US2616925A - Organic alkaline earth metal complexes formed by use of thiophosphoric promoters - Google Patents

Description

Patented Nov. 4, 1952 UNITED STATES PATENT OFFICE oItGANic ALKALINE EARTH, METAL COM- PLEXES FORMED BY USE OF THIOPHO'S PHORIC PROMOTERS Peter A. Assert, Thomas W. Mastin, and Alan Rhodes, Cleveland, Ohio, assigno'rs to The Lubrizol Corporation, Wickliffe, Ohio, at corporation of Ohio No Drawing, Original application m n 16,

1951, SerialsNo. '216,103. Divided and this application December 28, 1951, Serial No. 263,961

No 279,258, filed March 23, 1952.

This invention relates to organic metal complexes and novel methods for the production of such complexes.

It is now well known that when preparing a salt or soap of an organic acid, the mereuse of an excess of neutralizing agent, which in the prior art has beenv in the form of the-oxide, hydroxide, carbonate, etc. of the desired metal, may result in a product which contains an amount of metal in excess of that theoretically required to replace the acidic hydrogens of the organic acid used as the starting'materialr Work with this type of product has shown that for many uses, particularly where extreme care must be exercised to prevent the composition from being corrosive, as for example in lubricants, desirable results are secured by the use of these so-called basic salts or soaps.

Among the earlier workers in the art who rec.- ognized this factor and indicated that the use of basic soaps was desirable was Bergstrom who,

in his Patents Nos. 2,270,577 and 2,279,086, made reference to the desirability of using the basic soap without, however, giving any specific method for the preparation of such soaps. 'A similar disclosure is foundin Van Ess- Patent No. 2,372,411.

With the demonstrated superiority of such basic soaps over the normal or slightly acidic soa s, the prior art workers then attempted to find ways of increasing the b'asicity of the soaps, or stated in another way, increasing the amount of metal, for example, held in stable form in what was termed as a metal complex. One of the earliest patents referring to these basic salts as complexes or coordination compounds is McNab No. 2,418,894, who gives'no indication in his patent as to the molecular structure of the product. As might be expected, one of the first steps employed to produce a metal salt having an intended large excess-of metal in combination was to use an unusually large excess of neutralizing 19 Claims. (Cl. 260-504) 2 agent, such as lime. A representative patent disclosing this procedure is Griesinger et al. No. 2,402,325 who suggested the use of neutralizing agent up to 220% of the theoretical amount. This large excess of neutralizing agent was employed in a process more or less conventional for producing salts or soaps excepting that the processwas carried out in the presence of steam in order to facilitate the formation ,of the product.

The work of Griesinger' was followed by the Work of Campbell and Dellinger as given in Patent No. 2,465,861. These patentees base their disclosure on the hypothesis that minor amounts of an alkaline earth metal hydroxide or carbonate can be peptized, or held in a state of coll'oidal suspension in oil by means of an oil-soluble mahogany sulphonate. Another worker in' the art who sought to combine in such complexes an excess amount of metal was Mertes' whose Patent No. 2,501,731 was granted March 28, 1950; Merte's' first prepared the normal soap and stated that such soap or soap concentrate may have additional base combined'therewith' by a'more or'less simple mixing and heating operation followed by filtering. The disclosure in Mertes appears to' i'ndic'ateqthat his product is similar to that of Campbell and Dellin'ger', in that theexcess' neutralizing agent was held in the product in the form of a colloidal suspension.

1 All of the previously enumerated processes. have been tried, not only duplicating certain of the examples given in the above-identified patents, but also using different acids and different neutralizing agents. As a result of these" experiments, it has been found that there is a definite upper limit to the amount of alkaline earthm'etal which can be held incombination or in colloidal suspension by means of these prior art processes. The grea'test'total amount of alkaline earth in tail which can possibly bethus incorporated inth produc't'by' mea'ns' of any of these prior artl rocesseshasbeen obtained when using barium and in that caseitis equal to about 2.3 timesjthe'the' oretica-l' amount present in the normal salt; For

the purpose of the present invent-m th -5 of" the total metal in the complex to the amount of meta-1' which i'si-n the form of the normal salt of the oil'solub'leor'gan ic aci'cl-willhereinafter bereferred to r as the "metal ratio? By means of the resent invention, it is now possible to obtain alkaline earth metal organic complexes which contain more metal or higher metal ratios than is possible by prior art processes. With regard to lubricants, these high metal containing complexes are for example particularly suited as detergents, and by reason of the metal concentration can be used in amounts appreciably less than other additives known in the prior art in order to attain a desired level of performance. It will also be observed that by virtue of the more eifective nature of the present complexes in lubricants, usually it will cost less to obtain a desired result, because appreciably less additive is required. The alkaline earth metal organic complexes are produced in accordance with the present invention as a fluid, which is readily adapted for application where high concentrations of alkaline earth metal are desired, e. g. in lubricants. For example, if the complex alone is desired, it can be produced in mineral oil solutions of at least about 20% concentrations; whereas if the complex is wantedin combination with other additives, it can be available in concentrations of at least about in mineral oils.

It is a principal object of our invention to provide an alkaline earth metal organic complex which contains in stable form an amount of metal substantially greater than that contained in any of the so-called alkaline earth metal complexes previously produced. It has been found that a metal ratio substantially greater than that possible with the prior art processes give results which are strikingly superior, especially in the field of lubricants in which these products have particular utility.

It is a further object of this invention to produce by our improved process, complexes which, while containing the same amount of alkaline earth metal as in complexes produced by the prior art process above described, are nevertheless different from and superior to such prior art complexes.

Still another object of this invention is to provide novel methods of producing organic alkaline earth metal complexes.

Further objects of our invention will appear as the description proceeds.

'To the accomplishment of the foregoing and related ends, said invention then comprises the features hereinafter fully described and particularly pointed out in the claims, the following description setting forth in detail certain illustrative embodiments of the invention, these being indicative, however, of but a few of the various ways in which the principle of the invention may be employed.

' In its broadest aspects, the process of the present invention comprises combining a salt-forming material with an organic acid compound (to be understood hereinafter as the acid itself and/or an alkaline earth metal salt thereof) in the presence of a material which is referred to hereinafter as the promoter." The precise function of the promoter material is not specifically understood since it has not been possible to specifically identify the molecular structure of the product produced. At present, it appears that none of the complexes, i. e., either those prepared by prior art techniques or those obtained under the present invention are susceptible of precise identification. This is clearly shown with respect to the prior art complexes by reason of the apparent disagreement among workers as to the nature of compounds which contribute metal in excess of the normal salt. In one-in stance, it is held that this phenomenon is a result of partial replacement of the hydroxyl groups in the inorganic metal compound, whereas among another group of prior art workers it is held that the high metal containing complexes are actually colloidal suspensions or dispersions in which the salt of the organic acid is the peptizing agent. In the present invention, the immediate product is produced by the use of a promoter, and at least one stage contains the promoter in chemical combination. It is possible, however, to recover the promoter from the product by suitable treatment as hereinafter explained, and the final product which then has a constitution different from the initial end product is, similar to the initial product, of utility as a lubricant additive.

Stated more particularly, the present invention comprises the improvement in the process of producing an alkaline earth metal complex of oil-soluble organic acids, wherein an organic acid compound (to be understood hereinafter as the acid itself and/or an alkaline earth metal salt thereof) is caused to combine with a saltforming metal compound under conditions which produce a normal salt, which comprises increasing the amount of metal which will be thus combined by having present in the process mass.

((1) an amount of such metal compound substantially in excess of the stoichiometric amount required to form the normal metal salt;

(b) an organic compound selected from the class consisting of those organic compounds which are water-soluble at a temperature of 50 C. to the extent of at least 0.0005% and which in the presence of water have an ionization constant greater than about l 10 at about 25 C.; and the salts of such organic compounds; and

(0) water, including free and combined water in the other components;

and maintaining the mass at a temperature and for a period of time sufficient to drive off substantially all free water and water of hydration which may be present.

A more specific aspect of the process comprising this invention may be defined as the process of producing an alkaline earth metal organic complex which comprises:

I. Preparing and mixing a mass in which, at 50 C., at least 50% of the components are in the liquid state and which mass the active components consist of:

A. An oil soluble organic acid compound;

B. An organic compound containing an element of group VI of the periodic chart which has an atomic number less than 17, which compound is selected from the class consisting of: v

(1) An organic compound AH in which H is hydrogen and A is an organic anionic radical, having:

(a) An ionization constant in water of at least about 1X 10* at about 25 C.;

(b) A water solubility at 50 C. of

at least about 0.0005%; and

(c) In saturated aqueous solutions at about 25 C. a pH of not greater than about 7;

(2) The alkaline earth metal salts of such organic compounds;

the relative amounts of A andB used bein iii'the range of from about one equivalent of A toabout equivalents of B to about 10 equiva- -lents':o'f A to about one equivalent of B;

' C; inorganic alkaline 'earth'metal comia'ound v (1) Which is water-soluble at a temperature of 50 C. of at least0.0003% (2) In an amount such that there are present in the mass substantially more than 1 equivalent of alkaline earth metal, including the alkaline earth metal present in the remaining components'per equivalent of A plus B;

and

51). Water, in an amount equal to at least about one mole per mole of C. II. And then maintaining the mass at a temperature and for a periodof'time sufl'icient to drive off substantially all free water and water of hydr a'itiori Which maybe present. in the above-outlined processes, following Step II, the-mass or, product can be optionally treated inaccordancewith Steps III and IV given below.

Then treating the mass or product with a 'rhaterial which in the presence of the mass or product will form a material having a higher ionization constant than the promoter, and optionally;

IV. removing from the mass or product so much of the liberated or released promoter as may have been formed by Step III.

Thefollowing examples give the preparation of a plurality of products which range in metal content from about that of the normal salt up to many times that amount.

We have found that sulphate ash and/or metal content values, and the metal ratio values calculated therefrom, are-one means for characterizing certain of the salt complexes. As the description of the invention proceeds, it will become apparent that the neutralization number of .a salt complex is'in certain instances an unreliable index of the amount of excess metal in such complex, since it is greatly affected by the type 'of inorganic alkaline earth compound emplayed and can be varied within wide limits without significantly changing the metal content of the product by treatment of them as with air, C.z,"-and:the like. v

The above is not to be construed as a statement that the neutralization number is not an importantproperty of a salt complex. .For some uses, for "example in lubricants, it is advantageoiis in certain instances to employ a salt complex of a substantially neutral character, whereas'iii dther-instances a salt complex of high alkamay has beenv found to produce the desired resuits.

' EXAMPLE 1 1980 "grams of the barium salt of petrolatum sulphonic acid (which contains 9.2% sulphate asht-an'd is derived from Pa. amber petrolatum) and 132 grams of para-tertiary-butyl phenol wereplaced intoa'fielit'er, 3-neck flask and heated to 95 C. To; this mixture was added a barium oxide: slurry (417grams of barium oxide and 1100 grams of water) and the mixture was heated for about one hour at reflux temperature. Then the temperature was slowly raised to about ISO-160 C. "and maintained there for one hour to removeisubstantiallyall of the water. The

6 product was then filtered. The salt complex is a viscous liquid, light brown in color and having a very slight odor. The salt complex had the following properties:

Basic No. 1 23.1 Per cent sulphate ash a. 13.96 Metal ratio Solubility Percent Appear. Appear- Initral of ance ance Solvent Product S533 after '1 after 1 added Week month Pa. 150 Neutral on 50 Clear-" clear oies'r. Do. 10 do d'-- Do; 1 do Do.

The above preparation, which is an example of the present 'i'rlV'ehti'oh, is com ared With a'basic sulphonate prepared in accordance with a conventional technique and which is' described de low.

