DISPERSANT AND ANTI-OXIDANT ADDITIVE AND LUBRICATING OIL COMPOSITION CONTAINING SAME

ADDITIF DISPERSIF ET ANTI-OXYDANT ET COMPOSE D'HUILE LUBRIFIANTE CONTENANT CET ADDITIF

English Abstract

Disclosed are an additive composition comprising a
graft and amine-derivatized copolymer prepared from ethylene
and at least one C3-C10 alpha-monoolefin and, optionally, a
polyene selected from non-conjugated dimes and trienes
comprising from about 15 to 80 mole percent of ethylene, from
about 20 to 85 mole percent of the C3-C10 alpha-monoolefin and
from about 0 to 15 mole percent of the polyene having an
average molecular weight ranging from about 1,000 to 40,000
which has been reacted with at least one olefinic carboxylic
acid acylating agent to form one or more acylating reaction
intermediates characterized by having at least about 1.5 weight
percent of a carboxylic acid acylating function within their
structure and reacting the reaction intermediate with an amino-aromatic
polyamine compound from the group consisting of an
N-arylphenylenediamine, an aminothiazole, an aminocarbazole, an
aminoindole, an aminopyrrole, an amino-indazolinone, an
aminomercaptotriazole, and an aminoperimidine to form the graft
and amine-derivatized copolymer, and a lubricating oil
composition containing same.

Claims

CLAIMS:
1, An additive composition prepared by a process
comprising the steps of:
(A) providing a polymer intermediate having at least
about 1.5 weight percent of a carboxylic acid acylating
function grafted thereon, the polymer intermediate being based
on a polymer substrate backbone which is (i) a copolymer of
from about 15 to about 80 mole percent of ethylene and from
about 85 to about 20 mole percent of at least one C3-C10
alpha-monoolefin or (ii) a terpolymer of from about 15 to about
80 mole percent of ethylene, from about 85 to 20 mole percent
of at least one C3-C10 alpha-monoolefin and from about 0.1 to
about 10 mole percent of a non-conjugated dime or triene and
which has an average molecular weight ranging from about 1,000
to 40,000 and onto which at least one ethylenically unsaturated
carboxylic acid material has been grafted, and
(B) then reacting the polymer intermediate with an
amino-aromatic polyamine compound selected from the group
consisting of:
(a) an N-arylphenylenediamine represented by the
formula:
<IMG>
in which Ar is an aromatic hydrocarbon radical, R1 is hydrogen,
-NH-aryl, -NH-arylalkyl, a branched or straight chain radical
having from 4 to 24 carbon atoms that is an alkyl, alkenyl,
alkoxy, aralkyl, alkaryl, hydroxyalkyl or aminoalkyl radical,
R2 is -NH2, -CH2-(CH2)n-NH2,-CH2-aryl-NH2 in which n has a
value from 1 to 10, and
-25-

R3 is hydrogen or an alkyl, alkenyl, alkoxy, aralkyl or alkaryl
radical each having 4 to 24 carbon atoms;
(b) an aminothiazole selected from the group
consisting of aminothiazole, aminobenzothiazole,
aminobenzothiadiazole and aminoalkylthiazole;
(c) an aminocarbazole represented by the formula
<IMG>
in which R and R1 represent hydrogen or an alkyl or alkenyl
radical having from 1 to 14 carbon atoms
(d) an aminoindole represented by the formula:
<IMG>
in which R represents hydrogen or an alkyl radical having from
1 to 14 carbon atoms;
(e) an aminopyrrole represented by the formula:
<IMG>
in which R is a divalent alkylene radical having 2 - 6 carbon
atoms and R1 is hydrogen or an alkyl radical having from 1 to
14 carbon atoms;
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(f) an amino-indazolinone represented by the formula:
<IMG>
in which R is hydrogen or an alkyl radical having from 1 to 14
carbon atoms;
(g) an aminomercaptotriazole represented by the
formula:
<IMG> and
(h) an aminoperimidine represented by the formula:
<IMG>
in which R represents hydrogen or an alkyl, alkenyl, or alkoxy
radical having from 1 to 8 carbon atoms.
2. A composition according to Claim 1 in which the
polymer intermediate has a number average molecular weight from
about 5,000 to 20,000.
3. A composition according to Claim 1, in which the
polymer intermediate has a number-average molecular weight from
about 8,000 to 17,000.
-27-

4. A composition according to any one of Claims 1 to 3,
in which the polymer substrate is a copolymer of from about 25
to 75 mole percent ethylene and from about 75 to 25 mole
percent of a C3 to C8 alpha-monoolefin.
5. A composition according to any one of Claims 1 to 3,
in which the polymer substrate is a copolymer of from about 25
to 55 mole percent ethylene and from about 45 to 75 mole
percent of propylene.
6. A composition according to any one of Claims 1 to 4,
in which the polymer substrate is a terpolymer of from about 25
to 75 mole percent ethylene, from about 75 to about 25 mole
percent of a C3 to C8 alpha-monoolefin and from about 0.1 to 10
mole percent of a non-conjugated dime or triene.
7. A composition according to any one of Claims 1 to 6,
in which the ethylenically unsaturated carboxylic acid material
is malefic anhydride.
8. A composition according to any one of Claims 1 to 6,
in which the ethylenically unsaturated carboxylic acid material
is itaconic anhydride.
9. A composition according to any one of Claim 1 to 8,
in which the amino-aromatic polyamine compound is the
N-arylphenylenediamine of the formula (I).
10. A composition according to Claim 9, in which the
N-arylphenylene diamine is N-phenylphenylenediamine.
11. A composition according to Claim 9, in which the
N-arylphenylene diamine is N-phenyl-p-phenylenediamine.
12. A composition according to Claim 9, in which the
N-arylphenylene diamine is N-phenyl-1,3-phenylenediamine.
-28-

