U.S. patent number 3,764,536 [Application Number 05/189,370] was granted by the patent office on 1973-10-09 for overbased calcium salts of alkenylsuccinimide.
This patent grant is currently assigned to Texaco Inc.. Invention is credited to Walter W. Hellmuth, Elmer E. Schallenberg.
United States Patent |
3,764,536 |
Hellmuth , et al. |
October 9, 1973 |
**Please see images for:
( Certificate of Correction ) ** |
OVERBASED CALCIUM SALTS OF ALKENYLSUCCINIMIDE
Abstract
An improved dispersant and rust inhibiting additive for
automotive lubricating oils comprising overbased calcium salt of
alkenylsuccinimide characterized by the formula: ##SPC1## Where R'
is alkenyl of from 30 to 300 carbons and y is an integer of from
about 0.1 to 18, said overbased calcium salt prepared by contacting
alkenylsuccinimide of the formula: ##SPC2## Where R' is as
heretofore defined with a CO.sub.2 blown calcium 2-alkoxyalkoxide
complex characterized by the formula: ##SPC3## Where R is H,
CH.sub.3 and/or C.sub.2 H.sub.5 and x is from 0.5 to 1.5 at a
temperature of between about 50.degree. and 180.degree.C. in the
presence of water and preferably in the presence of an inert liquid
diluent.
Inventors: |
Hellmuth; Walter W. (Beacon,
NY), Schallenberg; Elmer E. (Fishkill, NY) |
Assignee: |
Texaco Inc. (New York,
NY)
|
Family
ID: |
22697038 |
Appl.
No.: |
05/189,370 |
Filed: |
October 14, 1971 |
Current U.S.
Class: |
508/287;
252/389.61 |
Current CPC
Class: |
C10M
159/20 (20130101); C07D 207/46 (20130101); C10N
2010/04 (20130101); C10M 2223/045 (20130101); C10M
2215/28 (20130101); C10M 2215/086 (20130101); C10M
2207/028 (20130101); C10M 2219/046 (20130101); C10M
2205/024 (20130101); C10M 2229/02 (20130101); C10M
2205/02 (20130101); C10M 2229/05 (20130101); C10M
2209/084 (20130101); C10M 2205/026 (20130101); C10N
2020/01 (20200501) |
Current International
Class: |
C07D
207/46 (20060101); C07D 207/00 (20060101); C10M
159/20 (20060101); C10M 159/00 (20060101); C10m
001/20 () |
Field of
Search: |
;252/33.6,34,34.7,49.7,389,51.5A ;260/326.5FU |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Wyman; Daniel E.
Assistant Examiner: Sneed; H. M. S.
Claims
We claim:
1. An overbased calcium alkenylsuccinimide characterized by the
formula: ##SPC17##
where R' is alkenyl of from 30 to 300 carbons and y is an integer
of from 0.1 to 18.
2. A compound in accordance with claim 1 wherein R' is
polyisobutene of an average molecular weight of about 1200.
3. A lubricating oil composition comprising a major amount of a
refined mineral lubricating oil and a small amount sufficient to
improve detergency and rust inhibition thereof of an overbased
calcium alkenylsuccinimide characterized by the formula:
##SPC18##
where R' is alkenyl of from 30 to 300 carbons and y is an integer
of from 0.1 to 18.
4. A lubricant composition according to claim 3 containing between
about 0.5 and 10 wt. % of said additive.
5. A lubricant composition according to claim 3 wherein R' is
polyisobutene of an average molecular weight of about 1200.
6. A method of producing overbased calcium alkenyl-succinimide
characterized by the formula: ##SPC19##
where R' is alkenyl of from 30 to 300 carbons and y is an integer
of from about 0.1 to 18 comprising contacting an alkenylsuccinimide
of the formula: ##SPC20##
where R' is as heretofore defined with a CO.sub.2 blown calcium
methoxyethoxide characterized by the formula: ##SPC21##
where R is H, CH.sub.3, and/or C.sub.2 H.sub.5, where x is between
about 0.5 and 1.5 in the presence of water at a temperature between
about 50.degree. and 180.degree.C. utilizing a mole ratio of said
alkenyl-succinimide to calcium reagent to said water of between
about 1:0.5:0.1 and 1:9.5:12.
