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Publication numberUS2616904 A
Publication typeGrant
Publication dateNov 4, 1952
Filing dateDec 28, 1951
Priority dateMar 16, 1951
Publication numberUS 2616904 A, US 2616904A, US-A-2616904, US2616904 A, US2616904A
InventorsRhodes Alan, Peter A Asseff, Thomas W Mastin
Original AssigneeLubrizol Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Organic alkaline earth metal complex and method of making same
US 2616904 A
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Description  (OCR text may contain errors)

Patented Nov. 4, 1952 ORGANIC ALK ALINE EARTH METAL COM- PLEX AND METHOD OF MAKING SAME Peter A. Asseff, Thomas W. Mastin, and Alan 7 Ohio, assignors to The Rhodes, Cleveland,

Lubrizol Corporation ration of Ohio Wicklifle, Ohio, a corpo- No Drawing. Original application March=16,

1951, Serial No. 216,103. Divided and this ap plication December 28, 1951, Serial No. 263,963

. This application is a division of our copending application Serial No. 216,103, filed March 16, 1951, and is related to copending applications; Ser. No. 216,101, filed March 16, 1951; Ser'. No. 216,102, filed March 16, 1951 Ser. No.'224,458, filed May 3, 1951; Ser. No. 263,961; filedDecember 28, 1951; Ser. No. 263,962, filed December 28, 1951; Ser, No. 276,462, filed March 13, 1952; and Ser. .No. 279,258, filed March 28, 1952. This invention relates to organic metal complexes and novel methods for the production of such complexes.

Itis now well known that when preparing a salt or soap of an organic acid, the mere use of an excess of neutralizing agent, which in the prior art has been 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 used as the starting material.

. ioiaims. (01.260-399) Work with this type of product has shown that for many uses, particularlyfwh'ere extreme care must be exercised to prevent the composition from being corrosive, as for example in lubricants, desirable resultsare secured by the use of these so-called basic salts or soaps. 3 5

Among the earlier workers in the art who firecognized'thisfactor 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 soa without, however, giving any specific method for the preparation of such soaps. A similar disclosure is-found in Van Ess Patent No. 2,372,411.

With the demonstrated superiority of such basic soaps over the normal or slightly acidic soaps, the

prior art workersthen attempted to find ways of increasing'the basicity 'of theso'aps, or stated in another way; increasing the amount of metal, for

.Iexample, held in stable form in'what was termed as a metal complex-r 'One ofthe earliest patents referring to these basic saltsas complexes or coas lime. A representative patent disclosing this procedure Griesinger et al. No, 2,402,325 who suggested the use of neutralizingagent 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 process was" carried 2 a out in the presence of steam inorder 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. 2,485,861. ilhese 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 colloidal 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. Mertes 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. Th'e disclosurein Mertes appears to indicate that his product is sim'ilar to that of Campbelland Dellinger, in that the excess neutralizing agent was held in the product in the form of a colloidalsuspension. 1

All of the previously enumerated processes have been tried, not only duplicating certain of the examplesgiven in theabove-identified patents, but also usingdifferent acids and different neutralizing agents. As a result of these experiments, it has been found that there is a definite upper limitto the amount of alkaline earth metal which can be held in'combination or in colloidal suspension by means of these prior art processes. The greatesttotal amount of alkaline earth metal which can possibly be thus incorporated in the product by means of any of these prior art processes has been obtained when using barium and in that case it is equal to about 2.3 times the theoretical amount present in the normal salt. For the purpose of the present invention the ratio of the total metal in thecomplex to the amount of metal which is in the form of thenormal'saltof the oil soluble organicacid will hereinafter be referred to as the m etal ratio,

By'means of the present invention, it is now, possible to, obtain alkaline earth metal'org'ani'c complexes which contain more metal 1 or higher metal ratios than is possible by prior art processes. With regard to lubricants, these high metal containing complexes areflfor example particularly suited as detergents, and by reason of'themetal concentration canbe used in amounts apprecia- "blyless than other, additives known in the prior art inorder to attain a desired level ofperformance. It'will alsobe observed that by virtue of "the moreefiecti ve nature of the present Iconi- -plexes in lubricants, usually. it will, cost less to obtain a desired result, because appreciably less additive is required. The alkaline earth "metal pressi: invn 3 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 wanted in combination with other additives, it can be available inconcentrations of at least about in mineral oils.

It is a principal object of our invention to' pro-fvide an alkaline earth metal organic complex which contains in stable form an amount of metal substantially greater than that containedin 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 these products have particular utility. 7 x I 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 complexe produced by the prior art process above described, are nevertheless different from and superior to such prior art complexes.

\ Still another object of this inventionis to provide novel methods of producing organic alkaline earth metal complexes. v p o Fiirther objects of our invention will appear asthe dscription proceeds. a i,

To the accomplishment of the foregoing and related ends, said invention then comprises the features hereinafter fully described andparticu- 1am pointed out the claims, the following description setting forth in detailcerta-in illustrative embodiments of the invention,- these bein indicative, however, of but a fevv of the various ways in which the principle of the invention may segmented. it

Inits b oadest aspects, the process of themeseiit invention comprises combining a saltforming material with an organic acid compound (to be understood hereinafter as the acid itself and/bran alkaline e 'th metal salt thereof} in the presence of a material which is referred to hereinafter as the promoter. The precise {functio'fi of the promoter material is not specifically erstood since it has not been possible res eci c'ally identify the'hilecmar structure of the product produced, At present; it appears that hone-cf the completes, i. e., either those prepared by' prior art techniques or those obtained under" the present invention are susceptible of preciseiidentificatio'n. I Tl'iisis clearly shown with respect to the prio'rart' complexes reason of the apparent disagreement among workers as to the nature of corn oii ds which contribute metal in excess of the nor 1 salt. In one instance, it is held that this phenom lion is a result of partial replacement of the hydroxyl groups in the inormetal compath whereas 'aghpfig ano h gr p or prior art workers it hem that th high metal containing complexes are actually colloidal suspensions or dispersions in which the salt of the organic acid is the p'e uzifig agent. iii the the immediate product is pro'- duced by the use of a promoter, and at least one stage contains the promoter in chemical combination. n is possime twevr, te'recbver the promoter from the product by suitable treatment as hereinafter explained, and the final product which then has a constitution different from the 4 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 producin an alkaline earth metal complex of oilsoluble 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 salt-forming metal compound under conditions which would produce a normal salt, which comprises increasmg the amount of metal which will be thus combined by having present in the process mass.

(a) amount of such metal compound substan tially in excess of the stoichiometric amount required to form the normal metal salt;

(17') 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 1 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 sufiicient 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 nixinga mass in which, at 50 Q, at least 50% of the components are in the liquid state and which mass the active components consist of: v g o A. An oil soluble organic acid compound;

B. An organic compound containing an element of groupVI of the periodic chart which has an atomic number less than 1'7, which compound is selected from the class consisting of: v o

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

(a) An ionization constant in water of at least about IX 10- at about .2 v, p (b) A Water solubility at 50 C; of atleast about 0.0005%; and (c) saturated aqueous solutions at about 251C. a pH of not greater than about '7;

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

the relative amounts or A; and B used being inthe range of from about one equivalentof A toabout l0 equivalents of B toabout l0 equivalents of A to about one equivalent of B;

C. An inorganic alkaline earth metal com (1) Which is water-soluble at a temperatu-re of 50 C; of atleast 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;

i and D; -Water, in an amount equal to at least about one mole per mole of 'C, 4

II; And then. maintaining the mass at atemperatureand for a period of time sufficient to;

