US2223130A - Lubricant - Google Patents

Description

Patented N UNITED STATES PATENT OFFICE LUBRICANT Carl F. Prutton, East Cleveland, Ohio, assig'nor to The Lubri-Zoi Corporation, Wicklifie, Ohio, a

corporation of Ohio No Drawing. Application May 8, 1940,

Serial No. 334,082

28 Claims.

This invention relates, as indicated, to lubricating compositions and more particularly to lubricating compositions which are predominantly hydrocarbon oil, the properties of which ail'ecting its use for particular purposes are improved by the addition of materials which are particularly effective in rendering the lubricants suitable for use under conditions of extreme stress as imposed by high temperatures, high loads, etc.

In my co-pending applications, Ser. Nos. 737,070, filed July 26, 1934; 216,153, filed June 27, 1938; and 245,226, filed December 12, 1938, I have disclosed a broad class of lubricating compositions of general utility, particularly in the field of use where extreme pressures are encountered.

My present invention relates to the discovery that a certain class of such materials is particularly suitable for use in lubricants subjected to conditions of extreme stress such as those involved in the lubrication of heavily loaded gears, and in the lubrication of internal combustion engines operating under severe service conditions; for example, those encountered by internal combustion engines particularly of the aviation and Diesel types.

It is the principal object of my invention, therefore, to provide a lubricating composition .10 which is especially suited for the purposes described.

Other objects of my invention will appear as the description proceeds.

To the accomplishment of the foregoing and related ends, said invention, then, consists of the means hereinafter fully described and particularly pointed out in the claims; the following description setting forth in detail certain approvedcombinations of ingredients embodying my invention, such disclosed means constituting, however, but one of various forms in which the principle of the invention may be used.

Broadly stated. this invention comprises the provision of a lubricating composition for the purposes specified, characterized by the fact that the same contains a lubricating oil, preferably of the hydrocarbon type, as a major constituent with the properties of such composition affecting its use as a lubricant, especially under the conditions specified, by the incorporation therein of a minor amount, based on the amount of lubricating oil present, of a stable, oil-soluble salt of an aromatic acid containing an inorganic substituent.

More especially, my invention comprises the discovery that salts of aromatic acids, of the type which contain an inorganic substituent as well as a substituent selected from the class consisting of aliphatic and cycle-aliphatic radicles, 5 are particularly suited for use.

Tm: On. Base The oil base of my lubricating compositions is a lubricating oil of the type best suited for the particular use for which the ultimate composition is designed. When the lubricating compositions of my invention are designed for the lubrication of automobiles, the oil base will of course preferably consist of a refined mineral lubricating oil of lubricating viscosity for the particular point of application. In other words, a conventional gear oil may be used for the lubrication of the gears and generally a lighter, more highly refined, oil will be used in the crank 20 case.

This invention is applicable to lubricating compositions in which the base may consist either entirely or in part of synthetic oils, hydrogenated oils, and voltolized oils.

The oil base may also desirably contain other well-known constituents such as those which improve the oiliness, pour point, cold test, and oxidation properties, etc., of the oil. In general, compositions of my invention may be employed so with any commercially available addition agents for the above defined purposes since they are generally compatible with the same in the amounts usually used.

THE ADDITION Assn-rs 35 As above indicated, the addition agents may be generally defined as salts of aromatic acids containing an inorganic substituent. The term salts as used herein is intended to include the organic salts of these aromatic acids as well as the inorganic salts of these aromatic acids. The inorganic salts such as the metallic salts of these aromatic acids will generally be found to give best results, and of these, those salts in which the metal is present in divalent form, will usually be preferred.

The halogen bearing salts of aromatic acids containing an inorganic substituent are a particular class of addition agents which have been 50 found to be notably effective.

For certain uses, the salts of aromatic acids of the type which contain an inorganic substituent and also a substituent selected from the class consisting of aliphatic radicles and cyclo- 5 aliphatic radicles have been found very useful. Thislatterclassofsaltsmayopiionally additionally contain a halogen such as chlorine.

A convenient way of more specifically identifying the various salts which may thus be used in accordance with this invention as addition agents in the improved lubricating compositions is to first identify the aromatic acids containing an inorganic substituent; to then refer to the various radicles or bases, both organic and inorganic, which may be combined with such aromatic acids; and to then list a representative number of salts which may thus be produced.

In the identification of the aromatic acids which may thus be employed in the production of salts, the use of which is concerned in the present invention, reference may be had to convenient modes of preparation of such acids.

Since the aromatic acids from which the organic and inorganic salts are prepared are characterized by the inclusion therein of an inorganic substituent, it is believed desirable to first list a number of such characterizing inorganic substituents.

Tum: I.Inorganic substituents .By the term inorganic substituents" as used herein, I mean to include all substituents which either consist of, or contain, one or more of the following elements:

When nitrogen is present in a substituent group, such group may be selected from the following.

(1) Amino R a (NH, n i (2) Imino (=NH, =NR) (3) Azo (--hN=R) (4) Hydrazo A (NHNHR) (5) Hydrazine (NHNH:) (6) Nitrile (-CEN) When sulphur is present as part of a substituent group, it may be present as in any of the following:

( 1) Mercapto (2) sulphide where the radicle is directly attached to a carbon atom (-BR) (3) Polysulphide where :r is at least 2 (-&-R) (4) Thio-cyanate (-SCN) (6) Thio-aldchyde (7) Thio-carboxyl (8) .ThiO-QStl E 8H) When the inorganic substituent also contains oxygen in addition to the characterizing inorganic element, such substituent may be any of the following, for example:

(1) (O-M where M is a metal) (2) Amide and substituted amide (3) Where the oxygen is directly attached to a carbon atom: arsenite, hydrochlorite, phosphite, thiophosphate, thiophosphite, and p hydroxylamines.

(4) Where the oxygen is indirectly attached through the means of some other atom, e. g.: arsenate, chlorate, chlorite, cyanate, a hydroxylamine, nitrate, nitrite, nitro, nitroso, oxime, perchlorate, phosphate, sulphate, sulphite, sulphinic acid, suiphone, suiphonic acid, sulphoxide, and thiosulphate.

Additional examples of inorganic substituents are those thio substituents which correspond to the oxygen containing substituents given immediately above \mder (1), (2), (3) and (4), but in which one or more of the oxygen atoms in any of the substituents of (1), (2), (3) and (4) above are replaced with sulphur, for example,

Mercaptide (S-M) Thioamide, etc.

