US3832227A - Use of triazinylaminoalkyl phosphonates for the flameproofing of textiles - Google Patents

Abstract

A PROCESS FOR THE FLAMEPROOFING OF TEXTILES BY TREATING THE TEXTILE WITH A NOVEL CLASS OF TRIAZINYLAMINOALKYL PHOSPHONATES AND THE CROSSLINKING OF THE PHOSPHONATES TO YIELD A FIRE RETARDANT FINISHED FOR THE TEXTILE IS DISCLOSED. THESE TRIAZINYLAMINOALKYL PHOSPHONATES ARE FOUND TO BE LOW IN COST AND OF MINIMAL TOXICITY AND THEIR USE OF THE FLAMEPROOFING OF TEXTILES PROVIDES HIGHLY DURABLE FINISHES.

Description

United States Patent Oflice 3,832,227 Patented Aug. 27, 1974 USE OF TRIAZINYLAMINOALKYL PHOSPHO- NATES FOR THE FLAMEPROOFING OF TEXTILES Edward D. Weil, Hastings-on-Hudson, and Ralph Fearing, Bardonia, N.Y., assignors to Stauifer Chemical Company, Westport, Conn.

No Drawing. Original application June 26, 1970, Ser. No. 50,364, now Patent No. 3,755,323, dated Aug. 28, 1973. Divided and this application Oct. 2, 1972, Ser. No. 293,973

. Int. Cl. C09d 5/18 US. Cl. 117-136 3 Claims ABSTRACT OF THE DISCLOSURE A process for the fiameproofing of textiles by treating.

the textile with a novel class of triazinylaminoalkyl phosphonates and the crosslinking of the phosphonates to yield a fire retardant finish for the textile is disclosed. These triazinylaminoalkyl' phos'phonates are found to be low in cost and of minimal toxicity and their use for the fiameproofing of textiles provides highly durable finishes.

This is a division of application Ser. No. 50,364, filed June 26, 1970, now US. Pat. No. 3,755,323, issued Aug. 28, 1973.

BACKGROUND OF THE INVENTION The literature discloses numerous examples of attempts to achieve flame retardant textile finishes based on phosphorus containing triazine or melamine compounds. Early eflorts in this area are exemplified by the use of co-condensates of methylol melamines with acidic phosphorus compounds as is taught in US. Pats. Nos. 2,582,961; 2,781,281 and 2,711,998. These textile finishes were rather inefiicient inasmuch as they contained phosphorus which was in the form of acidic or ionic structures and which could, therefore, be leached out during laundering or which would undergo ion exchange with sodium and calcium ions in the wash water so as to render the phosphorus inelfectual for flame retardancy purposes. Such finishes are at best semi-durable, being capable of surviving, at most, only one or two launderings.

The prior art also discloses flame retardant textile finishes containing phosphoramide or phosphoramidate linkages, i.e.

0 ll PN linkages. Such'products are described in British Pat. No. 835,581 and in US. Pat. No. 2,971,929. However, the durability of phosphoramide finishes is again somewhat inadequate as noted by Jones et al., J. Applied Chem., 12 (9), 397405 (1962) and by Frick et al. in PB Report 151550 (US. Govt. Research Rept., 31, 340). Y

Another group of triazine-phosphorus flame retardants have the phosphorus attached directly to the triazine ring and are prepared by means of the Arbuzov reaction between cyanurie chlorides with alkyl phosphites. Although such compounds may be thought to possess a stable struc. ture, it has been found that they are, in fact, readily hydrolyzable as was commented upon by Morrison,=,.l. Org. Chem., 22, 444 (1957). Thus,.such textile finishes are quite deficient in their durability as noted by Frick et al. in PB Report 151550 (US. Govt. Research Rept.,

U.S. Pats. Nos.

the. co-condensation of phosphine derivatives with methylolmelamines, e.g. the use of dibutyl phosphine as taught in US. Pat. No. 3,050,522 and the use of tetrakis (hydroxymethyl) phosphonium-chloride or hydroxide as taught in British Pats. Nos. 882,993 and 384,785 and in 2,722,108; 2,809,941; 2,812,311 and 2,911,322. H l I Although the latter class' of textile finishes has been more successful than those described hereinabove, they still enjoy little or no commercial usage because of several inherent deficiencies. Thus, the phosphorus in these products is brought into the system in a relatively expensive form involving the use of 'a toxic phosphine. Secondly, the phos'phir'ie derivatives are, in general, quite toxic and ditficult to handle during the textile finishing operation wherein a careful control of pH is required.

- In addition, the tetrakis (hydroxymethyl) phosphonium chloride based finishes have been found to impart a generally,poor hand to the resulting finished fabrics. A critique of this-class of finishes may be found in Hall, Textile Recorder, February 1966, pp. 64-7 and Reeves I et al., Textile Chemist & Colorist, I, 365 (1969).

TECHNICAL DISCLOSURE OF THEdNVENTION It has now been discovered that anovelclass of rela- .tively inexpensive and non-toxic triazinylaminoalkyl phosphonatesis-capa'ble of Pmviding durable flame retar'dant finishes for both natural and synthetic textiles, which retain their flame retardant properties after numerous launderings.

' The triazinylaminoalkyl.phosphonatesof this invention may be described as those compounds corresponding to the structural formula:

I where A, B, and'C are selected from the group consisting 3I,- 340) and in US. Pat. No. 3,210,350. In addition, it

disclosed in the priorart are the products resulting from ene oxymethy lene, methylol, Ci-C alkoxymethyl and Z,

where is a phosphonate radical of the structure mon-qmsei (g mme).

where n i ..an integer having ayglue otfrofn-O, to 1,3 1,

and R are selected fromthegroiip consistingsof hydrogen and C -C alkylfand R and R are selected from the group consisting of alkyl, C C alkoxyalkyl, allyl, Q C 2-haloalkyl, C r-Q 2-hydroxyalkyl, and aryl,'with the ,proyiso.'thatratleast,.oneZ-group -is present in the molecule ot said triazinylaminoalkylphosphonate and that where R and/or R is a methylene ormethyleneoxymethylene group, the remaining valencethereof is attached to another triazine nucleus having substituents' as here defined.

group are:

elm-00H, N om-i o-cm") l J i O NEURA O-CH;GH=CH1) N N L J-Nnom0H N- omocrn) (cmocu, 001131) cmoorn onao cm "N N ar -e M a euro-cu,

7 ii lute-0H1 H (CHaOC N \\N N\ r CHz-P-OCH:

Within the above defined preferred group of triazinylaminoalkyl phosphonates, it may be noted that optimum results in the fiameproofing of cotton textiles, whereby the resulting treated textiles exhibit outstanding durability to laundering are obtained with mixtures containing two or more of the compounds corresponding to the structure:

yleneoxymethylene, C -C alkoxymethyl, and Z where Z is a phosphonate radical of the structure cr-r,i -[0(0 Ct alkynh, with the proviso that at least one of the R and R groups in the molecule is a Z group and that at least one of the R and R groups in the molecule is a methylol or C -C alkoxymethyl group and that no more than two of the R and R groups in the molecule is hydrogen.