13. A composition according to any one of Claims 1 to 9,
in which the amino-aromatic polyamine compound is the
aminothiazole(b).
14. A composition according to any one of Claims 1 to 13,
in which the polymer intermediate has from 2 to 5 weight
percent of the grafted carboxylic acid acylating function.
15. A composition according to any one of Claims 1 to 14,
in which the polymer intermediate has from about 2.25 to 3
weight percent of the grafted carboxylic acid acylating
function.
16. A process for producing the additive composition as
defined in any one of Claims 1 to 14, which comprises:
(A) obtaining the polymer intermediate having a
number-average molecular weight of from about 1,000 to about 40,000
and having at least 1.5 weight percent of a carboxylic acid
acylating function grafted thereon, by:
(1) providing a polymer substrate which is (i) a
copolymer of from about 15 to about 80 mole percent of ethylene
and from about 85 to about 20 mole percent of at least one
C3-C10 alpha-monoolefin or (ii) a terpolymer of from about 15
to about 80 mole percent of ethylene, from about 85 to about 20
mole percent of at least one C3-C10 alpha-monoolefin and from
about 0.1 to about 10 mole percent of a non-conjugated diene or
triene and which has a number-average molecular weight of above
about 75,000,
(2) grafting the polymer substrate with an ethylenically
unsaturated carboxylic acid material, and
(3) degrading the polymer substrate by a mechanical or
thermal shearing process to reduce the number-average molecular
weight to from about 5,000 to 40,000,
-29-

where the steps (2) and (3) may be conducted
simultaneously or sequentially in any order; and
(B) then reacting the polymer intermediate with the
amino-aromatic polyamine compound.
17. A process according to Claim 16, in which the
grafting step (2), of the polymer substrate with the
ethylenically unsaturated carboxylic acid material is effected
using a mechanical shearing process.
18. A process according to Claim 16, in which the
grafting step (2) of the polymer substrate with the
ethylenically unsaturated carboxylic acid material is effected
using a thermal or melt grafting process at a temperature which
is from about 150 to about 400°C and at which the polymer
substrate is molten.
19. A process according to Claim 18, in which the thermal
or melt grafting process is effected in an extruder.
20. A process according to any one of Claims 16 to 19, in
which the grafting step (2) and the degrading step (3) are
effected simultaneously.
21. A process according to any one of Claims 16 to 20, in
which the polymer substrate has a number-average molecular
weight of 100,000 to 300,000.
22. A composition which is a mixture of the additive
composition of any one of Claims 1 to 15 or the additive
composition prepared by the process of any one of Claims 16 to
21 and a reaction product of a grafted polymer and an amine
other than the amino-aromatic polyamine having in its structure
one primary amine group and either a tertiary or a highly
hindered secondary amine group, wherein the grafted polymer has
the same characteristics as the polymer intermediate.
-30-

23. A composition according to Claim 22, wherein the
amine other than the amino-aromatic polyamine is selected from
the group consisting of aminopropylmorpholine,
aminoethylmorpholine, and N-methylaminopropylpiperazine.
24. A lubricating oil composition comprising a major
amount of an oil of lubricating viscosity and a minor amount
effective to impart dispersancy and anti-oxidant properties to
the oil of the additive composition of any one of Claims 1 to
15 or the additive composition produced by the process of any
one of Claims 16 to 21.
25. A lubricating oil composition according to Claim 24,
which contains from about 0.1 to about 30 weight percent of the
additive composition.
26. A lubricating oil composition according to Claim 24,
which contains from about 0.5 to about 15 weight percent of the
additive composition.
27. A lubricating oil composition comprising a major
amount of an oil of lubricating viscosity and a minor amount
effective to impart dispersancy and anti-oxidant properties to
the oil of the composition of Claim 22 or 23.
28. A single grade lubricating oil composition comprising
an oil of lubricating viscosity and from about 0.5 to 15 weight
percent of the additive of Claim 11.
-31-

Description

. CA 02021959 2000-02-03
rr
DISPERSANT AND ANTI-OXIDANT ADDITIVE
AND LUBRICATING OIL COMPOSITION CONTAINING SAME
(D#79,173 -F)
Background of the Invention
This invention relates to a novel bi-functional lubricant
additive which provides dispersancy and anti-oxidant properties
when employed in a single grade lubricating oil composition.
Disclosure Statement
Ethylene-propylene copolymers and ethylene-alpha olefin
non-conjugated diene terpolymers which have been grafted and
derivatized to provide valuable properties in lubricating oil
compositions are well known.
U.S. 3,522,180 discloses a method for the preparation of
an ethylene-propylene copolymer substrate effective as a
viscosity index improver for lubricating oils.
U.S. Pat. No. 4,026,809 dicloses graft copolymers of a
methacrylate ester and an ethylene-propylene-alkylidene
norbornene terpolymer as a viscosity index improver for
lubricating oils.
U.S. Pat. No. 4,089,794 discloses ethylene copolymers
derived from ethylene and one or more C3 to C2a alpha olefin
solution grafted with an ethylenically-unsaturated carboxylic
acid material followed by a reaction with a polyfunctional
material reactive with carboxyl groups, such as a polyamine,
a polyol, or a hydroxyamine which reaction product is useful
as a sludge and varnish control additive in lubricating oils.
U.S. Pat. No. 4,137,185 discloses a stabilized imide
graft of an ethylene copolymer additive for lubricants.
U. S. Pat. No. 4, 146, 489 discloses a graft copolymer where
the backbone polymer is an oil-soluble ethylene-propylene
copolymer or an ethylene-propylene-diene modified terpolymer
with a graft monomer of C-vinylpyridine or N-vinylpyrrolidone

