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Description  |
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FIELD OF THE INVENTION
This invention relates to hydrocarbons including hydrocarbon fuel oils and
lubricating oil. More particularly, it relates to hydrocarbons which
contain graft polymers which permit attainment of improved properties.
BACKGROUND OF THE INVENTION
As is well known to those skilled in the art, hydrocarbon fuels and
lubricating oils must be formulated, as by addition of various additives,
to improve their properties.
In the case of hydrocarbon fuels, typified by fuels boiling in the gasoline
boiling range, kerosene, middle distillate fuels, home heating oils etc.,
it is found that after extended periods of storage, they are characterized
by undesirable characteristics typified by formation of solid deposits
within the system.
In the case of lubricating oils, typified by those employed in railway,
automotive, aircraft, marine etc. service, it is found that they become
degraded during use due inter alia to formation of sludge which may be
generated by deterioration of the oil or by introduction of undesirable
components from other sources including the fuel or the combustion air. In
order to maintain and improve the properties of the lubricating oil,
various additives have heretofore been provided; and these have been
intended to improve the viscosity index, dispersancy, oxidative stability,
etc. It is an object of this invention to provide an additive system which
permits attainment of improved hydrocarbons. Other objects will be
apparent to those skilled in the art.
STATEMENT OF THE INVENTION
In accordance with certain of its aspects, this invention is directed to a
graft polymer comprising an oil-soluble, substantially linear,
carbon-carbon backbone polymer having bonded thereto (i) first graft units
derived from a first monomer amine containing a polymerizable,
ethylenically unsaturated double bond and (ii) second units derived from a
second monomer containing at least one of nitrogen, sulfur, or oxygen in a
heterocyclic ring compound.
DESCRIPTION OF THE INVENTION
The charge polymer which may be employed in practice of the process of this
invention may include an oil-soluble, substantially linear, carbon-carbon
backbone polymer. Typical carbon-carbon backbone polymers prepared from
monomers bearing an ethylenically unsaturated polymerizable double bond
which may be employed include homopolymers or copolymers prepared from
monomer
##STR1##
wherein A may be: hydrogen; hydrocarbon such as alkyl, aryl, etc.; phenyl;
acetate or less preferred acyloxy (typified by --COOR); halide; etc. R"
may be divalent hydrocarbon typified by alkylene, alkarylene, aralkylene,
cycloalkylene, arylene, etc.
Illustrative of such monomers may be acrylates, methacrylates, vinyl
halides (such as vinyl chloride), styrene, olefins such as propylene,
butylene, etc., vinyl acetate; dienes such as butadiene, isoprene,
hexadiene, ethylidene norbornene, etc. Homopolymers of olefins, (such as
polypropylene, polybutylene, etc.), dienes, (such as hydrogenated
polyisoprene), or copolymers of ethylene with e.g., butylene and higher
olefins, styrene with isoprene and/or butadiene may be employed. The
preferred carbon-carbon backbone polymers include those selected from the
group consisting of ethylene-propylene copolymers (EPM or EPR) and
ethylene-propylene-diene third monomer terpolymers (EPDM or EPT).
When the charge polymer is an ethylene-propylene copolymer (EPM, also
called EPR polymers), it may be formed by copolymerization of ethylene and
propylene under known conditions preferably Ziegler-Natta reaction
conditions. The preferred EPM copolymers contain units derived from
ethylene in amount of 40-70 mole %, preferably 50-60 mole %, say 55 mole
%, the remainder being derived from propylene.
The molecular weight M.sub.n of the EPM copolymers which may be employed
may be 10,000-1,000,000, preferably 20,000-200,000, say 140,000. The
molecular weight distribution may be characterized by M.sub.w /M.sub.n of
less than about 15, preferably 1.2-10, say 1.6.
Illustrative EPM copolymers which may be employed in practice of the
process of this invention may be those set forth in the following table,
the first listed being preferred:
A. The Epsyn brand of EPM marketed by Copolymer Rubber and Chemical
Corporation containing 60 mole % of units derived from ethylene and 40
mole % of units derived from propylene, having a molecular weight M.sub.n
of 140,000 and a M.sub.w /M.sub.n of 1.6.
B. The Epcar 505 brand of EPM marketed by B. F. Goodrich Co., containing 50
mole % of units derived from ethylene and 50 mole % of units derived from
propylene and having a M.sub.n of 25,000 and a polydispersity index of
2.5.
