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United States Patent (19) 11 Patent Number: 5,126,062

Barnes 45) Date of Patent: Jun. 30, 1992
54 CALCIUM SULFONATE GREASE AND 4,560,489 12/1985 Muir et al. ......................... 252A33.4
METHOD OF MANUFACTURE 4,597,880 7/1986 Eliades ............................... 252A33.4
4,728,578 3/1988 Higgins et al. ...................... 252/.393
75) Inventor: John F. Barnes, Arlington, Tex.
73) Assignee: NCH Corporation, Irving, Tex. Primary Examiner-Prince Willis, Jr.
Assistant Examiner-Jerry D. Johnson
(21) Appl. No.: 641,468 Attorney, Agent, or Firm--Ross, Howison, Clapp &
Korn
22 Filed: Jan. 15, 1991
51) Int, C. ................. C10M 123/02; C1OM 141/00 57 ABSTRACT
52 U.S. Cl. ...................................... 252/18; 252/33.3 An overbased calcium sulfonate grease comprising neu
58) Field of Search ................................... 252/8, 33.3 tral oil, calcium sulfonate, calcium carbonate, dodecyl
(56) References Cited benzyl sulfonic acid, isopropyl alcohol, water, calcium
U.S. PATENT DOCUMENTS hydroxide, 12-hydroxy stearic acid, phosphoric acid
and an antioxidant.
2,967,151 / 1961 Morway ................................ 252/18
3,655,558 4/1972 Geyer et al. .......................... 252/18
3,850,823 11/1974 Kjonaas ................................ 252/18 20 Claims, No Drawings
 5,126,062
1. 2
carbonate, dodecyl benzylsulfonic acid. isopropyl alco
CALCUM SULFONATE GREASE AND METHOD hol, water, calcium hydroxide, 12-hydroxy stearic acid,
OF MANUFACTURE phosphoric acid and an antioxidant.
According to a particularly preferred embodiment of
BACKGROUND OF THE INVENTION 5 the invention, the subject composition comprises from
1. Field of the Invention about 22.5 to about 32.5 weight percent solvent neutral
This invention relates to greases, and more particu oil, from about 66.0 to about 47.4 weight percent cal
larly, to an overbased calcium sulfonate grease having cium sulfonate, from about 5 to about 15 weight percent
improved physical properties. calcium carbonate having a maximum particle size less
2. Description of the Prior Art 10 than about 20 microns and a quartz content less than
Overbased greases are well known in the art, and are about 0.05 percent, from about 1.10 to about 1.50
characterized by a metal content in excess of that which weight percent dodecyl benzyl sulfonic acid, from
would be present according to the stoichiometry of the about 2.50 to about 3.50 weight percent isopropyl alco
metal and the particular organic compound reacted 15
hol, from about 3.00 to about 6.00 weight percent water,
with the metal, for example, a carboxylic or sulfonic from about 2 to about 4 weight percent 12-hydroxy
acid. Various processes are disclosed in the prior art stearic acid, from about 1.75 to about 2.25 weight per
which are useful for making a product containing more cent phosphoric acid, and a minor effective amount of
than the stoichiometic amount of metal. Following an antioxidant.
these procedures, the sulfonic acid or an alkali or alka The use of dodecyl benzyl sulfonic acid and phos
line earth metal salt thereof can be reacted with a metal phoric acid in the compositions of the invention is found
base and the product will contain an amount of metal in to contribute significantly to high temperature charac
excess of that necessary to neutralize the acid. The teristics, anti-wear and extreme pressure properties of
actual stoichiometic excess of metal can vary considera the subject greases. More particularly, the greases dis
bly, for example, from about 0.01 equivalent to about 30 closed herein are found to have a significantly higher
or more equivalents, depending on the reactions, pro 25
dropping point than the overbased calcium sulfonate
cess conditions, and the like. greases disclosed in the prior art.
Prior art greases and lubricants are disclosed, for
example, in the following U.S. Pat. Nos.: 2,977,301; DESCRIPTION OF THE PREFERRED
2,978,410; 3,186,944; 3,242,079; 3,376,222; 3,492,231; EMBODIMENTS
3,907,691; 3,929,650; 4,376,060; 4,560,489; 4,597,880; 30
and 4,824,584.
The compositions of the invention are preferably
U.S. Pat. No. 4,560,489 discloses greases comprising a made by blending the neutral oil, calcium sulfonate and
combination of (1) a highly overbased calcium sulfonate calcium carbonate in an open kettle while heating to a
of a high molecular weight oil-soluble sulfonic acid, temperature range of from about 150 to about 200 F.
