Note: Descriptions are shown in the official language in which they were submitted.
1224803
ONE-STEP PROCESS FOR PREPARATION OF OVERBASED
CALCIUM SULFONATE GREASES AND T~ICKENED CO~POSITIONS
Backgrouna of the Invention
Fiela of the Invention
My present .invention is directed to an
improved l-step process for the preparation of
overbased calcium sulfonate greases and thickened
compositions. The greases and thickened compositions
of the present invention are of the heretofore known
thixotropic type which comprise, advantageously, a
volatile and/or nonvolatile liquid carrier or solvent,
122a~E~03
sueh as, for example, Varsol* or mineral spirits, or a
mineral oil or equivalent oil medium in their
produetion, and oil-soluble ealeium sulfonates derived ..
from oil-soluble higher moleeular weight sulfonie
aeids, whieh greases and thiekened eompositions also
eontain ealeium earbonate as ealeite in eolloidal or
extremely finely divided form. In aeeordanee with my
invention, while sueh types of greases and thiekened
eompositions have heretofore been prepared by what is
known to the art as the l-step proeess, sueh l-step
proeesses, as heretofore known and practiced, have had
various deficiencies which are overcome by my present
invention.
Background of the Invention and
Brief Description of the Prior Art
Thixotropic greases or thickened overbased
caleium sulfonate eompositions having
corrosion-inhibiting properties, and having utility for
a variety of uses sueh as, for instanee, in automobile
and truek body undercoatings, and for various other
purposes" are known to the art and are disclosed in
various publications and patents, illustrative of which
are U. ';. Patents Nos. 3,242,079; 3,372,115; 3,376,222;
3,377,2~3; 3,3523,898; 3,661,622; 3,671,012; 3,746,643;
3,730,895; 3,816,310, and 3,492,231; and Canadian
Patent No. 949,055. Such greases or thickened
compositions have gone into quite widespread use either
as sueh, or admixed with other ingredients to produce
compositions for use in a variety of environments, and,
generally speaking, they are characterized by
reasonably good E. P. and antiwear properties, high
dropping points, reasonably good resistance to
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1224803 3
meehanieal breakdown, salt spray and water-eorrosion
resistanee, thermal stability at high temperatures, and
other desirable properties, as deseribed in the
aforesaid patents. Sueh heretofore known greases or
thickened compositions are conventionally prepared by
what is known as a 2-step proeess, as more partieularly
shown in the aforesaid U. S. Patents Nos. 3,242,079;
3,372,115; and 3,492,231. They have also been prepared
by what is known as a l-step proeess, as noted above,
and as is shown, for instanee, in the aforementioned U.
S. Patents Nos. 3,671,012; 3,746,643; and 3,816,310;
and Canadian Patent No. 949,055, whieh also diselose
heretofore known 2-step processes.
In the 2-step process, as shown particularly
in U. S. Patents Nos. 3,242,079; 3,372,115; and
3,492,231, as referred to above, there is initially
prepared, by way of illustration, a Newtonian solution
by admixing a normally liquid oil, eommonly a mineral
oil or a mixture comprising a mineral oil and a
non-mineral oil volatile organic solvent, usually a
hydrocarbon solvent such as hexane, with a normally
liquid sulfonic aeid comprising or containing an
aliphatie straight or branehed chain having at least 12
carbon atoms but preferably having a moleeular weight
in the range of about 370 to about 700, to which are
added calcium oxide and/or calcium hydroxide and with a
so-ealled promoter whieh serves to produee an overbased
caleium sulfonate whieh commonly may have a metal ratio
of at least 4.5, usually substantially higher, and the
resulting mixture is heated, under conditions of
agitation, and then carbonated. This results in a
Newtonian solution containing the overbased calcium
sulfonate dissolved or colloidally dispersed in the
mineral oil or the like, which solution is then
1224803
filtered to form a clear solution. The resulting clear
Newtonian solution, produced in this first step, is
then subjected to treatment by a second step which
involves generally vigorous admixing, and usually
heating, said first-step produced solution with a
so-called converting agent which may, for instance, be
water, or water-soluble alcohols or glycol ethers such
as methylcellosolve~tmono-methyl ether of ethylene
glycol), or mixtures of water and such alcohols; or
water-soluble acids, such as acetic acid or propionic
acid, which second step results in converting the
Newtonian solution to a non-Newtonian disperse system
in the form of a grease or a thickened composition.
