US2432095A - Lubricating composition - Google Patents

Description

Patented Dec. 9, 1947 LUBBICATING COMPOSITION Delton R. Frey, East Cleveland, Ohio No Drawing. Application December 29, 1941, Serial No. 424,823

13 Claims. (Cl. 252-46.?)

This invention relates, as indicated, to the stabilization of liquid hydrocarbon compositions. The term liquid hydrocarbon compositions" as used herein is intended to include liquid compositions which are essentially derivatives of petroleum, naturally occurring oils of the types represented by animal, vegetable and marine oil and derivatives of the same.

More specifically this invention relates to the stabilization of liquid hydrocarbon compositions which are essentially mineral oil and particularly mineral oil of the character commonly employed as lubricants. My invention, however, is likewise applicable to the stabilization of lighter fractions of petroleum such as are used for fuels. Liquid hydrocarbon compositions of the character above identified are subject during storage, handling and particularly during use, to deterioration which may be occasioned either by oxidation-or poiymerization, and such deterioration usually proceeds at an accelerated rate when, for example, the liquid hydrocarbon composition is subjected to elevated temperatures and similar conditions encountered when the same are used as lubricants in internal combustion engines.

This deterioration, which, as indicated, may occur either during storage, handling or use, is generally manifested by discoloration of the liquid hydrocarbon body; generation within the body of fiocculent material; the precipitation from the body of the more serioustypes of deterioration products such as sludge; and the deposit of varnish or shellac-like deposits on metallic surfaces with which the compositions come in contact especially during use.

Inasmuch as deterioration is usually accelerated by the severe conditions, such as temperature, to which the hydrocarbon composition is subjected, it will be observed that my invention is particularly'suited for the stabilization of hydrocarbon compositions such as mineral lubricating oils used as the lubricant in the crank case of internal combustion engines whether of the ignition or Diesel type. My invention is particularly applicable to the stabilization of lubricants used in Diesel engines on account of the more severe stresses to which the lubricating composition is subjected in that type of engine.

It is a principal object of my invention therefore to provide for the stabilization of compositions of the character defined in order to reduce the tendency of the same to decomposition, particularly in the manner indicated.

It will also be observed that the addition agents employed for the described purposes, especially when prepared in the manner hereinafter more specifically defined, are in themselves new compositions of matter.

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

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

Broadly stated, this invention comprises the stabilization of liquid hydrocarbon compositions of the character previously identified, by the inclusion therein of a minor proportion of an oilsoluble compound having in the samemolecule a cycloaliphatic radicle and the phosphite radicle.

The compounds contemplated for use by my invention are believed to have the following structure:

one or more of the radicles A, B and C may be a cycloaliphatic radicle; and when for example the cycloaliphatic radicle is at A, then B and C may be the same or different radicles selected from the class consisting of hydrogen, the metals and any organic radicle. The metals which may be used are those which are capable of producing oils oluble derivatives of the remainder f the molecule. Generally the polyvalent metals are preferred and the following metals will be found particularly suitable for use, the same being arranged in the order of their preference:

Table I Calcium Zinc Magnesium Cadmium Barium Cobalt Beryllium Nickel Strontium Tin Aluminum Silver Chromium Copper As previously indicated, any organic radicle.

may be utilized at one of the positions A, B or C (see B or C for illustration where the cycloali- 3 phatic radicie is positioned at A) and in this connection reference may be had to the following table for a classification and identification of specific organic radicles which may be utilized for this purpose.

Table II I. Hydrocarbon radicles (A) Alkyl radlcles Amyl (n, iso, sec. and tertiary) Laur l I Ccty (amaubyl Ceryl Montanyl Mellisyl Laoceryi Psyllicyl B lradlcles lhen l E Xenv Naphthyl (alphsand beta-) Allih I (C) radicles (D) Alkylatcd aryl radicies Radicles formed by the alkylation of aryl radicles. such as those listed above B). with any or the alkyl radicles. e. f those lsted above (A), or with any or the la] owing:

Methyl Ethyl Prupyl (n-. and l'o-) Butyl (n-, isoand sec-) Spefiific examples of alkylated aryl radlclel are as o uws:

Phcnyl-ethyl Phenyl-amyl Phenyl-lauryl Phcnyi-cetyl Naphthyiethyl (1i) Cyelo-alkylated alkyl radlcles, e. 5.,

