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Patented Aug. 27, 1946 ' 2,406,423 UNITED STATES PATENT OFFICE 2,406,423 ORGANIC PHOSPHORUS AND NITROGEN CONTAINING COMPOUNDS Willard H. Woodstock, Flossmoor, Ill., assignor to Victor Chemical Work s, a corporation of Illi nois No Drawing. Application April 20, 1944, 1 Serial No. 531,999 13 Claims. (Cl. 260—461). 2 This invention relates to organic phosphorus and nitrogen containing compounds and more particularly to compounds of the type formula: su?iciently so to cause the reaction mass to solid ify. After the metaphosphate ester is completely added the mixture is agitated for a period of about one hour or suiliciently long for completion of the reaction and the product then allowed to cool to room temperature. As an alternate procedure it is sometimes desirable to carry out the reaction in which each of the R's represents an alkyl or in an inert liquid solvent medium such as carbon aryl group, or in the case of R’, R2 and R4 may tetrachloride or toluene. In this case the solvent represent hydrogen or its equivalent, and in which 10 is evaporated off after the reaction is completed. either R.3 or R5 contains a straight chain aliphatic As a speci?c example, one mole of ethyl meta group or its equivalent. phosphate was reacted with two moles of com Products produced by the method herein de mercial lauryl amine in the manner described scribed and having the formula above given are of above. This commercial material contained about particular value as surface active agents. In the 15 90% of the mono amine. It was melted and held preferred form R3 contains an alkyl group of 8 or at a temperature of about 50 to 60° C., while add more carbon atoms. Compounds of this type have ing the mole equivalent of ethyl metaphosphate. strong wetting out properties and are cation ac This was chosen as the amount required to form tive, when R5 is a short chain alkyl group of less a product having a pH of 6.5 to 7.0 in 0.5% aque than 5 carbon atoms. The aqueous solutions of 20 ous dispersion. The product in this case was the such materials possess the property of substan laury1 amine salt of the lauryl amide of ethyl or tially completely discharging on cotton, silk and thophosphoric acid. It was a slightly colored oily paper ?bres. liquid which solidi?ed at a temperature slightly This application is a continuation-in-part of above normal room temperature. my copending application Serial No. 417,412, ?led 25 When solid the product was tan-colored and October 31, 1941. of butter-like consistency, It had an ammonical The products are preferably prepared by re odor and a melting range of about 45 to 50° C. acting neutral esters of metaphosphoric acid with Its speci?c gravity at 55° C. was 0.91. It had a ammonia or amines in accordance with the for Draves sinking time of 19.4 seconds at 0.4% con 30 centration. In a similar manner a stearyl amine salt of the stearyl amide of ethyl orthophosphoric acid was produced. This product was a tan colored solid of butter-like consistency with a melting point 35 of 50 to 60° C. In a jacketed kettle of suitable size equipped with a stirrer and temperature indicator, 427 parts by weight of a commercial stearyl amine .Either anhydrous ammonia or organic pri (86-92% amine) is melted at 55 to 60° C. and 74 mary or secondary amines may be employed. In 40 parts of ethyl metaphosphate (65.8% P205 con~ tent) slowly added at such rate that the heat of the preferred case, however, two molecular equiv reaction does not raise the temperature above 80° alents of the nitrogen bearing material are em ployed with one molecular equivalent of the meta C. This takes about 5 hours and the charge is phosphoric acid ester. It is not necessary to use held at 70 to 80° C. for three hours longer to the same nitrogen bearing compound in each of allow reaction to be completed. The molten prod the above formulae. The product produced may‘; duct is then poured into trays and allowed to cool be a mixed composition as, for example, by using and solidify. The product is a tan-colored butter~ ammonia for the primary reaction and an amine like solid, having an ammonical odor with a melt for the second or vice versa. ing range of about 50 to 60° C. In 0.5% aqueous As a typical example of my procedure, two mole 60 dispersion, it has a pH value between 6.7 and 7.2. equivalents of a long chain aliphatic amine are It has a speci?c gravity of 0.89 at 55° C. and a melted in a reaction vessel and vigorously stirred Draves sinking time of 30 seconds at 1.0% con while slowly adding one mole equivalent of a neu centration. tral organic metaphosphate ester. The heat of The'above lauryl and stearyl compositions have ' reaction is removed by external cooling, but not 55 characteristics which are quite similar in that 2,406,428 they are both soluble in mostorganic solvents , was inert towards calcium and other salts in such as benzene, alcohol, ether, mineral oil, car- , hard waters. bon tetrachloride, lubricating oil, butyl acetate, linseed oil, etc. Both disperse in water giving opaque togel-like solutions. A 5% aqueous solu tion of the stearyl compound and a 10% solution of the lauryl compound are gelatinous starch-like ' ' In another example where octyl metaphosphate was reacted with ethylene diamine, the product was yellow and butter-like. It did not foam in water andwas much more soluble in organic sol . vents than in water. 