The mixtures of the above defined compounds are products of the various processes described hereinbelow wherein precursor triazine compounds containing methylol groups in those positions where Z groups are desired in the final reaction product are reacted in liquid or slurry phases with a (C -C alkyl-O) P reagent until trivalent phosphorus is substantially absent from the reaction mix ture. Where C -C alkoxymethyl groups, rather than methylol groups are to be converted to Z groups, an appropriate precursor alkoxymethylmelamine is treated by means of one of two basic reaction processes: (1) an acid chloride-trialkyl phosphite method, several variations of which are described hereinbelow and (2) heating in the liquid phase with a (C -C alkyl-O) PHO reagent until bonds are substantially undetectable in the reaction mixture by the usual mercurometric or infrared analytical methods. In each of these three types of reactions for preparing these preferred mixtures of compounds, some condensation of methylol or C -C alkoxymethyl groups to methylene or methyleneoxymethylene bridges conjoining melamine nuclei occurs to a greater or lesser degree depending on the particular conditions of time, pH and temperature, etc. which are utilized in the reaction. The products of these processes are, therefore, usually mixtures of condensed as well as mononuclear compounds as is commonly the case in the art of melamine/formaldehyde resins. As was noted above, these mixtures are particularly useful for the flameproofing of cotton textiles and it is also to be pointed out that they are Well suited for this purpose since they may be applied from either aqueous or organic solvent solutions.

1 This invention, therefore, comprehends the preparation and use of: (1) mixed products of a typical resinous nature, both the individual components of these mixtures and the mixtures per se being within the scope of the invention and (2) individual molecular species such as can be systematically synthesized as, for example, from cyanurie chloride by means of a process involving the stepwise replacement of the chlorine atoms by reagents containing HNR R groups wherein R and R are as defined above and which may be the same or different.

As has been noted, there are a number of preparative procedures which may be used to synthesize the novel triazinylaminoalkyl phosphonates, and the mixtures thereof, of this invention. In brief, the various processes for the preparation of these triazinylaminoalkyl phosphonates comprise reacting, at from about 20200 C., at least one precursor triazine compound selected from the group consisting of polymethylol or methylolated melamines, polyalkoxymethylmelamines, cyanuric chloride, chloromethylmelamine and Q-C alkoxymethyl melamines and from about 0.3 to 6 moles, per mole of said precursor melamine compound, of at least one phosphorus containing reagent selected from the group consisting of trialkyl phosphites, phosphorus trihalides, dialkyl l-aminoalkyl phosphonates, dialkyl phosphonates and hydroxyalkyl phosphonates. The details of these various processes are described hereinbelow.

PROCESS NO. 1

The derivatives of this invention can be prepared by means of a liquid phase reaction between from about 0.3 to 6, and preferably 1-5, moles of a trialkyl phosphite, such as triethyl phosphite, and one mole of a methylolmelamine or of a substituted methylolmelamine having suflicient methylol groups to react with substantially all of the trialkyl phosphite. The reaction may be conducted with pure methylolmelamines which dissolve when phosphonated or with crude methanolic reaction solutions or inert solvent suspensions such as one might directly obtain by means of known prior art procedures from melamine and formaldehyde. The reaction is conducted at temperatures in the range of from about 0 to 200 C. until all of the phosphite has reacted to form phosphonate groups as may be determined by such means as a mercurometric assay for phosphite groups, by nuclear magnetic resonance or by distillation of the evolved alkanol byproduct. The reaction mixture may then be stripped, usually under vacuum, at a temperature of from about 0 to 200 C. yielding the desired triazinylaminoalkyl phosphonate as a residue which may be in the form of a syrup or gummy resin that is soluble in water and in many organic solvents such as alcohols, trichloroethylene and chloroform. The preparation of triazinylaminoalkyl phosphonates by means of this type of reaction is surprising since 1) reaction conditions, even when the methylol melamine is insoluble in the trialkyl phosphite, are unexpectedly mild, (2) the reaction is rapidly quantitative (3) pure intermediates are not required, and (4) the pentavalent phosphonate is obtained rather than the phosphite which might be expected by mere transesterification,

PROCESS NO. 2

These-derivatives can be prepared by means of the reaction, in the liquid phase, between one mole of an alkoxymethylmelamine, such as hexamethoxymethylmelamine, about 0.1 to 2 moles of a phosphorus trihalide, such as phosphorus trichloride and from 0.3 to 6 moles of a trialkyl phosphite such as trimethyl phosphite. The latter reagent is first preferably added to the melamine derivative, although premixing with the phosphorus trichloride, as well as other modes of addition, are also permissible. It is believed that the conversion is a sequence of two exothermic reactions which is carried out at a temperature of from about 20 to 180 (3., and preferably at 0-120" 0., and for a period of from about 1 minute to 50 hours de* pending upon the temperature that is utilized. The first reaction in this sequence is a conversion, by PCl of the methoxymethyl groups on the resin intermediate to the form of chloromethyl groups while the second reaction in the sequence is between these chloromethyl groups and the trialkyl phosphite to produce the desired amino methylphosphonic diester groups. If the phosphorus trichloride is premixed with excess trialkyl phosphite, dialkyl phosphorochlorid'ite is formed which can react with the resin in a manner which can be represented as a one step overall equation. In either case, the reaction mixture may be heated, after the addition of the trialkyl phosphite, until trivalent phosphorus is no longer detectable, whereupon it is stripped of the alkyl chloride by-product.

PROCESS NO. 3

Triazinylaminoalkyl phosphonates can be prepared by reacting one mole of cyanuric chloride with from about 1 to 3 moles of a dialkyl l-aminoalkylphosphonate, such as diethyl 1-aminoisopropylphosphonate, in the optional presence of an equivalent amount of a base which serves as an HCl acceptor as, for example, triethylamine, sodium carbonate, pyridine or the like. Or, the dialkyl l-aminophosphonate may itself serve as the acid acceptor in which case one mole out of each two moles introduced will serve in this capacity while the other will be introduced into the reaction product molecule. This reaction is conducted in the liquid phase, preferably in a solvent for cyanuric chloride, at a temperature of from about 0 to 150 C. until the desired 1 to 3 moles of chloride ion is released. After removal of the by-product chloride salt formed by reaction of the base with the evolved hydrogen chloride, the desired reaction product is generally isolated by evaporation of the solvent, by chilling, or by addition of a non-solvent therefor. This process is especially useful for preparing halotriazinylaminoalkylphosphonates, and specific isomers of the compounds of this invention, since the three chlorine atoms of cyanuric chloride react stepwise, the first very rapidly, the second much less rapidly, and the third quite slowly. By successive use of different reactants, having the structure NHR R i.e. ammonia, primary amines or secondary amines, compounds can be produced having --NR -R groups, as defined above, where at least one of the R or R groups is a phosphonate group.

The synthesis of individual molecular species is straightforward by this method. Thus, two or three different N-R -R groups can be placed on the triazine ring. The reaction conditions for these successive steps are in themselves known for non-phosphonated amines, and are described, for example, by Gysin and Knusli, in Advances in Pest Control Research, Vol. III, Interscience Publishers, Inc. New York, pp. 295-300 (1960). The preparation of the requisite HNR R reactants where at least one of the R and R groups is a phosphonoalkyl .group Z may be conducted by means of any of the methods set forth in Vol. 12/1, pp. 483-489 of Houben-Weyl, Methoden der Organischen Chemie.