Nuphthenyl Hexahydrohenzyl Cyclotexyl-etiiyl Cyclohexyl-amyl (I) Arylated cyclo-nikyi radicles, e. g.,

Phcnyl-cyclohexyl Xcnyl-cyclotexyl Nophthyl-cyciohexyl (J) Mixed radicies e.g.,

-. Methylcyciolnexyl-phenyl Amylcycloifexyl-fhenyl Cyclohexyl-cresy Cyclohexyl-xylyl Cyclobexyl amyl-phenyl Cyclohexyi-bcnzyl Xylyl-cycloiexyl Lauryihenylcyclohex'yl Cetyl-p enylcyeiohexyl Phenyi-methylcyclolzexyl Phenyl-amylcyclotexyl Xyiyl-methylcyclohexyi Benzyl-eyclohexyi Benzyi-meth lcyclohexyl Methylcyclo exyl-amyl Methylcyclohexyl-lauryl col) (B) the ketone type, e. g.,

(C) 0! ester type,

erived from by the removal of the hydroxyl group, as (or example, by the removal of the hydroxyl group from ti.e following esters:

(l) Esters oi hydroxy acids, o. 5.,

Esters iormed by substitution oi any of the "R" groups listed above (or one or more ol the acid hydrogen atoms of the following acids: 0 Lactic acid v Tartarlc acid Ricinoleic acid Hydroxy-stcaric acid Hydrnxy-chlorstearic acid Cyclohcmnol carboxylic acids Hydroxybenwic acids Salicylic acid Hydroxy-phthaiic acids Hydroxy phcnyl-benzoic acids Naphthol curboxylic acids 1 (2) Esters oi polyhydroxy alcohols and phenols in which at least one hydroxyl group remains unsubstituted, ior exan le, esters formed by esicriiying the (ol owing so that at least one hydroxyl group remains in the resulting ester:

Ethylene glycol Diethylene lyool Propylene g yools Butylenc glycols Poly-hgdroxy benzenes Di droxy-benzenes esorcinol Catcchol Hydroquinone I Tri-hydroxyhcnzenes Pyroga 101 III. Sulphur-containing radicles, e. g.,

Any of the examples of oxy era-containing radicles in which at least one oxygen atom as been replaced with sulphur. Specific examples or sulphur-containing radicles are: (A) 0! the thiocthyl type Thio-phenoxy-phenyl (CsHr-SC.H Thio-phenoxy-ethyl (CsHs-$-CrHr-) Thio-lauroxy-phenyl (CnHzs$C| 4) Thio-t-amyl-phenoxy-phcnyl (C H||-C H|S- CrHn CsHu Table II-Conttnued C 1H:- 8 C IHG'" '(B) 0! thelhio-ketone type Tho acetylhenyl. Th o-benzoy -pbenyl Th -o-stearo l-phenyl T -o-napht enoyllion 1 Thio-stearoyl-cyclo exy (C) 01 the thio-cstcr type, c. g., derived from hydroxyesters of tbio-carboxylic acids. Examples oi such radicles are:

Where R is moth l, ethyl, butyl, amyl, lauryl,

stearoyl,napbt en 1, etc. (D) Radiclcs derived from ydroxy-organic polysulphides by removal 0! the hydroxy group, a. g.,

l gig I i where R is hydrogen or an alkyl or cyclo-alkyl K P t l R-S.-R--

where R. is an alkyl or cyclo-alkyl group and R is an alkylene group.

where Y is a halogen, and A and .B' are either the same or different halogens, or the same or different radicles selected from the class consisting of those having the formulas "XR and R where x is oxygen or sulphur and R is an organic radicle or hydrogen.

The reactant (b) will have the formula R'XH where R is an organic radicle and X is either oxygen or sulphur.

The pair of reactants (a) and (b) selected are such that at least one of them contains a. cycloaliphatic radicle; i. e., at least one of the radicles,

6 v R and R is a cycle-aliphatic radicle. Preferably the reactant (b) is one in which R is cycloaliphatic.

Examples of the reactant (a) are:

Phosphorus trichloride, PCla Phosphorus tribromide, PBra Compounds having the I formulas ROPQlz, (ROMPCI. RSPCh, (RShPCl, RPCiz and RaPCl where R is an organic radicle selected from the list under Table II.