7. A method in accordance with claim 6 where R is H.
8. A method in accordance with claim 7 where said contacting is
conducted in the presence of inert liquid diluent in an amount of
between about 10 and 50 vol. % of the reaction mixture.
9. A method in accordance with claim 8 wherein said solvent is
toluene, hydrocarbon mineral lubricating oil, or 2-methoxyethanol
and said R' is polyisobutene of an average molecular weight of
about 1200.
Description
BACKGROUND OF INVENTION
Mineral lubricating oil employed as crankcase lubricants in
internal combustion engines tend to oxidize at the high
temperatures to which they are subjected in this type of service
with the resultant formation of gums, sludges which clog the oil
feed lines and form varnish-like deposits on the surfaces of rings,
pistons, cylinders and other engine parts. Further, with emission
control devices being installed on the presently manufactured
automotive vehicles, much of the corrosive bodies of the engine
exhuast system are not introduced into the crankcase oil. The gums
and sludges lead to piston sticking and varnish on the cylinder
walls. This coupled with the attack of the corrosive bodies on the
engine metal surfaces cause substantial deterioration of the engine
operation.
In order to counteract these negative factors, additives are added
to crankcase oils in small amounts such as dispersants to
counteract the formation of gums and sludges and anticorrosives to
inhibit the corrosive action of the exhaust gases introduced into
the crankcase system. One of the suitable known dispersants are the
normal metal salt derivatives of the alkenylsuccinimide where the
alkenyl portion ranges from 15 to 30 carbons as represented in U.
S. Pat. No. 2,628,942.
Hereinbefore and hereinafter the term "normal" when referring to
the salt of the alkenylsuccinimide denotes the ratio of the number
of equivalents of metal moiety to the number of equivalents of
alkenylsuccinimide moiety is about 1 and the term "overbased" when
utilized in connection with the alkenylsuccinimide salts denotes
the ratio of the number of equivalents of metal moiety to the
number of equivalents of alkenylsuccinimide moiety is greater than
about 1.
Although the prior normal metal alkenylsuccinimide as represented
in U. S. Pat. No. 2,628,942 are satisfactory as crank-case
dispersants, there is a need due to the burden placed by auto
emission control devices on crankcase oils to also incorporate
anticorrosive properties in such type additives.
SUMMARY OF INVENTION
We have discovered and this constitutes our invention a novel
additive for lubricating oils having superior dispersancy and
corrosion inhibiting properties for use in crankcase oils for
automotive, diesel and airplane engines. Further, we have
discovered a method for manufacturing said additive and lubricant
compositions resulting therefrom. Specifically, the novel additive
of the invention having detergent-dispersant and rust inhibiting
properties is the overbased calcium salt of alkenylsuccinimide
characterized by the formula: ##SPC4##
where R is alkenyl of from 30 to 300 carbons and y is an integer of
from about 0.1 to 18.
The overbased calcium salt additives are prepared by contacting
alkenylsuccinimide characterized by the formula: ##SPC5## with
CO.sub.2 blown calcium 2-alkoxyalkoxide characterized by the
formula: ##SPC6##
where R is H, CH.sub.3 and/or C.sub.2 H.sub.5, x is an integer of
from about 0.5 to 1.5 and water initially utilizing an imide to
CO.sub.2 blown calcium reagent to water mole ratio of between about
1:0.5:0.1 and 1:9.5:12 at a temperature between about 50 and
180.degree.C., normally for a period of between about 1 and 3
hours. Under preferred conditions, the reaction is conducted under
conditions of agitation and in the presence of an inert liquid
diluent. The inert diluent when employed advantageously constitutes
between about 10 and 50 vol. % of the reaction mixture.
At the end of the reaction period, the crude product is preferably
stripped with inert gas blowing such as nitrogen blowing,
preferably under reduced pressure, to remove volatile materials
therefrom. The resultant overbased products, normally in liquid
form, are desirably filtered via standard means to remove any solid
impurities therefrom.