The l-step process of forming the greases or
thickened compositions differs from the 2-step process
in that, in the l-step process, generally speaking,-
essentially all of the ingredients are mixed together
and then carbonated, and there is no separately formed,
or separately formed and recovered, Newtonian solution
of an overbased calcium sulfonate dissolved or
colloidally dispersed in mineral oil or other suitable
liquid medium or carrier. From an economic standpoint,
the l-st:ep process has a definite advantage over the
2-step process, but the l-step process has not gone
into commercial use to nearly the extent that has been
the case with the 2-step process because the l-step
process, as heretofore known and as heretofore
commercially practiced or sought to be practiced, has
been characterized by numbers of significant
disadvantages.
U. S. Patent No. 3,746,643 discloses a l-step
process of preparing thixotropic overbased calcium
sulfonate greases and rust-inhibiting compositions
wherein small amounts of water and an alcohol are
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1224~3~3 5
incorporated into a mixture of a nonvolatile diluent
oil, a calcium carbonate complex, and an oil-soluble
calcium sulfonate complex dispersing agent. In said
mixture, the calcium sulfonate dispersing agent is
stated to range from about 2 to about 65 wt.%; the
nonvolatile diluent oil is stated to range from about 5
to 80 wt.~; the calcium carbonate complex is stated to
range from about 1 to about 25 wt.%; and the water and
alcohol are stated to range from about 1 to about 6
wt.~, and from about 1 to about 40 wt.%, respectively.
In addition, the mixture of said ingredients is stated
to include, optionally, up to 60 wt.~ of a volatile
processing solvent. The resulting mixture of
ingredients is then stated to be heated under
controlled conditions to convert the mixture to a
grease or rust-inhibiting composition (when cut back
with a light hydrocarbon solvent). The patent points
out that, to obtain the desired products, the mixture
must be heated to a temperature exceeding 50 C (122
F), and that it is necessary in traversing the
temperature zone from about 50 C (122 F) to about
100 C (212 F) that the rate of temperature increase
not exceed a certain maximum limit where the amount of
water present in the mixture is less than 2.5 moles of
water per mole of calcium metal present as the
carbonate complex .
U. S. Patent No. 3,671,012 discloses a l-step
process of preparing thixotropic overbased calcium
sulfonate greases and grease-like compositions. This
is disclosed more particularly in Column 6, Lines 40 to
the bottom of the page, extending through Columns 7 and
8 and through Line 25 in Column 9. The procedure
described in U. S. Patent No. 3,671,012 is generally
similar to that shown in U. S. Patent No. 3,746,643
12248~3 6
except that the disclosure in U. S. Patent No.
3,671,012 is in greater detail than is described in U.
S. Patent No. 3,746,643.
U. S. Patent No. 3,816,310 is generally
similar in its disclosure of known l-step processes to
the l-step process disclosed in the above referred to
U. S. Patents Nos. 3,746,643 and 3,671,012. Taking as
illustrative the l-step process as described in U. S.
