Note: Descriptions are shown in the official language in which they were submitted.
;" ~
~ L-2174B 126~08
Title: WATER-~ASED MæTAL-CONTAINING ORGANIC PHOSPHATE
- COMPOSITIONS
Technical Field
This invention relates to water-based
metal-containing organic phosphate compositions which
are useful as corrosion-inhibiting coatings, ~etal
working lubricants and drilling ~luids for well-drill-
ing operations. These compositions comprise water. an
overbased non-Newtonian colloi~al disperse ~ystem and a
metal-containing organic phosphaee complex. These
compositions also preferably contain an effective
amount of at least one alkali or alkaline earth metal
alt of an organic acid, at least one carboxylic acid
and at least one N-(hydroxyl-subs~itu~ed hydrocarbyl)
amine to enhance the dispersion of the non-Newtonian
colloidal disperse system and metal-containing organi~
phosphate complex with the water.
Backqround of ~he Invention
The corrosion of metal articles is of obvious
economi~ significance in any industrial application
and, as a consequence, ~e inhi~ition of such corrosion
is a matter of prime consideration. It i8 particularly
significant to users of steel and other ferrous
alloys. The corrosion of such ferrous metal alIoys is
lar~ely a matter of rust formation. which in turn
involves the overall conversion of the free me~al to
its oxides.
' .
'~
~26~
--2--
The theory which best explains such oxidation
of ferrous metal articles postulates the essential
presence of both water and oxygen. Even ~inute traces
of moisture are sufficient, according to this theory,
to induce dissolution of iron therein and the Pormation
~nf ferrous hydroxide until the wa~er becomes saturatd
with ferrous ions. The presencs of oxy~en causes
oxidation of the resulting ferrous hydroxide to ferric
hydroxide, which settles out of solution and i8
ultimately converted to ferric oxicle or rust.
The above sequence of reactions can be
preven~ed, or at least in large mea~ure inhibited, by
relatively impermeable coa~ings which have the effec~
of excluding moisture and/or oxygen from contact with
the metal surface. It is important, therefore, that
these coatings adhere tightly to the metal surface and
resist flaking, crazing, blistering, powdering, and
other forms of loss of adhesion. A satisactory
corrosion-proofing coating, therefore, must have the
ability to resist weathering, high hummidity, and
corrosive atmospheres such as salt-laden mist or fog,
air contaminated with industrial waste, etc., so that a
uniform protective film is maintained on all or most of
the metal surface.
U.S. Patents 3,215,715 and 3,276,916 disclose
metal-containing phosphate complexes for inhibiting the
corrosion of metal. These complexes are prepared by
the reaction of (A) a polyvalent metal salt of the acid
phosphate esters derived from the reaction of phos-
phorus pentoxide wi~h a mixture of a monohydric alcohol
and from 0.25 to 4.0 equivalents of a -polyhydric
alcohol, with (B) at least about 0.1 equivalent o~ an
organic epoxide.
r ~2~ 8
-
U.S. Patent 3,411,923 discloses metal-con-
taining organic phosphate compositions for inhibiting
the corrosion of metals which comprise (A~ a me~al-
containing organic phosphate complex prepared by the
process which comprises the reaction of ~I~ a
polyvalent metal salt of an acid phosphate ester
derived from the reaction of phosphorus pentoxide or
phosphoric acid with a mixture of a monohydric alcohol
and from about 0.25 to ab~ut 4.0 equivalents of a
polyhydric alcohol with (II) at least about 0.1
equivalent of an organic epoxide, and (B) a basic
alkali or alkaline earth metal salt of a sulfonic or
carboxylic acid having at least about 12 aliphatic
carbon atoms, said salt having a metal ratio of at
least about 1.1.
The foregoing corrosion-inhibiting composi-
tions are oil-based compositions. That is, they are
usually diluted with mineral oil or volatile diluents
such as benzene, xylene, aromatic petroleum spirits,
turpentine. etc. It would be advantageous to replace
these oil-based compositions with water-based composi-
tions wherever possible.
Metal working operations, for example,
rolling, forying, hot-pressing, blanking, bending,
stamping, drawing, cutting, punching, spinning and the
like generally emplo~ a lubricant to facilitate the
same. Lubricants greatly improve these operations in
~hat they can reduce the power required for the
operation, prevent sticking and decrease wear of dies,
cutting bits and the like. In addition, they
frequently provide rust inhibiting properties to the
metal being treated. These lubricants are usualy
~2~;16~
oil-based and it would be advantageous to replace such
oil-based lubricants with water-based lubricants
wherever possible.
The use of drilling fluids in well-drilling
operations has been known for a~ least 100 years. See,
for example, the discussion in Kirk-Othmer, "Encyclo-
pedia of Chemical Technology". Second Edition, Vol. 7,
pages 287 e~ ~eq. Aqueous drilling fluids or muds
usually c~ntain a thickening agent such as clay and
often a density-increasing agent such as barites. The -~
use of other additives in drilling fluids or muds is
also known. See, for example, John ~cDermott,
"Drilling Mud and Fluid Additives", Noyes-Data
Corporation, New Jersey, 1973~ ~
Among the types of additives used in drilling
~uds or fluids are lubricants or lubricity agents.
Such additives reduce drag on the drill string and bi~
and thereby reduce the possibilities of twist off,
reduce trip time, lessen differential sticking and
lower the amount of energy required to turn the rig
(that is, the torque reguirements). Methods for
evaluating such drilling ~luid lubricants are also
known. See, for example, the article by Stan E. Alford
in l'World Oil", July, 1976, Gulf Publishing Company.
Other additives which enhance the lubricating
properties of drilling fluids or muds have been
reported in the patent literature. See, for example,
U.S. Patents 3,214,379 and 4,064,055. The use of
petroleum sul~onates as extreme pressure additi~es in
oil emulsion and aqueous drilling fluids is also
known. See the articcle by M. Rosenberg et al in AIME
Petroleum Transactions, Vol. 216 (1959), pages 195-202
and U.S. Patent No. 4,064,056.
~ ~L2~i~L6~3~ r
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U.S. Patent 4,230,586 discloses agueous
well-drilling fluids which comprise (A) a~ least one
non-Newtonian colloidal disperse system comprising:
solid metal-containing colloidal parti-
cles at least a portion of which are
predispersed in
. (2) at least one liquid dispersing medium: and
(3) as an essential componen~, at least one
organic compound which is soluble in said
dispersing medium, the molecules of said
: organic compound being characterized by a
hydrophobic portion and a~ least one
polar substituent
and (B) at least one emulsifier.
Despite the foregoing, the search for
effecti~e drilling fluids, which aid in achieving more
efficient and economical rotary drilling operations,
has continued.
Summary of the Invention
The present invention con~emplates the
provision of water-based metal-containing organic
phosphate compositions which are useful as corrosion-
inhibiting coatinq compositions, metal working
:lubricants and drilling fluids for well-drilling
operations.
Broadly stated, the present invention pro~ides
for a composition comprising: (A) water; (B) an
overbased non-Newtonian colloidal disperse system
comprising ~B)~l) solid metal-containing colloidal
particles predispersed in (B)(2) a dispersing medium of
at leas~ one inert organic liguid and (B)(3) at least
one member selected from the` class consisting of
' '' ''' .. ~.
--6--
organic compounds which are substantially soluble in
said dispersing medium, the molecules of said organic
compound being characterized by polar substituents and
hydrophobic portions and (C~ a metal-containing
organic phosphate complex derived ~rom the reaction of
(C)(l) at least one polyvalent metal salt of an acid
phosphate ester, said acid phosphate ester being
derived from the reac~ion of phosphorus pentoxide or
phosphoric acid with a mixture of at least one
monohydric alcohol and at least one polyhydric alcohol.
with (C)(2) at least one organic epoxide; components
(B~ and (C) being dispersed with said water.
In a preferred embodiment, ~he present
invention provides for a drilling fluid comprising (A)
a major amount of an aqueous drilling mud, and a minor
torgue reducing amount of a mixture of: (B) an
overbased non-Newtonian colloidal disperse system
comprising ~B)(l~ solid metal-containing colloidal
particles predispersed in (B)(2) a dispersing medium of
at least one inert organic liguid and (B)(3) at least
one member selected from the class consisting of
organic compounds which are substantially soluble in
said dispersing medium, the molecules of said organic
compound being characterized by polar substituents and
Aydrophobic portions: and (C) a metal containing
organic pAosphate complex derived from the reaction of
(C)~l) at least one polyvalent metal salt of an ~cid
phosphate ester, said acid phosphate ester being
derived from the reaction of phosphorus pentoxide or
phosphoric acid with a mixture of a monohydric alcohol
and a polyhydric alcohol, with (C)(2) at- least one
organic epoxide.
.
--7--
The foregoing compositions and drilling fluids
preferably include an effective amount of (D) an alkali
or an alkaline earth metal salt of an organic acid, (E)
a carboxylic acid and (F) an N-(hydroxyl-substituted
hydrocarbyl) amine to enhance the dispersion of
components (B) and (C) with said water or drilling mud
(A).
Detailed Description of the Preferred ~mbodiment
The Water or Drillinq Mud (A):
When the compositions of the present invention
are to be employed as corrosion-inhibiting coating
compositions or metal working lubricants, component (A)
is water.
When the compositions of the present invention
are in the form of a drilling fluid, component (A) is an
aqueous drilling mud. These drilling muds are usually
suspensions of solids in water; these solids form the
bulk of the mud filter cake. In general, the solids are
clays and barite and their relative amounts present in
the bulk mud are controlled within limits set by the
required mud density. The drilling muds contemplated
herein are entirely conventional and well known to those
skilled in the art. Reference is made to John
McDermott, "Drilling Mud and Fluid Additives",
Noyes-Data Corporation, New Jersey, 1973.
The Overbased Non-Newtonian Disperse System (B):
The terminology "disperse system" as used in
the specification and claims is a term of art generic
to colloids or colloidal solutions, e.g., "any
homogeneous medium containing dispersed entities of any
size and state", Jirgensons and Straumanis, "A Short
-8-
Textbook on Colloidal Chemistry~ ~Znd Ed.) The Mac-
Millan Co., New York, 1962 at page 1. However, the
particular disperse systems of the present invention
orm a subgenus within this broad class of disperse
system, this subgenus being characterized by several
important features.
So long as the solid particles remain
dispersed in the dispersing medium as colloidal
particles the particle size is no~ critical. Ordinar-
ily, the particles will not exceed 5000A. However, it
is preferred that ~he maximum unit particle size be
less than about 1000A. In a particularly preferred
aspect of the invention, the uni~ particle size is less
than about 400A. Systems having a unit particle size
in the range of 30A to 200A are useful. The minimum
unit particle size is at least 20A and preferably at
least about 30A.
The language "unit particle size" is intended
~o designate the average particle size of the solid,
metal-containing particles assuming maximum dispersion
of the individual particles throughout the disperse
medium. That is, the unit particle is that particle
which corresponds in size to the average size of the
metal-containing particles and is capabie of indepen-
dent existence within the disperse system as a discrete
colloidal particle. These metal-containing particles
are found in two forms in the disperse systems.
Indi~idual unit particles can be dispersed as such
throughout the medium or unit particles can form an
aqglomerate, in combination with other materials (e.g.,
another metal-containing particle, the disperse medium,
etc.) which are present in the disperse systems. These
~26~6~ ~
g
agglomera~es are dispersed through the system as
"metal-containin~ particles". Obviously, the "particle
size" of the agglomerate is substantially grsater than
the unit particle size. Furthermore, it is equally
apparent that this agglomerate size is sub~ect to wide
variations, even ~ithin the same disperse system. The
agglomerate size varies, for example, with the degree
of shearing action employed in dispersing the unit
particles. That is, mechanical agitation of the
disperse system tends to break down the agglomerates
into the individual components thereof and disperse
these individual components throughout the disperse
medium. The ultimate in dispersion is achie~ed when
each solid, metal-containing particle is individually
dispersed in the medium. Accordingly, the disperse
systems are characterized with reference to the unit
particle size, it being apparent to those skilled in
the art that the unit particle size represents the
average size of solid, metal-containing particles
present in the system which can exist independently.
The average particle size of the metal-containing solid
particles in the system can be made to approach the
unit particle size value by the application of a
shearing action to the existent system or during the
formation o the disperse system as the particles are
being formed in situ. It is not necessary that maximum
particle dispersion exist to have useful disperse
systems. The agitation associated with homogenization
of the overbased material and conversion agent produces
sufficient particle dispersion.
Basically, the solid metal-containing
particles are in the form of metal salts of inorganic
~2~
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acids, and low molecular weight organic acids, hydrates
thereof, or mixtures of these. These salts are usually
the alkali and alkaline earth metal formates, acetates,
carbonates, hydrogen carbonates, hydrogen sul~ides,
sulfites, hydrogen sulfi~es, and halides, particularly
chlorides. In other words, the metal-containiny
particles are ordinarily par~icles of metal salts, the
uni~ particle is the individual salt particle and the
unit particle size is the average particle size of the
salt particles which is readily ascertained, as for
example, by conventional X-ray diffraction ~echniqueæ.
Colloidal disperse systems possessing particles of this
type are some~imes referred to as macromolecular
colloidal systems.
Because of the composition of the colloidal
disperse systems of this invention, the me~al contain-
ing particles also exist ~s components in micellar
colloidal particles. In addition to the solid metal-
containing particles and the disperse medium, the
colloidal disperse systems of the invetion are charac-
terized by a third essential component, one which is
soluble in the medium and contains in the molecules
thereof a hydrophobic portion and at least one polar
substituent. This third component can orient itself
along the external surfaces of ~he above metal salts,
the polar groups lying along the surface of these salts
with the hydrophobic portions extending from the salts
into the disperse medium forming micellar colloidal
particles. These micellar colloids are formed through
weak intermolecular forces, e.g., Van der Waals forces,
etc. Micellar colloids represent a type of agglomerate
particle as ~iscussed hereinabove. Because of the
6~,608 r
--1 1 .
molecular orientation in these micellar colloidal
particles, such particles are characterized by a
metal-containing layer ~i.e., the solid metal-contain-
ing particles and any metal present in the polar
substituent of the third component, such as the metal
in a sulfonic or carboxylic acid salt group), a
hydrophobic layer formed by the hydrophobic portions of
the molecules of the third component and a polar layer
bridging said metal-containing layer and said hydro-
phobic layer, said polar bridging layer comprising the
polar substituents of the third component of the
system, e.g., the
O
Il
o--
O
group if the third component is an alkaline earth metal
petrosulfonate.
The second essential component of the
colloidal disperse system is the dispersing medium.
The identity of the medium is not a particularly
critical aspect of the invention as the medium
primarily serves as the liquid vehicle in which solid
particles are dispersed. The medium can have
components characterized by relatively low boiling
points, e.g., in the range of 25C to 120C to
facilitate subsequent removal of a portion or
substantially all of the medium from the aqueous
compositions or drilling fluids of the invention or the
components can have a higher boiling point-to protect
against removal from such compositions or drilling
,
~L2~
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~luids upon standing or hea~ing. There is no criti-
cality in an upper boiling point limitation on these
liquids.
Representative liquids include mineral oils,
the alkanes and haloalkanes of 5 ~o 1~ carbon atoms,
polyhalo- and perhaloalkanes of up to about 6 carbons,
~he cycloalkanes o~ 5 or more carbons, the correspond-
inq alkyl- and/or halo-substituted cycloalkanes, the
aryl hydrocarbons, the alkylaryl hydrocarbons, the
haloaryl hydrocarbons, ethers such as dialkyl ethers,
alkyl aryl ethers, cycloalkyl ethers, cycloalkylalkyl
ethers, alkanols, alkylene glycols, polyalkylene
glycols, alkyl ethers of alkylene glycols and
polyalkylene glycols, di~asic alkanoic acid diesters,
silicate esters, and mixtures of these. Specific
examples include petroleum e~her, Stoddard Solvent,
pentane, hexane, octane, isooctane, undecane,
tetradecane, cyclopentane, cyclohexane, isopropyl-
cyclohexane, 1,4-dimethylcyclohexane, cyclooctane,
benzene, toluene, xylene, ethyl benzene, tert-butyl-
benzene, halobenzenes especially mono- and polychloro-
benzenes such as chlorobenzene per se and 3,4-dichloro-
toluene, mineral oils, n-propylether, isopropylether,
isobutylether, n-amylether, methyl-n-amylether,
cyclohexylether, ethoxycyclohexane, methoxybenzene,
isopropoxy benzene, p-methoxy-toluene, methanol,
ethanol, propanol, isopropanol, hexanol, n-octyl
alcohol, n-decyl alcohol, alkylene glycols such as
ethylene glycol and propylene glycol, diethyl ketone,
dipropyl ketone, methylbutyl ketone, acetophenone,
1,2-difluoro tetrachloroethane, dichlorofluoromethane,
1,2-dibromotetrafluoroethane, trichlorofluoromethane,
3-
l-chloropentane, 1~3-dichlorohexane, formamide,
dimethylformamide, acetamide, dimethylacetamide,
diethylacetamide, propionamide, diisooctyl azelate,
ethylene glycol, polypropylene glycols, hexa-2-ethyl-
butoxy disiloxane, etc.
Also useful as dispersing medium are the low
molecular weight, liquid polymers, generally classified
as oligomers, which include the dimers, tetramers,
pentamers~ etc. Illustrative of this large class of
materials are such liquids as the propylene tetramers,
isobutylene dimers, and the like.