dissolved in an oil, containing extremely finely divided 35 (66 to 93 C.). A steam-jacketed kettle having double
calcium carbonate; and (2) a product formed by the acting paddles is satisfactory for use in blending these
reaction of boric acid with a calcium compound such as components. Although 600 solvent neutral oil is pre
calcium hydroxide or calcium oxide; and (3) a product ferred for use in the compositions of the invention, it
formed from calcium hydroxide/calcium oxide and a will be appreciated by those of ordinary skill in the art
soap-forming aliphatic monocarboxylic or fatty acid. that other similar oils can also be used and that lighter
In making overbased greases, conversion agents are oils can be used where better improved low tempera
used to convert the Newtonian homogeneous, single ture properties are desired.
phase overbased materials into non-Newtonian colloi A preferred calcium sulfonate for use in the composi
dal disperse systems. U.S. Pat. No. 3,492,231 discloses tions of the invention is a 400TBN. If desired, 300TBN
the use of phosphorous acids as conversion agents in 45 calcium sulfonate can be substituted, but more is re
forming colloidal disperse systems. quired, or else more calcium hydroxide is needed to
provide enough calcium to react with the other compo
SUMMARY OF THE INVENTION nents of the composition.
According to the present invention, an overbased The preferred calcium carbonate for use in the grease
calcium sulfonate complex grease is provided that dem 50 disclosed herein is a natural mined material that is
onstrates excellent physical properties without requir ground to a powder having a maximum particle size less
ing calcium borate modification as disclosed in U.S. Pat. than about 20 microns, and most preferably, to an aver
No. 4,560,489. age particle size of about 10 microns. Although coarser
The greases of the invention preferably comprise grinds of mined calcium carbonate are generally less
mined and ground calcium carbonate having a maxi 55 expensive, particle sizes greater than about 20 microns
mum particle size less than about 20 microns and a may tend to clump during wear rather than remaining
quartz content less than about 0.05 percent. The use of evenly distributed throughout the grease. Because the
mined and ground calcium carbonate in the composi preferred calcium carbonate for use in the invention is
tions of the invention is particularly advantageous as naturally occurring, it may contain minor amounts of
compared to calcium sulfonate greases in which the quartz, and preferably will contain less than about 0.05
calcium carbonate is formed in situ. The use of ground percent quartz by weight. Although precipitated or
calcium carbonate eliminates the need for a pressurized formed calcium carbonate can be substituted in the
kettle, greatly simplifies the process of making the composition of the invention, the use of calcium carbon
grease, and avoids the necessity of repeatedly checking ate formed in situ is preferably avoided.
the alkalinity of the mixture during preparation. 65 According to a preferred embodiment of the inven
According to a preferred embodiment of the inven tion, the grease as disclosed herein will comprise from
tion, the calcium sulfonate grease disclosed herein com about 22.5 to about 32.5 weight percent neutral oil, from
prises solvent neutral oil, calcium sulfonate, calcium about 36.0 to about 47.4 weight percent calcium sulfo
 5,126,062 4
3
nate, and from about 5 to about 15 weight percent cal cent is not cost effective. It will be appreciated, how
cium carbonate. As used herein, all weight percents are ever, by those of ordinary skill in the art, that the
noted as percentages of the weight of the final product. amount of 12-hydroxy stearic acid utilized in the com
After the blend is prepared as described above, iso positions of the invention can vary depending upon the
propyl alcohol, water and dodecyl benzylsulfonic acid 5 amount of calcium carbonate that is present.
are preferably added to the mixture. The compositions Similarly, the amount of phosphoric acid used in
of the invention preferably comprise from about 2.50 to preparing the subject greases depends upon the amount
about 3.50 weight percent isopropyl alcohol, from of calcium hydroxide used so that the desired physical
about 3.00 to about 6.00 weight percent water, and from properties are achieved while the final product remains
about 1.10 to about 1.50 weight percent dodecyl benzyl 10 alkaline. According to a particularly preferred embodi
sulfonic acid. The isopropyl alcohol and water are de ment of the invention, the amount of phosphoric acid
sirably added to promote gelling. When added to the used in preparing the subject calcium sulfonate greases
mixture, the water is preferably at ambient temperature. will range from about 1.75 weight percent to about 2.25
After adding the alcohol, water and sulfonic acid, the weight percent where the amount of calcium hydroxide
mixture is preferably heated to a temperature ranging 15 ranges from about 1.90 weight percent to about 2.70
from about 220 to about 230 F. (104 to 110° C.) and weight percent. As used herein, "phosphoric acid' re
held while stirring for a period ranging from about 30 fers to an aqueous solution of ortho-phosphoric acid
minutes to about one hour, depending upon atmo having a concentration of about 75% by weight.
spheric conditions. Within this time, the blended mix Alternatively, it is believed that lesser amounts of
ture should gel to form a grease. If the mixture is held at relatively stronger inorganic acids, such as, for exam
too low a temperature, the gelling process takes too ple, sulfuric or nitric acid, can also be used to produce
long. Conversely, if the mixture becomes too hot, the satisfactory overbased calcium sulfonate greases in a
isopropyl alcohol will boil off prematurely. similar manner.
The use of dodecylbenzylsulfonic acid in the compo According to a particularly preferred embodiment of
sitions of the invention is believed to be important for 25 the invention, from about 0.15 to about 0.40 weight
achieving adequate dispersion of the calcium carbonate percent glacial acetic acid is added to the mixture and
throughout the grease. mixed for about 20 minutes prior to addition of the
Once gelling has occurred, calcium hydroxide is pref. 12-hydroxy stearic acid. The prior addition and mixing
erably added in an amount ranging from about 1.90 to of acetic acid will permit it to react before the 12
about 2.70 weight percent of the final product, and the 30 hydroxy stearic acid is added. Although 20 minutes is
Rmaterial is further heated to about 240 F. (116 C.). The not viewed as a critical mixing time, it is believed to be
calcium hydroxide component is needed to provide a satisfactory mixing time when preparing an 8,000
enough extra alkalinity so that acids can be added for pound batch in a blending kettle as described above.
the final gel while maintaining an alkaline finished prod While glacial acetic acid is preferred for use in mak
uct. An alkaline finished product is desirable in order to 35 ing the greases of the invention, preferably in an amount
promote storage stability, lengthen the working life of ranging from about 0.15 to about 0.40 weight percent, it
the finished grease, and avoid the corrosive effects of should be understood that greases falling within the
acids that may be formed during wear. scope of the invention can also be produced without the
Following addition of the calcium hydroxide, the use of acetic acid.
12-hydroxy stearic acid and phosphoric acid compo Following addition of the above-mentioned acid
nents are preferably slowly added sequentially. Slow components, the grease is preferably heated to a tem
addition of the stearic acid and phosphoric acid compo perature range between about 250 and 300 F. (121 C.
nents is desired in order to minimize foaming that might to 149 C.), at which time from about 0.50 to about 3.50
otherwise occur due to the presence of water in the weight percent of polystyrene isoprene added to im
system. The 12-hydroxy stearic acid is mixed for about 45 prove the properties of the final grease. According to a
20 minutes. After the 12-hydroxy stearic acid is added particularly preferred embodiment of the invention, the
and permitted to react, the phosphoric acid is slowly polystyrene isoprene is added in the form of a crumb
added and also mixed for about 20 minutes. polymer. Following addition of the polystyrene iso
Phosphoric acid is a stronger acid and better scaven prene, the mixture is preferably heated to a temperature
ger than the relatively weaker organic acid, and is 50 ranging from about 320' to 330 F. (I60' to 166 C.) and
therefore added last. The use of phosphoric acid in the cooked for about one hour, then allowed to cool.
greases of the invention is believed to contribute to the When the resultant grease has cooled to a tempera
enhanced physical properties observed with the subject ture under about 200' F. (93. C.), a mid-to-high range
greases. The use of organic acids alone yields greases antioxidant such as Vanlube PNA is preferably added to
that lack the desirable high temperature properties. 55 the mixture. At this time, other additives such as disper
According to a preferred embodiment of the inven sants, tackifiers, and the like, can be mixed into the final
tion, the amount of 12-hydroxy stearic acid used in the composition, preferably mixing for up to about an hour
subject greases ranges from about 2 to about 4 weight to ensure thorough dispersion.
percent, and most preferably about 3 weight percent, by The overbased calcium sulfonate grease of the inven
weight of the finished product. The use of 12-hydroxy tion and the physical properties achieved thereby are
stearic acid is preferred in the compositions of the in further described and explained in relation to the fol
vention for its contribution to the work stability of the lowing example:
resultant grease, the ease with which it can be mixed EXAMPLE 1
into the other components, and its wide general avail
ability and relatively inexpensive costs. Greases com In a steam-jacketed, open kettle having doubleacting
prising less than about 2 weight percent of the 12 paddles, 27.55 weight percent neutral oil, 41.44 weight
hydroxy stearic acid may lack the desired long term percent 400TBN calcium sulfonate and 7.89 weight
stability, and the use of more than about 4 weight per percent calcium carbonate are blended while heating to
 5,126,062
5 6
a temperature of 150' F. (66° C.). To this blend, 3.16 9. The grease of claim 8 comprising about 3 weight
weight percent isopropyl alcohol, 4.74 weight percent percent 12-hydroxy stearic acid.
water and 1.3 weight percent dodecyl benzyl sulfonic 10. The grease of claim 1 comprising from about 2.50
acid are added, and the resultant mixture is heated to to about 3.50 weight percent isopropyl alcohol.
about 225 F. (107 C.) and stirred for about an hour, 11. The grease of claim 1 comprising from about 1.90
during which time gelling occurs. About 2.29 weight to about 2.75 weight percent calcium hydroxide.
percent calcium hydroxide is then added and the mix 12. The grease of claim 1 comprising from about 3.00
ture is heated to 240 F. (116 C.). About 0.3I weight to about 6.00 weight percent water.
percent glacial acetic acid is added slowly and mixed 13. The grease of claim 1 comprising from about 0.10
for about 20 minutes, followed by the slow addition of 10 to about 5.00 weight percent of an antioxidant.
2.96 weight percent 12-hydroxy stearic acid and 1.97 14. The grease of claim 1 further comprising from
weight percent phosphoric acid, with each acid addi about 0.25 to about 8.4 weight percent glacial acetic
tion being followed by about 20 minutes of mixing. The acid.
15. The grease of claim 1 further comprising from
resultant grease is heated to about 250 F. (121 C.) and 15 about
1.26 weight percent polystyrene isoprene is added in the isoprene. 0.50 to about 3.50 weight percent polystyrene
form of a crumb polymer. Following addition of the
polystyrene isoprene, the grease is heated to about 325 16. An overbased calcium sulfonate grease compris
F. (163 C.), cooked for one hour, then allowed to cool ing from about 22.5 to about 32.5 weight percent sol
overnight. The penetration of the resultant grease is vent neutral oil, from about 36 to about 47.4 weight
about 260 pen. 20 percent calcium sulfonate, from about 5 to about 15
When the grease is cooled to about 200 F. (93. C.), weight percent calcium carbonate having a maximum
1.97 weight percent Vanlube PNA, 2.96 weight percent particle size less than about 20 microns and a quartz
of 50% Moly Graph dispersant, and 0.2 weight percent content less than about 0.05 percent, from about 1 to
Paratac are added and mixed for one hour. A final test 25 about 1.5 weight percent dodecyl benzyl sulfonic acid,
shows a penetration of about 280 pen. from about 2.5 to about 3.5 weight percent isopropyl
The subject grease is found to have a dropping point alcohol, from about 3 to about 6 weight percent water,
greater than about 600, a much higher dropping point from about 2 to about 4 weight percent 12-hydroxy
than is observed in the calcium borate-modified over stearic acid, from about 1.75 to about 2.25 weight per