C. The Esprene brand of EPR marketed by Sumitomo Chemical Co., containing
55 mole % of units derived from ethylene and 45 mole % of units derived
from propylene and having a M.sub.n of 25,000 and polydispersity index of
2.5;
When the charge polymer is a terpolymer of ethylene-propylene-diene third
monomer (EPT or EPDM), it may be formed by copolymerization of ethylene,
propylene and diene third monomer. The third monomer is commonly a
non-conjugated diene typified by dicyclopentadiene; 1,4-hexadiene; or
ethylidene norbornene. Polymerization is effected under known conditions
generally comparable to those employed in preparing the EPM products. The
preferred terpolymers contain units derived from ethylene in amount of
40-70 mole %, preferably 50-65 mole %, say 60 mole % and units derived
from the propylene in amount of 20-60 mole %, preferably 30-50 mole %, say
3 mole % and units derived from third diene monomer in amount of 0.5-15
mole %, preferably 1-10 mole %, say 2 mole %. The molecular weight M.sub.n
of the terpolymers may typically be 10,000-1,000,000, preferably
20,000-200,000, say 120,000. Molecular weight distribution of the useful
polymers is preferably narrow viz a M.sub.w /M.sub.n of typically less
than 15, preferably 1.5-10, say 2.2.
Illustrative EPT terpolymers which may be employed in practice of the
process of this invention may be those set forth in the following table,
the first listed being preferred:
TABLE
A. The Epsyn 4006 brand of EPT marketed by Copolymer Rubber and Chemical
Corp., containing 58 mole % of units derived from ethylene, 40 mole % of
units derived from propylene, and 2 mole % of units derived from
ethylidene norbornene and having a M.sub.n of 120,000 and a polydispersity
index M.sub.w /M.sub.n of 2.2.
B. The Ortholeum 5655 brand of EPT marketed by DuPont containing 62 mole %
of units derived from ethylene, 36 mole % of units derived from propylene,
and 2 mole % of units derived from 1,4-hexadiene and having a M.sub.n of
75,000 and a polydispersity index M.sub.w /M.sub.n of 2.
C. The Ortholeum 2052 brand of EPT marketed by DuPont containing 62 mole %
of units derived from ethylene, 36 mole % of units derived from propylene,
and 2 mole % of units derived from 1,4-hexadiene and having a M.sub.n of
35,000 and a polydispersity M.sub.w /M.sub.n of 2.
D. The Royalene brand of EPT marketed by Uniroyal containing 60 mole % of
units derived from ethylene, 37 mole % of units derived from propylene,
and 3 mole % of units derived from dicyclopentadiene and having a M.sub.n
of 100,000 and a polydispersity index M.sub.w /M.sub.n of 2.5.
E. The Epsyn 40A brand of EPT marketed by Copolymer Rubber and Chemical
Corp., containing 60 mole % of units derived from ethylene, 37 mole % of
units derived from propylene, and 3 mole % of units derived from
ethylidene norbornene and having a M.sub.n of 140,000 and a polydispersity
index M.sub.w /M.sub.n of 2.
The EPM and EPT polymers may contain minor portions (typically less than
about 30%) of other units derived from other copolymerizable monomers.
It is a feature of the process of this invention that there may be grafted
onto these oil-soluble, substantially linear carbon-carbon, backbone
polymers, first graft units derived from a first graft amine monomer.
The functional amine monomer which may be grafted onto the EPM or EPT as
the first graft monomer in practice of the process of this invention may
be characterized by the formula RNR'R" wherein R is a hydrocarbon moiety
possessing a polymerizable ethylenically unsaturated double bond. R may be
an alkenyl or cycloalkenyl group (including such groups bearing inert
substituents) typified by vinyl, allyl, C.dbd.C--C.sub.6 H.sub.4 --, etc.
or R", may be hydrogen or a hydrocarbon including alkyl, alkaryl, aralkyl,
cycloalkyl, and aryl. The moiety-NR'R", may include a heterocyclic ring
(formed by joining R' and R") as in the preferred N-vinyl pyrrolidone;
1-vinyl imidazol; or 4-vinyl pyridine. R' and R" may be a hydrogen or a
hydrocarbon moiety containing nitrogen, sulfur, or oxygen. Illustrative
amines which may be employed include those listed in the following table,
the first listed, N-vinyl pyrrolidone, being preferred:
TABLE
______________________________________
N--vinylpyrrolidone
1-vinylimidazole
4-vinylpyridine
allyl amine
______________________________________
The first graft monomer may be a more complex amine reaction product formed
by the reaction of an amine, typified by morpholine or N-methyl
piperazine, and an epoxy compound typified by allyl glycidyl ether. It may
be a monomer formed for example from the reaction of croton aldehyde and
N-(3-aminopropyl) morpholine.