Any of the above-mentioned inorganic substituents may be combined by known means with any representative aromatic acids such as those specifically identified in Table 11 below as well as those whose mode of preparation is hereinafter defined, in the production of arcmatic acids containing an inorganic substituent from which either organic or inorganic salts may be prepared.

(5) Thioketone Taau IL-Aromati Benzoic acid Benzoic acid derivatives Azobenzoic acid Mercapto benzoic acid Lauryl benzoic acid Salicylic acid Salicylic acid derivatives Ethyl salicylic acid Carboxylic acid derivatives Pyrrole carboxylic acid Thiophene carboxylic acid Acetic acid derivatives Phenyl acetic acid Diphenyl acetic acid stearic acid derivatives Phenyl stearic acid Phenyl mercapto stearic acid Xenyl stearic acid Naphthyl stearic acid Tolyl stearic acid Furoic acid Cinnamic acid Phthalic acid Toluic acid Mercapto rosolic acid Naphthyloic acid Any of the foregoing which have been halogenated.

In the preparation of those salts of aromatic acids containing an inorganic substituent and additionally a substituent selected from the class consisting of aliphatic radicles and cyclo-aliphatic radicles, such acids may be conveniently prepared either by:

(l) Condensing an aromatic compound, which may or may not, itself, contain an inorganic substituent included in the end product, with (a) An aliphatic unsaturated acid containing an inorganic substituent, or

(b) A halogenated aliphatic acid which may optionally contain another inorganic substituent not completely replaced in the condensation reaction, and thus forming a part of the end product, or

(c) A cycle-aliphatic unsaturated acid containing an inorganic substituent, or

(d) A halogenated cyclo-aliphatic acid optionally containing a further inorganic substituent not replaced in the condensation reaction, and thus occurring in the end product; or by (2) Condensing an aromatic acid, which may or may not contain an inorganic substituent in-- cluded in the end product, with (a) An unsaturated aliphatic compound containing an inorganic substituent, or

(b) A halogenated aliphatic compound,

which may optionally contain a further inorganic substituent not fully replaced during the condensation reaction, and thus occurring in the end product, or

00) An unsaturated cyclo-aliphatic compound containing an inorganic substituent, or

(d) A halogenated cycle-aliphatic compound optionally containing a further inorganic substituent not fully replaced during the condensation reaction, and thus occurring in the end product.

male 5612, *biaka use em-iples of aromatic compounds which" a'y be used in any of the condensation reactions identified under (1 above in the preparation of aromatic acids containing inorganic substituents, and from which appropriate salts may be prepared.

Tanu: III-Aromatic commands (1) With no inorganic substituent:

Benzene Toluene Naphthalene Diphenyl Xylene Retene Mesitylene 2) When the inorganic substituent is a halogen: Chlorbenzene Dichlorbenzene Chlornaphthalene Chlortoluene Chlor retene Chloranthracene Chlor benzophenone Chlor acetophenone Chlor diphenyl oxide Methylchlorphenyl ether Ethylchlorphenyl ether Chlor p naphthyl ketone (3) When the inorganic substituent contains sulphur:

Phenyl mercaptan Diphenyl sulphide Diphenyl disulphide Dlnaphthyl sulphide Dinaphthyl disulphide Amyl phenyl sulphide Dimethyl phenyl sulphide Mercapto phenyl sulphide Mercapto phenyl disulphide (4) When the inorganic substituent contains nitrogen:

Nitrobenzene Phthalimide (5) When the inorganic substituent contains nitrogen and sulphur:

Phenylthiazole Phenyl nitro mercaptan Nitro derivative of phenyl disulphide Nitro derivative of phenyl phenyl monosulphide Thiobenzamide Thiobenzanalide In Table IV below are given a number of representative long chain fatty acids with and without inorganic substituents.

TABLE IV.--Long chain fatty acids (1) With no inorganic substituent:

Laurie Palmitic Stearic Myristic Oleic Linoleic Ricinoleic Hypogolic Erucic Linolenic Muconic Mono esters of muconic acids (2) Where the inorganic substituent includes a halogen:

Any of the halogen derivatives of the acids of class (1) above, as well ashalogenated saturated fatty acids, such as Chlorinated stearic acid, e. g.

Dichlor stearic acid Hydroxy chlor stearic acids (3) Where the inorganic substituent includes sulphur: Mercapto stearic acids Thiostearic acids Mercaptc oleic acids 'I'hio oleic acids Chlor mercapto stearic acids Chlor thiostearic acids Thiomuconic acids Acids obtained by the treatment of unsaturated fatty acids with sulphur, sulphur monochloride, or sulphur dichloride, for example, sulphurized linoleic acid. (4) Where the inorganic substltuent includes nitrogen: Nitrostearic acids Amino stearic acids Amino mercapto stearic acids Nitro hydroxy stearic acids Amino hydroxy stearic acids Amino chlor stearlc acids Amino oleic acids Nitrochlorstearic acids Amino thio oleic acids Mono-amides of muconic acid, e. g.

o HOl-(CH=CH)g-5NH,

Mono-thioamides of muconic acid, e. g.

Any suitable condensation reaction may be employed for the purpose of carrying out the 5 condensation between the aromatic compounds and the long chain fatty acids above identified. It will be observed that generally the long chain fatty acid should either be of the unsaturated type, or have a replaceable halogen in order that the condensation reaction may be conveniently carried out. Thus, in the foregoing lists where particular examples of .long chain fatty acids given are saturated, it will be understood that a halogen derivative of the same will be prepared as an intermediate step in carrying out the condensation reaction.

It will be observed that the condensation reaction contemplated under (1) above contemplates the condensation or an aromatic compound which contains an inorganic substituent with various acids. When the aromatic compound contains an inorganic substituent, such as for example any of the list under Table 111 (2), (3), (4) and (5), then the components of the con- 5 densation reaction identified under (1) (a), (b), (c), and (d) may be any of those listed in the following Tables V to VIII, inclusive.

TABLE V.-Aliphatic unsaturated acids Linolenic acid Maleic acid l'umaric acid Linoleic acid Elaeostearic acid Propiolic acid Stearolic acid Methyl acrylic p pentanoic acid Undecylenic Myristolenic Palmitolenic Tm: VI.--Haloacnated aliphatic acids TABLI VlI.-Cuclo-dliphatic unsaturated acids cnammooenc acid Hydrocarpic acid Tsar: VIlI.Halogenated cvclo-aliphatic acids Chlorinated naphthenic acids Chlorhexahydrobenzoic acid Chlorchaulmoogrlc acid Chlorhydrocarpic acid When the aromatic acid, forming one component of the condensation reaction identified under (2) above, contains an inorganic substituent, then the components of such condensation reaction identified under (2)-(a) (b) (c) and (d) above may for example be any of the compounds identified in Tables E to XII below.