EXANLPLE. 2

500 grams of the barium salt of the petrolatum sulphonic acid given in Example 1 were mixed with a slurry of barium oxide (containing 38- grams of barium oxide and 50 grams of water) and placed in a 2-liter, 3-neck flask, heated at about 160 C. for one hour until substantial ly all of the water was removed, and then the product was filtered. The resultant basic sulphonate has the following properties:

Basic No. 5127 Per cent'sulphate ash 9.85

Metal ratio 1.08

EXAMPLE 3 1009 grams of the barium .salt of unsaturated paraffin wax sulphonic acid containing 13.1% sulphate ash were mixed with 455 grams of a mineral oil having a viscosity of 160 SSU at 100 F. and 109.5 grams of para-tertiary-butyl phenol (ratio of equivalents is 1.54), placed in a suitable vessel and heated to about C.

with stirring. To this mixture was added a slurry of barium oxide (containing 269 grams of barium oxide and 920 grams of water) and the total mixture was heated at about C. forone hour. The temperature was slowly raised to about C. and held there for about one hour until substantially all of the water was removed. Then about 3% Hyflo (a filter-aid) wasadded to the product to facilitate filtering. The salt complex was then separated by filtration. The salt complex thus prepared had the following properties:

The salt complex product was fluid, brown in color, and did not contain any odor.

The preparation given in Example 3 is a typical illustration of the present invention. In

Example 4 given below, a basic sulphonate was prepared in accordance with a conventional technique for comparison with the product given in Example 3.

EXAMPLE 4 511 grams of the barium salt of unsaturated parafiin wax sulphonic acid given in Example 3 were mixed with '75 grams of water and heated to about 60 C. with stirring. 58 grams of barium oxide were added to the mixture, which was then heated to about 150 C. and held there for one hour until substantially all of the water was removed. The product was filtered with the aid of Hyfio in order to separate the complex salt. The salt complex had the following properties:

Basic No. 16.2 Per cent sulphate ash 19.7 Metal ratio 1.63

The salt was a waxy solid, brown in color, and did not contain any odor.

EXANIPLE5 1000 grams of the barium salt of mono-paraffin wax substituted napththalene sulphonic acid containing 8.63% sulphate ash were mixed with 445 grams of mineral oil having a viscosity of 160 SSU at 100 F. and 64.5 grams of paratertiary-butyl phenol (ratio of equivalents is 1.7) and heated to about 90 C. A slurry of barium oxide (203.5 grams of barium oxide and 543 grams of water) was added, and the mixture was heated for two hours at the reflux temperature, and then dehydrated at about 165 C. for a period of one hour. Hyflo was then added to the product and the salt complex was recovered by filtration. The salt complex contained the following properties:

Basic No. 44.1 Per cent sulphate ash 17.9 Metal ratio 2.37

The salt complex prepared in accordance with Example 5 was compared with a product which was made by a conventional technique, as shown in Example 6 below.

EXAMPLE 6 1000 grams of the barium salt of mono-paraffin wax substituted naphthalene sulphonic acid given in Example 5 were heated to about 95 C. and barium oxide slurry (113 grams barium oxide and 100 grams water) was added to the mixture. The total mixture was held at a temperature of 100 C. for about one hour, and then dehydrated at a temperature of about 150 C. for about one hour. The salt complex was separated by filtration. Throughout the above preparation a nitrogen atmosphere was maintained above the mixture. The resultant salt complex was liquid and black in color. The following properties were determined for the product:

Basic No. 18.9

Per cent sulphate ash 12.2

Metal ratio 1.45

EXAMPLE 7 400 grams of the barium salt of mono-parraifin wax substituted naphthalene sulphonic acid disulphide containing 8.2% sulphate ash and 27 grams of para-tertiary-butyl phenol were placed in a suitable vessel and heated to 90 C. (ratio of equivalents is 1.54). A barium oxide slurry constituting 66.5 grams of barium oxide and 180 cc.

of water was added to the mixture and refluxed for about one hour. The temperature was then slowly raised to about 160 C. over a period of about four hours and held at that level for about 1.5 hours until substantially all of the water was removed. The salt complex was separated by filtering. The product was a viscous liquid, black in color, and contained a very slight odor. The following properties were determined for the salt complex:

Basic No 69.7 Per cent sulphate ash 24.3 Metal ratio 3.50

The product obtained in accordance with Example 7 was then compared with a salt complex obtained under a conventional technique as shown in Example 8 below.

EXAMPLE 8 20 ml. of water were added to 450 grams of the barium salt of mono-parafiin Wax substituted naphthalene sulphonic acid disulphide given in Example 7 and heated to a temperature of about 60 C. 27.5 grams of barium oxide were then added to the mixture and the temperature was slowly raised to about 160-170" C. and held there for about one hour until substantially all of the water was removed. The salt complex was then separated by filtration. The product was fluid in consistency, black in color, and contained a slight odor. The following properties were determined for the product:

Basic No. 5.27 Percent sulphate ash 8.95 Metal ratio 1.10

It is to be noted that the barium salt of monoparaffin wax substituted naphthalene sulphonic acid disulphide has a sulphate ash of about 8.2% and that the complex formed by the conventional technique did not increase the sulphate ash content appreciably. However, as shown in Example 7, the method of the present invention produces a complex containing substantially more metal in combination.

Other types of oil-soluble organic acids or salts thereof were combined in accordance with the method of the present invention. In the following examples, it is to be noted that in every instance a salt complex was formed containing more metal than is possible by known techniques.

EXAIVIPLE 9 6000 grams of a 30% by weight oil solution of barium petroleum sulphonate (sulphate ash content 7.6%) were mixed with 848 grams of parateritary-butyl phenol in a 12-liter, 3-neck flask (ratio of equivalents 1.7) and heated to C. A slurry of barium oxide constituting 1,100 grams of barium oxide and 2,911 grams of water was then added and the mixture held there for about one hour at a temperature of about 90-95 C. The total mixture was then slowly raised in temperature to C. and dehydrated at that temperature over a period of about 4% hours. The salt complex was separated by filtration and was found to be a slightly viscous liquid, black in Metal ratio 3.59

9. EXAMPLE 10.

phenol (ratio of equivalents. 1.52) and 473 grams of solvent extracted Mid-Continent oil having a viscosity of 160 SUS 100 F. were mixed together and heated to 50 C. A slurry comprising 387 grams ofBaO and 1,030 cc. of water was added quickly, maintaining the temperature at about 65 C. The mixture was then heated to 100C. and held there for one hour. Then the temperature was raised to 150 C. over a period of 2 /2 hours and held there for one hour. The product was obtained by filtering the mass and was found to be a slightly viscous liquid, red in color, and contained a slight odor. The following properties were determined for the product:

Basic No. 7.6.0

Per cent barium 20.0

Percent sulphate ash. 3 .0

(calculated from metal content) Metal ratio 3.65

620 grams of di-(Z-ethyl-hexyl) mono-thicphosphoric acid, 310 grams ofisononyl phenol (ratio of equivalents. is 1.52), 755 grams of mineral oil having 160 SUS 100 F., and 2060 ml. of water were mixed together. Then 774 grams of BaO were added over a. half hour period. The total mixture was then refluxed for one hour at 100 0., whereupon the temperature was raised to 150 C. and held at that level for one hour. The temperature of the mixture was allowed to cool to 50-60 C., and then blown with CO2 to obtain a neutral product. The complex obtained had the following properties:

Acid No. 6.85

Per cent barium 17.2

Metal ratio 2.65

' EXAMPLE 12 -77? grams of di-(2-ethy1 hexyl) dithiophosphoric acid, 308 grams of iso-nonyl phenol (ratio of equivalents 1.52 and 914 grams of solvent extracted Mid-Continent oil having a viscosity of 160 SUS 100 F. were mixed together followed by an addition of BaO- slurry consisting 773 grams of BaO. and 2,060 cc; of H20, while keeping the temperature below 65 C. The total mixture was then heated at 100 C. for one hour, followed by a raise in temperature to 150 C. over a period of 2 hours, and maintained at that level for one hour. was a slightly viscous liquid, red in color, and contained a slight odor. The product had the following properties:

Basic No 78.0

Per cent barium 22.7

Per cent sulphate ash 38.6

(calculated from metal content) Metal ratio 4.52

EXAMPLE 13 172 grams of di-(n-hexyl) dithiophosphorio acid, 500 grams of petroleum sulphonic acid, 159 grams of iso-nonyl phenol (ratio of equivalents of oil soluble acids to iso-nonyl phenol is 1.52), and 1,170 cc. of water weremixed together, then 437 grams of BaO were added over a period of hour. The mixture was heated at refluxtemperature for 1 hour,'followed by heating to 150 .C. over a period of 2 hours, and. then main- The desired product 'taining that temperature for: 1 hour.

.the quality of the product.

The desired product was a viscous-liquid, brown in color, and contained a slight odor. The following properties were determined:

Basic No 87.1

Per cent barium 28.6

Per cent sulphate ash 48.8 (calculated from metal content) Metal ratio 5.22

EXAMPLE .14

172 grams of di-(n-hexyl) dithiophosphoric acid. 500 grams of petroleum sulphonic acid and 98 grams of para-tertiary-butyl phenol (ratio of equivalents of oil soluble acids to paratertiarybutyl phenol is 1.52) were mixed together. To this mixture was added a slurry of 387 grams of BaO and 1,080 cc. of water. The mixture was heated at 100 C. for one hour, and then the temperature was raised to 150 C. and held at that level for one hour. The product was a highly viscous liquid, brown in color, and contained a slight odor. The. following properties of the product were determined:

Basic No; 121 Per cent barium 30.05 Sulphate ash 51.0

(calculated from metal content) Metal ratio 5.36

EXAMPLE? 249 grams of petroleum naphthenic acid,. 88.6 grams of para-tertiary butyl phenol (ratio of equivalents is 1.70),. l212'grams of a conventionally-refined Mid-Continent oil having a viscosity of 110 SUS 100 F., 347 grams of BaO, and 700' ml. of H were placed in a 5 liter; 3 neck flask and heated to 100 C. with stirring. The mixture was held at 100-105 C. for 1 hour, and then the temperature was raised to 150-160 C. After holding the temperature for 1 hour at 150-160 C., the mixture was blown with CO2 for hour, keeping the temperature at about 150-160 C. The mixture was then filtered with Hyilo,v and the separated product had the following properties.

Basic No 1.98 Per cent sulphate ash 25.10 Metal ratio 4.10

A mixture of diiferent oil-soluble metal sulphonates was treated in accordance with a conventional technique and by the method of, the present invention to determine what effect if any the two types of sulphonates would have on are given in Examples 16 and1'7 below.

EXAMPLE 16 A mixture containing 500 grams of the barium salt of petrolatum sulphonic acid (sulphate ash 9.2%) 197 grams of the barium salt of petroleum sulphonic acid (sulphate ash 7.6%), and grams of para-tertiary-butyl phenol (ratio of equivalents of the sulphonates to promoter is 1.54) was heated to C. A slurry of barium oxide constituting 123 grams of barium oxide and 330 grams of water was added to the mixture. The total mixture was refluxed for one hour at C'. and then the temperature was slowly raised to C. for a period of one hour to substantially remove all the water. The complex wasseparated by filtration and was found Such preparations 11 'tobe a liquid, and black in color. Thefollowin properties were determined: Basic No. 27.7 Per cent sulphate ash 17 Metal ratio 2 41 EXAMPLE 17 Basic No 20.2 Per cent sulphate ash 11.72 Metal ratio 1.51

While most of the examples given herein use either a neutral or normal salt of the organic acid as a starting material to produce the high metal content complex, nevertheless it is contemplated for the purposes of this invention to employ the complexes produced by conventional techniques as a starting material. illustrates this concept:

EXAMPLE 18 1634 grams of a barium petroleum sulphonate- BaO complex (obtained by dehydrating a barium petroleum sulphonate, 7.6% sulphate ash, water and BaO mixture at 150 C. for one hour, and producing a complex which has a basic number of 40, metal ratio of 2.25 and a 16% sulphate ash) and 121 grams of di-isobutylphenol (ratio of equivalents 1.7) were combined and heated to To this mixture was added 665 cc. of water, followed by a slow addition of 175 grams of BaO.

The entire mixture was then refluxed for one.

hour, and the temperature was raised to 150 C. over a three hour period and held there for one hour. Prior to filtering, the mass was blown with CO2 at a rate of 3.6 cubic foot/hr. for 1% hours at 150 C. The product analyzed as follows:

Basic No 8.67 Per cent sulphateash 24.8 Metal ratio 4.13

It can be seen from the sulphate ash analyses.

of the product and overbased sulphonate used as a starting material that there was an increase from 16.0 to 24.8 in sulphate ash. Clearly, therefore, the conventionally overbased materials can be used as starting materials in the present inv vention.

