3,671,511;
and 3,821,302.
[0057] The Mannich base dispersants are preferably a reaction
product of an alkyl phenol, typically having a long chain alkyl
substituent on the ring, with one or more aliphatic aldehydes
containing from 1 to about 7 carbon atoms (especially formaldehyde
and derivatives thereof), and polyamines (especially polyalkylene
polyamines). Examples of Mannich condensation products, and methods
for their production are described in U.S. Pat. Nos. 2,459,112;
2,962,442; 2,984,550; 3,036,003; 3,166,516; 3,236,770; 3,368,972;
3,413,347; 3,442,808; 3,448,047; 3,454,497; 3,459,661; 3,493,520;
3,539,633; 3,558,743; 3,586,629; 3,591,598; 3,600,372; 3,634,515;
3,649,229; 3,697,574; 3,703,536; 3,704,308; 3,725,277; 3,725,480;
3,726,882; 3,736,357; 3,751,365; 3,756,953; 3,793,202; 3,798,165;
3,798,247; 3,803,039; 3,872,019; 3,904,595; 3,957,746; 3,980,569;
3,985,802; 4,006,089; 4,011,380; 4,025,451; 4,058,468; 4,083,699;
4,090,854; 4,354,950; and 4,485,023.
[0058] Polymeric polyamine dispersants suitable as the ashless
dispersants of the present invention are polymers containing basic
amine groups and oil solubilizing groups (for example, pendant
alkyl groups having at least about 8 carbon atoms). Such materials
are illustrated by interpolymers formed from various monomers such
as decyl methacrylate, vinyl decyl ether or relatively high
molecular weight olefins, with aminoalkyl acrylates and aminoalkyl
acrylamides. Examples of polymeric polyamine dispersants are set
forth in U.S. Pat. Nos. 3,329,658; 3,449,250; 3,493,520; 3,519,565;
3,666,730; 3,687,849; and 3,702,300.
[0059] Olefin copolymer dispersants are described in U.S. Pat. Nos.
5,075,383 6,117,825; 6,107,258; 5,266,223; 5,350,532; 5,435,926;
4,952,637, 5,356,999, 5,374,364, and 5,424,366.
[0060] The various types of ashless dispersants described above may
be phosphorylated by procedures described in U.S. Pat. Nos.
3,184,411; 3,342,735; 3,403,102; 3,502,607; 3,511,780; 3,513,093;
3,513,093; 4,615,826; 4,648,980; 4,857,214 and 5,198,133.
[0061] The dispersants of the present invention may be boronated.
Methods for boronating (borating) the various types of ashless
dispersants described above are described in U.S. Pat. Nos.
3,087,936; 3,254,025; 3,281,428; 3,282,955; 2,284,409; 2,284,410;
3,338,832; 3,344,069; 3,533,945; 3,658,836; 3,703,536; 3,718,663;
4,455,243; and 4,652,387.
[0062] Preferred procedures for phosphorylating and boronating
ashless dispersants such as those referred to above are set forth
in U.S. Pat. Nos. 4,857,214 and 5,198,133.
[0063] In the alternative, the dispersants described above may be
glycolated and Mannich base coupled as described in U.S. Pat. Nos.
4,633,322; and 5,122,161.
[0064] The amount of ashless dispersant on an active ingredient
basis is generally within the range of about 0.5 to about 7.5
weight percent (wt %), typically within the range of about 0.5 to
5.0 wt %, preferably within the range of about 0.5 to about 3.0 wt
%, and most preferably within the range of about 2.0 to about 3.0
wt %, based on the finished oil.
[0065] Suitable friction modifiers are described in U.S. Pat. Nos.
5,344,579; 5,372,735; and 5,441,656. Seal swell agents are
described, for example, in U.S. Pat. Nos. 3,794,081 and 4,029,587.
Antiwear and/or extreme pressure agents are disclosed in U.S. Pat.
Nos. 4,857,214; 5,242,613; and 6,096,691. Suitable antioxidants are
described in U.S. Pat. Nos. 5,559,265; 6,001,786; 6,096,695; and
6,599,865. Foam inhibitors suitable for compositions and additives
described herein are set forth in U.S. Pat. Nos. 3,235,498;
3,235,499; and 3,235,502. Rust or corrosion inhibitors are
described in U.S. Pat. Nos. 2,765,289; 2,749,311; 2,760,933;
2,850,453; 2,910,439; 3,663,561; 3,862,798; and 3,840,549.
