US2616911A

US2616911A - Organic alkaline earth metal complexes formed by use of sulfonic promoters

Info

Publication number: US2616911A
Application number: US263962A
Authority: US
Inventors: Peter A Asseff; Thomas W Mastin; Rhodes Alan
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 1951-03-16
Filing date: 1951-12-28
Publication date: 1952-11-04
Anticipated expiration: 1969-11-04

Description

Patented Nov. 4, 1952 ORGANIC ALKALINE EARTH METAL COM- PLEXES FORMED BY USE OF SULFONIC PROMOTERS Peter- A. Assefi, Thomas W. Mastin, and; Alan Rhodes, Cleveland, Ohio, assignor s' to The Lubrizol Corporation, Wickliffe, Ohio; a corporation of Ohio No Drawing. Original application March 16,

1951, Serial No. 216,103. Divided and this application December 28, 1951,'S'eria1 No; 263,962

17 Claims. 1

This application is a division of our: copending application Serial No; 216,103Lfi1ed March 16, 1951, and is related to:copending applications: Ser. No. 216,101, filed March; 16, 1951;-Ser. No. 216,102, filed Marci-1 16,1951; Ser-. No. 224,458, filed May 3, 1951; Sen-N0. 263,961, filed December 28, 1951; Ser. No. 263,963, filed December 28',' 1951; Ser. No. 276,462," filed March-13', 1952;and Ser. No. 279,258, filed March 128; 1952'.

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

It is now well known that when-preparinga salt or soap of an organicacid, the mere-use of an excess of neutralizing agent, which-inthe, prior art has been in theiorinof theoxide, hydroxide, carbonate, etc. of the desired-metal, may result in a product which contains anamount of metal in excess of that theoretically required to replace the acidic hydrogens of the organic acid used as the starting material. 7 I

Workwith this type of product has shown that for many uses, particularly'whereextreme care must be exercised to prevent the composition from beingcorrosive, as-ior example inlubricants, desirable results are secured fiby the useof these so-called basic salts or soaps.-

Among the earlier workersin the art who recognized this factor andindicated that the use of basic soaps was desirable -=Was Bergstrom who, in hisPatents Nose-2270p and 2,27 9,086, made reference to the desirability of "using the basic soap without, however, givingan-y specific method for the preparation of such soaps. A similar disclosure is found'in Van EssP-atent No. 2,372,411.

With the demonstrated.- superiority of such basic soaps overthe normal or slightly acidic soaps, the prior art workers then attempted to find Ways ofincreasingthe basioity of the soaps, or stated in another way,- increasing the amount of metal, for-example; heldin stable form in What was termed asa metal com-plex.- One of the earliestgpatents referring to these basic salts ascomplexes or coordination compounds is -McNab No. 2,418,894, who gives noindicationin his patent as to the molecular structure of the product. As might be expected, one 'of the first steps employed to produce ametalsalt having an intended large excess of metaLin-combination-was to'use an unusually largeexcessof neutralizingagent, such as lime. Arepresentative patent disclosing this procedure isGriesinger et al. No; 2,402,325 who su gested the use of neutralizin agent up to 220% of the theoretical amount, This large excess of neutralizing agent was employed in a process moreor lessconventional for producing salts or soaps exceptinglthat-the process was-carried out in the presence oi st ean'i in order to facilitate the formation of-the product;

The Work of Griesinger was followed by the work of Campbell and Dellinger' as g'iveninPatentNo. 2,485,861 These patenteesba'se their-"disclosure on the hypothesis that minor amounts of an alkaline earth man hydroxide or carbonate can be p'eptized, orh n'astatebf colloidal suspension in oil by means off'anoi1-solub1e"'mahog any sulphonate. Another worker in the art who sought to combine in such complexes ariexc'ess amount of metal wasMertes whose" Patent No. 2,501,731 Wasgranted' Mai lf-2BL1950'J M ertes first prepared the normal-soap aiidstated that such soap-or soap comes at any haveadditional base combined ther byj'a' more or less simple mixing and heati tiori'followed by filtering. Th'edisclosure in Mertes appears to indicate that his roduct 'issimilar to" that of Campbell and Dellinger, in that the e'x'cess neutralizi'ng agent was held in the product in'the form ofaco'll'oidal suspension.

All of the previously enumerated processeshave been tried, notonlyduplicating ce'rtainof the examples given in the above-identified pa'tents, but

also using diifer'ent acids andfdifierent neutralizing' agents? As a result of f theseexperiinents; it has been'foun'd" that there isadefinite upper limit to the amount'of alkaline earth' metal which can be held in combination or in colloidalsuspension byrn'ean's of th'es'ejprior'artprocessesfi The greatest total amount of alkaline earth metal which can' 'possiblybe thus incorporated in the product by" means of any Of thse" prior art processes has been obtained when usingbarium-and in that case it is equalto about 2.3 timestheftheoretical .a'mou'nt present in thenormal salt." For thepurpose of the present inventionthe'ratio'of the'total metal iIlWhiGdlIliilGX to the amount of metal which is in the form of the normal salt of theoil soluble organic 'acid" will hereinafter 'be' "referred to as the metal ratio? By meansof'the present invention, it is now possible to 'obtain' alkaline earth mtal organic complexes which" contain "more" metal or higher metal .rati'os than" is possible by 'prior art processes'. With-regard tdlubridint's, these-Thigh metal containingcornplexes ari'fsr'iexsmpieparticularly suited-as'detrgents, and by'reasqn' of the metal concentrationcasts used "in amounts appreciably less" than other additives known in the prior art in order to attain a desired level of performance." t will a1s o"b"obseryed"that by virtue of the ef fectiv natur'epf'thefprs'snt complexes lubricants, usually 'itfw'illcost'less to obtain a desired result,; becausefappreciahly l-'ss additive is required. Theialk'aline' earth-metal 2% 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 complexalone 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 in concentrations of at least about in mineral oils.

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

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

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

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

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

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

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

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

(1)) 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 1X10- at about 25 0.; and the salts of such organic compounds; and

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

and maintaining the mass at a temperature and for a period of time sufficient to drive off substantially all free water and Water of hydration which may be present. 1

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

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

A. An oil soluble organic acid compound;

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

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

(a) An ionization constant in water of at least about l l0 at about 25 C.;

(b) A water solubility at 50 C. of

at least about 0.0005%; and

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

(2) The alkaline earth metal salts of such organic compounds; the relative amounts of A and B used being in the range of from about one equivalent of A to about 10 equivalents of B to about 10 equivalents of A to about one equivalent of B;

C. An inorganic alkaline earth metal compound (1) Which is water-soluble at a temperature of 50 C. of at least 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 'metalpresent in the remaining components, per equivalent of A plus B; and

D. Water, in an amount equal to at least about one mole per mole of C.,

sulphonic a id (W h. 99 ta s .2%.

II. And then maintaining; the mass at a tern- -v perature and for a period of time suifieient to drive off substantially all free water:- and water hy at w ich. may b Pr sent- I eab s eutl ned.emt sscs. tauntinge the was s 2 E ll9t tan e entiqnalli at d n acqqrdan e it Ste ii ami- W gi en e owa h e dmr me al r t le v lu s. ca

uareiliable ndex Q he a t f: e. at metal n such c mplex sreat a a tes d by the type of inorganic alkaline earth compound employed and can be varied within wide limits with u s gni an h ng t e meta Q011- en at e r du y: r a m n i; themas th air, Q02, and the like.

Th abo is; n t to be ons rued; state e t tha hen u 'aliz tt qn number s not an im r ant pr p r yf a sa omp ea Fqrsome e tor e amp e in ubr c te-tau. is ad an ageo s in ce tain. stanqe 9 mplct a a t. complex of a ub tant a y neutral. 9 am 1 ea moth instances a salt amb e s Q gh been auna 9 Pra ti e he esif ki.

19.8.0 ramsoi t. 111 a t t-e latum ash, d is. der ve .nm. E retr a and 132 grams of para-tertiary-bu yl phenol were la i a Miter. eqk. flask. and heat d to 95. C. Tothi's mixture was added a barium oxi-de slurry (417 grams of barium oxide and 1100 grams of water) the ture was heated for about o e ur at efluxv empfi at ta T the temper u e s, s owly ra sed t9 ab ut. Ka i-16 Q- an qma ntaine the e tor 11 1 2 to remq u t l y all of the a -fir- The. p qduct. was th n fi red. The'salt mplex. a. v sc s liq id. i h rqwn. n color a i hav ng a very light odor.- IIi sa t. c mplex had. he f iqw ns mom ie M' alra ie I. I

' Solvent Ba 9. Nc traloi The above preparation, which is an: example of the. present invention, is compared" with. a. basic sulphonate prepared in accordance with a con: ventional technique and; which is described below.