One of the essential features in the manufacturing process is the
employment of the CO.sub.2 blown calcium reagent as defined.
Substitution of normally considered overbasing equivalents such as
calcium oxide, calcium hydroxide or calcium oxide and calcium
hydroxide solutions in lower alkanol will produce the normal
calcium salts of alkenyl-succinimide as disclosed in U. S. Pat. No.
2,628,942 but not the desired overbased calcium salts.
The alkenylsuccinimide reactants are prepared by standard means
such as reacting the maleic anhydride with a polyalkene polymer of
from 30 to 300 carbons, e.g., containing three to five carbon atoms
repeating groups, such as ##SPC7##
at an elevated temperature, e.g., 200.degree. to 300.degree.C. and
then subsequently passing ammonia through the resultant solution at
a temperature between about 100.degree. and 250.degree.C. to form
the alkenylsuccinimide as heretofore defined.
Specific examples of the succinimide reactant characterized by the
formula: ##SPC8##
are where R' is polyisobutene of an average molecular weight of
about 500, R' is polyisobutylene of an average molecular weight of
about 800, R' is polyisobutene of an average molecular weight of
about 1200, R' is polypropylene of an average molecular weight of
about 1500, R' is polypentylene of an average molecular weight of
about 2000 and R' is polybutene of an average molecular weight of
about 3000.
The CO.sub.2 blown calcium-2-alkoxyalkoxide reagent is prepared by
the reaction of calcium carbide and 2-alkoxy-alkanol utilizing a
temperature of between about 150.degree. and 250.degree.F. and a
mole ratio of alcohol for calcium carbide of between about 3:1 and
100:1. The resultant mixture is then blown with carbon dioxide at a
temperature between about 50.degree. and 150.degree.C. utilizing a
calcium to carbon dioxide mole ratio of between about 0.5:1 and
1.5:1 to form the CO.sub.2 blown reagent as precedingly
defined.
Examples of the calcium reagent characterized by the formula:
##SPC9##
are where x is 0.5, x is 1, x is 1.2 and x is 1.5 where R is
respectively H, CH.sub.3, C.sub.2 H.sub.5.
Examples of the solvent suitable in the manufacture of the
overbased calcium additive are benzene, toluene and other alkyl
substituted liquid aromatic hydrocarbons; hydrocarbon lubricating
oil of an SUS viscosity of between about 50 and 500 at
100.degree.F.; alkanes such as heptane, isooctane, etc. as well as
saturated cyclic and alicyclic hydrocarbon solvents such as
cyclohexane, methylcyclohexane, etc. When lubricating oils are
employed, a lube oil concentrate of overbased calcium succinimide
is formed as the final product. Volatile substances such as
benzene, toluene and cyclohexane are removed during stripping.
Examples of the overbased calcium salt product of the invention
characterized by the formula: ##SPC10##
are where R' is polyisobutene of an average molecular weight about
500 and y is 0.5; R' is polyisobutene of an average molecular
weight of about 800 and y is 1; R' is polyisobutene of an average
molecular weight of about 1200 and y is 2; R' is polypropylene of a
molecular weight of about 2000 and y is 2.5; R' is polybutene of an
average molecular weight of about 3000 and y is 3.5.
In the formulation of the lubricant composition of the invention,
suitable base oils include a wide variety of hydrocarbon
lubricating oils such as naphthetic base, paraffinic base and mixed
base mineral oils or other hydrocarbon lubricants, e.g.,
lubricating oil derived from coal products and synthetic
hydrocarbon oils, e.g., alkylene polymers such as polypropylene,
polyisobutylene of a molecular weight of between about 250 and
2500. Advantageously, the lubricating oils having an SUS viscosity
at 100.degree.F. between about 50 and 2000 are employed. The
overbased calcium additives are incorporated in the base oils in an
amount of between about 0.5 and 20 wt. %, preferably between about
0.5 and 5.0 wt. %. In the finished lubricating oil compositions
other additives may be included. These other additives may be any
of the standard suitable pour depressors, supplementary sludge
dispersants, antioxidants, silver corrosion inhibitors, viscosity
index improvers and friction modifiers. Exactly what other
additives are included in the finished oil compositions and
particular amounts thereof will, of course, depend on the
particular use and conditions desired for the finished oil
products.