From the standpoint of availability, cost, and
performance, the alkyl, cycloalkyl, and aryl hydro-
carbons represent a preferred class of disperse
mediums. ~iquid petroleum fractions represent anothe
pre~erred class of disperse mediums. Included within
these preferred classes are benzenes and alkylated
benzenes, cycloalkanes and alkylated cycloalkanes,
cycloalkenes and alkylated cycloalkenes such as found
in naphthene-based petroleum fractions, and the alkanes
such as found in the paraffin-based petroleum
fractions. Petroleum ether, naphthas, mineral oils,
Stoddard Sol~ent, toluene, xylene, etc.`, and mixtures
thereof are examples of economical sources of suitable
inert organic liquids which can function as the
disperse medium in the colloidal disperse systems of
t~e present invention. Mineral oil can serve by itself
as the disperse medium.
Preferred disperse systems include those
containin~ at least some mineral oil as a component of
the disperse medium. Any amount of mineral oil is
beneficial in this respect. However, in this preferred
~21Ei~ 8
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~lass of systems, it is desirable that mineral oil
comprise at least about 1% by weight of the total
medium, and preferably at least about 5~ by weight.
Those mediums comprising at least 10% by weight mineral
oil are especially useful. Mineral oil can serve as
the exclusive disperse medium.
In addition to the solid, metal-containing
particle~ and the di~perse medium, the disperse sys~ems
employed herein reguire a third essential component.
This third component is an organic compound which is
soluble in the disperse medium, and the molecules of
which are characterized by a hydrophobic portion and at
least one polar substituent. As explained, infra, the
oryanic compounds suitable as a third component are
e~tremely diverse. These compounds are inherent
constituents of the d}sperse systems as a result-of the
methods used in preparing the systems. Furt~er
characteristics oP the components are apparent from ~he
following discussion of methods for preparing the
colloidal disperse systems.
Preparation of the Overbased Non-Newtonian Disperse
System ~B):
Broadly speaking, the coll~idal disperse
systems of the invention are prepared by treating a
single phase homogeneous, Newtonian system of an
"overbased", "superbased", or "hyperbasedl~, organic
compound with a conversion agent, usually an acti~e
hydrogen containing compound, the treating operation
being simply a thorough mixing together of the two
components, i.e., homogenization. This treat~ent
converts these single phase systems into- the non-
Newtonian colloidal disperse systems utilized in the
compositions of the present invention.
~ 6~
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The terms ~overbased~ superbased", and
"hyperbased", are terms of art which are generic to
well known classes of metal-containing materials.
These overbased materials have also been referred to as
"complexes", "metal complexes", "higb-metal containing
; salts", and the like. O~erb~sed materials are
characterized by a metal content in excess of that
which would be present according to the stoichiometry
of the me~al and the particular organic compound
reacted with the metal, e.g., a carboxylic or sulfonic
acid. Thus, if a monosulfonic acid,
:
o
11
R S - OH
11
is neutralized with a basic metal compound, e.g.,
calcium hydroxide, the "normal" metal salt produced
will contain one equivalent of calcium for each
eguivalent of acid, i.e.,
O O
11 11
R S O - Ca - O S R
O O
However, as is well known in the art, various processes
are a~ailable which result in an inert organic liquid
solution of a product containing more than the
stoichiometric amount of metal. The solutions of these
products are referred to herein as overbased
materials. Following these procedures, the sulfonic
acid or an alkali or alkaline earth metal salt thereof
-16-
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can be reacted with a metal base and the product will
contain an amount of metal in excess of that necessary
to neutralize the acid, for example, 4.5 times as much
metal as present in the normal salt or a metal excess
of 3.5 eguivalents. The ac~ual stoichiometric excess
of metal can vary considerably, for example, from about
0,1 equivalent to about 30 or more equivalents
~epending on the reactions, the process conditions, and
the like. These overbased materials useful in
preparing the disperse systems usually contain from
about 3.5 to about 30 or more equivalents of metal for
each equivalent of material which is overbased.
In the present specification and claims the
term "overbased" is used to designate materials
containing a stoichiometric excess of metal and is,
therefore, inclusive of those materials which have been
referred to in the art as overbased, superbased,
hyperbased, etc., as discussed upra.
The terminology "metal ratio" is used in the
prior art and herein to designate the ratio of the
total chemical equivalents of the metal in the
overbased material (e.g., a metal sulfonate or
carboxylate) to the chemical equivalents of the metal
in the product which ~ould be expected to result in the
reaction between the organic material to be overbased
(e.g., sulfonic or carboxylic acid) and the metal-
containing reactant (e.g., calcium hydroxide, barium
oxide, etc.) according to the known chemical reactivity
and stoichiometry of the two reactants. Thus, in the
normal calcium sulfonate discussed above, the metal
ratio is one, and in the overbased sulfonate, the metal
ratio is 4.5. Obviously, i~ there is present in the
~Z~ 8
-17-
material to be overbased more than one compound capable
of reacting with the metal, the "metal ratio" of the
product will depend upon whether the number of
equivalents of metal in the overbased product is
compared to the number of equivalents expected to be
present for a given single component or a combination of
all such components.
The overbased materials are prepared by
treating a reaction mixture comprising the organic
material to be overbased, a reaction medium consisting
essentially of at least one inert, organic solvent for
said organic material, a stoichiometric excess of a
metal base, and a promoter with an acidic material. The
methods for preparing the overbased materials as well as
an extremely diverse group of overbased materials are
well known in the prior art and are disclosed for
example in the following U.S. Patents:
2,616,904; 2,616,905; 2,616,906; 2,616,911; 2,616,924;
2,616,925; 2,617,049; 2,695,910; 2,723,234; 2,723,235;
2,723,236; 2,760,970; 2,767,164; 2,767,209; 2,777,874;
2,798,852; 2,839,470; 2,856,359; 2,859,360; 2,856,361;
2,861,951; 2,883,340; 2,915,517; 2,959,551; 2,968,642;
2,971,014; 2,9~9,463; 3,001,981; 3,027,325; 3,070,581
3,108,960; 3,133,019; 3,146,201; 3,147,232; 3,152,991;
3,155,616; 3,170,880; 3,170,881; 3,172,855; 3,194,823;
3,223,630; 3,232,883; 3,242,079; 3,242,080; 3,250,710;
3,256,186; 3,274,135; 3,492,231; 4,230,586; 4,436,855;
and 4,443,577. These patents disclose processes,
materials which can be overbased, suitable metal bases,
promoters, and acidic materials, as well as a variety of
specific overbased products useful in producing the
disperse systems of this invention.
~161~
a-
An impor~ant characteristic of the organic
materials which are overbased is their solubility in
the particular reaction medium utilized in the
overbasing process. As the reaction medium used
previously has normally comprised petroleum fractions,
particularly mineral oils, these organic materials have
generally been oil-soluble. However, i~ another
reaction medium is employed (e.y., aromati~ hydro-
carbons, aliphatic hydrocarbons, ~erosene, etc.~ it is
not esential that the organic materials be soluble in
mineral oil as long as it is soluble in the given
reaction medium. Obviously, many organic materials
which are soluble in mineral oils will be soluble in
many of the other indicated suitable reaction mediums.
It should be apparent that the reaction medium usually
becomes the disperse medium of the colloidal disperse
system or at least a component thereof depending on
whether or not additional inert organic liquid is added
as part of the reaction medium or the disperse medium.
Materials which can be overbased are generally
oil-soluble organic acids including phosphorus acids,
thiophosphorus acids, sulfur acids, carboxylic acids,
thiocarboxylic acids, and the like, as well as the
corresponding alkali and alkaline earth metal salts
thereof. U.S. Patent 2,777,874 discloses organic acids
suitable for preparing overbased materials which can ~e
converted to disperse systems for use in the composi_
tions of the invention. Similarly, U.S. Patents
2,61~,909: 2,695,910; 2,767,164; 2,767,209 3,147,Z32;
and 3,274,135 disclose a v~riety of organic acids
sui~able for preparing overbased materials as well as
representative examples of overbased products prepared
~L~2S~L6~3 r
--19--
from such acids. Overbased acids wherein the acid is a
phosphorus acid, a thiophosphorus acid, phosphorus
acid-sulfur acid combination, and sulfur acid prepared
from polyolefins are disclosed in U.S. Patents
2~883,340, 2,915,517; 3,001,981 3,108,960 and
3,Z3~,~83. Qverbased phenates are disclased in U.S.
Patent 2,959,551 while overbased ketones are found in
U.S. Patent 2,798,a52. A variety of overbased
materials derived from oil-soluble metal-free,
non-tautomeric neutral and basic organic polar
compounds such as esters, amines, amides, alcohols,
ethers, sulfides, sulfoxides, and the liXe are
disclosed in U.S. Patents 2,968,642; 2,971,014: and
2,989,463. Another elass of materials which can be
overbased are ~he oil-soluble, ni~ro-substituted
aliphatic hydrocarbons, particularly nitro-substituted
polyolefins such as polyethylene, polypropylene,
polyisobutylene, etc. Materials of this type are
illustrated in U.S. Patent 2,959,551. Likewise, the
oil-soluble reaction product of alkylene polyamines
such as propylene diamine or N-alkylated propylene
diamine with formaldehyde or formaldehyde producing
compound te.g., paraformaldehyde) can be overbased.
O~her compounds suitable for overbasing are disclosed
in the above-~ited patents or are otherwise ~ell known
in the art.
The organic liguids used as the disperse
medium in the colloidal disperse system can be used as
solvents for the overbasing process.
The metal compounds used in preparing the
overbased materials are normally the basic salts of
metals in Group I-A and Group II-A of the Periodic
~2~
-20-
Table al~hough other metals such as lead, zinc,
manganese, e~c., can be used in the preparation of
overba~ed matarials. The anionic portion of the salt
can be hydroxyl, oxide, carbona~e, hydro~en carbonate,
nitrate, sulfite, hydrogen sulfite, halide, amide,
sulfate etc., as disclosed in the above-cited patents.
Preferred overbased materials are prepared from the
alkaline earth metal oxides, hydroxides, and
alcoholates such as the alkaline earth metal lower
alkoxides.
The promoters, that is, the materals which
permit the incorporation of the excess metal into the
overbased material, are also quite diverse and well
known in the art as evidenced by the above-cited
patents. A particularly comprehensive discussion of
suitable promoters is found in U.S. Patents z,777,a79
2,695,910: and 2,616,904. These include the alcoholic
and phenolic promoters which are preferred. The
alcoholic promoters include the alkanols of 1 to about
12 carbon atoms such as methanol, ethanol, amyl
alcohol, octanol, isopropanol, and mixtures of these
and the like. Phenolic promoters include a ~ariety of
hydroxy-substituted benzenes and naphthalenes. A
par~icularly useful class of phenols are the alkylated
phenols of the type listed in U.S. Patent 2,777,87~,
e.g., heptylphenols, octylphenols, and nonylphenols
~ixtures of various promoters are sometimes used.
Suitable acidic mater;als are also disclosed
in the above-cited patents, for example, U.S. Patent
2,616,904. Included within the known group of useful
acidic materials are liquid acids such as formic acid,
acetic acid, nitric acid, sulfuric acid, hydrochloric
~ zq~ 8
-21-
acid, hydrobromic acid, carbamic acid, subs~ituted
carbamic acids, etc. Acetic acid is a very useful
acidic material although inorganic acidic materials
such as EICl, S02, S03, C02, H2S, Nz03,
etc., are ordinarily employed as the acidic materials.
Pre~erred acidic materials are carbon dioxide and
acetic acid.
In preparing overbased materials, the material
to be o~erbased, an inert non-polar organic solvent
there~or, the metal base, ~he promoter and the acidic
material are brought ~ogether and a chemical reaction
ensues. The exact nature of the resulting overbased
product is not known. However, it can be adequately
described for purposes of the present specification as
a single phase homoyeneous mixture o~ the solvent and
(1] aither a metal complex form~d from the metal base,
the acidic material, and the materal being overbased
and/or ~2) an amorphous metal salt formed from the
reaction of the acidic material with the metal base and
the material which is said to be overbased. Thus, if
mineral oil is used as the reaction medium, petro-
sulfonic acid as the material which is overbased,
Ca(OH)2 as the metal base, and carbon dioxide as the
acidic material, the resulting overbased material can
be described for purposes of this invention as an oil
solution of either a metal conta}ning complex of the
acidic material, the metal base, and the petrosulfonic
acid or as an oil solution of amorphous calcium
carbonate and calcium petrolsulfonate.
The temperature at which the acidic material
is contacted with the remainder of the reaction mass
depends to a large measure upon the promoting agent
~.26~ 3 r
z ~
used. ~ith a phenolic promoter, the temperature
usually ranges from about 80C to 300C, and preferably
from about loooc to about 200c. When an alcohol or
mercaptan is used as the promoting agent, the temper-
ature usually will not exceed the reflux temperature of
the reaction mixture and preferably will not exceed
about 100Co
In view of the foregoing, it should be
apparent that the overbased materi.als may retain all or
a portion of the promoter. That is, if the promoter is
noS ~olatile (e.q., an alkyl phenol3 or otherwise
readily removable from the overbased material, at least
some promoter remains in the overbased product.
Accordingly, the disperse systems made from such
products may also contain the promoter. The presence
or absence of the promoter i~ the overbased material
used to prepare the disperse system and likewise, the
presence or absence of the promoter in the colloidal
disperse systems themselves does not represent a
critical aspect of the invention. Obviously, it is
within the skill of the art to select a volatile
promoter such as a lower alkanol, a.g., methanol,
ethanol, etc., so that the promoter can be readily
removed prior to incorporation with the compositions or
drilling fluids of the present invention.
A preferred class of overbased materials used
as starting materials in the preparation of the
disperse systems of the present invention are the
alkaline earth metal-overbased oil-soluble organic
acids, preferably those containing at least 12
aliphatic carbons although the acids may contain as few
as 8 aliphatic carbons if the acid molecule includes an
~z~
-23-
aromatic ring such as phenol, naphthyl, etc. Repre-
sentative organic acids suitable for preparing these
overbased materials are discussed and identified in
detail in ~he above-cited patents. Particularly U.S.
Patents 2,616,904 and 2,777,874 disclose a variety of
suitable organic acids. Overbased oil-soluble
carboxylic and sulfonic acids are particularly
suitable. Illustrative of ~he carboxylic acids are
palmitic acid, stearic acid, myristic acid, oleic acid,
linoleic acid, behenic acid, heeatriacontanoic acid,
tetrapropylene-substituted glutaric acid, polyisobutene
M.W.-5000)-substituted succinic acid, polypropylene,
(M.W.-10,00~)-substituted succinic acid, octadecyl-
substituted adipic acid, chlorostearic acid, 9-methyl-
stearic acid, dichlorostearic acid, stearylbenzoic
acid, eicosane-substituted naphthoic acid, dilauryl-
decahydronaphthalene carboxylic acid, didodecyl-
tetralin carboxylic acid, dioctylcyclohexane carboxylic
acid, mixtures of these acids, their alkali and
alkaline earth metal salts, and/or their anhydrides.
Of the oil-soluble sulfonic acids, the mono-, di-, and
tri-aliphatic hydrocarbon substituted aryl sulfonic
acids and the petroleum sulfonic acids (petrolsulfonic
acids) are particularly preferred. Illustrative
examples of suitable sulfonic acids include mahogany
sulfonic acids, petrolatum sulfonic acids,
monoeicosane-substituted naphthalene sulfonic acids
dodecylbenzene sulfonic acids, didodecylbenzene
sulfonic acids, dinonylbenzene sulfonic acids,
cetylchlorobenzene sulfonic acids, dilauryl
beta-naphthalene sulfonic acids, the sulfonic acid
derived by the treatment of polyisobutene having a
~ ~2~6~8
-24-
molecular weight of 1500 with chlorosulfonic acid,
nitronaphthalene sulfonic acid, paraffin wax sulfonic
acid, ce~ylcyclopentane sulfonic acid, lauryl-cyclo-
hexanes~lfonic acids, polyethylene ~M.W.-750) sulfonic
acids, etc. Obviously, it is necessary that the size
tbe number of aliphatic groups on the aryl sulfonic
acids be sufficient to render the acids soluble.
Normally the aliphatic groups will be alkyl and/or
al~enyl groups such that the total number of aliphatic
carbons is at least 12.
Within this preferred group of overbased
carboxylic and sulfonic acids, the barium, and calcium
overbased mono~, di-, and tri-alkylated benzene and
naphthalene (including hydrogenated forms thereof),
petro6ulfonic acids, and higher fa~ty acids are
especially preferred. Illustrative of the synthe-
tically produced alkylated benzene and naphthalene
sulfonic acids are those containing alkyl substituents
having ~rom 8 to about 30 carbon atoms therein. Such
acids include di-isododecyl-benzene sulfonic acid,
wax-substituted phenol sulfonic acid, wax-substituted
benzene sulfonic acids, polybutene-substituted sulfonic
acid, cetyl-chlorobenzene sulfonic acid, di cetylnaph_
thalene sulfonic acid, di-lauryldiphenylether sulfonic
acid, di-isononylbenZene sulfonic acid, di-isoocta-
decylbenzene sulfonic acid, stearylnaphthalene sulfonic
acid, and the like. The petroleum sulfonic acids are a
well known art recognized class of materials which have
been used as starting materials in preparing overbased
products since the inception of overbasing tech~iques
as illustrated by the above patents. = Petroleum
sulfonic acids are obtained by treating refined or
ir ~Z6~66~8
z~
semi-refined petroleum oils with concentrated or fuming
sulfuric acid. These acids remain in the oil after the
settling out of sludges. These petroleum sulfonic
acids, depending on the nature oE the petroleum oils
from which they are prepared, are oil-soluble alkane
sulfonic acids, al~yl-su~stituted cycloaliphatic
sulfonic acids inluding cycloalkyl sulfonic acids and
cycloalkene sulfonic acids, and alkyl, alkaryl, or
aralkyl ~ubstituted hydrocarbon aromatic sulfonic acids
including ~ingle and condensed aromatic nuclei as well
as partially hydrogenated forms thereof. Examples of
such petrosulfonic acids in~lude mahogany sulfonic
acid, white oil sulfonic acid, petrolatum sulfonic
acid, petroleum naphthene sulfonic acid, etc. This
preferred group of aliphatic fatty acids includes the
saturated and unsaturated higher fatty acids containing
from about lZ to about 30 carbon atoms. Illustrative
of these acids are lauric acid, palmitic acid, oleic
acid, linoleic acid, linoleic acid, oleostearic acid,
stearic acid, myristic acid, and undecalinic acid,
alphachlorostearic acid, and alpha-nitrolauric acid.