In practice of the process of this invention, 100 parts of charge EPM or
EPT may be added to 100-1000 parts, say 300 parts of solvent. Typical
solvent may be a hydrocarbon solvent such as hexane, heptane,
tetrahydrofuran, or mineral oil. Preferred solvent may be a commercial
hexane containing principally hexane isomers. Reaction mixture may then be
heated to reaction conditions of 60.degree. C.-180.degree. C., preferably
150.degree. C.-170.degree. C., say 155.degree. C. at 15-300 psig,
preferably 180-220 psig, say 200 psig.
In the preferred two step process, there are admitted to the reaction
mixture first graft monomer, typically N-vinyl-pyrrolidone in amount of
1-40 parts, say 5 parts, and a solution in hydrocarbon of free radical
initiator. Typical free radical initiators may include dicumyl peroxide,
di-t-butyl peroxide, benzoyl peroxide, di-isopropyl peroxide,
azobisisobutyronitrile, etc. The solvent is preferably the same as that in
which the EPM or EPT is dissolved. The initiator may be added in amount of
0.2-10 parts, say 2 parts in 0.8-40 parts, say 16 parts of solvent.
The reaction is carried out at a temperature at least as high as the
decomposition temperature of the initiator, typically 60.degree. C. or
higher.
Reaction is typically carried out at 60.degree. C.-180.degree. C., say
155.degree. C. and 180-220 psig, say 200 psig which time graft
polymerization of the amine onto the base EPM or EPT polymer occurs. The
final product graft polymer may be typically characterized by the presence
of the following typical units:
##STR2##
Typically there may be 0.1-80 say 6 amine units per 1000 carbon atoms in
the polymer backbone. R'" is a saturated moiety derived from R.
It is a feature of the process of this invention that there may be bonded
onto these oil-soluble, substantially linear, carbon-carbon, backbone
polymers bearing units derived from a first graft monomer, units derived
from a second functional monomer containing at least one of sulfur,
nitrogen, or oxygen in a heterocyclic ring. Although it may be possible to
effect bonding and graft polymerization simultaneously, it is preferred to
effect graft polymerization first and thereafter bonding.
The second functional monomer which may be employed may be monocyclic or
polycyclic; and the nitrogen, sulfur, and oxygen may be contained in the
same or a different ring. In the preferred embodiment, the second
functional monomer may be polycyclic and the nitrogen and sulfur may be in
the same heterocyclic ring. This monomer may contain both heterocyclic and
aromatic rings as is the case with the preferred phenothiazine.
The functional monomer may be a heterocyclic/aromatic or heterocyclic
compound containing sulfur, nitrogen or oxygen, or combination thereof.
The compound which may be used as the functional monomer include:
1. Phenothiazine and ring or/and N-substituted phenothiazine. Substituents
may include hydrocarbon radicals selected from the group consisting of
alkyl, alkenyl, cycloalkyl, aryl, alkaryl, or heterocyclic, including such
radicals when containing oxygen, nitrogen, sulfur, halide or their
combinations. Typically, the ring-substituted phenothiazine may include
alkyl or alkenyl phenothiazines, alkoxy phenothiazine, hydroxy alkyl
phenothiazines, amino phenothiazines, nitrophenothiazines,
3-formyl-10-alkyl-phenothiazine, 2-amino-4-(2-phenothiazinyl) thiazole,
alpha-(2-phenothiazinyl) thioacetomorpholide, etc. Typical N-substituted
phenothiazine may include N-vinyl phenothiazine, N-acrylamidomethyl
phenothiazine, beta-(N-phenothiazinyl)-ethyl vinyl ether,
beta-(N-pheothiazinyl)-ethyl methacrylates, reaction products of allyl
glycidyl ether or glycidyl methacrylate with phenothiazine.