1000 grams of the barium salt of unsaturated paraffin wax sulphonic acid containing 13.1% sulphate ashvwere mixed with 455. grams of a mineral oil having a viscosity of 160 SSU at 100 F. and 109.5 grams of paraetertiary-butyl phenol, (ratio of equivalents is 1.54), placed in a suitable vessel and heated; to about C. with stirring. To this mixture was added a slurry of barium oxide (containing; ZGQg-rams of barium oxide and 920 grams of water)- andthe total mixture was heated at abqut C tor one hour. The temperature was slowlyrais ed' to about C. and held there for about one hour until substantially all of thewater was removed. Then about 3% Hiyflo (a filter-aid) was addedto the product to facilitate filtering. The salt complex was then separated by filtration. The salt complex thus prepared had; the following properties:

T sal comp ex. oduct was fluid, brown, i co r. ndydid nctcoi ain an de I he P aration. giv n i Exampl a W121. cal; illu t at on of t P s t. nv ntion. In. Example s y nbelow. a b sic ulnhonatewas pr.ep red in a co dan e, with. a pnven ional team ni ue f r co par son wi h the produc ive Eitamplea EXAMP E. 4.

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

EXAMPLE 1000 grams of the barium salt of mono-parafiin 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-tertiarybutyl phenol (ratio of equivalents is 1.7) and heated to about 90 C. A slurry of barium oxide (203.5 grams of barium oxide and 543 grams of water) was added, and the mixture was heated for two hours at the reflux temperature, and then dehydrated at about 165 C. for a period of one hour. Hyflo was then added to the product and the salt complex was recovered by filtration. The salt complex contained the following properties:

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

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

EXAMPLE 6 1000 grams of the barium salt of mono-parafiln wax substituted naphthalene sulphonic acid given in Example 5 were heated to about 95 C. and barium oxide slurry (113 grams barium oxide and 100 grams water) was added to the mixture. The

total mixture was held at a temperature of 100 C. for about one hour, and then dehydrated at a temperature of about 150 C. for about one hour. The salt complex was separated by filtration. Throughout the above preparation a nitrogen atmosphere was maintained above the mixture. The resultant salt complex was liquid and black in color. The following properties were determined for the product:

Basic No. 18.9

Per cent sulphate ash 12.2

Metal ratio 1.45

EXAMPLE 7 400'grams of the barium salt of mono-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 hours and held at that level for'about 1.5 hours until substantially all of the water was removed. The salt complex was separated by filtering. The product was a viscous liquid, black in color, and contained a, very slight odor.' The following properties were determined for the salt complex:

Basic No. 69.7

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

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

Basic No. 5.27 Per cent sulphate ash 8.95 Metal ratio 1.10

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

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

EXAMPLE 9 6000 grams of a 30% by weight oil solution of barium petroleum sulphonate (sulphate ash content 7.6%) were mixed with 348 grams of para-tertiary-butyl phenol in a 12-liter, 3-neck flask (ratio of equivalents 1.7) and heated to C. A slurry of barium oxide constituting 1,100 grams of barium oxide and 2,911 grams of water was then added and the mixture held there for about one hour at a temperature of about 90-95 C. The total mixture was then slowly raised in temperature to 150 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 of the salt complex were as follows:

\ Basic No. 72.1 Per cent sulphate ash 23.1 Metal ratio -1 3.59

EXAMPLE 10 405 grams of vdi-(2-ethyl hexyl) dithiophos- .phoric acid, 99 grams of para-tertiary-butyl phenol (ratio of equivalents 1.52) and 473 grams of solvent extracted Mid-Continent oil having a viscosity of 160 SUS 100 F. were mixed together and heated to 50 C. A slurry comprising 387 grams of BaO and 1,030 cc. of water was added quickly, maintaining the temperature at about 65 C. The mixture was then heated to 100 C. and held there for one hour. Then the temperature was raised to C. over a period of 2 /2 hours and held there for one hour. The product was obtained by filtering the mass and was found to be a slightly viscous liquid, red in color, and contained a slight odor. The following properties were determined for the product:

Basic No. 72.1 Per cent barium 20.0 Per cent sulphate ash 34.0

(calculated from metal content) Metal ratio 3.65

, 620 grams of. di-(2-ethyl-hexyl) 'mono-thiophosphoric acid, 310 grams of isononyl phenol (ratio ofequiv'alents is 1.52), 755 grams of mineral oil having 160 SUS 100 F., and 2060 m1. of water were mixed together. Then 774 grams of BaO were added over a half hour period. The total mixture was then refluxed for one hour at 100? C., whereupon the temperature was raised to 150 C. and held at that level for one hour. The temperature of the mixture was allowed 'to cool to 50-60 C., and then blown with CO2 to obtain a neutral product. The complex obtained had the 777 grams of di-(2-ethyl hexyl) dithiophospho'ric acid, 308 grams of 'iso-non'yl phenol (ratin of equivalents 1.52) and 914 grains 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 273 grams of BaO and 2,060 cc. of H20, while keeping the temperature below 65 C. The total mixture was then heated at 100 C. for one hour, followed by a raise in temperature to 150 C. over a period of 2 /2 hours. andmaintained 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 Per cent barium 227 Per centsulphate ash 38.6 (calculated from metal content) Metal ratio 4.52

172 grams of .di-(n-hexyl) dithiophosph'oric acid, 500 grams of petroleum sulphonic acid, 159 grams of iso-nonyl phenol (ratio of equivalents of oil soluble acids to isononyl phenol is 1.52),

' and 1,170 cc. of water were mixed together, then 437 grams of 'BaO were added over a periodof hour. The inixture was heated at refl x te nper'a'tu're for -1 hour, followed by heating to 150 C.

over a period of 2 -ho rs, and then maintaining that temperature for 1 hour. The desired product was a viscous liquid brown in color, and containeda slight odor. The following properties were determined: 7

Basic No 87.1

Per cent barium 28.6

Percent sulphate ash 48.8 (calculated from metal content) Metal ratio -1 5.22

172 grams of di-(n-hexyl) dithiophosphoric acid, 500 grams of petroleum sulphonic acid and 98 grams of para-tertiary-butyl phenol (ratio of equivalents of oil soluble acids to paratertiarybutyl phenol is 1.52) were mixedtogether. To this mixture was added a slurryof 387 grams of BaO and 1,080 cc. of water. The mixture was heated at 100 C. for one hour, and then the temperature was raised to 150 C. and held at that level for one hour. The product wasa highly viscous liquid, brown .incblor, and contained a slight odor. The following properties of the productwere determined": r Basic.No

EXAMPLE 249 grams of petroleumv 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 100F., 347 grams of BaO, and 700 m1. of H were placed in a 5 liter, 3 neck flask and heated to 100. C. with stirring. The mixture was held at 100-105 C. for 1 hour, and then the temperature was raised to 150-160 C. After holding the temperature for 1 hour at 150- 160 C., the mixture was blown with CO2 for hour, keeping the temperature at about 150- 160 C. The mixture was then filtered with 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 eifect if any the two types of sulp-honates would 113V on the quality of the product. Such preparations are given in Examples 16 and 17'below.