As shown by the representative examples of the
preferred classes of sulfonic and carboxylic acids, the
acids may contain non-hydrocarbon substituents such as
halo, nitro, alkoxy, hydroxyl, and the like.
It is desirable that the overbased materials
used to prepare the disperse system have a metal ratio
of at least about 3.5 and preferably at least about
4.5. An especiallY suitable group of the preferred
sulfonic acid overbased materials has a metal ratio of
at least about 7. ~hile overbased materials having
metal ratios as high as 75 have been prep~red and can
~26~L~al8
-26-
be used, normally the maximum metal ratio will not
exceed about 30 and, in most cases, not more than about
20.
The overbased materials used in preparing the
disperse systems utilized in the compositions and
drilling fluids of the present invention usually
contain from about 10% to about 70% by weight of
metal-containing components. As explained hereafter,
the exact nature of these metal-containing components
is not known. While not wishing to be bound by theory,
it is believed that the metal base, the acidic
material, and the organic material being overbased form
a metal complex, this complex being the metal-contain-
ing component of the overbased material. On the other
hand, it has also been postulated that the metal base
and the acidic material form amorphous metal compounds
which are dissolved in the inert organic reaction
medium and the material which is said to be overbased.
The material which is overbased may itself be a
metal containing compound, e.g., a carboxylic or
sulfonic acid metal salt. In such a case, the metal
containing components of the overbased material would
be both the amorphous compounds and the acid salt. The
remainder of the overbased materials consist essen-
tially of the inert organic reaction medium and any
promoter which is not removed from the overbased
product. For purposes of this patent application, the
organic material which is subjected to overbasing is
considered a part of the metal-containing components.
Normally, the liquid reaction medium constitutes at
least about 30~ by weight of the reac~ion mixture
utilized to preyare the overbased materials.
~Z6~ 8
-27-
As mentioned above, the colloidal disperse
sys~ems used in the composition of the present
invention are prepared by homogenizing a "conversion
agent~' and the overbased starting material. Homogeni-
zation is achieved by vigorous ayita~ion of the two
components, preferably at the reE~Lux temperature or a
temperature sligh~ly below the reflux temperature. The
reflux temperature normally will depend upon the
boiling point of the conversion agent. However,
homogenization may be achie~ed within the range of
about 25C to about 200OC or slighsly higher. Usually,
there is no real advantage in exceeding about 150C.
The concentration of the conversion agent
necessary to achieve conversion of the overbased
material is usually within the range of from about 1%
to about 80% based upon the weight of the overbased
material excluding the weight of the inert organic
solvent and any promoter present therein. Preferably
at least about 10~ and usually less than about 60% by
weigh~ of the conversion agent is employed. Concentra-
tions beyond 60% appear to a~ford no additional
advantages.
The terminology "con~ersion agent" as used
herein is intended to describe a class of very diverse
materials which possess the property of being able to
convert the Newtonian homogeneous, single-phase,
overbased materials into non-Newtonian colloidal
disperse systems. The mechanism by which conversion is
accomplished is not completely understood. However,
with the exception of carbon dioxide, these conversion
agents all possess active hydrogens. The conversion
agents include lower aliphatic carboxylic acids, water,
~ ÇL6~ ~
-28-
aliphatic alcohols, cycloaliphatic alcohols, arylali-
phatic alcohols, phenols, ketones, aldehydes, amines,
boron acids, phosphorus acids, and carbon dioxide.
Mixtures of two or more of these conversion agents are
also useful. Particularly useful conversion agents are
discussed below.
The lower aliphatic carboxylic acids are those
containing less than about 8 carbon atoms in the
molecule. Examples of this class of acids are formic
acid, acetic acid, propionic acia, butyric acid,
valeric acid, isovaleric acid, isobutyric acid,
caprylic acid, heptanoic acid, chloroacetic acid,
dîchloroacetic acid, trichloroacetic acid, etc. Pormic
acid, acetic acid, and propionic acid, are preferred
with acetic acid being especially suitable. It is to
be understood that the anhydrides of these acids are
also useful and, for the purposes of the speciication
and claims of this invention, the term acid is intended
to include both the acid per se and the anhydride of
the acid.
Useful alcohols include aliphatic, cycloali-
phatic, and arylaliphatic mono- and polyhydroxy
alcohols. Alcohols having less than about 12 carbons
are especially ussful while the lower alkanols, i.a.,
alkanols having less than about 8 carbon atoms are
preferred for reasons of economy and effectiveness in
the process. Illustrative are the alkanols such as
methanol~ ethanol, isopropanol, n-propanol, isobutanol,
tertiary butanol, isooctanol, dodecanol, n-pentanol,
etc.; cycloalkyl alcohols exemplified by cyclopenta-
thol, cyclohexanol, 4-methylcyclohexanol, 2-cyclohexyl-
ethanol, cyclopentylmethanol, etc.; phenyl aliphatic
.
~ 6~
alkanols such as benzyl alcohol, 2-phenylethanol, and
cinnamyl alcohol; alkylene glycols of up to about 6
carbon atoms and mono-lower alkyl ethers thereof such
as monomethylether of ethylene glycol, diethylene
glycol, ethylene glycol, trimethylene glycol,
hexamethylene glycol, triethy~ene ~lycol, 1,9-butane-
diolO 1,9-cyclohexanediol, glycerol, and pentaery-
thritol.
The use o~ a mixture of ~ater and one or more
of the alcohols is especially effective ~or con~erting
the overbased material ~o colloidal disperse systems.
Such combinations often reduce the length of time
required for the process. Any water-alcohol combin-
ation is effecti~e bu~ a very effecti~e combination is
a mixture of one or more alcohols and water in a weight
ratio of alcohol to water of from about 0.05:1 to about
29:1. Preferably, at least one lower alkanol is
present in the alcohol component of these water-alkanol
mixtures. Water-alkanol mixtures wherein the alcoholic
portion is one or more lower alkanols are especially
suitable.
Phenols suitable for use as conversion agents
include phenol, naphthol, ortho-cresol, para-cresol,
catechol, mixtures of cresol, para-tert-butylphenol,
and other lower al~yl substituted phenols, meta-poly-
isobutene tM.W.-350)-substituted phenol, and the like.
Other useful conversion agents include lower
aliphatic aldehydes and ketones, particularly lower
alkyl aldehydes and lower alkyl ketones such as
acetaldehydes, propionaldehydes, butyraldehydes,
acetone, methylethyl ketone, diethyl ketone. Various
aliphatic, cycloaliphatic, aromatic, and heterocyclic
~LZ~L6~
-30-
amines are also useful providing they contain at least
one amino group having at least one ac~ive hydroyen
attached there~o. Illustrative of these amines are the
mono- and di-alkylamines, particularly mono- and
di-lower alkylamines, such as methylamine, ethylamine,
propylamine, dodecylamine, me~hyl ethylamine, diethyl-
amine; the cycloalkylamines such as cyclohexylamine,
cyclopentylamine, and ~he lower alkyl substituted
cycloalkylamines such as 3-methylcyclohexylamine
1,4-cyclohexylenediamine: arylamines such as aniline,
mono-, di-, and tri-, lower alkyl-substituted phenyl
amines, naphthylamines, l,~-phenylene diamines: lower
alkanol amines such as ethanolamine and diethanolamine;
alkylenediamines such as ethylene diamine, triethylene
tetramine, propylene diamines, octamethylene diamines
and heterocyclic amines such as piperazine, 4-amino-
ethylpiperazine~ Z-octadecyl-imidazoline, and
oxazolidine. Boron acids are also useful conversion
agents and include boronic acids (e.g., alkyl-B(OH)2
or aryl-B(OH2~), boric acid ti.e., H3B03),
tetraboric acid, metaboric acid, and esteLs of such
boron acids.
The phosphorus acids are useful conversion
agents and include the various alkyl and aryl
phosphinic acids, phosphinus acids, phosphonic acids,
and phosphonous acids. Phosphorus acids obtained by
the reaction of lower alkanols or unsaturated hydro-
carbons such as polyisobutenes with phosphorus oxides
and phosphorus sulfides are particularly useful, e.g.,
p305 and pZs5.
Carbon dioxide can be used as the-con~ersion
agent. However, it is preferable to use this conver-
6~ ~
sion agent in combination wi~h one or more of theforegoing conversion agents. Yor example, the
combination o~ water and carbon dioxide is particularly
effective as a conversion agent for transforming the
o~erbased materials into a colloidal disperse system.
As previously mentioned, ~he overbased
materials are single phase homogeneous systems.
However, depending on the reaction conditions and ~he
choice of reactants in preparing the overbased
materials, there some~imes are presen~ in the product
insoluble contaminants. These contaminants are
normally unreacted basic materials such as calcium
oxide, barium oxide, calcium hydroxide, barium
hydroxide, or other metal base materials used as a
reactant in preparing the overbased material. It has
been found that a more uniform colloidal disperse
system results if such contaminants are removed prior
to homogenizing the overbased material with the
conversion agents. Accordingly, it is preferred that
any insoluble contaminants in the overbased materials
be removed prior to converting the material in the
colloidal disperse system. The removal of such
contaminants is easily accomplished by conventional
techniques such as filtration or centrifugation. It
should be understood, ~owever. that the remo~al o~
these contaminants, while desirable for reasons just
mentioned, is not an absolute essential aspect of the
invention and useful products can be obtained when
o~erbased materials containing insoluble contaminants
are converted to the colloidal disperse systems.
The conversion agents or a proportion thereof
may be retained in the colloidal disperse system. The
~2~ 8 r
-32-
conversion agents are, however, not essential
components of these disperse systems and it is usually
desirable that as little of the conversion agents as
possible be retained in the disperse systems. Since
these conversion agents do not react with the overbased
material in such a manner as to be permanently bound
~hereto through some type of chemical bonding, it is
normally a simple matter to remove a major proportion
of the conversion agents and, qenerally, substantially
all of the conversion agents. Some of the conversion
agents have physical proper~ies which make them readily
removable from the disperse systems. Thus, most of the
free carbon dioxide gradually escapes from the disperse
system during the homogenization process or upon
standing thereafter. Since the liquid conversion
agents are generally more volatile than the remaining
components of the disperse system, they are readily
removable by conventional devolatilization techniques,
e.g., heatinq, heating at reduced pressures, and the
like. For this reason, it may be desirable to select
conversion agents which will have boiling points which
are lower ~han the remaining components of the disperse
system. This is another reason why the lower alkanols,
mixtures thereof, and lower alkanol-water mixtures are
preferred conversion agents.
Again, it is not essential that all of the
conversion agent be removed from the disperse systems.
However, from the standpoint of achieving unifcrm
results, it is generally desirable to remove the
conversion agents, particularly where they are
volatile. In some cases, the liquid conversion agents
may facilitate the mixing of the colloidal disperse
-33-
system with the aqueous compositions of the invention.
In such cases, it is advantageous to permit the
conversion agents to remain in the disperse system
until it is mixed with such aqueous compositions.
Therea~ter, the conversion agents can be removed ~rom
such compositions by conventional devolatilization
techniques if desired.
To better illustrate the colloidal disperse
sys~ems utilized in the invention, the procedure for
preparing a preferred system is described below: -
As stated above, the essential materials for
preparing an overbased product are (l) the organic
material to be overbased, (2) an inert, non-polar
organic solvent for the o_ganic material, (3) a metal
base, (4) a promoter, and (5) an acidic ~aterial. In
this example, these materials are (l) calcium petro-
sulfonate, ~2) mineral oil, (3) calcium hydroxide, (4)
a mix~ure of methanol, isobutanol, and n-pentanol, and
(5) carbon dioxide.
A reaction mixture of l~05 grams of calcium
sulfonate having a metal ratio of 2.5 dissolved in
mineral oil, Z20 grams of methyl alcohol, 72 grams of
isobutanol, and 38 grams of n-phenatanol is heated to
35C and subjected to ~he following operating cycle
four times: mixing with 143 grams of 90% calcium
hydroxide and treatinq the mixture with carbon dioxide
until it has a base number of 32-39. The resulting
product is then heated to 155C during a period of nine
hours to remove the alcohols and then filtered at t~is
~emperature. The filtrate is a calcium overbased
petrosulfonate having a ~etal ratio of 12.2.
-34-
A mixture of 150 parts of the foregoing
o~erbased material, 15 parts of methyl alcohol, 1~.5
parts of n-pentanol and 95 parts of water is heated
under reflux conditions at 71-74C for 13 hours. The
mixture becomes a gel. It is then heated to 144C
cover a period of six hours and diluted with 126 parts
of mineral oil having a viscosity of 2000 SUS at 100F
and ~he resul~ing mixture heated at 144C for an
additional 4.5 hours with stirring. This thickened
product is a colloidal disperse system of the type
contemplated by the present in~ention
The disperse systems are characteri~ed by
t~ree essential components: ~1) solid, metal-contain-
inq particles, (2) an inert, non-polar, organic liquid
which functions as the disperse medium, and ~3) an
organic compound which is soluble in the disperse
medium and the molecules of which are characterized by
a hydrophobic portion and at least one polar substi-
tuent. In the colloidal disperse system described
immediately above, these components are as follows:
(1) calcium carbonate in the form of solid particles,
(2) mineral oil, and (3) calcium petrosulfonate.
From the foregoing example, it is apparent
that the sol~ent for the material which is overbased
becomes the colloidal disperse medium or a component
thereof. Of course, mixtures of other inert liquids
can be substituted for the mineral oil or used in
conjunction with the mineral oil prior to forming the
o~erbased material.
It is also readily seen that the solid,
metal-containing particles possess the same chemical
composition as would the reaction products of the metal
~L26~6~ ~
-35-
base and ~he acidic material used in preparing the
overbased materials. Thus, the actual chemical
identity of the metal-containing particles depends upon
both the particular metal base or bases employed and
the particular acidic material or materials reacted
therewith. For sxample, if the metal base used in
preparing the overbased material were barium oxide and
if the acidic material was a mixture of formic and
acetic acids, the metal-con~aining particles would be
barium formates and barium aceta~es.
However, the physical characteristics of the
metal-containing particles formed in the conversion
step are quite different from the physical character-
istics of any particles present in the homocleneous,
single-phase overbased material which is su~iected to
the conversion. Particularly, such physical charac~er-
istics as particle size and structure are quite
different. The solid, metal-containing particles of
the colloidal disperse systems are of a size sufficient
for detection by X-ray diffraction. The overbased
material prior to conversion are not characterized by
the presence of these detectable particles.
X-ray diffraction and electron microscope
studies have been made of both overbased organic
materials and colloidal disperse systems prepared
therefrom. These studies establish the presence in the
disperse systems of the solid metal-containing salts.
For example, in the disperse system prepared herein
above, the calcium car~onate is present as solid
calcium carbonate having a particle size of about 40 to
A. Sunit particle size) and interplanar spacing
(dA.) of 3.035. But X-ray diffraction studies of the
r ~2l6~
-36-
overbased material from which it was prepared indicate
~he absence of calcium carbonate of ~his type. In
fact, calcium carbonate present as such, if any,
appears to be amorphous and in solution. While not
wishing to be bound by theor~y, it appears that
conversion permits particle formation and growth. That
is, the amorphous, metal-coneaining apparently
di~solved ~alts or complexes present in the overbased
material form solid, metal-containing particles which
by a process of particle growth become colloidal
particles. Thus, in the abo~e example, ~he dissolved
amorphous calcium carbonate salt or complex is
transformed into solid particles which then "grow". In
this example, they grow to a size of gO to 50 A. In
many cases, these particles apparently are crystal-
lites. Reqardless oP the correctness of the postulated
mechanism for particle formation the fact remains that
no particles of the type predominant in the disperse
systems are found in the overbased materials from which
they are prepared. Accordingly, they are unquestion-
ably formed during conversion.
As these solid metal-containing particles
formed come in~o existence, they do so as pre-wet,
pre-dispersed solid particles which are inherently
uniformly distributed throughout the other components
of the disperse sys~em. The liquid disperse medium
containing these pre-wet dispersed particles is readily
incorporated into the compositions and drilling fluids
of the invention thus facilitating the uniform distri-
bution of the particles throughout such compositions
and drilling fluids. This pre-wet, pre-dispersed
character of the solid metal-containing partic}es
~L26~08
-37-
resulting from their forma~ion is, thus, an important
feature of the disperse systems.
In the foregoi~g example, ~he third component
of the disperse system (i.e., the organic compound
which is soluble in ~he disperse medium and which is
characterized by molecules having a hydrophobic portion
and a polar substituent) is calcium petrosul~onate,
O O
~ 1 - S - O - Ca - - I R
O O
wherein Rl is the residue of the petrosulfonic acid.