",h 'ave.bee n formed by StepIII: I v I The following examples-give the pr'eparation'of a plurality of products which range in metal content. from. about that of the normal salt 'up to many times thatlamount. v

a We have found that sulphate ash and/ or metal content values, and the metal ratio values calcu-- lated therefrom, are one means for characterizing' certain' of the salt complexes. As the description of. the invention proceeds, it will become apparent;thattheneutralization number of a salt complexis in certaminstances 5 an unreliable index'of the amount. of -excess metal in such complex, since it is greatly affected by thetype of inorganic alkaline earth compound employed and canlbe varied within wide'limits without significantlychangingthe metal content. of the product by treatment-of the mass-withainCOz, and the like. t

{The above is not to be construed-as a statement that} the; neutralization number is not animportant property of a salt-complex. For. some uses,'.for example in lubricants-it is advantageous incertain instances to employ a salt complex of a l substantially neutral character, whereas in other instances a salt complex of highalkalinity halsbeen found to produce the desired results,

"'1Q 8 jgra'ms of the barium salt of petrolatum sulphonic acidfiwhichcontains 9.2%; sulphate ash, and isderivedfrom Pa. amber petrolatum) and 132 grams of para-tertiary-butyl phenol were plated into a -li-ter, 3-neck'fiask andheatedto 95 0. To this mixture was added a barium oxide slurry (417 grams 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 150-16'0" C. and maintained therefor one hour to remove substantially all of the water. Theproduct'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:

easic'iN 231 Befcentsulphate ash r 13.96 Metal ratior e l 1.70

' a sawm- Percent Appear- ;Appeer-' {of 5 221. ance ancev .Product pp afterl afterl added week month I .150 Neutral oil Clear.

with a slurry of barium oxide'(containing 38 grams of bariumoxide and 50 grams of water) and placed in a 2-liter, 3-neck flask; heated at about 160 C.- for one hour until substantially all of the water wasremoved, and then the product was filtered. The resultant basic sulphonate has the following properties:

Basic No'. 5.2"7 Per cent sulphate ash 'f9.85 Metal ration- 1.08

1000 grams of the barium salt of unsaturated paraffin; wax sulphonic. acid. containing 13.1% sulphate ash were mixed with 455 gram-sofa mineral oil having a viscosity 0f1160 SSU at; 100 F. and 109.5 grams of para-tertiary-butyl phenol (ratio of equivalents is 1.5 1} placed in a suitable vessel and heated to about. C. withstirring. To this'rrlixture was added a slurryIof barium oxide (containing 269 rams of barium oxide and 92 0 gramsof water) an'djjthe totalmixture'was heated at about C. .for one hour. The tern-1 perature Wasslowly raised toabout .150? C. and held there for about one hour 'untilsubstantially all of the water was removed. Then about 3% Hyfio (a filter-aid) was added to the product to facilitate filtering. The salt complexwas'then separatedby filtration. The salt compl'exthu's prepared hadthe following properties: j Basic No; r 53.8

The; salt complex product was fluid, brown in color, and did not containanyodor. 1, The preparation given in Example 3 is at pical illustration of the present invention. In Example {1 given below, a basicsulphonatewas prepared in accordance with a conventional technique for comparison with the product given in Example 3.

1x AMPLE 4 r ',-51-;1' grams of the barium salt of unsaturated paraflin wax sulphonic acid given in Example 3 were mixed with 75 grams of water and heatedto about 60 C. with stirring; .58 gramsof barium oxide were added to the" mixture, which was then Basic No i 16.2 Per cent sulphate ash 19.7 Metal-z ratioI l ;l 1.63

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

EXAMPLE 1000 grams of the barium salt of mono-paraffin wax substituted naphthalene 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 para-tertiary-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. Hyfio 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 wasmade 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 mix-' ture. The total mixture was held at a temperature of 100 C. for about one hour, and then de-.

Basic No. 18.9

Percent sulphate ash 12.2

Metal ratio 1.45

400 grams of the barium salt of mono-parafiin 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 hoursand held at that level for about 115 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:

BasicNo; 69;! Percent sulphate ash 243 Metal ratio 3.50

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

EXAMPLE 8 ml. of water were added to 450 grams of the barium salt of mono-paraflin wax substituted 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 disulphite 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.

EXAMPLE9 6000 grams of a 30% by weight oil solution of barium petroleum sulphonate (sulphate ash content '7.6%) were mixed with 348 grams of paratertiary-butyl phenol in a 12-liter, 3-necl flask (ratio of equivalents 1.7) and heated to C. A slurry of barium oxide constituting 1,100 grams of barium oxide and 2911 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 color, and did not contain any odor. The properties ofthe salt complex were as follows:

Basic No. 72.1 Percent sulphate ash 231 Metal ratio 3.59

' 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. 76.0 Percent barium 20.0 Percent sulphate ash 34.0

(calculated from metal content) Metal ratio 3.65

fcontained a slight odor. ties were determined:

9 EXAMPLE 11 620 grams of di-(2-ethyl-hexyl) mono-thicphosphoric acid, 310 grams of isononyl 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. 7 The total mixture was then refluxed for one hour at 100 C., whereupon the temperature was raised to 150%0. and-held at that level for one hour- The temperature of the mixture was allowed to cool to 50-60 0., and then blown with CO2 to obtain a neutral product. The complex obtained had the following properties:

Acid No. 6.85 Percent barium 17.2 'Metal ratio -1 2.65 EXAMPLE12 777 grams of di-(2-ethyl hexyl) dithiophos- .phoric 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 of 773 7 grams of BaO and 2,060 cc. of H20, while keeping the temperature below65 C. 'I'hetotal mixture was thenheated 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. The desired product 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 centsulphate ash 38.6 (calculated from metal content) Metal at... 4.52

, EXAMPLE 13 H 172 grams of di-(n-hexyl) dithiophosphoric .acid, 500 grams of petroleum sulphonic acid, 159

gramsof iso-nonyl phenol (ratio of equivalents of oil soluble acids to iso-nonyl phenol is 1.52), and 1,170: ccof water were mixed together, then 437' gramsof'BaO were added over a period of hour. The mixture was heated at reflux temperature for 1 hour, followed by heating to 150 'C. over a period of 2 hours, and then maintaining that temperature. for -1 hour. Th desired product was a viscous liquid, brown in color. and

The following proper- Basic No. 87.1

Per cent barium 28.6

Percent sulphate ash 1 48.8

1 I (calculated from metal content) :Metal ratio 5.22

EXAMPLE 14 172" grams of di-(n-hexyl) dithiophosphoric acid, 500grams of petroleumisulphonic acid and 98 grams of para-tertiary-butyl phenol (ratio of equivalents of oil soluble acids to'para-tertiary- I :butyl 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.

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 The mixture was 'stantially remove all the water.

10 Basic'No. 121 Percent barium 30.05 Sulphate ash 51.0

(calculated from metal content) Metal ratio 5.36

EXAMPLE 15 249 grams of petroleum naphthenic acid,88.6

grams of para-tertiary butyl phenol (ratio of equivalents is 1.70), 1212 grams of. a conventionally-refined Mid-Continent oil having a viscosity of 110 SUS 100 F., 347grams of BaO, and 700 m1. of H20 were placed in a 5 liter, 3

neck fiask'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. n Themixture was then filtered with Hyflo, 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 different 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 the quality'of the product. Such preparations are given in Examples 16 and 17 below.