Specific examples of these compounds are those in which R is;

Phenyl Tolyl Xylyl Naphthyl Xenyl Ethyl phenyl Butyl phenyl Amyl phenyl Lauryl phenyl Cyclohexyl phenyl Naphthenyl phenyl Naphthenoyl phenyl Amyl pctyl Lauryl Cyclohexyl Methyl cyclohexyl -Cyclohexyl-cyclohexyl Certain compounds of the class having the formulas ROPCI: and (RO )2PC1 may be prepared by adding an organic hydroxy compound slowly to phosphorous trlchloride in such proportions that the molecular ratio of organic hydroxy compound to PC]: is two or less; Examples of such i reagents are those prepared by adding slowly to one mole of phosphorus t-rlchloride one or two moles of a hydroxy-ester, such as, for example:

Trimethyl citrate Tributyl citrate Methyl lactate Ethyl lactate Butyl lactate Lauryl lactate Cyclohexyl lactate Methyl salicylate La'uryl salicylate Cyclohexyl salicylate Examples of the reactant (b) are those betting the formula R'OH and R'SH, where R is any cyclo-aliphatic radicle selected from the list under Table II. Specific examples of such compounds are:

Cyclohexanol e Methyl cyclohexanols Dimethyl cyclohexanols Ethyl cyclohexanols Propyl cyclohexanols Butyl cyclohexanols Amyl cyclohexanols .Lauryl cyclohexanols Phenyl cyclohexanols Cyclohexyl cyclohexanols Cyclohexyl carbinol Cyclopentanol Methyl-cyclopentanol Cycloheptanol Decahydro-naphthols Tetrahydronaphthols Naphthenyl alcohols those listed under Table II. Specific examples of reactant (b) to be used in this way are:

n-Octyl alcohol Capryl alcohol Lauryl alcohol Benzyl alcohol Phenol alcohol Cresols alcohol Amyl phenols Methyl lactate Methyl salicylate From the foregoing it will be observed that a very large number of specific addition agents are contemplated for use by this invention. This large number of specific materials may be conveniently divided into a number of groups. The criteria which determine theallocation of a specific material to a particular group may generally be considerations such as (a) the precise nature of the material, (b) the mode of its manufacture, and (c) its particular utility.

I shall therefore in the further identification of the numerous specific examples contemplated for use refer to them by groups.

Group 1 The addition agents of this group may be subgenerically defined as the oil-soluble phosphorus bearing products resulting from the reaction of a trivalent phosphorus-and-halogen-containing compound with a material of the class consisting of cyclohexanol, homologs of cyclohexanol, mixtures of cyclohexanol and its homologs, and mixtures of homologs of cyclohexanol.

Group 2 a The addition agents of this group may be subgenerically defined as those which contain sulphur; for example the oil-soluble phosphorusand-sulphur-containing products resulting from the reaction of a trivalent phosphorus-andhalogen containing compound with a material of the class consisting of cyclohexanol, homologs of cyclohexanol, mixtures of cyclohexanol and its homologs, and mixtures of homologs of cyclohexanol.

Group 3 The addition agents of this group may be subgenerically defined as those which contain a halogen; for example the phosphorus-and-chloripe-containing products resulting from the reaction of a trivalent phosphorus-and-halogen containing reagent with chlor-phenyl cyclohexanol.

Group 4 convenience in identification hereinafter referred to as P. C. Y. In the preparation of this material the commercial grade of cyclohexanol may be employed since it contains in addition to cyclohexanol minor amounts of certain of the homologs such as methyl cyclohexanol.

The relative proportions of this commercial grade of cyclohexanol and PC]; used in the preparation of P. C. Y. are given in the following table, as well as the properties of the end product:

cyclohexanol parts by weight 1215 PCh do.. 2655 Weight of product do 2545 Weight of material removed by distillation -do 514 'Percent yield based on PCI; per cent 84 Percent yield based on CsHuOH do 88 Boiling point C 150-165 Melting point Liquid at room temperature Sp. gr. at 24 C 1.06 Color Light yellow Phosphorus per cent-.. 11.6 Chlorine do 5.6 Acid number 166 Solubility:

H2O Insoluble Ethyl alcohol Completely miscible Mineral oil At least 5% The cyclohexanol is placed in a reaction vessel equipped with an agitator and reflux condenser. The vessel and agitator are preferably of glass or enamel. The PC]: is added slowly and the temperature of the reactants maintained between 50 0. and 60 C. during the addition of the PC13. The mixture is stirred continuously during the addition of the PCla. The temperature of the reactants may be controlled by the rate of the addition of the PCla. After all of the PC]: has been added in the manner above described the reacting materials are heated in a water bath to 100 C. and then by use of such water'bath maintained at a temperature of 100 C. for three hours. The reactants are mechanically agitated throughout the periods of addition of PCla; elevation to 100 C.; and the three hour period while maintained at 100 C.

After being maintained at 100 C. for three hours the reaction material is distilled at an absolute pressure of eight inches of mercury and all materials. boiling below 70 C. are discarded. A sharp break in the vapor temperature will be noted indicating completion of the distillation of the low boiling fraction and the fact that the residue is the end product suitable for use. The material which is distilled over is probably largely minor amounts of unreacted PC13 and cyclohexanol. If desired the end product may be water washed since such water washing step will be found to remove a certain amount of chlorine which would otherwise remain. The properties of the composition given in the foregoing table are those for material which has been water washed.

We believe that the principal products of the reaction of PCla. with a compound of the class consisting of cyclohexanol and homologs of cyclohexanol are esters of phosphorous acid (such as (ROMP, (ROMPOH and ROP(OH) 2, where R is the cyclohexyl radicle or a homolog of it), and that halogen-bearing derivatives of such esters may also be formed, as well as other halogenbearing derivatives of ROH, for example RC1. It appears that the phosphorus-bearing constitucuts of the reaction product are responsible for the stabilizing efiect when the product is used in accordance with our invention. However, for most purposes, theother constituents are not deleterious, and for some purposes may even be advantageously included, The phosphorus-bearing constituents are in general much less volatile than the other constituents; the latter may adjusted to maintain a value of 12.7 to 1'.

In the first test, a S. A. E. 20 motor oil having a viscosity index of about 105 was employed as the lubricant and in a second test, the same oil to which .03% of P. C. Y. was added was employed as a lubricant. The engine was fitted with new pistons and rings before the start of each test' and after completion of the first test, the engine therefore be easily removed, if desired, by diswas taken down, thoroughly cleaned and fitted tillation at atmospheric or sub-atmospheric pres- 10 with a new piston and rings. sure. At the conclusion of the first test, nearly the The following table gives the results obtained entire skirt of the piston was very black, while at by the addition of minor amounts of P. C. Y. prethe end of the second test only 60% of the skirt pared as above indicated to several different repshowed only very light deposits of light brown resentative commercial oils and oils treated with material. The inside of the piston skirt at the other addition agents. end of the first test showed a light shellac-like Composition Oxidation tests Conradson Q I Corro- Vis. in SUB at 210 F. Naphtha Insolubles E I N Carbon sion test, Hexachlor Ortho Math 1 Butyi Per 1 Lead- Diphenyi Dir-blot swam? Stearent Bronze Oxide Benzene rate PCY o i Fm 1 O 1 At 48 Pelr 'tcent H": for for weight r g. a r g. e.

r Hours Increase mg. 100 mg. 48 hrs.

MID-CONTINENT SAE 30 MOTOR 01L 1 (untreated) .32 1. e1 63. 1 74. 4 17. a 1s. 5 44 121 1s 2 37 1.16 62. 9 68. 8 9. 4 2 5 2b) 41 16 27 1.30 63.5 67.9 6.9 24.0 b) 94 1. 82 63. 6 73. 1 16.0 17 46 111 51 45 1. 27 62. l 67. 9 8. 3 22 (b) 79 22 41 2. 05 61. 6 72. 2 17. 2 13 118 02 40 1. 30 62. l 69. 0 11. 1 28. 5 (b) 76 23 PENNSYLVANIA SAE 40 MOTOR 01L 1. 25 3. 52 82. 7 104. 0 26. 3 (a (b; 5 08 1.26 2. 84. 3 95. 3 13. l (a b 3 31 1. 46 2. 31 81. 8 95. 1 16. 3 ti) b 2 1. 67 3. 54 82. 3 104. 0 26. 5 a) 3 38 30 1.66 2. 61 82.1 95. 2 16. 0 a) (b 4 16 50 1. 19 2. 80 79. 6 98. 9 24. 2 Eli). (0g 6 1. 53 2. 41 81. 7 93. 6 g 14 6 a) (b 2 18' PENNSYLVANIA SAE 10 MOTOR OIL I I J.