PROCESS NO. 4

The derivatives of this invention can be prepared by first reacting one mole of an alkoxymethylmelamine with from about 0.3 to 6, preferably 1 to 5, moles of phosgene gas at a temperature of from about 0 to 50 C. for a period of about 1 to 5 hours to obtain a chloromethylmelamine. This reaction is set forth in US. Pat. No. 3,317,529. After vacuum distilling to remove volatiles, each mole of the residue is slowly reacted with about 0.3 to 6, preferably 1 to 5, moles of a trialkyl phosphite, such as triethyl phosphite, at 20 to C.; the concentration of the latter reagent being equivalent to the number of moles of phosgene used is the prior step. Distillation yields an alkyl chloride as a by-product leaving the de: sired triazinylaminoalkyl phosphonate as a residue.

PROCESS NO 5 These derivatives can be prepared by reacting about 0.3 to 6, preferably 1 to 5, moles of a dialkyl phosphonate, such as a dimethyl phosphonate, with one mole of an alkoxymethylmelamine, such as hexamethoxymethylmelamine at a temperature of from about 20 to200 C. for a period of from about 0.1 to 48 hrs. until substantial completion of the reaction is shown by infra-red, nuclear magnetic resonance or oxidimetric analysis for unreacted dial-' kyl phosphonate or by dist'alliation of the desired quantity of -by-product alkanol. A trialkyl phosphite may also be present in the system in order to scavenge any acids formed by side reactions. If desired, the resulting reaction mixture may be used as is or it may first be stripped free of traces of unrecated dialkyl phosphonate and by-product alkanol.

PROCESS NO. 6

Another synthetic route involves the reaction between one mole of an alkoxymethylmelamine, such as hexamethoxymethylmelamine, and 0.3 to 6, preferably 1 to moles of a trialkyl phosphite, such as trimethyl phosphite, and from about 0.3 to 6, preferably 1 to 5, moles of a proton donor which may be an organic acid, such as acetic acid, a. phenol or an alcohol. This reaction is run at a temperature of from about 20 to 200 C. for a period of from about 0.1 to "48 hours until substantial completion of the reaction is shown by infra-red, nuclear magnetic resonance or oxidimetric analysis for unreacted dialkyl phosphonate or by distillation of the desired quantity of by-product alkanol. If desired, the resulting reaction mixture may be used as is or it may be stripped free of traces of unreacted trialkyl phosphite and proton donor. The alkylation product of the proton donor, such for example as alkyl acetate where acetic acid is used as the proton donor, is also formed as a by-product and may be removed by distillation.

PROCESS NO. 7

A synthetic route suitable for the preparation of the compounds of this invention where i Z=CHzOCR R P(OR comprises reacting, in the liquid phase, 1 mole of a precursor melamine derivative having a methylol or 0 -0 alkoxymethyl group where the group Z is to be present in the product, with from about 0.3-6 moles of a selected dialkyl l-hydroxyalkyl phosphonate having the structure 0 HO OR IUi" (ORQz.

This reaction is preferably run at about 20-200 C. in the presence of an acid catalyst until substantially one molar equivalent of water (in the case where the precursor melamine compound contains a -CH OH group) or alcohol (in the case where the precursor melamine compound contains a CH Oalkyl group) has been evolved, as determined by means of some suitable analytical technique such as by distillation and collection of the water or alcohol.

In any of the above-described processes, where the resulting product contains CH OH groups, it is possible to subsequently etherify such CH OH groups by the addition of an alcohol, preferably a primary alcohol, in the presence of an acid catalyst. Such etherification processes are, of course, well known in the melamine/formaldehyde resin art. Furthermore, in any of the above described processes, where the resulting product contains NH groups, it is possible to methylolate such NH groups so as to convert them into N(CH OH) groups by reaction with formaldehyde in the manner well known in the melamineformaldehyde art. Such N (CHQOH) groups may then be etherified in the manner described hereinabove.

In conducting the above described reaction processes of this invention, those involving the use of at least one liquid reactant can be run without the use of a diluent or solvent. However, in order to improve upon heat transfer, case of mixing and other engineering considerations, diluents or solvents can be employed with the proviso that they are sufficiently non-reactive towards the respective reagents and reaction products. Suitable diluents include, for example, hydrocarbons, halogenated hydrocarbons such as chloroform, trichloroethylene, and the like. In some cases ketones, alcohols and water can be used provided that the reaction rate of these solvents with the trivalent phosphorus compound are slower than the desired reaction.

In the appropriate reaction procedures described hereinabove, trimethyl, triethyl, tripropyl, tributyl, trioctyl, trioctadecyl, triallyl, tris-2-chloroethyl, tris-2-chloropropyl, dimethyl ethyl, diethyl propyl, methyl diethyl and ethyl dipropyl phosphite, etc. are all applicable for use as trialkyl phosphites; dimethyl, diethyl, dipropyl, dibutyl, diallyl, bis (2-chloroethyl), dioctyl, methyl ethyl and methyl propyl phosphorochloridite, etc. are all applicable for use as dialkyl phosphorochloridites; dimethyl l-aminomethyl phosphonate, diethyl l-aminomethyl phosphonate, diethyl laminoethylphosphonate, dimethyl l-aminoethylphosphonate, diethyl lethylaminornethylphosphate, diisopropyl l n propylaminoisopropylphosphonate, tetraethyliminobis methylphosphonate and diallyl 1 methylamino n butylphosphonate, etc. are all applicable for use as dialkyl l aminoalkylphosphonates; dimethyl, diethyl, di-propyl, dibutyl, diallyl, 'bis(2-chloroethyl), dioctyl, didodecyl, dioctadecyl, methyl ethyl and methyl propyl phosphonate, etc. are all applicable for use as dialkyl phosphonates; and, dimethylolmelamine, trimethylolmelamine, tetramethylolmelamine, pentamethylolmelamine, hexamethylolmelamine, tetramethylol methylenebismelamine, tris(methoxymethyl)melamine, tetra-, pentaand hexakis(methoxymethyl)melamine, partially methylated tri-, tetra-, pentaand hexamethylolmelamine, and, partially or fully ethylated tri-, tetra-, penta-, or hexamethylolmelamine are all applicable for use as alkoxymethylmelamines. Also suitable are methoxymethylated methylene (or methylene oxymethylene) bismelamine dimers and trimers, etc.

The novel triazinylaminoalkyl phosphonates of this invention may be characterized as colorless viscous liquids or syrups or as readily fusible resins all of which are at least partially soluble in water and in many of the common organic solvents such, for example, as alcohols, ketones, methylene chloride, methyl chloroform, chloroform, ethylene dichloride, trichloroethylene, xylene and perchloroethylene. At 50 0., these compounds generally hydrolyze at a rate of less than about 1%, by weight, per hour. They are distinguished from the phosphorus substituted melamine compounds of the prior art since they are non-ionic neither ionizing nor, as noted above, undergoing extensive hydrolysis in water under ordinary conditions of use. And, as will be noted, hereinbelow, these compounds can be cured, by acid catalyst, so as to form insoluble thermoset resins.

As has already been noted, hereinabove, the triazinylaminoalkyl phosphonates of this invention provide excellent results when utilized as fiame proofing finishes for both natural and synthetic textile materials. It is also noteworthy to point out that the finishes derived from these derivatives may also be characterized as durable press finishes since they permit the textiles to which they have been applied to retain their orginal shape and remain wrinkle-free after being laundered without any need for having them ironed.

Textiles may be treated with the derivatives of the invention while the latter are dissolved in an aqueous medium or, if desired, they may be applied while in the form of organic solvent solutions utilizing such essentially non-polar solvents as methylene chloride, ethylene dichloride, trichloroethane, perchloroethylene, etc. and mixtures thereof. This ability to employ the novel derivatives of this invention in organic solvent media, the use of which is becoming increasingly more important in the textile finishing art, represents a distinct advantage with respect to the flame retardant compositions of the prior art which generally lacked organic solvent solubility.