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to provide a dispersant VI improver for lubricating oils.
U.S. Pat. No. 4,320,019 discloses a multipurpose
lubricating additive prepared by the reaction of an
interpolymer of ethylene and a C3-Cg alpha-monoolefin with an
olefinic carboxylic acid acylating agent to form an acylating
reaction intermediate which is then reacted with an amine.
U.S. Pat. No. 4,340,689 discloses a process for
grafting a functional organic group onto an ethylene copolymer
or an ethylene-propylene-dime terpolymer.
U.S. Pat No. 4,357,250 discloses a reaction product
of a copolymer and an olefin carboxylic acid via the "ene"
reaction followed by a reaction with a monoamine-polyamine
mixture.
U.S. Pat No. 4,382,007 discloses a dispersant - VI
improver prepared by reacting a polyamine-derived dispersant
with an oxidized ethylene-propylene polymer or an ethylene-
propylene dime terpolymer.
U.S. Pat. No. 4,144,181 discloses polymer additives
for fuels and lubricants comprising a grafted ethylene
copolymer reacted with a polyamine, polyol or hydroxyamine and
finally reacted with an alkaryl sulfonic acid.
U.S. Pat. No. 4,863,623 discloses multi-functional
grafted and derivatized copolymers which provide viscosity
index improvement, dispersancy and anti-oxidant properties in a
multi-grade lubricating oil composition.
An object of this invention is to provide a novel
derivatized graft copolymer composition.
Another object of the invention is to provide a
bi-functional lubricant additive effective for imparting
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dispersancy and anti-oxidant properties to a single grade
lubricating oil composition.
A further object is to provide a novel lubricating
oil composition containing the graft copolymer additive of the
invention as well as to provide concentrates of the novel
additive of invention.
Summary of the Invention
The novel reaction product of the invention comprises
an ethylene copolymer or terpolymer of a C3 to Cl0 alpha-
monoolefin and optionally a non-conjugated dime or triene,
having a molecular weight ranging from about 1,000 to 40,000 on
which has been grafted an ethylenically unsaturated carboxylic
function in the amount of at least 1.5 weight percent which is
then further derivatized with an amino-aromatic polyamine
compound selected from the group consisting of:
(a) an N-arylphenylenediamine represented by the
formula:
g R3
R1 Ar-N O ( I )
R2
in which:
Ar is aromatic,
Rl is H, -NHaryl, -NHarylalkyl or a branched or
straight chain radical having from 4 to 24 carbon atoms that
can be an alkyl, alkenyl, alkoxy, aralkyl alkaryl, hydroxyalkyl
or aminoalkyl group,
- 3 -

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"''
R2 is -NH2, -CH2-(CH2)n-NH2, CH2-aryl-NH2-aryl-NH2 in
which n has a value from 1 to 10, and
R3 is hydrogen or an alkyl, alkenyl, alkoxy, aralkyl
or alkaryl group each having from 4 to 24 carbon atoms,
(b) an aminothiazole selected from the group
consisting of aminothiazole, aminobenzothiazole,
aminobenzothiadiazole and aminoalkylthiazole,
(c) an aminocarbazole represented by the formula:
R ~ ~/
R
H
in which R and R1 each represent hydrogen or an alkyl or
alkenyl radical having from 1 to 14 carbon atoms,
(d) an aminoindole represented by the formula:
in which R represents hydrogen or an alkyl radical having from
1 to 14 carbon atoms,
(e) an aminopyrrole represented by the formula:
R NH2
Rl N
H
- 4 -

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.r
in which R is a divalent alkylene radical having 2-6 carbon
atoms and Rl is hydrogen or an alkyl radical having from 1 to
14 carbon atoms,
(f) an aminoindazolinone represented by the formula:
/O
NH2
U /NH
R I
H
in which R is hydrogen or an alkyl radical having from 1 to 14
carbon atoms,
(g) an aminomercaptotriazole represented by the
formula:
N NH2
HS
and
N
H
(h) an aminopermidine represented by the formula:
NH2
N NH
R
in which R represents hydrogen or an alkyl radical having from
1 to 14 carbon atoms.
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The novel lubricant of the invention comprises an oil
of lubricating viscosity and an effective dispersant and anti-
oxidant amount of the novel reaction product. This unique
product is characterized as a single grade lubricating oil
composition.
Concentrates of the reaction product of the invention
are also contemplated.
- 5a -