'Two moles of octyl amine were reacted with ethyl metaphosphate to give an amber colored 10 oil which foamed in, water, but was not a good emulsifying agent. It was only partially soluble ly discharging on cotton, silk and paper ?bres. pastes of equal consistency. . ‘ Both compounds are cation-active, their aque ous solutions possessing the property oi! complete For example, cotton skeins when immersed in a in oils. ' 1 - The lauryl amine salt of the lauryl amide or with distilled water anddried, showed adsorption - methyl orthophosphoric acid prepared by react equivalent to 3.8% and 2.4% respectively for the 15 ‘mg two moles of the amine with methyl meta phosphate was found to be an excellent wetting lauryl and stearyl compounds based on the and cationic active agent. I ‘weight 01' the cotton. Both compounds possess This may be prepared as follows: wetting out properties and are strong emulsify In a one-liter ?ask equipped with a bath, ing agents. For example, eight grams of each product in 100 cc. of water were agitated with 20 stirrer, and thermometer, 600 g. commercial lauryl amine (92% amine) is heated to' 50° C. ' 100cc. of mineral oil to produce thick creamy and 141 g. methyl metaphosphate slowly added stable emulsions of the water-in-oil type. while maintaining the temperature at 50 to 70° C. In the two examples above given, the alkyl' with cooling bath. The charge was then held at groups in the salt and amide positions of the 80° C. for 2 hours to complete the reaction. The molecule were the same, but products may be charge was poured and allowed to solidify forming made in which the groups are unlike by carrying a tan-colored, butter-like solid, having an am out the reaction in two stages employing di?er monical odor, and a melting range near 45° C. ent organic amines for the two stages of the re Its speci?c gravity at 75°v C. was 0.935, and the action. -For example, one mole of ethyl meta phosphate may be reacted with one mole of 30 Draves sinking time was 16 seconds at 0.5% con centration. It has a pH value range of 6.7 to 7.2 lauryl amine, and this reaction product further in 0.5% aqueous dispersion. In aqueous disper reacted with one mole of a different organic sion it hasstrong cationic activity. It is soluble amine. A compound of this type was prepared by reacting one mole of ethyl metaphosphate with in methanol, ether, kerosene, toluene, etc. one mole of lauryl amine and subsequently ,re-‘ 35 A particularly desirable amine from the stand; point of economic availability is cocoa amine acting with one mole of ethylene diamine. The which contains a mixture of various amines product was a clear oil of alkaline reaction. It ranging from 8 to 18 carbon atoms. The reac would not-disperse in water.- When treated with tion product of one mole oi! methyl metaphos concentrated hydrochloric acid a crystalline hy drochloride of the compound was formed which 40 phate and two moles of the cocoa amine had wetting out properties and was cation active. It was dispersible in water giving a foaming solu may be prepared as follows: tion. It discharged on cotton and exhibited other‘ In a, two-liter ?ask equipped with stirrer, cationic active properties. thermometer, and cooling bath, 187 g. methyl In another example, lauryl amine is reacted metaphosphate is slowly added to 671 g. commer with ethyl metaphosphate, and, the resulting cial. coco-amine at a temperature not greater product reacted with one mole of stearyl amine to produce a product having good wetting and ' than 70° C. ‘After stirring 3 hours at 70 to 75° C. the charge is poured and allowed to cool. The excellent cationic active properties. product is a tan-colored semi-liquid having a This experiment may be carried out as follows: In a one-liter 3-necked ?ask equipped with 50 melting range between 25 and50" C. and an am monical odor. It is a good wetting agent, and is ' cooling bath, stirrer, and thermometer, 108 g. strongly cation-active. It has a speci?c gravity ethyl metaphosphate was slowly added to 185 g. .Of 0.927 at 55° C., a pH of 6.5 in 0.5% aqueous commercial lauryl amine 'at 50. to 55° C. with dispersion, and is soluble in methanol, ether, some cooling, and the productthen heated at 80° C. for 1 hour. This product was then cooled 55 kerosene, toluene, and similar solvents. Long chain amines in the salt position increase to_55 to 60° C., 268 g. molten commercial stearyl the stability and dispersibility oi! the product in amine added, and the charge heated to 80° C. for water. They also increase the organic nature 2 hours. After pouring and cooling the product and oil solubility of‘ the product. Alkyl groups was a tan-colored