The solutions, either aqueous or organic solvent, containing one or more of the triazinylaminoalkyl phosphonate derivatives of this invention, may be applied to textiles by the use of any desired procedure. It is merely necessary to have the triazinylaminoalkyl phosphonate absorbed throughout the mass of the textile and/or to apply it to at least one surface thereof by means of any convenient procedure. Thus, they may be applied by being sprayed onto one or both surfaces of the textile or, as is more frequently the case, the textile may be passed or padded through the solution while the latter is being held in a tank or other suitable container. Such a process is commonly referred to as a padding technique with the solution being referred to as a padding bat or padding solution.

The concentration of the triazinylaminoalkyl phosphonate within the padding bath, or other applicable solution, will be dependent upon a number of factors including the nature of the fibers which comprise the textile, the weight and weave of the textile, the degree of flameproofing that is desired in the finished textile, as well as other technical and economic considerations known and understood by those skilled in the art. However, it is generally desirable that the padding bath should contain from about to 75%, by weight, of one or more of the triazinylaminoalkyl phosphonate; the latter concentration being sufiicient to deposit a finish upon the textile which will contain from about 5 to 75 by weight of the textile, of the triazinylaminoalkyl phosphonate which, in turn, will provide the thus treated textile with about 0.2 to 7.5%, by weight of the textile, of phosphorus. Again, it is to be stressed that the latter limits are merely illustrative and may be varied so as to provide a textile finish having any desired degree of flame retardancy.

Subsequent to their deposition upon and/or their absorption by a textile, the triazinylaminoalkyl phosphonates contained within the padding solution may be cured, or crosslinked, so as to yield a highly durable, fire retardant finish. This curing operation may be accomplished by maintaining the treated fabric for a period of from about one hour to 10 days at ambient temperatures, or, a more rapid cure may be affected by the application of heat at temperatures of up to about 200 C. Under the latter conditions, a curing time as short as only about one second may be required. Additional control of the curing rate may be achieved by the optional presence in the padding solution of various adjuvants including pH controlling substances such as acid releasing salts which accelerate or catalyze the rate of cure or basic substances which will, on the other hand, retard the cure rate.

Rate retarding substances include, for example, alkali metal hydroxides, such as sodium hydroxide, and alkali metal bicarbonates and carbonates such as sodium bicarbonate and sodium carbonate. Cure accelerators, or catalysts, are exemplified by ammonium, alkaline earth and transition metal salts such as ammonium chloride, magnesium chloride, zinc chloride and zinc nitrate; amine hydrochlorides such as diethanolamine hydrochloride triethylamine hydrochloride; and, organic and inorganic acids such as acetic, oxalic, maleic, malic, citric, trichloroacetic, hydrochloric and phosphoric acids and alkyl acid phosphates. These optional curing rate retarders and accelerators may, respectively, be used alone or in combination with one another in a concentration which is sufficient to attain the cure rate desired by the practitioner. An exception to the foregoing discussion regarding catalysts and retarders comprises the compositions of this invention wherein A, B, or C are halogen. In these special cases,'alkaline substances are accelerators of the desired reaction for the attachment of these special reagents to a cellulosic textile substrate while acid substances retardthis reaction.

Another class of optional adjuvants which may be included withinthe solution containing the triazinylaminoalkyl phosphonate derivatives of this invention, when the latter are being used for the preparation of flame retardant textile finishes, are various so called co-reactants. These co-reactants are materials which will undergo a reaction with the triazinylaminoalkyl phosphonate and which are used for various purposes such as to control the crosslink density of the finish, to improve the hand and durability of the finished textile as well as its durability, flame retardance, durable press, laundering and crease resistance properties. Particularly useful as co-reactants are aminoplast forming reagents such, for example, as urea condensation products of urea-formaldehyde, ureaglyoxal or urea-glyoxal-formaldehyde; melamine; melamine-formaldehyde condensation products; N methylolated O-alkyl carbamates; ammonia, and formaldehyde, Each of the above described co-reactants are capable of use either alone or admixed with one another. It is to be understood, that the use, in the above given list, of the term urea is meant to include within its scope various cyclic ureas such, for example, as ethyleneurea, propyleneurea, uron, triazones, glyoxaldiurein and isocyanuric acid.

Other suitable co-reactants include formamide, acetamide, propionamide, dialkyloxyphosphonopropionamide or the N-methylol derivatives thereof, tetrakis(hydroxymethyl) phosphonium chloride or hydroxide, trimethylolphosphine, aminated phosphonitrilic chloride, phosphoric triamide and termal condensation products thereof, ammonium phosphates, glycols such as the phosphorus-containing glycols and the hydroxyalkyl esters of all phosphorus acids. Particularly useful as coreactants are the novel ureidoalkylphosphonates disclosed in copending application Ser. No. 50,304, filed June 26, 1970 and now US. Pat. No. 3,763,281.

In general, the triazinylaminoalkyl phosphonate finishing reagents of this invention can be made to condense during the above described curing process with co-reactant compounds having either -OH, -NH, NCH OH or NCH OCH groups and the proper selection of such co-reactants in order to achieve a desired modification of crosslink density, crease resistance, durable press, and flame retardant properties will be evident to those skilled in the art. Some specific co-reactants which may be named are: dimethylolmelamine; trimethylolmelamine; dimethylol dihydroxyethyleneurea; trismethoxymethylmelamine; dimethyloluron; dimethylolethyleneurea; dimethylolpropyleneurea; N,N dimethylol methyl carbamate; N,N-dimethylolethylcarbamate, N,N-dimethylol Z-hydroxyethylcarbamate; N,N-dimethylol methoxyethylcarbamate; urea methylolurea; dimethylolurea; partially methylated pentamethylolmelamine; tetramethylolglyoxaldiurein; N-methylol 2 (dimethoxyphosphono) propionarnide; and N-methylolacrylamide.

Various other classes of optional adjuvants may also be present in the textile finishing solutions of this invention. Thus, the padding bath containing the triazinylaminoalkyl phosphonates of this invention, and the textile finishes derived therefrom, may contain other ingredients in order to modify the finish in accordance with practices known to those skilled in the art of textile finishings.

For example, these other adjuvants may include hand modifiers such as polyethylene emulsions, long chain fatty amides, paraffin waxes, long chain quaternary ammonium salts, and the like; auxiliary flame retardants such as chloroparaflins, chlorinated polyethylene, polyvinyl chloride, polyvinylidene chloride, homoor copolymers of vinylphosphonates and antimony compounds such as anti mony oxide, antimony phosphate, and the like; soil release, anti-soiling agents and water and oil-repellents such as polyfluoroalkyl compounds, silicones, acrylic acid copolymers, and the like; abrasion resistance agents such as polyacrylates, polyurethanes, and the like; colorants and color-modifying agents such as dyes, pigments, bleaches, anti-fading agents, ultraviolet screening agents and the like; anti-static agents such as quaternary ammonium compounds; humectants; bonding agents; antimicrobial agents which will supplement the inherent rot-resistance and antimicrobial action of the triazinylaminoalkyl phosphonate containing finishes of this invention; and, pH modifying agents. The padding bath may also contain adjuvants intended to directly facilitate the padding operation per se, such as emulsifying and wetting agents, swelling agents, and buffers.