Taau: Iii-Unsaturated aliphatic compounds Ethylene Propylene Butylene Isobutylene Decene Acetylene Butadiene Aliene Amylene As well as those unsaturated products derived from petroleum and petroleum fractions and derivatives such as paraflln wax as by cracking or for example removal of H01 by NaOH from monochlor paramns. The unsaturated products derived from cracked gasoline, gas oil etc. will be found particularly useful.

TAB X.--Halogenated aliphatic compounds Ethyl chloride Butyl chloride Amyl chloride Lauryl chloride Benzyl chloride Ethylene dichloride. Carbon tetrachloride Chlorparaflin wax Chlor naphtha Chlor decane Amyl dichloride Chlorinated aliphatic paraflin derivatives as 5 well as the chlorinated derivatives of the various materials and compounds listed in Table IX above.

Taau: XL-Unsaturated cycle-aliphatic compounds Cyclohexene Cyclohexadiene Cyclopentene Cyclobutene TABLE XIL-Halogenated cycle-aliphatic compounds Chlorcycloparaflines Chlorcyclobutane Chlorcyclopentane Chlorethylcyclobutane Chlorcyclohexane Dichlorcyclohexane Chlorcyclopentene In the following table XIII will be found listed several representative examples of components (a), (b), (c), and (d) for use in the condensation reaction under (1) above, which components 30 contain an inorganic substituent, in addition to such examples round in Table IV.

TABLE XIII (b) Halogenated aliphatic acids containing an additional inorganic substituent:

Chlor nitrobutyric acids Chlor thiobutyric acids Chlor thioacetic acids (0) Cycle-aliphatic unsaturated acids containing an inorganic substituent: 55 Thio hydrocarpic acids Amino chaulmoogric acids (d) Halogenated cyclo-aliphatic acids containing an additional inorganic substituent:

Chlorinated thio naphthenic acids Chlor nitro hexahydrobenzoic acids In the following Table XIV will be found listed several representative examples of components (a), (b), (c), and (d) for use in the condensa- 05 tion reaction under (2) above, which components contain an inorganic substitucnt.

Tana: XIV

(a) Unsaturated aliphatic compounds contain- 70 ing an inorganic substituent: Dichlor ethylene Tetrachlor ethylene Dichlor butylene Acrylic acid amide 75 Acrylic acid thio amide Oleic acid amide Oleic acid thio amide Tri-allyl phosphite Tri-allyl phosphate Esters oi thio unsaturated fatty acids, 5

such as those of thio-acrylic, thiocrotonic, thio-oleic and thio-linoleic acids, e. 2:.

Methyl thio-crotenate Cyclohexyl thio-crotenate l0 Lauryl thio-crotenate Methyl thio-oleate Cyclohexyl thio-oleate Lauryi thio-oleate 15 (b) Halogenated aliphatic compounds which contain a further inorganic substituent.

Chlor acetamide Chlor nitro acetamide Nitro acetyl chloride Thio acetyl chloride Chlor thio acetamide Chlor stearic acid amide Chlor nitro stearic acid amide Nitro stearoyl chloride Thio stearoyl chloride Chlor stearic acid thio amide Tri (chlor ethyl) phosphite Tri (chlor ethyl) phosphate Chlor esters of thio fatty acids such as those of thio acetic acid and thio stearic acid, e. g.

Chlor methyl thio acetates Chlor cyclohexyl thio acetates Chlor lauryl thio acetates Chlor methyl thio stearates Chlor cyclohexyl thio stearates Chlor lauryl thio stearates Chlor cyclohexyl crotonate Cyclohexyl thio-oleate Chlor cyclohexyl thio-oleate (c) Unsaturated cycle-aliphatic compounds containing an inorganic substituent:.

Dichlor cyclo-hexene Nitro cyclo-hexene (d) Halogenated cyclo-aliphatic compounds containing an inorganic substituent.

Chlor nitro cycle-hexane Chlor cyclo-hexyl thio-acetates 0 Chlor cyclo-hexyl thio-stearates Cyclo hexyl chlor thio-stearates Amides of chlor thio-naphthenic acids Tri (chlor cyclo-hexyl) phosphate Tri (chlor cyclo-hexyl) phosphite The acid chloride of cyclo-hexyl thiostearic acid amides oi chlor thio-stearic acids Many of the aromatic acids which contain a substituent selected from the class consisting of aliphatic radicles and cyclo-aliphatic radicles, in addition to an inorganic substituent, may be prepared by first carrying out the condensation reaction to produce an aromatic acid containing the aliphatic or cyclo-aliphatic radicle and another substituent the latter being then converted to the desired inorganic substituent. The acid thus produced may then be used to form the salt which is the addition agent contemplated herein. For example, in the preparation of amino phenyl stearic acid, nitro-benzene may be condensed with oleic acid to form nitro-phenyl stearic acid, and the latter compound reduced, for example by means of zinc and hydrochloric acid,

contain these substituents in addition to an aliphatic or a cycle-aliphatic substituent are to be prepared, an aromatic acid which contains only the hydroxyl radicle may be formed as an intermediate step. For example from hydroxy phenyl stearic acid the following may be prepared:

1. By the reaction of phosphorus penta sulphidemercapto phenyl thio stearic acids;

2. By the reaction of phosphorus trichloridethe phosphite of hydroxy phenyl stearic acid;

3. By the reaction of phosphorus oxygen chloride-phosphate of hydroxy phenyl stearic acid; and

4. By the reaction of acid chlorides of thio organic acids, for example thio acetyl chloride-the thio esters (such as the thio acetate) 'of hydroxy phenyl stearic acid.

It may be preferable to use an ester of the aromatic acid (e. g. the methyl ester of hydroxy phenyl stearic acid in the above examples) rather than the acid itself in carrying out reactions of this type.

The aromatic acids forming one component of the condensation reaction identified under (2) above may, of course, be any of the aromatic acids of Table 11 above, or such derivatives of the same as may be provided by combining, with the aromatic acids of Table 11 above, any of the inorganic substituents of Table I above.