.23 94 4a. 3 4o. 0 1. 0 0 b 54 .75 16 52 46. 1 47. 7 3. 5 43 b 12 15 .17 .43 46.2 48.3 4.6 39 b N v .151' 15 1. 40 46,3 50. 6 9. 3 22 b 65 1. 40 .22 .58 46.1 47.5 3.0 34.5 b 12 --.22 .21 1.19 46.5 50. 0 7. 5 23.0 (b 85 40 18 55 46. 1 47. 5 3. 0 41. 0 (b 14 23 z,

I (0) did not produce 10 mg. inngliours. (b) did not produce 100 mg. in 48 hrs.

The determinations which appear in the foredeposit with a dark brown deposit on the vertical. going table such as, for example, Conradson ribs while the inside of the pisto skirt at the end carbon, viscosity determinations, and naphtha) oi the second test showed no di coloration. insoluble, were determined on samples prepared -7 In general,the materials I thisdnvention will by an oxidation test procedure which is in every not be found incompatible ith common y emrespect similar to that prescribed by the Standployed anti-oxidants such as are used in gasolines ard of Indiana oxidation test, excepting that a and the like. piece of iron wire is submerged in the oil during In general, we have found that the materials the test. The data given in the column headed of the present invention do not detrimentally aicorrosion" has been determined in accordance fect the extreme pressure characteristics of a with'the standard Shell corrosion test using lead mineral lubricating oil, for example, which char-1,, bronze as the metal. acteristics are the result of the presence therein The effectivenessof P. C. Y. in improving the o! the extreme pressure addition a'gents aboveproperties of a lubricating composition for use in 6 named. Moreover, where th e materials of the internal combustion engines with particular represent'invention have been tested in lubricating gard to the stability of the lubricant during use compositions which also containmertain other adhas been demonstrated by tests conducted on a dition agents, the extreme. pressure characterliquid-ceoled single cylinder 4-cycle gasoline enistics of the resultant composition" has been somegine rated at 2 /2 H. P. at 1800 R. P. M. This what improvedand such improvement has been engine was run at 1600 R. P. M. under a load of traceable to the presence therein ot the com- 2 H. P. for a period of 100 hours for each test. pounds ofthe present invention.

The coolingfiuid temperature was maintained at Throughout the foregoing specification and in 250 F. and-the 'temperatureof-the lubricant in the appended claims, reference is made to "oilthe crankcase "at, 225v The air-fuel ratio was 591 11216 and by such term, as used herein, it is 11 intended to indicate the ability of the thus defined material to form not only true solutions with the oil to which the same are added, but also the ability to form therewith any form of substantially permanently homogeneous composition.

As indicated above, my invention also contemplates the production and use of oil-soluble derivatives of the compounds above specifically identified. Such derivatives include the oil-soluble salts and ester-salts which may be produced by substituting a metal or basic radicle for one or more of the alcohol derived radicles of the immediate reaction product'of P013 and the alcohol. This is conveniently accomplished by partly or completely saponifying such reaction product I with an alkali (e. g., sodium potassium, ammonium or substituted ammonium hydroxide) in aqueous solution. Similar salts and ester-salts of metals other than the alkyl metals may be formed directly by reacting said immediate reaction product with the metallic base, or more readily by double decomposition of the alkyl salt (or ester-salt) with a salt of the other metal.

The reaction product of P013 prepared in the manner above described is for certain uses preferable over pure tricycloh'exyl phosphite.

It will be found that the products resulting from the reaction of P013 with homologs of cyclohexanol and particularly mixtures of such homologs and mixtures of such homologs with cyclohexanol will produce materials which are quite preferable over the remaining compounds of the class previously identified. The halogen-containing reaction products, whether such halogen is present as a result of the P013 reaction or introduced by direct halogenation, will be found to give decidedly improved results. In view of the character of the reaction products of PC]; with the homologs of cyclohexanol as well as the halogen-bearing derivatives above referred to, they may be employed in concentrations considerably greater than those previously specified for the entire class of compounds wh ch may be employed as addition agents to lubricating compositions.