~0219~9
DETAILED DESCRIPTION OF THE INVENTION
The polymer or copolymer substrate employed in the novel
additive of the invention may be prepared from ethylene and
propylene or it may be prepared from ethylene and a higher
olefin within the range of C3 to Coo alpha-monoolefins.
More complex polymer substrates, often designated as
interpolymers, may be prepared using a third component. The
third component generally used to prepare an interpolymer
substrate 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 bi-cyclo 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 dime for
preparing a terpolymer of interpolymer substrate is 1,4-
hexadiene.
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 of the invention are 1-isopropylidene-3a,4,7,7a-
tetrahydroindene, 1-isopropylidenedicyclopentadiene, dehydro-
isodicyclopentadiene, and 2-(2-methylene-4-methyl-3-
pentenyl)[2.2.1] bicyclo-5-heptene.
The polymerization reaction to form the polymer substrate
is generally carried out in the presence of a catalyst in a
solvent medium. The polymerization solvent may be any suitable
inert organic solvent that is liquid under reaction conditions
for solution polymerization of monoolefins which is generally
conducted in the presence of a Ziegler type catalyst. Examples
of satisfactory hydrocarbon solvents include straight chain
D#79,173 - 6 -

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.,
paraffins having from 5-8 carbon atoms, with hexane being
preferred. Aromatic hydrocarbons, preferably 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, are particularly suitable. The solvent selected may be
mixture of one or more of the foregoing hydrocarbons. It is
desirable that the solvent be free of substances that will
interfere with a Ziegler polymerization reaction.
In a typical preparation of a polymer substrate,
hexane is first introduced into a reactor and the temperature
in the reactor is raised moderately to about 30°C. Dry
propylene is fed to the reactor until the pressure reaches
about 40-45 inches of mercury. The pressure is then increased
to about 60 inches of mercury and dry ethylene and 5-
ethylidene-2-norbornene are fed to the reactor. The monomer
feeds are stopped and a mixture of aluminum sesquichloride and
vanadium oxytrichloride are added to initiate the
polymerization reaction. Completion of the polymerization
reaction is evidenced by a drop in the pressure in the reactor.
Ethylene-propylene or higher alpha monoolefin
copolymers may consist of from about 15 to 80 mole percent
ethylene and from about 20 to 85 mole percent propylene or
higher monoolefin with the preferred mole ratios being from
about 25 to 75 mole percent ethylene and from about 25 to 75
mole percent of a C3 to C10 alpha monoolefin with the most
preferred proportions being from 25 to 55 mole percent ethylene
and 45 to 75 mole percent propylene.
* Trade-mark
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Terpolymer variations of the foregoing polymers may
contain from about 0.1 to 10 mole percent of a non-conjugated
dime or triene.
The polymer substrate, that is the ethylene copolymer
or terpolymer is an oil-soluble, substantially linear, rubbery
material having a number average molecular weight from about
1,000 to 40,000 with a preferred molecular weight range of
5,000 to 20,000 and a most preferred range from about 8,000 to
17,000. The molecular weight of the polymer substrate is
determined as number average molecular weight.
It will be appreciated that many polymerization
processes produce high molecular weight polymers having
molecular weights substantially above 75,000 and commonly
ranging from 100,000 to 300,000 molecular weight and above.
These high molecular weight polymers which inherently provide
viscosity index improvement properties in lubricating oil
compositions are not suitable as substrates for the present
invention which is intended to provide a dispersant-anti-
oxidant additive for single grade motor oil compositions. The
high molecular weight polymer substrates must be degraded,
usually mechanically or thermally, to the prescribed molecular
weight range.
Low molecular weight ethylene copolymer substrates
having molecular weights ranging from 1,000 to 40,000 and, more
particularly, from about 5,000 to 20,000 molecular weight
suitable for preparing the reaction product of the invention
are not available commercially. High molecular weight polymer
substrates or interpolymers are available commercially such as
those containing from about 40 to about 60 mole percent
ethylene units and about 60 to about 40 mole percent propylene
units. Examples are "Ortholeum 2052*" and "PL-1256*" available
* Trade-mark
- g _

