Process for making a mixed oxyaluminum acylate composition useful in grease manufacture

An improved process for making a mixed oxyaluminum acylate composition wherein the mole ratio of aromatic to aliphatic radicals ranges from about to 2:3 to 19:1 and improved aluminum complex greases made using a mixed oxyaluminum acylate wherein the mole ratio of aromatic to aliphatic radicals is from about 2:3 to 3:1.

BACKGROUND OF THE INVENTION 
The field of this invention lies in the art of making oxyaluminum acylates 
for use in manufacturing aluminum complex greases. 
Previously I have discovered that new oxyaluminum acylates can be prepared 
by utilizing three carboxylic acids: An aromatic acid, an aliphatic acid, 
and a lower alkanoic acid. The lower alkanoic acid, during the synthetic 
preparation procedure, produces, as explained in my application U.S. Ser. 
No. 096,933, an ester by-product which is easily volatilized and removed. 
This process can be used to prepare oxyaluminum acylate containing not 
more than about 75 mole percent of aromatic carboxylic acid, and 
oxyaluminum acylates so produced were found to be useful in the 
manufacture of aluminum complex grease of apparent commercial quality. 
When such three acid route is used to prepare oxyaluminum acylates 
containing more than about 75 mole percent of an aromatic carboxylic acid, 
the product oxyaluminum acylates do not appear to be useful for the 
manufacture of aluminum complex greases of apparent commercial quality (by 
using, for example, the grease preparation procedure described in my 
application U.S. Ser. No. 096,933). 
Oxyaluminum acylate synthesized by the three acid route tend to produce 
product acylates which are characteristically not clear when the product 
acylate contains more than about 75 mole percent of an aromatic carboxylic 
acid. In addition, such acylates are heterogeneous in composition and are 
not readily soluble in organic liquids of the type conventionally used for 
making greases. Furthermore, greases made with such product acylates are 
not uniform and characteristically contain opaque solid particles. It is 
theorized (but there is not intent herein to be bound by theory) that the 
three acid route results in the production of product oxyaluminum acylates 
which contain lower alkanoate substituents which cause such undesirable 
properties for grease making purposes, particularly when one is dealing 
with oxyaluminum acylates containing more than about 75 mole percent of 
aromatic carboxylic acid. 
In addition, it has now been learned that even with the oxyaluminum 
acylates containing up to 75 mole percent of aromatic carboxylic acid as 
described in my application U.S. Ser. No. 096,933, certain disadvantages 
exist from the standpoint of making aluminum complex greases. For one 
thing, during grease manufacture by the methodology described in my 
application U.S. Ser. No. 096,933, an acrid odor occurs, which odor 
suggests acetic acid vapor, are given off. These vapors are considered 
undesirable by grease makers. 
In addition, product greases made with such oxyaluminum acylates prepared 
by the three acid route tend to demonstrate so-called false set 
characteristics (that is, the grease demonstrates an ability to become 
relatively rigid on standing even after a brief period of time at ambient 
conditions). Even though agitation of a false set grease can result in 
lessened viscosity, in a manner comparable to common thixotropic systems, 
false set is generally considered undesirable in the grease industry in a 
product grease for some purposes, as when the grease is to be marketed in 
a cartridge for cartridge-gun application (a cartridge holding viscous 
grease may not be applicable from the gun). 
Therefore, it would be desirable to have a process for preparing 
oxyaluminum acylates suitable for use in making aluminum complex greases 
of commercial quality which does not utilize the three acid route. 
BRIEF SUMMARY OF THE INVENTION 
More particularly, the present invention provides an improved process for 
making a mixed oxyaluminum acylate composition wherein the mole ratio of 
aromatic to aliphatic radicals ranges from about 2:3 to 19:1 and which is 
adapted for use as an intermediate in the manufacture of aluminum complex 
greases. Also, the present invention is directed to methods for making 
improved aluminum complex greases using such a mixed oxyaluminum acylate 
composition wherein the mole ratio of aromatic to aliphatic radicals 
ranges from about 2:3 to 3:1 and to the greases so prepared. 
Thus, the present invention in one aspect provides a process for making a 
composition comprised on a 100 mole percent basis of about 50 mole percent 
of mixed oxyaluminum acylate with the balance up to 100 mole percent 
thereof being mixed esters of carboxylic acid material. Not only does such 
a product composition appear to avoid the hereinabove described problems 
associated with mixed oxyaluminum acylates made by the three acid route, 
but also and surprisingly the product compositions appear to be readily 
dispersible (including solubilizable) in organic liquids of the type 
conventionally used in making greases. It is theorized that the presence 
of mixed esters of carboxylic acid material in combination with the mixed 
oxyaluminum acylate product for some reason not now clear promotes the 
dispersibility and solubilization of the mixed oxyaluminum acylate in such 
organic liquid. 
By using such product intermediate compositions in the manufacture of 
aluminum complex greases, it is found that the acrid odors and the false 
set characteristics associated with the use of mixed oxyaluminum acylates 
containing up to about 75 mole percent of aromatic carboxylic acid (as 
made by the three acid route) are avoided. 
By the present invention, then, greases can be prepared by a process step 
sequence wherein an aluminum alkoxide is first converted to a mixed 
oxyaluminum acylate in combination with mixed esters of carboxylic acid 
material after which such system is subject to reaction with carboxylic 
acids in a grease making liquid to produce a product grease. 