Other experiments were conducted in order to determine the effect of a higher dehydration temperature in the preparation of the salt complex of the present invention. amples 19 and 20 below illustrate the effect of higher temperatures.

EXAMPLE 19 2000 grams of a oil solution of barium petroleum sulphonate (sulphate ash 7.6%) were mixed with 120 grams of para-tertiary-butyl phenol (1.52 ratio of equivalents) and heated to 95 C. To said mixture was added a slurry of barium oxide containing 520 grams of barium The following example In this respect, Ex-v V 12 oxide and 1390 ml. of water. The total mixture was heated for one hour at 100 C., and then was slowly raised in temperature over a period of three hours to 200 C. The mixture was maintained at this high temperature for a period of one-half hour. The salt complex was separated by filtering and was found to be an oily liquid, reddishbrown in color, and contained a faint odor. The following properties were determined:

Basic No 71.5 Per cent sulphate ash 24.3 Metal ratio 3.80

EXAMPLE 20 2036 grams of 30% oil solution of barium petroleum sulphonate (sulphate ash 7.6%) were mixed with 74.5 grams of phenol (1.67 ratio of equivalents) and heated to 100 C. A barium oxide slurry containing 483 grams of barium oxide and 1290 ml. of water was added and the mixture refluxed slowly for a period of one hour at 100 C. The mixture was then dehydrated by heating slowly to 200 C. and maintaining such a temperature for a period of about one-half hour. The salt complex was separated by filtration and was found to be an oily liquid, reddish-brown in color, and contained a slight odor. The following properties were determined for the complex:

Basic No 111.5 Per cent sulphate ash 32.8 Metal ratio 5.56

In addition to the promoters tested above, various other promoters were tried to determine the efiectiveness thereof in preparing the complexes of the present invention.

EXAMPLE 21 A mixture of 2280 grams of a 30% oil solution of barium petroleum sulphonate (sulphate ash 7.6%) and 83 grams of phenol (ratio of equivavents is 1.53) was heated to a temperature of 60 C. 496 grams of barium oxide and 1300 grams -of water were added to the above mixture and the temperature was raised to 90-100 C. After holding at said temperature for one hour, the temperature was raised over a period of three hours to 150 C. and held at that level for onehalf hour. The resultant salt complex was fluid in consistency and dark red in color. The following properties were determined:

Basic No 91.4

Per cent sulphate ash 268 Metal ratio 4.37

EXAMPLE 22 The ionizable organic compound or promoter employed in this test was prepared by reacting grams of tertiary-butyl benzene with 71 grams of chlorosulphonic acid at a temperature of 30-40 C. for a period of one hour. The resultant product, tertiary-butyl benzene sulphonic acid, was dissolved in a little Warm water and admixed with 1550 grams of a 30% oil solution of barium petroleum sulphonate (ratio of equivalents of sulphonate to sulfonic acid is 1.52). The mixture was heated to C., whereupon 284 grams of barium oxide and 760 ml. of water were added. The mixture was stirred for one hour at a temperature of -102 C. The temperature was thereupon raised to 200 C. for a short period and then reduced to C. and held at that level for a period of one hour. The salt complex thus obtained was an oily liquid, reddish-brown in colorgand contained-afaint-odor. The properties ofthe product are as follows:

BasicNo 64.7

Per cent sulphate ash 27.0

Metal ratio 4.73

EXAMPLE 23 2500 grams of 30% oil solution of barium petroleum sulphonate (sulphate ash 7.6%) were admixed with 173 grams of para-tertiary-butyl' benzoic' acid (1.68 ratio'of equivalents) and, heated to 95 C. 458 grams of barium oxide'and 1215 grams of water were added to the mixture and the temperature was maintained at 100 C. for about one hour. Thereafter the temperature was slowly raised to 150 C. and maintained at that level for a, period of one hour. The salt complex was filtered from the total mixture and was an oily liquid, brown in color and contained a faint odor. The following properties were: de-

termined:

BasicfNo 32.1 Per'centsulphate ash 19.1 Metal ratio 2.88

EXAMPLE 24' 630 grams of a 30% oil solution of barium petroleum sulphonate (7.6% sulphate ash) were admixed with 350 grams of nitro-p'arafiin wax (ratio of equivalents is 0.59). Then 760 cc. of water was added, followed by the addition of 296 grams of BaO. For one hour the mixture was agitated at 90-100 (1., whereupon the temperature was raised to 150 C. and held at that level for one hour. The mixture was filtered, and the complex obtained had the following properties:

Basic No 132 Percent sulphate ash 33.3

"Metalratio 6.47

EXAMPLE 25 2050 grams of a 30% oil solution of barium petroleum sulphonate (sulphate ash 7.6%) were admixed with 73.5 grams of l-nitro-propane (ratio of equivalents is 1.62) and heated to a tempera- Basic'No 78.2 Percent sulphate ash 28.2

Metal ratio 4.60

EXAMPLE 2'6 1500' grams of a 30% oil solution of barium petroleum sulphonate having a sulfate ash of 7.6%, 93 grams of i-so-propyl phenol (ratio of equivalents 1.7), and 670 grams of water were placed in a 3-li-ter flask and heated to 60 C.

.250 grams of BaO were then added, and the temperature was allowed to rise to 100 C. The mixture was held at 100 C. for one hour, followed by a rise in temperature to 150 C. over a two hour period, where the temperature was held for onehalf hour. The total mixture was filtered, and the filtered product had the following properties:

Basic No -1 87.8 Per cent sulphate ash 25.95 Metal ratio 3.88

EXAMPLE 27 j 1140 grams of a 30% oil solution of barium petroleum sul honate having a sulphate ash of 7.6% and grams of para-tertiary-a-myl phenol (ratio of equivalents 1.54) were heated to 70 C. Thereafter 600 cc. of water were added, followed by a slow addition of 227 grams of BaO. The mixture was refluxed for one hour, and then the temperature was raisedto 160 C. over a period of four hours and held there for one-half hour. The product was separated by filtration, and had the following analyses:

Basic No Per cent sulphate ash 24.60 Metal ratio 3.96

EXAMPLE 28 2583 grams of a 30% oil solution of: barium petroleum sulphonate having a 7.6% sulphate ash, 1442 grams of beta-nap-hthol (ratio of equivalents is 1.69) and 1262 ml. of Water were combined and mixed thoroughly. Then 472 grams of BaO were added over a one hour period, followed by maintaining the total mixture at C. .for one hour. The temperature was then raised to C. and held there for one hour. Prior to filtering the. mixture, it was blown with CO2 for 75 minutes at which time the mixture had a basic number of 0.8. After filtering, the

product analyzed as follows: 7 7

Basic No; 4.88

Sulphate ash 23.8

Metal ratio 3.90

EXAMPLE 29 1530 grams of a 30% oil solution of' barium petroleum sulphonate having a 7.6% sulphate ash, 129 grams of iso-nonyl phenol (ratio of equivalents is 1.7) and 727 m1. of water were combined and thoroughly mixed. Then 271 grams of BaO were added and the total mixture was held at 100 C. for one hour. The temperature was then raised to 150-160 C. and held there for one hour. Prior to filtering, 'the mass was blown at about 150 C. with CO2 until a basic number of about 1. was obtained. The filtered product analyzed as follows:

Basic No 3.9

Sulphate ash 25.0

Metal ratio 4.17

EXAMPLE 30 2600' grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash, 215 grams of tertiary-butyl chlorophenol (ratio of equivalents is 1.7 and 1265 cc. of water were combined, followed by an addition of 459 grams of BaO. 'The temperature of the total mixture was raised to 100 C. and held there for one hour. Then the temperature was raised to 150 C. where it was held for one hour.- Prior to filtering the mixture, it was blown for three hours with CO2 at l35-145 C. until the mixture was slightly basic. The filtered product analyzed as follows:

Basic No. 13.3 Per. cent sulphate ash 25.45

Metal ratio 1. 4.38

EXAMPLE 31 1530 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash and 210 grams of trichlorodiphenyl ether sulphonic acid (ratio of equivalents is 1.7) were heated to 70 C. To this mixture were added 725 grams of water followed by the addition of 271 grams of BaO. The entire mixture was refluxed for one hour, then heated to 150 C. over a three hour period and held there for one hour. Prior to filtering, the mixture was blown with CO2 at 150 C. and at a rate of 3.6 cu. ft./hr. for one and one-half' hours. The filtered product analyzed as follows:

Acid No. 0.45 Per cent sulphate ash 24.7

Metal ratio 4.34

EXAMPLE 32 1530 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash and 175 grams of tertiary-butyl naphthalene sulphonic acid (ratio of equivalents is 1.7) were combined and heated to 70 C. To this mixture wasadded 725 grams of H20, followed by a slow addition of 271 grams of BaO. The entire mixture was then refluxed for one hour, and then heated to 150 C. over a three hour period. The mixture was held at 150 C. for one hour. Prior to filtering, the mass was blown at 150 C. with CO2 at a rate of 3.6 cu. ft./hr. for 1 hours. The filtered product analyzed a follows:

Acid No. 0.41

Per cent sulphate ash 24.1

Metal ratio 4.12

EXAMPLE 33 1530 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash and 131 grams of methyl naphthalene sulphonic acid (ratio of equivalents is 1.7) were combined and heated to 70 C. 725 grams of water were added to the mixture, followed by a slow addition of 271 grams of BaO'. The entire mixture was refluxed for one hour, then the temperature was raised to 150 C. over a three hour period, and held there for one hour. Prior to filtering, the mass was blown with CO2 at a rate of 3.6 cu. ft./hr. for 1 /2 hours at 150 C. The filtered product analyzed as follows:

Basic No. Nil Per cent sulphate ash 25.9 Metal ratio 4.41

EXAMPLE 34 4 1530 grams of a 30% oil solution of barium follows:

Basic No. 0.23 Per cent sulphate ash 24.6 Metal ratio 4.10

EXAMPLE 35 Di-isopropyl benzene sulphonic acid obtained by reacting 162 grams of di-isopropyl benzene sulphate ash and 1220 ml. of water.

16 with.122 grams of chlorosulphonic acid for one hour at C. were combined with 2600 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash and 1220 The filtered product analyzed as follows:

Acid No. 1.22

Per cent sulphate ash 25.4

Metal ratio 4.33

EXAMPLE 36 Cymene sulphonic acid obtained by reacting 134 grams of cymene with 122 grams of chlorosulphonic acid at 70100 C. for 1 /2 hours were combined with 2600 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% The ratio of equivalents of oil soluble sulphonate to sulphonic acid is 1.7. To this mixture was added 461 grams of BaO and the entire mixture was then held at 85100 C. for one hour. Then the temperature was raised to 150 C. and held there for one hour. Prior to filtering, the mass was blown with CO2 for one-half hour at C. The filtered product analyzed as follows:

Acid No. 0.95 Per cent sulphate ash 25.8

4 Metal ratio 4.38

EXAMPLE 37 2600 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash, 2219 grams of tertiarybutyl dichlorophenol (ratio of equivalents is 1.7) and 1265 grams of water were combined, followed by an addition of 459 grams of BaO over a 45 minute period. The entire mixture was held at 100 C. for one hour, followed by maintaining the temperature at 150 C. for one hour. Prior to filtering, the mass was blown with CO2 for 90 minutes at -150 C. until it was slightly acidic. The filtered product analyzed as follows:

Basic No 6.45 Percent sulphate ash 23.2 Metal ratio 3.85

EXAMPLE 38 2600 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash, 236 grams of di-isopropyl dithiophosphoric acid (ratio of equivalents is 1.7). and 1220 ml. of water were combined, followed by a slow addition of 461 grams of BaO. The mixture was held at 100 C. for one hour, and then heated to C. and held there for one hour. Prior to filtering, the mass was blown with CO2 for 20 minutes at l25-150 C. The filtered product analyzed as follows:

Acid No. 0.27 Percent barium 14.25 Percent sulphate ash 24.2

(calculated from metal content) Metal ratio 4.15

EXAMPLE 39 2600 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash, 100 grams of acetyl-acetone (ratio of equivaeraees 17 alents is 1.7) and 1265 cc. of water were combined, followed by a'slowaddition of 459 grams of BaO over aone hour period. The entire mixture'was held at 94 C. forone hour, followed by a one hour period of heating at 150 C. Prior :to

filtering, the mass was blown with COz'fOl one hour at 135-150 C. The filtered product analyzed as follows:

Acid No. in 11.2

Percent :sulphate ash i 1-... 322,8

Water were then added, followed by a slow :addition of 2'71 grams of .BaO. "The mixture was refluxed for one hour, and then held at 150 C. for one hour. Prior to filtering, the mixture was blown With'COz .at a rateof 73.6 cu. ft/hr. for 1.25 hours at a temperature-of 150 C. The filtered product analyzed as follows:

Acid .Nor :24 Percent lsulphate ash l .235 Metal'ratio r n The salt complex cania'lso be prepared'by starting with the oil-:solub'l'e sulphonic acid and treating with a "promoter and the inorganic "metal compound. This technique differs .from those given above because as'shown in 'all'th'e above examples, the normal metal sulphona'te or conventionally overbased sulphonate was employed as 'a'starting material; In order to demonstrate that the metal ratio of the salt complex .obtained byrthis method is. greater than .by conventional techniques, a comparison was :made "with a conplayed as a starting material. In this respect, Examples 41 and 42 below are illustrative.