The following is a list of a few aromatic acids containing an inorganic substituent and from which organic and inorganic salts may be prepared:

Mercapto benzoic acid Nitro benzoic acid Mercapto phthalic acid Mercapto toluic acid Nitro toluic acid Nitro naphthoic acid Mercapto naphthoic acid Monosulphide and disulphide of benzoic acid, i. e.

Dlcarboxyl diphenyl sulphide Dlcarboxyl diphenyl disulphide Monosulphide of nitrobenzoic acid Monoand disulphide of salicylic acid Thiobenzoic acids Thionaphthoic acids Thiophenyl benmic acids Thiocyclohexyl benzoic acids Phenyl thiostearic acids Chlorbenmic acids Chlornaphthoic acids Chlorphenylbenzoic acids Cyclohexyl chlorbenzoic acids Chlorphenyl stearic acids Mercaptophenyl stearic acids Phenyl mercapto stearic acids Chlorphenyl mercapto stearic acids Chlorphenyl thiostearic acids Thiosalicylic acids Chlorsalicylic acids Lauryl thiosalicylic acids Lauryl chlorsalicylic acids In the following will be found listed a number of organic radicles or bases which may thus be employed in the preparation of organic salts of the various aromatic acids containing inorganic substituents as'above specifically identified, or as to which the mode of preparation has been indicated.

TABLE XV.Organic radicles or bases Amino compounds, such as: Monoethanolamine Diethanolamine Triethanolamine Analine Benzylamine Laurylamine Diphenylamine Triphenylamine Diethylamine Triethylamine Putrescine Amido compounds such as:

Among the specific organic salts of aromatic acids containing an inorganic substituent which may thus be prepared for use may be listed the following as illustrative examples.

TABLE xvii-Organic salts Benzylamine Mercapto phenyl stearate Benzylamine nitro phenyl stearate Benzylamine nitro mercapto stearate Benzylamine phenyl mercapto stearate Benzylamine phenyl nitro stearate Condensation product of diphenyl sulphide and an organic acid Benzylamine salt of that Laurylamine salt of phenyl mercapto hydroxy stearic acid Salatcg laurylamine phenyl mercapto stearic Benzylamine phenyl sulphurized organic acid Benzylamine phenyl sulphurized rescinoleic acid The corresponding aniline salts of the foregoing In the following table are listed a number 01' inorganic bases which maybe combined with any organic substituent which may thus be prepared for use.

TABLE XVII-Inorganic bases Sodium Potassium Ammonium Lithium Magnesium Calcium Strontium Barium Cobalt Zinc Nickel Manganese Aluminum Chromium Stannous Lead Copper Cadmium Bismuth Silver Mercury Vanadyl (VOE In the following table are given a list of representative examples of inorganic salts of aromatic acids containing an inorganic substituent which may be produced by the combination of certain of the aromatic acids above specifically identifled, or as to which the mode of preparation has been given with certain of the inorganic bases of Table XVII above.

TABLE XVHI Calcium chlorphenyl stearate Magnesium chlorphenyl stearate Aluminum chlorphenyl stearate Beryllium chlorphenyl stearate Cobalt chlorphenyl stearate Nickel chlorphenyl stearate Copper chlorphenyl stearate Manganous chlorphenyl stearate Stannous chlorphenyl stearate Stannic chlorphenyl stearate Cadmium chlorphenyl stearate Cyclohexyl amine chlorphe yl stearate Benzyl amine chlorphenyl stearate Tribenzyl amine chlorphenyl stearate Magnesium stearoyl chlorbenzoate Stannous stearoyl chlorbenzoate Cyclohexylamine stearoyl chlorbenzoate Aluminum salt of the mono-octyl ester of chlorphthalic acid Benzylamine salt oi. the mono-(methvl-cyclohexyl) ester of chlorphthalic acid Magnesium lauryl-thiobenzoate Magnesium lauryl-chlorbenzoate Magensium thio-stearoyl benzoate Magnesium stearoyl thiobenzoate Magensium stearoyl mercapto benzoate Magnesium octyl salt-ester of chlorphthalic acid Magnesium lauryl salt-ester of chlorphthalic acid Magnesium cetyl salt-ester of chlorphthalic acid Magnesium salt of the acid octyl mono-thio-ester of phthalic acid, 1. e.

Mg [OOC CsH4) COSCaHn]:

nesium thio-salt oi' the acid octyl ester of phthalic acid. 1. e. Mg[SOC(CsH4)COOCaH11]2 Magnesium butyl salt-ester oi' tetrachlorphthalic acid Calcium salt of lauryl thin-salicylic acid Magnesium salt of stearoyl thio-salicylic acid Calcium phenyl mercapto stearate Calcium chlorphenyl mercapto stearate Calcium phenyl thiostearate Calcium chlorphenyl thiostearate Cobalt chlorphenyl thiostearate Calcium chlorcresyl stearate 7 Calcium chlornaphthyl stearate Calcium chlorxenyl stearate Calcium cyclohexyl-chlorphenyl stearate Calcium and cobalt salts or the acids formed by the condensation of oleic acid with:

Phenyl mercaptan Dipheny1 sulphide Dipheny1 disulphide chlorphenyl mercaptan Chlordiphenyl sulphide Benzyl mercaptan Dibenzyl sulphide Dibenzyl disulphide Chlorbenzyl mercaptan Chlordibenzyl sulphide Di(chlorbenzyl) disulphide Chlorbenzyl acetate Benzyl thio-acetate Benzyl thio-stearate Methyl thiobenzoate Cyclohexyl thiobenzoate Lauryl thiobenzoate Cyclohexyl chlorbenzoate Thiobenzoyl chloride Thiobenzamide N-lauryl thiobenzamide N-cyclohexyl thiobenzamide Chlor-thiobenzoyl chloride Chlor-thiobenzamide N-lauryl chlor-thiobenzamide Phenyl cyanide Benzyl cyanide Phenyl thiocyanate Benzyl thiocyanate Tribenzyl phosphate Tribenzyl phosphite Tri(chlorbenzyl) phosphate Tri (chlorbenzyl) phosphite Chlor diphenyl ether Chlor acetophenone Chlor benzophenone Thio-acetophenone Thiobenzophenone Chlor-thiobenzophenone Calcium salts of the acids formed by the condensation of thio-crotonic acids with:

Stearoyl-benzene Stearoyl-diphenyl Stearoyl-naphthalene Stearoyl-dibenzyl Calcium salts of the acids formed by the condensation of crotonic acid with:

Stearoyl-chlorbenzene Stearoyl-chlordiphenyl Stearoyl-chlomaphthalene Thiostearoyl-benzene Thiostearoyl-diphenyl Thiostearoyl-chlorbenzene Stearoyl-cyclohexylthiophenol Stearoyl-cyc1ohexylchlorthiophenol Calcium salts of the acids formed by the condensation of esters of oleic acid (e. g. cyclohexyi oleate, and methyl oleate) with:

Chlorbenzoic acid Thiobenzoic acid Chlorsalicylic acid Thiosalicylic acid Chlomaphthoic acid Mono-esters of chlor-phthalic acids, e. g. mono-methyl, mono-cyclohexyl, an d mono-lauryl esters of chlor-phthalic, acids Calcium salts of the acids formed by the condensation of substituted amides of oleic acid (e. g. N-cycloheiwl, and N-lauryl, oleic acid amide) with:

Benzoic acid Chlorbenzoic acid Thiobenzoic acid Chiornaphthoic acid Salicylic acid Chlorsalicylic acid Thiosalicylic acid Mono-methyl and mono-cyclohexyl esters of phthalic acid and chlorphthalic acids Calcium salts of the acids formed by the condensation of substituted thio-amides of oleic acid (e. g. N-cyclohexyl, and N-lauryl, thio-oleic acid amides) with:

Benzoic acid Chlorbenzoic acid Thiobenzoic acid Chlornaphthoic acid Salicylic acid Chlorsalicylic acid Thiosaiicylic acid Mono-methyl and mono-cyclohexyl esters of phthalic acid and chlorphthalic acids Salts of each of the following amines:

Dilauryl amine Dicyclohexyl amine Stearoyl aniline Thiostearoyl aniline Stearoyi di-phenylamine Lauryl phenthiazine Stearoyl phenthiazine With each of the following acids: Chlorphenyl stearic acid Phenyl thiostearic acid Mercapto phenyl stearic acid stearoyl chlorbenzoic acid Stearoyl thiobenzoic acid Stearoyl mercapto benzoic acid Mono-methyl ester of chlorphthalic acids Mono-butyl ester of chlorphthalic acids Mono-lauryl ester of chlorphthallc acids Mono-cyclohexyl ester of chlorphthalic acids The basic calcium, magnesium, copper and nickel salts of chlor-phenyl stearic acid. These were prepared by dissolving about 20% of chlorphenyl stearic acid in a mineral 011, adding twice the theoretical amount of freshly precipitated metal hydroxide required to neutralize the acid and heating for about two hours at about 100 C. An equal volume of benzol was then added, and after filtering the benzol and water removed by heating the oil-benzol solution under vacuum up to a temperature of about 120 C. The oil solutions of the basic salts thus produced were then added to motor oil to make a lubricating composition containing about 1% of the basic salt.

Instead of preparing the salts designed for use as the addition agents of the present invention by treating any of the acids, of the type above identified, with an alkali for example such as sodium hydroxide in the preparation of the corresponding sodium salt of the acid, it is also possible to prepare corresponding salts by first preparing an ester of the acid, and then reacting such ester with an alkali such as sodium hydroxide to prepare, for example, the sodium soap of the acid, and then treating such soap with another salt in the preparation of a salt of a different inorganic radicle. Thus, for example, the methyl ester of chlorphenylstearic acid may be reacted with sodium hydroxide in the production of sodium chlorphenylstearate which is in turn reacted with calcium chloride in the production of calcium chlorphenylstearate.

It may be preferable to prepare the ester, employed in the foregoing preparation of the salt, where such ester is one of an aromatic acid belonging to classification 2 on page 9 above, by condensing an ester of an aromatic acid with an unsaturated compound or halogenated organic compound instead of condensing the aromatic acid itself with such compound. For example, in the preparation of salts of stearoyl chlorbenzoic acid, methyl chlorbenzoate may be condensed with stearoyl chloride to form methyl stearoyl chlorbenzoate, this ester saponified with sodium hydroxide, and the resulting sodium salt reacted with magnesium chloride in aqueous solution to form magnesium stearoyl chlor-benzoate. An example of the preparation of magnesium stearoyl chlor-benzoate in detail is as follows:

A mixture of 1 mole each of methyl chlorbenzoate and stearoyl chloride is dissolved in an equal weight of carbon bisulphide. One mole of anhydrous aluminum chloride is added slowly with the temperature at C. and the mixture held at that temperature for one hour longer. The materials are then poured into a mixture of cracked ice and concentrated hydrochloric acid, and the carbon bisulphide layer removed and washed with warm water. Carbon bisulphide and moisture are then removed by distilling under vacuum leaving the condensation product, namely methyl stearoyl chlor-benzoate. The latter is saponified by adding 1 mole of sodium hydroxide in the form of a 10% aqueous solution, the mixture being refluxed until the aqueous solution is approximately neutral. One-half mole of magnesium chloride is added in the form of an aqueous solution'which causes the precipitation of magnesium stearoyl chlor-benzoate. The water layer is decanted from the precipitate which is then dissolved in benzol and dried by removing the benzol and water by distilling under vacuum. The resulting product when dissolved in a naphthenic type 011 in a concentration of 1% will be found to materially improve the oil for use in an internal combustion engine. particularly in preventing the formation of harmful deposits on the piston and piston rings.

Included among the compounds contemplated for use by this invention are stable oil soluble salt-esters of polybasic aromatic acids containing an inorganic substituent. These may. be formed for example by neutralizing an acid ester of a polybasic aromatic acid, which contains an inorganic substituent, with a base. or by partially saponifying a neutral ester of sucha polybasic aromatic acid with a base so that each molecule of the saponifled material retains at least one ester group in addition to at least one basic group.

Examples of such compounds are the saltesters of the following:

1. Benzene polycarboxylic acids containing an inorganic substituent, e. g.

Thio, mercapto, amino, nitro, or chloro substituted:

Phthalic acids Trimesic acid Trimellitic acid Hemimellitic acid yromeilitic acid Mellophanic acid Prehnitic acid Benzene pentacarboxylic acid 2. Naphthalene polycarboirylic acids containing an inorganic substituent, e. g.

Thio, mercapto, amino, nitro, or chloro substituted:

Naphthalic acids 3. Pyridine polycarboxylic acids, e. g.