EXAMPLE 16 A mixture containing 500 grams of the barium salt of petrolatum sulphonic acid (sulphate ash 9.2%) 97 grams of the barium salt of petroleum sulphonic acid (sulphate ash 7.6% and grams of para-tertiarybutyl phenol (ratio of equivalents of the sulphonates to promoter is 1.54) was heated to C. A slurry of barium oxide constituting 123 grams of bariumoxide and 330 grams of water was added to the mixture. The total mixture was refluxed for one hour at C. and then the temperature was slowly raised to C. for a period of one hour to substantially remove all the water. The complex was separated by filtration and was found to be a liquid, and black in color. The following properties were determined:

Basic No. 27.7 Per cent sulphate ash 17.25 Metal ratio 2.41

EXAMPLE 17 By the'c-onventional technique, 480 grams of the bari'm salt of petrolatum sulphonic acid and 200 grams of the barium salt of petroleum sulphonic acid of Example 16 were mixed with a barium oxide slurry containing 68 grams of water and 60.8 grams of barium oxide. The components were heated to a temperature of C. for one hour until substantially all the water was removed. The 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:

Basic No. 20.2 Per cent sulphate, ash 11.72 Metal ratio 1.5 1

EXAMPLE 13 1634 grams of a barium petroleum sulphonate- BaO complex (obtained by dehydrating a barium petroleum sulphonate, 7.6% sulphate ash, water and BaO mixture at 150 C. for one hour, and producing a complex which has a basic number of 40, metal ratio of 2.25 and a 16% sulphate ash) and 121 grams of di-isobutyl-phenol (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 was then refluxed for one hour, and the temperature was raised to 150 C. over a three hour period and held there for one hour. Prior to filtering, the mass was blown with CO2 at a rate of 3.6 cubic foot/hr. for 1 hours at 150 C. The product analyzed as follows:

Basic No. 8.67 Per cent 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, there- EXAMPLE 19 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 oxide and 1390 ml. of water. The total mixture was heated for one hour at 100 C., and then was slowly raised in temperature over a period of three hours to 200 C. The mixture was maintained at this high temperature for a period of onehalf 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 24.3

Metal ratio 3.80

EXAMPLE 20 2036 grams of 30% oil solution of barium petroleum sulphonate (sulphate ash 7.6%) were mixed with 74.5 grams of phenol (1.67 ratio of equivalents) and heated to 100 C. A barium oxide slurry containing 483 grams of barium oxide and 1290 ml. of water was added and the mixture refluxed slowly for a period of one hour at 100 C. The mixture was then dehydrated by heatin slowly to 200 C. and maintaining such a 12 temperature for a period of about one-half hour. The salt complex was separated by filtration and was found to be an oily liquid, reddish-brown in color, and contained a slight odor. The following properties were determined for the complex:

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

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

EXANIPLE 21 consistency and dark red in color. The following properties were determined:

Basic No. 91.4 Percent sulphate ash 26.8 Metal ratio 4.37

EXAMPLE 22 The ionizable organic compound or promoter employed in this test was prepared by reacting grams tertiary-butyl benzene with 71 grams of chlorosulphonic acid at a temperature of 30-40 C. for a period of one hour. The resultant prod uct, tertiary-butyl benzene sulphonic acid, was dissolved in a little warm water and admixed with l550'grams of a 30% oil solution of barium petroleum sulphonate (ratio of equivalents of sulphonate to sulfonic acid is 1.52). The mixture was heated to C., whereupon 284 grams of barium oxide and 760 ml. of water were added. The mixture was stirred for one hour at a temperature of 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 faint odor. The properties of the product are as follows:

Basic No 64.7

Percent sulphate ash 27.0

Metal ratio 4.73

EXAMPLE 23 2500 grams of 30% oil solution of barium petroleum sulphonate (sulphate ash 7.6%) were admixed with 173 grams of para-tertiary-butyl benzoic acid (1.68 ratio of equivalents) and heated to C. 458 grams of barium oxide and 1215 grams of water were added to the mixture and the temperature was maintained at C. forabout 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 de- Metal ratio 2 2.88

a eiaen Basic No. 132 Percent sulphate ash 33.3 Metal ratio 6.47

EXAMPLE 25 2050' grams of a 30% oil solution of barium petroleum sulphonate (sulphate ash 7.6%) were admixed with 73.5 grams of l-nitro-propane (ratio of equivalents is 1.62) and heated to a temperature of 95 C. 388 grams of barium oxide and 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 C. over 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:

Basic No. 78.2

Percent sulphate ash 28.2

Metal ratio 4.60

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

Basic No 87.8 Percent sulphate ash 25.95 Metal ratio 3.88

EXAMPLE 27 1140 grams of a 30% oil solution of barium petroleum sulphonate having a sulphate ash of 7.6% and 80 grams of paratertiary-amyl phenol (ratio of equivalents 1.54) were heated to 70 C. Thereafter 600 cc. of water were added, followed by a slow addition of 227 grams of 132.0. The mixture was 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. The product was separated by filtration, and had the following analyses:

Basic No 85.5 Percent sulphate ash 24.60 Metal ratio 3.96

EXAMPLE 28 2583 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash, 144.2 grams of beta-naphthol (ratio of :14 equivalents is 1.69) and 1262:1111. of water were combined and mixed thoroughly. Them 472 grams of'BaO'wer-e added over a one hour period, followed by maintaining the total mixture at 100 C.for onehour. The temperature was 'then raised to 150 'C. and held there for one hour. Prior to filtering the mixture, it was blown with CO2 for minutes at which time the mixture had a basic number of 0.8. After filtering, the product analyzed as follows:

Basic No. .l. 4.88

Sulphate ash 23.8

Metal ratio c 3.90

1530 grams of a 30% oil solution of barium petroleum su'lp'honate having a 7.6% sulphate ash, 129 grams of iso-non'yl phenol (ratio of equivalents is 1.7) and 727 m1. of water were combined and thoroughly mixed. Then 271 grams of 'BaO were added and the total mixture was held at C. for one hour. Thetemperature was then raised to 150l60 'C. and held therefor one hour. Prior to filtering, the mass was blown at about 150 C. with CO2 until a basic number of about 1 was obtained. The filtered product analyzed as follows:

Basic No. 3.9 Sulphate ash 25.0 Metal ratio 4.17

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

Basic No. 13.3 Percent sulphate ash 25.45 Metal ratio 4.38

EXAMPLE 31 1530 grams of a 30% oil solution of barium petroleum sulphonate having a, 7.6% sul hate ash and 210 grams of trichlorodiphenyl ether sulphonic acid (ratio of equivalents is 1.7) were heated to 70 C. To this mixture were added 725 grams of water followed by the addition of 271 grams of BaO. The entire mixture was refluxed for one hour, then heated to C. over a three hour period and held there for one hour. Prior to filtering, the mixture was blown with C02 at 150 C. and at a rate of 3.6 cu. ft./hr. for one and one-half hours. The filtered product analyzed as follows:

Acid .No 0.45

Percent sulphate ash 24.7

Metal ratio 4.34

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

Acid No. 0.41

Percent sulphate ash 24.1

Metal ratio -1 4.12 EXAMPLE 33 1530 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash and 131 grams of methyl naphthalene sulphonic acid (ratio of equivalents is 1.7) were combined and heated to 70 C. 725 grams of water were added to the mixture, followed by a slow addition of 271 grams of BaO. The entire mixture was refluxed for one hour, then the temperature was raised to 150 C. over a three hour period, and held there for onehour. 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 Percent 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 combined and 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 C. prior to filtering, to obtain a substantially neutral mass. The filtered product analyzed as follows:

Basic No 0.23 Percent 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 chlorosulphonic 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. of water. The ratio of equivalents of oil soluble sulphonate to sulp-honic acidis 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 with CO2 for one half hour at 120-140 C. The filtered product analyzed as follows:

Acid No 1.22

Percent 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 70-100 C. for 1 /2 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 16 of BaO, and the entire mixture was then held at -100 C. for one hour. Then the temperature was raised to 150 C. and held there for one hour. Prior to filtering, the mass was blown with CO2 for one-half hour at 13 C. The filtered product analyzed as follows:

Acid No 0.95

Percent sulphate ash 25.8

Metal ratio 4.38

EXAMPLE 37 Basic No 6.45 Percent sulphate ash 23.2 Metal ratio 3.85

EXANIPLE 38 2600 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash, 236 grams of di-isopropyl dithiophosphoric acid-(ratio of equivalents is 1.7 and 1220 ml. of

, water were combined, followed by a slow addition of 461 grams of BaO. The mixture was held at C. for one hour, and then heated to 150 C. and held there for one hour. Prior to filtering, the mass was blown with CO2 for 20 minutes at -150 C. The filtered product analyzed as follows:

Acid No 0.27 Percent barium 14.25 Percent sulphate ash 1- 24.2

(calculated from metal content) Metal ratio 4.15

EXAMPLE 39 2600 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash, 100 grams of acetyl-acetone (ratio of 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 a one hour period of heating at 150 C. Prior to filtering, the mass was blown with CO2 for one hour at 150 C. The filtered product analyzed as follows:

Acid No 0.2

Percent sulphate ash 22.8 Metal ratio 3.48

EXAMPLE 40 1350 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 at 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

'pl'oye'd as a starting material. Examples Hand 42 below are: illustrative.

period of one hour;

1.1.25 hours. atza temperature. of 150 Q. The

ter'ed product. analyzed as follows:

Aci No -l 0.24

Percent sulphate ash 23.6 Metal ratio 4112 that the metal ratio of the salt complex obtained .by this method is greater than by conventional techniques, a comparison was made with a conventional technique in which the acid was em. In this. respect,

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 auowingthe reaction mixture. to stand. about 12' hours, it was filtered twice through. a glass cloth. 2875 grams oi the product just. described were combined with 205.7 grams of paratertiary-butyl phenol (ratio of equivalentsis 11.39) .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 heatedfor' ofiehour at a. tem- PLE 42 500 grams of the oil-soluble petroleum sulphonic acid given in Example 41 above were heated to 75 C. 55 grams of waterwere then added andgfol-lowed by a slow addition of162.2 grams of barium oxide; The total m iX-turewas maintained at a temperature o t- 150 JG; for a The V desired; complex was separated filtration andwas. foundto be a very viscous liquid black in color, anddidnot containany odor. The. following. properties were determined for the desired product: i

4.3 g 1000 grams or the, barium-salt. oi di -paraffin 1 wax substituted phenol sulphonicacid (sulphate ash; 6.61%.): were admixed with 55 grainsof paratertiary-butyl phenol (ratio off equivalents is vempolyecl as the promoter.