Various other features, objects, aims, purposes, advantages, embodiments 
and the like, of the present invention, will be apparent to those skilled 
in the art from the teachings of the present invention. 
DETAILED DESCRIPTION 
To prepare a composition containing about 50 mole percent mixed oxyaluminum 
acylate, with the balance up to 100 mole percent being mixed esters of 
carboxylic acid material, one heats a mixture of an aluminum alkoxide 
material and a carboxylic acid material to a first temperature which is 
above the melting point of the carboxylic acid material, but which is 
below the boiling point of an alkanol material while agitating the 
mixture. Such first heating is continued for a time sufficient to form a 
substantially single phase liquid or a substantially uniform slurry 
comprised of such mixture. 
In such mixture, the aluminum alkoxide material is characterized by the 
formula: 
EQU Al(OR).sub.3 ( 1) 
where R is a lower alkyl radical. 
Also, in such mixture, the carboxylic acid material is comprised of: 
(a) at least one aliphatic monocarboxylic acid containing from 8 to 40 
carbon atoms per molecule, 
(b) at least one aromatic monocarboxylic acid containing from 7 to 17 
carbon atoms per molecule, and 
(c) the mole ratio of said aromatic acid to said aliphatic acid ranging 
from about 2:3 to 19:1. 
Also, such alkanol material is characterized by the formula: 
EQU ROH (2) 
where R is as defined above and where ROH is derived from reaction between 
said aluminum alkoxide material and said carboxylic acid material. 
In such first heating, such mixture is characterized by having a mole ratio 
of said aluminum alkoxide material to said carboxylic acid material of 
about 1 to 2. 
Preferably, before said first heating, said carboxylic acid material is 
heated to such first temperature and the aluminum alkoxide material is 
then admixed therewith. 
After the desired single phase liquid or a substantially uniform slurry is 
produced by such first heating, a second heating is undertaken, preferably 
without any cooling. The second heating is preferably conducted with 
continuous agitation of the liquid, and during the second heating the 
liquid is heated to second temperatures in the range where such alkanol 
material is distilled off. The second heating is maintained or continued 
for a time sufficient to remove the equivalent of at least about two 
theoretical moles of said alkanol (per mole of aluminum alkoxide 
material). 
Next, and preferably without cooling, the product from such second heating, 
a third heating is undertaken. In the third heating, the resulting product 
from the second heating is gradually heated to third temperatures ranging 
from a temperature corresponding to the final temperature of the second 
heating up to a temperature of about 200.degree. C., thereby converting 
the resulting product from the second heating into a homogeneous liquid 
which has characteristically a viscosity which is substantially less than 
that of the product resulting from the second heating. 
Preferably, the third heating is continued at such 200.degree. C. for a 
time of at least about 1/4 hour, and more preferably such third heating is 
continued at such 200.degree. C. for a time of at least about 0.5 hour. 
In one presently preferred procedure, after such third heating, the final 
liquid so produced is subjected to a vacuum distillation so as to remove 
from such final liquid any organic material therein which at atmospheric 
temperature and pressure boils at a temperature not more than about 
250.degree. C. Preferably, such a vacuum distillation is conducted at a 
pressure not above about 700 mm Hg. At such a reduced pressure, it is 
preferred to keep the distillation temperatures below about 200.degree. C. 
During the second heating, it is theorized that the reaction which occurs 
is represented by the following equation: 
##STR1## 
In the above equation, R is as defined above in relation to Formulas 1 and 
2 and R' is selected from the group consisting of aliphatic monocarboxylic 
acids and aromatic monocarboxylic acids as defined above in relation to 
the carboxylic acid material described. 
In the third heating step, it is presently theorized that a reaction occurs 
which is representable by the following equations: 
##STR2## 
and/or 
##STR3## 
Equation III shows the reaction of preparing compounds represented by the 
Formula: 
##STR4## 
Similarly, Equation III shows the reaction of preparing compounds 
represented by the Formula: 
##STR5## 
In the preceding Formulas (3) and (4), R' has its above defined meaning. 
As those skilled in the art will appreciate, oxyaluminum acylates of 
Formulas (3) and (4), which are the mixed oxyaluminum acylates employed in 
the practice of the present invention, are presently believed to exist in 
either a monomeric form or in a cyclic trimeric form (as shown). The 
conditions underwhich one form exists as opposed to the other form are at 
this time completely unknown. 
The process of the present invention through the above described third 
heating step is preferably carried out as a mass reaction ("neat"), but 
sometimes the reaction apparently can be carried out advantageously in the 
presence of an organic liquid phase, particularly when it is desired to 
use the product of such third heating step as an intermediate for grease 
making (as herein below described). 
A presently preferred composition for use in grease manufacture comprises 
on a 100 weight percent total weight basis (a) from about 30 to 70 weight 
percent of at least one group of compounds of the Formula: 
##STR6## 
and of the Formula 
##STR7## 
wherein R.sup.1 is selected from the group of radicals consisting of: Type 
(A): aliphatic radicals each containing from 10 to 38 carbon atoms, and 
Type (B): aromatic radicals each containing from 6 to 16 carbon atoms, and 
wherein, in any given group of such compounds, the ratio of the number of 
radicals of said Type (B) to said Type (A) ranges from 2:3 to 3:1, and 
correspondingly (b) from about 70 to 30 weight percent of a petroleum 
derived hydrocarbon having a viscosity at 100.degree. F. ranging from 
about 35 to 50,000 SUS. Such components (a) is uniformly dispersed in such 
component (b) and such composition is prepared by the process above 
summarized and contains from about 30 to 70 weight percent of the esters 
above described (on a total percent weight basis). 