The following examples further illustrate the product, method of
producing and lubricant compositions thereof but are not to be
construed as limitations thereof.
EXAMPLE I
This example illustrates the preparation of the alkenylsuccinimide
reactant.
Into 5280 grams (2.0 mole) of polyisobutene (1200 m.w.) succinic
anhydride dissolved in polyisobutene (1200 m.w.), heated to
100.degree.C. there was introduced at a rate of 500 mls./min.
ammonia for 1 hour, then at 140.degree.C. for 0.5 hour and at
180.degree.C. for 0.5 hour. The resultant ammonia treated reaction
mixture was then flushed with nitrogen for 15 minutes and filtered
through diatomaceous earth. Approximately 5000 grams of product
were recovered and analysis found it to contain 0.56 wt. %
nitrogen. It was identified as polyisobutene (1200 m.w.)
succinimide characterized by the formula: ##SPC11##
where R' is polyisobutene of an average molecular weight of about
1200.
EXAMPLE II
This example illustrates the preparation of the CO.sub.2 blown
calcium-2-alkoxyalkoxide reagent.
To 150 lbs. of 2-methoxyethanol there was introduced 25 lbs. of
finely divided calcium carbide and the reaction mixture was stirred
at 251.degree.-253.degree. F. for 1 hour. To the resultant product
weighing 164 lbs. and identified as calcium 2-methoxyethoxide there
was introduced CO.sub.2 at a rate of 11 lbs. per hour for 1.5 hours
at 258.degree.F. At the end of the reaction period the resultant
product was filtered through diatomaceous earth and was identified
as CO.sub.2 blown calcium2-methoxyethoxide characterized by the
formula: ##SPC12##
where x is 1 and analyzed 8.0 wt. % Ca.
EXAMPLE III
This example illustrates the preparation of an overbased calcium
alkenylsuccinimide species.
To 259 grams (0.10 mole) of polyisobutene (1200 m.w.) succinimide
solution of the type prepared in Example I dissolved in 100 mls. of
toluene there was added 100 grams of CO.sub.2 blown calcium
2-methoxyethoxide of the type prepared in Example II and 3.3 mls.
(0.15 mole + 25 percent mole excess) water. The resultant mixture
was stirred 1 hour at 100.degree.C., stripped with nitrogen blowing
to a temperature of 180.degree.C., then stripped using a water
aspirator (20 mm Hg) to 180.degree.C. and filtered through
diatomaceous earth. The recovered liquid product weighed 262 grams
and was characterized by the formula: ##SPC13##
where R' is polyisobutene (1200 m.w.) and y is 3.0. Analysis of the
product found a nitrogen content of 0.49 wt. % (0.51 calc.) and a
calcium content of 3.0 wt. % (2.91 calc.).
EXAMPLE IV
This example further illustrates the preparation of the overbased
calcium alkenylsuccinimide and the lube oil concentrate.
To 1000 grams of naphthenic oil having an SUS viscosity of 100 at
100.degree.F. there was added 259 grams (0.102 mole) of
polyisobutene (1200 m.w.) succinimide solution as prepared in
Example I. The resultant mixture was heated to 90.degree.C. and
there was added 50 mls. of CO.sub.2 blown calcium 2-methoxyethoxide
as prepared in Example II. The resultant mixture was heated to
90.degree.C. for a period of 15 minutes whereupon an additional 50
mls. of calcium reagent and 5 mls. of water were added. The
temperature was again held at 90.degree.C. for 15 minutes. The
calcium reagent and water additions and stirring period were
repeated four more times and the resultant mixture was stripped
with nitrogen blowing to 180.degree.C., filtered through
diatomaceous earth and 60 grams of solid product were removed on
the filter. A total of 250 grams of calcium reagent and 18 grams of
water are employed. The resultant liquid filtrate was identified as
a lube oil solution containing about 15 wt. % of an overbased
calcium polybutene (1200 m.w.) succinimide characterized by the
formula: ##SPC14##
where R' is polyisobutene of an average molecular weight of about
1200, y is 4. The product was analyzed and found to contain 0.10
wt. % nitrogen (calc. 0.094) and 0.7 wt. % calcium (calc. 0.9).