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from E. I. DuPont deNemours and Co. The former is a terpolymer
containing about 48 mole percent ethylene units, 48 mole
percent propylene units and 4 mole percent, 1,4-hexadiene
units, having an inherent viscosity of 1.35. The latter is a
similar polymer with an inherent viscosity of 1.95. The
viscosity average molecular weights of these polymers are on
the order of 200,000 and 280,000, respectively. As previously
noted, these are not suitable for a single grade lubricating
oil and must be degraded until the polymer is within the
prescribed molecular weight range.
The terms polymer and copolymer are used generically
to encompass ethylene copolymers, terpolymers or interpolymers.
These materials may contain minor amounts of other olefinic
monomers so long as their basic characteristics are not
materially changed.
An ethylenically unsaturated carboxylic acid material
is next grafted onto the prescribed polymer backbone. These
materials which are attached to the polymer contain at least
one ethylenically unsaturated bond and at least one, preferably
two, carboxylic acid or its anhydride groups or a polar group
which is convertible into the carboxyl groups by oxidation or
hydrolysis. Malefic anhydride or a derivative thereof is
preferred. It grafts onto the ethylene copolymer or terpolymer
to give two carboxylic acid functionalities. Examples of other
unsaturated carboxylic materials include chlormaleic anhydride,
itaconic anhydride, or the corresponding dicarboxylic acids,
such as malefic acid, fumaric acid and their monoesters.
The amount of the carboxylic acid material that is
grafted onto the prescribed polymer backbone is critical. This
amount should be at least 1.5 weight percent of carboxylic acid
material on the polymer backbone. It is preferable that the
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carboxylic acid material amount to 2.5 percent or higher based
on the total weight of the grafted polymer. In general, the
carboxylic acid material should constitute from 1.5 to 5 weight
percent of the grafted polymer backbone with the preferred
range being from about 2.25 to 3 weight percent.
The ethylenically unsaturated carboxylic acid
material may be grafted onto the polymer backbone in a number
of ways. It may be incorporated onto an unsaturated backbone
by a thermal process known as the "ene" process or by grafting
onto saturated or unsaturated polymer backbone in solution or
in solid form using a radical initiator. The free-radical
induced grafting of ethylenically unsaturated carboxylic acid
materials is preferably done using a mechanical or thermal
shearing technique. It is carried out at an elevated
temperature in the range of about 100°C to 250°C, preferably
120°C to 190°C and more preferably at 150°C to
180°C.
The free-radical initiators which may be used are
peroxides, hydroperoxides, and azo compounds and preferably
those which have a boiling point greater than about 100°C and
decompose thermally within the grafting temperature range to
provide free radicals. Representative of these free-radical
initiators are azobutyronitrile and 2,5-dimethyl-hex-3-yne-2,5
bis-tertiary-butyl peroxide. The initiator is used in an
amount of between about 0.005°s and about to by weight based on
the weight of the reaction mixture solution. The grafting is
preferably carried out in an inert atmosphere, such as under
nitrogen blanketing. The resulting polymer intermediate is
characterized by having carboxylic acid acylating functions
within its structure.
In the solid or melt process for forming a graft
polymer, the unsaturated carboxylic acid with the optional use
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of a radical initiator is grafted on molten rubber using rubber
masticating or shearing equipment. The temperature of the
molten material in this process may range from about
150°C-400°C. Preferably, the melt process is carried out in an
extruder.
The preparation of the grafted copolymer intermediate
may be conducted in a number of ways. A high molecular weight
copolymer may be degraded to the prescribed molecular weight
range by a mechanical shearing or thermal process and then
reacted with the carboxylic acid material according to known
procedures. Alternatively, the high molecular weight copolymer
may be grafted with the carboxylic acid material and the
resultant grafted copolymer then subjected to a degrading
process, e.g. mechanical shearing or thermal shearing to
produce a grafted copolymer having the prescribed molecular
weight. In still another procedure, a high molecular weight
copolymer and the carboxylic acid material may be mixed
together and simultaneously reacted under conditions that
degrade the copolymer, i.e. by effecting mechanical or thermal
shearing while effecting the grafting reaction.
The polymer intermediate possessing carboxylic acid
acylating functions is reacted with the amino-aromatic
polyamine compound described above. Examples of preferred
polyamines include:
(a) an N-arylphenylenediamine represented by the
formula:
R3
R1 Ar-N
Rz
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in which Ar is aromatic and Rl is hydrogen, -NH-aryl, -NH-
arylkyl, a branched or straight chain radical having from 4 to
24 carbon atoms that can be alkyl, alkenyl, alkoxyl, aralkyl,
alkaryl, hydroxyalkyl or aminoalkyl,
R2 in NH2, CH2-(CH2)n-NH2, -aryl-NH2, in which n has a value
from 1 to 10, and R3 is alkyl, alkenyl, alkoxyl, aralkyl,
alkaryl having from 4 to 24 carbon atoms,
(b) an aminothiazole from the group consisting of
aminothiazole, aminobenzothiazole, aminobenzothiadiazole and
aminoalkylthiazole, and
(c) an aminocarbazole represented by the formula:
R ~Ij ~ ~Rl
H
in which R and Rl represent hydrogen or an alkyl, alkenyl, or
alkoxyl radical having from 1 to 14 carbon atoms,
(d) an aminoindole represented by the formula:
R
H2N ~N~
in which R represents hydrogen or an alkyl radical having from
1 to 14 carbon atoms,
(e) an aminopyrrole represented by the formula:
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R NH2
Ri N
H
in which R is a divalent alkylene radical having 2-6 carbon
atoms and R1 is by hydrogen or an alkyl radical having from 1
to 14 carbon atoms,
(f) an amino-indazolinone represented by the formula:
NH2 /O
/NH
\N/
R I
H
in which R is hydrogen or an alkyl radical having from 1 to 14
carbon atoms,
(g) an aminomercaptotriazole represented by the
formula:
N NH2
HS
N N
I
H
(h) an aminoperimidine represented by the formula:
NH2
N NH
O O R
in which R represents hydrogen or an alkyl or alkoxyl radical
having from 1 to 14 carbon atoms.
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Particularly preferred N-arylphenylenediamines are
the N-phenylphenylenediamines, for example, N-phenyl-1,4-
phenylenediamine, N-phenyl-1,3-phenylenediamine, N-phenyl-1,2-
phenylenediamine, N-naphthyl-phenylenediamine, N-phenyl-
naphthalenediamine and N~-aminopropyl-N-phenylphenylenediamine.
The reaction between the polymer substrate
intermediate having grafted thereon carboxylic acid acylating
function and the prescribed amino-aromatic polyamine compound
is conducted by heating a solution of the polymer substrate
under inert conditions and then adding the amino-aromatic
polyamine compound to the heated solution generally with mixing
to effect the reaction. It is convenient to employ an oil
solution of the polymer substrate heated to 140°C to 175°C
while maintaining the solution under a nitrogen blanket. The
amino-aromatic polyamine compound is added to this solution and
the reaction is effected under the noted conditions.
The following examples illustrate the preparation of
the novel reaction product additive of the invention.
L'Y11MDT L' T
Preparation of the dispersant-antioxidant from
ethylene-propylene copolymer (15,000 Number Avg. MW) grafted
with 2.5s malefic anhydride
A 62.5 weight percent mixture of ethylene-propylene
copolymer grafted with 2.5 weight percent malefic anhydride in
oil (600 g) was charged into a 3000 mL 4-neck kettle along with
100 P Pale oil (600 g). The kettle was equipped with a
mechanical stirrer, thermometer, thermocouple, and nitrogen
inlet and heated to 160°C. Next, N-phenyl-p-phenylenediamine
(28 g, 0.153 moles) was added along with Surfonic N-40* (30 g,
0.076 moles). The reaction temperature was maintained at 160°C
* Trade-mark
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CA 02021959 2000-02-03
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for 3 hours. The product (an approximately 30~ concentrate)
analyzed as follows: oN = 0.37 (0.34 calc.), Total Acid Number
(TAN) - 1.90, and Total Base Number (TBN) - 6.08.
EXAMPLE II
The mechanical/thermal shearing preparation of
dispersant-antioxidant from ethylene-propylene copolymer
utilizing an extruder
The ethylene-propylene copolymer (100,000 Number Avg.
MW) was chopped and processed through an extruder in a molten
state at a temperature near 400°C. Just prior to entering the
extruder screw, malefic anhydride was mixed with the molten
polymer and the polymer exiting from the die face of the
extruder was grafted with 2.2°s malefic anhydride. The ethylene-
propylene copolymer grafted with 2.2 weight percent malefic
anhydride (1000 g) was dissolved in 100 P Pale oil (1691 g) in
a 4000 mL 4-neck kettle at 160°C. The kettle was equipped with
a mechanical stirrer, thermometer, thermocouple, and nitrogen
inlet. Next, N-phenyl-p-phenylenediamine (44.5 g, 0.242 moles)
was added along with Surfonic N-60* (80 g). The reaction
temperature was maintained at 160°C for 6 hours. The product
(an approximately 37% concentrate) analyzed as follows:
%N = 0.37 (0.24 calc.), Total Base Number (TBN) - 7.4, and
Kinetic Viscosity (100°C) - 23,008 cst.
EXAMPLE III
The synthesis of dispersant-antioxidant from
ethylene-propylene copolymer (15,000 Number Avg. MW) grafted
with 2.5o malefic anhydride
A 62.5 weight percent mixture of ethylene-propylene
copolymer grafted with 2.5 weight percent malefic anhydride in
oil (400 g) was charged into a 3000 mL 4-neck kettle along with
* Trade-mark
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CA 02021959 2000-02-03
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100 P Pale oil (400 g). The kettle was equipped with a
mechanical stirrer, thermometer, thermocouple, and nitrogen
inlet and heated to 160°C. Next alkylated N-phenyl-p-
phenylenediamine (20 g, 0.066 moles) was added along with
Surfonic N-40* (20 g). The reaction temperature was maintained
at 160°C for 6 hours. The product (an approximately 31%
concentrate) analyzed as follows: %N = 0.30 (0.17 calc.), Total
Acid Number (TAN) - 4.0, Total Base Number (TBN) - 0.1, and
Kinetic Viscosity (100°C) - 712 cst.
EXAMPLE IV
The synthesis of dispersant-antioxidant from
ethylene-propylene copolymer (15,000 Number Avg. MW) grafted
with 2.5% malefic anhydride using a mixture of amines
A 62.5 weight percent mixture of ethylene-propylene
copolymer grafted with 2.5 weight percent malefic anhydride in
oil (1200 g) was charged into a 4000 mL 4-neck kettle along
with 100 P Pale oil (1200 g). The kettle was equipped with a
mechanical stirrer, thermometer, thermocouple, and nitrogen
inlet and heated to 160°C. Next, N-phenyl-p-phenylenediamine
(17.3 g, 0.094 moles) and N,N-dimethylaminopropylamine (9.6 g,
0.094 moles) was added along with Surfonic N-40* (60 g). The
reaction temperature was maintained at 160°C for 6 hours. The
product (an approximately 31% concentrate) analyzed as follows:
%N = 0.31 (0.42 calc.), Total Acid Number (TAN) - 2.1, Total
Base Number (TBN) - 3.1, and Kinetic Viscosity (100°C) - 1382
CSt.
EXAMPLE V (Comparison Exam le)
The synthesis of dispersant-antioxidant from
ethylene-propylene copolymer (15,000 Number Avg. MW) grafted
with 1.0% malefic anhvdride