In this case, the hydrophobic portion of the molecule
is the hydrocarbon moiety of petrosulfonic, i.e.,
-Rl. The polar substituent is the metal salt moiety,
O O
- S O - Ca - O S -
11 11
O o
The hydrophobic portion of the organic
compound is a hydrocarbon radical or a substantially
hydrocarbon radical containing at least about 12
aliphatic carbon atoms. Usually the hydrocarbon
portion is an aliphatic or cycloali~hatic hydrocarbon
radical although aliphatic or cycloaliphatic substi-
tuted aromatic hydrocarbon radicals are also suitable.
In other words, the hydrophobic portion of the organic
compound is the residue of the organic material which
is overbased minus its polar substituents For
example, if the material to be overbased is a carbox-
~6~6~
-3a-
-
ylic acid, sulfonic acid, or phosphorus acid, the
hydrophobic portion is the residue of these acids which
would result from the removal of the acid functions.
Similarly, if the material to be overbased is a phenol,
a nitro-substituted polyolefin, or an amine, tbe
hydrophobic portion of the oryanic compound is the
radical resulting from the remo~al of the hydroxyl,
nitro, or amino group respectively. It is the
hydrophobic portion of the molecule which renders the
organic compound soluble in the solvent used in the
overbasing process and later in the disperse medium.
Obviously, the polar portion of these organic
compounds are the polar substituents such as the acid
salt moiety discussed above. When the material to be
overbased contains polar substituents which will react
with the basic metal compound used in overbasing, for
example, acid groups such as carboxy, sulfino, hydroxy-
sulfonyl, and phosphorus acid groups or hydroxyl
groups, the polar substituent o~` the third component is
the polar group formed from the reaction. Thus, the
polar substituent is the corresponding acid metal salt
group or hydroxyl group metal derivative, e.g., an
alkali or alkaline earth metal sulfonate, carboxylate,
sulfinate, alcoholate, or phenate.
On the other hand, some of the materials to be
overbased contain polar substituents which ordinarily
do not react with metal bases. These substituents
include nitro, amino, ketocarboxyl, carboalkoxy, etc.
In the disperse systems derived from overbased
materials of this type the polar substituents in the
third component are unchanged from their identity in
the material which was originally overbased.
f~ 6~8
-3~-
The identity of the third essential component
of the disperse system depends upon the identity of the
starting materials (i.e., the material to be overbased
and the metal base compound) used in preparing the
overbased material. Once the identity of these
starting materials is known, the identity of the third
component in the colloidal disperse system is
automatically established. Thus, from the identity of
the original material, the identity of the hydrophobic
por~ion of the ~hird component in the disperse system
is readily established as being the residue o~ that
material minus the polar substituents attached
thereto. The identity of the polar substituents on the
third component is established as a matter of
chemistry. If the polar groups on the material to be
overbased undergo reaction with the metal base, for
example, if they are acid functions, hydroxy groups,
etc., the polar substituent in the final product will
correspond to the reaction product of the original
substituent and the metal base. On the other hand, if
the polar substituent in the material to be overbased
is one which does not react with me~al bases, then the
p~lar substituent of the third component is the same as
the original substituent.
As previously mentioned, this third component
can orient~itself around the metal-containing particles
to form micellar colloidal particles. Accordingly, it
can exist in the disperse system as an indi~idual
liquid component dissol~ed in the disperse medium or it
can be associated with the metal-containing particles
as a component of micellar colloidal particles.
~26~
--40--
-
Examples 1-66 illustrate ~arious o~erbased
materials and colloidal disperse systems prepared from
these ove~based materials. Unless otherwise indicated,
I'percentages~ and "parts" refer to percent by weight
and parts by weight. Where ~emperatures exceed the
boiling points of the components of the reaction
mixture, obviously reflux conditions are employed
unless the reaction products are being heated to remove
~olatile components.
~ xamples 1 through 23 are directed to the
prepara~io~ of Newtonian oYerbased materials illus-
trative of the types which can be used to ~repare
non-Newtonian colloidal disperse systems. The term
"naphtha" as used in the following examples refers to
petroleum distillates boiling in the range of about
90C to about 150C and usually designated Varnish
Maker's and Painter's Naphtha.
Example 1
To a mixture of 3,24s parts (12.5 eguivalents)
of a mineral oil solution of barium petroleum sulfonate
(sulfate ash of 7.6%), 32.~ pa~ts of octylphenol, 197
parts of water, ~here is added 73 parts of barium oxide
within a period of 30 minutes at 57-84C. The mixture
is heated at lOO~C for one hour to remove substantially
all water and blown with 75 parts o~ carbon dioxide at
13~ to 170C within a period of three hours. A
mixture of 1,000 parts of the above carbonated
intermediate product~ lZ1.8 parts of octylphenol, and
234 parts of barium hydroxide is heated at 100C and
then at 150C for one hour. The mixture is then blown
with carbon dioxide at 150C for one hour at a rate of
3 cubic feet per hour. The carbonated product is
~2~ 8
_ -41
filtered and the filtrate has a sulfate ash content of
39.8% and a metal ratio of 9.3
I:xample ?
To a mixture of 3,245 parts (12.5 equivalents)
of barium petroleum sulfonate, 1,460 parts (7.5
eguivalents) of heptylphenol, and 2,100 parts of water
in 8,0~5 parts of mineral oil there is added at 180C
7,400 par~s (96.5 equivalents) oE barium oxide. The
addition of barium oxide causes the temperature to rise
to 143C which temperature is maintained until all the
water has been distilled. The mixture is ~hen blown
with carbon dioxide until it is substantially neutral.
The product is diluted with 5,695 par~s of mineral oil
and filtered. The filtrate has a barium sulfate ash
content of 30.5% and a metal ratio of 8.1.
Example 3
A mixture of 1,285 parts (1.0 equivalent) of
90% barium petroleum sulfonate and 500 milliliters
(12.5 eguivalents) of methanol is stirred at 55-60C
while 301 parts (3.9 equivalents) of barium oxide is
added portion-wise over a period of one hour. The
mixture is stirred an additional two hours at 45-55C,
then ~reated with carbon dioxide at 55-65C for two
hours. The resulting mixture is freed of methanol by
heating to 150C. The residue is filtered t~rough a
siliceous filter aid, the clear. brown filtrate
analyzing as: sulfate ash, 33.2%: slightly acid: metal
ratio, ~.7.
Example 4
(a) To a mixture of 1,145 parts of a mineral
oil solution of a 40% solution of barium mahogany
sulfona~es (1.0 eguivalent~ and 100 parts of methyl
. .
~616al~` ~
- -42-
alcohol àt 55C, there is added Z20 parts of barium
oxide while the mixture is being blown with carbon
dioxide at a rate of 2 to 3 cubic feet per hour. To
this mixture there is added an additional 78 parts of
methyl alcohol and then ~6~ parts of barium oxide while
the mixture is blown with carbon dioxide. The
carbona~ed product is heated to 150C for one hour and
filtered, The fil~rate has a barium sulfate ash
conten~ o~ 53.a% and a metal ratio of ~.9.
~ b) A carbonated basic metal salt is prepared
in accordance with ~he procedure of (a) except that a
total of 16 equivalents of barium oxide is used per
equivalent of the barium mahogany sulfonate. The
product has a metal ratio of 13.4.
Example 5
- A mixture of 520 parts of a mineral oil, 480
parts of a sodium petroleum sulfonate (molecular weight
of 480), and 8~ parts of water is heated at 100C for
four hours. The mixture is then heated with 86 parts
of a 76% aqueous solution of calcium chloride and 72
parts of lime (90% purity) at 100C for two hours,
dehydrated by heating to a water content of less than
0.5%, cooled to 50OC, mixed wi~h 130 parts of methyl
alcohol, and then blown with carbon dioxide at 50C
until substantially neutral. The mixture is then
heated to 150C to remove the methyl alcohol and water
and the resulting oil solution of the basic calcium
sulfonate filtered. The filtrate is found to have a
calcium sulfate ash content of 16% and a metal ratio of
2.5.
A mixture of 1,305 par~s of the above
carbonated calcium sulfonate, 930 parts of mineral oil,
, -43--
.
220 parts of methyl alcohol, 72 parts o~ isobutyl
alcohol, and 38 parts of primary amyl alcohol is
prepared, heated to 3~C, and subjec~ed ~o the
following operating cycle four times: mixing with 143
parts of 90% calcium hydroxide and treating the mixture
with carbon dioxide until it has a base number of
32-39. The resulting product is then beated to 155C
during a period of nine hours to remove the alcohols
and filtered through a siliceous filter aid at this
temperature. Tha fil~rate has a calcium sulfate ash
content of ~9.5~ and a metal ratio of 12.2.
Example 6
A basic me~al salt is prepared by the
procedure described in Example 5 except that the
slightly hasic calcium sulfonate having a metal ratio
of 2.5 is replaced with a mixture of that calcium
sulfonate (280 parts) and tall oil acid (970 parts
having an equivalent weiqht of 340) and that the total
amount of calcium hydroxide used is 930 parts. The
resulting highly basic metal salt of the process has a
calcium sulfate ash content of 48~, a metal ratio of
7.7, and an oil content of 31~.
Example 7
A highly basic metal salt is prepared by the
procedure of Example 5 except that the slightly basic
calcium sulfonate starting material ha~ing a metal
ratio of Z.5 is replaced with tall oil acids (1,250
parts ha~ing an equi~alent weight of 390) and the total
amount of calcium hydroxide used is 772 parts. The
resulting highly ~asic metal salt has a metal ratio of
5.2, a calcium sul~ate ash content of 41%, and an oil
content of 33%.
~26~
-44-
Example 8
A normal cal~ium mahogany sulfonate is
prepared by meta~hesis of a 60% oil solution of sodium
mahogany sulfonate (750 parts) with a solution of 67
parts of calcium chloride and 63 parts of water. The
reactîon mass is heated Por four hour~ at gO to lOO~C
to effect the conversion of the sodium mahogany
sulfonate to calcium mahogany sulfonate. Then 54 parts
of lime is added and the whole is heated to 150C over
a period of five hours. ~hen the whole has cooled to
40C, g8 parts of methanol is added and 152 parts of
carbon dioxide i5 introduced over a period of Z0 hours
at 42-43C. Water and alcohol are then removed by
heating the mass to 150C. The residue in the reaction
vessel is diluted with loo parts of low Yiscosity
mineral oil. The filtered oil solution of the desired
carbonated calcium sulfonate o~erbased material has the
following analysis: sulfate ash content, 16.42
neutralization number, 0.6 (acidic); and a metal ratio
of 2.50. By adding barium or calcium oxide or
hydroxide to this product with subsequent carbonation,
the metal ratio can he increased to a ratio of 3.5 or
greater as desired.
Example 9
A mixture comprisinq 1,595 parts of the
overbased material of Example 7 (1.54 equivalents based
on sulfonic acid anion), 167 parts of the calcium
phenate prepared as indicated below (0.19 equivalent~,
616 parts of mineral oil, 157 parts of 91% calcium
hydroxide (3.86 equivalents~, 288 parts of methanol. 88
parts of isobutanol, and 56 parts of mixed isomeric
primary amyl alcohols ~containing about 65~ normal
-g5-
amyl, 3~ isoamyl and 32~ o~ 2-methyl-1-~utyl alcohols)
is s~irred vigorously at ~onc and 25 parts of carbon
dioxide is introduced over a period of two hours at
40-50C. Thereafter, three additional portions o
calcium hydroxide, each amounting to 157 parts, are
added and each such addition is followed by the
introduction of carbon dioxide as previously
illustrated. After the fourth calcium hydroxide
addition and the carbonation step is completed, the
reaction ~ass is carbonated for an additional hour at
4~-47C ~o reduce neutralization number of the mass to
.0 (basic). The substantially neutral, carbonated
reaction mixture is freed from alcohol and any water
reaction by heating to 150C and simultaneously blowing
it with nitrogen. The residu~ in the reaction vessel
is filtered. The filtrate, an oil solution of the
desired substantially neutral, carbonated calcium
sulfonate overbased material of high metal ratio, shows
the following analysis: sulfate ash content, 41.112
neutralization number 0.9 (basic); and a metal ratio of
12.55.
The calcium phenate used above is prepared by
adding 2,Z50 parts of mineral oil, 960 parts (5 moles~
of heptylphenol, and 50 parts of water into a reac~ion
~essel and stirring at 25C. The mixture is heated to
40C and 7 parts of calcium hydroxide and 231 parts t7
moles) of 91% commercial paraformaldehyde is added over
a period of one hour. The whole is heated to 80OC and
200 additional parts of calcium hydroxide (making a
total of 207 parts or 5 moles) is added over a period
of one hour at 80-90C. The whole is heated to 150C
and maintained at that temperature for 12 hours while
126~L6~
-~6-
nitrogen is blown ~hrough the mixture to assist in the
removal of water. If foaming is encountered, a few
drops of polymerized dimethyl silicone foam inhibitor
may be added to control the foaming. The reaction mass
is then fil~ered. The filtrate, a 33.6~ oil solution
of the desired calcium phenate of heptylphenol-ormal-
dehyde condensation product is found to contain 7.56%
sulfate ash.
ExamPle 10
A mixture of 574 parts (0.5 equivalents~ of
40% barium petroleum sulfonate, 98 parts (1.0 eguiv-
alent~ of furfuryl alcohol. and 762 parts of mineral
oil is heated with stirring at 100C for an hour. then
treated portionwise over a 15-minute period with Z30
parts (3.0 equivalents~ of barium oxide. During t~is
latter period, the temperature rises to 120C (because
of the exothermic nature of the reaction of barium
oxide and the alcohol). The mixture then is heated to
1~0-160C for an hour, and treated subsequently at
this te~perature for 1.5 hours with carbon dioxide.
The materials concentrated by heating to a temperature
of 150C at a pressure of 10 mm. ~g. and ~hereafter
filtered to yield a clear, oil-soluble filtrate having
the following analysis: sulfate ash content, 21.~
neutralization number, 2.6 (basic): and a metal ratio
of 6.1.
Example 11
To a mixture of 1,614 parts (3 equivalents) of
a polyisobutenyl succinic anhydride (prepared by the
reaction of a chlorinated polyisobutene having an
average chlorine content of 4.3% and an average of 67
carbon atoms with maleic anhydride at about 200~C~,
~2~
-~7-
4, 13 parts of mineral oil, 3~5 parts (1.8 equivalents)
of heptylphenol, and 200 parts of water, at 80~C, there
is added 1,038 parts (2~.7 equivalents) of lithium
hydroxide monohydrate over a period of 0.75 hour while
heating to 105C. Isooctanol (75 parts) is added while
the mixture is heated to 150C over a 1.5-hour period.
The mixture is maintained at 150--170C and blown with
carbon dioxide at a rate of four cubic ~eet per hour
for 3.5 hours. The reaction mixture is filtered
through a filter aid and the filtrate is the de~ired
product having a sulfate ash content of 1~.9% and a
metal ratio of 8Ø
Example 12
A mixture of 244 parts (0.87 equivalentl f
oleic acid, 180 parts of primary isooctanol, and ~00
parts of mineral oil is heated to 70C whereupon 172.6
parts ~2,7 equivalents) of cadmium oxide is added. Tbe
mixture is heated for three hours at a temperature of
150 to 160C while removing water. Barium hydroxide
monohydrate (324 parts, 3.39 equivalents) is then added
to the mixture over a period of one hour while contin-
uing to remove water by means of a side-arm water
trap. Carbon dioxide is blown through the mixture at a
temperature of from 150-160C until the mixture is
sli~htly acidic to phenolphthalein. Upon completion of
the carbonation, the mixture is stripped to a temper-
ature of 150C at 35 mm. Hg. to remove substantially
all the remaining water and alcohol. The residue is
the desired overbased product containing both barium
and cadmium metal.
~L2~66~8
-48-
Example 13
The procedure of Example 10 is repeated except
that ~he barium sulfonate is replaced by an equivalent
amount of potassium sulfonate, and potassium oxide is
used in lieu of the barium oxide resulting in the
preparation of the corresponding potassium overbased
ma~erial.
Exampls 14
To a mixture of 423 parts (1.0 equivalent) of
sperm oil, 124 parts (0.6 equivalent) of heptylphenol,
500 parts of mineral oil, and 150 parts of water there
are added 308 parts (4.0 equi~alents~ of barium oxide.
The ~emperature of ~he mixture is 70C during such
addition. This mixture is heated at reflux temperature
for one hour, dried by ~eating at about lsooc and
thereafter carbonated by treatment with carbon dioxide
at the same ~emperature until the reaction mass was
slightly acidic. Filtration yields a clear, light
brown, non-viscous overbased liquid material having the
following analysis: sulfate ash content, 32.0~;
neutralization number 0.5 (basic) metal ratio, ~.5.
Example 15
A mixture of 6000 par~s of a 30% solution of
barium petroleum sulfonate (sulfate ash 7.6~), 348
parts of paratertiary butylphenol, and Z,911 parts of
water are heated to a temperature 60C while slowly
adding 1,100 parts of barium oxide and raising the
temperature to 94-98C. The temperature is held
within this range for about one hour and then slowly
raised over a period of 7.5 hours to 150C and held at
this level for an additional hour assuring -substantial
removal of all water. The resulting overbased material
66~
-49-
is a brown liguid having the following analysis:
sulfate ash content, 26.0%; metal ratio, 4.35.
This product is then treated with SOz until
327 parts of the mass combined with the overbased
material. The product thus obtained has a neutral-
ization number of zero. The SO2-treated material is
liquid and brown in color.
