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 8 5 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. At this temperature a rapid rise in tem dles. During this interval, ammonia was evolved perature occurred and the heating was discontin and cyclicization was effected. The product was ued, the beaker and its contents being immersed 65 precipitated in the form of a thick crystalline in an ice bath. The temperature of the reaction mass which was collected on a filter, the filter reached 190° C. and on cooling a white hard resin cake was washed until the washing were no longer formed. The product was soluble in hot water, alkaline, whereupon the filter cake was dried and precipitating out upon cooling. This melamine recrystallized from hot water. Ihe product, glycidol condensation product was then heated O Valeroguanamine, solidified as a thick Crystalline together with an additional or third 8.1. g. portion mass which was collected on a filter, washed until of glycidol. At 120° C. an exothermic reaction no longer alkaline, dried and recrystallized from took place and the temperature rose to 180° C. hot water. The purified product crystallized in On cooling a very viscous, opalescent resin was ob the form of shiny needles having a M. P. of 172 tained. This resin was readily soluble in hot wa 5 to 173° C., soluble with difficulty in cold water, 2,881,121 3 but more easily soluble in hot water and readily this interval, the temperature of the reaction was soluble in alcohol and ether. One mol, equiv maintained at 132 to 137°C. by cooling the re alent of valeroguanamine was reacted with ten action vessel in a water bath. Cooling the mass, . mol. equivalents of glycidol by the method de yielded a pale yellow, transparent, viscous resin scribed in Example III. The viscous resin ob which was readily soluble in hot water. Its solu tained was readily soluble in water. tions foamed abundantly upon shaking and dis played highly desirable wetting and softening Eacample X properties. In a manner similar to that given in Example These reaction products of compounds contain X hexano guanamine was prepared by using O ing an ethylene oxide ring and a triazine or a caproic instead of valeric acid. The product, substituted triazine are of particular utility in the however, even after the addition of sodium hy formation of surface-active agents of the cation droxide could not be recrystallized. Hence the active type. For this reason they are well suited reaction mixture itself was used without further for wetting and softening wool, cotton, cellulose purification by dissolving the unpurified base in acetate, cellulose nitrate, viscose and similar ma dilute hydrochloric acid, the resultant solution terials. They are also useful in the emulsifica filtered and the filtrate partially evaporated and tion of mineral oils, glycerides, fats, oils and the allowed to form a crystalline product. This crys like. They find application in the formulation of talline product was dissolved in water and precipi printing inks, dye pastes, dye baths, leather prep tated with sodium hydroxide to yield the desired 20 arations and flotation agents. By their use it is product, hexanoguanamine having a M. P. of 177 possible to secure fullness, resistance to unravel to 178° C. The compound was reacted with 10 ing, and increased wet strength in rayons and mol. equivalents of glycidol giving a product other fabrics. They reduce the tendency of which was readily soluble in water. treated cloth materials to wrinkle or crease. 25 These products, particularly those having waxy Eacample XI or paste-like properties are useful assistants in 17 g. of stearic acid (0.6 mol.) was dissolved the textile, leather, paper, rubber, lacquer and in 300 cc. of denatured ethyl alcohol. The SO similar industries. In many of the examples, lution was heated to 65° C. and 36.3 g of guani particularly when polyamines are incorporated, dine (0.3 mol.) added, with occasional stirring, 30 or when temperatures are not carefully regulated, while carbon dioxide was being evolved. This re mixtures result containing several different sub action mixture was heated on a steam bath until stances. When used as textile assistants or in all the guanidine carbonate had dissolved and leather and similar processing industries it is not the alcohol entirely evaporated. The product re necessary to isolate the desired products; instead, maining, guanidine stearate, was heated while 35 the mixtures can be used directly. being stirred for 1 hour and 45 minutes at 215 The products described herein may be further to 230 C, on a hot plate. During this interval reacted with an amine, either primary or second ammonia was evolved and a cyclicization was ef ary, or with a fatty acid to yield highly desirable fected and the desired product, stearoguanamine, and useful surface-active Compounds. deposited on the sides of the container as a dark 40 In addition to the triazines above mentioned brown material. Purification of this crude prod various others may be reacted with the alkylene ict was difficult and therefore it was condensed