EXAMPLE 4:].

The oil-soluble petroleum sulphonic acid employed in this test was 'derivedby reacting a 60% oi'llsolution of sodium petroleum sulphonate with the :stoichiometric amount of sulfuric :acid (19.6% strengthat a 'temperaturewof Gil-70 C. for a period of two :hours. .After allowingitheireaction mixture. to stand.:ab0ut .12 hours, it was'filtered twice through :a .g-la'ss :cloth. .2875 grams iofzthe product ,just :described were combined with 205;? grams 'of ,para-tertiary-butyl :phenol, :(ratio -:;of equivalentsxis 1.39),, 1-16-47 :grams :of a low-viscosity mineral oil having a viscosity of about 120 $115 at 100 R, 9-27 .6 gramsof barium oxide and 2480 grams of water and x heated .for onexhour .at'a temperature of 9.8: C. The mixture was then dehydrated for one hour at -a temperature 'of 150 C. so as toremovesubstantially all of the water. The product was a viscous ;liquid,.:brown ventional technique in which. the acid was emin color, and contained a mild odor. The following properties were -determined-for the desired product:

500 grams of the oil-soluble petroleum sulphonic acid given in Example 41 above were heated to 175 3.55 grams :of water were then added and riollowed ibyaa :slow :ad'ditiomof 162:2 {'75 grams of barium oxide. The total mixture was maintained at a temperature of 150 C. for a period of one hour. separated by filtration and was found to be a very viscous liquid, black in color, and did not contain any odor. The following propertieswere determined fcr'th'e salt complex:

Basic No. 53.7 .Percent sulphate ash 25.6.5 Metal ratio 1,74

The salt complexes of the present invention .can 5 be prepared by first adding water to the mixture j of the oil-soluble metal sulphonate or sulphonic acid and promoter, and then adding the inorganic metal compound in a :dry :state. In this respect,

Example 43 given below illustrates an alternative method by which the salt complex can beprepared.

EXAMPLE 43 1-000 grams of the ba-rium saltef -di paraflin wax substituted phenol sulphonic acid "(sulphate ash-6.6 were admixed-with 55 grams -of paratertiary-butyl phenol (ratio of equivalents *is 1154) and heated to a temperature o-f C. 800

cc. of water were 'thenadded'. The mixture was mixed thoroughlyand then 300 grams of dry barium -ox ide were added. The total mixture was refluxed for two hour-s followed by an-addition of 5'73 grams of a mineral oil havinga viscosity of 160 'SUS at F "The temperature was raised over a period of four hours .to 170C.

and. then maintained there one hour. The salt complex was obtained :by filtering the product and was found to be a viscous liquid,dark browniin color, .and'contained .a faint odor. .The following propertieswere deterniinedfor the .salt complex':

Basic No. .6748 Per cent sulphate ash 23.8 Metal ratio 2.657

Another experiment was performed inwhich the salt of the ionizable organic compound'was employed as the-promoter. Example "44 below illustrates this feature of the invention.

- EXAMPLE .44

1 7-00 grams of a 30% oil solution of barium petroleum sulp'honate (sulphate ash 7.6% were admixedwith grams of barium phenate (ratio of equivalents is 1.70),:ar1d 570 grams of water. The mixture was heated to "Z5100 C. whereupon 214 grams of barium oxide were added. The

temperature of the "mixture wasymaintained at 100 'Crfor'one hourand. then raised slowly to Basic Nor 68 v Per :cent sulphate ash 21.4 A Metalratio i .3. 23

The following examples by comparison illustrate the substantial increase in metal :con'tent of the complex WhiChiS-0btMIl8d by treating the mass with an acid-icmaterial before filtering -to separate the :desired product.

EXAMPLE I45 1700 :grams :of 1a :30% toilasolution ;of barium petroleum :sulphonate having a sulphate as'hzof 77.6% were mixed with 134 grams of diisobu'tyl The desired complex was slight odor. The following properties of the products were determined:

Basic No. 4.1 66 Per cent sulphate ash 22.2 Metal ratio 3.64

EXAMPLE 46 1700 grams of a 30% oil solution of barium petroleum sulphonate having a sulphate ash of 7.6%..were mixed with 134 grams of diisobutyl phenol (ratio of equivalents is 1.7 and heated to 70 C. Then 800 cc. of H20 and 302 grams of BaO were added and the mixture refluxed for one hour. The temperature was raised to 150 C. and maintained there for one hour. CO2 was then injected therethrough at 150 C. and at a rate of 1,650 cc./min. for 38 minutes. The mass was then cooled and filtered to separate the complex. The product was liquid, brown in color, and contained a faint odor. The following properties of the product were determined:

Basic No. 5.05

Per cent sulphate ash 26.0

Metal ratio 4.52

EXAMPLE 4'7 400 lbs. of a 30% oil solution of barium petroleum sulphonate having a sulphate ash of 7.6% were heated to 80 C., and 32.5 lbs. of diisobutylphenol (ratio of equivalents is 1.67) were added thereto.- Then 197 lbs. of water were added to the mixture, with stirring to insure thorough mixing. 73 lbs. of BaO were added thereto over a 30 minute period at 55-80 C. The mixture was agitated for about minutes more at 80 C., then the temperature was raised to 100 C. and held there for one hour. Thereafter, the temperature was raised to about 150 C. and maintained at that level for one hour. Following this step, CO2 was blown through the mass until about 75 lbs. thereof had been used over a period of three hours and at a temperature of 135-l70 C. The mass was then filtered and the product was found to have the following properties:

' EXAMPLE 48 4590 grams of a 30% oil solution of barium petroleum sulphonate having a 7.8% sulphate ash, 363 grams of diisobutylphenol (ratio of equivalents is 1.7) and 2,800 grams of H20 were heated to 60 C. 1,042 grams of BaO were added slowly and then thetemperature of the mixture was raised to 94-98 C. and held there for one hour. Thereafter the temperature was raised to 150 C. in four hours, and maintained there for one hour. A small portion of the mass, 361 grams, was removed and filtered to give product A, whereas the remainder (5,296 grams) was blown with S02 at 170 C. until 330 grams thereof was used. This latter mass was then filtered and the product given below as product B was obtained. The analyses of products A and B are as follows;

Product A Product 13 Basic No 63 4. 5 Percent Sulphate Ash 19.5 29. 5 Metal Ratio 3.18 5. 35

1700 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash were mixed with 61 grams of phenol (ratio of equivalents is 1.70) and the mixture was heated to 75 C. 261 grams of barium oxide and 710 grams of water were then added and the total mixture was raised in temperature to C. and held at that level for one hour. Thereafter, the temperature was raised slowly to C. and held there for about one hour. The total mixture was allowed to settle overnight, followed by decantation and filtering. In this experiment 450 grams of sediment were produced. The filtered salt complex was a viscous liquid, light brown in color, and contained a slight odor. The following properties of the product were determined:

Basic N0. 59.5 Percent sulphate ash 21.2 Metal ratio 3.20

The sediment obtained in Example 49 was employed in the preparation of a salt complex in the method given in the following Example No. 50.

EXAMPLE 50 1700 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash, 20 grams of phenol, 450 grams of sediment obtained from the preparation given in Example 49, 710 grams of water and 261 grams of barium oxide (barium oxide added slowly) were mixed together and heated to a temperature of 100 C. for about one hour. The total mixture was then raised in temperature in a slow manner to about 150160 C. and held there for one hour until substantially all the Water was removed. The salt complex was separated by filtration and was found to be a viscous liquid, light brown in color, and contained a slight odor.

The following properties were determined for the salt complex:

Basic N0 82.6 Per cent sulphate ash 26.4

EXAMPLE 51 1050 grams of a 45% oil solution of calcium petroleum sulphonate having a sulphate ash of- 6.5% were mixed with 97.5 grams orpara-tertiary-butyl phenol (ratio of equivalents is 1.54) and heated to about 80 C. To this mixture were then added about 148 grams of Ca(OI-I)2 and about 300 cc. of water, and the total mixture was refluxed at about 100 C. for a period of two hours to insure thorough mixing. Thereafter the mass was heated to about 170 C. over a period of about four hours, then maintained at that temperature for 0.5 hour. The product wass'ep'arated from the mass by filtration, and was found to be a liquid, brown in color and contained a faint odor. The following properties were determined for the product:

Basic N 25.0

Percent sulphate ash 9.3

Metal ratio 1.57

EXAMPLE 52 1,050 grams of a 45% oil solution of calcium petroleum sulphonate having a sulphate ash content of 6.5% were mixed with 98 grams of para-tertiary-butyl phenol (ratio of equivalents is 1.54) and heated to about 70 C. To this mixture were added 112 grams of CaO and 300 cc. of water, and the total mixture was refluxed at the above temperature for about two hours to insure thorough mixing. Thereafter, the temperature was raised to about 160 C. over a period of about hours and maintained there for about 0.5 hour. The product was separated by filtration and was found to be a liquid, brown in color, and having a faint odor. The following properties were determined for the product:

Basic N0 25.2

Per cent sulphate ash 9.09

Metal ratio 1 1.53

EXAMPLE 5 For the purpose of comparison, calcium petroleum sulphonate was overbased with Ca(Ol-I) 2 in accordance with a conventional technique.

EXAMPLE 54.

1,565 grams of a 30% oil solution of calcium petroleum sulphonate having a sulphate ash of 4.3% were mixed with a slurry of 3'7 grams of Ca(OH)2 and 150 cc. of water. The mixture was heated with stirring to 80-90 C. and held at that level for about one hour. The temperature was then raised to 160 C. and held at that level for about one hour. The product obtained was a viscous liquid, deep red in color, and had the following properties:

Basic No. -1 7.90 Per cent sulphate ash 5.15 Metal ratio 1.29

The following example illustrates the use of a 22 different promoter when employing the calcium metal in the components:

EXAMPLE 55 A mixture of 459 grams of "phenol, 244 grams of water and 90.5 grams of Ca(OH)z was stirred at reflux temperature for two hours. Thereafter 1046 grams of "a oil solution of calcium'petroleum sulphonate having a 6.7% sulphate ash (ratio of equivalents is 0.41 were added. The temperature of the mixture was then raised' to 125 'C., at which level substantially all of-the water was removed. Prior to filtering the mixturegit was blown with CO2 for three hours at a temperature of about 120-150 C. The complex was fluid, brown in "color and did not contain any odor. The complex had the following analyses:

Basic No. I Y Per c'e'nt'sulfate ash 18.35 Metal ratio 3107 Another preparation was made in which dis 7 similar alkaline earth metals were present in the organic'acid compound and inorganic metalcornpound. The following example illustrates this feature of the invention.

EXAMPLE 56 1793 grams of a 45% oil solution of calcium petroleum sulphonate having a 6.45% sulfate ash, 206 grams of octyl phenol (ratio of equivalents is 1.7) and 954 grams of water were mixed together. Then 358 grams of BaO were added, and the mixture was agitated thoroughly. While insuring thorough mixing the temperature was raised to 90-100 C. for one hour. Thereafter, the temperature was raised to 150 C; over atwo hour period and held at that level for one hour. The complex obtained by filtering the mixture had the following properties:

Basic No. 1 4.2 Per cent sulfate ash Metal ratio 3.94

The complexes of this invention'can be also obtained by using a mixture of oil soluble organic acid and the alkaline earth metal salt thereof. The following example illustrates this concept.