In such a composition, such component (a) is dissolved in such component 
(b) preferably. Also preferably, in such component (a), such Type (A) 
radicals are comprised of stearyl and such Type (B) radicals are comprised 
of benzyl. Also preferably, in such composition, such Type (A) radicals 
are derived from hydrogenated tallow acids, or hydrogenated fish oils, and 
said Type (B) radicals are derived from benzoic acid. 
A presently preferred intermediate composition from the third heating step 
intended for use in grease manufacture comprises on a 100 weight percent 
total weight basis 
(a) from about 30 to 70 weight percent of at least one composition from the 
third heating step, 
(b) from about 70 to 30 weight percent of a petroleum derived hydrocarbon 
having a viscosity at 100.degree. F. ranging from about 35 to 50,000 SUS, 
said component (a) being uniformly dispersed in said component (b). In such 
preferred grease making compositions, component (a) is dissolved in said 
component (b) and the total quantity of ester percent ranges from about 30 
to 70 weight percent (total weight percent basis). 
Aluminum trisopropoxide is presently preferred because of its availability 
and the relatively low boiling point of its alcohol and esters; however, 
other alkoxides may be used such as aluminum tri sec butoxide, and the 
like. The total amount of such aluminum tri alkoxide so admixed is equal 
to about one more aluminum alkoxide per two moles of acid. 
As indicated above, such intermediate compositions can be converted into 
greases by the teachings of this invention without producing the 
undesirable acrid odor (like acetic acid), and the product greases 
characteristically are substantially free from unwanted false set 
properties when making greases using mixed oxyaluminum acylate compounds 
whenever the mole ratio of aromatic radicals to aliphatic radicals is less 
than about 3:1 in such intermediate compositions. 
To make a grease of this invention using an intermediate composition as 
described above, one admixes such composition with a mineral starting oil 
having a viscosity at 100.degree. F. of from about from about 35 to 50,000 
SUS. To such product mixture, at least one carboxylic acid material as 
described above is added with such mixed oxyaluminum acylate with 
preferably both reactant types being dispersed (more preferably dissolved) 
in the oil. Thereafter, this mixture is heated to a temperature sufficient 
to produce reaction between said carboxylic acid material and said 
oxyaluminum acylate compound, and such contacting is continued until at 
least some of such oxyaluminum acylate compound has been converted into an 
aluminum soap. The product aluminum soap is an hydroxy aluminum diacylate. 
The resulting grease containing such hydroxy aluminum diacylate is then 
milled, if desired, and packaged. Milling can be conducted at room 
temperatures or at any elevated temperatures up to about 200.degree. C. 
with temperatures below about 150.degree. C. being presently preferred. 
In one presently preferred grease making grease process of the present 
invention, the following steps are employed: 
First, one heats mixtures of petroleum derived hydrocarbon oil having a 
viscosity at 100.degree. F. of from about 35 to 50,000 SUS and a grease 
making composition as above described. This mixture contains a total 
amount of aluminum in the range from about 0.01 to 2.0 weight percent 
based on total mixture weight. Such heating is conducted at temperatures, 
and for times, sufficient to substantially completely disperse and 
preferably dissolve all starting mixed oxyaluminum acylates present in 
said hydrocarbon oil. 
Next, one admixed with the resultant such mixture of step (A) a total of 
from about 0.8 to 1.2 moles (based on the total quantity of aluminum 
present in said resultant such mixture) of at least one carboxylic acid 
material selected from the group consisting of aliphatic monocarboxylic 
acids containing from 15 through 40 carbon atoms each and aromatic 
monocarboxylic acids containing from 6 through 16 carbon atoms each. 
Finally, one heats and gradually raises the temperatures of the product 
mixture, all the while agitating such product mixture, until at least some 
of such starting mixed oxyaluminum acylates present in the first step have 
been converted into hydroxy aluminum diacylate aluminum soap by reaction 
in situ with said carboxylic acid material. 
As indicated, in such grease making process of this invention starting 
mixed oxyaluminum acylates of composition of the third heating step in a 
base oil are reacted at least partially (preferably substantially 
completely) with carboxylic acid materials. A starting such mixed 
oxyaluminum acylate provides from a stoichiometric standpoint 
approximately one-half of the acylate radicals needed to produce an 
aluminum soap which is formed from the reaction of such mixed oxyaluminum 
acylate with carboxylic acid material, such aluminum soap being a compound 
which contains approximately two acyl groups and one hydroxyl group, each 
group being directly bonded to an aluminum atom (one name for such soap 
being hydroxyaluminum diacylate). 
This hydroxyaluminum diacyl soap is made directly without the production of 
by-product alcohol and without water being present. The following chemical 
equations are illustrative of this addition reaction whereby no 
by-products are formed: 
Equation IV where the compounds of this invention are represented by 
Formula (3) 
##STR8## 
Equation V where the compounds of this invention are represented by 
Formula (4) 
##STR9## 
where R' is as defined above and R" is either aromatic, aliphatic or 
mixtures thereof, said R" radicals being supplied by the acids added by 
grease manufacturers practicing this process. For example, R" can 
preferably be the same as R' except that the ratio in any given instance, 
of type (B) radicals to said type (A) radicals can range from 0 to about 
5:1. 
