Patented Aug. 7, 1945 2,381,121 UNITED STATES PATENT office CONOENSATON PRODUCTS OF TRAZINES AND SUBSTITUTE TRAVANES WITH AL KYLENE OXDES Walter P. Ericks, Cos Cob, Conn., assignor to aAmerican corporation Cyanamid of Maine Company, New York, N.Y., Application January 17, 1941, Seria No. 374,834 8 Claims. (CI. 260-2) This invention relates to the preparation of new and useful reaction products of triazines and is temporarily arrested and completed only after substituted triazines with alkylene oxides, the product, resinous or waxy or in emulsion More particularly, it embraces the preparation form, is applied to a cloth and the latter heated of reaction products by reacting triazines such or passed over a hot roller. In place of an as melamine, ammeline, guanamine and substi alkylene oxide containing compound, an epi tution and polymerization products thereof with halogenhydrin may be used, or a similar sub alkylene oxides such as ethylene oxide, glycidol stance which has an alkylene oxide group or a or compounds capable of yielding an alkylene group which under the conditions of the reaction. Oxide-containing substance during the conden forms an intermediate having an alkylene oxide sation reaction. grOp. : It is an object of this invention to prepare 10 The following examples illustrate the inven these compounds cheaply and efficiently. A still tion in more detail: further object is to prepare surface active ma \ , Eacample I terials which find use, as textile and leather as : 6.3 g of melamine (0.05 mol.) and 11.1 g of sistants and in the paper, lacquer, resin, cos 5 glycidol (0.15 mol.) were heated slowly with stir metic and similar industries as highly effective ring to 130 C, whereupon the external heating Wetting, emulsifying and detergent agents. The was discontinued. The stirring was continued products of this invention are especially useful and the temperature rose slowly to 140 C. At for softening purposes as well as anti-crease and this temperature, a sudden reaction took place wrinkle prevention in cloth, leather, fabricoid 20 and even after the beaker was placed in ice and similar materials and are particularly water, the temperature of the reaction medium valuable when used as alkali and acid resistant rose to 220° C. The product was a non-trans wetting, detergent and emulsifying agents, as parent soft resin, soluble in hot water, from well as for the resolution of emulsions such as which a precipitate (probably unreacted mel petroleum emulsions. They also find use as mer 25 amine) was obtained On cooling. Upon heating cerizing assistants. Further and more impor the resinous product to 250 C. it assumed an tant uses are suggested in the following descript amber color, became viscous and was soluble in tion. both hot and cold Water. With these objects 30 may hereinafter appear,in view the andinvention such others consists as Eacample II in the novel products and processes described be 1.26 g. of melamine (0.01 mol) and 74 g. of low and more particularly defined in the claims. glycidol (0.1 mol.) were heated slowly with con The accompanying flow sheet represents the stant stirring to 140° C. Even after the reaction process diagrammatically. As shown, the neces 85 mixture and its container were placed into cold sary reactants are mixed together with a diluent water, the reaction temperature rose continuous or as alternatively shown in broken lines with ly to 220 C. The product was an amber colored, a portion of a recycled liquid reaction product. a transparent, very viscous resin which was readily The product is then obtained by evaporation of soluble in hot water. the diluent. 40 The compounds of this invention are prepared Eacomple III in general by reacting a triazine, substituted or unsubstituted with a compound containing an 1.29 g, of 4-N-p-tertiary amylphenyl formo ethylene oxide ring. If desired the reaction is guanamine, M. P. 196 to 197° C. (0.005 mol.) and accelerated by using a temperature of 150 to 200° 45 3.7 g. of glycidol (0.05 mol.) were heated to 110° C. and a suitable organic or inorganic base, pref C. whereupon an exothermic reaction occurred. erably an alkali-metal or alkaline earth metal The reaction mixture was cooled in an ice bath hydroxide, such as sodium hydroxide, potassium and stirred constantly while the temperature hydroxide, and calcium hydroxide, or pyridine, rose to 220° C. The product was a dark amber and the like. Usually the reaction is exothermic colored viscous resin which gave clear foaming and hence must be controlled as by the use of solutions in water. It possessed surface active an efficient cooling device. The reaction product properties in neutral, acid and alkaline solutions, is then filtered off, washed and dried on a steam Eacample IV bath. If desired, complete condensation of the Octadecoxy propylamine hydrochloride was reactants is not effected. Instead, the reaction 55 prepared by reacting OctadecOxy primary anine 2 2,881,121 with an equimolecular quantity of hydrochloric ter without forming a precipitate on cooling. The acid in ethyl alcohol and subsequently filtering bottom of the beaker, however, still held a small of the product obtained. r' quantity of unreacted melamine. 