All types of textiles may be treated by means of the process of this invention so as to provide them with durable, fire retardant finishes. Thus, one may treat textiles derived from natural fibers such as cotton, wool, silk, sisal, jute, hemp and linen and from synthetic fibers including nylon and other polyamides; polyolefins such as polypropylene; polyesters such as polyethylene terephthalate; cellulosics such as rayon, cellulose acetate and triacetate; fiber glass; acrylics and modacrylics, i.e. fibers based on acrylonitrile copolymers; saran fibers, i.e. fibers based on vinylidene chloride copolymers; nytril fibers, i.e. fibers based on vinylidene dinitrile copolymers; rubber based fibers; spandex fibers, i.e. fibers based on a segmented polyurethane; vinal fibers, i.e. fibers based on vinyl alcohol copolymers; Vinyon fibers, i.e. fibers based on vinyl chloride copolymers; and, metallic fibers. Textiles derived from blends of any of the above listed natural and/or synthetic fibers may also be treated by means ofthe process of this invention.

As used in this disclosure, the term textile r textiles is meant to encompass woven or knitted fabrics as well as non-woven fabrics which consist of continuous or discontinuous fibers bonded so as to form a fabric by mechanical entanglement, thermal interfiber bonding or by use of adhesive or bonding substances. Such non-woven fabrics may contain a certain percentage of wood pulp as well as conventional textile fibers in which case part of the bonding process is achieved by means of hydrogen bonding between the cellulosic pulp fibers. In non-woven fabrics, the finishing agents of this invention can serve not only as flame retardant finishes but can also contribute to the interfiber bonding mechanism by serving as all or part of the adhesive or bonding resin component. This dual role can also be played by the finishing agents of this invention in fabric laminates where the finishing agent can at the same time serve as the interlaminar bonding agent and as the flame retardant. In both of these systems, i.e. non-woven fabrics and laminated fabrics, the finishing agents of this invention can also be blended with the usual bonding agents such, for example, as acrylic emulsion polymers, vinyl acetate, homoand copolymer emulsions, styrene-butadiene rubber emulsions, urethane resin emulsions, polyvinylchloride emulsions, polyvinylchloride acrylate emulsions, polyacrylates modified by vinylcarbox ylic acid comonomers and the like.

In addition to being used for the preparation of fire retardant textile finishes, the novel triazinylaminoalkyl phosphonates of the invention may also be used in various other applications in which. their fiame retarding properties are advantageous. These include their being cured into thermoset resins which may be employed for the preparation of molded objects and coatings or for laminating or impregnating paper or wood. When used in molding resins, the novel compositions of this invention may be compounded with other thermosetting resins as well as with various fillers such as wood flours, clays, mica and the like. The uncured or thermoset resins of this invention may also be used as flame retardant additives for other resins. For example, they may be employed to crosslink hydroxyl containing polymers such, for example, as alkyds and curable acrylic polymers so as to form coatings and laminates.

In addition, certain of these triazinylaminoalkyl phosphonates display useful biological properties which include, for example, their ability to function as pre emergence herbicides especially in those compounds of this invention'where A and/ or B is halogen. In the latter use, these compounds need merely be applied to the locus of the weeds, i.e. the soil, the weeds per se or to the water in the case of aquatic weeds, in a phytotoxic concentration such, for example as from 0.5 to 50 pounds per acre depending upon the weed species, soil type, duration of control required and similar factors.

12 The following examples further illustrate the embodiment of this invention. In these examples all parts given are by weight unless otherwise noted.

EXAMPLE I This example illustrates the preparation of one of the novel triazinylaminoalkyl phosphonates of this invention by means of reaction process No. 1 as described hereinabove.

A commercially available trimethylolmelamine (43.2 g.) and 100 g. of triethyl phosphite were stirred and heated slowly up to 153 C. until ethanol ceased to evolve (6 hours) whereupon the reaction mixture was stripped under vacuum at 150 C. to leave 91.2 g. of syrupy residue which set to a colorless water soluble solid, mp. -1l0. The product had a reasonable proton N.M.R. spectrum, LR. spectrum, and analysis (calc. P 13.6, N 18.4; found P 13.7, N 18.8) for O IIIHCHz1 (0 C2 5):

N HOCHzNH- k J-NHCHzP (O C H Comparable triazinylaminoalkyl phosphonate derivatives were obtained by the reaction, under the above described conditions, of trimethylolmelamine with trimethyl phosphite.

EXAMPLE II This example illustrates the use of one 'of the novel triazinylaminoalkyl phosphonate derivatives in this preparation as a thermoset coating and as part of an epoxy resin system.

Part A.-An aqueous solution containing 20 parts of water, 10 parts of the derivative whose preparation is described in Example 1, hereinabove, and 0.2 parts of zinc nitrate was allowed to dry on the surface of a wooden board and was then heated for 12 hours at 95 C. The resultant cured coating was hard, infusible, clear, and completely resisted attack by water or aqueous sodium carbonate. When exposed to flame, this coating intumesced yielding a foamy char which affords fire protection to the underlying flammable substrate.

Part. B.-A mixture of 2.8 parts of the tria-zinylaminoalkyl phopshonate derivative whose preparation was described in Example I, hereinabove, and 3.4 parts of Epon 828 (a commercial epoxy resin sold by the Shell Chemical Company which is mainly the diglycidyl ether of bis-phenol A) was heated to 95 C. and stirred to, obtain a clear melt which was degassed under vacuum and then allowed to cure over 10 hrs. at 95 C. The cooled resin was clear, had a Barcol hardness of 37, and was selfextinguishing when ignited by means of a Bunsen burner.

EXAMPLE III This example illustrates the preparation of another of the novel triazinylaminoalkyl phosphonates of this invention; the procedure utilized in this case being reaction process No. 2 as described hereinabove. Y I

Phosphorus trichloride (27.5 grams, 0.2 mole) was mixed with 200 grams of trimethyl phosphite and maintained at 30-40 C. for three hours so asto obtain redistribution to a mixture estimated as containing up'to 0.6 mole of dimethyl phosphorochloridite and 1.2 moles of excess trimethyl phosphite. This was then slowly added at 50 C. to 156 grams of hexamethoxymethylmelamine (0.4 moles). The exothermic reaction period was followed by an additional 1 /2 hours of heating (65-75 C.).

Successive stripping at 250 mm., mm., and 0.1 mm., yielded the expected methyl chloride (B.P. 22) and excess trimethyl phosphite. The desired reaction product weighed 200 grams. Analysis calculated for 1% phosphonate groups per mole:

Total P, 9.1; P nil. FoundP, 8.0; P 0.64.

By means of column chromatography on silica gel, monoand diphosphonate fractions may be separated and isolated. However, the crude mixture is suitable for use in many applications such, for example, as the below described textile treatment process- EXAMPLE IV This example illustrates the use of one of the novel triazinylaminoalkyl"phosphonate derivatives in the preparation of a durable, .flame'retardant textile finish.