In calculating the molar quantity of carboxylic acid material to be used 
(added) for reaction with a mixed oxyaluminum acylate in making a grease 
according to this invention (based on the number of carboxyl groups 
present in the carboxyl acid material), it is sometimes convenient to use 
a mole ratio ranging from about 0.8 to 1.2 of total quantity of carboxylic 
acid material to one mole of mixed oxyaluminum acylate. 
In a grease prepared by the teachings of this invention, such an aluminum 
soap is preferably characterized by having the total number of acyl 
radicals of any given soap molecule composed of a weight ratio of 
aliphatic acyl groups to aromatic acyl groups ranging from about 1.3:0.7 
to 0.7:1.3. Presently preferred aliphatic acyl groups are derived from 
fatty carboxylic acids each mixture containing an aliphatic group of at 
least about 16 carbon atoms. Also, presently preferred aromatic acyl 
groups are derived from benzoic acid. 
In a grease prepared by the teachings of this invention, it is not 
necessary to have all of the starting mixed oxyaluminum acylate compounds 
converted to such an aluminum soap, although for reasons of obtaining a 
maximum thickening of a given base oil based upon a given quantity of 
mixed oxyaluminum acylate in admixture therewith, it is presently 
preferred to achieve a substantially complete conversion of starting mixed 
oxyaluminum acylate compounds into aluminum soap. However, partial 
conversion is sometimes preferred as when, in a given grease manufacturing 
situation, excess oxyaluminum acylate beyond a theoretical or calculated 
quantity of mixed oxyaluminum acylate is added to a starting reaction 
system so as to permit processing flexibility. For example, with such an 
excess quantity, in solution in an oil, one can add only sufficient 
carboxylic acid material as is necessary to achieve some predetermined 
system viscosity at some predetermined processing temperature, such a 
system viscosity having previously been determined to be characteristic of 
a given grease viscosity desired at ambient temperatures, according to the 
wishes of a given grease maker in some given instance. Such a grease could 
be further thickened by adding more acid later, or such a grease could be 
used as a "master batch" (that is, more oil and acid could subsequently be 
added thereto). 
Although in making a grease in accordance with this invention, it is 
presently preferred to use, as the starting organo aluminum compound which 
is convertible into aluminum soap by reaction with carboxylic acid 
materials, only a mixed oxy aluminum acylate composition prepared by the 
three heating steps (because of the circumstance that no by-product 
alcohol is produced in converting this compound to an aluminum soap), 
nevertheless, as those skilled in the art will appreciate, such mixed 
oxyaluminum acylates may be used, if desired, in combination with other 
such starting organoaluminum compounds known to the prior art of grease 
making by forming aluminum soaps. For example, a grease maker may desire 
to use up stocks on hand of such prior art organoaluminum compounds 
gradually, or he may desire to use the compounds of this invention in 
combination with such prior art materials as aluminum stearate for reasons 
of economy or for other reasons. 
In general, when such a starting organoaluminum compound mixture is used, 
it is preferred to employ a mixture wherein at least about 50 weight 
percent thereof, on a total mixture weight basis, is comprised of mixed 
oxyaluminum acylates present. 
In its reaction with mixed oxyaluminum acylates, the hydroxyl group of a 
carboxyl moeity automatically goes to the aluminum of the starting mixed 
oxyaluminum acylates as the soap is being formed. 
In addition, or in an admixture with, petroleum derived (mineral) grease 
making base oils, suitable specialized starting oils adapted for use in 
the grease making process of the present invention include lubricating 
oils of napthenic base, paraffinic base hydrocarbons, mixed base mineral 
oils, vegetable oils, synthetic oils, including synthesized hydrocarbon 
base fluids, alkylene polymers, polysiloxanes, ester-type oils such as 
dicarboxylic acid ester type oils, liquid esters of phosphorous acids, 
such as are shown in U.S. Pat. No. 2,768,138), and the like. In general, 
preferred starting base oils have viscosities at 100.degree. F. ranging 
from about 35 to 50,000 SUS. 
To make a grease using an oxyaluminum acylate composition of this invention 
in an oil, a grease maker need use no particular type of carboxylic acid 
material for reaction therewith. For example, it now appears that the 
teachings of the prior art with respect to the use of various carboxylic 
acids, combinations thereof, order of contacting, temperature conditions, 
and the like in connection with the use of the prior art aluminum 
alkoxides in grease making can be employed to make greases from such an 
oxyaluminum acylate composition, except that here no by-product alcohol is 
produced and no water is needed. Mono and dicarboxylic acids can be used, 
as can halo substituted such acids, like monochloroacetic acid, 
dichloroacetic acid, and the like. Examples of suitable dicarboxylic acids 
include succinic. One particularly preferred monocarboxylic acid is 
presently isostearic because such acid which is a branched C.sub.18 
saturated acid, is a relatively low viscosity liquid at ambient conditions 
and tends to bring down the melting point and softening point of 
derivatives thereof, including especially aluminum soaps thereof. For 
examples of U.S. patents teaching extremely wide variability in types of 
acids that can be added to an oil for reaction with the mixed oxyaluminum 
acylates of this invention to make an aluminum soap, as desired in grease 
making, see U.S. Pat. No. 3,476,684 (involving mono and dichloro acetic 
acids), U.S. Pat. No. 3,413,222 (involving succinic acid), etc. Dimer 
acids, such as dimerized vegetable oil carboxylic acids, such as are 
offered commercially by Emery Industries, can also be used as the 
carboxylic acid material. 