2. Immidazoles or benzimidazoles, such as 2-mercaptobenzimidazole,
2-mercapto toluimidazole or 2-mercapto-1-methyl imidazole.
3. Thiazoles or benzothizoles, such as 4-methyl-5-vinylthiazole,
2-amino-4-methyl-thiazole, 2-mercapto-4-phenylthiazole, 2-mercaptobenzo
thiazole.
4. Triazoles and benzotriazoles, such as 3-mercapto-1H-1,2,4, triazole,
3-amino-5-methylthio-1H-1,2,4-triazole.
5. Thiadiazoles, benzothiadiazoles, thiazolines and benzothiazolines,
thiazolidine, including 2-mercapto-thiazoline, 1,2,5-thiadiazoline.
6. Pyrimidine, including 2-amino-4-methylpyrimidine, 2-mercaptopyrimidine.
7. Pyridines, including 2-mercapto pyridine, 4-mercaptopyridine,
2-mercaptopyridine-N-oxide
8. Piperidines and pyrrolidinones.
9. Oxazoles and benzoxazoles, such as 2-mercaptobenzoxazole.
10. Mercaptoanilines, mercaptophenols, thiomorpholine, 6-mercaptopurine,
thiophene methyl amine.
Preferred of the second functional monomers is phenothiazine which is a
three-ring aromatic/heterocyclic compound containing nitrogen and sulfur
in the same ring.
In practice of the process of this invention 100 parts of charge EPM or EPT
(bearing units grafted thereon from the first graft monomers) may be added
to 100-1000 parts, say 300 parts of diluent-solvent. Typical
diluent-solvent may be a hydrocarbon solvent such as n-hexane, n-heptane,
tetrahydrofuran, or mineral oil. Preferred solvent may be a commercial
hexane containing principally hexane isomers. Reaction mixture may then be
heated to reaction conditions of 60.degree. C.-180.degree. C., preferably
150.degree. C.-170.degree. C., say 155.degree. C. at 15-300 psig,
preferably 180-220 psig, say 200 psig.
Second functional monomer, typically phenothiazine is admitted in amount of
1-40 parts, say 4 parts, as a solution in 1-40 parts, say 16 parts of
diluent-solvent-typically tetrahydrofuran (THF). This is followed by a
solution in hydrocarbon of free radical initiator. Typical free radical
initiators may include dicumyl peroxide, di-t-butyl peroxide, benzoyl
peroxide, di-isopropyl peroxide, azobisisobutyronitrile, etc. The solvent
is preferably the same as that in which the EPM or EPT is dissolved. The
initiator may be added in amount of 0.2-40 parts, say 2 parts in 0.8-40
parts, say 6 parts of solvent hexane.
The reaction is carried out at a temperature at least as high as the
decomposition temperature of the initiator, typically 60.degree. C. or
higher.
Reaction is typically carried out at 60.degree. C.-180.degree. C., say
155.degree. C. and 180-220 psig, say 200 psig during which time bonding of
second monomer onto the base EPM or EPT polymer occurs. The final product
graft polymer may be characterized by the presence of units derived from
first and second monomers.
Typically there may be 0.1-60, say 3 units derived from second monomer per
1000 carbon atoms in the charge polymer backbone.
For ease of handling, the polymerization solvent may be exchanged with a
heavier solvent such as SUS 100 Oil. product graft polymer is typically
obtained as a solution of 4-20 parts, say 8.5 parts thereof in 80-96
parts, say 91.5 parts of solvent.
Although it is preferred to graft the first monomer onto the base polymer
and to thereafter bond the second monomer onto the so formed graft
polymer, it is possible to effect simultaneous reaction of first and
second monomers.
The product so formed may be an oil-soluble, substantially linear,
carbon-carbon backbone polymer of molecular weight M.sub.n of
10,000-1,000,000, preferably 20,000-200,000, say 140,000, bearing thereon
(per 1,000 carbon atoms in the polymer backbone) 0.1-80 units, preferably
1-15 units, say 6 units of first graft monomer and 0.1-60 units,
preferably 1-12 units, say 3 units of second monomer.