EXAMPLE 5'? 2875 grams of petroleum sulphonic acid and 6000 grams of a 30% oil solution of barium petroleum sulphonate (sulfate ash is 7.6%) were mixed with 553.7 grams of para-tertiary-butyl phenol (ratio of equivalents is 1.60). The mixture was heated to about C. whereupon a slurry of BaO (consisting of 2027.6 grams of 39.0 and 5395 grams of water) was added and the mixture was then maintained at a temperature of about -05 C. for an additional hour. Upon inspection, the mixture appeared thoroughly mixed, therefore the temperature was slowly raised to 150 C. and held there for approximately one hour. The product analyzed as follows:

Basic No. -1 73.0 Per cent sulfate ash 233 Metal ratio 3.73

EXAMPLE 58 1,000 grams of petroleum sulphonic acid, 98.1 grams of para-tertiary butyl phenol and 989 grams of water were mixed together and heated to 50 C. Thereafter, 258 grams of SrO were added-to the mixture, the total mixture was raised in temperature to C. and held at that level for about one hour.

Thereafter, the total mixture was raised in temperature to about 150 C. and held at that level for about one hour. The product obtained was a viscous liquid, brown in color, and had the following properties:

Per cent sulphate ash 13.95 Metal ratio 1.67

The salt complexes formed with compounds containing barium metal possess exceptionally high metal ratios as compared to those complexes which are obtained when using other alkaline earth metal containing compounds. Consequently, in determining the maximum amount of metal which can be incorporated into a complex prepared by conventional techniques, the barium containing complexes were employed for such a purpose. Pursuant thereto, Examples 59 and 60 given below serve to show the highest amount of metal which can be incorporated into a salt complex by conventional techniques. Furthermore, the oil-soluble petroleum sulphonic acids are exceptionally better in producing high metal content salt complexes than other types of oil-soluble organic acid compounds.

EXAMPLE 59 2500 grams of a 30% oil solution of barium petroleum sulphonate containing 7.6% sulphate ash were heated to 95 C. and a slurry of barium oxide containing 386 grams of barium oxide and 1215 grams of water was added thereto. The mixture was stirred for one hour at a temperature of 100 C. and then heated slowly over a period of three hours to a temperature of 150 C. This temperature was maintained for about one hour until substantially all the water was removed. The salt complex thus produced had the following properties:

Basic No. 38.4

Per cent sulphate ash 16.0

Metal ratio 2.25

EXAMPLE 60 In this example the procedure employed in Example 59 was followed except that the dehydration step was conducted at a temperature of 200 C. for a period of one-half hour. The product obtained had the following properties:

Basic No. 29.0 Per cent sulphate ash 15.3 Metal ratio 2.16

From the above Examples 59 and 60 it can be seen that salt complexes obtained by conventional techniques will only have metal ratios as high as 2.25 or approximately 2.3. By comparison, the process of the present invention will in every instance, wherein a substantial amount of excess inorganic alkaline earth metal compound is employed, and when using the same organic acid compound, produce products containing more metal than is possible by any of the prior art tehniques. Furthermore, in every instance where the salt complexproduced by the process of this invention is treated with an acidic material and then distilled so as to remove substantially all of the ionizable organic compound, the remaining salt complex which constitutes essentially the promoter-free salt complex in combination with the acidic material, will have a higher ratio of total metal to metal in the normal salt of the organic acid than is possible with any prior art techniques. By Examples 63-74 inclusive given hereinafter, it will be shown that the treatment of the salt complex produced by the process of the present invention with an acidic material does not significantly affect the metal ratio of the complex. Furthermore, it is shown in those examples that the distillation of the thus acidic material treated complex so as to recover the ionizable organic compound does not significantly affect the metal ratio of the complex.

In another pair of experiments, a comparison was made between the process of the present invention and a conventional process, when using duplicate amounts of components. It is clearly evident from the following examples that this invention will give substantially better results with respect to metal concentration of the complex than is obtainable by the conventional technique.

EXAMPLE 61 1530 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash, 88 grams of para-tertiary butyl phenol (ratio of equivalents is 1.7), 271 grams of BaO and 725 ml. of water were mixed together at 60-70 C. The temperature of the mixture was raised to -l05 C. and held there for one hour while perature was raised to 150-160 C. and held at insuring thorough mixing. Thereafter the temthat level to remove substantially all the water. The complex was separated by filtration and had the following analyses:

Basic No. 85.2

Per cent sulphate ash 25.5

Metal ratio 4.12

EXAMPLE 62 1530 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash were mixed with 725 ml. of Water at about 60 C. Then 271 grams of BaO were added. The temperature of the mixture was raised to IOU- C. and held there for one hour while insuring thorough mixing. Thereafter the temperature was raised to l50-160 C. and held there for one hour to substantially remove all the water. The complex was separated by filtration and had the following properties.

Basic N o 36.0 Per cent sulphate ash 15.34 Metal ratio 2.14

From the foregoing it will be noted that by following the process of the present invention, two types of metal complexes may be produced, both of which are different from any produced by any of the prior art processes. The first form of such complex is the immediate product with the promoter included therein in chemical combination. The second form of novel product is that which results from the treatment of the end product just described with an acidic material which has the effect, as stated above, of liberating the promoter from the complex without any substantial change in the metal ratio of the complex. The liberation of the promoter by this step of treating the first-named complex with an acidic material may be followed by a recovery, as by distillation, of the promoter thus liberated, leaving the end product and complex substantially free of the promoter material. A third product which is probably difierent from each of the two named above may be produced by treating the complex initially formed with an acidic material prior to the removal by filtration of the excess inorganic alkaline earth metal compound. When following 25 this latter procedure, the promoter material is permitted to remain in the complex, and when this procedure is followed it has been found that unusually high metal ratios may be secured in the ultimate end product.

As previously indicated, the immediate end product formed by the use of the promoter material may. be modified to recover therefrom a substantial portion of the promotermaterial used, by treating such immediate end product with a sufficient amount of an acidic material which in the presence of the mass will form a material having a higher ionization, constant than the enizab e or n com un eed s he om te Aiter a portion or th romoter mate ial. as-been t s r enera e by t eat n the i m d teprod not with acidic mate al there enerated promot r m y th n be s a at d t er from by an one o he s eral k own mean or the re enerated promoter material may be left in the mass and the latter then treatedwith an additional amount of a salt-forming material, and it will be found that the concentration of the stablyheld metal can be further increased, The folo i e e p e of such furthere eps n ou process.

pas f C 2v th o h he m x u and he basic number of the mixture Was tested every minutes, until the analysis showed a basic number of 2.5.. The salt complex-CO2 product was then separated and was found to be liquid in consistency, brown in color, and contained a very slight odor. The following properties were determined for the product:

asic No 2.5 Per cent sulphate ash 23.2

By comparison, the product of Example 43 contained a sulphate ash of 23.8% whereas the same product after blowing with CO2 contained a sulphate ash of 232. Therefore, it can be seen that the metal ratio of the salt complex is substantially the same after treatment with CO2.

EXAMPLE 64- 6043 grams of the salt complex prepared in accordance with Example 9 were placed in a suit.- able vessel and CO2 gas was injected at the bottom of the vessel at a rate. of 3.75.0..cc. per minute for a period of 1 /6 hours. During this period, the temperature was in the range of Bil-70 C. At t e nd f the bl win ope at on. h product I weighed 6346 grams, showing a gain in weight of 311 grams. The product fluid. dark, red in color, and contained no odor. The following properties were determined for the salt complex- CO2 product:

Basic No 4.3 r cent su phat ash- 2.2-

Itcan be seen, therefore, by the gain in weight of the product that the G02 actually enters into combination with the salt. complex. Furthermore, the metal ratio ofthe product is substantially the same as the salt complex prior to being blown with (20g, since the sulphate. ,ash content is substantially the same. asbefore. CD2 treatment.

1288 grams of the salt complex prepared inaccordance with the method 'of Example 5 was blown withCOz at a temperature of 301-50 C. until the product showed an acid reaction. Following this CO2 treatment, the product was blown with nitrogen for a period of 15 minutes. The product thus produced was very viscous, reddish brown in color, and did not contain any odor. e following p op rties w re d e min d Acid No 5.36 Per cent sulphate ash 17.94

2500 grams of a 30% oil solution of barium petroleum sulphonate containing 7.6% sulphate ash wer emixed with 45.6 grams of phenol (ratio of equivalents is 3.36) and heated to C. A slurry of barium oxide containing 422 grams of barium oxide and 1125 ml. of waterwas-added to the mixture, with stirring, and held at a temperature of 97-.102 C. for a period ofone hour. The temperature was then slowly raised over a period of three hours to C. and maintained at that level for an additionalperiod of one hour until substantially all the water was removed. The desired salt complex was separated by filtering and was found to be an oily liquid, brown in color, and contained a faint odor. The following properties were determined:

1250 grams of the salt complex produced in accordance with the method given in Example 66 above were blownwith CO2 for approximately two hours at a temperature below60." (3., until an acid number of 5.0 wasobtained. The weight o o ct o tain was lzfi era ns- The qOz-sa teomnlex.product w s then heated a a tem erature. c1120, unde a of mm. producin a dist late we hing a out 10 grams. The distillate was then dissolved inisop pyl ether and then ried over ma esium s p e filt reda d hen he. naene iumsnlphate w s removed b f ltra ion. grams of r s due em n d h esidnewae found t b phenol, thus indicating that treatment of the salt complex with an acidic material liberates at ast a p tio of h io zab or ani co pound from complex formation.

After the d st llat on step he. iollo ine. prop r-ties or e s omp x were determ ned:

Basic No 2.96 Percent sulphate ash -n 22.4

T p rcent sulph t sh of he 7 811". com: p e product dicates that i e rno metal i removed from the complex, as a. result. of the-(30,2 treatment. and the dist lati n st p o ecover-the ionizable organic compound.

'tained a slight odor.

27 EXAMPLE 68 1440 grams of the salt complex obtained by the method given in Example 49 was blown with CO2 for about two hours at a temperature of 3 -60 C. until the product showed an acid number of 6. The product thus obtained was then heated at a temperature of 200 C. under vacuum of 4 mm. to recover approximately 15 grams of phenol. The residue of the distillation was a viscous liquid, light brown in color, and con- This product possessed the following properties:

'Basic No 1.06

Percent sulphate ash 22.6

. Here again it is shown that the treatment of the salt complex with an acidic material liberates the promoter from complex formation. On a quantitative basis, it was determined that approximately of the original phenol was still held in complex formation in the COz-treated product.

The salt complex prepared in accordance with Example 69 below was treated with S02 as shown in Example '70 which is given below.

EXAMPLE 69 6000 grams of a 30% solution of barium petroleum sulphonate (sulphate. ash 7.6%), 348 grams of para-tertiary-butyl phenol, (ratio of gequivalents is 1.70), and 2915 grams of water were mixed and heated to a temperature of 60 C. 1100 grams of barium oxide were added slowly and the tem erature of the total mixture was raised to 94-98 C. and held there for one hour. The temperature of the mixture was then slowly raised over a period of 7 hours to about 150 C. and held at that level for an additional hour until substantially all the water was removed. The salt complex obtained is a liquid, brown in color, and did not contain any odor. The following properties were determined:

Basic No -1. 82.5

Percent sulphate ash 26.0

Metal ratio 4.2

EXAMPLE 70 6623 grams of the product produced in accordance with Example 69 were treated with S02 at 25-50 C. until 327 grams of the gas were combined with the salt complex. The product thus obtained had a neutralization number or a basic number of 0. The SOz-salt complex product was liquid, brown in color, and did not contain any over a period of 1%; hours while not permitting the temperature to go above 65 C. The total 'mixture was held at 100 C. for one hour, then heated to 150 C. over a period of 4.8 hours and held there for one hour. was fluid, dark red,

The desired product and possessed the following properties:

Basic No 80.5

Percent sulphate ash 26.0

Metal ratio 4.2

EXAMPLE '72 600 grams of the product produced in Example 71 were placed in a 12-liter, 3-necked flask and heated to 175 C. The mass was then blown with air until a basic number of 1 was obtained. The final product contained a sulphate ash of 26.4% indicating substantially no change in the amount of metal present.