The following formulation was prepared:

This solution was brought to a pH of 6 by the addition ofaqueous ammonia and 'was then padded onto 8 oz. cotton squares to a 75-97% wet pickup, dried and cured at 161 C. for 4.5 minutes. The add on of the phosphonate, after warm water rinsing, was found to be in the range of 2.1 to 32% of the totalweight of the treated textile. The concentration of phosphorus found in the cloth samples was 1.08 to 1.3% of the total weight of the treated textile;

Flame-retardancy was evaluated by the St. Hilaire semicircular frame test as described by P. St. Hilaire, K. Knoettner and L. E. Rossiter in Proc. A.A.T.C.C. (Nov. 18, 1968), p. 61. In this test, each of the curved or semicircular mounted textile samples is oriented at various positions ranging from vertical to horizontal and a flame is ignited at its lower edge. If the textile is self-extinguishing in the vertical position, it is acceptable for use in all applications. If self-extinguishing when positioned at a 45 angle but not self-extinguishing in a vertical position, it is acceptable for use in less critical applications. However, if the treated textile is only self-extinguishing when in a horizontal-position, the finish is only marginally acceptable and should be used only in non-critical applications. Atthe lowest add-on, i.e. 21%, the cloth did not maintain a flame, with only a 1%" char length resulting at the nearvertical end of the curved test strip.

Moreover, after a three hour 90-95 C. treatment with 210.5% soap-0.2% sodaash solution, the samples lost about 2% of weight (10% of the phosphonate add-on). Thereafter, in the flame retardancy test, flames were extinguisllied without afterglow at angles of 40-70 from the vertica EXAMPLE v This example illustratesthe preparation of two more of the novel triazinylaminoalkyl phosphonates of this invention, the procedure utilized in this case being reaction process No. 3 as described hereinabove.

To 3.68 grams of cyanuric. chloride in 40 ml. of acetone, therejwas added 16 grams of diethyl l-aminoisopropylphosphonate and the resulting mixture was then heated at reflux for 1 hour. On cooling and addition of ethyl ether, 'crystals were'obtainedwhich were identified by their water solubility and infrared spectrum as the hydrochloride of diethyl 1raminoisopropylphosphonate. The filtrate was evaporated andthe gummy residue triturated with water to removemore hydrochloride. The residual material was taken up in ether and chilled to obtain successive crops "comprising twocompounds. The less soluble was a colorless crystalline solid, m.p. 152-1525 C. having thecorrect analysis (Cl calcd. 21.6, C1 found 21.7) for Reaction of this product with ethylamine aifords the corresponding ethylaminochlorotriazinylisopropyl phosphonate which is an efiective pre-emergence herbicide.

The more soluble compound derived from the residual material was a. colorless crystalline solid, m.p. 128 C. having the correct analysis (Cl calcd. 7.5, Cl-found 7.5.). for

When applied to weed-infested soil pre-emergence at 20 lbs./ acre, this compound substantially prevented the growth of annual grassy weeds.

In a similar manner, cyanuric chloride is reacted with ethylamine and then with diethyl l-aminoethylphosphonate in order to obtain 2-chl oro-4-ethylamino-6-(1- [diethoxyphosphino]ethylamine) 5 triazine which also functions as a pre-emergence herbicide.

EXAMPLE VI This example illustrates the preparation of another of the novel triazinylaminoalkyl phosphonate derivatives of this invention, the procedure utilized in this case being reaction process No. 4 as described hereinabove.

A total of 26 grams of hexamethoxymethylmelamine was treated With a slow stream of 20 grams of phosgene gas at room temperature over a period of 2% hours.

Vacuum stripping removed the methyl chloroformate by-product. To the remaining residue, there was slowly added 0.2 moles of triethyl phosphite (34 grams in tetrahydrofuran).

Stripping at 55 C. removed the ethyl chloride and about 14% of the original triethyl phosphite. Product analyses, of the residue remaining after stripping at C./0.01 mm. yielded 42 grams, of a product containing about 2 /2 phosphonate ester groups per mole.

Calculated for 0 ll CsNa(CH2OCH3)3[( 2 2 15): atris(PO Et Found, percent TotalP 13.1% 11.1

Trivalent P Nil 0.03

By means of column chromatography, it is possible to separate the difrom-the tri-phosphonated isomers from the latter product.

EXAMPLE VII This example again illustrates the use of another of the novel triazinylaminoalkyl phosphonates of this invention in the finishing of textiles.

A total of 3.75 grams of the triazinylaminoalkyl phosphonate derivative whose preparation was described in Example VI, hereinabove, was mixed with 0.7 g. urea; a nonionic wetting agent comprising 0.75 grams of a 5% aqueous solution of octylphenoxypolyethoxyethanol; and, 0.75 grams of a zinc nitrate eatalysL'The resulting formulation was then diluted to 10 grams by the addition of water. The preparation-of the latter formulation was. then repeated with the addition, in this instance, of 1.0 grams of a co-reactant comprising a'50% aqueousrsolutionsof a 15 16 partially methylated polymethylolmelamine and dimeth- The hand of this treated fabric was more pleasing than yloiated ethyleneurea. that of the previously prepared sample. The LOI of 28.1, One gram strips of 8 oz./yd. cotton twill fabric were observed after cure, was reduced only to 27.8 after the soaked in each of the resulting solutions, wrung to a unihot water rinse and five detergent washes as described form add-on and dried. The following table reveals that the above thus indicating good retention and durability on the losses of phosphorus during curing and hot rinsing, such part of this additive.

losses being evident when the melamine phosphonates l made by means of reaction process No. 2 (see Examples EXAMPLE IX 1 III and IV) are used as finishing agents, are considerably This example illustrates the preparation of a triazinylreduced with the phosphonates resulting from the use of aminoalkyl phosphonate by means of reaction process No. reaction process No. 4. 5 as described hereinabove.

RELATIVE LOSS OF PHOSPHORUS AS A PERCENTAGE OF THE ORIGINAL PHOSPHORUS ADD-ON Method of preparation of additive compound, Process oi- Example 6 plus Example 3 Example 6 the coreactant Loss on drying plus curing at 160 C 8.5% of original P 2% of original P 243% 0! original P. Loss in a 56 0. water rinse 18% of original P 7% of original P-. 645% of original P. Loss in a soap-soda ash boiL- 14% of original P 15% of original P. 12% of original P. 1 LOT /percent P 30.5/1.1 26.8/114 26/1.5.

l LOI=Li1niting oxygen Index as determined by the rocedure described by Fenimore and Martin in the November, 1966 issue of Modern Plastirm. In brief, this procedure directly re ates flame retardaney to a measurement of the minimum ercentage concentration of oxygen in an oxygenmitrogen mixture which peirimits the sample to burn; the LOI being calculated as to ows:

I=X--X100 XlOzl'HNE Thus, a higher LOI is indicative of a higher degree oi flame retardancy.

EXAMPLE VIII A mixture of 330 g. (3 moles) of dimethyl phosphonate d 390 g. (1 mole) of hexamethoxymethylmelamine was This example illustrates the preparation, on a large an a scale, of a triazinylaminoalkyl phosphonate by the use of 30 beam? at 130'160 over peilod of 5 hours W i reaction process 2 allowing 88 g. of distillate, primarily methanol, to d still A total of 625 granis of hexamethoxymethylmelamine off at a vapor temperature which did not exceed the boiling (1 6 m 01 es) was dissolved in 372 grams of trimethyl phos point of methanol. The residual reaction mixture was then i (3 0 moles) and treated dropwise at 2 32o stripped free of unreacted dimethyl phosphonate and about P 35 45 g. of volatile by-products leaving the desiredphos- 11 rams of PCI 0.8 mole, 2.4 e uivalents of ma gamed with 6 grams of toluege After the phonated trrazrnylamrnoalkyl reaction product as a colorless viscous syrup.

three hour addition period, the mixture was left standing I overnight. Distillation at appropriate pressures yielded at Ana for least 80 grams of methyl chloride and 176 grams of tri- 40 methyl phosphite (plus toluene contamination). The yield 0 00H,

of product at 70 C./0.1 mm. was 840 grams. These data czNawHzocHm CHI/ P 163%; indicate a level of phosphonation of approximately the H theoretical 1 /2 phosphonate groups per mole of triazine. To illustratet the usefulness of the thus prepared composition, a padding solution was prepared containing:

Pe by weight P 14% pp P sphorus atoms per mole). 1 The above descnbed reaction product Nuclear magnetic resonance showed P OCH A 5% aqueous solution of octylphenoxypolyethoxy- 02 (5 3J5), OCH3 groups (5 .333) groups ethanol (6 5.2), and NCH --P groups (6 4.2). No -P-'-H signals A by Welght aqueous solutlon of mm mtrate could be detected, and mercuric chloride was not reduced Water by the product, indicating the absence of dimethyl hydro- This solution had a pH of 2.5. gen phosphonate therein.