based calcium sulfonate complex greases as disclosed in cent phosphoric acid, and a minor effective amount of
30 an antioxidant.
U.S. Pat. No. 4,560,489. Additionally, less than 3 per 17. A method for making an overbased calcium sulfo
cent loss is experienced when the grease of the inven nate grease comprising the steps of:
tion is used in a conventional wheel bearing test, a. blending from about 22.5 to about 32.5 weight
(ASTM D1267) as compared to a loss of about 8 per percent solvent neutral oil, from about 36 to about
cent for calcium borate-modified overbased calcium 35 47.4 weight percent calcium sulfonate, from about
sulfonate greases. 5 to about 15 weight percent calcium carbonate in
Other alterations and modifications of the invention an open kettle while heating to a temperature range
disclosed herein will become apparent to those of ordi of from about 150 F. (66° C.) to about 200 F. (93
nary skill in the art upon reading the present disclosure, C.);
and it is intended that the scope of the invention be b. adding to the blend from about 2.5 to about 3.5
limited only by the broadest interpretation of the ap weight percent isopropyl alcohol, from about 3 to
pended claims to which the inventor is legally entitled. about 6 weight percent water, and from about 1.1
I claim: to about 1.5 weight percent dodecyl benzyl sul
1. A calcium sulfonate grease comprising neutral oil, fonic acid;
calcium sulfonate, calcium carbonate, dodecyl benzyl 45 c. heating the mixture thus formed to a temperature
sulfonic acid, isopropyl alcohol, water, calcium hydrox ranging from about 220 F. (104°C.) to about 230
ide, 12-hydroxy stearic acid, phosphoric acid and an F. (110 C.), and holding the mixture at that tem
antioxidant; perature while stirring for a period ranging from
wherein said grease comprises from about 36.0 to about 30 minutes to about 1 hour to cause gelling;
about 47.4 weight percent calcium sulfonate, from 50 d. after gelling, adding calcium hydroxide in an
about 5 to about 15 weight percent calcium carbon amount ranging from about 1.9 to about 2.7 weight
ate, and from about 1.10 to about 1.50 weight per percent of the grease;
cent dodecyl benzylsulfonic acid. e. heating the material thus produced to a tempera
2. The grease of claim 1 wherein said calcium carbon ture of about 240 F. (116 C.).
ate is ground. 55 f. slowly adding from about 2 to about 4 weight per
3. The grease of claim 1 wherein said calcium carbon cent 12-hydroxy stearic acid and mixing for about
ate is precipitated. 20 minutes; and
4. The grease of claim 1 comprising about 8 weight g. thereafter slowly adding from about 1.75 to about
percent calcium carbonate. 2.25 weight percent phosphoric acid and mixing
5. The grease of claim 1 wherein said calcium carbon for about 20 minutes.
ate has a maximum particle size of about 20 microns. 18. The method of claim 17, further comprising the
6. The grease of claim 1 wherein said calcium carbon step of adding from about 0.15 to about 0.4 weight
ate has an average particle size of about 10 microns. percent glacial acetic acid and mixing for about 20 min
7. The grease of claim 1 wherein said calcium carbon utes prior to the addition of the 12-hydroxy stearic acid.
ate comprises less than about 0.05 weight percent 65 19. The method of claim 17, comprising the addi
quartz. tional steps of heating the grease to a temperature rang
8. The grease of claim 1 comprising from about 2 to ing from about 250 F. (121 C) to about 300 F. (149
about 4 weight percent 12-hydroxy stearic acid. C.), adding thereto from about 0.5 to about 3.5 weight
 5, 126,062
7 8
percent polystyrene isoprene, heating to a temperature tional steps of cooling the grease to a temperature under
Egg, O.S.S.)
(166° C.), and cooking at that temperature for about 1 about 200 F. (93° C),w adding an antioxidant, and there
hour. after mixing to achieve thorough dispersion.
20. The method of claim 19, comprising the addi- 5 xx : x x .

15

25

35

40

45

50

55

65
 UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT NO. : 5, 126,062
DATED JUNE 30, 1992
INVENTORS) : JOHN F. BARNES
It is certified that error appears in the above-identified patent and that said Letters Patent is hereby
corrected as shown below:

COLUMN 2, LINE 7:
Delete 66.0) and insert --36. 0--.

Signed and Sealed this

Thirty-first Day of August, 1993

Attest. (a (4-4-
BRUCE LEHMAN

Attesting Officer Commissioner of Parents and Trademarks :