Lutidinic acid Dipicolinic acid Cynchomeronic acid Isocynchomeronic acid Dinicotinic acid Alpha-carbocynchomeronic acid Beta-carbocynchomeronic acid Berberonic acid Trimesitinic acid Pyridine tetracarboxylic acids Pyridine pentacarboxylic acid Pyrrole polycarboxylic acids Quinoline polycarboxylic acids Thiophene polycarboxylic acids 'Ihiazole polycarboxylic acids Dlphenyi polycarboxylic acids containing an inorganic substituent, e. g.

Thio, mercapto, amino, nitro, or chloro substituted:

Diphenic acid 9. Dibenzyi polycarboxylic acids containing an inorganic substituent Anthracene polycarboxylic acids containing an inorganic substituent Phenanthrene polycarboxylic acids containing an inorganic substituent Thianthrene polycarboxylic acids containing an inorganic substituent Acids formed by the condensation of an unsaturated polycarboxylic acid with an aromatic compound containing an inorganic radicle Where such salt-esters are employed, it will generally be found advantageous to have at least one of the ester groups consist of an aliphatic QQQUIIB a or cycle-aliphatic group and preferably one containing four or more carbon atoms. For example, salts of the acid butyl or amyl esters of thiophthalic acids have been found suitable.

Specific examples of such salt-esters are:

1. The magnesium salt of the mono lauryl ester of mono-thio phthalic acid 2. The calcium salt of the mono-(lauryl-benzyl) ester of di-thio phthalic acid 3. The calcium salt of the mono-(cyclohexylcyclohexyl) ester of chlor-phthalic acid 4. The cobaltous salt of the mono-cyclohexyl ester of dichior diphenic acid Also included among the compounds contemplated for use by this invention are stable oil soluble salts of the amides and thioamides of polybasic aromatic acids in which at least one carboxyl group has not been converted to the amide. As examples of this class of compounds are those having the general formula:

in which R is a metal or radicle derived from a base, and R is an aromatic radicle. Examples of sulphur-containing compounds of this class are those in which one or more of the oxygen atoms of the above general formula have been replaced by sulphur, e. g.

This class of compounds also includes those in which one or both of the hydrogen atoms of the above general formulas have been replaced by organic radicles. Compounds of the latter type are often preferred because of improved oil solubility.

Examples of polybasic aromatic acids from which salts, of the above type, may be prepared are the following:

1. Benzene polycarboxylic acids, e. g.

Phthaiic acids Trimesic acid Trimellitic acid Hemimellitic acid Pyromeilitic acid Mellophanic acid Prehnitic acid Benzene pentacarboxylic acid 2. Naphthalene polycarboxylic acids, e. g.

Naphthaiic acids 3. Pyridine polycarboxylic acids, e. g.

Lutidinic acid Dipicolinic acid Cynchomeronic acid Isocynchomeronic acid Dinicotinic acid Alpha-carbocynchomeronic acid Beta-carbocynchomeronic acid Berberonic acid Trimesitinic acid Pyridine tetracarboxylic acids Pyridine pentacarboxylic acid Pyrrole polycarboxylic acids Quinoline polycarboxylic acids Thiophene polycarboxylic acids Thiozole polycarboxylic acids Diphenyl polycarboxylic acids, e. g. diphenic acid Dibenzyl polycarboxylic acids Anthracene polycarboxylic acids 11. Phenanthrene polycarboxylic acids 12. Thianthrene polycarboxylic acids 13. Acids formed by the condensation of an unsaturated polycarboxylic fatty acid with an aromatic compound 1 Specific examples of these salts of amide-aromatic acids are: 1. The magnesium salt of mono-(N-lauryl amido) phthalic acid 2. The calcium salt of mono-(N-lauryl-benzyl thio-amido) phthalic acid Another class of compounds also included among those contemplated by this invention are the basic" oil-soluble salts of aromatic acids containing an inorganic radicle. By the term basic salt is intended the product which is obtained by reacting the acid with twice the amount of base theoretically required to neutralize the acid. These products are conveniently made by dissolving the aromatic acid in mineral oil in a concentration up to about 30% and adding twice the theoretical amount of freshly precipitated metallic hydroxide required to neutralize the acid and heating to a temperature of about 100 C. for about two hours. An equal volume of benzol or other suitable solvent is added and. the oilsolvent mixture filtered. The resultant filtrate will be found to contain twice the amount of metal, as compared with the amount of aromatic acid radicle, which would be present in the normal salt. After filtration the mixture is heated under vacuum in order to remove the solvent together with the water which may have been added with the metallic hydroxide and that formed by the reaction of the hydroxide with the acid. The oil solution of the basic salt may then be used as a material to add to the mineral oil which forms the major portion of the lubricating composition which is the subject of this invention.

In the preparation of these basic salts, presumably all of the metallic hydroxide has reacted since any unreacted metallic hydroxide or oxide.

would be removed by the filtration step. Although the resultant salt is characterized as basic, it does not necessarily have a basic reaction when shaken with water. The foregoing is the assumption of what takes place in the carrying out of the reaction just described and is believed to be correct. The mineral oil used in carrying out the foregoing reaction was a 150 pale Mid-Continent neutral oil. It may be that some of themetal combined with components present in the oil. 'Whatever may have been the precise occurrence and the exact nature of the end product, such and product was found to be of practical utility.

In view of the particular uses for which my compounded lubricants are intended, it is apparent that of the salts included in the foregoing enumeration of the addition agents which may be employed, those which are readily oil-soluble are the ones preferred for use. When these compounded oils are designed for use under conditions where high tempe atures are usually encountered, the addition agents should be stable at elevated temperatures. For use in crankcase lubricants for internal combustion engines, they should preferably be stable to the extent where there will be substantially no decomposition, when the lubricating composition is exposed to temperatures up to 250 F.

The addition agents which are to beselected from the class described should be such that they are relatively non-corrosive with respect to the metallic surfaces with which they come in contact during use. Certain of the named addition agents may be found to be detrimentally corrosive to certain sensitive bearing metals, in which case an appropriate corrosion inhibitor may be employed in conjunction therewith in the composi- 5 tion.

A lubricating composition prepared in accordance with my invention and which is predominantly hydrocarbon oil may contain froman effective amount to 20% of the salt addition agent above identified. In general, it will be found that an amount as low as .1% will often be quite effective and that amounts in excess of 10% are seldom necessary. A preferred range of concentrations for the salt in the oil is from .5% to about 2%.