18 1.5.4) and heated to a temperature of C. 800 cc. of water were then added. The mixture'was mixed thoroughly and then 300 grams of dry barium oxide were added. The total mixture was refluxed for two hours followed by an addition of 573 grams of amineral oil having a viscosity of 160 SUS at F. The temperature was 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; a;- c l ll 67.8 Per cent sulphate ash 23.8 Metal r'atio 2.67

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

. EXAMPLE 44 170.0 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 heatedto 75-100 0,. whereupon 2141 grams of barium oxide. were added. 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:

The following examples by comparison illustrate the substantial increase in metal contentof the complex which is obtained by treating the masswith an acidic material before filtering to separate the desired product.- i

l XA PLE45 V 1700 grams of a 30% oil solution of barium petroleum sulphonate'having a sulphate ash-fof 7.6% were mixed with 1 34 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 then raised to C. over a period of 6 hours and maintained at that temperature for one hour. The mass was filtered and the product obtained was a liquid, brown in color, and contained a slight odor.

1700: v grams of at 30% oil solution .ofibarium petroleum sulphonate having a" sulphat 'a's'hl of 72.6%. were mixed. with 134 grams of d'iis'obutyl phenol (ratio; of equivalents is 1.7)"an'd heated to 70 C. Then 800 cc. of H20 and 302 grams of BaO were addedand the mixture refluxed for one 01 he t mp ature was raised to 150 C. and maintained there for on ehour. CO2

The following properties of the. product 19 was then injected therethrough at 150 C. and at a rate of 1,650 cc./min. for 38 minutes. The mass was then cooled and filtered to separate the complex. The product was liquid, brown in color, and contained a faint odor. The following properties of the product were determined:

Basic No 5.05 Percent sulphate ash 26.0 Metal ratio 4.52

EXAMPLE 4'7 400 lbs. of a 30% oil solution of barium petroleum sulphonate having a sulphate ash of 7.6% were heated to 80 C., and 32.5 lbs. of diisobutylphenol (ratio of equivalents is 1.67) were added thereto. Then 197 lbs. of water were added to the mixture, with stirring to insure thorough mixing. 73 lbs. of BaO were added thereto over a 30-minute period at 5580 C. The mixture was agitated for about minutes more at 80 0., 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 N0 5.0 Per cent sulphate ash 25.7 Metal ratio 4.35

EXAMPLE 48 4590 grams of a oil solution of barium petroleum sulphonate having a 7.8% sulphate ash, 363 grams of diisobutyl-phenol (ratio of equivalents is 1.7) and 2,800 grams of H20 were heated to 60 C. 1,042 grams of BaO were added slowly and then the temperature of the mixture was raised to 9498 C. and held there for one hour. Thereafter the temperature was raised to 150 C. in four hours, and maintained there for one hour. A small portion of the mass, 361 grams, was removed and filtered to give product A, whereas the remainder (5,296 grams) was blown with S02 at 170 C. until 330 grams thereof was used. This latter mass was then filtered Product A l Product B Basic No 63 4. 5 Percent Sulphate Ash 19. 5 29. 5 3.18 5.

Metal Ratio From the foregoing examples it is shown that the method of treating the mass prior to filtering with an acidic material results in substantial increase in sulphate ash of the complex and thus correspondingly higher metal ratios.

The salt complexes can also be prepared by combining the oil-soluble metal sulphonate and inorganic metal compound in the presence of the sediment which forms occasionally in some of the methods illustrated above. The following examples illustrate the utility of the sediment for preparing salt complexes of the present invention.

EXAMPLE 49 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 C. 261 grams of barium oxide and 710 grams of water were then added and the total mixture was raised in temperature to C. and held at that level for one hour. Thereafter, the temperature was raised slowly to C. and held there for about one hour. The total mixture was allowed to settle overnight, followed by decantation and filtering. In this experiment 450 grams of sediment were produced. The filtered salt complex was a viscous liquid, light brown in color, and contained a slight odor. The following properties of the product were determined:

Basic No 59.5 Per cent sulphate ash 21.2 Metal ratio 3.20

The sediment obtained in Example 49 was employed in the preparation of a salt complex in the method given in the following Example 50.

EXAMPLE 50 1700 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash, 20 grams of phenol, 450 grams of sediment obtained from the preparation given in Example 49, 710 grams of water and 261 grams of barium oxide (barium oxide added slowly) were mixed together and heated to a temperature of 100 C. for about one hour. The total mixture was then raised in temperature in a slow manner to about 150-160 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 compounds containing a metal other than barium were combined in the presence of a promoter to produce overbased products.

EXAMPLE 5 l 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 para-tertiary-butyl phenol (ratio of equivalents is 1.54) and heated to about 80 C. To this mixture were then added about 148 grams of Ca(OI-I)z and about 300 cc. of water, and the total mixture was refluxed at about 100 C. for a period of two hours to insure thorough mixing. Thereafter the mass was heated to about 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 termined for the product:

B sie No. 25.2

Percent sulphate as 9.09

Metal ratio c 1.53

7 EXAMPLE 53 1.12.0 grams. of a 45% oil: solution of calcium petroleum sulphonate having a sulphate ash contentof 6.5%,. 59'grams. of l-nitro-propane (ratio of equivalents. is 1.52), 150: gramsof Ca(OH') 2 and .830 m1. 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:

BasicNo 36.1 Percent sulphate ash 13.15 Metalratio 2.36

For: the purpose of comparison, calcium petroleum sulphonate was overbased with Ca(OI-1) 2 in accordance with a conventional technique.

EXAMPLE 54;.

Basie-Now; 7.9 Percent sulphate ash- 5.15 Metalratioqnfln; 1.29

.,-The following exampleillustrates the use of a different promoter when employing the calcium metalin the components:

EXAMPLE 5,5

A mixture of 459 grams of phenol, 244 grams oi waterand 90.5 grams-ofCa(OH- z 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-- ofequivalents is 0.41) were added. The temperature of the mixture was then raised to 125 Ci, at which level substantially all of the water was' removed. Prior to filteringthe mixture, 'it* was blown with CO2 for three hours at a temperature-of' about 120-150 C. The complex was fluid; brown in color and did not contain any odor. Thecomplex-had the following analyses BaslciNol'w 8.07 Percentsulfateash 1835 Metal ratio 3.07

Anotherpreparation. was made in which dissimilar alkaline. earth metals were present in the organic acidcompound and inorganic metal compound- The following example illustrates this feature of the invention.

22' EXAMPLE 56 1793 grams of a oil solution of calcium petroleum sulpho'nate having a 6.45% sulfate ash, 206 grams of octyl phenol (ratio of equivalents is 1.7) and 954 grams of water were mixed together. Then 358 grams of BaO' were added, and the mixture was agitated thoroughly. While insuring thorough mixing the temperature was raised to 90-100 C. for one hour. Thereafter,- the temperature was raised to 150 C. over" a. two hour period and held at that level for one hour. 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

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

EXAMPLE 57 2875 grams of petroleum sulphonicacid: and 6000 grams of a 30% oil solution of barium petroleum sulphonate (sulfate ash is 716%) were mixed with 553.7 grams of paratertiary-butyl phenol (ratio of equivalents is 1.60). The mixture was heated to about C; whereupon a slurry of BaO (consistingof 2027 .6' grams ofBaO and 5395 grams of water) was added and the mixture wasthen. maintained at a temperature of about -95 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 approximate-j ly onehour. The product. analyzed as follows Basic-No 73.0

Per cent sulfate ash 2313 Metal ratio 3.73

1,000 grams of petroleum sulphonic acid, 98.1 grams of para-tertiary butyl/phen'ol and 989 grams'o'f water were mixed together and heated to 50 C. Thereafter, 258 grams of Sro' were added to the mixture, the total mixture was raised in temperature to C. and held at that level for about one hour. Thereafter, the total mixture wasraised in temperature to about150" C. and held at that level for about one hour. The product obtained was a viscous liquid, brown in color, and had the following properties Per cent sulphate ash 13.95 Metal ratio' c 1.67

The salt complexes formed with compounds containing barium metal possess exceptionally high metalratios as compared to those complexes which are obtained when usingother alkaline earth metal containing compounds. Consequently, in determining-the maximum amount of metal which can be incorporated intoa 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 metalwhich can be incorporated into a salt complex' by conventional techniques. Furthermore, the oil-soluble petroleumsulphonic acids are exceptionally. better in producing high metal content salt complexes than other types of oil soluble organioacidcompounds.