oxides. Among such compounds may be specific without further isolation with ten mol. equiva ally cited guanamides, ammelides, cyanuric chlo lents of glycidol by heating at 110 to 220 C. The ride, their substitution products such as cyanuric resultant product gave turbid dispersions which 45 acid or polymerization products of these triazines foamed readily. It was found to be a useful wet such as melam, melem, melon, hydromelonic acid, ting, emulsifying, detergent and softening agent. and the like. Further examples of substituted In addition to ethylene oxide and glycidol, melamines include mono-, di-, and tri-laurylme various other ethylene oxide ring compounds may lamine, mono-, di-, and tri-octadecylmelanine, be used, namely propylene oxide, isobutylene ox 50 benzyl melamine, mono-, di-, and triphenyl mela ide, tetramethylene. Oxide, n-hexyl-ethylene ox mine and their isomers, monoformyl melanine, ideas well as ethylene chlorohydrin, epichlorhy and other monoacyl derivatives, diacetyl mela drin, chloroglycerol, and similar and correspond nine, triamino-melamine, hexa-chloro-triphenyl ing compounds having a reactive ethylene oxide melamine and other cyanuric chloro-anilides, tri ring present or which are capable of forming an 55 p-diphenylene-diamino-melamine, tri-carbanine ethylene oxide ring in the course of the reaction melamine, 2,4,6-tri-p-naphthyl melamine and the and their derivatives and substitution products like.line, 4,6-N-dimethylammeline,Among the ammelines such 4,6-N-diethylam as thio amme may be used. Various alkylene oxides or alkylene meline, monolaurylammeline or 4,6-dilaurylam oxide containing compounds may be used. How 60 meline, monostearylammeline or 4,6-distearylam ever, if the compound chosen for the reaction meline, mono- or di-phenyl ammeline, and the with a triazine has a low boiling point, i. e. like, may be reacted with ethylene oxide, glycidol ethylene oxide, propylene oxide, and the like, it and similar alkylene oxide containing compounds. is advantageous to carry out the reaction in a Among the guanamines, such compounds as the closed system and under elevated pressure in 65 following may be reacted with alkylene oxides: order to raise the temperature of the reaction to benzoguanamine, toluoguanamine, isobutylformo a point at which the reaction proceeds at a Sufi guanamine, 4-N-pentadecylformoguanamine, 4 ciently rapid rate to make the process commer N-piperidyliformoguanamine, 4-N-benzyl stearo cially feasible. guanamine, 4-N-phenyl lauroguanamine, the a. Eacaniple XII 70 idoguanamines, and the like. It is to be understood that the examples are 13.25 g. of lauroguanamine (0.05 mol.) and 22.2 merely specific embodiments and that the inven g. of glycidol (0.3 mol.) were heated with stirring tion is not limited thereto, but is to be broadly to 130 C, whereupon an exothermic reaction took construed within the scope of the appended place, continuing for about 15 minutes. During 5 claims.- 4. 2,381,121 I claim: amine, lauroguanamine and stearoguanamine, 1. A condensation product of glycidol and 4-N- each member of the group containing a replace p-tertiary amylphenyl formoguanamine. able hydrogen attached to a nitrogen atom, with 2. The process for the preparation of conden glycidol. sation products which comprises reacting a com 5 5. The condensation product of a compound se pound selected from the group consisting of a lected from the group consisting of a formoguan formoguanamine having an N substituted hydro amine having an N substituted hydrocarbon radi carbon radical, Valeroguanamine, heXanoguan cal, Valeroguanamine, hexanoguanamine, lauro amine, lauroguanamine and stearoguanamine, guanamine and stearoguanamine, each member of each member of the group containing a replace O the group containing a replaceable hydrogen at able hydrogen attached to a nitrogen atom, with tached to a nitrogen atom, with a compound con a compound containing an alkylene oxide ring. taining an alkylene oxide ring. 3. The process for the preparation of conden 6. The Condensation product of a compound se sation products which comprises reacting a COm lected from the group consisting of a formoguan pound selected from the group consisting of a 5 amine having an N substituted hydrocarbon radi formoguanamine having an N substituted hydro cal, Valeroguanamine, hexanoguanamine, lauro carbon radical, valeroguanamine, hexanoguan guanamine and stearoguanamine, each member amine, lauroguanamine and Stearoguanamine, of the group containing a replaceable hydrogen at each member of the group containing a replace tached to a nitrogen atom, with a compound con able hydrogen attached to a nitrogen atom, with 20 taining an ethylene oxide ring, a compound containing an ethylene oxide ring. 7. A condensation product of glycidol and 4. The process for the preparation of conden Valeroguananine. sation products which comprises reacting a com 8. A condensation product of glycidol and pound selected from the group consisting of a stearoguanamine. formoguanamine having an N substituted hydro 25 WAER P. ERICKS. carbon radical, Valeroguanamine, hexanoguan