1000 par~s of the SOz-treated overbased
material producea according to the preceding paragraph
is mixed with 286 parts of water and heated to ~
temperature o~ about 60C. Subsequently, 107.5 parts
of barium oxide are added slowly and the temperature is
maintained at 9~-98C for one hour. Then the total
reaction mass is heated ~o 150C over a 1-1~16-hour
period and held there for a period of one hour. The
resulting o~erbased ma~erial is purified by iltration,
the filtrate being a brown, liquid overbased material
having the following analysis: sulfate ash content,
33.7%; basic number, 38.6; metal ratio, 6.3.
- Example 16
~ a) A polyisobutylene having a molecular
weight of 700-800 is prepared by the aluminum
chloride-catalyzed polymerization of isobutylene a~
0-30C, is nitrated with a 10~ excess (1.1 moles) o~
70% agueous nitric acid at 70-75C for four hours.
The volatile components of the product mixture are
removed by hea~ing to 75C at a pressure of 75 mm.
Hg. To a mixture of 151 parts (0,19 equivalent) of
this ni~rated polyisobutylene, 113 parts (0.6
equivalent) of heptylphenol, 155 parts of water, and
2,057 parts of mineral oil there is adaed 612 parts (8
equivalents) of barium oxide. The mixture is at 70OC
:L;26~
-50-
during such addition. This mixture is hea~ed at 150C
for an hour, then treated with carbon dioxide at this
same temperature until the mixture is neutral (phenol-
phthalein indicator; ASTM D-97~-53T procedure at 25C;
a measurement of the degree of conversion of the metal
reactant, i.e., barium oxide, bicarbona~ion). The
product mixture is filtered ancl filtrate has the
followin~ analysis: sulfate ash content, 27.6S;
percent N, 0006; and metal ratio, 9.
(b) A mixture of 611 parts ~0.75 mole) of the
nitrated polyisobu~ylene of part (a), 96 parts (0.095
mole) of heptylphenol, 2,104 parts of mineral oil, 188
parts of water and 736 parts ~4.8 moles) of barium
oxide is heated at reflux temperature Xor one hour.
The water is vaporized and carbon dioxide passed into
the mixture at 150C until the mixture is no longer
basic. This carbonated mixture is filtered and the
clear fluid filtrate has the following analysis:
~ulfate ash content, 26.3% percent N, 0.15; base
number 2.4; metal ratio 6.7.
Exam~le 17
A mixture of 630 parts (2 e~uivalents~ of a
rosin amine ~consisting essentially of deh~droabietyl
amine) having a nitrogen content of 44% and Z45 par~s
~1.2 equi~alents) of heptylphenol ha~ing a hydroxyl
content of 8.3% is heated to gooc and thereafter mixed
with 230 parts (3 equivalents) of barium oxide at
90-140C. The mixture is purged with nitrogen at
140C. A 600-part portion is diluted with 400 parts o~
~ineral oil and filtered. The filtrate is blown with
carbon dioxide, diluted with benzene, heated to remove
the benzene, mixed with xylene, and filtered. The
-51-
filtrate, a 20% xylene solution of the product, has a
barium sulfate ash content of 25.1%, a nitrogen content
of 2%, and a reflux base number of 119.
The term ~reflux base number~' refers to the
basicity of tbe metal composition and is expressed in
terms of milligrams of ~OH which a~e eguivalent to one
gram of the composition.
Example la
To a mixture of 40~ parts (2 eguivalents~ of
heptylphenol having a hydroxy con~ent of 8.3~ and 264
parts o xylene there is added 383 parts (5 eguiva-
lents) of barium oxide in small increments at 850-
110C. Thereafter, 6 parts of water are added and the
mixture is carbonated at 100-130C and filtered. The
filtrate is heated to lOO~C and diluted with xylene to
a 25~ xylene solution. This solu~ion has a bar;um
sulfate ash content of 41% and a reflux base number of
137.
ExamPle 19
A mixture of alkylated benzene sulfonic a~ids
and naphtha is prepared by adding 1,000 parts of a
mineral oil solution of the acid containing 18~ by
weight mineral oil (1.44 equivalents of acid) and 222
parts of naphtha. ~hile stirring the mixure, 3 parts
of calcium chloride dissolved in 90 parts of wa~er and
53 parts of Mississippi lime (calcium hydroxide) is
added. This mixture is heated to 97-99C and held at
this temperature for 0.5 hour. Then 8D parts of
Mississipei lime are added to the reaction mixture with
stirring and nitrogen ~as is bubbled therethrough to
remove water, while heating to 150C over a three-hour
period. The reaction mixture is then cooled to 500C
~2~
-52-
and 170 parts of methanol are added. The resulting
mixture is blown with carbon dioxide at a rate of two
cubic feet per hour until substan~ially neutral. The
carbon dioxide blowing is discontinued and the water
and methanol are stripped from the reaction mixture by
heating and bubbling ni~rogen gas therethrough. ~hile
heating to remo~e the water and methanol, the tem~er-
ature rose to 146C over a 1.75-hour period. At this
point the metal ratio of the overbased material is ~.5
and the product is a ~lear, dark-brown viscous liquid.
This material is permit~ed to cool to 50~C and
thereafter 1,256 parts thereof are mixed with 57~ parts
o~ naphtha, 222 parts o~ methanol, 496 parts of
Mississippi lime, and 111 parts of an equal molar
mixture of isobutanol and amyl alcohol. The mixture is
thoroughly stirred and carbon dioxide is blown there~
through at the rate of two cubic feet per hour for 0.5
hour. An additional lZ4 parts of Mississippi lime are
added to the mixture with stirrinq and the Co2
blowing continued. Two additional 124-part increments
of Mississippi lime are added to the reaction mixture
while continuing the carbonation. Upon the addition of
the last increment, carbon dioxide is bubbled through
t~e mixture for an additional hour. Thereafter, the
reaction mixture is gradually heated to about 1~6~C
over a 3.25-hour period while blowing the nitrogen to
remove water and methanol from the mixure. Thereafter,
the mixture is permitted to cool to room temperature
and filtered producing 1,895 parts of the desired
overbased material having a metal ratio of 11.3 The
material contains 6.8~ mineral oil, 4.18% of the
isobutanol-amyl alcohol and 30.1% naphtha.
r ~ ial8
-53-
, .
~m~
1274 parts of methanol, 11.3 parts of calcium
chloride and 90.6 parts of ~ap water are added to a
resin reactor equipped with a heating mantle, thermo-
couple, gas inlet tube, condenser and metal stirrer.
The mixture is heated to 48C with stirring, 257.~
parts of Silo lime (calcium hydroxide) are added to
provide a slurry. 2,~30 parts of alkylated benzene
sulfonîc acid are added to the whole over a period of
on~ hour. The temperature of the whole rises to 53C.
2,510 parts of SC Solvent 100 (a high-boiling alkylated
aromatic solvent supplied by Ohio Solvents) are added.
The whole is stirred for 0.5 hour. ~hree increments of
709.1 parts each of Silo lime are added ~o the whole
and carbon dioxide at a rate of five cubic feet per
hour is bubbled through the whole after each incre-
ment. Total blowing with carbon dioxide i6 approxi-
mately seven hours with the temperature of the whole
varying from 40 to 55C. The reactor is equipped with
a trap. Methanol and water are stripped from the whole
by bubbling nitrogen at a rate of two cubic feet per
hour through the whole over a 12-hour period while
maintaining the temperature of ~he whole at 155C. The
whole is held at a temperature of 155C for 15 minutes,
and then cooled to room temperature. The whole is
filtered through a Gyro Tester clarifier. The solids
content is adjusted to 70~ solids with SC Solvent loo.
Example 21
A mixture of 406 parts of naphtha and 21~
parts of amyl alcohol is placed in a three-liter flask
equipped with reflux condenser, gas inlet tubes, and
s~irrer. The mixure is stirred rapidly while heating
~ 269.~
-59-
~o 38OC and adding 27 parts of barium oxide. Then 27
parts of water are added slowly and the temperature
rises to s5Oc. stirring is maintained while adding 73
parts of oleic acid over a 0.25-hour period. The
mixture is heated to 95C with continued mixing,
Heating is discontinued and 523 parts of barium oxide
are slowly added to the mixture. The temperature rises
to aboul 115C and the mixture is permitted to cool to
90C whereupon 67 parts of water are slowly added to
the mixture and the temperature rises to 107C. The
mixture is then heated within the range of 107-120C
to remove water over a 3.3-hour period while bubbling
nitrogen through the mass. Subsequently, 427 parts of
oleic acid are added over a 1.3-hour period while
maintaining a temperature o 120-125C. Thereafter
heating is terminated and 236 parts of naphtha are
added. Carbonation is commenced by bubbling carbon
dioxide through the mass at two cubic feet per hour for
1.5 hours during which the temperature is held a~
108-117C. The mixture is heated under a nitrogen
purge to remo~e water. The reaction mix~ure is
filtered twice producing a filtrate analyzing as
follows: sulfate ash content, 34.42%; metal ratio,
313. The filtrate contains 10.7% amyl alcohol and 32%
naphtha.
Example 22
A reaction mixture of 1,800 par~s of a calcium
overbased petrosulfonic acid containing Zl.7% mineral
oil and 36.14% naphtha, ~26 parts naphtha, 255 parts of
msthanol, and 127 parts of an equal molar mixture of
isobutanol and amyl alcohol are heated to-45C under
reflux conditions and 148 parts of Mississippi lime
~26~16~ ~
-55-
(commercial calcium hydroxide) are added thereto. The
reaction mass is then blown with carbon dioxide at a
rate of two cubic feet per hour and thereafter 148
parts of additional Mississippi lime are added.
Carbonation is continued for another hour at the same
rate. Two addi~ional 197-part increments of Missis-
sippi lime are added to the reaction mixture, each
increment followed by about a one-hour carbonation
prscess. Thereafter, the reaction mass is heated to a
temperature of 138C while bubbling nitrogen thece-
through to remove water and methanol. After filtra-
tion, 2,2~0 parts of a solution of the dispersed barium
overbased petrosulfonate acid is obtained having a
metal ratio of 12.2 and containing 12.5% mineral oil,
34.15% naphtha, and 4.03% of the isobutanol-amyl
alcohol mixture.
Example Z3
A mixture of 1000 parts of a 60% mineral oil
solution of sodium petroleum sulfonate (having a
sulfated ash content of about 8.5%) and a solution of
71.3 parts of 96% calcium chloride in 84 parts of water
is mixed at 100C for 0.25 hour. Then 67 parts of
hydrated lime is added and the whole is heated at 100C
for 0.25 hour then dried by heating to 145C to remove
water. The residue is cooled and adjusted to 0.7%
water content. 130 parts methanol are added and the
whole is blown with carbon dioxide at 45-50C until i~
is substantially neutral. Water and alcohol are
removed by heating the mass to 150C and the resulting
oil solution is filtered. The resulting product is
carbonated calcium sulfonate overbased material
containing 4.78% calcium and a metal ratio of 2.5.
~263lS~315 gr
,,
-56-
A mixture of 1000 parts of the above
carbonated calcium sulfonate overbased material, ~16
parts of mineral oil, 176 parts o~ methanol, 58 parts
of isobutyl alcohol, ~0 parts of primary amyl alcohol
and 52.6 par~s o~ the calcium phenate of Example 8 is
prepared, heated to 35C, and sublected to tbe follow-
ing opera~ing cycle four times: mixing with 93.6 parts
of ~7,3~ calcium hydroxide and ~reating the mixture
with carbon dioxide until it has a base number of
35-45. The resulting product is heated to 150C and
simultaneously blown with nitrogen to remove alcohol
and water, and then filtered. The filtrate has a
calciurn content of 12.0% and ~ metal ratio of 12.
Examples 1-23 illustrate various means for
preparing overbased materials suitable for use in
conversion to the non-Newtonian colloidal disperse
systems utilized in the present invention. Obviously,
it is wi~hin the ~kill of the art to vary ~hese
examples to produce any desired overbased material.
Thus, other acidic materials such as mentioned here-
before can be substituted for the acidic materials used
in the above examples. Similarly, other metal bases
can be employed in lieu of the metal base used in any
given example, or mixtures of bases and/or mixtures of
materials which can be overbased can be utilized.
Similarly, the amount of mineral oil or other non-
polar, inert, organic liquid used as the overbasing
medium can be ~aried widely both during overbasiDg and
in the overbased product.
Examples 24-66 illustrate the conversion of
Newtonian overbased materials into non-Newtonian
colloidal disperse systems by homogenization with
conversion agents.
~:Z6~ 8
-57-
Example 24
To 733 parts of the overbased material of
Example ~(a), there is added 179 parts of acet;c acid
and 275 parts of a mineral oil (having a viscosity of
2000 SUS at 1000F) at 90C over a period of 1.5 hours
with vigorous agitation. The mixture is then homo-
genizecl at 150C for two hours and the resulting
material is the desired colloidal disperse system.
Example 25
A mixture oP 960 parts of the overbased
material of Example 4(b), 2s6 parts of acetic acid, and
200 parts of a mineral oil (having a viscosity of 2000
SUS at 100C) is homogenized by vigorous stirring at
150C for two hours. The resulting product is a
non-Newtonian colloidal disperse system of the type
contemplated for use by the present invention.
The o~erbased material of Examples 24 and 25
can be con~erted without the addition of additional
mineral oil or if another inert organic liquid is
substituted for the mineral oil.
Example 26
A mixture of 150 parts of the overbased
material of Example 5, 15 parts of methyl alcohol, 10.5
parts of amy~ alcohol, and 45 parts of water is heated
under reflux conditions at 71-79C for 13 hours
whereupon the mixture gels. The gel is hea~ed for six
hours at 144C. diluted with 126 parts of the mineral
oil. The diluted mixture is heated to 144~C for an
additional 4.5 hours. The resulting thickened product
is a colloidal disperse system. Again, it is not
necessary that the material be diluted with-mineral oil
in order to be useful.
601~ ~
-58-
Example 27
A mixture of 1000 parts of the product of
Example 9, ao part~ of methanol, 40 parts of mixed
primary amyl alcohols (containing about 65% normal amyl
alcohol, 3% isoamyl alcohol, and 32% of 2-methyl-1-
butyl alcohol) and 80 parts of water are added to a
reaction vessel an~ heated ~o 70C and maintained at
that temperature for 4.2 hours. The overbased material
is converted to a gelatinous mass, the latter is
stirred and heated at 150C for a period of about two
hours to remove subs~antially all the alcohols and
water. The residue is a dark-green gel.
- Example 2~
The procedure of Example 27 is repeated except
that 120 parts of water is used to replace the water-
alkanol mixture employed as the conversion agent
therein. Conversion of the Newtonian overbased
material into the non-Newtonian colloidal disperse
system reguires about five hours of homogenization.
The disperse system is in the form of a gel.
Example ~9
To 600 parts of the overbased material of
Example 5, there is added 300 parts of dioctyl-
phthalate, 48 parts of methanol, 36 parts of isopropyl
'alcohol, and ~6 parts of watar. The mixture is heated
~o 70-77C and maintained at this temperature for four
hours during which the mixture becomes more viscous.
The viscous solution is then blown with carbon dioxide
for one hour until substantially neutral to phenol-
phthalein. The alcohols and water are removed by
heating to approximately 150C. The residue is the
desired colloidal disperse sys~em.
~'
~:26~60~3 ~
--59--
.
Example 30
To 800 parts of the overbased material Q~
Example 5, there is addea 300 parts of kerosene, 120
parts of an alcohol-wa~er mixture comprising 64 parts
of methanol, 32 parts of water and 32 parts of primary
amyl alcohol. The mixture is heated to 75~C and
maintained at this temperature for two hours during
which time the viscosity of the mix~ure increases. The
water and alcohols are removed by heating ~he mixture
to about 150C while blowing with nitrogen for one
hour. The residue is the desired colloidal disper~e
system having the consistency of a gel.
Example 31
mixture of 340 parts of the product of
Example 5, 68 parts of an alcohol-water solution (the
alcohol-water solution consisting of 27.2 parts of
methanol, Zo.~ parts of isopropyl alcohol and 20.4
parts of water), and 170 parts of heptane is heated to
65~C. During this period, the viscosi~y of the mixture
increases from an initial value of 6,250 to 54,000.
The thickened colloidal disperse system is
further neutralized by blowing the carbon dioxide at
the rate of f ive pounds per hour for one hour. The
resulting mass has a neutralization number of 0.87
~acid to phenolphthalein indicator).
Example 3Z
The procedure o~ Example 31 is repeated except
tha~ the calcium overbased material of Example 5 is
replaced by an equivalent amount of the cadmium and
barium overbased material of Example 12. Xylene (200
parts~ is used in lieu of the heptane and the further
carbonation step is omitted.
6~6al8
. ~o
Example 33
A mix~ure of 500 parts o the overbased
material of Example 5, 31Z parts of ~erosene, 40 parts
of met~ylethyl ketone, Z0 parts of isopropyl alcohol,
and 50 parts of water is prepared and heated to 75C.
The mixture is maintained a~ a temperature of 70-75C
for five hours and then heated ~o 150C to remove the
vola~ile components. The mix~ure is thereafter blown
with ammonia for 30 minutes to remove most of the final
traces of volatile materials and thereafter permitted
to cool to room temperature. The residue is a
brownish-tan colloidal disperse system in the form of a
gel.
Exam~le 3~
A mixture of 500 parts of the product of
Example 5, 312 parts of kerosene, 40 parts of acetone,
and 60 parts of water is heated to reflux and
maintai~ed at this temperature for five hours with
stirring. The temperature of the material is then
raised to about 155C while removing the volatile
components. The residue i5 a ~iscous gel-like material
which is the desired colloidal di~perse system.