In all of the foregoing examples, the ratio of equivalents of the organic acid or salt thereof to the promoter has been within the preferred range, viz. 1.5-3.5 to 1. The following examples illustrate the preparation of end-products wherein the ratio of equivalents falls outside of said preferred range, but comes within the broad range found to be operable.

EXAMPLE 73 1000 grams of a 30% oil solution of barium petroleum sulphonate containing 7.6% sulphate ash were mixed with 750 grams of water at 50 C. 282 grams of BaO were added thereto, followed by the addition of a slurry consisting of 460 grams of water, 87 grams of BaO,and 115 grams of para-tertiary-butyl phenol (ratio of equivalents of sulphonate to phenolic compound is 0.77). The mass was stirred for one-half hour at about C., then it was heated to 200 C. and maintained at that temperature for 2 hours.

The salt complex was separated by filtration. It was a red-brown, viscous liquid, and had the following properties:

Basic No 46. Percent sulphate ash 27.9 Metal ratio 5.4

EXANEPLE 74 Basic No 34. Percent sulphate ash -1 17.3 Metal ratio 2.4

It should be noted that in all of the specific examples given above, the mahogany soaps were referred to as either calcium or barium petroleum sulphonate, and likewise a similar designation was used for the mahogany acid.

Component A-The oil soluble organic acid compounds used as starting materials The organic acid compound used as one of the starting materials in our process may be the oil soluble organic acid themselves and/or an alkaline earth metal salt thereof. At this point it should be noted that whereas Mertes found it is necessary to first prepare a normal metal salt and then react such normal salt with an additional amount of a salt-forming material, our process can be carried on as a one-step process by beginning with the oil-soluble organic acid. While 29 it. is: possible. to first prepare: the normal. metal s lt f h Or anic acid. inthe usual. way-ibya conventional. salt-formin procedure,v and, then begin our process by utilizing such normal metal Salt as. one; of the; starting materials, it may. be more convenient to employ as the starting material. the organic acid ratherthan the. salt; thereof. Our: process is operable for the production of certain types of. compounds; when utilizing as starting materials any of the products produced by. the priorgart processes. Also, as a starting material, mixtures of acids, and, salts, can be used; to; producethe complex, The variety of classes: of organic. acids; which can be, employed are.. f.or'example, sulphur acids, carboxylic acids,

phosphorus acids, etc. of the aliphatic and, cyclic types... and, the corresponding thin-acids.

More specific examples of organic acids. re the sulphur acids including sulphonic, sulphamic, sulphinic, thiosulphonic etc, and of these the sulphonicacids will find, particular application under the present invention. A more specific identification ofthe sulphonic acids is given hereinbelow.

The carboxylic acids include the fattyacids whereinthere are present at least about 12 carbonatoms, such as, for example, palmitic, stearic,

myristic, oleic, linoleic, etc. acids. The carboxylic acids of the aliphatic type. can contain elements in the aliphatic radical other than carbon and hydrogen; examples of: such acidsxare the carbamic. acids, ricinoleic acids, chlorostearic acids, nitro-lauric acids, etc. In addition to the allphatic carboxylic acids, itis intended to employ the cyclic types such as those containing a benic acids, di-octyl cyclopentane, carboxylic acids,

etc. It is also contemplated to employ the thio carboxylic acids, that is, those carboxylic acids in which one or both. of the oxygen atoms of the carboxylic. group are. replaced by sulphur.

These. carboxylic and thio-carboxylic: acids can,

be represented by the. following formulae:

I (R'):c- TCX2H. II. Rr--CX2-H wherein R is an aliphatic radical, a: is at least 1, and (RM contains a total of at least about 15 to 18 carbon atoms; T is a cyclic nucleus such as benzene, naphthalene, diphenyl ether, diphenylene oxide, diphenyl sulphide, diphenylene sulphide, phenol, hydroxy-naphthalenes. phenol disulphides, petroleum naphthenes, cyclohexane, cyclopentane, chloro-cyclohexane, nitrocyclopentane, deca-hydronaphthalene, mercapto-deca--hydro-naphthalene, etc; and X is either oxygen or sulphur. In Formula II, R is an aliphatic group containing at least 12 carbon atoms" and X is either oxygen or sulphur. R, R, and T can also contain other substituent groups suchiasnitro, amino, hydroxy, mercapto, halogen,

.etc, Representative examplesareznitrostearic.

acids, cery1-chlorosalicu1 c acids,,chlcrcpalmi .icacids, cetylranthranilic acids, steam-mercantonaphthoic acids, etc.

The phosphorus acids include tri, and pentavalent organic phosphorus acids and the corresponding thio-acids, which: are, for example, phosphorus, phosphoric, thiophosphoric, thiophosphorous, phosphinic, posponic, thiophosphinic, thiophosphonic, etc. acids. Among the most. useful of the phosphorus acids are those represented by the following formulae:

wherein X and X are either exygfi r s lph and at least dne X and one X. is. sulphur, and R. and. R are. each either the same. or. different organic radicals or hydrogen, and wherein. at least one is an organic radical and at least one R is hydrogen and wherein at least one B is an organic radical and at least one R. is hydrogen. Therefore, such formulae include the. oil-soluble organic thio-acids of phosphorus, more particularly the organic thiophosphoric acids and the organic. thiophosphorous acids. The organic radicals R and R can be aliphatic, cyclo-aliphatic, aromatic, aliphaticand cycloaliphaticsubstituted aromatic, etc. The organic radicals R and R. preferably contain a total of at least about 12. carbon atoms in each of the above thioacid types I and II. Examples of such acids are dicapryl dithiophosphoric acids, di-(methylcyclohexyl) dithiophosphoric acids, dilauryl dithiophosphoric acids, dicapryl dithiophosphorous acids, di-(methyl-cyclohexyl) dithiophosphorous acids, lauryl monothiophosphoric acids, di-(butyl-phenyl) dithiophosphoric acids, and mixtures of two. or more of the foregoing acids.

Certain of the above. described thio-acids of phosphorus such as for example di-capryl dithiophosphoric acid are also commonly referred to as acid esters.

As indicated, our process is applicable not only when using the oil-soluble organic acid as such as one of the starting materials, but also the alkaline earth metal salts of such organic acids. The. present process will produce a high metal content organo metallic material when as one of the startin terials o e uses a y of t metal organic complexes produced by the prior art workers, such as for example, Bergstrom, Griesinger, Campbell et al., and Mertes. We thus may utilize as a starting material the end product produced by these prior art workers and from them produce the novel high metal content complex of our invention.

From the broad class of available organic acid compounds, it is preferred to employ the oilsoluble sulphonic acid compounds. Furthermore, of the available alkaline earth metal salts of organic acids, the barium salts thereof are preferred for the reason that unexpectedly excellent results are obtained by the use thereof. These oil-soluble sulphonic acids, and the alkaline earth metal salts thereof can be represented by the following structural formulae:

, bon atoms.

31 In theabove formulae M is either an alkaline earth metal, preferably barium, or hydrogen; T is a cyclic nucleus either of the monoor polynuclear type including benezenoid or heterocyclic nuclei such as benzene, naphthalene, an-

thracene, phenanthrene, diphenylene, thianthrene, phenothioxine, diphenylene sulphide, di-

phenylene oxide, diphenyl oxide, diphenyl sulphide, diphenyl amine, etc.: R is an aliphatic group such as alkyl, alkenyl, alkoxy, alkoxyalkyl, carboalkoxy-alkyl, or aralkyl groups, a: is at least 1, and Ra: contains a total of at least about 15 to 18 carbon atoms; R in Formula II is an aliphatic radical containing a total of at least about 15 to 18 carbon atoms, and M is either an alkaline earth metal, preferably barium, or hydrogen. When R is an aliphatic substituted cycloaliphatic group, the aliphatic substituent should contain a total of at least about 12 car- Examples of types of the R radical are alkyl, alkenyl, and alkoxy-alkyl radicals, and aliphatic substituted cycloaliphatic radicals where the aliphatic group is alkyl, alkoxy, alkoxyalkyl, carboalkoxyalkyl, etc. Specific examples of R are cetyl-cyclohexyl, lauryl-cyclohaxyl, ceryloxyethyl, and octadecenyl radicals, and radicals derived from petrolatum, saturated and unsaturated paraifin wax, poly olefins, includin poly-C3, C4, C5, C6, C7, C8, olefin hydrocarbons. The groups T, R and R in the above formulae can also contain other organic or inorganic substituents in addition to those enumerated above, such as for example, hydroxy, mercapto, halogen, nitro, amino, nitroso, carboxy, ester, etc.

In Formula I above, 1', y, z and b are at least one: whereas in Formula II, a, d, and c are at least one.

The following are specific examples of oilsoluble sulphonic acids coming within Formulae I and II above, and it is to be understood that such examples serves to also illustrate the alkaline earth metal salts of the sulphonic acids. In other words, for every sulphonic acid, it is intended that the alkaline earth metal salt thereof is also illustrated. This includes specifically, the barium, strontium, calcium and magnesium salts of the hereinbelow illustrated sulphonic acids.

Such sulphonic acids are mahogany sulphonic acids; petrolatum sulphonic acids; monoand polywax substituted naphthalene sulphonic, phenol sulphonic, diphenyl ether sulphonic, diphenyl ether disulphonic, naphthalene disulphide sulphonic, naphthalene disulphide disulphonic, diphenyl amine disulphonic, diphenyl amine sulphonic, thiophene sulphonic, alphachloronaphthalene sulphonic acids, etc.; other substituted sulphonic acids such as ce tyl chlorobenzene sulphonic acids, cetyl-phenol sulphonic acids, cetyl-phenol disulphide sulphonic acids, cetyl-phenol mono-sulphide sulphonic acids, cetoxy capryl-benzene sulphonic acids, di-cetyl thianthrene sulphonic acids, di-lauryl betanaphthol sulphonic acids, and di-capryl nitronap-hthalene sulphonic acids; aliphatic sulphonic acids such as paraiiin wax sulphonic acids, unsaturated paraffin wax sulphonic acids, hydroxy substituted parai'fin wax sulphonic acids, tetraisobutylene sulphonic acids, tetra-amylene sulphonic acids, chloro-substituted paraffin wax sulphonic acids, nitroso paraffin wax sulphonic acids, etc.; cycloaliphatic sulphonic acids, such as petroleum naphthene sulphonic acids, cetylcyclopentyl sulphonic acids, lauryl-cyclo-hexyl sulphonic acids, bix-(diisobutyl)-cyclohexyl sulphonic acids, monoand poly-wax substituted cyclohexyl sulphonic acids, etc.

With respect to the sulphonic acids, it is intended herein to employ the term petroleum sulphonic acids to cover all sulphonic acids which are derived from petroleum products. Additional examples of sulphonic acids and/or alkaline earth metal salts thereof which can be employed as starting materials are disclosed'in the following U. S. Patents: 2,174,110; 2,174,506; 2,174,508; 2,193,824; 2,197,800; 2,202,791; 2,212,- 786; 2,213,360; 2,228,598; 2,233,676; 2,239,974; 2,263,312; 2,276,090; 2,276,097; 2,315,514; 2,319,- 121; 2,321,022; 2,333,568; 2,333,788; 2,335,259; 2,337,552; 2,346,568; 2,366,027; 2,374,193 and 2,- 383,319.

Of the various types of organic acids and alkaline earth metal salts thereof enumerated above, i. e. sulphur acids, carboxylic acids, phosphorus acids, etc., it is preferred to employ the sulphurbearing organic acids or alkaline earth metal salts thereof. However, it is to be understood that all of organic acids and salts thereof are not equivalent in their ability to complex with unusual amounts of inorganic alkaline earth metal compounds in the presence of a promoter, because under certain conditions, some organic acids or salts thereof are more effective than others.

Component B-The promoter material The promoter employed in the process of this invention can be the organic compound AH wherein H is hydrogen and A is an anionic organic radical and/or the alkaline earth metal salt thereof. More particularly, the organic compound AXH is employed, wherein A and H are defined as given above for the compound AH and X is either oxygen or sulfur. Also the alkaline earth metal salt of AXH can be used alone or in admixture with the compound AXH. The compounds AH or AXH should have ionization constants measured in water at 25 C. greater than about 1 10- water solubilities of at least about 0.0005% at 50 C. and saturated aqueous solutions of which at about 25 C. exhibit a pH not greater than seven.

