CA1261608A - Water-based metal-containing organic phosphate compositions - Google Patents

Abstract

Title: WATER-BASED METAL-CONTAINING ORGANIC PHOSPHATE
COMPOSITIONS

Abstract of the Disclosure Water-based metal-containing organic phosphate compositions which are useful as corrosion-inhibiting coating compositions, metal working lubricants and drilling fluids for well-drilling operations are disclosed. These compositions comprise: (A) water or an aqueous drilling mud: (B) an overbased non-Newtonian colloidal disperse system comprising (B)(1) solid metal-containing colloidal particles predispersed in (B)(2) a dispersing medium of at least one inert organic liquid 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 hydrophobic portions; and (C) a metal-containing organic phosphate complex derived from the reaction of (C)(1) at least one polyvalent metal salt of an acid phosphate ester, said acid phosphate ester being derived from the reaction 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. These compositions 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).

Description

;" ~

~ 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.

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~26~

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 - --5-- .

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 ' '' ''' .. ~.

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.

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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 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~
--10-- .

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~

~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, 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 ~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~

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 R S - OH

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

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 -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 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.

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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 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~

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 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~

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 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 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 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~ ~

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~

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 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 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.

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~ ~

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~

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 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 -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~

-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~` ~

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~

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 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~

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~

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 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~

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 , .
~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.~

~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~ ~

(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 ,, 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 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~ ~

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 ~

.

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 , ~

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 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~ ~

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~

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~ ~

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~

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

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~

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~ ~

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~

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 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-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~

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.

.. :
:

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 , 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~

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~

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 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~

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 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 and ( 1 HZCH20) ZH ~ (CH2CH20~XH

~ (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 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~

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 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~ ~

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.

Claims (41)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A composition comprising:
(A) water:
(B) an overbased non-Newtonian colloidal disperse system comprising (B)(1) solid metal-containing colloidal particles predispersed in (B)(2) a dispersing medium of at least one inert organic liquid 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 hydrophobic portions; and (C) a metal-containing organic phosphate complex derived from the reaction of (C)(13 at least one polyvalent metal salt of an acid phosphate ester, said acid phosphate ester being derived from the reaction 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.

2. The composition of claim 1 wherein said solid metal-containing colloidal particles (B)(1) are characterized by an average unit particle size of about 20 A. to about 5000 A.

3. The composition of claim 1 wherein said dispersing medium (B) (2) is a combination of mineral oil and at least one other organic liquid miscible with said mineral oil.

4. The composition of claim 1 wherein said solid-metal containing particles (B)(1) are selected from the group consisting of alkali and alkaline earth metal salts.

5. The composition of claim 1 wherein component (B)(3) comprises at least one member selected from the group consisting of alkali and alkaline earth metal salts of an oil-soluble organic acid.

6. The composition of claim 1 wherein said solid metal-containing colloidal particles (B)(1) are selected from the group consisting of alkaline earth metal acetates, formates, carbonates, hydrogen carbonates, hydrogen sulfides, sulfites, hydrogen sulfites, and chlorides.

7. The composition of claim 1 wherein the ratio of monohydric and polyhydric alcohols to phosphorus pentoxide or phosphoric acid in derivation of said acid phosphate ester is about 2 to about 6 moles of said monohydric and polyhydric alcohols per mole of said phosphorus pentoxide or phosphoric acid.

8. The composition of claim 1 wherein the ratio of polyhydric alcohols to monohydric alcohols in the derivation of said acid phosphate ester is about 0.25 to about 4 equivalents polyhydric alcohol per equivalent of monohydric alcohol.

9. The composition of claim 1 wherein the metal of said polyvalent metal salt (C)(1) is selected from the group consisting of zinc, cadmium, lead, iron, cobalt, nickel, barium, calcium, strontium, magnesium, copper, bismuth, tin, chromium and manganese.

10. The composition of claim 1 wherein said organic epoxide (C)(2) contains at least one linkage of the formula wherein x is zero or an integer of from 1 to about 12.

11. The composition of claim 1 wherein the ratio of components (C)(1) to (C)(2) is in the range of about 0.1 to about 2 equivalents of (C)(2) per equivalent of (C)(1).

12. The composition of claim 1 wherein the weight ratio of component (B) to component (C) is from about 0.25:1 to about 10:1.

13. The composition of claim 1 with an effective amount of (D) an alkali or alkaline earth metal salt of an organic acid to enhance the dispersion of components (B) and (C) with said water (A).

14. The composition of claim 1 with an effective amount of (E) a carboxylic acid to enhance the dispersion of components (B) and (C) with said water (A).

15. The composition of claim 1 with an effective amount of (F) an N-(hydroxyl-substituted hydrocarbyl) amine to enhance the dispersion of components (B) and (C) with said water (A).