EXAMPLE 16 The total mixture was refluxed for one hour at 100 C. and then the temperature was slowly raised to 150- C. for a period of one hour to sub- The complex was separated by filtration and was found to be a'liquid, and black in color. erties were determined:

The following prop- Basif c No.'; 1 27.7

Per cent sulphate ash 17.25

,Metal ratio 2.41

EXAMPLE 17 I By the conventional technique, 4801 gramsTof the barium salt of petrolatum sulphonic acid and '200 grams of the barium salt of petroleum sulphonic acid of Example. 16 ,were mixed with a bariumoxide slurry containing 68 grams of water and 60.8 grams of barium oxide. The components were heated to a temperature of 160 C. for one hour until substantially all the water was removed. The complex was separated by filtration and was found tobe a viscous liquid, light brown in color, and contained a slight odor. The following properties were determined: Basic No. 20.2 Per cent sulphate ash 11.72 Metal ratio 1.51

slight odor. The following properties of the prodnot were determined:

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 conoxide and 1390 ml. of water.

'templated for the purposes of this invention to employ the complexes produced. by conventional techniques as a starting material. The following example illustrates this concept:

EXAMPLE I8 1634 grams of a barium petroleum sulphonate- BaO complex (obtained by dehydrating a barium petroleum. sulph'onate,v 7'.6%-su1phate 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-isobutyl-pheno'l (ratio of equivalents 1.7) were combined and heated to 70 'C'.

To this mixture was added 665 cc. of water, followed. by a slow addition of 175 grams of BaO. The entire-mixture wasthen 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 asfollows:

Basic No. 8.67 Per cent sulphate ash 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 invention.

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. In this respect, Examples 19 and 20' below illustrate the effect of higher temperatures.

2000 grams of :a 30% oil solution of barium petroleum sulphonate (sulphate ash 7.6%) were mixed with 120 grams of paratertiary-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 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, reddish-brown in color, and contained a faint odor. The following properties were determined:

Basic No. 71.5 Per cent sulphate ash 243 Metal. ratio 3.80

EXAMPLE 20 2036 grams of 30% oil solution of barium petroleurn sulphonate (sulphate ash 7.6%) were The total. mixture sulphonate to sulfonic acid is 1.52).

brown in color, andcontained a slight odor.

half hour.

tion and was found to be an oily liquid, reddish- The following properties were determined for the complex:

Basic No. as... 111.5 Per cent sulphate ash a 32.8 Metal ratio a 5.56

holding at said temperature for one hour, the

temperature was raised more period of three hours to 150 C. and'held at that level for one- 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 26.8 Metal ratio- 4.37

EXAMPLE 22 The ionizable organic compound or promoter employed in this test was prepared by reacting '80 grams tertiary-butyl benzene with 71 grams oiv chlorosulphonic acid at a temperature of 30 40 C. fora 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 I 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 100-102 C. The temperature was thereupon raised to 200 C. for a short period and then reduced to 150 C. and held at that level for a period of one hour. The salt complex thus obtained was an oily liquid, reddish-brown in color, and contained a faintodor. The properties of the product are as follows:

Basic No. 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 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 atemperature for a period of about one-half hour. The salt complex was separated by filtrabenzoic acid (1.68 ratio of equivalents) and heated to C. 458 grains "of barium oxide and 1215 grams of water were added to the mixture and the temperature was maintained at C. for about one hour. Thereafter the temperature was slowly raised to 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 determined:

Basic No; 32.1 Per cent sulphate ash 19.1 Metal ratio 2.88

Basic No. -1 132 Per cent sulphate ash 33.3 Metal ratio -1 6.47

EXAMPLE 2050grams of a 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 temperature of 95 C. 388 grams of barium oxideand 1035 ml.'of water were added to the mixture and the temperature was maintained for a period of one hour'at 100 C. Thereafter the temperature of the mixture was slowly raised to 150 Clover a period of 2%; hours and maintained at that level for a period of one hour. The product was an oily liquid, reddish-brown in color, and contained a slight odor. The following-properties were determined for the product:

Ba'Sic'NO 78.2

Per cent sulphate ash 28.2

Metal ratio 4.60 1.

5 1 EXAMPLE 26 1500 grams of a 30% oil solution of barium petroleum sulphonate having a sulfate ash of .7.6%, 93 grams of iso-propyl phenol (ratio of equivalents 1.7), and 670 grams of water were placed in a 3-liter flask and heated to C. 250 grams of BaO Were then added, and the temperature was allowed to rise to 100 C. The mixture was heldat 100 C. for one hour, followed by arise in temperature'to 150 C. over a two hour period, where the temperature was held for one-half hour. -The total mixture was filtered, and the filtered product'had the following properties:

Perpent sulphate ash 25.95

Metal ratio' 3.88

EXAMPLE 2'7 1140 grams of a 30% oil solution of barium petroleum sulphonate having a sulphate ash of 7.6% and 80 grams of para-tertiary-amyl phenol (ratio of equivalents 1.54) were heated to C.

Thereafter 600 cc. of water were added, followed by'a, slow addition of 227 grams of BaO. The mixturelfwas refluxed for one hour, and then the "temperature was raised to 160 C.'over a period of four hours and held there for one-half hour. Theproduct was separated by filtration, and had the following analyses: 1

Basic No Q 85.5 Per cent sulphate ash; 24.60

Metalratiou 3.96 EXAMPLE 2s 2583 grams of a 30% 011 solution of barium petroleum sulphonate having a 7.6% sulphate jash, 144.2 grams of beta-naphthol (ratio of 1'4 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 bymaintaining 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:

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 ml. 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: i

Basic No 3.9

Sulphate ash 25.0

Metal ratio 4.17

EXAMPLE 30 2600 grams of a 30% 011 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 follows:

Basic No 13.3 Per cent sulphate ash 25.45

Metal ratio I 4.38

- EXAMPLE 31 V 1530 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash and 210 grams of trichloro-diphenyl 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 mix ure 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 CO: at 150 C. and at a rate of 3.6 cu. ft./hr. for one and one-half hours. The filtered product analyzed 'asfollows:

Acid No 0.45 Per cent sulphate. ash 24.7

Metal ratio -1 4.34

I EXAMPLE32 I -1530 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash and grams of tertiary-butyl naphthalene sulphonic acid (ratio of equivalents, is 1.7)- were combined and heated to 70 C. To this mixture 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.15T C. for one hour. Prior to filtering, the mass was blown at 150 C.. with CO2 atarate-of' 3.6 cu. ft./hr. for 1. hours. The filtered product analyzed as 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 temperaimre 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 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 1530 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash, 113 grams of diisobutenyl sulphonic acid (ratio of equivalents is 1.7) and 725 grams of H20 were combinedand heated to 70 C. To this mixture were added 271 grams of BaO, and the entire mixture was heated at 100 C. for one hour. The mixture was then heated at 150 C. for one hour, followed by blowing with CO2 at 150 0. prior to filtering, to obtain. a substantially neutral mass. The filtered product analyzed as 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 with 122 grams of chloro sulphonic acid for one hour at 100 C. were combined with 2600 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash and 1220 ml. ofwater. The ratio of equivalents of oil soluble sulphonate to sulphonic acid is 1.7. Then 461 grams of BaO were added slowly and the mixture held at 100 C. for one hour. The temperature was raised to 150 C. and held there for one hour. Prior to filtering, the mixture was blown .withCOz for one half hour at l20-140 C. The

filtered product analyzed as follows:

'AcidNo 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 70l00 C. for 1 hours were combined with 2600 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% Sulphate ash and 1220 ml. of water. 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 85-100 C. for one hour. Then the temperature 11.6 was raised to 150 C. andheld there for one hour. Prior to filtering, the mass. was blown with CO2 for one-half. hour. at 130 C. The filtered product analyzed as follows:

Acid No 0.95

Per cent sulphate ash 25.8

Metal ratio 4.38

EXAMPLE 37 2600 grams of a oil solution of barium petroleum sulphonate having a 7.6% sulphate ash, 2219 grams of tertiary-butyl dichlorophenol (ratio of equivalents is 1.7) and 1265 grams of waterwere combined, followed by an addition of 459 grams of BaO over a 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 minutes at 135-150 C. until it was slightly acidic. The filtered product analyzed as follows:

Basic No 6.45 Per cent. sulphate. ash 23.2

F Metal ratio 3.85

Acid No 0.27 Per cent 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. grams of acetyl-acetone (ratio of equivalents is 1.7)- and 1265 cc. of water were combined followed by a slow addition of 459 grams of BaO over a one hour period. The entire mixture was held at 94 C. for one hour, followed by av one hour period of heating at 150 C. Prior to filtering, the mass was blown with CO2 for one hour :fitn-150" C. The filtered product analyzed as o ows:

AcidNo 0.2 Percent sulphate ash 22.8 Metal ratio 1 3.48

EXAMPLE 40 1530 grams of a 30% oil solution of. barium petroleum sulphonate having a 7.6% sulphate ash and 206 grams of .di-t-butyl-naphthalene sulphonic acid (ratio of equivalents is 1.7) were combined and heated to 70 C. 725 grams of water were then added, followed by a slow addition of 271 grams of BaO. The mixture was refluxed for one hour, and then held at C. for one hour. Prior to filtering, the mixture was blown with CO2 at a rate of 3.6 cu. ft./hr. for 1.25 hours at a temperature of 150 C. The filtered product analyzed as follows:

Acid No 0.24 Per cent sulphate ash 23.6 Metal ratio 4.12

The salt complex can also be prepared by starting with the oil-soluble sulphonic acid and treating with a promoter and the inorganic metal compound. This technique differs from those given above because as shown in all the above examples, the normal metal sulphonate or con- EXAMPLE 41 The oil-soluble petroleum sulphonic acid employed in this test was derived by reacting a 60% oil solution of sodium petroleum sulphonate with the stoichiometric amount of sulfuric acid (96% strength) at a temperature of 60-70 C. for a period of two hours. After allowing the reaction mixture to stand about 12 hours, it was filtered twice through a glass cloth. 2875 grams of the product just described were combined with 205.7 grams of para-tertiary-butyl phenol, (ratio of equivalents is 1.39), 1647 grams of'a' low-viscosity mineral oil having a viscosity of about 120 SUS at 100 F., 927.6 grams of barium oxide and 2480 grams of water and heated for one hour at a temperature of 98 C. The mixture was then dehydrated for one hour at a temperature of 150 C. so as to remove substantially all of the water.

The product was a viscous liquid, brown in color,

and contained a mildodor. The following properties were determined for the desired product:

Basic N 74.2 Per cent sulphate ash 24.4 Metal ratio r 4.02

EXAMPLE 42 500 grams of the oil-soluble petroleum sulphonic acid given inExample 41 above were heated to 75 C. 55 grams of water were then added and followed by a slow addition of 162.2 grams of barium oxide. The total mixture was maintained at a temperature of 150 C. for a period of one hour. The desired complex was separated by filtration and was found to be a very viscous liquid, black in color, and did not contain any odor. The following Basic No 53.7 Per cent sulphate ash 25.65 Metal ratio 1.74

The salt complexes of the present invention can be prepared by first adding water to the mixture 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 be prepared.

EXAMPLE 43 raised over a period of four hours to 170 C. and then maintained there one hour. The salt complex was obtained by filtering, the product and was found to be a viscous liquid, dark brown in color, and contained a faint odor. The following properties were determined for the salt complex:

Basic No -1 67.8 Per cent sulphate ash 23.8 Metal ratio- 2.67

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

. EXAMPLE 44 1700 grams of a 30%'oil solution of barium petroleum sulphonate (sulphate ash 7.6%) were admixed with grams of barium phenate (ratio of equivalents is 1.70), and 570 grams of water. The mixture was heated to 75-100 C. whereupon 214 grams of barium oxide wereadded. The temperature of the mixture was maintained at 100 C. for one hour and then raised slowly to C. and held at this level for a period of one hour. The salt complex was then 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 No 68 Per cent sulphate ash"; 21.4 Metal ratio 3.23

Thefollowing examples by comparison illustrate the substantial increase in metal content of the complex which is obtained by treating the mass with an acidic material beforefiltering to separate the desired product.

EXAMPLE 45 Y 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. 302 grams of BaO and 800 cc. of water were added thereto, and the mixture was refluxed for one hour. The temperature was raised to C. over a period of 6 hours and maintained at that temperature for one hour. The mass was filteredancl Basic No a 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 diisobutylphenol (ratio of equivalents is 1.7) and heated to 70 G. Then 800cc. 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 oneihour. 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:

Metal ratio.. 4.52

EXAMPLE 47' 400 lbs. of a 30%:oil s'olution of barium petroleum sulphonate having a sulphate ash or 7.6% were heated to 80 0., and 32.5 lbsLof diisobutylphenol (ratio of equivalents is 1.67) were added thereto. Then 197 lbs. of water were added to the mixture;withstirringto insure thorough mixing. -73-lbs. of BaOwere 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 135-170 C. The mass was then filtered and the product was found to have the following properties Basic N 5.0 Percent sulphate.ash 25.7 Metal ratio- 4.32

EXAMPLE 48 4590 grams ofa 30% oil solution of barium petroleum sulphonate having a 7.8% sulphate ash, 363 grams of diisobuty'l-phenol (ratio of equivalents is 1.7) and 2,800 grams of H were heated to 60 C. 1,042 gramsof BaO were added slowly and then thetem-perature 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.until330 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 B Basic No 63 4. 5 Percent Sulphate Ash l9. 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 100 C. and held at that level for one hour. Thereafter, the temperature was raised slowly to 150 C. and held there for about-one hour. The total mixture was allowed to settle overnight, followed by decanta- .20 complex was a viscousliquid, light brown in color, and contained a slight odor. The following properties of the product were determined:

Basis No 59.5 Percentsulphate ash 21.2 .Metal ratio 3.20

EXAMPLE 50' 1700 grams of a 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 l50160 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 No 82.6 Percent sulphate ash 26.4

In the following examples, organic acids or salts thereof and inorganic alkaline earth metal com- 9 pounds containing a metal other than barium tion and filtering. In this experiment 450 grams of sediment were produced. The filtered salt were combined in the presence of a promoter to produce over based products.

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 of paratertiary butyl phenol (ratio of equivalents is 1.54) and heated to about -'C. To this mixture were then added about 148 grams of Ca(OH)z and about 300 cc. of water, and the total mixture was refluxed at about 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 was separated 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 No 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 paratertiary-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 C. over a period of about 5 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:

21 Ex l rLEss 1,120 grams of a 45% oil solution of calcium petroleumsulphonate having a sulphate ashcontent of 6.5%, 59 grams of l-nitro-propane (ratio of equivalents is 1.52), 150 grams of Ca(Ol-I)2 and 830 ml. of water were mixed. together, and heated to about 100 C. for about one hour. .The temperature was then raised to 150 C. and held at that level for one hour. The product was separated by filtering, and was found to be a viscous liquid, brown in color, and contained a faint odor. The product possessed the following properties:

Basic No 36.1 Per cent sulphate ash 13.15 Metal ratio 2.36

For the purpose of comparison, calcium petroleum sulphonate was overbased with Ca(OH) 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 37 grams of Ca(H)z 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 7.90 Per cent sulphate ash 1 5.15 Metal ratio 1.29

The following example illustrates the use of a 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(OI-I)2 was stirred at reflux temperature for two hours. Thereafter 1046 grams of a 45% 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 mixture,

it was blown with CO2 for three hours at a temperature of about 120-450 C. The complex was fiuid, brown in color and didnot contain any odor. The complex had the following analyses:

Basic No 8.07 Per cent sulfate ash Metal ratio Another preparation was made in which dissimilar alkaline earth metals were present in the organic acid compound and inorganic metal compound. The following example illustrates this feature of the invention.

EXAMPLE 56 The complex obtained by filtering the mixture had the following properties:

Basic No 4.2

Per cent sulfate ash 25.2 Metal ratio. 3.94

EXAMPLE 57 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 50 C. whereupon a slurry of BaO (consisting of 2027.6 grams of BaO and 5395 grams of water) was added and the mixture was then maintained at a temperature of about 9'0-05 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 73.0

Per cent sulfate ash; 23.3

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 100 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 ration 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 com- .plex 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 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 onehour at a temperature of C. and then heated slowly over a period of three hours to a temperature of C. This temperature was maintained for about one hour until substantially all the water was removed. The salt complexf thus produced had the following properties:

Basic No 1 58.4

Per cent sulphate ash 16.0 Metal ratio 2.25

Example 60 Basic No 29.0 Percent 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 techniques. Furthermore, in every instance where the salt complex produced 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 promotor-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 Basic No 85.2

Per cent sulphate ash 25.2 Metal ratio 4.12

EXAMPLE 62 1530 grams 6r a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash were mixed with 725 ml. 0f water at about 60 C. Then 271 grams of'BaO were added. The

Basic No 36.0 Per cent sulphate ash 15.34 Metal ratio 2.14

From the foregoing it will be noted that by following th 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 withan 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 disillation, of the promoter thus liberated, leaving the end product and complex substantially free of the promoter material. A third product which is probably different 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 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 promoter material 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 ionizable organic compound used as the promoter. After a portion of the promoter material has been thus regenerated by treating the immediate product with an acidic material, the regenerated promoter may then be separated therefrom by any one of the several known means, or the regenerated promoter material may be left in the mass and the latter then treated with an additional amount of a saltforming material, and it will be found that the concentration of the stably-held metal can be further increased. The following are examples of such further steps in our process.

EXAMPLE 63 The salt complex produced in Example 43 was mixed with 1239 grams of mineral oil and heated to a temperature of 190 C. While maintaining this temperature for a period of 1 /2 hours, CO2 was blown through the mixture. The temperature was then lowered to C., continuing the passage of CO2 through the mixture, and the basic number of the mixture was tested every 10 minutes, until the analysis showed a basic number of 2.5. The salt complexCOz product was 25 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:

Basic No. 2.5 Percent 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 23.2. 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 suitable vessel and CO2 gas was injected at the bottom of the vessel at a rate of 3750 cc. per minute for a period of 1%; hours. During this period, the temperature was in the range .of 3070 C. At the end of the blowing operation the product weighed 6346 grams, showing a gain in weight of 311 grams. The product was fluid, dark red in color, and contained no odor. The following properties were determined for the salt complex-COz product:

Basic No. l 4.3 Percent sulphate ash 22.7

It can be seen, therefore, by the gain in weight of the product that the CO2 actually enters into combination with the salt complex. Furthermore, the metal ratio of the product is substantially the same as the salt complex prior to being blown withCOz, since the sulphate ash content is substantially the same as before CO2 treatment.

EXAMPLE 65 1288 grams of the salt complex prepared in accordance with the method of Example 5 was blown with CO2 at a temperature of 30-50 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. The following properties were determined:

Acid No. v 5.36 Percent sulphate ash 17.94

The above examples clearly show that it is mssible to treat the salt complex with an acid anhydride gas and obtain a product which is definitely acid. Furthermore, treatment with an acid-anhydride gas to such extent does not change the metal ratio of the salt complex, since the sulphate ash content is substantially the same as before treatment.

Another salt complex product which was blown with CO2 is given in Example 66 below.

EXAMPLE 66 2500 grams of a 30% oil solution of barium petroleum sulphonate containing 7.6% sulphate ash were mixed with 45.6 grams of phenol (ratio of equivalents'is 3.36), and heated to 95 .C. A slurry of barium'oxide containing 422 grams of barium oxide and 1125 ml. of water was added to the mixture, with stirring, and held at a tem-, perature of 97102 C. for a period of one hour. The temperature was then slowly raised over a period of three hours to 150 C. and maintained at that level for an additional period of one hour until substantially all the water was removed. The desired salt complex was separated by-filter- Basic No. -2. 60.6 Percent sulphate ash 22.3 Metal ratio 3.34

EXAMPLE 67' 1250 grams of the-salt complex produced in accordance with the method given in Example 66 above were blown with CO2 for approximately two hours at a temperature below 60 C., until an acid number of 5.0 was obtained. The weight of product obtained was 1260 grams.

The COz-salt complex product was then heated at a temperature of 190 C. under a vacuum of 10 mm. producing a distillate weighing about 10 grams. The distillate was then dissolved in isopropyl ether and then dried over magnesium sulphate, filtered and then the magnesium sulphate was removed by filtration, 5 grams of residue remained. This residue was found to be phenol, thus indicating that treatment of the salt complex with an acidic material liberates at least a portion of the ionizable organic compound from complex formation.

After the distillation step, the following properties for the salt complex were determined:

Basic No. 2.96 Percent sulphate ash 22.4

The percent sulphate ash of the COz-Salt complex product indicates that little or no metal is removed from the complex as a result of the CO2 treatment and the distillation step to recover the ionizable organic compound.

EXAMPLE 68 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 fromcomplex formation. On a quantitative basis, -it was determined that approximately of the original phenol was still held in complex formation in the C0z-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 s9 6000 grams of a 30% solution of barium petroleum sulphonate (sulphate ash 7.6%), 348 grams of para-tertiary-butyl phenol (ratio of equivalents is 1.70), and 2915 grams of water were mixed and heated to a temperature of 60 C. 1100 grams of bariumoxidewere added slowly and the temperature 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 C. and held at that level for an additional hour until 27 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: 7

Basic NO. Q 82.5 Percent sulphate ash 26.0 Metal ratio 4.2

6623 grams of the product produced in accord- EXAMPLE 71 380 lbs. of a 30% oil solution of barium petroleum sulphonate were mixed with 21.9' lbs. of para-tertiary-butyl phenol (ratio of equivalents is' 1.7) and 1 84 lbs. ofwater. This mixture was heated to 50 C. and 68 lbs. of BaO were added over a period of 1 /ghOu1S while not permitting the temperature togoabove 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. The desired product was fluid, dark red, and possessed the following properties:

Basic No. 80.5

Percent sulphate ash 26.0

Metal ratio 4.2

6000 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 ofequivalents falls outside of said preferred range, but. comes within the broad range found to be operable.

EXAIVIPLE 73 1000 grams of a 30% oil solution of barium petroleum sulphonatecontaining 7.6% sulphate ash were mixed with 750 grams of water at 50 C). 282 grams of BaQ 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 100 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:

28. EXAMPLE 74 2760 grams of a 30% oil solution of barium petroleum sulphonate containing 7.6% sulphate ash were mixed with 217 grams of 39.0, 580 grams of water and 41 grams of diisobutenyl sulphonic acid in that order. The ratio of equivalents of sulphonate to sulphonic acid is 9.

The mass was heated for one hour at about C., then the temperature was raised to C. and maintained there for one hour. The salt complex was separated by filtration. It was a viscous, brown liquid, and had the following properties:

Basic No. 34. Percent sulphate ash 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 AThe 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 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 it is possible to first prepare the normal metal salt of the organic acid in the usual way, by a conventional salt-forming procedure, 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 rather than 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 prior art processes Also, as a starting material, mixtures of acids and salts can be used to produce the complex. The variety of classes of. organic acids which can be employed are, for

example, sulphuracids, carboxylic acids, phosphorus acids, etc. ofthe aliphatic and cyclic types, and the corresponding thio-acids.

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

The carboxylic acids include the fatty acids wherein there are present at least about 12 carbon atoms, such as,v 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 acids are the carbamic acids, ricinoleic acids, chlorostearic acids, nitro-lauric acids, etc. In addition to the aliphatic carboxylic acids, it is intended to employ the cyclic types such as those containing a benzenoid structure, i. e., benzene naphthalene, etc., and an oil-solubilizing radical or radicals having a total of at least about 15 to 18 carbon atoms. Such acids are the oil-soluble oxygen or sulphur.

' 29. aliphatic substituted aromatic acids as for example, stearyl-benzoic acids, monoor polywax substituted benzoic or naphthoic acids whereinv the wax group contains at least about 18 carbon atoms, cetyl hydroxy-benzoic acids, etc. The cyclic type of carboxylic acids also includes those acids which have present in the compound a cycloaliphatic group. Examples of such acids are petroleum naphthenic acids, cetyl cyclohexane carboxylic acids, di-lauryl. deca-hydronaphthalene carboxylic 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 thiocarboxylic acids can be represented by the following formulae:

wherein R is an aliphatic radical, x is at least 1,

and (R'n; contains a total of at least about 15 to 18 carbon atoms; T is a cyclic nucleus such as benzene, naphthalene, diphenyl ether, diphenyl ene oxide, diphenyl sulphide, diphenylene sulphide, phenol, hydroxy-naphthalenes, phenol disulphide s, petroleum naphthenes, cyclohexane, cyclopentane, chloro-cyclohexane, nitro-cyclopentane, deca hydronaphthalene, mercaptodeca-hydro-riaphthalene, etc.; and X is either 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 such as nitro, amino, hydroxy, mercapto, halogen, etc.

Representative examples are nitro-stearic acids,

cerylchloro-salicylic acids, chloro-palmitic acids,

cetyl-anthranilic acids, stearyl -mercaptonaphthoic acids, etc.

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

I R-X wherein X and X are either oxygen or sulphur was;

and at least one X and 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 R 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 thiophosphorie acids and the organic thiophosphorous acids. The organic radicals R and R can be aliphatic, cycloaliphatic, aromatic, aliphaticand cyeloaliphatic-substituted aromatic, etc. The organic radicals R and R preferably contain a total'of at least about 12 carbon atoms in each of the above thio-acid types Iand .II. Examples of such acids are dicapryl dithiophosphoric acids, di-(methyl-cyclohexyl) l 3o 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 ormore 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 oilesoluble organic acid as such as one of the starting materials, but also the alkaline earth metal salts of such organic acids.

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:

In the above formulae M is either an alkaline earth metal, preferably barium, or hydrogen; T is a cyclic nucleus either of the monoor polynuclear type including benzenoid or heterocyclic nuclei such as benzene, naphthalene, anthracene, phenanthrene, diphenylene, thianthrene, phenothioxine, diphenylene sulphide, diphenylene oxide, diphenyl oxide, diphenyl sulphide, diphenyl amine, etc.; R is an aliphatic group such as alkyl, alkenyl alkoxy, alkoxy-alkyl, carboalkoxy-alkyl,

oriaralkyl groups, a: is atleast 1, and Rx contains atotal 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 carbon atoms. Examples of types of the R radical are alkyl, alkenyl, and alkoxyalkyl radicals, and aliphatic substitutedcycloaliphatic radicals where the aliphatic group is alkyl, alkoxy, alkoxy-alkyl, carboalkoxyalkyl, etc. Specific examples of R are cetyl-cyclohexyl, lauryl-cyclohexyl, .ceryloxyethyl, and octadecenyl radicals, and radicals derived from petrolatum, saturated and unsaturated paraffin wax, poly olefins, including poly-C3, C4, C5, C6, C7, Ca, 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. V

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

' The following are specific examples of oil- Such sulphonic acids are mahogany sulphonic acids; petrolatum sulphonic acids; monoa and polywax substituted naphthalene sulphonic, phenol sulphonic, diphenyl ether sulphonic, dipheny-l ether disulphonic, naphthalene disulphide sulphonic, naphthalene disulphide disulphonic, diphenyl amine disulphonic, diphenyl amine sulphonic, thiophene sulphonic, alpha-chlorate naphthalene sulphonic acids, etc.; other substituted sulphonic acids such as cetyl chioro benzene sulphonic acids, cetyL-phenol sulphonic acids, cetyl-phenol disulphide sulphonic acids, cetyl-phenol mono-sulphide sulphonic acids, cetoxy capryl-benzene sulphonic acids, dicetyl, thianthrene sulphonic acids, di-lauryl beta.- naphthol sulphonic acids, and di-capryl nitronaphthalene sulphonic acids; aliphatic sulphonic acid such as paraffin wax sulphonic acids, un saturated parafli-n wax sulphonic acids, hydroxy substituted parailin wax sulphonic acids, tetra.- isobutylene sulphonic acids, tetra-amylenesulphonic acids, chloro-substituted parafiin wax sulphonic acids, ni-troso paraflin 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 alt sulphonic acids which. are derived from petroleum products. Additional; examples of sulphonic acidsiand/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;- 2,114,508; 2,193,824; 2,191,800; 2,202,791; 2,212,786.; 2,2i3:,-= 360 2,228,598; 2,233,616; 2,239,97d; 2,263,312; 2,276,090; 2,276,097; 2,315,514; 235199. 21; 2,32'l',,- 0221; 2,333,568; 2,333,188 2,335,259; 2,33%,552.;:. 2,346,568; 2,366,027; 2,37%,19-32 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 sulphur-bearing organic acids: 'or: alkaline: earth metalv salts thereof. However, it is to: be understoodthat all: of organic acids: and salts: thereof are not equivalent in their ability to complex with unusual amounts of inorganic alkaline: earth metal compounds inthe presence: of a. promoter, because under certain-- conditions, some organic acids or salts thereof are more effective; than others.

Component BThe promoter: material,

32 with the compound AXH. The compounds AH or should have ionization constants measured in, water at 25- C. greater than about l-X l0. 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. V 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-parafiins, lower molecular weight aromatic: carboxylic acids, lower molecular weight organic thiophosphoric; acids, the lower molecular weight sulphonic acids, hydroxyaromatic compounds, lower molecular weight hydroxy aromatic acids, etc. To. better illustrate the wide variety of classes of com-pounds which can be employed in formin 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.