Squares of 80 x 80 3.2 ounce cotton print cloth were To facilitate formulation asan ingredient of textile padded in this solution using two dips and two trips. They finishing solutions, the viscous product was diluted with were then dried 5 minutes at 110 C., and cured 5 minutes methanol to a concentration of 70%. It was then further at 163 C. to a 19% add-on, based on the original cloth diluted with water to obtain a 30% concentration suitable weight. for padding onto fabric.

The LOI of the cured fabric was 29.5. After one A portion of this solution was also heated at 100-110 C-) hot Water rinsing using agitation with ten towels as 60 C. in order to produce a White insoluble, i.e. thermoset, ballast, the rinsed fabric was equilbrated at relative resin having flame resistant properties. 7 humidity. It was found to be self-extinguishing in the vertical position with a 4.75 inch char length. It displayed :1 EXAMPLE X fairly good hand and no discoloration. i The thu treated loth wa then subjected to five 5 This example illustrates the preparation of a trlazlnyllaundry cycles, using 100 grams of detergent to 16 gallons aminoalkyl phosphonate by means of reaction process No. of water (200 ppm. hardness expressed as CaO with 6 as described hereinabove. i ten towels, as ballast, in a Maytag washer. When dry, the A mixture of 390 g. (1- mole) of hexamethoxymethylcloth had an LOI of 28.0. melamine, 372 g. (3 moles) of trimethyl phosphite and Another padding bath was prepared in which the con- 180 g. (3 moles) glacial acetic acid was heated at'98-153" centration of the above described reaction product was C. over a 6 hour period while allowing distillate to come reduced to 25%, by weight. However, it contained 5%, off at 52-63 vapor temperature until 256 g. of distilled on a solids basis, of a dimethylolethyleneurea. A cured had been collected. This distillate was found to be an cloth which had been padded in this bath had a 16.2% equimolar mixture of methanol and methylacetate. The dry add-on of this composition. residual reaction mixture was then vacuum stripped at 17 '1 105 C. and 20 mm. pressure so as to remove dissolved volatiles thereby leaving behind 631 g. (theory for of a viscous colorless syrup.

Anal.Calcd. for

v .H oaNnomoormxomr-(o-onm 3; P 16.0.

EXAMPLE XI This example illustrates the use, in a textile finishing operation, of the triazinylaminoalkyl phosphonate whose preparation was described in Example X hereinabove.

An aqueous formulation containing the following ingredients was prepared:

Percent Triazinylaminoalkyl phosphonate whose preparation is described in Example X 30 Polyoxyethylated alkylphenol Wetting agent 0.5 Zinc nitrate 2.5

Samples of 8 oz. cotton twill were padded to an 88% wet pickup of this formulation. After drying, the samples were cured at 160 C. for five minutes, followed by a half hour rinsing in hot running water. After three hours stirring and active boiling in water containing 0.5 soap and 0. 2% soda ash, the cloth samples were found to have retained 0.6 to 0.75% phosphorus out of the original 1.44 to 1.64% which was present immediately after the curing step. With another padding solution which contained.23% of a commercial methylolmelamine co-reactant inaddition to the above listed ingredients, retention was improved to two thirds of the original concentration of phosphorus which was present on the textile immediately subsequent to the cure. v

, EXAMPLE XII This example illustrates the preparation of a triazinylaminoalkyl phosphonate by means of a reaction process No. 5 as described hereinabove. i

7 Two hundred sixty grams'of .hexamethoxymethylmelamine- (0.67'moles) and 300 gramsof diethyl phosphite (2.17 moles) were heated for twenty hours at 110 to 138 C. while under reduced pressure (80-120 mm.) so as to remove methanol and ethanol, the latter having resulted from transesterificationwith.unreacted diethyl phosphite. v v

Stripping at a higher vacuum .yielded 441 grams of ,'.a syrupy product which was found, by an analysis',.tohave about 2.5 phosphonate groups per mole.

EXAMPLE XIII This example illustrates the use of reaction:iproisess'- N0. 1 for the preparation of a triazinylaminoalkyl phosphonate employing, in thisinstance, 50% aqueous solution of a partially methylated polymethylolmelamine and a dimethyl olated 'ethyleneurea as the starting reagent.

The starting reagent was stripped of its water, then 96 grams of the resulting residue was mixed with 111 grams of trimethyl phosphite (0.89 moles); the latter concentration being roughly calculated to produce a trisubstituted melamine. As the mixture was heated, it became homogeneous and, after being maintained for four hours at 92-120 C. and then briefly at 130 C./200 mm.,

about 75% of the theoretical methanol had distilled. The

stripped residue was warmed with twice its weight of methanol at a pH of 4'whereupon it was neutralized and stripped. The latter operation-converted any free N-meth-i' ylol groups to methoxymethyl groups, thereby increasing.

the pourability of the product. The .yield of mixed melamine N-methylphosphonic ester represented about 2.4.

per melamine molecule.

phosphonate groups EXAMPLE xiv I This example illustrates the use, in a textile finishing;

operation, of the triazinylaminoalkyl phosphonate whose preparation was described in Example XIII hereinabove.

An aqueous solution containing 30 parts of the triazinylaminoalkyl phosphonate derivative of Example XIII, 1 part: of a 25%, by weight, zinc nitrate solution and 0.2 parts;

of octylphenyloxypolyethoxyethanol was applied, via padding, to a 3.2 oz. per square yard cotton print cloth. The

fabric was then dried at C. for 5 minutes whereupon;

it was ,cured for 5 minutes at 163 C. 1 The cured fabric contained 1.6%, by weight, of phosphorus and produced an LOI of 28. Upon subjecting theztreated-fabric to one deteregnt-free hot water wash cy-.

cle in a washing machine, the fabric was found to have re-, tained 1.2% of phosphorus. The latter concentration was also retained after subjecting additional samples of this treated fabric to 5 repeated detergent wash cycles with 10 bath towels present as ballast.

EXAMPLE XV This example illustrates the preparation of a triazinylaminoalkyl phosphonate by means of reaction process No: 5 as described hereinabove.-

A total of 210 grams of a polymethoxymethylmelamine which was approximatelypentasubstituted with groups was heated to 143-165 C./ -250 mm. together with grams of dimethyl phosphite and 24 grams of trimethyl phosphite, the latter reagent being present to scavenge acidity, for a period of six hours so as to yield 43 grams of a slightly contaminated methanol"by-product. Heating'in a hot water bath, under 0.1 mm. pressure, then yielded 34 grams of unreacted dimethyl phosphite along with a residue which weighed 306 grams, thereby .;-indicating incorporation of 1.23 phosphonate groups in the desired reaction product. Thus, about 40% of all of the available methoxymethyl groups were converted to methylenephosphonic ,ester' groupjs.