.metal ratio of the complex.

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

Basic No. 38.4 Per cent sulphate ash 16.0 Metal ratio 2.25

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

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

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

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

EXAMPLE 61 1530 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash, 88 grams of para-tertiary butyl phenol (ratio of equivalents is 1.7), 271 grams of BaO and 725 ml. of water were mixed together at 60- 70 C. The temperature of the mixture was raised to 100-105 C. and held there for one hour while 24 insuring thorough mixing. Thereafter the temperature was raised to ISO-160 C. and held at that level to remove substantially all the water. The complex was separated by filtration and had the following analysses:

Basic No. 85.2

Per cent sulphate ash 25.5

Metal ratio 4.12

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

Basic No. 36.0 Per Cent sulphate ash 15.34 Metal ratio 2.14

From the foregoing it will be noted that by following the process of the present invention, two types of metal complexes may be produced, both of which are difierent from any produced by any of the prior art processes. The first form of such complex is the immediate product with the promoter included therein in chemical combination. The second form of novel product is that which results from the treatment of the end product just described with an acidic material which has the effect, as stated above, of'liberating the promoter from the complex without any substantial change in the metal ratio of the complex. The liberation of the promoter by this step of treating the first-named complex with an acidic material may be followed by a recovery, as by distillation, of th 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 salt-forming 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.

abrupt:

slight odor. The following properties were determined for the product:

Basic No 2.5 Per cent sulphate ash 23.2

By comparison, the product of Example 4 contained a sulphate ash of 23.8% where s t e same product after blowing with CO2 contained a sulphate ash of 232. Therefore, it can be seen that the metal ratio of the salt complex is substantially the same aftertreatment with CO2.

. EXAMPLE 64 1 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 oi 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 30-70 C. Atthe-end of the blowing operation the product weighed 6346 grams, showing a gain in weight of 311 grams. The product was fluid, dark red incolor, and contained no odor. The following properties were determined for the salt complex- COz product:

Basic No. 4.3 Percent sulphate ash 22.7

Itcan 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 with CO2, since thesulphate ash content is substantially the same as before CO2 treatment.

1288 grams of the salt complex prepared in accordance with the method of Example. 5 was blown with CO2 at a temperature of 3050 C. until the product showed an acid reaction. Following this CO2 treatment, the product was blown with nitrogen for a period of 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. -Q 5.36 Per cent sulphate ash 17.94

26 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 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 temperature of 97-102 C. for a period of one hour.

The temperature was then slowly raised over a period of three hours to 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 separatedby filtering and was found to be an oily liquid, brown in color, and contained a faint odor. The following properties were determined:

Basic No 60.6 Percent sulphate ash 22.3

Metal ratio j 3.34

EXAMPLE 6'7 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 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 sulpha-te, 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 heated at a temperature of 200 C. under vacuum of 4; mm. to recover approximately 15 grams of phenol. The residue of the. distillation was a viscous liquid, light brown in color, and contained a slight odor. This product possessed the following properties:

Basic No 1.06 Percent sulphate ash 22.6

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

Thesalt complex prepared in accordance with 27 Example 69 below was treated with S02 as shown in Example 70 which is given below' EXAMPLE 69 6000 grams of a 30% solution of barium petroleum sulphonate (sulphate ash 7.6%), 348 grams of para-tertiary-butyl phenol (ratio of equivalents is 1.70), and 2915 grams of water were mixed and heated to a temperature of 60 C. 1100 grams of barium oxide were added slowly and the 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 150 C. and held at that level for an additional hour until substantially all the water was removed. The salt complex obtained is a liquid, brown in color, and did not contain any odor. The following properties were determined:

Basic No. 82.5 Percent sulphate ash 26.0 Metal ratio 4.2

EXAMPLE 70 6623 grams of the product produced in accordance with Example 69 were treated with S02 at 25-50 C. until 327 grams of the gas were combined with the salt complex. The product thus obtained had a neutralization number or a basic number of 0. The SOs-salt complex product was liquid, brown in color, and did not contain any odor.

An experiment was conducted in order to de- Basic No 46.

, Per cent sulphate ash 27.9 Metal ratio 5.4

EXAMPLE 7 1 termine whether air which contains CO2 would be effective as an acidic material. The examples below illustrate the utility of air for this purpose.

EXAMPLE '7 1 380 lbs. of a oil solution of barium petroleum sulphonate were mixed with 21.9 lbs. of paratertiary-butyl phenol (ratio of equivalents is 1.7) and 184 lbs. of water. This mixture was heated to C. and 68 lbs. of BaO were added over a period of 1 /2 hours while not permitting the temperature to go above C. The total mixture was held at C. for one hour, then heated to C. over a period of 4.8 hours and held there for one hour. fluid, dark red, and possessed the following properties:

Basic No. 80.5

Percent sulphate ash 26.0

Metal ratio 4.2

EXAMPLE 72 6000 grams of the product produced in Example 71 were placed in a 12-1iter, 3-necked flask and heated to C. The mass was then blown with air until a basic number of 1 was obtained. The j petroleum sulphonate containing 7.6% sulphate ash were mixed with 750 grams of water at 50 C.

The desired product was 2760 grams of a 30% oil solution of barium petroleum sulphonate containing 7.6% sulphate ash were mixed with 217 grams of BaO, 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 100 C., then the temperature was raised to 150 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. Per cent 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 A--The oil soluble organic 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 b 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, sulphur acids, carboxylic acids, phosphorus acids, etc. of the 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 whereinthere arepresent at least about 12 carbon atoms, such as, for example, palmitic, stearic, myristic, oleic, linoleic, etc. acids. The carboxylic acids of the aliphatic type can contain elements in the aliphatic radical other than carbon and hydrogen; examples of such acids are the carbamicacids, ricinoleic acids, chlorostearic acids, nitro-lauric acids, etc. In addition to the allphatic carboxylic acids, it is intended to employ the cyclic types such as those containing a benzenold 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 aliphatic substituted aromatic acids as for example, stearylbenzoic acids, monoor polywax substituted benzoic or naphthoic acids wherein the wax group containsat 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." Itls also contemplated to employ the thiocarboxylic acids, that is, those carboxylic acids in which one or both of the oxygen atoms of the carboyxlic group are replaced by sulphur. These carboxylic and thic-carboxylic acids can be represented by the following formulae:

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

Representative examples are nitro-stearic acids,

ceryl-chloro salicylic acids, chloro-palmitic acids, cetyl anthranilic acids, stearyl mercaptonaphthoicacids, etc. a

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

an organic radical and at least one B ishyidrogen. Therefore, such formulae include the-.oil-f soluble organic thio-acids of phosphorus, more particularly the organic thiophosphorlc acids and the organic thiophosphorous' acids. .The organic radicals R and R. can be aliphatic, cycloaliphatic, aromatic, aliphatic--v and. cycloaliphatic-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 I and II. Examples.v of such acids are dicapryl dithiophosphoric acids; di-(methyl-cyclohexyD- dithiophosphoric acids, dilauryl dithiophosphoric acids, dicapryl dithiophosphorous acids, di-(methyl-cyclohexyl) die thiophosphorous acids lauryl mon9thiophosphoric acids, di-(butyl-phenyl) dithiophosphoric acids, and mixtures of two or moreoi the forcev going acids.