A class of oxyaluminum acylate compounds to have present in a presently 
preferred intermediate composition prepared by the teachings of this 
invention comprises compounds wherein the number ratio of such Type (B) 
radicals to such Type (A) radicals (as defined above) ranges from about 
2:3 to 3:1. In such class, the Type (B) radicals are preferably derived 
from benzoic acid. Such preferred compounds are relatively easy for a 
grease maker to convert into a grease in the presence, for example, a 
hydrocarbon oil. Such compounds containing a higher ratio of benzoic acids 
to aliphatic acids than is disclosed in the prior art, presently appear to 
be particularly desirable in grease making because a smaller quantity of 
benzoic acid is subsequently needed to complete the in situ reaction which 
forms the hydroxy aluminum stearate/benzoate soap. Benzoic acid itself is 
difficult for a grease maker to handle because of its tendency to sublime 
at temperatures above 100.degree. C. Another advantage is the circumstance 
that, when using such a high benzoic acid derivative, one does not have to 
be concerned about the exact order of sequential addition of the 
carboxylic acid materials being reacted therewith in grease making. Both 
aromatic and aliphatic acids can be added simultaneously to the synthesis 
reaction zone. With mixed oxyaluminum acylates of the prior art which are 
relatively low in benzoic acid content (that is, whose content of such 
acid is lower than the bottom of the radical ratio just above indicated), 
one apparently should follow a sequential acid addition procedure 
(involving, for example, the addition first of long chain aliphatic fatty 
acid before adding benzoic acid) in order to produce a maximum thickening 
of oil base for a minimum total quantity of such mixed oxyaluminum 
acylate. Also, with such a high benzoic acid derivative, it may be that it 
is not necessary to have a complete reaction with mixed oxyaluminum 
acylate compound to produce such a maximum viscosity increase for a 
minimum amount of such mixed oxyaluminum acylate compound of this 
invention; there is presently at hand no conclusive data on this point. 
Further, it may be that the effect of sequential addition of carboxylic 
acid material is not as pronounced in this invention as it apparently is 
with the prior art aluminum alkoxides (see, for example, Polishuk U.S. 
Pat. No. 3,591,505), but, as indicated above, in the present invention, no 
by-product alcohol is formed during grease manufacture. 
Greases made with preferred intermediate compositions prepared as taught by 
this invention containing mixed oxyaluminum acylates as explained can be 
formulated with the various additives heretofore employed in the grease 
making art, if desired. Thus, for example, a grease of this invention can 
contain one or more of such additives as rust inhibitors, anti-corrosion 
agents, antioxidants, dispersants, fillers, metal deactivators, pressure 
or anti-wear agents, tackiness agents or systems, and the like, as those 
skilled in the art will appreciate. Such additives may be added to a 
grease prior to, during, or after the aluminum soap forming step following 
the teachings of this invention. The quantity of additives in any given 
grease can, of course, vary, but a presently preferred preference is to 
employ less than about 15 weight percent (total grease weight basis) of 
such additives so as to aim toward quality product greases.

EMBODIMENTS 
The present invention is further illustrated by reference to the following 
Examples. Those skilled in the art will appreciate that other and further 
embodiments are obvious and within the spirit and scope of this invention 
from the teachings of these present Examples taken with the accompanying 
specifications. 
EXAMPLE 1 
To a 1,000 ml. 3-neck flask the following ingredients are placed: 333.2 
grams hydrogenated tallow fatty acid, 48.8 grams benzoic acid, and 67.5 
grams isopropyl alcohol. This mixture is heated to approximately 
80.degree. C. at which point the contents of the flask comprises a 
homogeneous clear liquid system. To the flask next is added 272.3 grams of 
a 60% solution of aluminum isopropylate in isopropanol. This mixture is 
stirred and heat is applied to the flask until isopropyl alcohol begins to 
distill off. As the distillation continues, temperature readings are taken 
at 30 minute intervals and the following Table results: 
TABLE I 
______________________________________ 
Pot Temperature Vapor Temperature 
______________________________________ 
87.degree. C. 80.degree. C. 
96.degree. C. 80.degree. C. 
114.degree. C. 80.degree. C. 
120.degree. C. 80.degree. C. 
130.degree. C. 80.degree. C. 
155.degree. C. 80.degree. C. 
______________________________________ 
At this point, 92% of the theoretical isopropyl alcohol has been distilled 
off. More heat is then applied to the flask causing the temperature to 
rise to 200.degree. C. over a period of an hour. During this time, the 
remainder of the alcohol on a theoretical basis is distilled off of the 
reaction mixture. As the temperature approaches 200.degree., it is 
observed that the mixture in the flask is a low viscosity clear amber 
liquid. The temperature is maintained at 200.degree. C. for one hour. The 
reaction mixture is thereafter allowed to cool to room temperature. The 
product is a low viscosity clear amber liquid. The aluminum is analyzed to 
be 4.80% and by analysis the oxyluminum acylate is found to have 42.7% 
benzoic radicals. The oxyaluminum acylate is dissolved in a mixture of 
isopropyl benzoate and isopropyl hydrogenated tallowate. 