EXAMPLE V
This example further illustrates the preparation of the calcium
overbased alkenylsuccinimide.
To 368 grams (0.1 mole) of polyisobutene (1200 m.w.) succinimide
solution heated to 80.degree.C. there was added 24.4 grams of
CO.sub.2 blown calcium 2-methoxyethoxide of the type prepared in
Example II over a 5 minute period and the resultant mixture was
stirred 5 minutes, stripped with nitrogen to 150.degree.C., cooled
to 90.degree.C. Then 24.5 grams of calcium reagent of the type
perpared in Example II simultaneously with 5 mls. of water and 25
mls. of 2-methoxyethanol were added over 5 minutes and the
aforedescribed stirring, stripping and cooling sequence were
repeated until a total of 146 grams of calcium reagent, 25 mls. of
water and 125 mls. of 2-methoxy-ethanol were added. The resultant
mixture was then stripped to 180.degree.C. with CO.sub.2 blowing
(1000 mls./min.) and filtered through diatomaceous earth. The
resultant product filtrate was recovered in an amount of 258 grams
and was identified as characterized by the formula: ##SPC15##
where R is polyisobutene in an average molecular weight of about
1200 and y is 6. Further analysis of the product found it to
contain 2.8 wt. % calcium (3.95 calc.) and 0.29 wt. % nitrogen
(0.35 calc.).
EXAMPLE VI
This example illustrates the preparation of over-based calcium
polyisobutene succinimide.
Three hundred sixty eight grams (0.10 mole) of polyisobutene (1200
m.w.) succinimide were heated to 90.degree.C. and there were added
24.4 grams of CO.sub.2 blown calcium 2-methoxyethoxide of the type
produced in Example II. The resultant mixture was stirred 10
minutes, stripped to 150.degree.C. with carbon dioxide blowing (500
mls./min.) and the temperature reduced to 90.degree.C. There was
then added additional 24.4 mls. of calcium reagent of Example II
and 5 mls. water and 25 mls. of 2-methoxyethanol simultaneously
over a 5 minute period. The resultant mixture was stripped and
cooled as before and repeated until all the calcium reagent and
water solution was employed and the resultant mixture was stripped
to 180.degree.C. with CO.sub.2 blowing and the resultant mixture
was filtered through diatomaceous earth with the recovery of 288
grams of product. A total of 97.6 grams of calcium reagent (0.4
equivalents) were utilized. The product was analyzed and determined
to be overbased calcium polyisobutene (1200 m.w.) succinimide
characterized by the formula: ##SPC16##
wherein R' is polyisobutene of an average molecular weight of about
1200 and y is 2.5. Analysis of the mixture found 1.4 wt. % Ca, 0.28
wt. % N.
EXAMPLE VII
This comparative example illustrates the importance of employing
the method of the invention to prepare the overbased calcium
alkenylsuccinimide.
To 269 grams of polyisobutene (1200 m.w.) succinimide (0.10 mole)
solution there was charged 14 grams calcium oxide (0.25 mole), 100
grams ethylene glycol (1.6 mole), 100 mls. toluene and 4.5 mls.
water (0.25 mole + 25 mole % excess). The resultant mixture was
refluxed at about 115.degree.C. for 3 hours with CO.sub.2 blowing
(500 mls./min.) then stripped to 100.degree.C. utilizing a water
aspirator (20 mm Hg). Eighty five mls. of toluene and 864 grams of
polar material were stripped out. The product was unfilterable and
of a grease-like quality. No useful lubricating oil additive as
obtained by this process.
The foregoing procedure was repeated utilizing 233 grams of
polyisobutene (1200 m.w.) succinimide, 14 grams calcium oxide, 100
mls. ethylene glycol, 100 mls. toluene, 4.5 mls. water and 149
grams of naphthenic mineral oil having an SUS viscosity at
100.degree.F. of 100. The resultant mixture was refluxed for 3
hours at about 120.degree.C. while simultaneously passing 700
mls./min. CO.sub.2 therethrough. The resultant mixture was stripped
to 180.degree.C. utilizing a water aspirator (20 mm Hg). The
resultant product would not filter and analysis indicated that no
overbased product was formed.