It is a feature of this invention that the so-prepared polymers may find
use in middle distillate fuel oils as dispersant when present in effective
amount of 0.001-2 w %, say 0.5 w %. Typical fuel oils may include middle
distillate fuel oils including kerosene, home heating oils, diesel fuel,
etc.
Lubricating oils in which the dispersant viscosity index improvers of this
invention may find use may include automotive, aircraft, marine, railway,
etc., oils; oils used in spark ignition or compression ignition; summer or
winter oils; etc. Typically the lubricating oils may be characterized by
an ibp of 570.degree. F.-660.degree. F., say 610.degree. F.; an ep of
750.degree. F.-1200.degree. F., say 1020.degree. F.; and an API gravity of
25-31, say 29.
A typical lubricating oil in which the polymer of this invention may be
present may be a standard SAE 5W-30 hydrocarbon motor oil formulation
having the following composition:
TABLE
______________________________________
W %
______________________________________
Base Oil 82
Viscosity Index Improver
9
(10 w % ethylene-propylene copolymer in
90% inert oil)
Standard Additive Package
9
Polyisobutenyl (--M.sub.n 1290) succinimide
(dispersant);
calcium sulfonate (detergent);
Zinc dithiophosphate (anti-wear);
di-nonyl diphenyl amine (anti-oxidant);
4,4'-methylene-bis (2,6-di-t-butyl phenol)
(antioxidant);
______________________________________
Use of the additive of this invention makes it possible to readily increase
the viscosity index by 25-40 units, say 35 units and to obtain improved
ratings on the tests measuring the dispersancy of the system. The
viscosity index is determined by ASTM Test D-445.
The novel polymers are also characterized as anti-oxidants as determined by
the Bench Oxidation Test. In this test, a solution (8.5 wt. %) of test
polymer in SNO-100 oil is diluted with SNO-130 oil to give a 1.5 wt. %
solution of the test polymer. The solution is heated with stirring and air
agitation. Samples are withdrawn periodically for analysis by Differential
Infrared Absorption (DIR) to observe changes in the intensity of the
carbonyl vibration band at 1710 cm.sup.-1. Higher carbonyl vibration band
intensity indicates a lower thermal-oxidative stability of the sample.
Dispersancy is determined by the Bench VC Test (BVCT). In this test, the
turbidity of an oil containing an additive is measured after heating the
test oil to which has been added a standard blow-by. The result correlates
with dispersancy is compared to three reference standards (Excellent,
Good, and Fair) tested simultaneously with the test sample. The numerical
rating decreases with an increase in dispersant effectiveness. Results
similar to or lower than that of the Good Reference indicate that the
additive is a good dispersant.
It appears that the first graft monomer used in practice of this invention
provides improved dispersant properties to the base polymer (which
provides viscosity index improvement); and the second functional monomer
provides improved anti-oxidant properties. Thus it is possible to obtain
product polymers which serve as multi-functional additives (dispersant,
anti-oxidant, viscosity index improvers) when added to a hydrocarbon
lubricating oil or to a synthetic type lubricating oil.
It is a feature of this invention that the so-prepared graft polymers may
find use in lubricating oils as dispersant anti-oxidant, viscosity index
improvers when present in effective amount of 0.2-5 w %, preferably 0.4-3
w %, say 0.9 wt %.
The novel polymers may also be characterized as deposit protection agents
as measured by the Single Cylinder CEC MWM-B Diesel Engine Test (DIN 51361
Parts I, II, and IV). In this test, a solution (8.5 wt. %) of polymer in
SNO-100 oil is blended into a fully formulated oil which does not contain
a VI improver. Results are presented in "Merits", a higher merit
evidencing better protection against deposits.
It is a feature of this invention that the polymer products of this
invention may be used in middle distillate fuel oils to permit attainment
of improved storage stability as measured by the Potential Deposit Test
(PDT) - ASTM Test D-2274.
A rating of 1 or 2 is good; and a rating of 3 or 4 is unsatisfactory.
It is possible by use of the compositions of this invention to improve the
PDT rating of a charge diesel fuel from 4+ to a satisfactory rating of 1
by use of only 25 PTB (pounds per thousand barrels) of active ingredient.
When used in fuels, the additives may be present in amount of 0.25-250,
preferably 10-100, say 25 pounds per thousand barrels (PTB).