EXAMPLE 2 
Grease for Example 1 
To 301.4 grams of a grease base oil having the viscosity at 100.degree. F. 
of 1766 SUS is added 36.4 grams of the compound from Example 1. The 
resulting mixture is stirred and gradually heated to 90.degree. C. where 
it is observed that a clear solution results. At this point there is added 
to the heated system simultaneously 8.7 grams hydrogenated tallow fatty 
acid and 3.4 grams benzoic acid with stirring. The amount of ingredients 
added to the base oil in this grease making Example is calculated in such 
a manner as to produce a final grease with an aluminum content of 0.5% 
aluminum metal, a fatty to benzoic ratio of 1.1 to 0.9 and a ratio of 1.92 
moles total acids per atom of aluminum. Heating is continued and the 
temperature is gradually raised to a temperature of 200.degree. C. and the 
mixture is held at 200.degree. C. for one-half hour. After the acids are 
added, and as the temperature is thus gradually increased, gradual 
thickening of the system is observed. The reaction mixture remains clear 
throughout the heating process and results in a clear grease. No acetic 
acid odor is detected during this process. After the reaction mixture is 
held for one-half hour at 200.degree. C., it is allowed to cool and 
physical properties are determined. The resultant clear grease has a 
dropping point of 495.degree. F. and an unworked penetration of 311. After 
working 60 strokes in a standard grease worker, the penetration is 288. 
The grease remains soft and pliable after standing overnight indicating 
the absence of false set properties. 
EXAMPLE 3 
To a 22 liter 3-neck flask is added the following ingredients: 4,998.6 
grams hydrogenated tallow fatty acid, 2,197.8 grams benzoic acid and 3,816 
grams isopropanol. This mixture is heated to approximately 60.degree. C. 
at which point the mixture is a clear low viscosity homogenous liquid. To 
this mixture is then added 3,675.6 grams granulated aluminum isopropylate. 
Heat is applied to the flask and the temperature gradually raised to the 
point where isopropanol begins to distill off. As the distillation 
continues temperature readings are taken at 60 minute intervals and the 
following Table results: 
TABLE II 
______________________________________ 
Pot Temperature Vapor Temperature 
______________________________________ 
84.degree. C. 81.degree. C. 
85.degree. C. 81.degree. C. 
85.degree. C. 81.degree. C. 
85.degree. C. 81.degree. C. 
93.degree. C. 81.degree. C. 
100.degree. C. 81.degree. C. 
120.degree. C. 81.degree. C. 
166.degree. C. 84.degree. C. 
______________________________________ 
At this point, the heating causes the temperature to begin rising much more 
rapidly and it reaches 200.degree. C. within another hour. 
During the time of the first and second steps of heating, both the added 
isopropyl alcohol and 2 moles of produced isopropyl alcohol on a 
theoretical basis are removed from the flask. The temperature is then 
maintained at 200.degree. C. for one more hour after which it is allowed 
to cool. The product is a light amber clear liquid which is analyzed to be 
5.67% aluminum and by further analysis it is determined that the 
oxyaluminum acylate so produced contained 75.3% benzoic radicals. The 
oxyaluminum acylate is dissolved in a mixture of isopropyl benzoate and 
isopropyl hydrogenated tallowate. 
EXAMPLE 4 
Grease from Example 3 
To 303.8 grams of a grease base oil having the viscosity at 100.degree. F. 
of 1766 SUS is added 30.8 grams of the compound from Example 3. The 
resulting mixture is stirred and gradually heated to 90.degree. C. where 
it is observed that a clear solution results. At this point there is added 
to the heated system simultaneously 14.3 grams hydrogenated tallow fatty 
acid and 0.9 grams benzoic acid with stirring. The amount of ingredients 
added to the base oil in this grease making Example is calculated in such 
a manner as to produce a final grease with an aluminum content of 0.5% 
aluminum metal, a fatty to benzoic ratio of 1.1 to 0.9 and a ratio of 1.92 
mole total acids per atom of aluminum. Heating is continued and the 
temperature is gradually raised to a temperature of 200.degree. C. and the 
mixture is held at 200.degree. C. for one-half hour. After the acids are 
added, and as the temperature is thus gradually increased, gradual 
thickening of the system is observed. The reaction mixture remains clear 
throughout the heating process and results in a clear grease. No acetic 
acid odor is detected during this process. After the reaction mixture is 
held for one-half hour at 200.degree. C., it is allowed to cool and 
physical properties are determined. The resultant clear grease has a 
dropping point of 509.degree. F. and an unworked penetration of 245. After 
working 60 strokes in a standard grease worker, the penetration is 286. 
The grease remains soft and pliable after standing overnight indicating 
the absence of false set properties. 
To a 3 liter resin kettle equipped with a stirring motor and a lid with 3 
openings is added the following ingredients: 687.3 grams hydrogenated 
tallow fatty acids, 503.7 grams benzoic acid, and 673.9 grams isopropyl 
alcohol. This mixture is heated until it becomes a homogenous clear 
solution at approximately 60.degree. C. To this mixture while stirring is 
then added 673.9 grams powdered aluminum isopropylate. Heat is then 
applied to the reaction vessel until it rises to a temperature where 
isopropyl alcohol begins to distill off. The distillation is continued and 
periodic temperature readings are taken and the following Table results: 
TABLE III 
______________________________________ 
Hours Pot Temperature 
Vapor Temperature 
______________________________________ 
0 85.degree. C. 81.degree. C. 