16. The composition of claim 1 with an effective amount of of (D) an alkali or 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 (A).

17. The composition of claim 1 with an effective amount of a sodium petroleum sulfonate, oleic acid and triethanol amine to enhance the dispersion of components (B) and (C) with said water (A).

18. The composition of claim 1 with an effective amount of water (A) to disperse components (B) and (C) in said water.

19. The composition of claim 1 wherein said water (A) is dispersed in components (B) and (C).

20. The composition of claim 1 wherein said composition comprises from about 5% to about 99% by weight water.

21. The composition of claim 1 wherein said composition comprises from about 25% to about 75% by weight water.

22. A method of inhibiting the corrosion of a metal surface comprising coating said surface with the composition of claim 1.

23. A method of working metal comprising contacting said metal with the composition of claim 1.

24. A drilling fluid comprising (A) from about 90% to about 99.5% by weight of an aqueous drilling mud, and from about 0.5% to about 10% of a mixture of:
(B) an overbased non-Newtonian colloidal disperse system comprising (B)(1) solid metal-containing colloidal particles predispersed in (B)(2) a dispersing medium of at least one inert organic liquid 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 hydrophobic portions; and (C) a metal-containing organic phosphate complex derived from the reaction of (C)(l) at least one polyvalent metal salt of an acid 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 wherein the weight ratio of (B) to (C) is generally from about 0.25:1 to about 10:1.

25. The drilling fluid of claim 24 wherein said solid metal-containing colloidal particles (B)(1) are characterized by an average unit particle size of about 20 A. to about 5000 A.

26. The drilling fluid of claim 24 wherein said dispersing medium (B)(2) is a combination of mineral oil and at least one other organic liquid miscible with said mineral oil.

27. The drilling fluid of claim 24 wherein said solid-metal containing particles (B)(1) are selected from the group consisting of alkali and alkaline earth metal salts.

28. The drilling fluid of claim 24 wherein (B)(3) comprises at least one member selected from the group consisting of alkali and alkaline earth metal salts of oil-soluble organic acids.

29. The drilling fluid of claim 24 wherein the solid metal-containing colloidal particles (B)(1) are selected from the group consisting of alkaline earth metal acetates, formates, carbonates, hydrogen carbonates, hydrogen sulfides, sulfites, hydrogen sulfites, and chlorides.

30. The drilling fluid of claim 24 wherein the ratio of monohydric and polyhydric alcohols to phosphorus pentoxide or phosphoric acid in derivation of said acid phosphate ester is about 2 to about 6 moles of said monohydric and polyhydric alcohols per mole of said phosphorus pentoxide or phosphoric acid.

31. The drilling fluid of claim 24 wherein the ratio of polyhydric alcohols to monohydric alcohols in the derivation of said acid phosphate ester is about 0.25 to about 4 equivalents polyhydric alcohol per equivalent of monohydric alcohol.

32. The drilling fluid of claim 24 wherein the metal of said polyvalent metal salt (C)(1) is selected from the group consisting of zinc, cadmium, lead, iron, cobalt, nickel, barium, calcium, strontium, magnesium, copper, bismuth, tin, chromium and manganese.

33. The drilling fluid of claim 24 wherein said organic epoxide (C)(2) contains at least one linkage of the formula wherein x is zero or an integer of from 1 to about 12.

34. The drilling fluid of claim 24 wherein the ratio of components (C)(1) to (C)(2) is in the range of about 0.1 to about 2 equivalents of (C)(2) per equivalent of (C)(1).

35. The drilling fluid of claim 24 wherein the weight ratio of component (B) to component (C) is from about 0.25:1 to about 10:1.

36. The drilling fluid of claim 24 with an effective amount of (D) an alkali or alkaline earth metal salt of an organic acid to enhance the dispersion of components (B) and (C) in said drilling mud.

37. The drilling fluid of claim 24 with an effective amount of (E) a carboxylic acid to enhance the dispersion of components (B) and (C) in said drilling mud.

38. The drilling fluid of claim 24 with an effective amount of (F) an N-(hydroxyl-substituted hydrocarbyl) amine to enhance the dispersion of components (B) and (C) in said drilling mud.

39. The drilling fluid of claim 24 with an effective amount of (D) an alkali or alkaline earth metal salt of an organic acid, (E) a carboxylic acid and (F) an N-(hydroxyl-substituted hydrocarbyl) amine to disperse components (B) and (C) in said drilling mud.

40. The drilling fluid of claim 24 with an effective amount of a sodium petroleum sulfonate, oleic acid and triethanol amine to disperse components (B) and (C) in said drilling mud.

41. A method of drilling a well comprising circulating the composition of claim 24 in said well during drilling.