Certain of the above'described'thio acids oi phosphorus such as for example di-capryl di-v thiophosphoric acid are also commonly referred to as acid esters. I

As indicated, our process is applicable not only when using the oil-soluble organicacid as such as one of the starting materials, but also the al: kaline earth metal salts of such organicacids. The present process will produce a high metal content organo metallic material when as one of the starting materials-one uses any of the metal organic complexes produced bythe prior art workers, such as for example, Bergstrom, Griesinger, Campbell et al., and Mertes. We thus may utilize as a starting material theend I product produced by these prior art workers and from them produce the novel high metal content complex of our invention. 7 r

From the broad class of available organic acid compounds, it is preferred to employ the oil soluble 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:

I [R:z:T-(SO3)1 ]zMb II [R'--(SO3)a]dMc nuclei such as benzene, naphthalene, anthracene;

phenanthrene, diphenylene, thianthrene, phenoq thioxine, 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, or aralkyl groups, in is at least 1, and. Ba: contains a total of at least about 15 to 18 carbon atoms; R in Formula II is an aliphatic radical containing a total of at least about 15 to 18 carbon atoms, and M is either an alkaline earth metal, preferably barium, or hydrogen. When R is an aliphatic substituted cycloaliphatic group, the aliphatic substituent should contain a total of at least about 12 carbon atoms.-

Examples of types of the R radical are alkyl, alkenyl, and alkoxy-alkyl radicals, and aliphatic substituted cycloaliphatic radicals where the aliphatic group is alkyl, alkoxy, alkoxy-alkyl; carboalkoxyalkyl, etc. Specific examples of R" are cetyl-cyclohexyl, lauryl-cyclohexy1,-' ceryloxyethyl, and octadecenyl radicals, and radicals derived from petrolatum, saturated and unsaturated paraifin wax, poly olefins, including poly- C3, C4, Ca, Ca, 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.

In Formula I above, :0, y, z and b are at least one; whereas in Formula II, a, d, and o are at least one.

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

Such sulphonic acids are mahogany sulphonic acids; petrolatum sulphonic acids; monoand polywax substituted naphthalene sulphonic, phenol sulphonic, diphenyl ether sulphonic, diphenyl ether disulphonic, naphthalene disulphide sulphonic, naphthalene disulphide disulphonic, diphenyl amine disulphonic, diphenyl amine sulphonic, thiophene sulphonic, alphachloronaphthalene sulphonic acids, etc.; other substituted sulphonic acids such as cetyl chlorobenzene sulphonic acids, cetyl-phenol sulphonic acids, cetyl-phenol disulphide sulphonic acids,

cetyl-phenol mono-sulphide sulphonic acids, cetoxy capryl-benzene sulphonic acids, di-cetyl thianthrene sulphonic acids, di-lauryl betanaphthol sulphonic acids, and di-capryl nitronaphthalene sulphonic acids; aliphatic sulphonic acids such as paraflin wax sulphonic acids, unsaturated paraffin wax sulphonic acids, hydroxy substituted parafiin wax sulphonic acids, tetraisobutylene sulphonic acids, tetra-amylene sulphonic acids, chloro-substituted parafiin wax sulphonic acids, nitroso 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 cyclo-hexyl sulphonic acids, etc.

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

or 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 metal salts thereof. However, it is to be understood that all of organic acids and salts thereof are not equivalent in their ability to complex with unusual amounts of inorganic alkaline earth metal compounds in the presence of a promoter, because under certain conditions, some organic acids or salts thereof are more effective than others.

Component B-The promoter material The promoter employed in the process of this invention can be the organic compound AH wherein H is hydrogen and A is an anionic organic radical and/ or the alkaline earth metal salt thereof. More particularly, the organic compound AXH i employed, wherein A and H are defined as given above for the compound AH and X is either oxygen or sulfur. Also the alkaline earth metal salt of AXH can be used alone or in admixture with the compound AXH. The compounds AI-I or AXI-I should have ionization constants measured in water at 25 C. greater than about 1 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.

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-paraffins, lower molecular weight aromatic carboxylic acids, lower molecular weight organic thiophosphoric acids, the lower molecular weight sulphonic acids, hydroxy aromatic compounds, lower molecular weight hydroxy aromatic acids, etc. To better illustrate the wide variety of classes of compounds which can be employed in forming the salt complexes in accordance with the present invention, specific examples are enumerated below. It is to be understood that while only the ionizable organic compounds are illustrated, it is intended that the alkaline earth metal salts thereof are included as specific examples. cium, barium, strontium, and magnesium salts of such illustrated ionizable organic compounds are intended.

The phenolic compound referred to hereinabove is for the purpose of this specification and the appended claims an organic compound having a hydroxyl group attached directly to a carbon atom of a benzenoid ring, and which compound is with or without other substituents on the benzenoid ring. It should likewise be understood that a phenol is a sub-class of a phenolic com ound, 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 hydrocarbon 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, n-p-ropyl-phenols, di-isopropylphenols, p-t-butyl-phenol, p-t-amyl-phenol, pcyclopentyl phenol, p-(4 methyl cyclohexyl) phenol, sec-hexyl-phenols, n-heptyl-phenols, diisobutyl-phenols, 3,5,5,-tri-methyl-n-hexyl-phenols, n-decyl-phenols, cetyl-phenols, etc; aryl substituted phenols, e. g., phenyl phenol, diphenyl phenol, etc.; poly-hydroxy aromatic compounds such as alizarin, quinizarin or polyhydroxybenzenes, e. g., hydroquinone, catechol, pyrogallol, etc.; monohydroxy naphthalenes, e. g., a-naphthol, l-l-naphthol, etc.; polyhydroxy naphthalenes, e. g., naphthohydroquinone, naphthoresorcinol, etc.; the alkylated polyhydroxy-aromatic com- More specifically, the calpounds such as octylcatechols, triiso-butyl-pyroo-chloro-benzoic" acid, p-toluic acid, p=tbutyl'- benzoic acid, alpha-naphthoi'c acid, etc;; lower molecular weight aromatic sulphonic" acids such as benzene sulphonic acid, p chlorobenzene sulphonic acid, p=nitrobenzenesuiphonic acid, ptolyl sulphonic acid, p t-butyl-b'enzene'sulphonic acid, t-amyl-naphthalene sulphonic acids, et'c;; lower molecular weight aliphatic sulphonic acids such as ethyl sulphonic acid, 'bet'a chloro-ethyl sulphonic acid, "gammaanitroi-propyl sulphonic acid, octyl sulphonic'acids', chlorodi-isobutyl'sulphonic acids, diisobutenylfsulphonic acids, etc.'; nitroparaifinssuchas' li-nitr'o' propane, 2-n'itron-butane, l-nitrc-I- (l r-diisobutyl phenoxy') pro= pane, etc.;' lower molecular" Weight thio -a'cids of phosphorus includingfaliphatic" dithiophosphoric acids, e. g., dieisopropyl dithiop'hosphoric' acid,

di-n-bu'tyl' dithioph'osphoric acids; etc.', aromatic dithiophosphoric acids,.e1' g1 di=(,ph'enyl) dithiophosphoric acids, etc;', the aliphatic mono thicphosphoric acids, e. gL, dieethyl monothiophoshoric acids, etc., thearomajtic monothiopho's phoric acids,v e. g., dit'olyl"monothiophosphoric acids, di- (iso-propyl phe'hyll 'monothiophosphor ic'a'cids, etc,

Additional examples. of compounds, which can be 'employedas promotersare given ihthe'follO'wingU. S. atents: '2;I'74;'11;0"; 22174111121741492;

2,335,259 and 2,,3-37,552.

However, it isto.-be-understoodthatthe above enumerated ioniza-bleorganiccomp'oundsandthe alkaline earthmetal salts thereof are not all equivalent as promoters, but that "under certain conditions-some are -more=efiective than others;

Component alkaline earthmetal "salt jomnmg' compounds The salt-forming compounds which: are employed to impart to. the processlmass thevspecified amountof. metalmay-b'e broadly defined as inorganic alkalineearth metallcompounds wherein anionic radicals may. be,. for. example,, hy-+ droxyl, oxide, carbonate, ,Idi carbOnate, sulphide, hydrosulphide, halide, hydride; ,aniid, b'asiccarbonate, etc; Of' the inorgfanidalkalineearth metal compounds, good results are obtainedwith those having a Water solubility oiiat leastabout 0.0003'% at50'C;, and preierablyati'least'about 0.006%; Still morepreferredgarethose' ion'or= ganic alkaline earthmeta'ilconlp'ounds'; saturated aqueous solutionsof whichgive'anialkaline' reactiorr'or pH" value 'greaterthan' 7'.