Practice of the process of this invention will be apparent to those skilled
in the art from the following examples wherein, as elsewhere in this
specification, all parts are parts by weight unless otherwise set forth.
Control examples are designated by an asterisk.
DESCRIPTION OF PREFERRED EMBODIMENTS
EXAMPLE I
In this example which describes the best mode presently known, the charge
EPM polymer is the polymer of molecular weight M.sub.n of 140,000 of
M.sub.w /M.sub.n ratio of 1.6, and containing 60 mole % of units derived
from ethylene and 40 mole % of units derived from propylene. 100 parts of
this polymer are dissolved in 300 parts of commercial hexane and added to
a reaction vessel.
In the first step, the mixture is heated to 155.degree. C. with agitation
under nitrogen atmosphere at 200 psig. N-vinyl pyrrolidone (5 parts
dissolved in 15 parts of hexane) is added followed by 5 parts of 25 w %
dicumyl peroxide in hexane. The reaction mixture is stirred for one hour.
In the second step, phenothiazine (4 parts) dissolved in 16 parts of
tetrahydrofuran is added followed by a solution of 2 part of dicumyl
peroxide initiator in 6 parts of commerical hexane. The mixture is stirred
at 155.degree. C. and 200 psig for 1 hour. Solvent Neutral Oil (SUS 100)
(1076 parts) is then added; and the hexane is distilled off at
90.degree.-120.degree. C. The resulting solution contains about 8.5 w %
polymer.
The product polymer contains (per 1000 carbon atoms of polymer backbone)
about 6 units derived from N-vinyl pyrollidone and 3 units derived from
phenothiazine.
The process of Example I may be carried out using the charge polymers of
Examples II-IV:
EXAMPLE II
The Epsyn 4006 brand of EPT marketed by Copolymer containing 58 mole % of
units derived from ethylene, 40 mole % of units derived from propylene,
and 2 mole % of units derived from ethylidene norbornene and having a
M.sub.n of 120,000 and a M.sub.w /M.sub.n of 2.2.
EXAMPLE III
The Ortholeum 2052 brand of EPT marketed by DuPont containing 62 mole % of
units derived from ethylene, 36 mole % of units derived from propylene,
and 2 mole % of units derived from 1,4-hexadiene and having a M.sub.n of
35,000 and a M.sub.w /M.sub.n of 2.
EXAMPLE IV
The Royalene brand of EPT marketed by Uniroyal containing 60 mole % of
units derived from ethylene, 37 mole % of units derived from propylene and
3 mole % of units derived from dicyclopentadiene and having a M.sub.n of
100,000 and a M.sub.w /M.sub.n of 2.5.
EXAMPLE V.sup.*
In this control Example, the N-vinylpyrrolidone grafted EPM (as a 25 w %
solution in hexane) is prepared as in Example I. Solvent hexane is
exchanged for SNO-100 oil (1076 parts) to give a solution containing 8.5 w
% polymer.
There are then added 4 parts of pheothiazine dissolved in 16 parts of
tetrahydrofuran; and the mixture maintained at 70.degree. C.-80.degree. C.
under nitrogen for one hour.
This mixture contains the same quantity of N-vinyl pyrrolidone and of
phenothiazine as does the product of Example I. In this Example V.sup.*,
the phenothiazine is merely admixed.
EXAMPLE VI.sup.*
In this control example, the procedure of Example V.sup.* is followed
except that the phenothiazine in tetrahydrofuran is not added.
EXAMPLE VII
In this experimental Example, the procedure of Example I is followed except
that the first graft monomer is (instead of N-vinylpyrrolidone) a monomer
(8 parts) prepared by heating, for one hour at 100.degree. C.-120.degree.
C., a mixture of equimolar amounts of allyl glycidyl ether and morpholine.
The polymer product contains (per 1000 carbon atoms in the polymer
backbone) 5 units derived from the reaction product of allyl glycidyl
ether and morpholine and 3 units derived from phenothiazine. It is
recovered as a 8.5 wt. % solution in SNO-100 oil.
EXAMPLE VIII.sup.*
In this control Example, the procedure of Example V.sup.* is followed
except that the first graft monomer is the reaction product of allyl
glycidyl ether and morpholine - prepared as in Example VII.
EXAMPLE IX.sup.*
In this control Example, the procedure of Example VI.sup.* is followed
except that the first graft monomer is the reaction product of allyl
glycidyl ether and morpholine - prepared as in Example VIII.sup.*.