Patent No. 3,816,310, as there described in a typical
or illustrative embodiment, an admixture is formed
consisting essentially of an oil-soluble sulfonic acid
or an oil-soluble calcium sulfonate as a dispersing
agent, e.g. linear or branched chain "NAB" Bottoms or a
Cls-Clg linear alkylbenzene sulfonic acid; liquid
medium or carrier material, for instance, a mineral
oil; a Cl-C3 alkanol, for instance, methyl alcohol;
calcium oxide and/or calcium hydroxide; and water; then
carbonating the resulting admixture with carbon dioxide
while maintaining the temperature below about 165 F to
the extent that at least 1.5 moles of the carbon
dioxide per mole of the calcium as calcium carbonate
are present in the mixture; and then heating the
carbonated admixture to a temperature above 212 F,
said heating step being characterized in that the time
required to heat to 212 F is from about 0.5 to about 8
hours, the process being characterized further in that,
alternatively, the water utilized initially may be
added after the carbonation step or just prior to the
heating step after the carrying out of the carbonation
step. Numbers of nonvolatile liquid media or carrying
materials are disclosed, mineral oils generally being
preferred where greases are preferred. U. S. Patent
No. 3,816,310 also teaches that a light or relatively
volatile hydrocarbon solvent, such as, by way of
1224803 7
example, n-decane, benzene, toluene, StDddard solvent
or n-hexane, though not a critical ingredient, may be
incorporated into the composition constituting the
aforementioned ingredients, and, when included, it is
preferable that it be employed in proportions, in terms
of wt.%, from about 20 to 80% of the total of the
calcium sulfonate and nonvolatile carrier present in
the composition to be processed. In those instances in
which the final composition produced by the process is
to be used as a grease, a high percentage of the
mixture of nonvolatile carrier and volatile hydrocarbon
solvent should be volatile hydrocarbon solvent;
whereas, if the final product produced by the process
is to be used as a rust or corrosion protective coating
or film, the nonvolatile carrier may be used alone as
the carrier or in admixture with relatively smaller
amounts of volatile carrier. The patent also
specifically states that, when the final product
produced by the process of said patent is to be used as
a grease, the consistency or thickness of the grease is
controlled by using, as the carrier, a relatively
nonvolat:ile mineral oil typically having the general
properties of a Bright Stock cut produced in petroleum
refining.
One of the main problems with such prior
known and practiced l-step processes was that of the
unpredictability as to whether the grease or thickened
products obtained would or would not be at least
reasonably satisfactory for commercial usage.
Reasonably satisfactory and commercially usable greases
and thickened compositions were obtainable in less than
50~ of the cases where the then-known l-step processes
were carried out to produce the desired greases or
thickened compositions. Efforts to ascertain why
lZ24l303
certain batches of greases or thickened compositions
were suitable whereas others were not successful
despite the fact that considerable studies and
experimental work were expended in such efforts.
The Present Invention
My present invention has resulted in
effeetively improving prior defeets in known praetices
in producing overbased ealeium sulfonate greases by the
use of a novel l-step process. It has been discovered
that, in the earrying out of the improved l-step
process of my present invention, by providing an
admixture containing the aforementioned volatile
carrier, for instance, VarsoI~ mineral spirits, or
n-hexane, or an admixture thereof with varying amounts
of a nonvolatile carrier, particularly a mineral oil of
the same kinds as have heretofore been disclosed and
used in the preparation of grease or thickened
composition of the type to which my present invention
relates; or an oil, particularly a mineral oil without
any mixture therewith of a volatile carrier; an
oil-soluble sulfonic acid or mixture of oil-soluble
sulfonic acids, as a dispersing agent, as have
heretofore been known and used; caleium oxide and/or
calcium hydroxide, all as heretofore known and used;
but including in the admixture of ingredients minor
proportions of water-soluble aliphatic acids such as
acetic acid and an aliphatic alcohol or alkoxyalkanol
such as methyl alcohol or methylcellosolve*, prior to
carrying out the carbonation step; and by carrying out
the carbonation step under conditions not re~uiring the
rigid controls specified, for instance, in said U. S.
Patent No. 3,816,310, and the other l-step disclosed
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12X48~3
processes in said other patents, improvements result
which make the l-step process very considerably more
practicable and very largely more consistent in
producing commercially satisfactory batches of the
overbased calcium sulfonate greases and thickened
compositions of the general type which are obtained by
the l-step process that has been the situation under
previously known and practiced l-step processes.