18.2 g. of octadecoxypropylamine hydrochlo This reaction mass was further reacted with a ride (0.05 mol.) and 3.15 g. of melamine (0.025 fourth 8.1 g. portion of glycidol. The reaction mol.) were heated at 200 to 210° C. for 3 hours. mixture was stirred and heated to 90 C. at which The brown colored product obtained was allowed temperature the application of external heat was to cool, and then ground and digested in Warm discontinued and by continuing the stirring of the water containing an excess of ammonia. The mixture, the temperature was maintained at 90° resultant slurry was cooled in an ice bath, fill O C. for about 15 minutes because of the exothermic tered, the filter cake was washed with Water and reaction which set in. When the temperature be digested in hot alcohol containing charcoal. The gan to drop, a small quantity (about 5 cc.) of alcohol extract was filtered and the filtrate was water was added, the mixture was heated to 140 evaporated on a hot plate and subsequently on C. and then allowed to cool. A pale yellow, vis a steam bath to yield a tan colored wax, Solidi 5 cous resin was obtained, readily soluble in water. fying at about 65° C. and weighing about 13 g. Eadmaple VII One mol, equivalent of this bis-OctadeCOxy propyl melamine was reacted in a container with 12.7 g. of ammeline (0.1 mol.) was dissolved in twenty mol. equivalents of glycidol by heating the 50 cc. of water containing 4.2g. of sodium hydrox 20 ide of 96% strength. This solution was heated reactants to 250 C. The product obtained was under reflux to a boiling temperature whereupon soluble in cold water and common organic Sol external heating was discontinued and 22.2 g of vents and gave clear foaming solutions. The re glycidol was added at such a rate that the solution action probably takes place according to the was held in its boiling state. After all the glycidol formula: 25 had been added the solution was refluxed for an Bis-octadecoxypropyl melanine--glycidol additional 15 minutes. The addition of a neutral NCO CH7 izing agent yielded a resinous precipitate. The product was isolated and could be easily dissolved in mildly alkaline aqueous solutions. Cotton cloth / YN impregnated with this solution and then cured in (-NHChocin -- - cytotor mad 30 the presence of acetic acid vapors gave a durable / finish. NCOC N roomgol (OCHCHCH - (-NHCitro C room / a The product was soluble and stable in strong Ecample VIII alkaline solutions and exhibited strong wetting In another experiment, 12.7 g. of ammeline properties. It could be used advantageously as a (0.1 mol.) and 22.7 g. of glycidol (0.3 moi.) were mercerizing assistant. heated with stirring to 140° C. whereupon a sud Eacample V den exothermic reaction caused the temperature In another experiment, 7.46 g. of bis-octadec to rise to 210° C. Cooling the mass, yielded a oxypropylmelamine (0.01 mol.), and 14.8 g. of Soft amber-colored transparent resin which was glycidol (0.2 mol.) were heated to 170° C. when Sparingly soluble in hot water. an exothermic reaction occurred, the heating be Eacample IX ing discontinued, sending the temperature to 220 50 C. The reaction mixture was cooled to 190 C. and Valeroguanamine was prepared by the follow then heated to 190° to 200 C. for 15 minutes to ing method: - yield a brown wax, easily Soluble in hot water 50 g. of guanidine carbonate was dissolved in and readily dispersible in cold water. The prod Water and then neutralized with valeric acid. uct showed excellent softening properties when 55 This solution was then evaporated in a porcelain applied to cellulosic fabrics, yarn or threads. dish and the product, a stiff, white mass, was heated in a flask at 220 to 230° C. for 14 to 2 Eacample VI hours or as long as any trace of ammonia was 6.3 g. of melamine (0.05 mol.) and a plurality evolved. The liquid reaction medium was treated of 8. g. portions of glycidol (0.15 mol. per por with an excess of sodium hydroxide until it was tion) up to about two portions (i. e., 16.2 g.) of all in Solution. Upon cooling, the valeric acid glycidol were reacted by heating to 155° C. with base separated out in the form of rhombic nee stirring.