Throughout the foregoing description where halogens have been referred to, it is to be understood that the chlorinated species are very much preferred although the brominated and fluorinated species will also be found to have utility for particular uses.

The materials to which this invention relates have been found to be particularly effective in preventing corrosion when added to lubricants and fuels employed in internal combustion engines. They have been found to be particularly effective as corrosion inhibitors when added to engine fuels such as gasoline which normally tend to show corrosive effects in which the fuel is burned.

Attention is directed to the fact that I am filing even date herewith an application Serial No. 424.824, which relates to these same materials and it is intended that this application include all of the disclosure of such other application filed even date herewith insofar as the present case does not include the disclosures of such other case. This application is a continuation-in-part of my co-pending application Serial No. 265.051, filed March 30. 1939, now Patent No. 2290,8'72.

Other modes of ap lying the principle of my invention may be employed instead of the one explained, change being made as regards the composition and method herein disclosed, provided 12 the ingredients or steps stated by any of the following claims or the equivalent of such stated ingredients or steps be employed.

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

1. A lubricating composition comprising principally a liquid hydrocarbon of the character which is normally subject to deterioration especially at high temperatures and when in contact with metals, and which has been stabilized against such deterioration by the inclusion therein of a minor amount, sufficient to effect such stabilization, of a mixture phosphorus-containing compounds, which mixture consists of at least a part of the reaction product of (a) a trivalent phosphorus-and-halogen-containing reagent containing an organic radicle selected from the class consisting of aromatic and aliphatic radicles with (b) a cycloaliphatic compound containing the XH group where X is an element selected from the class consisting of oxygen and sulphur, said reaction product prepared by mixing the reactants and exposing the mixture to reaction conditions which produce the primaryreaction product without any substantial decomposition of such primary reaction product.

2. A lubricating composition comprising principally a liquid hydrocarbon of the character which is normally subject to deterioration especially at high temperatures and when in contact with metals, and which has been stabilized against such deterioration by the inclusion therein of a 1 minor amount, sufficient to effect such stabilization, of an organic compound having the follow-,

ing structure:

wherein X is an element of the class consisting .organic radicle selected from the class consisting of aromatic and aliphatic radicles and X is selected from the class consisting of oxygen and sulphur.

5. A lubricating composition in accordance with claim 1 in which (b) is a cycloaliphatic alcohol.

6. A lubricating composition in accordance with claim 1 in which (1)) is an alcohol containing the cyclohexyl nucleus.

7. A lubricating composition in accordance with claim 1 in which (b) is a substituted cyclohexyl alcohol.

8. A lubricating composition in accordance with claim 1 in which (b) is a cycloaliphatic ester.

9. 'A lubricating composition in accordance with claim 1 in which (b) is a cycloaliphatic mercaptan.

10. A lubricating composition in accordance with claim 1 in which (b) is a mercaptan containing a cyclohexyl nucleus.

11. A lubricating composition in accordance with claim 1 in which (a) is the reaction product 13 of trimethyl citrate with phosphorus trichloride and (b) is cyclohexanol.

12. A lubricating composition in accordance with claim 1 in which (a) is the reaction product of methyl lactate with phosphorus trlchloride and (b) is cyclohexanol.

13. A lubricating composition comprising principally a liquid hydrocarbon of the character which is normally subject to deterioration especially at high temperatures and when in contact with metals, and which has been stabilized against such deterioration by the inclusion therein of a minor amount, sufllcient to effect such stabilization, of a material 01' the class consisting of (1) a mixture of phosphorus-containing compounds, which mixture consists of at least a part of the reaction product of (a) a trivalent phosphorusand-halogen-containing reagent containing an organic radicle selected from the class consisting of aromatic and aliphatic radicles with (b) a compound of the class consisting of cycloallphatic hydroxy and cycloaliphatic mercapto compounds said reaction product prepared by mixing the reactants and exposing the mixture to reaction 14 conditions which produce the primary reaction product without any substantial decomposition of suclrprimary reaction product, (2) salts derived irom (1), and (3), halogen-bearing derivatives of (1) and (2).

DELTON R. FREY.

REFERENCES CITED The following references are of recordin the file of this patent:

UNITED STATES PATENTS Schreiber Nov. 5, 1940