EXAMPLE X
In this experimental example, the procedure of Example I is followed except
that the first functional monomer is (instead of N-vinyl pyrrolidone) a
monomer (6 parts) prepared by heating for one hour at 100.degree.
C.-120.degree. C., a mixture of equimolar amounts of allyl glycidyl ether
and N-methylpiperazine. The polymer product contains (per 1000 carbons of
polymeric chain) 4 units derived from the reaction product of allyl
glycidyl ether and N-methyl piperazine and 3 units derived from
phenothiazine. It is recovered as a 8.5 wt. % polymer solution is SNO-100
oil.
EXAMPLE XI
In this experimental example, the procedure of Example I is followed except
that the first functional monomer is (instead of N-vinyl pyrrolidone) a
monomer (8 parts) prepared by heating for one hour at
90.degree.-100.degree. C., a mixture of equimolar amounts of croton
aldehyde and N-(3-aminopropyl)morpholine. The polymer product contains
(per 1000 carbons of polymeric chain) 4.5 units derived from the reaction
product of croton aldehyde and N-(3-aminopropyl) morpholine, and 3 units
derived from phenothiazine. It is recovered as a 8.5 wt. % solution in
SNO-100 oil.
EXAMPLE XII
In this experimental example, the charge EPM polymer has a molecular weight
M.sub.n of 140,000, M.sub.w /M.sub.n ratio of 1.6, and contains 60 mole %
of units derived from ethylene and 40 mole % of units derived from
propylene. 100 parts of this polymer are dissolved in 300 parts of
commercial hexane and added to a reaction vessel.
The mixture is heated to 155.degree. C. with agitation under nitrogen at
200 psig. There are added (i) 5 parts of N-vinylpyrrolidone, dissolved in
15 parts of hexane, (ii) 2 parts of phenothiazine, dissolved in 8 parts of
tetrahydrofuran, and (iii) 6.0 parts of dicumyl peroxide dissolved in 18
parts of hexane.
The mixture is stirred at 155.degree. C. and 200 psig for one hour under
nitrogen. Solvent Neutral Oil (SUS 100) is then added (1076 parts); and
the hexane is distilled off at 90.degree. C.-120.degree. C. The resulting
solution contains about 8.5 w % polymer.
The product poolymer contains (per 1000 carbon atoms in the polymer
backbone) about 6 units derived from N-vinyl pyrrolidone and 1.5 units
derived from phenothiazine.
Each of the products of Examples I and V.sup.* -XII is formulated with a
fully formulated base blend to yield a composition containing 0.85 wt. %
polymer; and these compositions are subjected to the Bench VC Test (BVCT).
The fully formulated base blend contains the following components:
TABLE
______________________________________
Components W %
______________________________________
SNO-130 Oil 75.25
SNO-320 Oil 21.64
Zinc dithiophosphate (anti-wear)
1.12
Naugalube 438 Brand of
4,4'-di-nonyl-di-phenyl amine
(anti-oxidant) 0.39
Surchem 521 Brand of Mg Sulfonate
(detergent) 1.50
Silicone polymer (anti-foamant)
150 ppm
______________________________________
This oil had the following properties:
TABLE
______________________________________
Property Value
______________________________________
Viscosity Kin 40.degree. C. CS
31.50
100.degree. C. CS 5.36
Pour Point .degree.F.
+5
Ash sulfated % (ASTM D-874)
0.93
Phosphorus % (X-ray) 0.11
Sulfur % (X-ray) total
0.40
Zinc % (X-ray) 0.12
Magnesium % 0.33
Cold Cranking Simulator
(cP @ -18.degree. C.)
1660
______________________________________
The products of Examples I and V.sup.* -XII are subjected to the Bench
Oxidation Test to determine whether the additive is a satisfactory
anti-oxidant. In this test, products of Examples I and V.sup.* -XII are
formulated with SNO-130 Oil to yield a solution containing 1.5 wt. %
polymer. The solution is heated with stirring and air agitation. Samples
are withdrawn periodically and analyzed by Differential Infrared
Absorption (DIR) to observe changes in the intensity of the carbonyl
vibration based at 1710 cm.sup.-1. They are also tested in the Clarity
Test and the Lumetron Turbidity Test.