More specifically, in the practice of my
present invention, the mixture of ingredients which is
to be subjected to the carbonation step utilizes (a) a
water-soluble or water-miscible aliphatic carboxylic
acid containing up to 4 carbon atoms, or an aromatic
carboxylic acid, such as acetic acid, propionic acid,
butyric acid or benzoic acid, especially acetic acid;
(b) a water-soluble or water-miscible alcohol,
preferably containing from 1 to 4 carbon atoms, or an
alkoxyalkanol, for instance, a water-soluble mono-alkyl
ether of a water-soluble glycol, such as
methylcellosolveAor ethylcellosolve~(mono-methyl or
mono-ethyl ether of ethylene glycol, particularly
methylcellosolve~; and (c) water. This combination of
ingredients may be premixed and added as such to the
other ingredients, or, alternatively, the (a), (b) and
(c) ingredients can be added separately or in any
mixture of two of them to the other ingredients. By so
proceeding when, as indicated above, the overall
mixture of the ingredients includes the (a), (b) and
(c) ingredients, prior to carrying out the carbonation
step, the desired formation of the colloidal calcium
carbonate in the form of calcite crystals and the
desired viscosity change to a grease or a thickened
composition occurs at the end of the carbonation step
or cycle. The volatile solvent may or may not be
driven off by distillation or may be driven off in
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1224803
part. The result of the practice of such l-step
process is to produce a non-Newtonian colloidal
disperse system, in the form of a grease or thickened
composition, containing calcium sulfonate and also
containing colloidally dispersed or extremely finely
divided calcium carbonate in the form of crystals of
calcite, sometimes admixed with minor proportions of
calcium carbonate in the form of vaterite.
The ratios of the (a), (b) and (c)
ingredients, as specifically and advantageously
exemplified by acetic acid, methyl alcohol or
methylcellosolve* and water, are variable within
reasonable limits but, in general, the amount of the
acetic acid (measured as glacial acetic acid) will be
substantially less than that of the methyl alcohol or
methylcellosolve~, and the amount of water will be in
the range of about that of the alcohol or
methylcellosolve*or somewhat less or somewhat more than
that of the alcohol or methylcellosolve.
With respect to the matter of the proportions
of such ingredients as the carriers, whether volatile
or nonvolatile, or mixtures thereof; the calcium oxide
and/or calcium hydroxide; the sulfonic acids, the
alcohols or glycol ethers or alkoxyalkanols; and the
water, no novelty is claimed in such proportions since
such proportions are variable and are generally
disclosed and taught by prior known l-step processes.
As to the use of the water-soluble acids, such as and
particularly acetic acid, no prior art of which I am
aware has utilized such acids nor, particularly, acetic
acid in a l-step process of producing overbased calcium
sulfonate complex greases or thickened compositions;
and the same is true as to the use of acids, such as
acetic acid, and alcohols such as methanol or glycol
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122~l303
ethers such as methylcellosolve*or other alkoxyalkanols
conjointly in a l-step process of the type to which my
present invention relates, which involves the best and
most important embodiments of my present l-step process
invention. The amount of such acids as acetic acid,
and the amount of such alcohols as methanol or
methylcellosolve*, constitute distinctly minor wt.
proportions of the ingredients mixture which is
prepared for reaction and carbonation, as can be seen
from the working EXAMPL~S set forth below in the
present specification. The acid, such as acetic acid,
will usually be somewhat below 0.5 wt.% of the total
ingredient mixture (prior to the carbonation step),
and, in general, may range from about 0.2 to about 2
wt.~ of said ingredient mixture. The alcohol or
methylcellosolve*or other alkoxyalkanols employed is
variable but will commonly be used in the range
optimally of about 4 to about 6 wt.~, more or less,
based on said ingredient mixture.
According to the l-step process disclosed in
the aforementioned V. S. Patent No. 3,816,310, at least
1.5 moles of carbon dioxide per mole of calcium should
be present in the mixture of ingredients. This is
brought out in the specification (e.g., Column 2, Step
B). In the l-step process of the present invention,
effective carbonation for the purposes of my invention
is sufficiently complete using in the range of only
about 0.78 to 0.9 moles per mole of calcium.
In U. S. Patent No. 3,816,310, the Cl-C3
alcohols are used in proportions in the range of 10 to
40 wt.~ levels, with 20 to 30~ being preferred and with
30~ being most preferred. In accordance with my
present invention, the said alcohols, where used, but
in conjunction or in admixture with a carboxylic acid
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~224803 12
such as acetic acid, can be used in proportions as low
ac about 4 to about 8 wt.% with the said acetic acid.
While U. S. Patent No. 3,816,31 stresses that
the temperature at which carbonation is effected should
not exceed 122~ F ~50~ C), in accordance with my
present invention, the carbonation step can be carried
out at temperatures in the range of about 100 to about
200 F.
Furthermore, whereas said U. S. Patent No.
3,816,310 requires a restricted time/temperature
distillation profile, following the carbonation step,
to obtain proper crystalline calcite structure and
ViSCoaity, my invention has no such restricted
"controlled" time/temperature profile but, rather,
possesses much wider latitude, further emphasizing
another of several different aspects of the process of
said patent and the l-step process of my present
invention in that, in my l-step process, no specific
distillation time table is required
In the area of the disclosure of said U. S.
Patent No. 3,816,310 as to feedstocks, said patent
states that thixotropy is obtained so long as such
sulfonic acids as "NAB" Bottoms Sulfonates are combined
with at least 60~ of branched chain alkylbenzenes.
Here, again, my invention has distinctly greater
flexibility in this respect, emphasizing that my
process is a process which differs in numbers of
respects from the l-step process described in U. S.
Patent No. 3,816,310.
In the practice of the novel l-step process
of my present invention, the essential ingredients
which are initially mixed to form a single composition,
with or without supplementary ingredients which are not
essential to my invention, are the following:
1224~03
~ 1) A liquid carrier which may be a light or
volatile hydrocarbon having a boiling point below 430
F, e.g. hexane, heptane or mineral spirits; or a
nonvolatile oil, particularly a mineral oil; or
mixtures of said volatile and nonvolatile liquid
carriers;
(2) A sulfonic acid which may be of the same
type which are disclosed herein and which are commonly
used in the production of thixotropic overbased calcium
sulfonate greases or thickened compositions,
(3) Calcium oxide and/or calcium hydroxide;
(4) Water-soluble aliphatic carboxylic
acids, particularlfy acetic acid;
(5) For optimum results, in conjunction with
the carboxylic acid, an alko~yalkanol which may be one
or more of the various available substituted or
unsubstituted alcohols containing from 1 to 8 carbon
atoms. The preferred alcohol is methanol, and the
preferred alkoxyalkanol is methylcellosolve'.
Water is generally produced during the
reaction, but additional water is most desirable.
In those instances in which the overbased
calcium sulfonate is not formed in situ by a reaction
which includes the reaction of the volatile solvent
solution of the sulfonic acid with the calcium oxide
and/or calcium hydroxide, the calcium sulfonate may be
preformed and incorporated as such into the other
ingredients.
The mixture of ingredients, prepared under
conditions of agitation, is desirably preliminarily
heated to temperatures in the range of about 95" F to
about 200 F, at which temperatures or during such
initial heating, carbonation is effected by introducing
carbon dioxide directly into the mixture for a period
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14 12248~3
of time to essentially convert from 80% to 100~ of the
calcium oxide and/or hydroxide to calcium carbonate.
In the finished product, the calcium carbonate is
present as crystalline calcite extremely finely divided
or colloidally dispersed in the carrier. Under certain
conditions, and in certain cases only, in the carrying
out of the l-step process of my invention, and as noted
above, the solid calcium carbonate which forms is not
solely calcite but contains some vaterite. At elevated
temperatures, as, for example, 190 F, vaterite tends
to form. This does not appear adversely to affect the
production of greases or thickened compositions or the
utility thereof or of thickened compositions where the
vaterite content is present in relatively low
proportions. However, where the calcium carbonate is
formed entirely or largely as vaterite, the desired
properties of the greases or thickened compositions are
adversely affected and such vaterite formation is
desirably to be avoided.
The greases or thickened complexes produced
in accordance with the l-step process of my present
invention should possess a metal ratio of at least 5,
better still at least 6, and for many uses desirably
possess a metal ratio of 10 or 12 or, indeed, as high
as about 25 or even somewhat greater. This is
controlled by, among other considerations, the amount
and selection of particular promoters. These matters,
without regard to the bases of my present invention,
are p~r se, known to the art and no patentable novelty
is predicated broadly on procedures for producing
overbased calcium sulfonate greases or thickened
compositions having metal ratios such as those referred
to above.
~2X4~303
While reference has been made to the
oil-soluble sulfonie acids which are useful in the
praetiee of my present novel l-step process or the
calcium salts thereof, which contain in their molecules
an aliphatic radical having at least 12 carbon atoms,
said sulfonic acids can be represented by the formula
[ (R)XA - S03 ]yM
wherein R is an aliphatie linear or branched chain
aliphatic, generally, alkyl radical containing at least
12 carbon atoms; A is a cyelie advantageously
hydrocarbon nucleus such as benzene, naphthalene,
phenanthrene, and the like; x is 1 or 2; and M is
calcium or hydrogen. When M is hydrogen, y = l; and
when M is calcium, y = 2. As noted above, the
overbased calcium sulfonates can be preformed and
dissolved in the liquid medium or carrier, or may be
formed in situ therein by incorporating into the
mixture of ingredients the sulfonic acid, desirably in
solution in a volatile organic solvent such as Varsol*
or mineral spirits or in an oil, particularly a mineral
oil, and calcium oxide and/or calcium hydroxide, most
desirably calcium hydroxide, the calcium sulfonate
forms in situ, and where promoters are used in amount
and character such as to produce calcium sulfonates
overbased to the desired metal ratio. I prefer to
utilize as the sulfonic acid a Varsol solution of a
mixture of sulfonic acids of linear mono-alkylbenzenes,
branched-chain alkylbenzenes, and dialkylbenzenes, said
sulfonie acids having a molecular weight in the range
of about 450 to about 550, but there is nothing
critical in the use of such sulfonic acids. In
general, the preferred sulfonic acids will fall within
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` 12Z4803
16
the range of those having a molecular weight in the
range of about 300 to about 650 or 700. They are, in
general, commercial articles of commerce and sold by a
number of chemical companies under various trade
designations. Many more sulfonic acids useful in the `
practice of my l-step process are disclosed in numbers
of the patents to which I have referred above, such as
. S. Patents Nos. 3,342,079; 3,372,115; 3,492,831;
3,746,643; and 3,816,310.
As noted above, the carbonation temperature
should generally fall within the range of about 95 to
200 F. After the carbonation step has been finished,
which, as noted above, may be from about 80~ to 100~ of
the theoretical, the carbonated otherwise finished
grease or thickened composition may be heated at higher
temperatures, for instance, at about 280 F or somewhat
higher to drive off volatiles to such extent as may be
desired.
The following numbered EXAMPLES are exemplary
of the production of illustrative greases or thickened ~`
compositions made in accordance with the improved
l-step process of my present invention. It will be
understood that my invention is not limited to the
specific conditions and details shown in said EXAMPLES
since various changes will readily occur to those
skilled in the art in light of the principles and
disclosures provided in the specification and the
guiding principles taught hereinabove. All parts
stated are in parts by weight and all temperatures are
recited in F.
i224803
~XAMPL~ 1
Laboratory 1. 3-necked creased
Apparatus distilling flask 3000 ml
Set-~p 2. Stirrer, variable speed,
explosion proof with 3"
diameter propeller, 12"
shaft.
3. Thermometer 0-300 C.
4. Friedricks Condenser.
5. Heating mantle.
6. General purpose CO2
2-stage flowmeter.
7. Gas sparger.
Ingredients
Charqed
Grams
870 28~ Active Varsol Solution of
Sulfonic Acid
173 Ca (OH)2
54 Methylcellosolve
Water
4.6 Glacial Acetic Acid
350 cc/min @ Carbon Dioxide (typical 2
hours for conversion).
Procedure:
The Varsol* solution of the Sulfonic Acid is
added to the 3-necked distillation flask, the
Friedricks condenser is hooked up, and mixing is
initiated. The Ca (OH)2 is added to the flask followed
by the addition of the methylcellosolve and then the
water. The flask is heated to 125 and the glacial
acetic acid is added, and the ingredients are
post-mixed for about 5 minutes. The gaseous CO2 is
then introduced through the glass sparger via the
flowmeter. The carbonate peak is monitored at 882-886
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i2241~03
18
via I.R. When all of the calcium carbonate is in this
form trather than 860), the reaction is complete. The
introduction of CO2 is discontinued.
_ ~ .
EXAMPLE 2
In a suitable plant set-up, involving a
reactor of adequate capacity and the otherwise general
set-up of equipment modified for plant size operation,
there is charged to the reactor 7135 pounds of a 28%
solution in Varso~ of the sulfonic acid, followed by
the addition in order of 1402 pounds of Ca (OH)2, 443
pounds of methylcellosolve* 369 pounds of water, the
reaction mixture is heated to about 125, and 36.9
pounds of glacial acetic acid are added, and then the
resulting mixture is carbonated at a rate of about 6.3
pounds per minute until the carbonation results in a
monitored carbonate peak at 882-886 via I.R.
Typical
Final Non-volatile 52.%
Product viscosity 80,000 #6 spindle
Brookfield at
10 ~PM
Viscosity at 20,000
40% N.V. ~~
EXAMPLE 3
In a suitable plant set-up, there is charged
to the reactor, under conditions of agitation, 4350
gallons of a 28% solution in Varso~ of a sulfonic acid
comprising a mixture of sulfonic acids of linear
mono-alkyl benzenes, sulfonic acids of branched chain
mono-alkyl benzenes and sulfonic acid linear dialkyl
benzenes, said mixed sulfonic acids having a molecular
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1224~303
weight of about 465; 6380 pounds of Mississippi
hydrated lime, 215 gallons of methylcellosolve*, 171
gallons of water, and 16.3 gallons of glacial acetic
acid. The resulting mixture, heated to a temperature
of 140, is then carbonated with 2640 pounds of carbon
dioxide pumped into the reaction mixture at a rate of
22.1 pounds per minute. The carbon dioxide temperature
profile is 125-137.
~XAMPL~ 4
A suitable reactor with heat exchange and
agitator facilities is charged with 140 parts of a 28
solution in Varsol* of an oil-soluble commercial
sulfonic acid comprising a mixture of mono-alkyl and
dialkyl sulfonic acids having a molecular weight of
about 465. To this solution are added:
Hydrated Lime 32 parts
Water 8 parts
Methyl Cellosolve~ 10 parts
Acetic Acid 0.8 parts
. ~. . ..
C2 is introduced into the agitated mixture
over a period of lOO minutes until the calcium
hydroxicle is substantially neutralized.
The temperature is maintained at about 130 F
during the reaction. After the reaction is complete,
water and methylcellosolve*are removed by distillation.
The reactor contents are filtered through a 200-mesh
screen to remove any coarse residual solids. The
purified composition is the desired thickened complex
in mineral spirits.
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122 4 ~03
EXAMPLE 5
A suitable reactor, as referred to above, is
charged with 130 parts of a 32~ solution of calcium
sulfonate in a pale oil mineral oil.
To this solution are added:
Hydrated Lime 60 parts
Naphtha 150 parts
Methanol 6 parts
Acetic Acid 6 parts
C2 is introduced in the agitated mixture
over a period of 120 minute~ until the calcium
hydroxide is substantially neutralized. The
temperature is maintained at about 185 F during the
reaction. After the reaction is complete, water,
methanol and naphtha were removed by distillation. The
reactor contents were filtered through a 200-mesh
screen to remove any coarse residual solids. The
purified composition is the desired thickened overbased
calcium sulfonate complex in said mineral oil.
~XAMPLES 6-14
- .. ,~ ","0",_ , .
Effect of carbonation time investigatio~s is
shown in the following experiments. The procedure of
~XAMPL~ 1 is followed and rate of carbon dioxide is
varied.
(--
12X48~3
21
Carbonation Time for
Example Reaction tMinutes)Product
6 30 Not thickened
7 40 Not thickened
8 50 Not thickened
9 60 Thickened
Thickened
11 100 Thickened
12 120 Thickened
13 160 Thickened
EXAMPLES 15-21
The effect of methylcellosolve*on the product
investigations. The procedure of EXAMPLE 1 is followed
but the amount of methylcellosolve*is varied.
Amount of
Example Methylcellosolve (parts) Proauct
4 Not thickened
16 6 Not thickened
17 8 Thickened
18 10 Thickened
~ 19 ~2 Thickened
ïs -~Thickened
21 20 Thickened
EXAMPLES 22-27
Effect of temperature of carbonation
procedure as for EXAMPLE 1 but temperature of reaction
* trade mark
- 22 -~224&03
is varied.
Temperature of
Example Reaction FProduct
22 122 Thickened
23 140 Thickened
24 158 Thickened
176 Thickened
26 194 Thickened
27 212 Thickened
EXAMPLES 28-30
Effect of acetic acid on product. Procedure as
for EXAMPLE 2 but acetic acid is varied.
Example Acetic Acid (Parts) Product
28 0 Not Thickened
29 3 Thickened
9 Thickened
EXAMPLES 31-35
Effect of water on product. Procedure as for
EXAMPLE 1 but water concentration is varied.
20 Example Water Added (Parts) Product
31 0 Thickened
32 3 Thickened
33 6 Thickened
34 15 Thickened
24 Thickened
The products of the improved l-step process of
my invention lmpart excellent rust protection when
1~224803
compounded as described in U. S. Patent No. 3,746,643,
as illustrated by EXAMPLE A.
EXAMPL A
Product from EXAMPLE 1 (30 parts) is blended
with wax (30 parts), Oxidized Petrolatum (10 parts) and
Mineral Spirits (40 parts). Steel panels coated with
this composition are tested in a salt fog cabinet in
accordance with ASTM B117.
Performance:
0.5 mil dry coating after 300 hours, no rust
is observed.
The foregoing ~XAMPLES illustrate the flexibility of
the process.
Various supplemental ingredients may, and
commonly are, incorporated into the greases or
thickened compositions made in accordance with the
l-step process of my invention, in very distinctly
minor proportions, but they are in no way essential-to~
my invention and no patentable novelty is-claimed in- - -
their use in those instances where they are included in
the preparation of greases or thickened compositions.
Illustrative of such supplemental ingredients are
oxidation inhibitors such as phenyl alpha naphthylamine
(PAN); viscosity improvers, which may comprise certain
polymers (Acryloid*155-C); and others for particular
and generally known properties in greases or thickened
compositions. They are preferably added after the
-' trade ma~k
~24803
24
preparation of the grease or thickened composition has
been completed.
The complex overbased calcium sulfonate
greases or thickened compositions made in accordance
with my l-step process can readily be admixed with
oleaginous materials such as oils and fats, as well as
with paraffin waxes, microcrystalline waxes, asphalts,
oxidized petrolatums and other materials, in accordance
with known practices, and other and variant practices,
to produce compositions having utility as greases,
rust-inhibiting coatings and for various other
purposes.