semi-liquid having an ammoni cal odor, and a melting range from 30 to 35° C. 60 of more than 3 carbon atoms in length in the gsiziet; position appear to decrease the water solu It had a speci?c gravity of 0.918 at 65° C., and a pH value of 6.25 in 0.5% aqueousdispersion, a All of the compounds the preparation of which Draves sinking time of 12 seconds at 0.5% con have been specifically described herein are stable centration, and analysis showed it to' contain 13.5% P205. It was soluble in methanol, ether, 65 against thermal decomposition at temperature up to at least 175° C. ' kerosene, toluene, and similar solvents,_ and was dispersible in water with strong cation-active‘ It is not essential that the esters and amines employed in our process be pure homogeneous character. ' . compounds, for example, the neutral. metaphos In another example one mole ofoctyl meta phate esters may be mixtures 01' several alkyl or phosphate was reacted with two ,moles- of anhy aryl groups. The amines may contain mixed drous ammonia in a toluol reaction medium. alkyl, alkaryl, or aryl-groups; however, it is es After completion of the reaction the toluolwas evaporated off. The product was a light yellow, ' sential that little it any aryl groups be present - in the amide forming step or the process if wet friable, non-crystalline solid. It was soluble in water with roaming. It was a wetting agent and. 75 ting and cationic properties are desired. Alkaryl 0.4% solution of these compounds, then washed 1 . - . 2,406,428 amines may be suitable for producing cationic active compounds where the straight ‘chain group has sufficient length preferably at least 8 carbon atoms in length. Aryl amide compositions, how ever, may be produced by the' reaction if desired. , Such compounds may be useful as plasticizers or oil treating agents. ' v The new surface active compounds of this in vention are compatible with other similar sur face active compounds and may be used in com 6 an alkyl group of 1 to 4 carbon atoms chain length. I I ~ ' 2. A compound as set forth in claim 1, in which R4 is hydrogen. ‘ 3. A compound as set forth in claim 1, in which R4 and R’ are hydrogemand R.2 is an alkyl group. 4. A compound as set forth in claim 1, in which RF and R3 are stearyl radicals. ‘ 5. A compound as set forth in claim 1, in which 10 R.2 and R3 represent stearyl radicals, R’ and R4 positions containing such compounds. For exam represent hydrogen, and R5 represents an alkyl ple, the cation active products may be mixed with group of 1 tov 4 carbon atoms. . other cation active products to give a surface 6. A compound as set forth in claim 1, in which active composition having the speci?c charac R5 represents an ethyl radical. teristic advantages of each type of component. 15 7. The long chain aliphatic amine salt of a In determining the number of carbon atoms long chain aliphatic amide of a short’chain alkyl in any particular chain compound the usual rules ester of orthophosphoric acid obtained by react of equivalents apply. ing one mole proportion of a neutral alkyl ester The Draves sinking time referred to herein, is‘ of metaphosphoric acid in which the alkyl group a test carried out in accordance with the “Braves” 20 contains from 1 to 4 carbon atoms with one mole method described in American Assoc. Textile proportion of each of two aliphatic amines in . Chem. Colorists Year-Book, p. 162 (1935-6). The which at least one of the amines has an aliphatic test comprises the determination of the time re radical containing a straight chain of at least 8 quired for a 5.0 g. skein of two-ply unboiled cot carbon atoms. ton yarn to sink when weighted with a 1.5 gram 25 8. A compound as set forth in claim "I, in which sinker and submerged in the wetting agent solu the metaphosphate is ethyl metaphosphate, and tion by means of an anchor. in which an amine is lauryl amine. 9. A compound as set forth in claim 7, in which The foregoing detailed description has been given for clearness of understanding only, and no the metaphosphate is ethyl metaphosphate, and unnecessary limitations should be understood 30 in which an amine is stearyl amine. therefrom. What I claim as new, and desire to secure by Letters Patent is: ' - ' . 10. A salt as set forth in claim "I, in which at least one of the reacting amines is primary. 11. A surface active composition consisting es-" 1. A surface active composition consisting es-. sentially of a monostearyl amine salt of the mono- ‘ sentially of a compound of the formula: 35 stearyl amide of ethyl phosphoric acid. . 12. A surface active composition consisting es sentially of a monolauryl amine salt of the mono lauryl amide of ethyl phosphoric acid. 13. A surface active composition consisting es-_ in which R‘. R2 and 34 represent a radical of 40 sentially of a monostearyl amine salt of the mono the class consisting of hydrogen and an alkyl stearyl amide of methyl phosphoric acid. group, I1‘.3 represents an alkyl group of at least. 8 carbon atoms chain length, and RB represents WILLARD H. woopsrocx.