The -phenolic compound referred to hereinaboveis for the purpose of this specification and theappended claims an organic compound having a hydroxyl group attached directly to a carbon atom of a benzenoid ring, and which com.- pound is with or without other substitutents on the benzenoid ring. It should likewise be understood that a phenol is a sub-class of a phenolic compound, in. which there is only a hydroxyl group on. the benzene ring or in addition to. the hydroxyl group, there. is also present in the. molecule a single hydrocarbonv group or a plurality thereof. Those phenolic compounds containing not more than 30 carbon atoms in. the 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, p.-propyl.-phenols, di-isopropylphenols, p-t-butyl-phenol, p-t-amyl phenol, pcyclopentylr-phenol, p-(4 methyl cyclohexyliphenol, sec.-hexyl-phenols, n-heptyI-phenols, diisobutyl-phenols, 3,5,5tri-methyl-n-hexyl-phe-- nols, n-decyl-phenols, cetyl-phenols, etc.; aryl substituted phenols, e. g., phenyl phenol, diphenyl phenol, etc.; poly-hydroxy aromatic compounds such as alizarin, quinizarin or polyhydroxy benzenes, e. g., hydroquinone, catechol, pyrogallol, etc.; monohydroxy naphthalenes, e. g., a-naphthol, fi-naphthol, etc.; polyhydroxy naphthalenes, e. g., naphthohydroquinone, naphthoresorcinol, etc.;, the alkylated polyhydroxyaroma-tic compounds such as, octylcatechols, triiso butyl-pyrogallols, etc.; substituted phenols such as p-nitro-phenol, picricv acid, o-chlorophenol, t-butyl-chlorophenols, p-nitro.-o-chlorophenol, p-amino-phenol, etc.; lower' molecular weight hydroxy aromatic carboxylic acids such as salicylic acid, chloro-salicylic acids, di-isopropyl-sa-licyclic acids, gallic acid, 4-hydroxy-1- naphthoic acid, etc.; lower-molecular weight aromatic sulphonic acids such as p-cresol sulphonic acids, p-t-butyl-phenol sulphonic acids, betanaphthol alphawsulphonic acid, etc. lower molecular weight: aromatic carboxylic acids. such as bBlIZQlC: acid, p-nitro benzoic: acid; o-chloro-benzoic: acid, p.-toluic acid, p-t-butyl-benzoic acid,

nitro-l-(p-diisobutyl-phenoxy) alpha-naphthoic acid, etc.;. lowermolecular weight aromatic sulphonic acids such as benzene including aliphatic dithiophosphoric acids, e. g.,

di-isopropyl dithiophosphoric acid, di-n-butyl dithiophosphoric acids, etc., aromatic dithiophosphoric acids, e. g., di-(phenyl) dithiophosphoric acids, etc., the aliphatic monothiophosphoric acids, e. g., di-ethyl monothiophosphoric acids, etc., the aromatic.monothiophosphoric acids, e. g.,

di-tolyl monothiophosphoric acids, di-(iso-propyl-phenyli monothiophos'phoric acids, etc. "Additional examples of compounds which can be employed as promoters are given in the enumerated ionizable organic compounds and the alkaline earth metal salts thereof are not all equivalent as promoters, but that under certain conditions some are more efiective than others.

Component C'.The alkaline earth metal saltforming compounds The salt-forming compounds which are'employed to impart to the process mass the specified amount of metal may be broadly defined as in- .organic'alkaline earth metal compounds wherein anionic radicals may be, for example, hydroxyl, oxide, carbonate, bi-carbonate, sulphide, hydrosulphide, halide, hydride, amide, basiccarbonate,

etc. of the inorganic alkaline earth metal compounds, good results are obtained withthose having a Water solubility of at least about 0.0003% at50 C., and preferably at least about 0.006%. 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 varietyof classes of inorganic compounds which can beemployed, specific examples thereof are enumerated below.

v Thealkaline earth metal-inorganic compounds .includethe barium containing compounds such as barium hydroxide, barium oxide, barium sul- .fide,,' bariumcarbonate, barium bi-carbonate,

barium hydride, barium amide, barium chloride, barium bromide, barium nitrate, barium sulfate,

barium borate, etc; the calcium containing compounds such as calcium hydroxide, calcium oxide, calcium sulfide, calcium carbonate, calcium bicarbonate, calcium hydride, calcium amide, calcium-chloride, calcium bromide, calcium nitrate,

calcium borate, etc.; the strontium-containing compounds such as strontium hydroxide, strontium oxide, strontium sulfide, strontium carbonate, strontium bicarbonate, strontium amide, strontium nitrate, strontium hydride, strontium nitrite, 'etc.; the magnesium-containing .com-, pounds such as magnesium hydroxide, mag

sulphonic acid, p-chlorobenzene sulphonic acid,

34 nesium oxide, magnesium carbonate, magnesium bicarbonate, magnesium nitrate, magnesium nitrite, magnesium amide, magnesium chloride, magnesium sulfate, magnesium hydrosulfide, etc. The corresponding basic salts of the above 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 present invention, because under certain conditions some are more eifective or desirable than others.

The acidic material As previously indicated, one form of the process .of the present invention includes the step of treating the immediate complex product with an acidic material for the purpose of; liberating therefrom at least a portion of the material previously referred to as the promoter. particularly effective acidic material which has been utilized for this purpose is carbon dioxide. We are aware of the fact that Mertes in his aboveidentified Patent No. 2,501,731 suggested transforming a sodium hydroxide-calcium sulphonate complex into the. sodium carbonate-calcium sulphonate complex or the corresponding bicarbonate complex by blowing the hydroxide complex with carbon dioxide at elevated temperatures.

In our process, the step of treating with an acidic material such-as carbon dioxide or'air has the effect of freeing from the immediate complex product formed atleast a portion of .the promoter used. Thus the presence in the immediate complexxproduct of the 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. How'- ever, 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. 7 I The following are additional specific example of acidic materials, v-iz HCl, S02, S03, 00;, air (considered acidic because of CO2 content), N02, 1:25, N203, PC13, SOCl-m-ClOz, HzSe, BFs, CS2, COS, e c.

I conditions, some are more than others.

It isto beunderstood, however, that all acidic materials are notv equivalent. for thepurposesoi the present invention, but that under certain effective or desirable .Thecomplex of the presentinventiomcan be produced by using the samealkaline earthmetal intthe organic acid compound, promoter and inprganic compound; .or such complexes can be fore possible toemploy variouscombinaticns of dissimilar alkaline earth metals inthe starting materials used in preparing the complex product.

Process conditions 'The salt complex of the present invention. is

"prepared by combining'the aforementionedi'com- *poundsin'the: presence ofwater. The water can be present as a result of addition thereofxtothe "mixture, or liberated'from either the essential components or other additionallypresent compounds as a result of being subjected to heat.

However, it is preferred toadd water to themixture to effect salt complex'formation. It has been "found that the metalcomplexcan be pre- -paried-when using small quantities of water such asa'bout -1 mole of waterper. mole of inorganic metal compound. However; more usually about Ste 50, and preferably about 15 to 30, moles :of water per moleof' inorganic metal 'compoundare -used.

"Generally the 'complex formed'with the .inorganic alkaline earth metal com'pouridytheoilsoluble 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 mixin 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'a'ddedto theoil-soluble 'normal'salt of the'organic acid, followed .by' adthereto; the mixture is held ata superatmos- 'pheric temperature for a reasonable length "of ti rne while effecting thorough mixing, and then the total mixture'is further heated to remove substantially all water whichmight be present;

'(b) The inorganic alkaline earth metal com- 'pond 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;

The acid of the desired salt of organic acid is mixed with the promoter, then an aqueous solution or suspension of the inorganical- 'kaline 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 sub- -jecting the total mixture to dehydration conditions-in orderto remove substantially allof the water; a b

(d) In any of the methods discussed herein all of the water from the process mixture.

36 for preparing, the salt complex, a substantial increase in-metal content is usually effected by treatin the mass containing the complex prodnot with an acidic material just aftersubstantial amounts of water are driven off and just before the mass is. filtered.

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

, Inall of the methods described above for preparing the salt complex, the step of removing substantially all of the water which isprcsent is accomplished at a temperature not substantially in excess of 350 0., preferably about C. to 200 C. The technique employed to remove the waterincludes, for example, a conventional flash 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 super-atmospheric pressure. At a later stage, the acidicmaterial when used in gaseous form, may be used toremove the last portion of water. It can therefore be seen thatthe 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 technique employed therefor. Generally, the time required to effect substantialremoval 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 atmospheric pressure for such an operation, and consequently it requires about 1 to 5 hours to remove substantially It was observed that satisfactorycomplexes are obtained when using any of the techniques described above, and that the final water content can be up to about 2% or more.