11/2 hrs. 85.degree. C. 81.degree. C. 
2 hours 85.degree. C. 80.degree. C. 
33/4 hrs. 205.degree. C. 65.degree. C. 
______________________________________ 
During the above distillation procedure, both the added isopropyl alcohol 
and the 2 moles isopropyl alcohol per atom aluminum produced by the 
reaction process are removed from the reaction vessel on a theoretical 
basis. Heating is continued at 200.degree. C. for 1 1/2 hours and then the 
reaction mixture is allowed to cool. The product is a light amber clear 
oily liquid. The aluminum is analyzed to be 5.86% and by further analysis 
it is determined that the oxyaluminum acylate contains 85% benzoic 
radicals. The oxyaluminum acylate is dissolved in a mixture of isopropyl 
benzoate and isopropyl hydrogenated tallowate. 
EXAMPLE 6 
Grease From Example 5 
To 303.7 grams of a grease base oil having 9 viscosity at 100.degree. F. at 
1766 SUS is added 29.8 grams of the compound from Example 5. The resulting 
mixture is stirred and gradually heated to 90.degree. C. where is is 
observed that a homogenous relatively clear mixture results. At this point 
there is added to the heated system simultaneously 16.3 grams hydrogenated 
tallow fatty acid and 0.1 grams benzoic acid with stirring. The amount of 
ingredients added to the base oil in this grease making Example is 
calculated in such a manner as to produce a final grease with an aluminum 
content of 0.5% aluminum metal, a fatty to benzoic ratio of 1.1 to 0.9 and 
a ratio of 1.92 moles total acids per atom of aluminum. Heating is 
continued and the temperature is gradually raised to a temperature of 
200.degree. C. and mixture is held at 200.degree. C. for one-half hour. 
After the acids are added, and as the temperature is thus gradually 
increased, gradual thickening of the system is observed. The reaction 
mixture remains clear throughout the heating process and results in a 
clear grease. No acetic acid odor is detected during this process. After 
the reaction mixture is held for one-half hour at 200.degree. C., it is 
allowed to cool and physical properties are determined. The resultant 
clear grease has a dropping point of 468.degree. F. and an unworked 
penetration of 307. After working 60 strokes in a standard grease worker, 
the penetration is 314. The grease remains soft and pliable after standing 
overnight indicating the absence of false set properties. 
EXAMPLE 7 
Attempt to Make 85 Mole % Benzoic Mixed Oxyaluminum Acylate Via the Acetic 
Acid Process 
To a 1000 ml. 3-neck flask is added the following ingredients: 183.2 grams 
Coray 22 which is a lubricating base oil having an approximate viscosity 
of 100 SUS at 100.degree. F., 50 grams isopropyl alcohol, 48 grams glacial 
acetic acid, 33.3 grams hydrogenated tallow fatty acids, and 83.0 grams 
benzoic acid. The temperature of this mixture is raised to 55.degree. C. 
at which point 163.4 grams powdered aluminum isopropylate is added to the 
flask. This mixture is stirred and gradually increased to a point where 
isopropanol begins to distill off. As the distillation continues, periodic 
temperature readings are taken and the following Table results: 
TABLE IV 
______________________________________ 
Hours Pot Temperature 
Vapor Temperature 
______________________________________ 
0 89.degree. C. 81.degree. C. 
0.5 96.degree. C. 81.degree. C. 
1.0 156.degree. C. 80.degree. C. 
1.25 198.degree. C. 81.degree. C. 
1.5 202.degree. C. 65.degree. C. 
2.0 210.degree. C. 30.degree. C. 
2.5 194.degree. C. 30.degree. C. 
4.0 192.degree. C. 30.degree. C. 
______________________________________ 
During this distillation procedure, the material in the flask never goes 
through a clear stage and does not end up clear. It is only thin when the 
temperature rises to approximately 200.degree. C.; however, it is still an 
opaque liquid at this point. Very little distillate is taken off between 
the temperatures of 156.degree. C. and 200.degree. C. indicating that only 
a small amount of isopropyl acetate ester is formed by this reaction. The 
total distillate measures 149 grams and accounts for little more than the 
theoretical isopropanol released by the acids plus the 50 grams sopropyl 
alcohol added to facilitate dispersion of the initial materials. 
EXAMPLE 8 
The experiment in Example 7 is repeated to make sure that the results are 
reliable. The quantities of ingredients are added in the same order and 
the mixture is stirred and the temperature gradually increased to a point 
where isopropanol begins to distill off. As the distillation continues 
temperature readings are taken and the following Table results: 
TABLE V 
______________________________________ 
Hours Pot Temperature 
Vapor Temperature 
______________________________________ 
0 90.degree. C. 81.degree. C. 
.5 93.degree. C. 81.degree. C. 
1.0 180.degree. C. 81.degree. C. 
1.5 200.degree. C. 35.degree. C. 
2.0 180.degree. C. 23.degree. C. 
2.5 202.degree. C. 23.degree. C. 
3.5 196.degree. C. 23.degree. C. 
4.0 194.degree. C. 23.degree. C. 
4.5 197.degree. C. 23.degree. C. 
5.0 197.degree. C. 23.degree. C. 
5.5 203.degree. C. 23.degree. C. 
6.0 200.degree. C. 23.degree. C. 