* Trade-mark
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A 62.5 weight percent mixture of ethylene-propylene
copolymer grafted with 1.0 weight percent malefic anhydride in
oil (1431.5 g) was charged into a 4000 mL 4-neck kettle along
with 100 P Pale oil (957.4 g). The kettle was equipped with a
mechanical stirrer, thermometer, thermocouple, and nitrogen
inlet and heated to 160°C. Next, N-phenyl-p-phenylenediamine
(18.4 g, 0.099 moles) was added along with Surfonic N-40*
(71.5 g). The reaction temperature was maintained at 160°C for
6 hours. The product (an approximately 37o concentrate)
analyzed as follows: °sN = 0.12 (0.11 calc.), Total Acid Number
(TAN) - 1.8, Total Base Number (TBN) - 0.2, and Kinetic
Viscosity (100°C) - 1486 cst.
EXAMPLE VI
The mechanical/thermal shearing preparation of
dispersant-antioxidant from ethylene-propylene copolymer
utilizincl a simple reaction vessel
The ethylene-propylene copolymer (43,000 Number Avg.
MW) grafted with 2.5o malefic anhydride (592 g) was dissolved in
100 P Pale oil (2370 g) at 160°C. This was done in a 3000 mL
4-neck kettle which was equipped with a mechanical stirrer,
thermometer, thermocouple, and nitrogen inlet. The temperature
was slowly raised to 325°C and held for 1 hour. Next, N-
phenyl-p-phenylenediamine (29.0 g, 0.163 moles) was added along
with Surfonic N-60* (47 g). The reaction temperature was
maintained at 160°C for 6 hours. The product (an approximately
25o concentrate) analyzed as follows: %N = 0.29 (0.27 calc.),
Total Acid Number (TAN ) - 0.6, Total Base Number (TBN) - 2.5,
and Kinetic Viscosity (100°C) - 501 cst.
EXAMPLES VII TO XIII
* Trade-mark
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CA 02021959 2000-02-03
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Derivatized graft polymers are prepared employing the
polymer and procedure described in Example I employing the
following amino-aromatic polymines:
Example VII: Aminothiazole
Example VIII: Aminocarbazole
Example IX: Aminoindole
Example X: Aminoperimidine
Example XI: Aminopyrrole
Example XII: Aminomercaptotriazole
Example XIII: N-phenyl-1,3-phenylenediamine
The prescribed graft and derivatized polymer of the
invention are useful as additives for lubricating oils.
Specifically, they provide dispersancy, and anti-oxidant
properties in single grade lubricating oils. They can be
employed in a variety of oils of lubricating viscosity
including natural and synthetic lubricating oils and mixtures
thereof. The novel additives can be employed in crankcase
lubricating oils for spark-ignited and compression-ignited
internal combustion engines. The compositions can also be used
in gas engines, or turbines, automatic transmission fluids,
gear lubricants, metal-working lubricants, hydraulic fluids and
other lubricating oil and grease compositions. Their use in
motor fuel compositions is also contemplated.
The base oil may be a natural oil including liquid
petroleum oils and solvent-treated or acid-treated mineral
lubricating oils of the paraffinic, naphthenic and mixed
paraffinic-naphthenic types.
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r
v
In general, the lubricating oil composition of the
invention will contain the novel reaction product in a
concentration ranging from about 0.1 to 30 weight percent. A
concentration range for the additive ranging from about 0.5 to
15 weight percent based on the total weight of the oil
composition is preferred with a still more preferred
concentration range being from about 1 to 7.5 weight percent.
Oil concentrates of the additives may contain from
about 1 to 50 weight percent of the additive reaction product
in a carrier or diluent oil of lubricating oil viscosity.
The novel reaction product of the invention may be
employed in lubricant compositions together with conventional
lubricant additives. Such additives may include additional
dispersants, detergents, anti-oxidants, pour point depressants,
anti-wear agents and the like.
The novel additive reaction product of the invention
was tested for its effectiveness as a dispersant and as an
anti-oxidant in a formulated lubricating oil composition. In
all of the examples, the polymer substrate was similar
comprising about 60 mole percent ethylene, 40 mole percent
propylene having an average molecular weight of about 15,000.
The base lubricating oil used in the dispersancy test was a
typical formulated lubricating oil as represented by the values
set forth in Table I.
TABLE I
Component Parts By Weight
Solvent neutral oil A 75.25
Solvent neutral oil B 21.64
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~"'
Zinc Dialkyldithiophosphate 1.22
4.4'dinonyldiphenylamine .39
Overbased magnesium sulfonate 1.50
Silicone anifoamant 150 PPM
Product 4-10
Analyses
Viscosity Kin 40C CS 30.4
Viscosity Kin 100C CS 5.33
Pour Point, F. +10
Ash Sulfated, % D874 O.gg
Phosphorus, % X-Ray 0.12
Sulfur, % X-Ray Total 0.32
Zinc, % X-Ray 0.13
Oil had a sp. Gr. 60/60°F of 0.858-0.868; Vis 100°F 123-133;
Pour Point 0°F. Oil B had a sp. Gr. 60/60°F of 0.871-0.887;
Vis. 100°F 325-350; Pour Point +10°F. Zinc salt is a salt of
mixed alcohols-isopropanol and P2S5 product as described in
U.S. Pat. No. 3,292,181. The overbased magnesium sulfonate had
a TBN of 395 and is a salt of branched C20-C40 monoalkylbenzene
sulfuric acid (MV 530-540) together with about 10% magnesium
carbonate, 14% magnesium hydroxide and 4% magnesium sulfate.
The dispersant properties of the additive-containing
oil are determined in the Bench VC Dispersancy Test (BVCT).
Dispersancy of a lubricating oil is determined relative to
three references which are the results from three standard
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blends tested along with the unknown. The test additives were
blended into a formulated oil containing no dispersant. The
additive reaction product was employed in the oil at
- 19b -