It is also within the contemplation of this invention to provide the addition agents in the form of a concentrate in a suitable oil, said oil containing rather high percentages of the addition agents. Such concentrates may be employed for further blending with a lubricating oil in the proportions desired for the particular conditions of use.

While mineral oil, generally, is the principal ingredient of the lubricant, it is not essential that it be the only ingredient other than the addition agents, provided that there be no additional ingredient which is incompatible with such addition agent. It is within the contemplation of this invention to include, if necessary or desirable, such other addition agents as are commonly, added to improve the viscosity index or cold test of the lubricants; and a lubricating composition according to this invention which also has a separate film-strength or oiliness increasing agent has been found to be especially effective.

When used in conjunction with a hydrocarbon lubricating oil, it is obvious that, generally, only such amounts of the addition agent may be included as are soluble in the specified amount of oil. By the term soluble, as herein used, it is intended to indicate the ability to form not only true solutions but also any form of substantially permanently homogeneous composition when incorporated in mineral oil. With most of the compounds there is usually little difliculty, especially if the incorporation is effected in the manner described in Cornell Patent No. 2,042,880, and since quite small percentages often give remarkably improved results, it is seldom of extreme importance that the addition agents be oilsoluble in all proportions. Also, certain compounds are of value as gelling or bodying agents when used in amounts greater than are strictly soluble.

The addition agents above enumerated for use in my compounded lubricants include certain ones which may be found to at least partially decompose under conditions of extreme stress such as the very high temperature encountered in certain classes of use, while others are quite stable even under such extreme conditions.

The use for which the lubricant is designed therefore determines the particular type of addition agent to be selected. A certain amount of decomposition, which proceeds at a relatively slow rate, is usually not harmful. Care should be exercised, however, to select for a particular set of operating conditions, an addition agent which in the oil base used, will not decompose under such operating conditions except at a low rate.

By the term stable as used herein in describ- 76 aaasnso ing the addition agents is meant the characteristic of the addition agents which enables them to resist decomposition in the oil under the condition oi use for which the lubricating composition is designed.

The lubricating compositions 01' this invention may be prepared by first preparing the salt and then dissolving the salt in the oil base, or they may be prepared by reacting the acid in solution in all or a portion of the oil with a suitable basic compound in order to form the desired salt directly in solution in oil. In the latter case, it is frequently desirable to remove the water formed by the reaction, or which may have been added with the basic compound, by some means such as by heating at atmospheric or sub-atmospheric, pressure.

In case the salt to be used is water-insoluble, an alternative procedure is as follows:

An aqueous solution of a water-soluble salt of the acid i first prepared, ior example by dissolvin the acid in an aqueous solution of caustic soda or caustic potash. The aqueous salt solution is then emulsified with oil and a water-soluble salt containing the cation of the desired salt is added to the mixture. The desired salt is thus precipitated from the aqueous medium and subsequently or simultaneously dissolved by the oil medium. Separation of the aqueous and oil layers is then effected for example by settling or centrifuging. Subsequent'water-washing 01 the oil solution to remove traces of inorganic salts may be desirable, and removal of moisture may also be required. 1

It will be observed that all or the salts contemplated for use as addition agents in the lubricants of my invention are salts which contain the radicle in which X is an element oi the class consisting of oxygen and sulphur and M is a member of the class consisting of metals and basic radicles.

This application is a continuation-in-part of my aforesaid co-pending applications Serial Numbers 737,070, 216,153 and 245,226.

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

I therefore particularly point out and distinctly claim as my invention:

1. A lubricating composition containin as a principal lubricating constituent a major amount of a mineral lubricating oil with the properties of such composition afiecting its use as a lubricant improved by incorporating therein a minor amount of a stable oil-soluble salt of an aromatic acid containing an inorganic substituent such salt containing the radicle in which X is an element or the class consisting of oxygen and sulphur and M is a member 01' the class consisting of metals and basic radicles.

2. A lubricating composition containing as a principal lubricating constituent a major amount or a mineral lubricating oil with the properties of such composition affecting its use as a lubricant improved by incorporating therein a minor amount of a stable oil-soluble salt 01' an aromatic acid containing a substituent selected from the of such composition aflecting its use as a lubricant improved by incorporating therein a minor amount of a stable oil-soluble salt 01 an aromatic acid containing a cyclo-aliphatic substituent and an inorganic substituent.

5. A lubricating composition containing as a principal lubricating constituent a major amount of a mineral lubricating oil with the properties of such composition aflecting its use as a lubricant improved by incorporating therein a minor amount of a stable oil-soluble metallic salt or an aromatic acid containing a sulphur containing radicie such saltcontaining the radicle in which X is an element of the class consisting of oxygen and sulphur and M is a member oi the class consisting of metals and basic radicles.

6. A lubricating composition containin as a principallubricatingconstituent a major amount of a mineral lubricating oil with the properties of such composition ail'ecting its use as a lubricant improved by incorporating therein a minor amount of a stable oil-soluble metallic salt of an aromatic acid containing a sulphide radicle.

7. A lubricating composition containing as a principal lubricating constituent a major amount of a mineral lubricating oil with the properties of such composition affecting its use as a lubricant improved by incorporating therein a minor amount of a stable oil-soluble metallic salt of an aromatic acid containing a polysulphide radicle.

8. A lubricating composition containing as a principal lubricating constituent a major amount of a mineral lubricating oil with the properties of such composition affecting its use as a. lubricant improved by incorporating therein a minor amount of a. stable oil-soluble metallic salt of an aromatic acid containing a nitrogen containing radicle such salt containing .the radicle in which X is an element of the class consisting of oxygen and sulphur and M is a member of the class consisting of metals and basic radicles.

9. A lubricating composition containing as a principal lubricating constituent a major amount of a mineral lubricating oil with the properties of such composition affecting its use as a lubricant improved by incorporating therein a minor amount of a stable oil-soluble metallic salt 01' an aromatic acid containing an oxygen containing radicle such salt containing the radicle in which X is an element of the class consisting of oxygen and sulphur and M is a member of the class consisting of metals and basic radicles.

10. A lubricating composition containing as a in which X is an element of the class consisting of oxygen and sulphur and M is a member of the class consisting of metals and basic radicles.

11. A lubricating composition containing as a principal lubricating constituent a major amount of a mineral lubricating oil with the properties of such composition ailecting its use as a lubricant improved by incorporating therein a minor amount of a stable oil-soluble metallic salt of an aromatic acid containing a nitrogen and sulphur containing radicle.