Generally, the 'ionizable organic compound or the alkaline metal salt thereof include a variety of classes of compounds such as, for example, phenolic compounds, enolizable organic nitro compounds, e. g., nitro-paraflins, lower molecular weight aromatic carboxylic acids, lower molecular weight organic thiophosphoric acids, the lower molecular Weight sulphonic acids, hydroxy aromatic compounds, lower molecular weight hydroxy aromatic acids, etc. To better illustrate the wide variety of classes of compounds which can be employed in forming the salt complexes in accordance with the present invention, specific examples are enumerated below. It is to be understood that While only the ionizable organic compounds are illustrated, it is intended that the alkaline earth metal salts thereof are included as specific examples. More specifically, the calcium, barium, strontium, and magnesium salts of such illustrated ionizable organic compounds are intended. a

The phenolic compound referred to hereinabove is for the purpose of this specification and the appended claims an organic compound having a hydroxyl group attached directly to a carbon atom of a benzenoid ring, and which compound is with or without other substituents on the benzenoid ring. It should likewise be understood that -a phenol? is asub-class of a phenolic 33 compound, inwhich there is only a hydroxylgroup on the benzene ring or in addition to the hydroxyl group, there is also present in the molecule a single hydrocarbon group or a plurality thereof. Those phenolic compounds containing not more than 30 carbon atoms inthe molecule are preferred as promoters.

The ionizable organic'compounds found useful as promoters are phenol; alkylated phenols such as, for example, cresols, xylenols, p-ethyl phenol, di-ethyl phenols, n-propyl-phenols, di-isopropyl-phenols, p-t-butyl-phenol, p-t-amyl-phen'ol, p-cyclo-pentyl-phenol, p- ('-metliylecyclohexyl) phenol, sec-hexyl-phenol's, n-heptyl-phenols, diisobutyl-phenols, 3,5,5,-tri-methyl-n-heXyl-phenols, n-decyl-phenols, cetyl-phenols, etc; 'aryl substituted phenols, e," g., phenyl phenol, diphe'nyl phenol, etc.; poly-hydroxy aromatic compounds such as alizarin, quinizarin' or polyhizdrofiybenzenes, e. g., hydroquinone, catechol', pyrogallol, etc.; mono-hydroxy n'aphthalenes, e. g., a-naphthol, fl-naphthol, etc.; pol'y-hydrox-y naphthalenes, e. g., naphthohydroquinone, naphthoresorcinol, etc.; the alkylated polyhdroxy-aromatic compounds such as octyl-catechol's, triiso-butylpyrogallols, etc.; substituted?- phenols such as p nitro phenol, pieric acid, chlorop-henol, t-butyl-chlorophenols, p-hitro-o-chlorophenol, p-amino-phenol, etc.; lower molecular weight hydroxy aromatic carboxylicacidssuch as salicylic acid, chloro-salicylic acids, di-isopropylsalicylic acids, gallic acid, i-hydroxy-l-naphthoic acid, etc.; lower molecular weight aromatic sulphonic acids such as p-cresol sulphonic acids,

p-t-butyl-phenol sulphonic acids, beta-naphthol alpha-sulphonic acid, etc.; lower molecular weight aromatic carboxylic acids such as benzoic acid, p-nitro-benzoic acid, o-chloro-benzoic acid, p-toluic acid, p-t-butyl-benzoic acid, alphanaphthoic acid, etc.; lower molecular weight aromatic sulphonic acids such as benzene sulphonic acid, p-chlorobenzene sulphonic-acid, p-nitrobenzene sulphonic acid, p-tolyl sulphonic acid, p-tbutyl-benzene sulphonic acid, t-amyl-naphthalene sulphonic acids, etc.; lower molecular Weight aliphatic sulphonic acids such as ethyl sulpho-nic acid, beta-chloro-ethyl sulphonic acid, gammanitro-propyl sulphonic acid, octyl sulphonic acids, chlorodi-isobutyl sulphonic acids; diisobutenyl sulphonic acids, etc.; nitroparafiins such as l-nitro propane, 2-nitro-n-butane, l-nitro-l-ipdiisobtuyl-phenoxy) propane, etc.; lower molecular weight thio-acids of phosphorous including aliphatic dithiophosphoric acids; e. g., di-isopr0-- pyl dithiophosphoric acid, di-n-butyl dithiophosphoric acids, etc., aromatic dithiophosphoric acids, e. g., di-(phenyl) dithicphosphoric acids, etc, the aliphatic mono thiophosphoric acids, e. g., di-ethyl monothiophosphoric acids, etc., the aromatic monothiophosphoric acids, e.-g., di-tolyl moncthiophosphoric acids, di-(iso-propyl-phenyl) mcnothiophosphoric acids, etc.-

'Additional examples of compounds'which can be employed aspromoters are givenin'the follow ing UKS. patents: 2,174,110; 2174, 111; 2,174,492; 2,174,565; 2,174,506; 2,174,507; 2,174,508; 2,174,- 509; 2,202,791; 2,228,598; 2,265,163; 2,276,097; 2,319,121; 2,321,022 2,333,788; 2,335,259 and 2,337,552.

However, it is to'beunderstood'that the above enumerated ionizable organic compounds and the alkaline earth metal salts thereof arenot all equivalent as promoters, but that under certain conditions some are more effective than others;

34 Component C'-The alkaline earth metal salt-forming compounds- The salt-forming compounds which are employed to impart to the process mass the specified amount of metalmay be broadly defined as inorganic alkaline earth metal compounds wherein anionic radicals maybe, for example, hydroxyl, oxide, carbonate, lei-carbonate, sulphide, hydrosu-lphide, halide, hydride, amide, basic carbonate, etc. Of the inorganic alkaline earth metal compounds, good results are obtained with those having a water solubility of at least about 0.G003-% at 50 0., and preferably at least about 0.066%. Still more preferred are those inorganic alkaline earth metal compounds, saturated aqueous" solutions of which give an alkaline reaction or pH value greater than 7.

To further illustrate the large number' and variety of'classes of inorganic compounds which can be emplqyed, specific examples thereoi are enumerated below,

T a n arth" me a in eamc c mpo n s include h b ri m, cont n n compoun s uc as barium hydroxide; barium oxide, barium sulbar m car on te; b rium b w r o te, barium hydride,- barium] amide, barium chloride, um bromid bar m ni rate; arium su barium borate, etc.;. e calcium containing compounds such as calciu hyd s de, 'ca'lciurn'oxide, a ium ulfi e. cal ium lar o a e ca c u b ca nat a iu h drid alcium ami e; ca c u ch o id calcium bremida c um-n a e calcium borate, etc.; the"'strontium containing mpou ds su h a s ro t um d x de, s r ntillm QXi'de'. strontium sulfide, strontium carbonate, strontium bicarbonate, strontium" amide, strontium nitrate, strontium hydride, strontium nitrite, etc.; the magnesium-containing" compounds" such as magnesium hydroxide, magnesium oxide, magnesium carbonate", magnesium bicarbonate, magnesium nitrate, magnesium nitrite, r'nagiiesiurhv amide, magnesium chloride, magnesium sulfate, magnesium hydros'ulfide, etc. The corresponding basic salts of theabove described compounds are also intended, however, it should be understood that the inorganic alkaline earth metal compounds are not equivalent for the purposes of the presentlinvention, because under certain conditions some are more efiective ordesirable than others.

- complex'into the sodium carbonate-cal ium sulph'onate complex 'or 'the" corresponding; bicarbonate complex" b'yblowi'ng the hydroxide complex with carbon dioXideatelvated tempera tures;

Inour process, the; step of treating withan acidic material" such as carbon dioxide or air has the eiiect. of freeingfrom the immediate comp x P duct formed at leas a n the promoter used. hus the presence inthe immediate complex product ofthe promoter material, in combined form, clearly distinguishes the immediate complex product from any metal organic complex type material heretofore produced. Moreover, the nature of the product formed by regenerating from the immediate end product at least a portion of the promoter material leaves that complex with a composition which is quite different from the other prior art metal organic complexes previously produced. It is recognized that in accordance with the present invention, the alkaline earth metal salt of the ionizable organic compound can be employed as the promoter in forming the salt complex. However, when such a salt is used as the promoter and the resulting complex is treated with an acidic material, the metal-free ionizable organic compound is freed from its salt.

For the purpose of releasing the ionizable organic compound used as a promoter from the complex, an important feature or characteristic of the acidic material is that it must, when present in the mass containing the complex, possess an ionization constant higher than the ionizable organic compound used as the promoter. Thus, for the purpose of this specification and the appended claims, it is to be understood that the acidic material can be either a liquid, gas, or solid, prior to being incorporated in the mass which contains the salt complex.

The acidic material usually employed is a liquid or a gas. The liquids can include the strong or weak acids, such as, for example, hydrochloric, sulphuric, nitric, carbonic acids, etc., whereas the gas is for the most part an anhydride of an acid or an acid anhydride gas.

The following are additional specific examples of acidic materials, viz.: HCl, S02, S03, CO2, air (considered acidic because of CO2 content), N02, H28, N203, PC13, 39012, C102, HzSe, BF3, CS2, COS, etc.

It is to be understood, however, that all acidic materials are not equivalent for the purposes of the present invention, but that under certain conditions, some are more effective or desirable than others. I

The complex of the present invention can be produced by using the same alkaline earth metal in the organic acid compound, promoter and inorganic compound; or such complexes can be derived from components containing dissimilar alkaline earth metals. In some instances it is desirable to employ a mixture of organic acid compounds which contain at least two or up to and including four dissimilar alkaline earth metals; or the same. distribution of metals can be obtained by varying the type of promoter and/or inorganic compound in various combinations with the organic acid compound. It is therefore possible to employ various combinations of dissimilar alkaline .earth metals in the starting materials used in preparing the complex product.

Process conditions The salt complex of the present invention is prepared by combining the aforementioned compounds in the presence of water. The water can be present as a result of addition thereof to the mixture, or liberated from either the essential components or other additionally present compounds as a result of being subjected to heat. However, it is preferred to add water to the mixture to effect salt complex formation. It has been found that the metal complex can be prepared when using small quantities of water technique employed therefor.

such as about '1 mole of water per mole of inorganic metal compound. However, more usually about 5 to 50, and preferably about 15 to 30, moles of water per mole of inorganic metal compound are used.

Generally the complex formed with the inorganic alkaline earth metal compound, the oilsoluble organic acid or the alkaline earth metal salt thereof, and the promoter is prepared by heating the components in the presence of water at a superatmospheric temperature while insuring thorough mixing and then still further heating said mixture to substantially remove all of the water. At least five methods are available by which the complex can be formed, namely:

(a) The promoter is added to the oil-soluble normal salt of the organic acid, followed by addition of an aqueous solution or suspension of the inorganic alkaline earth metal compound thereto; the mixture is held at a superatmospheric temperature for a reasonable length of time while effecting thorough mixing, and then the total mixture is further heated to remove substantially all waterwhich might be present;

(1)) The inorganic alkaline earth metal compound in a dry state is added to a mixture of organic acid or a normal salt of such organic acid, promoter and water heating while insuring thorough mixing, and then further heating to remove substantially all of the water;

(0) The acid of the desired salt of organic acid is mixed with the promoter, then an aqueous solution or suspension of the inorganic alkaline earth metal compound is added thereto, the mixture is heated and agitated at a superatmospheric temperature for a time sufficient to insure thorough mixing, and followed by subjecting the total mixture to dehydration conditions in order to remove substantially all of the, water;

(d) In any of the methods discussed herein for preparing the salt complex, a substantial in-. crease in metal content is usually effected by treating the mass containing the complex product with an acidic material just after substantial amounts of water are driven off and just before the mass is filtered.

(e) The sediment formed from any of the aforementioned methods can be employed either alone or with additional promoter in any of the three methods given above.