Example ~5
The procedure of Examp}e 34 is repeated with
the substitution of 312 parts of heptane for the
kerosene and 60 parts of water for the acetone-water
mixture therein. At tbe completion of the homogen-
ization, hydrogen gas is bubbled through the gel to
facilitate the removal of water and any other vola~ile
components.
;
r 61-
Example 36
To 500 parts of the overbased material of
Example 8, there is added 312 parts of kerosene, 40
parts of o-cresol, and 50 parts of water. This mixture
is heated ~o the re~lux ~emperature (70-75C7 and
maintained at this temperature for five hours. The
volatile components are then removed from the mixture
by heatinq to 150C over a period of two hours. The
residue is the desired colloidlal disperse system
containing about 16~ ~y weight of kerosene.
Example 37
A mixture of 500 parts of the overbased
material of Example 4(a) and 312 parts of heptane is
heated to 80C whereupon 149 parts of glacial acetic
acid (99.8%~ is added dropwise o~er a period of five
hours. The mixture is then heated to 150C to remove
the vola~ile components. The resultin~ gei-like
material is the desired colloidal disperse system.
E ample 3a
The procedure of Example 37 is repeated except
that 232 parts of boric acid is used in lieu of the
acetic acid. The desired gel is produced.
Example 39
~ he procedure of ~xample 35 is repeated except
tha~ the water is replaced by 40 parts of methanol and
40 parts of diethylene triamine. Upon completion of
the homogenization. a gel-like colloidal disperse
system is produc~d.
Example 40
A mixture of 500 parts of the product of
Example 5 and 300 parts of heptane is heated to 80C
and 68 parts of anthranilic acid is added over a period
. . - .~
~26~ 18
, ~
-6Z-
of one hour while maintaining the reaction temperature
between 80 and 95C. The reaction mixture is then
hea~ed to 150C over a two-hour period and then blo~n
with nitrogen for 15 minutes ~o remove the volatile
components. The resulting colloidal disperse system is
a moderately stiff gel.
Example 41
The procedure of Example ~0 is repeated except
that the anthranilic acid is rep]aced by 87 parts of
adipic acid. The resulting product is ~ery vis~ous and
is the desired solloidal disperse system. This gel can
be diluted, if desired, with mineral oil or any of the
other materials said to be suitable for disperse
mediums hereinabove.
ExamPle 92
A mixture of 500 par~s of the product of
Example 7 and 300 parts of heptane is heated to 80C
whereupon 148 parts of glacial acetic acid is added
over a period of one hour while maintaining the
temperature within the range of about 80l-8aoC. The
mixture is then heated tp 150C to remove the volatile
components. The residue is a viscous gel. This gel
may be diluted with a material sui~able as a disperse
mediu~.
Example 43
A mixture of 300 parts of toluene and 500
parts of an overbased material prepared according to
the procedure of Example 6 and having a sulfate ash
content of 41.8~ is heated to 80C whereupon 124 parts
of glacial acetic acid is added over a period of one
hour. The mixture is then heated to 175C to remove
the volatile components. During this heating, the
-63-
reaction mixture becomes very viscous and 380 parts of
mineral oil is added to facili~ate the removal of the
volatile components. The resulting colloidal disperse
system is a viscous grease~ e material.
Example 44
A mixture of 700 parts of the overbased
ma~erial of Example 4(b), 70 par~ts of water, and 350
parts of toluene is heated to reflux and blown with
~arbon dioxide at the ra~e of one cubic foot per hour
for o~e hour. The reaction product is a soft gel.
Example 45
The procedure of Example 41 is repeated except
that the adipic acid is replaced by 450 parts of
di(4-methyl-amyl) phosphorodithioic acid. The
resulting product is 3 gel.
Example 46
The procedure of Example 39 is repeated except
that the methanol-amine mixture is replaced by 250
parts of a phosphorus acid. The product is a viscous
brown gel-like colloidal disperse system. The
phosphorus acid is obtained by treating with steam at
150C the product obtained by reacting 1000 parts of
polyisobutene having a molecular weight of about
60,000, with 24 parts of phosphorus pentasulfide..
Example 47
The procedure of Example ~3 is repeated except
that the overbased material therein is replaced by an
equivalent amount of the potassium overbased material
of Example 13 and the heptane is replaced by an
equivalent amount of toluene.
~6~S~ ~
--64--
Example 48
The overbased material of Example 5 is
isolated as a dry powder by precipitation out of a
benzene solution through the ,addi~ion thereto of
acetone. The precipita~e is washed with acetone and
dried. A mixture of 45 parts of a toluene solution of
the above powder (364 parts of toluene added to 500
part~ of the powder ~o produce a solution having a
sulfate ash content of 43%), 36 parts of methanol, 27
par~s of water, and 18 parts of mixed primary amyl
alcohols (described in Example 27) is heated to a
temperature within ~he range of 700-75C. The mixture
is maintained at this ~emperature for 2.5 hours and
t~en heated to remove the al~anols. The resulting
material is a colloidal disperse system substantially
free from any mineral oil. If desired, the toluene
present in the colloidal disperse system as the
disperse medium can be removed by first diluting the
disperse system with mineral oil and thereafter heating
the diluted mixture to a temperature of about 160C
whereupon the toluene is vaporized.
xample 49
Calcium o~erbased material similar to tha~
prepared in Example 5 is made by substituting xylene
for the mineral oil used therein. The resulting
overbased material has a xylene content of about 25%
and a sulfate ash content of 39.3%. This o~erbased
material is con~erted to a colloidal disperse system by
homogenizing 100 parts of the overbased material with 8
parts of methanol, ~ parts of the amyl alcohol mixture
of Example 27, and 6 2arts of water. The reac~ion mass
is mixed for six hours while maintaining the tempera-
~26~
- -65-
ture at 750-7aoc. Thereafter, the disperse system is
heated to remove the alkanols and water. If desired,
the gel can be diluted by the adclition of mineral oil,
toluene, xylene, or any other suitable disperse medium.
Example 50
A solution of 1000 parts of the gel-liXe
colloidal disperse sys~em of Example 26 is dissolved in
1000 parts of toluene by continuous agitation of these
two components for about three hours. A mixture of
looo parts of the resulting solution, ~0 parts o~
water, and 20 parts of methanol are added to a
three-liter flask. Threafter, 92.5 parts o~ calcium
hydroxide is slowly added to the ~lask with stirring.
An exothermic reaction takes place raising the
temperature to 32C. The en~ire reaction mass is then
heated to about 60C over a 0.25-hour period. The
heated mass is then blown with carbon dioxide at the
rate of three standard cubic feet per hour for one hour
while maintaining the temperature at 60-70C. At the
conclusion of the carbonation, the mass is heated to
about 150C over a 0.75-hour period to remo~e water,
me~hanol and toluene. The resulting product is a
clear, light-brown colloidal disperse system in the
- form of a gel. In this manner additional metal-
contai~ing particles are incorporated into the
colloidal disperse system.
At ~he conclusion of the carbonation step and
prior to removing the water, methanol and toluene, more
calcium hydroxide coul~ have been added to the mixture
and the carbonation step repeated in order to add still
additional metal-containing particles to the colloidal
disperse syste~.
~L26~6~ ~
-66-
Example 51
A mixture of lZ00 parts of the gel produced
according to Example 26, 600 parts of toluene, and 98
parts of water is blown with carbon dioxide at two
standard cubic feet per hour while maintaining the
temperature at 55-65C for one hour. The carbonated
reaction mass is then hea~ed at 150C for 1.75 hours to
remo~e the wa~er and toluene. T~is procedure improves
the texture of the colloidal disperse systems and
converts any calcium oxide or calcium hydroxide present
in the gel into c~lcium carbonate particles.
Exam~le 52
A mixture comprising 300 ~arts of water, 70
parts of the amyl alcohol mixture identified in Example
27 above, 100 parts of methanol, and lOOo parts of a
barium overbased oleic acid prepared according to the
general technique of Example 3 by substi~uting oleic
acid for the petrosulfonic acid used therein and having
a metal ratio of about 3.5, is thoroughly mixed for
about 2.5 hours while maintaining the temperature
within the range of from about 7Z~-74C. At this point
the resulting colloidal disperse system is in the form
of a very soft gel. This material is then heated to
about 150C for a two-hour period to expel methanol,
the amyl alcohols, and water. Upon removal of these
liguids, the colloidal disperse system is a moderately
fitiff, gel-like material.
Example 53
A dark brown colloidal disperse system in the
form of a very stiff gel is prepared from the eroduct
of Example 19 using a mixture of 64 parts of methanol
and 80 parts of water as the conversion agent to
~ 26~
-67-
convert 800 parts of the overbased material. After the
conversion process, the resulting disperse system is
heated to about 150C to remove the alcohol and water.
Example 5~
5000 parts of the product o~ Example 20 are
placed in a resin reactor equipped with a heating
mantle, thermocouple, gas-inlet tube, condenser and
metal stirrer, and heated to 40C with stirring.
Carbon dioxide is bubbled through this product at ~he
rate of one cubic foot per hour for Z.4 hours, the
temperature of the whole ~arying fro~ sooc to 44C.
282.6 parts of isopropyl alcohol, 2~2.6 parts of
methanol and 434.8 parts of distilled water are added
over a five-minu~e period. ~he whole is heated to 7aoc
and refluxed for 30 minutes. 667 parts of SC Sol~ent
100 are added. The reactor is equipped with a trap.
Isopropyl alcohol, methanol and water are stripped from
the whole by bubbling nitrogen at two cubic feet per
hour through the whole over a period of five hours
while maintaining the temperature at 160C. The whole
is dried to 0.05% by weight water content and then
cooled to room temperature. The solids content is
adjusted to 60% solids with SC Solvent lo0.
ExamPle 55
1000 parts of t~e overbased material o
Example 21 is converted to a colloidal disperse system
by using as a conversion agent a mixture o~ 100 parts
of methanol and 300 parts of water. The mixture is
6tirred for seven hours at a temperature within the
range of 72-~0C. At the conclusion of the ~ixing,
the resulting mass is heated gradually to a-temperature
of about 150C over a three-hour period to remove all
L6a~ ~
-~8-
volatile liquid contained therein. Upon removal of all
volatile solven~s, a tan powder is ob~ained. By
thoroughly mixing this tan powder with a sui~able
organic liquid such as naphtha, it is again transformed
into a colloidal disperse sys~em.
Example 56
A mixture of 1000 parts of the product of
Example 22, 100 parts of wa~er, 80 parts of methanol,
and 300 parts of naphtha are mixed and heated to 72C
under reflux condi~ions for about five hours. A light
brown ~iscous liquid material is formed which is the
desired colloidal disperse system. This liquid is
removed and consists of tha colloidal disperse system
wherein about 11.8% of the disperse medium is mineral
oil and 88% is naphtha.
Following the techniques of Example 26,
additional overbased materials as indicated below are
converted to the corresponding colloidal disperse
systems.
Overbased material of below
examples converted to colloidal
Example No. disperse system
57 Example 11
58 Example 14
59 Example 15
Example 16
61 Example 17
62 Example 18
63 Example 19
64 Example 21
,
126~L60B
-69-
Example 6~
A mixture of 1000 parts of the overbased
material of Example 23 and 388.4 parts of mineral oil
is heated ~o 55~-60C and blown with carbon dioxide
until the base number is about one. 56.5 parts
methanol and 43.5 parts water are added and the whole
is mixed at 750-80OC under reflux until the viscosity
increases to a maximum. The maxi.mum viscosity can ~e
determined by visual inspection. 472.5 parts of 97.~%
calcium hydroxide and 675.4 parts of mineral oil are
added and the whole is blown with carbon dioxide at a
temperature of 75-80C until the whole is substan-
tially neu~ral. Alcohol and water are removed by
blowing the whole with nitrogen at 150C. The
resulting product has a calcium content of 13.75% and a
metal ratio of 36.
Example 66
A first mixture of 57 parts methanol and 43
parts water is prepared. A second mixture is prepared
by addinq 220 parts N-heptane to 1000 parts of the
product of Example 9. The second mixture is carbonated
by blowing carbon dioxide at 49O-55OC to reduce the
direct base number to 7-15. The irst mixture of
methanol and water is added to the carbonated second
mixture and mixed under re~lux conditions at 62-660C
until a gel is formed. This material is then heated to
149C and flash-s~ripped of N-heptane. alcohols and
water over into mineral oil. This material is furtheI
dried by nitrogen blowin~ at 149-160C. Mineral oil
is added to provide a No. 1 grease penetra~ion
specification.
~IL26~
-~ -70-
The change in rheological properties asso-
ciated with conversion of a Newtonian overbased
ma~er;al into a non-Newtonian colloidal disperse system
is demonstrated by the Brookfield Viscometer data
derived from overbased ma~erials and colloidal disperse
systems prepared therefrom. In the following samples,
the overbased material and the colloidal disperse
systems are prepared according to the above-discussed
and exemplified techniques. In each case, after
preparation of ~he overbased material and the colloidal
disperse system, each is blended with dioctylphthalate
~DOP) so that the compositions tested in the viscometer
contain 33.3% by weight DOP (Samples A, B and C) or 50~
by weight DOP (Sample D). In Samples A-C, the acidic
material used in preparing the overbased material is
carbon dioxide while in Sample D, acetic acid is used.
The samples each are identified by two numbers, (1) and
(2). The first is the overbased material-DOP composi-
tion and the second the colloidal disperse system-DOP
composition. The overbased materials of the samples
are further characterized as follows:
Sample A
Calcium overbased petrosulfonic acid having a
metal ratio of about 12.2.
Sample B
Barium overbased oleic acid having a me~al
ratio of about ~.5.
Sam~le C
Barium overbased petrosulfonic acid having a
metal ratio of about 2.5.
Sample D
Calcium overbased commercial higher fatty acid
mixture having a metal ratio of about 5.
~26~
-71-
The Brookfield Viscometer data for these
compositions is tabulated below. The data of all
samples is collected at 25C.
BROOKFIE~D VISCOMETER DATA
(Centipoises)
Sample A Sample B _ample C Sample D
R.p.m. (1) (2) (1) (2) (1) (2) (1) (2)
6 230 2,620 80 15,240 240 11,320 114 8,820
12 235 2,053 90 8,530 230 6,980 103 5,220
239 (1) 88 (l) 224 4,008 100 2,892
off scale.
The Metal-Containinq Orqanic Phosphate Complex (C):
The metal-containing organic phosphate complex
(C) is prepared by the process which comprises the
reaction of (C)(l) at least one polyvalent metal salt of
an acid phosphate ester derived from the reaction of
phosphorus pentoxide or phosphoric acid with a mixture
of a monohydric alcohol and from about 0.25 to about
four equivalents of a polyhydric alcohol with (C)(2) at
least about 0.1 equivalent of an organic epoxide. The
preparation of these phosphate complexes is described in
U.S. Patent No. 3,215,716.
The acid phosphate esters required for the
preparation of starting material (C)(l) are made, as
indicated, by the reaction of phosphorus pentoxide or
phosphoric acid with a mixture of monohydric alcohol
and a polyhydric alcohol. The precise nature of this
reaction is not entirely clear, but it is known that a
~'
~26~60a
_72-
.
mixture of phosphate esters is formed. This mixture
consists principally of acid phosphate esters, i.e.,
compounds of ~he general formula:
(R)XPo(oH)3-x
where x equals 1 or ~ and R is an organic group,
although ~ome neutral triesters of the formula
(RO)3PO may also be formed.
The nature and the stoichiome~ry of the
reaction are complicated further by the fact that one
of the reactants is a polyhydric alcohol. It is
possible, therefore, that the polyhydric alcohol forms
cyclic and/or polymeric phosphate esters when it reacts
with phosphorus pentoxide.
The acid phosphate esters resulting from the
reaction of one mole or phosphorus pentoxide with from
about 2 to about 6 equivalents of a mixture of
monohydric and polyhydric alcohols are useful in the
preparation of startin~ material (C)(l). The term
~equivalent~' as used herein reflects the hydroxyl
equivalency of the alcohol. Thus, for example, 1 mole
of octyl alcohol is 1 equivalent thereof, 1 mole of
ethylene glycol is 2 equivalents thereof, and 1 mole of
glycerol is 3 equivalents thereof.
Less than Z or more than 6 equivalents of
alcohol can be used, if desired, in the reaction with
one mole of phosphorus pentoxide, although such amounts
are not preferred for reasons of econcmy. When fewer
than 2 equivalents of alcohol are used, some unreacted
phosphorus pentoxide may remain in the -product or
precipitate there~rom. On the other hand, when
f ~ 8
-~ -73-
substantially more than 6 equivalents of alcohol are
used, unreacted alcohol would bs present in the
product. It is generally preferred to employ from
about 3 to about 5 equivalents of the alcohol mixture
per mole of phosphorus pentoxide or phosphoric acid.
The monohydric alcohols useful in the
preparation of starting material (C)~l) are principally
the non-benzenoid alcohols, i.e., the aliphatic and
cycloaliphatic alco~ols, although in some instances
aromatic and~or heterocyclic substituents may ~e
present. Thus, suitable monohydric alcohols include
propyl, isopropyl, butyl, isobutyl, amyl, hexyl,
cyclohexyl, heptyl, methylcyclohexyl, octyl, isooctyl,
decyl, lauryl, tridecyl, oleyl, benzyl, beta-phenethyl,
alpha-pyridylethyl, etc., alcohols. Mixtures of such
alcohols can also be used if desired. Substituents
such as chloro, bromo, fluoro, nitro, nitroso, ester,
ether, sulfide, keto, etc., which do not prevent the
desired reaction may also be present in the alcohol.
In most instances, however, the monohydric alcohol will
be an unsubstituted alkanol.