12. A lubricating composition containing as a principal lubricating constituent a major amount of a mineral lubricating oil with the properties of such composition affecting its use as a lubricant improved by incorporating therein a minor amount 01 a stable oil-soluble metallic salt of an aromatic acid containing a nitrogen, sulphur, and oxygen containing radicle.

13. A lubricating composition containing as a principal lubricating constituent a major amount of a mineral lubricating oil with the properties of such composition afiecting its use as a lubricant improved by incorporating therein a minor amount of a stable oil-soluble salt of an aromatic acid containing an inorganic constituent, which acid is of the type which may be produced by condensing an aromatic compound containing an inorganic substituent with a long chain fatty acid.

14. A lubricating composition containing as a principal lubricating constituent a major amount of a mineral lubricating oil with the properties of such composition afiecting its use as a lubricant improved by incorporating therein a minor amount of a stable oil-soluble salt of an aromatic acid containing an inorganic constituent, which acid is of the type which may be produced by condensing an aromatic compound containing a sulphide substituent with a long chain fatty acid.

15. A lubricating composition containing as a .principal lubricating constituent a major amount of a mineral lubricating oil with the properties of such composition ailecting its use as a lubricant improved by incorporating therein a minor amount of a stable oil-soluble salt of an aromatic acid containing an inorganic constituent, which acid is of the type which may be produced by condensing an aromatic compound containing a polysulphide substituent with a long chain fatty acid.

16. A lubricating composition containing as a principal lubricating constituent a major amount 7 of a mineral lubricating oil with the properties acid containing an inorganic constituent, which acid is of the type which may be produced by condensing an aromatic compound containing sulphur and oxygen with a long chain fatty acid.

18. A lubricating composition containing as a principal lubricating constituent a major amount of a mineral lubricating oil with the properties of such composition aflecting its use as a lubricant improved by incorporating therein a minor amount of a stable oil-soluble salt of an aromatic acid containing an inorganic constituent, which acid is of the type which may be produced by condensing an aromatic compound containing nitrogen and sulphur with a long chain fatty acid.

19. A lubricating composition containing as a principal lubricating constituent a major amount of a mineral lubricating oil with the properties of such composition aflecting its use as a lubricant improved byincorporating therein a minor amount of a stable oil-soluble salt of an aromatic acid containing an inorganic constituent, which acid is of the type which may be produced by condensing an aromatic compound containing nitrogen, sulphur and oxygen with a long chain fatty acid.

20. A lubricating composition containing as a principal lubricating constituent a major amount of a mineral lubricating oil with the properties of such composition afl'ecting its use as a lubricant improved by incorporating therein a minor amount of a stable oil-soluble salt of an aromatic acid containing an inorganic constituent, which acid is of the type which may be produced by condensing an aromatic compound with a long chain fatty acid containing an inorganic substituent.

21. A lubricating composition containing as a principal lubricating constituent a major amount of a mineral lubricating oil with the properties of such composition aflecting its use as a lubricant improved by incorporating therein a minor amount of a stable oil-soluble salt of an aromatic acid containing an'inorganic constituent, which acid is of the type which may be produced by condensing an aromatic compound with a sulphur bearing long chain fatty acid.

22. A lubricating composition containing as a principal lubricating constituent a major amount of a mineral lubricating oil' with the properties of such composition affecting its use as a lubricant improved by incorporating therein a minor amount of a stable oil-soluble salt of an aromatic acid containing an inorganic constituent, which acid is of the type which may be produced by condensing an aromatic compound with a nitrogen bearing long chain fatty acid.

23. A lubricating composition containing as a principal lubricating constituent a major amount of a mineral lubricating oil with the properties of such composition affecting its use as a lubricant improved by incorporating therein a minor amount of a stable oil-soluble salt of an aromatic acid containing an inorganic constituent, which acid is of the type which may be produced by condensing an aromatic compound with a long chain fatty acid containing a sulphide constituent.

24. A lubricating composition containing as a principal lubricating constituent a major amount of a mineral lubricating oil with the properties of such composition afiecting its use as a lubricant improved by incorporating therein a minor amount of a stable oil-soluble salt of an aromatic acid containing an inorganic substituent, which acid is of the type which may be produced by condensing an aromatic compound with a long chain fatty acid containing a polysulphide constituent.

25. A lubricating composition containing as a principal lubricating constituent a major amount of a mineral lubricating oil with the properties of such composition afiecting its use as a lubricant improved by incorporating therein a minor amount of a stable oil-soluble salt of an aromatic acid containing an inorganic substituent, which acid is of the type which may be produced by condensing an aromatic compound with a long chain fatty acid containing a sulphur and oxygen bearing substituent.

26. A lubricating composition containing as a principal lubricating constituent a major amount of a mineral lubricating oil with the properties of such composition aifecting its use as a lubricant improved by incorporating therein a minor amount of a stable oil-soluble salt of an aromatic acid containing an inorganic substituent, which acid is of the type which may be produced by condensing an aromatic compound with a long chain fatty acid containing a sulphur and nitrogen bearing substituent.

27. A lubricating composition containing as a principal lubricating constituent a major amount of a mineral lubricating oil with the properties of such composition affecting its use as a lubricant improved by incorporating therein a minor amount of a stable oil-soluble salt of an aromatic acid containing an inorganic substituent, which acid is of the type which may be produced by condensing an aromatic compound with a long chain fatty acid containing a sulphur, nitrogen and oxygen substituent.

28. A lubricating composition containing as a principal lubricating constituent a major amount of a mineral lubricating oil with the properties of such composition affecting its use as a lubricant improved by incorporating therein a minor amount of a stable oil-soluble salt -of an aromatic acid containing an inorganic substituent, which acid is of the type which may be produced by condensing an aromatic compound with a long chain fatty acid containing a nitrogen and oxygen bearing substituent.

CARL F. PRUTTON.

CERTIFICATE OF CORRECTION. Patent No. 2,225,150. November 26, 191m.

- CARL F. PRUTION. It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows; Page 12, first column, lines 57, ha, 5 and 69, and second column, lines h, 1b,, 22;, 56,

14,7, 58 and 69, claims 13 to 25 inclusive, for the word "constituent" read --eubatituent--; and that the said Lettere Patent should be read with this correction therein that the same mey conform to the record of the case in the Patent Office.

Signed and sealed this lhth day of January, A. n. 19in;

Henry Van Arsdale, (Seal) Acting Commissioner of Patents.