Usually, as indicated above, the components are combined and agitated at an elevated temperature to insure thorough mixing, and then water is removed therefrom. It should be understood that the process to form the complex can be effected-without the preliminary heating and mixing period, if desired. It is therefore not essential to this invention to have'such a preliminary step because all that appears necessary is to mix the components and remove substantially any water which is. present.

For the purposes of this specification and the appended claims, the relative amounts of oilsoluble organic acid or the alkaline earth metal :salt thereof and promoter is expressed in the ratio of equivalents of the former to the latter. In accordance therewith, the ratio of equivalents ofoil-soluble organic acid or the alkaline earth metal salt thereof to promoter is from about lto 10 to about 10 to 1, more usually from about 1 to l to about 10 to 1, and preferably from about 3 to 2 to about 7 to 2.

The amount of inorganicalkaline earth metal compound employed generally will be suflicient to have present in the total mass at least more than about one equivalent of alkaline earth metal, regardless of how combined, perequivalent of oilsoluble organic acid or the alkaline earth metal salt thereof plus promoter. In other words, the amount of inorganic alkaline earth metal compound employedmust be such that there is more than the theoretical amount required to form merelv a normal saltof the oil-soluble organic acid andthe promoter. .Thus, for the purposes 1A5 indicated hereinabove, treatment of the salt hydride gas may be accelerated by superatmos isdefinedasthe ratio of the total metal in th of this specification and the appended claims, the amount of inorganic alkaline earth metal compound employed will be expressed as an amount such that there are present in the mass more than one equivalentof alkaline earth metal, in- 5 cluding the alkaline earth metal which is present in the form of the salt of the oil-soluble organic acid and the promoter, per equivalent of oil-soluble organic acid and alkaline earth metal salt; thereof plus the promoter. 1.10

vary considerably, depending on the desired re-.

sult.; As would be expected, short periods of treatment may cause only partial'liberation or release of ionizable organic compound or small:

decreases in the basic number of the salt complex-3 However, in general, periods of treatment will rang from about 0.25 to hours or more.

In most cases, andparticularly where it is de''{ sired to recover the promoter, the amount of acidic material used should be at least equivalent to the amount of metal present as the salt of the ionizable form of promoter.

1 When it is desired to produce a product hav-y i g. substantially neutral reaction, the amount/{'35 of acidic material used should be at least equivalent: to the total metal in excess of that present as the normal salt of the oil soluble organic acid. *5 To substantially increase the metal content ofa'; theg'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 ifefl'ected at a .temperature of from about 25 to 250 C. preferably from about 50 to 170 C1 using from about 0.5 to 20% of acidic material,

based on the total'mass, and for a. period of from about 0.25 to 30 hours. The acidic material employed is preferably an acid anhydride gas, as dehereinabove. Treatment with the acid an-,

phg'eric pressure.

{As indicated above, in order to facilitate an understanding of the amount of metal which can present in the salt complex, the metal ratio salt complex to the amount of metal which is in the form of a normal salt of the oil-soluble or-* ganic acid. In accordance therewith, the saltcomplex as of this invention will have metal ratios greater than 1 and up to 10 or more, pref erably 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 s'amemetal ratios as given above will apply such treated product. In those instances where plex before treating with the acidic material.

By reason of the high metal ratio of the complexes produced in accordance with this inverir tion, the following theories are suggested as a possible explanation of how the metal is combined. It is to be understood, however, that such theories are advanced for the purpose of offering explanations, and are not to be construed as limitations on the scope of the present invention.

In the following equations, AXH represents a promoter in which H is an ionizable hydrogen and M- represents a divalent metal. Assuming that the promoter may act as a catalyzer for the formation of inorganic polymeric configurations, viz. (--M--O-)H, which are bonded to the acid group (e. g., the sulphonate radical in the preferred instance), the possible reactions that may occur with the sulphonate radical are:

2AXH M(OH)Z (AXhM (peptized into end product). The resultant complex, according to the above theory, can be a complex mixture of all the potential 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 leavingthe sulphur atom with? double positive charge.

When the sulphonate, excess inorganic metal compound, promoter, and water are reacted according to the present invention, a basic promoter salt, AX-M-OH 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:

and structure (b would have a metal ratio of 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. 1:..

After the' structures (a) and -(b) are'formed, if izhydroxyl ions 1 are present in the reaction mass lithe iollowing reactions 'may take place:

The AX- ions .may then react with M(O-H).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. q l

According to this electronic explanation, the

AX- residue of the basic promoter salt AX--M-OH appears to function as a carrier for the M(OH)2, and thus facilitating the communicating of the M(Ol-I)2-into close positionswith the-"negatively charged oxygen atoms of the sulphonate radical.

Having thus described the present invention by :fm'r'iishing specific examples thereof/it is to be -un'derstood'that no undue limitations'or restric r-tions-a'are :-to:be imposed .by reason thereof, but .thatthescope of this. invention isdefined by the appendedrclaims.

.The salt complexes .pro'duced in accordance awithfthe present invention can be employedin 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, fire- ,proofing andstabilizing agents in plasticizers and .plastics, .paint driers, 1 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, gum solvent compositions, iat .splittingag'ents,bonding agent for ceramics and asbestos, asphalt improving agents, flotation .agents,,improving agents for hydrocarbonfuels isuchaase. g.,,.gasolene and fuel oil; etc.

More particularly; thecomplexes 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,

a--:.'1o2:better' appreciate the wide variety of uses :to whichtheisalt'complexes of this inventionare ::adapted, the following specific examples 'are given:

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

Other modes of applying the principle of the invention. may be employed, change :beirigmade -astregards :the details described, :provided the features stated .Iin any of the .following claims .orzthe 'equivalenttof :snchfbe'employed.

"We-therefore; particularly point out and distinctly claim'as our; invention:

l. A process which comprises preparing and mixing-a "mass in which, at 50C. at'least 50% of the components :are in theliquid state, and in which massthe active components consist of:

A. An oil-soluble organic acid compound containing at least 12 carbon atoms in'the molecule"sele.cted from .theclassconsisting of the aliphatic and cyclic; sulphur. acids, carboxylic acids, phosphorus acids, the-thio acids, corresponding to any of the foregoing acidaand the alkaline earth metal salts of anyof .saidacids;

B. A low molecular weight aromatic carboxylic acid having;

(a) An ionization constantrin water'of "at '(b) A- Water. solubility; at- 50 .C.:=of :at least about 0.0005 and (c) In saturated aqueouszsolutions at about 25 C. 'a pH of less than-7;

the relative amounts of A and B usedbeing in the-range of from about'one equivalent'of 'A'to about 10 equivalents of B toabout'lO equivalents of 'A to about one equivalent of B;

C. An inorganic alkaline earth metal compound;

(1) Which iswater-soluble'ata temperature of 50 C. to the extent of 'at leastabout 0.0003%;

' (2) In an amount such that there are present in the mass substantially more than 1 equivalent'of alkaline earth metal,'=inc1uding the alkalineearth metal'present in'the remaining components, per equivalent of' -A plus'Bian'd v D. Watenin an amount equalto at least about onemole per mole of C;

maintaining the mass at .a temperature and'ior av period 'of time sufficient to drive off substantially all free water and water-of .hydration which may be presentyand form therorganicalkaline earth metal "complex :and then treating the organic-alkaline earth metal complex with an acidic material of whichzthe ionizationconstant is higher than the ionization constant of the organic salt-forming compound tof component B and in amounts sufiicient'todiberatea substantial proportion of said. organic compound of componentB.

:2. A process in-accordance withi-claiml characterized further :in v that the organic; compound

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