The polyh~dric alcohols useful in the
prepara~ion of starting material (C)(13 are principally
glycols, i.e., dihydric alcohols, although trihydric,
tetrahydric, and higher polyhydric alcohols may also be
used. In certain instances, they may contain aromatic
and/or heterocyclic substituents as well as chloro,
bromo, fluoro, nitro, nitroso, ether, ester, sulfide,
keto~ etc., substituents. Thus, suitable polyhydric
alcohols include ethylene glycol, diethylene glycol,
trie~hylene glycol, propylene glycol, dipropylene
glycol, 1,3-butanediol. glycerol, glycerol monooleate,
~ ~IL2~:1L60~ ~
-74-
mono-phenyl ether or glycerol, mono-benzyl ether of
glycerol, 1,3,5-hexane~riol, pentaerythritol, sorbitol
dioctanoa~e, pentaerythritol dioleate, and ~he like.
In lieu o~ a single polyhydric alcohol, mixtures o~ ~wo
or more of such alcohols may be employed.
As indicated, starting material (C~(l) is
prepared from a mixture of monohydric and polyhydric
alcohols, The mixture may contain a single monohydric
and a single polyhydric alcohol. or a plurality of one
or both of such alcohols. Preferably, about 0.25 to
about 4 equivalents of polyhydric alcohol per eguiva-
lent of monohydric alcohol are used. Mixtures of
isooctyl alcohol and dipropylene glycol are satis-
factory and a mixture in which these alcohols are
present in about equivalent amounts can be used.
The reaction between the alcohol mixture and
phosphorus pentoxide or phosphoric acid is exothermic
and can be carried out convenier~tly at a temperature
ranging from room temperature or below to a temperature
just beneath the decomposition point of the mixture.
Generally, reaction temperatures within the range of
from about 40C to about ZOOoC are most satisfactory.
The reaction time required varies according to the
temperature and to the hydroxyl activity of the
alcohols. At the hi~her temperatures, as little as 5
to 10 minutes may be sufficient for complete reaction.
On the o~her hand, at room temperature 12 or more hours
may be required. Generally it is most convenient to
i heat the alcohol mixture with phosphorus pentoxide or
phosphoric acid for 0.5 to 8 hours at 60-120C. In
any event, the reaction is carried out until periodic
` acid number determinations on the reaction mas.
:;
r ~6~6~
-75-
indicate that no more acid phosphate esters are being
formed.
The acid phosphate esters useful in the
process of this invention can also be prepared by
separately reacting phosphorus oxide or phosphoric acid
with the monohydric and polyhydric alcohols and then
mixing the esters ~o formed. As mentioned below,
solvents may be used when the phosphate esters are
viscous or otherwise dificult to handle.
To facilitate mixing and handling, the
reaction may be conducted in the presence of an inert
solvent. Generally such solvent is a petroleum distil-
late hydrocarbon, an aro~atic hydrocarbon, an e~her, or
a lower chlorinated alkane, although mixtures of any
such solvents can be used. Typical solvents include,
e.g., petroleum aromatic spirits boiling in the range
about 120-200C, benzene, xylene, toluene, mesitylene,
ethylene dichloride, diisopropyl ether, etc. In most
instances, the solvent is allowed to remain in the acid
phosphate esters and ultimately the metal-containing
organic phosphate complex, where it serves as a vehicle
for the convenient application of films to metal
surfaces.
The conversion of the acid phosphate es~ers to
the polyvalent metal salt may be carried out by any of
the various known methods for the preparatîon of salts
of organic acids such as, e.g., reaction of the
acid-esters with a polyvalent metal base such as a
metal oxide, hydroxide, or carbonate. Other suitable
methods include, e.g., reaction of the acid-esters with
a finely divided polyvalent metal, or the metathesis o
a monovalent metal salt of the acid-esters with a
~Z6.~ r
-76-
soluhle salt of the polyvalent metal such as, e.g , a
nitrate, chloride, or ace~ate thereof.
The polyvalent metal of s~arting material
~C)(l) may be any liqht or haavy poly~alent metal such
as, e.g., zinc, cadmium, lead, iron, cobalt, nickel,
barium, calcium, strontium, magnes,ium, copper, bis~uth,
tin, chromium, or manganese. A preference is expressed
for the polyvalent metals of Group II of the Periodic
Table and of these, zinc is particularly preferred.
preferred starting material (C)(l) is the zinc sal~ of
the acid phosphate esters formed by the reaction of ~
mixture of eguivalent amounts of isooctyl alcohol and
dipropylene glycol with phosphorus pentoxide.
The forma~ion of ~he metal-containing organic
phosphate complex o~ component ~C) involves, as
indicated, a reaction between starting material (C)(l),
the polyvalent metal salt of certain acid phosphate
esters, and starting material (C)(2), the organic
epoxide.
The organic epoxides are compounds containing
at least one
~ I I I
cx--C--
:
linkage where x is zero or an integer of ~rom 1 to
about 12. Examples of useful organic epoxides include
the various substituted and unsubstituted alkylene
oxides containing at least two aliphatic carbon atoms,
such as, e.g., ethylene oxide, 1,2-propylene oxide,
1,3-propylene oxide, 1,2-butylene oxide, pentamethylene
oxide. hexamethylene oxide, 1,2-octylene oxide,
cyclohexene oxide, methyl cyclohexene oxide, 1,2,11,12-
-77-
diepoxydodecane, styrene oxide, alpha-methyl styrene
oxide, beta-propiolactone, methyl epoxycaprylate, ethyl
epoxypalmitate, propyl epoxymyristate, butyl epoxy-
stearate, epoxidized soyabean oil, and the like. of
the various available organic epoxides, it is preferred
to use those which contain at leas~ 12 carbon atoms.
Especially preferred are those epoxides which contain
at least 12 carbon atoms and alsD a carboxylic ester
group in the molecule. ~hus, ~he commercially
available epoxidized carboxylic ester, butyl epoxy
stearate, is a preferred starting material (C)(2) for
the purpose of this invention. If desired, the organic
epoxide may also contain substituents such as, e.g.,
chloro, bromo, fluoro, nitro, nitroso, ether, sulfide,
keto, etc., in the molecule.
The stoichiometry of the reaction of the
polyvalent metal salt of the acid phosphate ester with
the organic epoxide, to form tha metal-containing
organic phosphate complex of component (C) is not
precisely known. There are indications, however, that
the reaction involves about one equivalent each of the
polyvalent metal salt and the organic epoxide (for this
reaction, one equivalent of an epoxide is the same as
one mole thereof). This i5 not to say that complexes
made from one equivalent of the polyvalent metal salt
and less than or more than one equivalent of the
organic epoxide are unsuited for the purpose of ~his
invention. Complexes prepared using as little as 0.1
or 0.25 equivalent or as much as 1.5 to 2 or more
equivalents of the organic apoxide per equivalent of
polyvalent metal salt are satisfactory for -the purpose
of this invention.
~2~;~6~
- 7 B -
The reaction be~ween the organic epoxide and
the polyvalent metal salt of the acid phospha~e esters
is only slightly exothermic, so in order to insur~
complete reaction some heat is generally supplied to
the reaction mass. The ~ime and tempera~ure for this
reaction are not particularly critical; satisfactory
results may be obtained by main1,aining the mass for
0.5-6 hours at a temperature within the range of from
about 40OC to about 150C. Ordinarily, the product is
clear and does not require a ~iltration. In some
instances, however, it may be desirable to filter the
product, particularly when the polyvalent metal salt
starting material has not been purified.
The following Examples 67-7~ are illustrative
of specific modes of preparing component (C). All
parts and percentages are by weight unless otherwise
indicated.
Example 67
49 parts of dipropylene glycol (0.73 equiva-
lent), 95 parts (0.73 equivalent) of isooctyl alcohol,
and 133 parts of aromatic petroleum spirits boiling in
the range of 158~176C are added to a reaction
vessel. The whole is stirred at room temperature and
60 parts (0.42 mole) of phosphorus pentoxide are added
portionwise over a period of about 0.5 hour. The heat
of reaction causes the temperature to rise to about
80C. After all of -the phosphorus pentoxide has been
added, the whole is stirred for an additional 0.5 hour
at 95C. The resulting acid phosphate esters show an
acid number of 91 with bromphenol blue as an indicator.
The mixture of acid phosphate esters i~
converted to the correspondi~g zinc salt by reacting it
6~ ~
_~ -79-
with 34,5 parts of zinc oxide for 2.5 hours at 95C.
Thereafter 356 parts (one equivalent per equi~alent of
zinc sal~) of butyl epoxystearate is added to the zinc
salt at 8~C over a period of about one hour and the
whole is stirred for four hours at 90C. Filtration of
.~ the mass yields 684 parts of a zi.nc-con~aining organic
phosphate complex having the following analysis:
Percent phosphorus, 3.55; percent zinc, 3.78; and
specific gravity, 1.009.
Example 68
- A cadmium-containing organic phosphate complex
is made in the manner set forth in Example 67, except
that 54.5 parts of cadmium oxide is used in lieu of the
specified amount of zinc oxide.
Example 69
A lead-containing organic phosphate complex is
made in the manner set forth in Example 67, except that
parts of lead monoxide are used in lieu of the
specified amount of ZiDC oxide.
Example 70
A barium-containing organic phosphate complex
~;~;is made in the manner set forth in Example 67, except
.that 73 parts of barium hydroxide are used in lieu of
~;the specified amount of zinc oxide.
Example 71
'A tin-containing organic phosphate complex is
made in the manner set forth in Example 67, except that
57 parts of stannic oxide are used in lieu of the
specified amount of zinc oxide.
Example 7z
520 parts of isooctyl alcohol (4 eguivalents),
:268 parts of isopropylene glycol ~4 equivalents), and
~, ' ' ' ' ' '' ' . :.
lZ~
-- --80--
1031 parts of ~oluene are added to a reaction vessel.
The whole is stirred and 2~3 parts (1.71 moles) of
phosphorus pentoxide are added portionwise o~er a
period of two hours. The exothermic character of the
reaction causes the temperature to rise from room
temperature to 60C. To insure complete reaction, the
whole is stirred for an additional ~our hours at 60C.
The resulting 50% solution of the acid phosphate esters
in toluene ~hows an acid number of 88 with bromphenol
blue as an indicator. -~
1000 parts of the toluene solution of acid
phosphate esters of the preceding paragraph are
converted to the corresponding zinc salt by reaction
with 83 parts of zinc oxide for 5.5 hours at 400-45C.
Filtration yields a clear, li~ht-yellow toluene
solution of the zinc salt. 360 parts of this toluene
solution (0.34 equi~alent) is heated with 25 parts
tO.34 quivalent) of beta-propiolactone for 5.5 hours at
s0O-60Oc to yield the desired zinc-containing organic
; phosphate complex as a 55% solution in toluene. It has
the following analysis: 4.26% phosphorus and 5~0s%
2lnc .
Example 73
A toluene solution of acid phosphate esters is
made in the manner set forth in Example 72.
999 parts of the indicated toluene solution of
acid phosphate esters is heated with 76 parts of ~al-
cium hydroxide for five hours at 95-60C. Filtration
yields the calcium salt of the acid phosphate esters as
a 51% solution in toluene.
325 parts (0.52 equivalent) of the toluene
solution of the calcium salt is heated with 220 parts
:
(0.52 equivalent) of 85~ butyl epoxystearate for five
hours at 50-60C to prepare the desired calcium-con-
taining organic phosphate complex as a 71% solution in
toluene. It has the ollowing analysis: 2.34%
phosphorus and 1.65~ calcium~
Example 7~
A batch of acid phosphat,e esters is ~ade in
the manner set forth in Example 72, except that the
amount of ~oluene solvent employed is reduced to 4q3
parts so as to yield a more concentrated (70%) solution
of the esters in toluene.
2gO parts of ~his toluene solution are
neutralized with a mixture of 28 . 2 parts of zinc oxide
and 11.2 parts of calcium hydroxide for three hours at
50-70C. Filtration of the mass yields a mixed zinc-
calcium salt of ~he acid phosphate esters as a 73%
solution in toluene.
116.2 parts of the above mixed zinc-calcium
salt (0.19 eguivalent) and 80.4 parts (O.lg equi~alent)
of 85~ butyl epoxystearate are heated for six hours at
50-60C to prepare an 84~ solution in toluene of a
calcium and zinc-containin~ organic phosphate complex.
It has the following analysis: 2.69% phosphorus; O.Z2%
calciu~; and 3.13~ zinc.
Example 75
A zinc-containing organic phosphate complex is
made in the manner set forth in Example 67, except for
the following differences: 58 parts of 1,2-propylene
oxide is used in lieu of the butyl epoxystearate and
the reaction between the zinc salt of the acid
phosphate esters and the },2-propylene oxide is carried
out at 30-35C, rather than 88-90C.
.. :
:
-82-
Example 76
A zinc-containing organic phosphate complex i8
made in the manner set forth in Example 67, except that
136 par~s (0.73 equivalent) of lauryl alcohol and 39
parts (0.73 equivalent) of diethylene glycol are used
in lieu of the specified amounts of isooctyl alcohol
and dipropylene glycol.
Example 77
A zinc-containinq organic phosphate complex i5
made in the manner set forth in Example 67, except that
185 parts (1.17 equivalents) of n-decanol-l and 7.9
parts (0.29 equivalent) of pentaerythritol are used in
lieu of the specified amounts of isooctyl alcohol and
dipropylene glycol.
Example 78
A solution of 49 parts (0.73 equivalent) of
dipropylene glycol, 95 parts (0.73 equivalen~) of
isoctyl alcohol and 133 parts of toluene is prepared,
and 60 parts (0.423 mole) of phosphorus pentoxide are
added over a period of about 0.5 hour at a temperature
of from about 50C to about 90C. After all of the
phosphorus pentoxide is added, the mixture is stirred
for an addi~ional five hours at about 90C. The
resulting acid phosphate ester mixture has an acid
number of 75 with bromphenol blue as an indicator.
This mixture of acid phosphate esters is
converted to the corresponding zinc salt by reaction
with 34.5 parts of zinc oxide for one hour at 93C.
The water and toluene is removed by heating the mixture
to 160C~100 mm. in nine hours. Thereafter, ~56 parts
(1 equivalent per equivalent of zinc saltl of butyl
epoxystearate is added to the zinc salt over a period
,
-83-
of one hour at about 125C and the mixture is then
maintained for four hours at about 95C. The mixture is
filtered and the filtrate has the following analysis:
4.71% phosphorus; 4.85% zinc; and a specific gravity of
1.0Sl5.
The Alkali and Alkaline Earth Metal Or~anic Acid Salts
(D):
The alkali and alkaline earth metal organic
acids of this invention are preferably those containing
at least 12 aliphatic carbons although the acids may
contain as few as 8 aliphatic carbon atoms if the acid
molecule includes an aromatic ring such as phenyl,
naphthyl, etc. Representative organic acids suitable
for preparing these materials are discussed and
identified in detail in U.S. Patent Nos. 2,616,904 and
2,777,874. Oil-soluble carboxylic and sulfonic acids
are particularly suitable. Illustrative of the
carboxylic acids are palmitic acid, stearic acid,
myristic acid, oleic acid, linoleic acid, behenic acid,
hexatriacontanoic acid, tetrapropylene-substituted
glutaric acid, polyisobutene (M.W.-5000)-substituted
succinic acid, polypropylene, (M.W.-10,000)-substituted
succinic acid, octadecyl-substituted adipic acid,
chlorostearic acid, 9-methylstearic acid, dichloro-
stearic acid, stearylbenzoic acid, eicosane-substituted
naphthoic acid, dilauryl-decahydro-naphthalene carboxy-
lic acid, didodecyl-tetralin carboxylic acid, dioctyl-
cyclohexane carboxylic acid, mixtures of these acids,
their alkali and alkaline earth metal salts and/or their
anhydrides. Of the oil-soluble sulfonic acids, the
mono-, di- and trialiphatic hydrocarbon substituted aryl
f ~61~
-84-
sulfonic acids and the petroleum sulfonic acids
(petrosulfonic acids) are particularly preferred.
Illustrative examples of suitable sulfonic acids
include mahogany sulfonic acids, petrolatum sulfonic
acids, monoeicosane-substituted naphthalene sulfonic
acids dodecylben~ene sulfonic acids, didodecylbenzene
sulfonic acids, dinonylbenzene sulfonic acids, cetyl-
~hlorobenzene sulfonic acids, dilauryl beta-naphthalene
sulfonic acids, the sulfonic acid derived by the
treatment of polyisobu~ene having a molecular weight of
1500 with chlorosulfonic acid, nitronaphthalenesulfonic
acid, paraffin wax sulfonic acid, cetyl-cyclopentane
sulfonic acid, lauryl-cyclohexanesulfonic acids,
polyethylene (M.W.-750) sulfonic acids, etc. Normally
the aliphatic groups will be alkyl and/or alkenyl
groups such that the total number of aliphatic carbons
is at least 12.