T" further illustrate the "large "number and variety of' classes ofinorganic compoundswhich can be employed,- specific examples "thereof are ennumeratedbelow:

The alkaline eartnmetal inorganiczcompounds incl-udathe barium" containing compounds such g-raoii 34 as barium hydroxide, barium oxide, barium sulfide, barium carbonate, barium bi-ca'rbonate, 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; calciumbromide, calcium nitrate, calcium borate, etcg the strontium containing compounds-such as strontium hydroxide; strontium'oxide; strontiumsulfide, strontium carbonate,

strontium bicarbonate; strontiumamide, strontium nitrate; strontium hydride; strontium nitrite, etc. the magnesium-containing compounds such as magnesium hydroxide; magnesium oxide; magnesiumcarbonate; magnesium bi-carbonate', magnesium nitrate, magnesium-nitrite; magnesium amide, magnesium chloride; magnesium sulfate, magnesium hydrosulfide, etc. The corre spondingbasic salts of the above described compoundsare also-intended, however; it sh'ouldbe understood that the inorganic" alkaline earth metal compounds-are not'--e qui valent for'the-pur poses' of'thepresent-invention; becauseundercertain C01'1 QitiOnSS0m B18re-' more effective-or-j desirable than" others:

The- 'aeidic-material" i ls-previouslyindicatedIone form'of the process of the pr'esentlinvention includes the step of treating: the immediate complex" product with an acidic materialT for the purpose of" liberating therefrom at least a portion of the materia1 pre viously refer-redlto as the promoter. A particularly effective acidic material which has been utilized for this purpose is carbon di-oxide. We are aware of thefactthatMertes in his aboveidentified Patent No. 2,501,731 suggested transforming aisodium hydroxide=calcium sulphonate complex" into "the sodii m 'ca'rbona te-calcium' sulphonate complexcr" the corresponding bicarbonate complex by blowingthe hydroxide complex with carbon dioxide at elevated temperatures:

In ounp'rccess, the step -oftreating with an acidic materialjsuch as carbon dioxide or air has the effect of freeing" from theimmediate complex product formed atleast a portion of the promoter use'd; 'Thusthapresence in the immediate complex productof the promoter material, in combined form, clearly; distinguishes the im mediate complex product "fromany metalorganiccomplex"typematerialheretofore 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 witha-composition which is quite different from thefiother prior art metar organic complexes previously-produced- It is -recog-nized that "j in accordance with the present invention, the alkaline earth metal salt of tl-ie' ionizable' or garlic compound be employed as the promoter informing'the salt complexi Ho'wcveh'wherisuch a salt is-used a's-the*promoter-' and theresulting complex is' treated 5 with an acidic material, the metal free' ioniza-ble organic compound-is freed from its salt; a

For "the purpose of 'rel'easingthe ionizable organic" compound used as -a-promoter from the complex, animportantfeature ci -characteristic of'the "acidicmaterial is -that it must when present-in *the mass contain g -*thecomplem possess an ionization constant higher than the ionizable organic compound u'sed' astha romoterr- Thus; for the purpose of this sp'e'ci'fi'r':'atioi i -andthe 4 appended claims, it is to be understood that the acidic material can be either a liquid, gas, or solid, prior to being incorporated in the mass which contains the salt complex.

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

The following are additional specific examples of acidic materials, viz.: HCl, S02, S03, CO2, air

of the present invention, but that under certain conditions, some are more effective or desirable than others. a

The complex of the present invention can be produced. by using the same alkaline earth metal in the organic acid compound, promoter and inorganic compound; or such complexes can be derived from components containing dissimilar alkaline earth metals. In some instances it is desirable to employ a mixture of organic acid compounds which contain at least two or up to and including four dissimilar alkaline earth metals; or the same distribution of metals can be obtained by varying the type of promoter and/or inorganic compound in various combinations with the organic acid compound. It is therefore possible to employ various combinations of dissimilar alkaline earth metals in the starting materials used in preparing the complex product. 1

Process conditions The salt complex of the present invention is prepared by combining the aforementioned compounds in the presence of water. The water can be present as a result of addition thereof to the mixture, or liberated from either the essential components or other additionally present compounds as a result of being subjected to heat. However, it is preferred to add water to the'mixture to effect salt complex formation. It has been found that the metal complex can be prepared when using small quantities of Water such as about 1 mole of water per mole of inorganic metal compound. However, more usually about 5 to 50, and preferably about 15 to 30, moles of water per mole of inorganic metal compounds are used.

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

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

(b) The inorganic alkaline earth metal comv36 pound in a drystate 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;

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

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

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

In all of the methods described above for preparing the salt complex, thestep of removing substantially all of the water which is present is accomplished at a temperature not substantially in excess of 350 C., preferably. about C. to 200 C. The techniqueemployed to remove the water includes, 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 superatmospheric pressure. At a later stage, the acidic material when used in gaseous form, may be used to remove thelast portion of water. It can therefore be seen that the temperature as well as the time for effecting substantial removal of water will vary considerably depending on the amount of material being processed and on the technique employed therefor. Generally, the time required to effect substantial removal of water is at least about 15 minutes or less and can be as high as 1045 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 all of the water from the process mixture. It was observed that satisfactory complexes 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 ofthisv specification and the appended claims, the relativeamounts 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 of Oil-soluble organic acid or the alkaline earth metal salt thereof to promoter is from about 1 material employed isfpref b me -1i 3.7 to IOto about o' tq-l nmreallyirdm about 11' to .lito about ,l'to 1', andprererably from, about 3to 2to about? to2. p j M H The amount of inorganic alkaline earth metal compound employed generally will be sufilcient tohave present ,in the total mass at least more than about one equivalent of alkaline earth metal, regardless" of" how combined, per equivalentof oil-soluble organic acid or the alkaline earth metal salt'thereof plus-promoter In other words, the amount of inorganic alkaline'earth metal compound employed must be such that there is more than: the theoretical amount required-to form merely a normalsalt of oilsoliible. or.- ganic acid and the pro ote 7 poses of this specification and the appended claims, the amount of inorganic alkaline earth metal compound employed will be: expressedas an amount such that there ar'e pres'em -m the mass more than one equivalent 'oflalkaline earth metal, including the alkaline. earth, metafwhich is present in the form of the'salt o'fthe oilsoluble organic acid and the promoter, per equivalent of oil-soluble organic acid; and; alkaline earth metal salt thereof plus the promoter:

As indicated hereinabovet, treatmenmof the salt complex. with an acidictmaterialds sd'one in instances .Where it is desirable-to lower; theibasic number of the salt complex and/or partially or substantially completely recover the-ionizable-organic compound. Thistreatment is effected at a temperatureof from about 25 to-2 0G'. preferably from about 50 to 1'10? C. and usually employing from about 0,5- to of acidic material, based 'on the weight-ofsalt complext The time of treatment with the acidic maitrial can vary considerably depending 'on' the desired result. As would be expected, shortiperiods otitreatm'ent may. cause only partialiliberatiomor:release: of ionizable organic :cohipoundr or smalldecreases in the basic number;oi the saltcomplex. Howe er. n gene al p r ods;ofir atment i l ran e from about 0.25; to hours or; ii-lore. In most cases, and particularly where it;, i$: desired to recover the promoter, the amount of acidic material usedshouldbe athleast equivalent to the amount of-metal present as the salt or theionizable. form of promoter.

. When .it is desiredto "produce .a...pro'duct; havingsubstantially :neutral .rea'ctiongrthe. amount of acidic. material used: should bexatgleastp; equivalent to'the totalmetalinzexcess ofithat present as the normal salt of the oil soluble organic acid.

To substantially increase the metal content of the salt complexit may be desirable to" treat the total mass with anacidicmaterial justprior to filtering same. This treatment may conveniently be effected-at a temperat re of from about 25 to 250 0. preferably from about 50 to 170 C.', using from about."0';'5 'to20% of acidic material, based on the totalfmass'ga'nd for a period of from about 0;25. t'o]30h The acidic an, acid anwith the acid anhydride gas may be accelerated vsupera h r p es ure-r. r e,

As d c dabov i n r ertc ac litatesn understanding of the amount oimetal. which. can be present in the salt complex, the:metal ratio! us, for tlipuiiis defined as the ratio of the total metal in the salt complex to the amountof-metal whichis in the form of anormal s'alt of fthe oil -soluble organic acid. In accordancetherewith; the salt complex as of this invention will-have metal 38 ratiosgreater than land up to lo'orinore; pref erably from about 2 to 8. As for the finished salt complex which is treated with an acidic material, the metalcontent issubstantially. the same as in the complex prior to treating. Consequently the same metal ratios as given above will apply to such treated product. In those instances where the finished salt complex is treated with an acidic material and the ionizable organic compound is removed from the resultant product by distillation, or otherwise it is found that the metal ratios will be substantially the same as in the salt complex before treating with the acidic material.