______________________________________ 
During this experiment extra care is taken to ensure that excessive heat 
does not damage or interfere with the reaction. At no time does the 
temperature ever exceed 205.degree. C. As can be seen by the Table, no 
appreciable isopropyl acetate is taken off as indicated by the low vapor 
temperatures which are recorded as the pot temperature moves towards 
200.degree. C. As with Example 7, the mixture in the flask never turns 
clear and remains an opaque heterogenous mixture. 
EXAMPLE 9 
An attempt is made to make a grease from the material produced in Example 
8. 302.2 grams of the same grease base oil as employed in Example 6 are 
placed in a beaker which contains a magnetic stir bar. This beaker is 
placed on a hot plate and heated with stirring to a temperature of 
160.degree. C. 31.4 grams of the product obtained from Example 8 is melted 
and added to the oil. During this addition, it is noted that solid 
particles start forming immediately. The size of the particles are about 
1/16th of an inch to 1/8th of an inch in diameter. The mixture is then 
heated to 200.degree. C. in an attempt to disperse the particles, but this 
is not successful. The temperature is then lowered to 95.degree. C. at 
which temperature 16.3 grams hydrogenated tallow fatty acid are added 
slowly to the mixture under agitation. Then 0.1 gram benzoic acid is added 
immediately following this addition of the hydrogenated tallow fatty acids 
and it is noted that the temperature is 100.degree. C. when the benzoic 
acid is in. The particles noted above do not disappear. The mixture is 
then raised again to a temperature of 200.degree. C. The mixture thickens 
slightly, but still contains the solid opaque particles. Because of the 
solid opaque particles, this material does not appear to be a usable 
grease. 
EXAMPLE 10 
Preparation of Mixed Oxyaluminum Acylate Containing 75 mole % Benzoic Acid 
Via the Acetic Acid Method 
To a 1000 ml. 3-neck flask is added 198.4 grams Coray 22 oil (lubricating 
base oil having an approximate viscosity of 100 SUS at 100.degree. F.). To 
this oil in such a flask is added the following ingredients: 50 grams 
isopropyl alcohol, 48 grams acetic acid, 55.5 grams hydrogenated tallow 
fatty acids, 73.3 grams benzoic acid. This mixture is warmed slightly to 
produce a homogenous clear liquid. The temperature is then raised to 
65.degree. C. and at this point is added to the system 163.4 grams 
aluminum isopropylate. 
This mixture is stirred and the temperature gradually increased to a point 
where isopropanol begins to distill off. As the distillation continues 
periodic temperature readings are taken and the following Table results: 
TABLE VI 
______________________________________ 
Hours Pot Temperature 
Vapor Temperature 
______________________________________ 
0 88.degree. C. 81.degree. C. 
.5 88.degree. C. 81.degree. C. 
1.0 90.degree. C. 81.degree. C. 
1.5 99.degree. C. 81.degree. C. 
2.0 110.degree. C. 81.degree. C. 
2.5 180.degree. C. 84.degree. C. 
3.0 200.degree. C. 87.degree. C. 
3.5 200.degree. C. 87.degree. C. 
4.0 204.degree. C. 87.degree. C. 
______________________________________ 
During the distillation a total of 2 moles isopropyl alcohol are removed 
after which 1 mole of isopropyl acetate is removed all on a theoretical 
basis. The reaction mixture is thereafter allowed to cool to room 
temperature. The product is a clear solid amber material having a melting 
point of approximately 130.degree. C. and by calculation is found to 
contain 5.44% aluminum indicating a 40.9% solution (in 100 SUS 100.degree. 
F. lubricating oil) of mixed oxyaluminum stearate/benzoate wherein the 
mole percent benzoate is 75%. 
EXAMPLE 11 
Grease Made From Example 10 
303.5 grams of the same grease base oil as employed in Example 6 are placed 
in a beaker which contains a magnetic stir bar. This beaker is placed on a 
hot plate and is heated with stirring to a temperature of 160.degree. C. 
32.2 grams of the product obtained from Example 10 is melted and added to 
the oil. Heating is continued with stirring and the temperature is 
gradually raised to a temperature of 200.degree. C. and it is observed 
that the mixture is uniformly dispersed. The temperature is then lowered 
to 95.degree. C. at which temperature 14.5 grams hydrogenated tallow fatty 
acid are added slowly to the mixture under agitation. Then, 0.9 grams 
benzoic acid are added immediately following this addition of the 
hydrogenated tallow fatty acids. The amount of ingredients added to the 
base oil in this grease making Example is calculated in such a manner as 
to produce a final grease with an aluminum content of 0.5% aluminum metal, 
a fatty to benzoic ratio of 1.1 to 0.9 and a ratio of 1.92 moles total 
acids per atom of aluminum. The mixture is again raised to a temperature 
of 200.degree. C. and during such a period of heating is observed an acrid 
odor resembling acetic acid. 
After the acids are added, and as the temperature is thus gradually 
increased, gradual thickening of the system is observed. The reaction 
mixture remains clear throughout the heating process and results in a 
clear grease. After the reaction mixture is held for 15 minutes at 
200.degree. C., it is allowed to cool and physical properties are 
determined. The resultant clear grease has a dropping point of 479.degree. 
F. and an unworked penetration of 301. After working 60 strokes in a 
standard grease worker, the penetration is 314. 
As those skilled in the art will appreciate, minor amounts of various 
carboxylic acids known to the art of grease making can be present, if 
desired, in the reactants employed to make a grease as described herein.