2Q21959
concentrations of 4 and 6.5 weight percent polymer solution.
The numerical value of the test results decreases with an
increase in effectiveness.
TABLE II
BENCH VC DISPERSANCY TEST
Results
Additive 4% Conc. 6.5% Conc.
Example I 25 21
Premium Grade Commercial Motor Oil 46 20
Example II 18 21
Example III 21 13
Example IV 25 19
Example V 26 22
Reference2 34 18
1. All Bench Sludge Test results are the average of
duplicate runs.
2. Alkenylsuccinimide dispersant.
The anti-oxidant properties of the novel reaction product
in a lubricating oil was determined in the Bench Oxidation
Test. In this test, the additive reaction product is blended
into solvent neutral oil (S.U.S. at 100°F of 130) at a nitrogen
concentration of 0.10 weight percent. The mixture is
continuously stirred while being heated accompanied by bubbling
with air. Samples are withdrawn periodically for analysis by
Differential Infrared Absorption (DIR) to observe changes in
the intensity of the carboxyl vibration band at 1710 cm-1. A
low carboxyl vibration band intensity indicates higher thermal-
oxidative stability of the sample.
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60288-2863
TTaTL' TTT
BENCH OXIDATION TEST
Additive Resultl
Example I 2.9
Reference2 20.7
lA number below 7 indicates the anti-oxidant properties of
the blend.
2Alkenylsuccinimide dispersant.
The test results above demonstrate substantial improve-
ments in anti-oxidant properties due to incorporation of the
novel reaction product of the invention in an oil composition as
compared to the results obtained from a known commercial motor
oil composition.
ASTM SeQUence VE Test
The ASTM Sequence VE test is used to evaluate the
performance of engine oils in protecting engine parts from sludge
and varnish deposits and valve train wear due to low temperature
"stop and go" operation. The test uses a Ford 2.3 L four-cylinder
Ranger truck engine. The engine is cycled through three test
stages, requiring four hours to complete, for 288 hours or 72
cycles. The Sequence VE engine test results shown in Table 2 were
run in a 30W single grade formulation.
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2021959
TABLE IV
Sequence VE Enctine Results
Test
Dispersant AS' AV PSV % ORC % OSC
Reference2~3 7.1 4.3 6.8 39.8 33.6
(2.4% Active)
Example I 9.5 5.0 7.3 5.0 0.0
(2.0% Active)
Example IV 9.5 4.8 7.1 23.0 0.0
(2.0% Active)
Example I 9.4 6.5 6.9 0.0 0.0
(1.3% Active)
mixed with
Alkenyl Succinimide
Dispersant (1.1% Active)
Limits 9.0 5.0 6.5 15.0 20.0
min min min max max
'AS, AV, PSV, ORC, and OSC denote: average sludge, average
varnish, piston skirt varnish, oil ring clogging, and oil
screen clogging, respectively.
zaverage of seven runs
3Alkenyl Succinimide Dispersant
The MWM-B engine test is used to evaluate the performance
of diesel engine oils. The test uses a one cylinder engine
that runs for 50 hours. The piston is rated for cleanliness
utilizing a merit system. The rating scale goes from 0 to 80,
with 80 being a perfectly clean piston. The engine test
results below show that a 2.5% graft level provides superior
diesel engine performance as compared to a 1% graft level for
the same MW polymer. The dispersants were evaluated in a SAE
40W single grade formulation at 6.5 weight percent:
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DISPERSANT MWM-B ENGINE TEST RESULT
Example I (2.5% Malefic Anhydride) 60 Merits
Example V (1% Malefic Anhydride) 54 Merits
Haze in a lubriating oil composition represents a
serious quality problem. The prescribed additives of the
invention which were prepared by a variety of processes were
tested for their effect on haze in oils in a Hazitron*
instrument. The Hazitron is an instrument which is used to
give a relative indication of light scattering caused by haze.
The method is based on measurements of transmitted light by the
sample placed in two positions of the sample compartment. A
cuvette filled with the sample is placed in the extreme right
side of the sample compartment, adjacent to the measuring
photocell and the instrument is balanced with the numbered dial
set on "0". The cuvette is then shifted to the extreme left
side of the sample compartment and the instrument is rebalanced
using the numbered dial. The reading on the numbered dial
minus the cuvette correction number gives the Hazitron number.
The higher the number the hazier the sample. The measurements
were done on the polymer concentrates diluted to 10 volume
percent in SNO-150. The results below show that samples
prepared from mechanical/thermal shearing have much better
clarity than samples produced from solution polymerization.
The dispersant-anti-oxidant additive of the instant
invention derives its effectiveness as an anti-oxidant from the
use of the specific N-arylphenylenediamine reactants described.
It is contemplated, however, that valuable economies may be
achieved when the prescribed reaction products of the invention
are used in combination with other reaction products prepared
from different amines. More specifically, grafted copolymers
having the prescribed molecular weight range and prescribed
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graft level may be reacted with an amine having in its
structure one primary amine group and either a tertiary amine
group or a highly hindered secondary amine group. Examples of
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2021959
such amines include aminopropylmorpholine,
aminoethylmorpholine, N',N'-dimethylaminopropylamine, N',N'-
dimethylethylamine, N-methylaminopropylpiperzine.
The following table illustrates the use of such mixed
reaction products.
DISPERSANT HAZITRON NUMBER
Example I 80
(Solution Polymerization)
Example II 19
(Mechanical/Thermal Shearing)
Example IV 44
(Solution Polymerization
w/Mixed Amine System)
Example VI 25
(Mechanical/Thermal Shearing)
The foregoing test results demonstrate that the
antioxidant moiety can be mixed in all proportions with other
polyamines on the polymer backbone and produce a useful
product. This technique was used to lower the Hazitron Number
of a product derived from solution polymerization from 80 to
44 without loss of engine performance.
35
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