EXAMPLE XVI Thisexample illustrates v,the use for the finishing of textiles of the derivative whose preparation was described in Example XV hereinabove. 7

An aqueous solution containing the following ingredients was prepared:

. Parts by weight The derivative of'Exarnple XV 30.0 "Zincfnitrate' (25%by wt., aqueous solution) 1.0

A total of 150 grams of 95% paraformaldehyde (4.7- 4.8 moles) was dissolved by heating it with 240 ml. of

19 methanol at pH 11.6 to 8.8. After adding 200 ml. of additional methanol, the resulting mixture was heated, at 75 C., with 126 grams of melamine (one mole) at pH 9, for three hours. The desired partial methylolation was achieved although the solid phase did not dissolve even after introducing an additional mole of methanolic formaldehyde. While being maintained at 4050 C. 250 grams of trimethyl phosphite (2 moles) was then added dropwise over three hours. Analysis showed no unreacted phosphite. Gradual heating of the resulting mixture for one hour with three additional moles of paraformaldehyde in methanol to a temperature of 70 C. resulted in a clear solution indicating methylolation of essentially all of the unphosphonated --N-H groups particularly after an additional twenty minutes of heating at 57 C. and a pH of 8.1. With the pH lowered to 5, these hydroxymethyl groups were then methylated, at 55 C., by the large excess of methanol now present (24 moles).i-With the pH readjusted to 7, substantially all of the methanol was stripped until the resulting concentrate displayed a convenient viscosity with about 85%, by weight, of solids. Variations may be made in proportions, procedures and materials without departing from the scope of this invention as defined by the following claims.

What we claim is:

1. A process for the fiameproofing of textiles, said process comprising the steps of:

(1) absorbing throughout the mass of said textile or applying to at least one surface thereof the triazinylaminoalkyl phosphonates corresponding to the structural formula:

where A, B and C are an -NR R group; wherein R and R are selected from the group consisting of hydrogen, C -C alkyl, (Z -C hydroxyalkyl, methylene, methyleneoxymethylene, C -C alkoxymethyl and Z where Z is a phosphonate radical of the structure (CH10),,CR R l '(0R )(OB) where n is an integer having a value of from to l, R and R are selected from the group consisting of hydrogen and C -C alkyl and where R and R are selected from the group consisting of C -C alkyl, C C alkoxyalkyl, allyl, Cg-C1 2-haloalkyl, and 0 -0 2-hydroxyalkyl with the proviso that at least one Z group is present in the molecule of said trizinylaminoalkyl phosphonate and that where R or R is a methylene or methyleneoxymethylene group the remaining valence thereof is attached to another triazine nucleus as here defined; and (2) crosslinking said triazinylaminoalkyl phosphonate which are thereafter present. in or on said textile as a result of Step (1), thereby yielding a fire retardant finish for said textile. 2. A process for fiameproofing of textiles, said process comprising the steps of:- r

. (1) absorbing throughout the mass of;said textile or applying to at least one surface thereof the triazinylaminoalkyl phosphonates corresponding to the structural formula:

wherein A, B and C are all -NR R in which R and R are selected from the group consisting of hydrogen, methylol, C -C alkoxymethyl, methylene, methyleneoxymethylene and Z, wherein Z is a phosphonate radical of the structure where n is an integer having a value of from 0 to 1, R and R are selected from the group consisting of hydrogen and l -C alkyl and where R and R are selected from the group consisting of C -C alkyl, (Z -C alkoxyalkyl, allyl, C C 2-haloa lkyl, and C -C3 2-hydroxyalkyl with the proviso that at least one Z group is present in the molecule of said triazinylaminoalkyl phosphonate and that where R or R is a methylene or methyleneoxymethylene group the remaining valence thereof is attached to another triazine nucleus as here defined; and

(2) crosslinking the triazinylaminoalkyl phosphonates which are thereafter present in or on said textile as a result of Step (1), thereby yielding a fire retardant finish for said textile.

3. A process for the flameproofing of textiles, said process comprising the steps of:

(1) absorbing throughout the mass of said textile or apply to at least one surface thereof triazinylaminoalkyl phosphonates wherein said phosphonates are present as part of mixtures containing at least two compounds corresponding to the structure:

where A, B and C are all NR R in which R and R are selected from the group consisting of hydrogen, methylol, C C alkoxymethyl, methylene,

methyleneoxymethylene and 2 where Z is a phosphonate radical having the structure with the proviso that from one to five of the R or R groups is Z and that at least one of the R or R groups is a methylol or a C -C alkoxymethyl group and that no more than two of the R and R groups is hydrogen; and

(2) crosslinking the triazinylaminoalkyl phosphonates which are thereafter present in or on said textile as a result of Step 1), thereby yielding a fire retardant finish for said textile.

References Cited UNITED STATES PATENTS 2,634,270 4/1953 Nielsen 117,l36 X 2,666,078 1/1954 Ferguson 117-436 X 3,551,422 12/1970 Tesoro et al. 260249.6

WILLIAM D. MARTIN, Primary Examiner T. G. DAVIS, Assistant Examiner U.S. Cl. X.R. 1l7l 38.8 B, 138.8 F, 138.8 N, 143 R, 144, 145

UNITED STATES PATENT OFFICE g CERTIFICATE OF CORRECTION Patent NO. 3,832,227 Dated ug st 27 1974 Inventorts) E. Weil, R- Fearing It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 2, line 5, change "384,785" to --884,785-;

Col. 4, in the formula between lines 1 and 9, change that portion reading "(CH OCH )-N-" to --(CH OCH -N- Col. 6, lines 3+ and 39, change 2 "-NR -R to NR R y Col. 6, line 62;, change "is" after "used". to --in-;

' Col. 6, line 72, before "at" insert -or a fully or partially methylated pentamethylolmelamine;-

Col. 7, line 1, change "distalliation" to --distillation-;

Col. 7, line 6, change "unrecated" to --unreacted---;

Col. 7, line 15, after "at a" insert -trialkyl phosphite, such as trimethyl phosphite, and from about 0.3 to 6, preferably- 1 to 5,

moles of a 7 Col.- 8, line 48, change "catalyst" to catalysis Col. 10, line 10, change "formaldehyde," to -formaldehyde.-; Col. 12, lines 35-36, change "in this preparation" to of this invention;

Col. 12, line 49, change phop'shonate" to phosphonate--; Col. 14, lines 51-53, delete contained inside the square brackets in the formula; v Col. 15, line 1, insert a-- after "and"; v Col. 15, the formula given in footnote 1 for the LOI should be changed to read [0 -LOI X Col. 15, line 44, change "illustratet" to --illustrate- Col. 15, line 67, change "CaO to --CaCO- Col. 18, line 23, change "deter'egnt" to --detergenc--; y 7 Col. 19, line 5 change "trizinylaminoalkyl" to---triazinyla'minoajkyl Col. 20, lines 6-8, change the formula to read 9 -(CH=0) CR RP(OR (0R Signed and sealedthis 1st day of April 1975.

(SEAL) Attest:

c. MARSHALL DANN RUTH C. MASON Commissioner of Patents and Trademarks Attesting Officer