EXAMPLE VIII
This example illustrates the lubricant compositions of the
invention contemplated herein and also illustrates the function of
the overbased calcium alkenylsuccinimide as an effective dispersant
in lubricating oils.
The test procedure employed comprises introducing into a bottle the
test lubricating oil compositions, titanium oxide (6 wt. %) in oil
and engine blowby. The bottle was agitated at an elevated
temperature for a period of time and a portion of the bottle
contents was centrifuged. Upon centrifuging, three phases are
formed, i.e., a top clear oil phase, a middle dirty oil phase in
which sludge remains dispersed and a bottom sediment phase. The
clear oil and sediment depth are measured in millimeters and
recorded as the first cycle. For the second and subsequent cycles
to the sample remaining in the bottle from the first cycle portions
of the following materials were added in the order listed: titanium
oxide (6 wt. %) in oil and engine blowby and the procedure of the
first cycle is repeated. The cycles are continued until the
centrifugal oil is clear and completely free of sediment. The
greater the depth of sediment and clear oil in the centrifuged tube
the less the dispersant capacity of the test oil composition.
The base oil composition employed on the foregoing test to which
the overbased calcium alkenylsuccinimide is added is of the
following composition:
TABLE I
Description Wt. % Paraffinic Oil 89 (.about.140 SUS at
100.degree.F.) CO.sub.2 blown 1:1 overbased barium alkylphenolate
Zinc dialkyldithiophos- 6 phate CO.sub.2 blown 1:1 overbased barium
sulfonate 750 ppm Silicone polymer antifoamant Copolymers of butyl
to 5 stearyl methacrylate (3500 SUS at 210.degree.F.)
TABLE II
Over- based Base Ca Run Oil Additive Bench Sludge Test No. Comp.
Wt. %* Cycle 1 2 3 4 A 100 0 Clear 41 38 -- -- Sediment 9 2 -- -- B
96.6 3.4 Clear 2 3 6 37 Sediment 4 9 8 11 *Product Ex. III
EXAMPLE IX
This example illustrates the rust inhibiting properties of
lubricant compositions containing the overbased calcium
alkenylsuccinimide and also illustrates lubricant compositions
containing said succinimide.
The rust test employed is a low temperature engine procedure which
comprises lubricating a 1964 289 CID V-8 engine. The engine is run
under the following test conditions.
TABLE III
Description Value Duration, hrs. 45 Speed, rpm 1500 Load, BHP 28
Fuel pressure, psi 4.5 Fuel/air ratio 0.085 Crankcase Ventilation,
.degree.F. Jacket Out 90 Oil Gallery 110 Rocker Arm Covers 60
Intake Air 110
At the end of the test period of the various engine runs the
external and internal area of the valve lifters and push rods were
inspected. A rating of 10 represented no rusting and a rating of
zero indicated heavy rusting of the entire surfaces. Three
compositions were subjected to this test. These formulations (Oils
C, D and E) all consisted of the same base composition, namely, a
paraffinic lubricating oil of .about.130 SUS viscosity at
100.degree.F. containing a zinc dialkyl dithiophosphate,
supplementary ashless dispersant and methacrylate VI improver.
Additionally, in Oil C there was also present an overbased
succinimide of the type described in Example III but R' was at 400
m.w. polybutene. In Oil D a comparative rust preventive compound,
calcium overbased P.sub.2 S.sub.5 -polybutene (400 m.w.), was
present. The calcium level in both Oils C and D was 0.175 wt. %.
Oil E was said base composition per se.
The test results in this rust test are as follows:
TABLE IV
Additive Test Oil Wt. % Ca Hours Internal External C 0.175 45 3.9
8.7 D 0.175 45 3.6 8.2 E 0 21 4.5 7.8 20 3.9 5.7 20 4.7 5.4
the above demonstrates the utility of overbased alkenylsuccinimide
products to prevent rusting in automotive engines.
* * * * *