In all of the methods described above for pre paring the salt complex, the step of removing substantially all of the water which is present is accomplished at a temperature not substantially in excess of 350 0., preferably about C. to 200 C. The technique employed to remove the water includes, for example, a conventional fiash stripping operation which involves passing the material in a thin film state over a large heated area of glass, ceramic, or metal; heating under sub-atmospheric pressure as well as heating under either atmospheric or superatmospheric pressure. At a later stage, the acidic material when used in gaseous form, may be used to remove the last portion of water. It can therefore be seen that the temperature as well as the time for effecting substantial removal of water will vary considerably depending on the amount of material being processed and on the Generally, the time required to effect substantial removal of water is at least about 15 minutes or less and can be as high as 10-15 hours or more. Usually, however, it is most convenient to employ atmosbheric pressureior. such an. operation. and cone sequently it requires aboutv 1 toffijholirsgto re.-.v mo substa ial y all ofthe waterf m the. pr ce mixture twas observed that atisfactor c mp ex s ar ob ained w en using any Ofthe. techniques described aboye, and that the final Water ontent can be. up. ta-a out 2%. or more.

sua ly as ind cated aboye, thecomponents re co bined and a itated at aneleyated teme erature to insure thorough mixin and tha wa er is removed. herefrom. It should be. unr. derstood that the process to formthe. ug mplex can be effected without the preliminary heating. and mixing period, ifdesired. It is. therefore. not ess n al o. t is inven ion to. have. such a pree. iminary ste beca se all t at ap ea s n cessar is to mix the components and remove substane. a y a y water. which is present.

For the purposes of this specification andthe. appended claims, the relative announts of oil: ol ni a idor the. alkaline earth. metal salt thereof and promoter expressed in the .ratio oi equiya1entS,.-Qf the. former to. the latter. In accordance therewith, the. ratio of eq ivalent of oil-soluble. organic acid, or the. alka n earth. m tal salt thereof to pr m t r is o out 1 to to about. l0.=.to.1,.more.usual1y. from about 1 to 1 to, aboutlO, to; .1 and pretext?v ably from about 3 to 2 to about '7 to 2.

The amount of inorganic alkaline earth metal compound employedgfenerally will be sufficient to have present in the total mass at least more thafaboiitfone equ valent of alh aline earth meta re a d s oighf cqmbined. er. QCllliYflml lent of oil-soluble organic acid or'the al lial e earth metal salt thereof plus promoter. 'In other words, the amount of inorganic alkaline earth metal om o n emnlc si In St. h th there is morethan I qu d of rm rh relsian soluble organic acid and the promoter. i for the purposes of this specification and the appended claims, the amount of inorganic alkaline earth metal compound employed; will. be. ex re' s d .2 amount sushth tthere arepres in t mess morethan a lliXttlentQf; alka in I i tl tli,metal e sa tiot' t As ndi ate...

cte na oye. tre salt complex with an acidic In si nqe Where. t s. d sirable o owe theba i c m er i he saltt m len and/or, ar ally or substantially completely recoven the ionizable organiccompound. v r a temperature'of from about 22} to 250F627, preferably from about{ to 1H0 Giand usually mployin'g from about; 0.5 td 29% Of--a0i;diC material;

ofitreatment with the ajcid-ic rhate'rial as. Yai y considerably depending on the: desired result; As wouldibeexpected, short;periodsiof -treatment may. cause only; partial liberation on release ionizable. organic. compound;- orasmall decreasesin. the basicnumberbfi the salt complexl "How- This-treatment is eire'ctedat when it is desiredto produce aproducthaving substantially neutrall'reaction, the amount: of acidic material usedshould be at least equiva: lent to the. total metal invexcess ofthatpres'ent as. the. normal salt of the 'oil' soluble. organic acid. X

To substantially increase the metal. content. of the salt complex, it may be desirable to treat the total mass with an acidic material just prior to filtering same. This treatment may conveniently be effected at a temperature of from about 25 to 250 C. preferably from about 50 to Q, sales from a out Q-fito. 2% Qt. acidic mat r d. n theto al. and its period 0 ac dic ta sa implor d pre erab y acid anhy ide gas, as defined hereinabove, ireat nent with e.

he saltcoin lexi. t e. metal. ratio?- the ratio. at the. total metal in, the a -com e t. l -..e amoun of metal; which is. in.

, the'form of a normal saltof: thex oilesoluble. 0.1:

ganic acid. In accordance therewith, the salt complex as of this invention will have metal ratios greater than 1 and up to 10 or more, preferably from about 2 to 8. As for the finished salt complex which is treated with an acidic material, the. metal content is substantially the same as in. the complex prior to treating. Consequently the. same metal ratios as given about will apply to such treated product. In those instances where the finished salt complex is treated with an acidic material and the ionizable organic. compound is removed from the resultant product by distillation, or otherwise it is found that the metal ratios will be substantially the same as in the salt; temples. before treating with the acidic .B 1 Qtth-.hieh.metalraticotthecome. Plates 112 see iniatco dance with, this inven-i. tiqlt the tqllow ng t eo ies are. su t a possible explanation of hovathe metalis come.

nanced the urpos n o er n 131?}. era-not. to. he,v construed as; the scope of the present inven- (2a) RSOaM-OH AXH nsostg xnsgnzo (a). AXE

nsoiM-oer 0119, asoiM o-M oH-H,o Qatalyst-l 25KB MWH)! )zM(peptized into end product) aerepas The resultant complex, according to the above theory, can be a complex mixture of all thepotential products listed above. It is apparent that high metal ratios are possible under this theory. Another theory is based upon an electronic interpretation. For example, in the case of the neutral sulphonate, the charges are distributed as follows:

The electron octets around the two oxygen atoms which are not-attached to a metal atom give to each of these atoms a unit negative charge, thus leaving the sulphur atom with a double positive charge.

When the-sulphonate, excess inorganic metal compound, promoter, and water are reacted according to the present invention, a basic promoter salt AXMOH is presumed to be formed. This normally oil-insoluble salt 'dissolves in the reaction mixture because of the electronic attracting force known-as a hydrogen bonding. structurally this can be shown as:

R- s y-o n ..H... o-m-xx and (b) O-...H...OMXA

Structure (41.) would have a metal ratio of 3.0, and structure (5) would have a metal ratio of 5.0. Combinations of neutral sulphonate and one or both structures would explain the whole number and fractions of metal ratios which are obtained in actual practice.

After the structures (a) and (b) are formed,"

The AX- ions may then react with M(OH)2 to produce more AXMOH, and the latter would in turn lead to the formation of additional amounts of structures (a) and (b). The cycle may occur repeatedly.

According to this electronic explanation, the AX- residue of the basic promoter salt appears to function as a carrier for the M(OH)2, and thus facilitating the communicating of the M(OH)2 into close positions with the negatively charged oxygen atoms of the sulphonate radical.

Having thus described the present invention by furnishing specific examples thereof, it is to be understood that no undue limitations or restrictions are to be imposed by reason thereof,

but thatthe'scope of this invention is defined by the appended claims.

The salt complexes produced in accordance with the present invention can be employed in lubricants including oils and greases, and for such purposes as in crankcases, transmissions, gears, etc. as well as in torque converter oils. Other suitable uses for such complexes are in asphalt emulsions, insecticidal compositions, fireproofing and stabilizing agents in plasticizers and plastics, paint driers, rust inhibiting compositions, pesticides, foaming compositions, cutting oils, metal-drawing compositions, flushing oils, textile treatment compositions, tanning assistants, metal cleaning compositions, emulsifying agents, antiseptic cleansing compositions, penetrating agents, gumsolvent compositions, fat splitting agents, bonding agent for ceramics and asbestos, asphalt improving agents, flotation agents, improving agents for hydrocarbon fuels such as e. g., gasolene and fuel oil, etc.

More particularly, the complexes of this invention are especially adapted for the preparation of lubricants, paint driers and plastics, particularly. the halogen bearing plastics. In these respects, the salt complex can be employed in the following concentrations based upon the weight of the total composition.

Broad Usual Preferred Range Range Range Percent Percent Percent Lubricant 0. 01-20 0. 2-15 0. 5-10 Stabilizing Agent for Plastics"... 0. 05-5 0. Hi 0. 2-2 Paint Drier 0. 2-25 0. 5-20 1. 0-15 To better appreciate the wide variety of uses to which the salt complexes of this invention are adapted, the following specific examples are given:

- Percent Use in a lubricant: by weight SAE 20 motor'oil 95.0

' Product of Example 47 4.0 Piss-treated turpentine 0.5 Zinc di-n-hexyl dithiophosphate 0.5

Use as a stabilizing agent for halogenbearing plastics: Poly-chloroprene 40.0 Di-lauryl sebacate 59.25 Product of Example 58 0.75

Use as a paint drier:

Enamel (alkyd resin) 98.5 Product of Example 55 1.5

A. An oil-soluble organic acid compound containing at least 12 carbon atoms in the molecule selected from theclass'consisting of the aliphatic and cyclic; sulphur acids, carboxylic acids, phosphorus acids, the thio acids corresponding' to any of the foregoing acids, and the alkaline earth metal salts of any of said acids;

Claims (1)

1. A PROCESS WHICH COMPRISES PREPARING AND MIXING A MASS IN WHICH, AT 50* C., AT LEAST 50% OF THE COMPONENTS ARE IN THE LIQUID STATE, AND IN WHICH MASS THE ACTIVE COMPONENTS CONSIST OF: A. AN OIL-SOLUBLE ORGANIC ACID COMPOUND CONTAINING AT LEAST 12 CARBON ATOMS IN THE MOLECULE SELECTED FROM THE CLASS CONSISTING OF THE ALIPHATIC AND CYCLIC; SULPHUR ACIDS, CARBOXYLIC ACIDS, PHOSPHORUS ACIDS, THE THIO ACIDS CORRESPONDING TO ANY OF THE FOREGOING ACIDS, AND THE ALKALINE EARTH METAL SALTS OF ANY OF SAID ACIDS; B. AN ORGANIC COMPOUND SELECTED FROM THE CLASS CONSISTING OF THE LOW MOLECULAR WEIGHT THIOACIDS OF PHOSPHORUS AND THE ALKALINE EARTH METAL SALTS THEREOF, SAID LOW MOLECULAR WEIGHT THIO-ACIDS OF PHOSPHOURS HAVING: (A) AN IONIZATION CONSTANT IN WATER OF AT LEAST ABOUT 1X10-10 AT ABOUT 25* C., (B) A WATER SOLUBILITY AT 50* C. OF AT LEAST ABOUT 0.0005%; AND (C) IN SATURATED AQUEOUS SOLUTIONS AT ABOUT 25* C A PH OF LESS THAN 7: THE RELATIVE AMOUNTS OF A AND B USED BEING IN THE RANGE OF FROM ABOUT ONE EQUIVALENT OF A TO ABOUT 10 EQUIVALENTS OF B TO ABOUT 10 EQUIVALENTS OF A TO ABOUT ONE EQUIVALENT OF B; C. AN INORGANIC ALKALINE EARTH METAL COMPOUND: (1) WHICH IS WATER-SOLUBLE AT A TEMPERATURE OF 50* C. TO THE EXTENT OF AT LEAST ABOUT 0.0003%; (2) IN AN AMOUNT SUCH THAT THERE ARE PRESENT IN THE MASS SUBSTANTIALLY MORE THAN 1 EQUIVALENT OF ALKALINE EARTH METAL, INCLUDING THE ALKALINE EARTH METAL PRESENT IN THE REMAINING COMPONENTS, PER EQUIVALENT OF A PLUS B; AND D. WATER, IN AN AMOUNT EQUAL TO AT LEAST ABOUT ONE MOLE PER MOLE OF C; MAINTAINING THE MASS AT A TEMPERATURE AND FOR A PERIOD OF TIME SUFFICIENT TO DRIVE OFF SUBSTANTIALLY ALL FREE WATER AND WATER OF HYDRATION WHICH MAY BE PRESENT, AND FORM THE ORGANIC ALKALINE EARTH METAL COMPLEX; AND THEN TREATING THE ORGANIC ALKALINE EARTH METAL COMPLEX WITH AN ACIDIC MATERIAL OF WHICH THE IONIZATION CONSTANT IS HIGHER THAN THE IONIZATION CONSTANT OF THE ORGANIC SALT-FORMING COMPOUND OF COMPONENT B AND IN AMOUNTS SUFFICIENT TO LIBERATE A SUBSTANTIAL PROPORTION OF SAID ORGANIC COMPOUND OF COMPONENT B.