Viscosity index improvers and processes for making them are taught
in, for example, U.S. Pat. Nos. 4,732,942; 4,863,623; 5,075,383;
5,112,508; 5,238,588; and 6,107,257. Multi-functional viscosity
index improvers are taught in U.S. Pat. Nos. 4,092,255; 4,170,561;
4,146,489; 4,715,975; 4,769,043; 4,810,754; 5,294,354; 5,523,008;
5,663,126; and 5,814,586; and 6,187,721. Demulsifiers are described
in U.S. Pat. Nos. 4,444,654 and 4,614,593.
[0066] Base oils suitable for use in formulating the compositions,
additives and concentrates described herein may be selected from
any of the synthetic or natural oils or mixtures thereof. The
synthetic base oils include alkyl esters of dicarboxylic acids,
polyglycols and alcohols, poly-alpha-olefins, including
polybutenes, alkyl benzenes, organic esters of phosphoric acids,
and polysilicone oils. Natural base oils include mineral
lubrication oils which may vary widely as to their crude source,
e.g., as to whether they are paraffinic, naphthenic, or mixed
paraffinic-naphthenic. The base oil typically has a viscosity of
about 2.5 to about 15 cSt and preferably about 2.5 to about 11 cSt
at 100.degree. C.
[0067] Accordingly, the base oil used which may be used may be
selected from any of the base oils in Groups I-V as specified in
the American Petroleum Institute (API) Base Oil Interchangeability
Guidelines. Such base oil groups are as follows: TABLE-US-00001
Sulfur Saturates Viscosity Base Oil Group.sup.1 (wt. %) (wt. %)
Index Group I >0.03 and/or <90 80 to 120 Group II
.ltoreq.0.03 And .gtoreq.90 80 to 120 Group III .ltoreq.0.03 And
.gtoreq.90 .gtoreq.120 Group IV all polyalphaolefins (PAOs) Group V
all others not included in Groups I-IV .sup.1Groups I-III are
mineral oil base stocks.
[0068] The additives used in formulating the compositions described
herein can be blended into the base oil individually or in various
sub-combinations. However, it is preferable to blend all of the
components concurrently using an additive concentrate (i.e.,
additives plus a diluent, such as a hydrocarbon solvent). The use
of an additive concentrate takes advantage of the mutual
compatibility afforded by the combination of ingredients when in
the form of an additive concentrate. Also, the use of a concentrate
reduces blending time and lessens the possibility of blending
errors.
[0069] The following example is given for the purpose of
exemplifying aspects of the embodiments and is not intended to
limit the embodiments in any way.
EXAMPLE
[0070] A heavy duty diesel lubricant formulation (SAE 15W-40) was
prepared in a CITGO/Yubase base stock and included 10% by weight
solution of HiTEC.RTM. 5777D (nitrogen containing olefin copolymer
solution in solvent neutral 100 diluent) available from Ethyl
Corporation of Richmond Virginia, 0.2% by weight pour point
depressant (HiTEC.RTM. 5789), 14.8% by weight dispersant inhibitor
package (HiTEC.RTM. 1229), and 0.2% by weight amine antioxidant
(HiTEC.RTM. 7190). ASTM D665 carbon steel rust pins were twice
dipped in the lubricant formulation set forth above and in a
lubricant formulation absent nitrogen containing olefin copolymer
component. The pins were then placed in 37 wt. % hydrochloric acid
at room temperature in closed glass jars. The corrosion potential
of the lubricants was assessed by monitoring the amount of gas
bubbles generated by the reaction of hydrochloric acid on the
metals. A ranking system ranging from 0-10 with 10 being the most
bubbles was used to compare the results. The lubricant formulation
containing the nitrogen containing olefin copolymer had a ranking
of 3 while the lubricant formulation having an absence of the
nitrogen containing olefin copolymer had a ranking of 8. It was
concluded that a lubricant formulation containing 10 wt. % or more
of the nitrogen containing olefin copolymer solution provided
superior corrosion protection in acid atmospheres.
[0071] At numerous places throughout this specification, reference
has been made to a number of U.S. patents. All such cited documents
are expressly incorporated in full into this disclosure as if fully
set forth herein.
[0072] The foregoing embodiments are susceptible to considerable
variation in its practice. Accordingly, the embodiments are not
intended to be limited to the specific exemplifications set forth
hereinabove. Rather, the foregoing embodiments are within the
spirit and scope of the appended claims, including the equivalents
thereof available as a matter of law.
[0073] The patentees do not intend to dedicate any disclosed
embodiments to the public, and to the extent any disclosed
modifications or alterations may not literally fall within the
scope of the claims, they are considered to be part hereof under
the doctrine of equivalents.
* * * * *