Within this preferred group of overbased
carboxylic and sul onic acids, the barium and calcium
over based mono-, di-, and trialkylated benzene and
naphthalene ~including hydrogenated forms thereof),
petrosulfonic acids, and higher fatty acids are
especially preferred. Illustrative of the synthe-
tically produced alkylated ~enzene and naphthalene
sulfonic acids are those containing alkyl substituents
having from 8 to about 30 carbon atoms tberein. Such
acids include di-isododecyl-benzene sulfonic acid,
wax-substituted phenol sulfonic acid, wax-substituted
benzene sulfonic acids, polybutene-substituted sulfonic
acid, cetylchlorobenzene sulfonic acid, di-cetylnaph-
thalene sulfonic acid, di-lauryldiphenylether sulfonic
acid, di-isononylbenzene sulfonic acid, di-isoocta-
3L~61~
-85-
decylbenzene sulfonic acid, stearylnaphthalene sulfonic
acid, and the like. The petroleum sulfonic acias are
particularly preferred. Petroleum sulfonic acids are
obtained by treating re~ined or semi-refined petroleum
oils with concentrated or fuming sulfuric acid, These
acids remain in the oil after the settling out of
sludges. These petroleum sulfonic acids, depending on
the nature of the petroleum oils from which they are
prepared, are oil-soluble alkane sulfonic acid,
alkyl-substituted cycloaliphatic sulfonic acids
including cycloalkyl sulfonic acids and cycloalkene
sulfonic acids, and alkyl, alkaryl, or aralXyl
substituted hydrocarbon aromatic sulfonic acids
including single and condensed aromatic nuclei as well
as partially hydrogenated ~orms ~hereof. ~xam~les of
such petrosulfonic acids include mahogany sulfonic
acid, white oil sulfonic acid, petrolatum sulfonic
acid, petroleum naphthene sulfonic acid, etc. This
especially pre~erred group of aliphatic fatty acids
includes the saturated and unsaturated higher fatty
acids containing from 12 to 30 carbon atoms.
Illustrative of these acids are lauric acid, palmitic
acid, oleic acid, linoleic acid, linolenic acid,
oleostearic acid, stearic acid, myristic acid~ and
undecalinic acid, alphachlorostearic acid, and
alpha-nitrolauric acid.
The metal base can be an alkali or alkaline
earth metal (e.g., sodium, potassium, calcium, barium,
etc.) oxide, hydroxide, bicarbonate, sulfide, mercap-
tide, hydride, alcoholate or phenate. The acid ~lts
are formed by mixing the metal base with the organic
acid using mixing procedures well known in the art.
"~aB r
86-
The Carboxylic Acid ~E~:
The carboxylic acîds of the present invention
are one or more mono- or polycarboxylic acids of one to
about 20 carbon a~oms such as fatty acids having 10 to
about 18 carbon atoms.
Typical monocarboxylic acids include saturated
and unsaturated ~atty acids, such as lauric acid,
s~earic acid, cleic acid, myristic acid, linoleic acid,
and the like. Anhydrides, when availabl~, and lower
alkyl esters of these acids can also be used. ~ixtures
of two or more such acids can also be used. An
extensive discussion of such acids is found in Kirk-
Othmer ~Encyclopedia of Chemical Technologyl~ 2nd
Edition, 1965, John Wiley & Sons, N.Y., pages 811-85$.
Acetic acid, propionic acid, butyric acid, acrylic and
benzoic acid as well as their anhydrides and lower
alkyl esters are also useful.
Among the useful polycarboxylic acids are
maleic acid, fumaric acid, itaconic acid, mesaconic
acid, succinic acid, phthalic acid, alkyl-substituted
ph~halic acids, isophthalic acid, malonic acid,
glutaric acid, adipic acid, citraconic acid, glutaconic
acid, chloromaleic acid, ataconic acid,' scorbic acid,
etc. Again anhydrides when available, and lower alXyl
esters and esters o~ these acids can be used.
Certain lower molecular weight substituted
succinic acids and anhydrides can also be used. A
number of these are discussed in the above-cited
Kirk-Othmer article at pages a47-849. The typical such
acylating agents can be represented by the formula:
.~ --
~ R* - ICHCO2H
CHzCH2H
~Z63L6~
- -B7-
wherein R* is a Cl to about a C10 hydrocarbyl
group. Preferably, R~ is an aliphatic or alicyclic
hydrocarbyl ~roup with less than 10% of its carbon-to-
car~on bonds being unsatura~ed. Examples of such
groups are 9-butylcyclohexyl, di(;sobutyl), decyl,
etc. The production of such substituted succinic acids
and their derivatives via alkylation of maleic acid or
its derivatives with a halohydrocarbon is well known to
those of skil} in the art and need not be discussed in
detail ~t this point.
~ The N-(H~droxYl-Substituted HYdrocarbyl~Amines (F):
; The N-(hydroxyl-substituted hydrocarbyl)
amines (F) of the present invention generally ~ave one
to about four, typically one to about two hydroxyl
groups per molecule. These hydroxyl groups are each
bonded to a hydrocarbyl group to ~orm a hydroxyl-sub-
stituted hydrocarbyl group which, in turn, is bonded to
the amine portion of the molecule. These N-(hydroxyl-
substituted hydrocarbyl) amines can be monoamines or
polyamines and they can have a total of up to about 40
carbon atoms; generally they have a total of ~bout 20
; carbon atoms. Typically, however, they are monoamines containing but a single hydroxyl group. These amines
can be primary, secondary or tertiary amines while the
N-(hydroxyl-substituted hydrocarbyl) polyamines can
have one or more of any of these types of amino
groups. Mixtures of two or more of any of the
a~ore-described amines can also be used to make the
component (F) of the invention.
Specific examples N-(hydroxyl-substituted
hydrocarbyl)amines suitable for use in this invention
are the N-(hydroxy-lower alkyl)amines and polyamines
:
6~8
-8~-
6uch as 2 hydroxyethylamine, 3-hydroxybutylamine,
di-(2-hydroxyethyl)amine, tri-(2-hydroxye~hyl~amine,
di-(2-hydroxypropyl~amine, N,N,N'-tri-(2-hydroxy-
ethyl)ethylenediamine, N.N,N',N'-tetra(2-hydroxy-
ethyl)ethylenediamine, N-(2-bydroxyethyl)piperazine,
N,N'-di-~3-hydroxypropyl~piperazine, ~-(2-hydroxy~
ethyl)morpholine~ N-(2-hydroxyethyl)-2-morpholinone,
N-t2-hydrcxy~thyl)-3-mathyl-2-morpholinone, N-(2-hy-
droxypropyl)-6-methyl-2-~orpholinone. N-(2-hydroxy-
propyl3-5-carbethoxy-2-piperidone, N-(2-hydroxy-
propyl~-S-c~rbethoxy-2-piperidone, N-(.2-hydroxyethyl~-
5-~N-butylcarba~yl)-2-piperidone, N-12-hydroxyethyl)
piperidine. N-(4-hydroxybutyl)piperidine, N,N-di-(2-
hydroxyethyl)glycine. and et~ers thereof with aliphatic
alcohols. especially lower alkanols, N,N-di(3-hydroxy-
propyl)glycine, and the like.
Furthsr amino alcohols are the hydroxy-
substituted primary a~ines described in U.S. Patent
3,576,743 by the formula
: a 2
~':
where R is a monovalent organic radical containing
a
at least one alcoholic ~ydroxy group. A~cording to
this patent, the total number of c~rbon atoms in Ra
will not exceed about 20. Hydroxy-substituted
aliphatic primary amines containing a total~of up to
about 10 carbon atoms are useful. Generally useful a~e
the polyhydroxy-substitUted alkanol primary amines
wherein there is only one amino group present (i.e., a
primary amino group) having one alkyl substituent
r
-89-
containing up to 10 carbon atoms and up to 4 hydroxyl
groups. These alkanol primary amines correspond to
RaNH2 wherein Ra is a mono- or polyhydroxy-
~ubstituted alkyl group. It is typical that at l~a6t
one of the hydroxyl groups be a primary alcoholic
hydroxyl group. Tris-methylolaminomethane is a ~ypical
hydroxy-substituted primary amine. Specific examples
of ~he hydroxy-substitu~ed primary amines i~clude
Z-amino-l-butanol, 2-amino-2-methyl-1-propanol,
p-(betahydroxyethyl)-analine, 2-amino-1-propanol,
3-amino-1-propanol, 2-amino-2-methyl-1,3-propanediol,
2-amino-2-athyl-1,3-propanediol, N-(betahydroxy-
propyl)-N~-beta-aminoethyl)piperazine, 2-amino-1-
butanol, ethanolamine, beta-(betahydroxy ethoxy)-ethyl
amine, ~lucamine, glusoamine, 4-amino-~-hydroxy-3-
methyl-l-butene (which can be prepared according to
procedures known in the art by reacting isopreneoxide
with ammonia), N-3-taminopropyl)-4(2-hydroxyethyl)-
piperadine, 2-amino-6-methyl-6-heptanol, 5-amino-1-
pentanol, N-(beta-hydroxyethyl)-1,3-diamino propane,
1,3-diamino-2-hydroxypropane, N-~beta-hydroxy
ethoxyethyl~-e~hylenediamine, and the like.
Typically, the amine (F~ is a primary,
secondary or tertiary alkanol amine or mixture
thereof. Such amines can be represented, respectively,
by the formulae:
H\ R
HzN - R' OH NR' OH and N R'- OH
R / R
-
~L26~L6~
--so-- ,
wherein each R is independently a hydrocarbyl group of
1 to about 8 carbon atoms or hydroxyl-substituted
hydrocarbyl group of 2 to about ~ carbon atoms and R'
is a divalen~ hydrocarbyl group of about 2 ~o about 18
carbon atoms. The group -R'-O~ in such formulae
represents the hydroxyl-substituted hydrocarbyl group.
R' can be an acyclic, alicyclic or aromatic group.
Typically, it is an acyclic s~raight or bra~ched
alkylene group such as an ethylene, 1,2-proeylene,
1,2-~utylene, 1,2-oc~adecylene, etc. group. Where two
R groups are present in the same molecule they can be
joined by a direct carbon-to-carbon bond or through a
heteroatom (e.g., oxygen, nitrogen or sulfur) to ~orm a
5-, 6-, 7- or 8-membered ring structure. Examples of
such heterocyclic amines include N-(hydroxyl lower
alkyl)-morpholines, -thiomorpholines, -piperidines,
-oxazolidines, -thiazolidines and the like. Typically,
however, each R is a lower alkyl group of up to 7
carbon atoms.
The amine (F) can also be selected from the
alkylene oxide condensates (i.e., alkoxylates) with
active hydrogen compounds such as alcohols, phenols,
amides and amines. The amides are often fatty acid
amides such as oleyl amides. A particularly useful
class are the e~hoxylated amines wherein the amine has
at least 12 carbon atoms. Such amines can be
represented by the general formulae:
~ (CH2CH20)XH
RN
(CE~2C~20)yH
r
--91--
and
( 1 HZCH20) ZH ~ (CH2CH20~XH
RNCH2CH2CH2N
~ (CH~CH2V) H
wherein R is an aliphatic hydrocarbyl group with at
least about 12 carbon atoms, x, y and z are integers of
zero to 40 and the sum of x ~ y is between 2 and 50.
Usually ~he aliphatic group R has a maximum of about ZZ
carbons. Often such R groups are fatty alkyl or
alkenyl groups such as coco (cl2), stearyl (C18),
tallow (C18)~ oleyl ~Cla), and the like. Typically
R is a tallow residue and the sum x + y is about 5.
Homologous alkoxylated amines wherein the ethoxyl
residue (-CHzCH2O-) is replaced, at least in part,
by a propoxyl residue
( -CH2C~l_o ~
CH
are also useful.
Mixtures of one or more of the afore-described
amines can be used.
The compositions of the present invention
contain an effective amount of water to provide a
stable dispersion or emulsion (water-in-oil or
oil-in-water) of the components of the compositions of
the invention. Generally, the compositions of the
in~ention have about 5% to about 99% preferably about
25~ to about 75% by weight water. These compositions
generally contain from about 5% to about 70~ by weight,
preferably about 40% to about 60%, and advantageously
~IL;i~63L6~3 r
-92- -
about 50% to about 55~ by weight of component (B~. The
weight ratio o component (B) to component ~C) is
generally from about 0.25:1 to ahout 10:1, preferably
about 1:1 to about S:l. These compositions generally
contain ~rom about 15~ to about 75% by weight,
preferably about 15% to about 30~ by weight of
componènt (D), The level of component (E) is generally
in ~he range of about 0.5% to about 10% by weight,
preferably about 1% to abou~ 5%, and advantageously
abou~ 2% to abou~ g~. The level of addition of
component ~F) is dependent upon the level of addition
of componen~ (E). It is preerable to provide a
stoichiometric excess of component ~F~ over component
(E) so as to neutralize component (E) and provide the
compositions of the present invention with a slightly
alkaline character. Generally these compositions have
a pH ranging from slightly alkaline to about 10,
preferably from about a to about 9.
The compositions of the present invention
include aqueous concentrate which contain an effective
amount of water to reduce the viscosity of such
compositions to facilitate shipping and handling.
Generally, these aqueous concentrates contain at }east
about 25% by weight water, preferably about 25~ to
about 75~ water, and advantageously about 60% to about
75% water. The aqueous concentrates of the invention
can often be used as such without additional water
depending upon the desired end use. Alternatively,
these concentrates can be further diluted by the
addition of water using standard mixing techniques if
desired.
~ 3L6~
~93-
Generally, the corrosion-inhibiting coating
compositions of the present invention contain about 6Q~
to about 90%, preferably about 70~ to about 80% by
weight water.
On the other hand, the compositions intended
for use as metal-wor~ing fluids require additional
levels of water. These metal working fluids generally
require about 80% to about 99%, preferably about 90~ to
about 97~ by weight water.
As indicated above, the compositions of the
invention also include aqueous drilling fluids. These
drilling fluids contain a major amount of an aqueous
drilling mud and a minor torque reducing amount of
components (B) and (C). preferably these drilling
fluids also contain an effective amount of components
(D), (E) and (F) to disperse components (B) and (C) in
the drilling mud. The relative rat-os of components
(B), tC), ~D), (E) and ~F) are within the ratios set
forth above. The drilling fluids of the invention
generally contain about 90~ to abou~ 99.5% by weigh~ of
an aqueous drilling mud. Components ~B), ~C), (D), (E)
and (F) can be added directly to the drilling mud or
they may be first formulated as an aqueous concentra~e,
as discussed above and then added to the drilling mud.
It is preferable to formulate these compositions in the
form of an aqueous concentrate of the type discussed
above for purposes of facilitating shipping and
handling prior to addition to the drilling mud.
The drilling fluids of the present invention
can also contain other materials which are known to be
used in such applications, such as clay thickeners,
density-increasing agents such as barites, rust-inhi-
. ~ .
2~i~6~
-94-
biting and corrosion-inhibiting agents, surfactants and
acid or basic reagents to adjust the pH of the drilling
fluid. A typical drilling fluid within the scope of
the present invention is made from a 5% by weight
bentonite clay ~lurry using well known techniques.
Example 79
2~0 par~s of oleic acid and 1~0 parts of
triethanolamine are mixed for two minutes at room
temperature. 1600 parts of sodium petroleum sulfonate
dispersed in oil (61% by weight sodium petroleum
sulfonate) and 1600 parts of the product of Example 67
are added and the whole is stirred for five minutes at
room temperature. 4400 parts of the product of Example
66 ars added to the whole over a period of one-half
hour while heating to 65C. The temperature of the
whole i5 maintained at 65C for an additional one-half
hour. The whole is cooled to ~9C while mixing over a
period of one-half hour and then cooled to room
temperature to provide the desired product which is in
the form of a pourable ~oft gel.
r.
~L2~
9 `.
Example 80
The produc~ of Example 7g is dispersed with
water at a temperature of 60C to form a series of
stable emulsions as indicated in Table I below.
TABLE I
Product of
Example 79 Water Type of
~Wt-%7_ (Wt.%) Emulsion PH
S 95 o/w* ~.16
o~w ~ . ~
1~ 85 o/w 8.02
; 20 80 o/w 8.22
o/w 8.0
o/w 8.12
Borderine ~.34
0 So w/o** 7.24
2~ w/o 7.33
*o/w is an abbre~iation for oil-in-water.
~w/o is an abbreviation for water-in-oil.
Example 81
240 parts of oleic acid and 160 parts of
dimethyl ethanol amine are mixed for about two minutes
,~ at room temperature. 800 parts of the sodium petroleum
sulfonate identified in Example 79 and 800 parts of the
product of Example 67 are added and the whole is
stirred for about five minutes at room temperature.
2000 parts of the product of ~xample 66 are added ~o
the whole o~er a period of about one-half hour while
~L~6~6~3
96
heating to about 650C. The temperature of the whole is
maintained at 650C for an additional one-half hour.
The whole is cooled to about sgoC' while mixing over a
period of one-half hour, and then cooled to room
temperature to provide the desired product.
Example R 2
The product o~ Example ~1 is mixed with water
having a temperature of ~-5C to provide stable
emulsions at levels of 60~, 65%, 70~, 75%, 80%, so% and
95% by weight water.
Example 83
290 parts of oleic acid and 160 parts of
dirnethyl ethanol amine are mixed for about two minutes
at room temperature. 1200 parts of the sodium
petroleum sulfonate identified in Example 79 and 1200
parts o the product of Example 67 are added, and the
whole is stirred ~or about five minutes at room
temperature. 1200 paets of the product of Example 66
are added to the whole over a period of about one-half
hour while heating to about 65C. The tamperature of
the whole is maintained at 650C for an additional
one-half hour. The whole is cooled to about 49C while
mixing, and then cooled to room temperature to provide
the desired product.
_xample 84
Stable emulsions are provided by mixing
appropriate amounts of the product of Example ~2 with
water having a temperature of about 2-50C to provide
emulsions containing 60%, 65%, 70~, 75%, 80%, 90% and
95% by weight water.
While the invention has been explained in
relation to its preferred embodiments, it is to be
:,
6~ ~
-97-
understood that various modifications ~hereof will
become apparent to those skilled in t~e art upon
reading the specificatio~. Therefore, it is ~o be
understood that the invention disclosed herein is
intsnded to cover sucb modifications as fall within the
scope of the appended claims.