The Oxidation Index is reported as the Carbonyl Group Absorbence in the
Differential Infrared Spectra after 144 hours of oxidation. The Oxidation
Index may range from 0 up to 100 and a low rating is desired. A rating
below 4 is considered excellent.
The Clarity of the samples is also reported visually and by the Lumetron
Turbidity Test after 144 hours. In the Lumetron Turbidity Test, product
turbidity is determined by a Lumetron Photoelectric Colorimeter.
The Lumetron Turbidity is reported on a scale of 0-100. A rating of below
about 20 is satisfactory; higher ratings are less satisfactory.
TABLE
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Clarity at 144 hours
Standards
Oxidation Lumetron Excellent/
Example
Index Visual Turbidity
BVCT Good/Fair
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I 1.8 Clear 16 32.1 9.1/31.0/61.0
V* 2.5 Turbid 100 --
VI* 9.5 Turbid 100 36.0 10.1/27.7/51.9
VII 2.5 Clear 20 34.8 9.1/31.0/61.0
VIII* 3.0 Turbid 100 --
IX* 13.0 Turbid 100 38.5 15.8/31.8/64.6
X 1.8 Clear 16 23.1 11.1/25.2/65.3
XI 1.7 Clear 14 37.1 13.7/25.8/68.2
XII 2.2 Clear 18 36.0 10.2/28.3/52.1
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From the above Table, it is apparent that the experimental Examples I, VII,
and X-XII are characterized by a desirably low Oxidation Index (i.e.
freedom from oxidation), by a visually clear reading, and by a desirably
low Lumetron Turbidity rating. Control Examples VI.sup.*, and IX.sup.*
which fall outside the scope of this invention are characterized by
undesirably higher oxidation indices, by a visually turbid reading, and by
undesirably high Lumetron Turbidity rating. Control Examples V.sup.* and
VIII.sup.* are unsatisfactory by the latter two criteria.
Experimental Examples I, VII, and X-XII are also characterized by
satisfactory BVCT ratings.
It is clear from these tests that the products of the instant invention
which contain polymers bearing first dispersant graft monomers and second
anti-oxidant monomers possess the ability to form lubricating oils
characterized by desirable properties including high dispersancy,
anti-oxidant activity, and desirable viscosity index.
EXAMPLE XIII.sup.*
In this control Example, a base diesel fuel having the following properties
is tested in the Potential Deposit Test and found to have an
unsatisfactory rating of 4+.
TABLE
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Property Value
______________________________________
Lumetron Turbidity 8
Sp. Gr. 60/60F 0.8606
Color ASTM 3.0
Kin.Vis. (cSt @ 100.degree. C.)
805.5
Flash Point (COC) 415
Ash % 0.02
______________________________________
EXAMPLE XIV
In this experimental Example, there is added to the base fuel of Example
XIII.sup.*, 8.5 w % of the polymer of Example I to yield a mix containing
25 PTB (corresponding to 0.01 wt. % or alternatively to a nitrogen content
of 0.054 w %).
The modified diesel fuel is found to have a PDT rating of 1 which is
satisfactory.
EXAMPLE XV.sup.*
In this control Example, a commercial olefin copolymer dispersant VI
improver is blended into formulated oil not containing a VI improver. The
blend is subjected to the single cylinder MWM-B Diesel Engine Test. In
this test, results are presented in merits which correlate with amount of
deposits. Higher merits correspond to lower deposits.
EXAMPLES XVI-XVII
In these experimental Examples, the procedure of Example XV.sup.* is
followed except that the product of Example I is added in Example XVI and
the product of Example X is added in Example XVII (instead of the
commercial olefin copolymer dispersant VI improver) to a formulated oil
not containing a VI improver.
TABLE
______________________________________
Polymer Product MWM-B
Example Example Merits
______________________________________
XV* Commercial DOCP VII
53
XVI I 64
XVII X 63
______________________________________
From the above table, it is apparent that the experimental Examples XVI and
XVII are characterized by a better deposit protection (higher merits) than
the commercial dispersant olefin copolymer VI improver of Example
XV.sup.*.
Although this invention has been illustrated by reference to specific
embodiments, it will be apparent to those skilled in the art that various
changes and modifications may be made which clearly fall within the scope
of this invention.
* * * * *
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