By. reason of the high metal ratio of the complexes produced in accordance with this invention; the following theories are suggested as a po's's'ibleexplanation or how the meta1:is.:com:- bined It is t'o be understood,- however, that such theories are advanced for the purpose. of offering explanations; and are not. to be cone strued as limitations on the scope of the present invention.

In the following; equations, represents a promoterin which H isanionizable hydrogen and M represents a divalent metal. Assuming that the promoter may act as a catalyzer for the formation of inorganic polymeric configurations, viz. (MO)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:

Catalyst- (m iisoi M o M o-Mon mo RSOaM'O'MFO MOH AXH (5) RSOaMOM OMXA+. HiO

2AXH I+ M(OH).2 (AXMM (peptized'intoendproduct.)

The resultantlcomplex, according to the above theory, can be a. complex mixture ota-ll' the potential products listed above. It is. apparent that high. metal ratios are. possible under. this theory: Another theory isbased upon an electronic in terpretation. For exarnple in. the casesof the neutral sulphonate, the charges. are distributed as follows::

i -o- M The electron octets aroundthe two oxygen atoms whichqare not attached-to a metal :atom give to-feach of; these-atoms a unit negative charge thus leaving thesulphuratom with a double" positive char'ge. Y When the sulphonate, *ex-cess inorganic metal compound; promoter, and water are reactedac,- cording't the present invention, a basic promoter sa-ltg is" presumed to be formed-Q normal-lyj oil insoluble salt dissolves' 'in the reaction" mixture because of -the electronicattractingforce'-known as a hy- Structure (b) zon- R- s++ o-1 tr 39 drogen bonding. structurally this can be shown V R (b ++)OM AX-MOH "...H... OMXA Structure (a) would have a metal ratio of 3.0.

and structure (1)) would have a metal ratio of' 5.0. Combinations of neutral sulphonate and one or both structures would explain the whole number and fractions of metal ratios which are obtained in actual practice.

After the structures (a) and (b) are formed, if hydroxyl ions are present in the reaction mass the following reactions may take place:

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

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

Having thus described the present invention by furnishing specific examples thereof, it is to be understood that no undue limitations or restrictions are to be imposed by reason thereof, but that the scope of this invention is defined by the appended claims.

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

More particularly, the complexes of this invention are especially adapted for the preparation of lubricants, paint driers and plastics, partic- 40 ularly the halogen bearing plastics. In these respects, the salt complex can be employed in the following concentrations based upon the weight of the total composition.

Broad Usual Preferred Range Range Range Percent Percent Percent Lubricant 01-20 0. 2-15 0. 5-10 Stabilizing Agent for Plastics-.. 0.05- 5 0.1- 3 0. 2- 2 Paint Drier 0 2 25 0. 5-20 1.0-15

To better appreciate the wide variety of uses to which the salt complexes of this invention are adapted, the following specific examples are iven:

' Per cent by weight Use in a lubricant:

SAE 2-0 motor oil 95.0 Product of Example 4'1 4.0 Pass-treated turpentine 0.5 Zinc di-n-hexyl dithiophosphate 0.5

Use as a stabilizing agent for halogen-bearing plastics:

' Poly-chloroprene 40.0

Di-lauryl sebacate 59.25

Product of Example 58 0.75

Use as a paint drier:

Enamel (alkyd resin) 98.5

Product of Example 55 1.5

Other modes of applying the principle of the invention may be employed, change being made as regards the details described, provided the features stated in any of the following claims or the equivalent of such be employed.

We, therefore, particularly point out and distinctly claim as our invention:

1 A process which comprises'preparing and mixing a mass in which, at 50 C., at least 50% of the components are in the liquid state, and in which mass the active components consist of:

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

B. An organic compound selected from the class consisting of the low molecular weight organic sulphonic acids and the alkaline earth metal salts thereof, said low molecular weight organic sulphonic acids having:

(a) An ionization constant in water of at least about l l0- at about 25 C.;

(b) A watersolubility at 50 C. of at least about 0.000592); and" (c) In saturated aqueous solutions at about 25 C.a pH of less than 7;

the relative amounts of A and B used being in the range of from about one equivalent of A to about 10 equivalents of B to about 10 equivalents of A to about one equivalent of B;

C. An inorganic alkaline earth metal compound;

(1) which is water-soluble at a temperature of 50 C.,to the extent of at least about Q-0

Claims

1. A PROCESS WHICH COMPRISES PREPARING AND MIXING A MASS IN WHICH, AT 50* C., AT LEAST 50% OF THE COMPONENTS ARE IN THE LIQUID STATE, AND IN WHICH MASS THE ACTIVE COMPONENTS CONSIST OF: A. AN OIL-SOLUBLE ORGANIC ACID COMPOUND CONTAINING AT LEAST 12 CARBON ATOMS IN THE MOLECULE SELECTED FROM THE CLASS CONSISTING OF THE ALIPHATIC AND CYCLIC; THE THIO ACIDS CORACIDS, PHOSPHORUS ACIDS, THE THIO ACIDS CORRESPONDING TO ANY OF THE FOREGOING ACIDS, AND THE ALKALINE EARTH METAL SALTS OF ANY OF SAID ACIDS; B. AN ORGANIC COMPOUND SELECTED FROM THE CLASS CONSISTING OF THE LOW MOLECULAR WEIGHT ORGANIC SULPHONIC ACIDS AND THE ALALINE EARTH METAL SALTS THEREOF, SAID LOW MOLECULAR WEIGHT ORGANIC SULPHONIC ACIDS HAVING: (A) AN IONIZATION CONSTANT IN WATER OF AT LEAST ABOUT 1X10-10 AT ABOUT 25* C.; (B) A WATER SOLUBILITY AT 50* C. OF AT LEAST ABOUT 0.0005%; AND (C) IN SATURATED AQUEOUS SOLUTIONS AT ABOUT 25* C. A PH OF LESS THAN 7; THE RELATIVE AMOUNTS OF A AND B USED BEING IN THE RANGE OF FROM ABOUT ONE EQUIVALNENT OF A TO ABOUT 10 EQUIVALENTS OF B TO ABOUT 10 EQUIVALENTS OF A TO ABOUT ONE EQUIVALENT OF B; C. AN INORAGINIC ALKALINE EARTH METAL COMPOUND; (1) WHICH IS WATER-SOLUBLE AT A TEMPERATURE OF 50* C. TO THE EXTENT OF AT LEAST ABOUT 0.0003%; (2) IN AN AMOUNT SUCH THAT THERE ARE PRESENT IN THE MASS SUBSTANTIALLY MORE THAN 1 EQUIVALENT OF ALKALINE EARTH METAL, INCLUDING THE ALKALINE EARTH METAL PRESENT IN THE REMAINING COMPONENTS, PER EQUIVALENT OF A PLUS B; AND D. WATER, IN AN AMOUNT EQUAL TO AT LEAST ABOUT ONE MOLE PER MOLE OF C; MAINTAINING THE MASS AT A TEMPERATURE AND FOR A PERIOD OF TIME SUFFICIENT TO DRIVE OFF SUBSTANTIALLY ALL FREE WATER AND WATER OF HYDRATION WHICH MAY BE PRESNT, AND FORM THE ORGANIC ALKALINE EARTH METAL COMPLEX; AND THEN TREATING THE ORGANIC ALKALINE EARTH METAL COMPLEX WITH AN ACIDIC MATERIAL OF WHICH THE IONIZATION CONSTANT IS HIGHER THAN THE IONIZATION CONSTANT OF THE ORGAINC SALT-FORMING COMPOUND OF COMPONENT B AND IN AMOUNTS SUFFICIENT TO LIBERATE A SUBSTANTIAL PROPORTION OF SAID ORGANIC COMPOUND OF COMPONENT B 1440 GRAMS OF THE SALT COMPLEX OBTAINED BY THE METHOD GIVEN IN EXAMPLE 49 WAS BLOWN WITH CO2 FOR ABOUT TWO HOURS AT A TEMPERTURE OF 3060* C. UNTIL THE PRODUCT SHOWED AN ACID NUMBER OF 6. THE PRODUCT THUS OBTAINED WAS THEN HEATED AT A TEMPERATURE OF 200* C. UNDER VACUUM OF 4 MM. TO RECOVER APPROXIMATELY 15 GRAMS OF PHENOL. THE RESIDUE OF THE DISTILLATION WAS A VISCOUS LIQUID, LIGHT BROWN IN COLOR, AND CONTAINED A SLIGHT ODOR. THIS PRODUCT POSSESSED THE FOLLOWING PROPERTIES: